TW202340364A - resin composition - Google Patents

resin composition Download PDF

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Publication number
TW202340364A
TW202340364A TW111149172A TW111149172A TW202340364A TW 202340364 A TW202340364 A TW 202340364A TW 111149172 A TW111149172 A TW 111149172A TW 111149172 A TW111149172 A TW 111149172A TW 202340364 A TW202340364 A TW 202340364A
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resin composition
group
resin
mass
epoxy resin
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TW111149172A
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Chinese (zh)
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藤島祥平
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日商味之素股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising 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
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • 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
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
    • H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Epoxy Resins (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention addresses the problem of providing a resin composition with which it is possible to obtain a cured product having excellent crack resistance. A resin composition containing (A) an epoxy resin, (B) a compound containing a radically polymerizable group, and (C) a curing accelerator, the component (C) containing (C1) a compound having a nitrogen-containing heterocyclic ring substituted with a hydrocarbon group having 7 or more carbon atoms.

Description

樹脂組成物resin composition

本發明係關於包含環氧樹脂的樹脂組成物。進一步地，關於使用該樹脂組成物而得到的樹脂片材、印刷配線板和半導體裝置。The present invention relates to a resin composition containing an epoxy resin. Furthermore, it relates to the resin sheet, the printed wiring board, and the semiconductor device obtained using this resin composition.

作為印刷配線板的製造技術，已知利用交替層合絕緣層和導體層的堆疊(build-up)方式的製造方法。在基於堆疊方式的製造方法中，一般而言，絕緣層使包含環氧樹脂的樹脂組成物硬化而形成(專利文獻1)。As a manufacturing technology for printed wiring boards, a manufacturing method using a build-up system in which insulating layers and conductor layers are alternately laminated is known. In a manufacturing method based on a stacking method, generally, an insulating layer is formed by hardening a resin composition containing an epoxy resin (Patent Document 1).

近年來，伴隨印刷配線板的配線的進一步微細化、高密度化、信號的高頻化，需求絕緣層的相對介電常數、介電損耗角正切的進一步的降低。作為其改善方法之一，研究了環氧樹脂與含有自由基聚合性基團的化合物的併用。In recent years, as wiring on printed wiring boards has become further miniaturized and denser, and signals have become higher frequency, there has been a need to further reduce the relative permittivity and dielectric loss tangent of the insulating layer. As one of the improvement methods, the combined use of an epoxy resin and a compound containing a radically polymerizable group has been studied.

然而，迄今為止，已知使用了含有自由基聚合性基團的化合物的情況下，有時硬化物的玻璃轉移溫度降低。為了防止玻璃轉移溫度的降低，需要除了使用含有自由基聚合性基團的化合物，而且使用硬化促進劑，但使用硬化促進劑的情況下，預硬化狀態下的硬化度顯著增加，過剩的內部應力蓄積，形成引起由含有自由基聚合性基團的化合物導致的裂紋的課題。 [先前技術文獻] [專利文獻] However, it has been known that when a compound containing a radically polymerizable group is used, the glass transition temperature of the cured product may be lowered. In order to prevent the glass transition temperature from lowering, it is necessary to use a hardening accelerator in addition to a compound containing a radically polymerizable group. However, when a hardening accelerator is used, the degree of hardening in the pre-hardened state significantly increases, resulting in excessive internal stress. There is a problem of accumulation and causing cracks caused by compounds containing radically polymerizable groups. [Prior technical literature] [Patent Document]

專利文獻1：日本特開2021-130780號公報Patent Document 1: Japanese Patent Application Publication No. 2021-130780

[發明所欲解決之課題][Problem to be solved by the invention]

本發明的課題在於提供能夠得到耐裂紋性優異的硬化物的樹脂組成物。 [用以解決課題之手段] An object of the present invention is to provide a resin composition capable of obtaining a cured product having excellent crack resistance. [Means used to solve problems]

為了實現本發明的課題，本發明人等進行了努力研究，結果發現：通過使用伴有具有被碳數7以上的烴基取代的含氮雜環的立體障礙的化合物作為(C)硬化促進劑，令人意外地能夠得到耐裂紋性優異的硬化物，從而完成了本發明。In order to achieve the object of the present invention, the present inventors conducted diligent research and found that by using a compound with a steric hindrance having a nitrogen-containing heterocyclic ring substituted with a hydrocarbon group having 7 or more carbon atoms as the (C) hardening accelerator, Surprisingly, a hardened material excellent in crack resistance can be obtained, and the present invention was completed.

即，本發明包含以下的內容。 [1] 一種樹脂組成物，其是包含(A)環氧樹脂、(B)含有自由基聚合性基團的化合物和(C)硬化促進劑的樹脂組成物， 其中(C)成分包含：(C1)具有被碳數7以上的烴基取代的含氮雜環的化合物。 [2] 根據上述[1]所述的樹脂組成物，其中 (C1)成分包含式(C)所示的化合物， That is, the present invention includes the following contents. [1] A resin composition containing (A) epoxy resin, (B) a compound containing a radical polymerizable group, and (C) a hardening accelerator, The component (C) includes: (C1) a compound having a nitrogen-containing heterocyclic ring substituted by a hydrocarbon group having 7 or more carbon atoms. [2] The resin composition according to the above [1], wherein (C1) component contains a compound represented by formula (C),

[式中， R 1表示碳數7以上的烷基或碳數7以上的烯基； R 2表示氫原子、可具有取代基的烷基、可具有取代基的烯基、可具有取代基的芳基，或可具有取代基的雜芳基； R 3和R 4分別獨立地表示氫原子或取代基，或者R 3和R 4一起鍵結而形成可具有取代基的芳環或可具有取代基的非芳環； 由虛線和實線組成的雙重線表示單鍵或雙鍵]。 [3] 根據上述[2]所述的樹脂組成物，其中 R 2為式(R2)所示的基團， [In the formula, R 1 represents an alkyl group having 7 or more carbon atoms or an alkenyl group having 7 or more carbon atoms; R 2 represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an alkenyl group which may have a substituent. Aryl, or heteroaryl that may have a substituent; R 3 and R 4 independently represent a hydrogen atom or a substituent, or R 3 and R 4 are bonded together to form an aromatic ring that may have a substituent or may have a substitution nonaromatic ring of the base; the double line consisting of a dashed and a solid line represents a single or double bond]. [3] The resin composition according to the above [2], wherein R 2 is a group represented by formula (R2),

[式中， X表示碳數1~6的伸烷基； Y表示單鍵、-O-、-CO-、-S-、-SO-、-SO 2-、-NH-、 -COO-、-OCO-、-CONH-或-NHCO-； *表示鍵結部位]。 [4] 根據上述[1]~[3]中任一項所述的樹脂組成物，其中將樹脂組成物中的不揮發成分設為100質量%時，(C1)成分的含量為0.001質量%~1質量%。 [5] 根據上述[1]~[4]中任一項所述的樹脂組成物，其中將樹脂組成物中的不揮發成分設為100質量%時，(A)成分的含量為10質量%~30質量%。 [6] 根據上述[1]~[5]中任一項所述的樹脂組成物，其中進一步包含(D)無機填充材料。 [7] 根據上述[6]所述的樹脂組成物，其中(D)成分的材料包含選自二氧化矽、氧化鋁和鋁矽酸鹽中的材料。 [8] 根據上述[6]或[7]所述的樹脂組成物，其中將樹脂組成物中的不揮發成分設為100質量%時，(D)成分的含量為70質量%以上。 [9] 根據上述[1]~[8]中任一項所述的樹脂組成物，其中進一步包含(E)環氧樹脂硬化劑。 [10] 根據上述[9]所述的樹脂組成物，其中(E)成分包含活性酯系硬化劑。 [11] 根據上述[9]或[10]所述的樹脂組成物，其中(E)成分包含酚系硬化劑。 [12] 根據上述[1]~[11]中任一項所述的樹脂組成物，其中在5.8GHz、23℃的條件下進行測定時，樹脂組成物的硬化物的相對介電常數(Dk)為3.5以下。 [13] 根據上述[1]~[12]中任一項所述的樹脂組成物，其中在5.8GHz、23℃的條件下進行測定時，樹脂組成物的硬化物的介電損耗角正切(Df)為0.005以下。 [14] 根據上述[1]~[13]中任一項所述的樹脂組成物，其中樹脂組成物的硬化物的線熱膨脹係數(CTE)在25℃~150℃的範圍內為25ppm/K以下。 [15] 根據上述[1]~[14]中任一項所述的樹脂組成物，其中樹脂組成物的硬化物的玻璃轉移溫度(Tg)為150℃以上。 [16] 一種硬化物，其是上述[1]~[15]中任一項所述的樹脂組成物的硬化物。 [17] 一種片狀疊層材料，其含有上述[1]~[15]中任一項所述的樹脂組成物。 [18] 一種樹脂片材，其具有：支承體，和設置於該支承體上的由上述[1]~[15]中任一項所述的樹脂組成物形成的樹脂組成物層。 [19] 一種印刷配線板，其具備絕緣層，所述絕緣層包含上述[1]~[15]中任一項所述的樹脂組成物的硬化物。 [20] 一種半導體裝置，其包含上述[19]所述的印刷配線板。 [發明的效果] [In the formula, X represents an alkylene group having 1 to 6 carbon atoms; Y represents a single bond, -O-, -CO-, -S-, -SO-, -SO 2 -, -NH-, -COO-, -OCO-, -CONH- or -NHCO-; *denotes the bonding site]. [4] The resin composition according to any one of the above [1] to [3], wherein the content of component (C1) is 0.001 mass% when the non-volatile components in the resin composition are 100 mass% ~1% by mass. [5] The resin composition according to any one of the above [1] to [4], wherein the content of component (A) is 10 mass% when the non-volatile components in the resin composition are 100 mass% ~30% by mass. [6] The resin composition according to any one of the above [1] to [5], further comprising (D) an inorganic filler. [7] The resin composition according to the above [6], wherein the material of component (D) contains a material selected from the group consisting of silica, alumina, and aluminosilicates. [8] The resin composition according to the above [6] or [7], wherein the content of component (D) is 70 mass% or more when the non-volatile components in the resin composition are 100 mass%. [9] The resin composition according to any one of the above [1] to [8], further comprising (E) an epoxy resin hardener. [10] The resin composition according to the above [9], wherein the component (E) contains an active ester-based hardener. [11] The resin composition according to the above [9] or [10], wherein the component (E) contains a phenolic hardener. [12] The resin composition according to any one of the above [1] to [11], wherein when measured under the conditions of 5.8 GHz and 23°C, the relative dielectric constant (Dk) of the cured product of the resin composition ) is less than 3.5. [13] The resin composition according to any one of the above [1] to [12], wherein when measured under the conditions of 5.8 GHz and 23°C, the dielectric loss tangent of the cured product of the resin composition is ( Df) is less than 0.005. [14] The resin composition according to any one of the above [1] to [13], wherein the linear thermal expansion coefficient (CTE) of the cured product of the resin composition is 25 ppm/K in the range of 25°C to 150°C. the following. [15] The resin composition according to any one of the above [1] to [14], wherein the glass transition temperature (Tg) of the cured product of the resin composition is 150°C or higher. [16] A cured product of the resin composition according to any one of the above [1] to [15]. [17] A sheet-like laminated material containing the resin composition described in any one of the above [1] to [15]. [18] A resin sheet having: a support body; and a resin composition layer formed of the resin composition described in any one of the above [1] to [15] and provided on the support body. [19] A printed wiring board provided with an insulating layer containing a cured product of the resin composition according to any one of the above [1] to [15]. [20] A semiconductor device including the printed wiring board according to the above [19]. [Effects of the invention]

根據本發明的樹脂組成物，能夠得到耐裂紋性優異的硬化物。According to the resin composition of the present invention, a cured product excellent in crack resistance can be obtained.

以下，以其優選的實施方式對本發明進行詳細說明。但是，本發明並不限定於下述實施方式及示例物，可在不脫離本發明的申請專利範圍及其均等範圍的範圍內任意變更實施。Hereinafter, the present invention will be described in detail with its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented without departing from the patentable scope of the present invention and its equivalent range.

＜樹脂組成物＞ 本發明的樹脂組成物包含(A)環氧樹脂、(B)含有自由基聚合性基團的化合物和(C)硬化促進劑，(C)硬化促進劑包含(C1)具有被碳數7以上的烴基取代的含氮雜環的化合物。根據這種樹脂組成物，能夠得到耐裂紋性優異的硬化物。 ＜Resin composition＞ The resin composition of the present invention contains (A) epoxy resin, (B) a compound containing a radically polymerizable group, and (C) a curing accelerator, and the (C) curing accelerator contains (C1) having a carbon number of 7 or more Hydrocarbyl-substituted nitrogen-containing heterocyclic compounds. According to this resin composition, a cured product excellent in crack resistance can be obtained.

本發明的樹脂組成物除了包含(A)環氧樹脂、(B)含有自由基聚合性基團的化合物，和(C)硬化促進劑以外，也可以還包含任意的成分。作為任意的成分，可舉出例如(D)無機填充材料、(E)環氧樹脂硬化劑、(F)熱塑性樹脂、(G)其他添加劑和(H)有機溶劑。The resin composition of the present invention may contain optional components in addition to (A) epoxy resin, (B) radically polymerizable group-containing compound, and (C) curing accelerator. Examples of optional components include (D) inorganic filler, (E) epoxy resin hardener, (F) thermoplastic resin, (G) other additives, and (H) organic solvent.

以下，對於樹脂組成物中包含的各成分進行詳細說明。Each component contained in the resin composition will be described in detail below.

＜(A)環氧樹脂＞ 本發明的樹脂組成物含有(A)環氧樹脂。(A)環氧樹脂是指具有環氧基的環氧當量5000g/eq.以下的硬化性樹脂。此處說明的(A)環氧樹脂是除屬於下述說明的(B)含有自由基聚合性基團的化合物，和(F)熱塑性樹脂的物質以外的成分。 ＜(A) Epoxy resin＞ The resin composition of the present invention contains (A) epoxy resin. (A) Epoxy resin refers to a curable resin having an epoxy group and an epoxy equivalent of 5000 g/eq. or less. The (A) epoxy resin described here is a component other than the following (B) radically polymerizable group-containing compound and (F) thermoplastic resin.

作為(A)環氧樹脂，可舉出例如聯二甲酚(bixylenol)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、雙環戊二烯型環氧樹脂、三酚型環氧樹脂、萘酚酚醛清漆(naphthol novolac)型環氧樹脂、苯酚酚醛清漆(phenol novolac)型環氧樹脂、叔丁基-鄰苯二酚型環氧樹脂、萘型環氧樹脂、萘酚型環氧樹脂、蒽型環氧樹脂、縮水甘油基胺型環氧樹脂、縮水甘油基酯型環氧樹脂、甲酚酚醛清漆(cresol novolac)型環氧樹脂、苯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、具有丁二烯結構的環氧樹脂、脂環族環氧樹脂、雜環式環氧樹脂、含有螺環的環氧樹脂、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、異氰脲酸酯型環氧樹脂、苯酚苯并吡咯酮(phenolphthalimidine)型環氧樹脂等。(A)環氧樹脂可以單獨使用1種，也可組合使用2種以上。Examples of the (A) epoxy resin include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol type epoxy resin. AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac 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, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac Varnish (cresol novolac) type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin , Heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane 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 resin may be used individually by 1 type, and may be used in combination of 2 or more types.

對於本發明的樹脂組成物而言，作為(A)環氧樹脂，較好是包含在1分子中具有2個以上環氧基的環氧樹脂。相對於(A)環氧樹脂100質量%，在1分子中具有2個以上環氧基的環氧樹脂的比例較好是50質量%以上，更好是60質量%以上，特別好是70質量%以上。In the resin composition of the present invention, the (A) epoxy resin preferably contains an epoxy resin having two or more epoxy groups per molecule. The proportion of the epoxy resin having two or more epoxy groups per molecule is preferably 50 mass% or more, more preferably 60 mass% or more, particularly preferably 70 mass%, based on 100 mass% of (A) epoxy resin. %above.

(A)環氧樹脂包括在20℃的溫度下為液態的環氧樹脂(以下有時稱為「液態環氧樹脂」)和在20℃的溫度下為固態的環氧樹脂(以下有時稱為「固態環氧樹脂」)。對於本發明的樹脂組成物而言，作為環氧樹脂，可以僅包含液態環氧樹脂，或者也可僅包含固態環氧樹脂，或者也可包含液態環氧樹脂和固態環氧樹脂這兩者，特別好是包含液態環氧樹脂和固態環氧樹脂這兩者。(A) Epoxy resin includes an epoxy resin that is liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resin") for "solid epoxy resin"). The resin composition of the present invention may contain only liquid epoxy resin, only solid epoxy resin, or both liquid epoxy resin and solid epoxy resin as the epoxy resin. It is particularly preferable to include both liquid epoxy resin and solid epoxy resin.

作為液態環氧樹脂，較好是在1分子中具有2個以上環氧基的液態環氧樹脂。As the liquid epoxy resin, one having two or more epoxy groups per molecule is preferred.

作為液態環氧樹脂，較好是甘草醇(Glycirol)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、縮水甘油基酯型環氧樹脂、縮水甘油基胺型環氧樹脂、苯酚酚醛清漆型環氧樹脂、具有酯骨架的脂環族環氧樹脂、環己烷二甲醇型環氧樹脂、環狀脂肪族縮水甘油基醚，和具有丁二烯結構的環氧樹脂。As the liquid epoxy resin, preferred are Glycirol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, and shrinkage type epoxy resin. Glyceryl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, cycloaliphatic epoxy resin with ester skeleton, cyclohexanedimethanol type epoxy resin, cycloaliphatic Glycidyl ether, and epoxy resin with butadiene structure.

作為液態環氧樹脂的具體例，可舉出Nagase ChemteX公司製的「EX-992L」、三菱化學公司製的「YX7400」、DIC公司製的「HP4032」、「HP4032D」、「HP4032SS」(萘型環氧樹脂)；三菱化學公司製的「828US」、「jER828EL」、「828EL」、「825」、「EPIKOTE 828EL」(雙酚A型環氧樹脂)；三菱化學公司製的「jER807」、「1750」(雙酚F型環氧樹脂)；三菱化學公司製的「jER152」(苯酚酚醛清漆型環氧樹脂)；三菱化學公司製的「630」、「630LSD」、「604」(縮水甘油基胺型環氧樹脂)；ADEKA公司製的「ED-523T」(Glycirol型環氧樹脂)；ADEKA公司製的「EP-3950L」、「EP-3980S」(縮水甘油基胺型環氧樹脂)；ADEKA公司製的「EP-4088S」(雙環戊二烯型環氧樹脂)；日鐵化學材料公司製的「ZX1059」(雙酚A型環氧樹脂與雙酚F型環氧樹脂的混合品)；Nagase ChemteX公司製的「EX-721」(縮水甘油基酯型環氧樹脂)；Nagase ChemteX公司製的「EX-991L」(含有伸烷氧基骨架和丁二烯骨架的環氧樹脂)；大賽璐公司製的「Celloxide 2021P」(具有酯骨架的脂環族環氧樹脂)；日鐵化學材料公司製的「ZX1658」、「ZX1658GS」(液態1,4-縮水甘油基環己烷型環氧樹脂)；大阪燃氣化學公司製的「EG-280」(含有茀結構的環氧樹脂)；Nagase ChemteX公司製「EX-201」(環狀脂肪族縮水甘油基醚)等。Specific examples of liquid epoxy resins include "EX-992L" manufactured by Nagase Chemte Epoxy resin); "828US", "jER828EL", "828EL", "825", "EPIKOTE 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807", " 1750" (bisphenol F type epoxy resin); "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidyl group) manufactured by Mitsubishi Chemical Corporation Amine type epoxy resin); "ED-523T" (Glycirol type epoxy resin) manufactured by ADEKA; "EP-3950L" and "EP-3980S" (glycidyl amine type epoxy resin) manufactured by ADEKA; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA; "ZX1059" (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd. ; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation; "EX-991L" (epoxy resin containing an alkyleneoxy skeleton and a butadiene skeleton) manufactured by Nagase ChemteX Corporation; "Celloxide 2021P" manufactured by Daicel Corporation (alicyclic epoxy resin with an ester skeleton); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel Chemical Materials Corporation (liquid 1,4-glycidylcyclohexane type epoxy resin) Oxygen resin); "EG-280" (epoxy resin containing fluorine structure) produced by Osaka Gas Chemical Co., Ltd.; "EX-201" (cyclic aliphatic glycidyl ether) produced by Nagase ChemteX Co., Ltd., etc.

作為固態環氧樹脂，較好是在1分子中具有3個以上環氧基的固態環氧樹脂，更好是在1分子中具有3個以上環氧基的芳族系的固態環氧樹脂。The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups per molecule, and more preferably an aromatic solid epoxy resin having three or more epoxy groups per molecule.

作為固態環氧樹脂，較好是聯二甲酚型環氧樹脂、萘型環氧樹脂、萘型四官能環氧樹脂、萘酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙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、苯酚芳烷基型環氧樹脂、四苯基乙烷型環氧樹脂、苯酚苯并吡咯酮型環氧樹脂。As the solid epoxy resin, preferred are dixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolak type epoxy resin, cresol novolac type epoxy resin, Dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type ring Oxygen resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenyl ethane type epoxy resin, phenol benzopyrrolone type epoxy resin.

作為固態環氧樹脂的具體例，可舉出：DIC公司製的「HP4032H」(萘型環氧樹脂)；DIC公司製的「HP-4700」、「HP-4710」(萘型四官能環氧樹脂)；DIC公司製的「N-690」(甲酚酚醛清漆型環氧樹脂)；DIC公司製的「N-695」(甲酚酚醛清漆型環氧樹脂)；DIC公司製的「HP-7200」、「HP-7200HH」、「HP-7200H」、「HP-7200L」(雙環戊二烯型環氧樹脂)；DIC公司製的「EXA-7311」、「EXA-7311-G3」、「EXA-7311-G4」、「EXA-7311-G4S」、「HP6000」(伸萘基醚型環氧樹脂)；日本化藥公司製的「EPPN-502H」(三酚型環氧樹脂)；日本化藥公司製的「NC7000L」(萘酚酚醛清漆型環氧樹脂)；日本化藥公司製的「NC3000H」、「NC3000」、「NC3000L」、「NC3000FH」、「NC3100」(聯苯型環氧樹脂)；日鐵化學材料公司製的「ESN475V」、「ESN4100V」(萘型環氧樹脂)；日鐵化學材料公司製的「ESN485」(萘酚型環氧樹脂)；日鐵化學材料公司製的「ESN375」(二羥基萘型環氧樹脂)；三菱化學公司製的「YX4000H」、「YX4000」、「YX4000HK」、「YL7890」(聯二甲酚型環氧樹脂)；三菱化學公司製的「YL6121」(聯苯型環氧樹脂)；三菱化學公司製的「YX8800」(蒽型環氧樹脂)；三菱化學公司製的「YX7700」(苯酚芳烷基型環氧樹脂)；大阪燃氣化學公司製的「PG-100」、「CG-500」；三菱化學公司製的「YL7760」(雙酚AF型環氧樹脂)；三菱化學公司製的「YL7800」(茀型環氧樹脂)；三菱化學公司製的「jER1010」(雙酚A型環氧樹脂)；三菱化學公司製的「jER1031S」(四苯基乙烷型環氧樹脂)；日本化藥公司製的「WHR991S」(苯酚苯并吡咯酮型環氧樹脂)等。這些固態環氧樹脂可以單獨使用1種，也可以組合使用2種以上。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 Resin); "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP- 7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", " EXA-7311-G4", "EXA-7311-G4S", "HP6000" (alkylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; Japan "NC7000L" (naphthol novolak type epoxy resin) manufactured by Nippon Chemical Industry Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Chemical Industry Co., Ltd. Resin); "ESN475V" and "ESN4100V" (naphthalene type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd.; "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd.; manufactured by Nippon Steel Chemical Materials Co., Ltd. "ESN375" (dihydroxynaphthalene type epoxy resin); "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; manufactured by Mitsubishi Chemical Corporation "YL6121" (biphenyl-type epoxy resin); "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" (phenol aralkyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Osaka Gas "PG-100" and "CG-500" manufactured by Chemical Corporation; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenyl ethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR991S" (phenol benzene) manufactured by Nippon Kayaku Corporation pyrrolone type epoxy resin), etc. These solid epoxy resins may be used individually by 1 type, or in combination of 2 or more types.

作為(A)環氧樹脂，組合使用固態環氧樹脂和液態環氧樹脂的情況下，它們的質量比(固態環氧樹脂：液態環氧樹脂)較好是10：1~1：50，更好是5：1~1：20，特別好是2：1~1：10。As (A) epoxy resin, when solid epoxy resin and liquid epoxy resin are used in combination, their mass ratio (solid epoxy resin: liquid epoxy resin) is preferably 10:1 to 1:50, more preferably A good time is 5:1~1:20, an especially good time is 2:1~1:10.

(A)環氧樹脂的環氧當量較好是50g/eq.~ 5000g/eq.，更好是60g/eq.~2000g/eq.，進一步較好是70g/eq.~1000g/eq.，進一步更好是80g/eq.~500g/eq.。環氧當量為每1當量環氧基的樹脂的質量。該環氧當量可按照JIS K7236進行測定。(A) The epoxy equivalent of the epoxy resin is preferably 50g/eq.~5000g/eq., more preferably 60g/eq.~2000g/eq., further preferably 70g/eq.~1000g/eq., Even better is 80g/eq.~500g/eq. The epoxy equivalent is the mass of the resin per 1 equivalent of epoxy groups. The epoxy equivalent can be measured in accordance with JIS K7236.

(A)環氧樹脂的重量平均分子量(Mw)較好是100~5000，更好是250~3000，進一步較好是400~1500。樹脂的重量平均分子量可以通過凝膠滲透層析(GPC)法，作為經聚苯乙烯換算的值而測定。(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, further preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a polystyrene-converted value by gel permeation chromatography (GPC).

樹脂組成物中的(A)環氧樹脂的含量沒有特別限定，將樹脂組成物中的不揮發成分設為100質量%時，較好是50質量%以下，更好是40質量%以下，進一步較好是35質量%以下，進一步更好是30質量%以下，特別好是25質量%以下。樹脂組成物中的(A)環氧樹脂的含量的下限沒有特別限定，將樹脂組成物中的不揮發成分設為100質量%時，較好是0.5質量%以上，更好是1質量%以上，進一步較好是5質量%以上，進一步更好是10質量%以上，特別好是15質量%以上。The content of (A) epoxy resin in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less. Further, The content is preferably 35 mass% or less, more preferably 30 mass% or less, and particularly preferably 25 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 component in the resin composition is 100% by mass, it is preferably 0.5% by mass or more, more preferably 1% by mass or more. , more preferably 5 mass % or more, still more preferably 10 mass % or more, particularly preferably 15 mass % or more.

＜(B)含有自由基聚合性基團的化合物＞ 本發明的樹脂組成物含有(B)含有自由基聚合性基團的化合物。(B)含有自由基聚合性基團的化合物是指在1分子中含有1個以上(較好是2個以上)的自由基聚合性基團的化合物。(B)含有自由基聚合性基團的化合物可以單獨使用1種，也可以組合使用2種以上。 <(B) Compound containing radically polymerizable group> The resin composition of the present invention contains (B) a compound containing a radically polymerizable group. (B) The compound containing a radically polymerizable group refers to a compound containing one or more (preferably two or more) radically polymerizable groups in one molecule. (B) The compound containing a radical polymerizable group may be used individually by 1 type, or may be used in combination of 2 or more types.

自由基聚合性基團是指具有自由基聚合性的烯屬性不飽和鍵的基團，作為例子，沒有特別限定，可舉出(1)丙烯醯基、(2)甲基丙烯醯基、(3)烯丙基、(4)甲基烯丙基(metallyl)、(5)被選自乙烯基和異丙烯基中的基團取代且可進一步被烷基取代的苯基(例如，乙烯基苯基(即4-乙烯基苯基、3-乙烯基苯基、2-乙烯基苯基)、異丙烯基苯基(即4-異丙烯基苯基、3-異丙烯基苯基、2-異丙烯基苯基)等)、(6)被選自乙烯基和異丙烯基中的基團取代且可進一步被烷基取代的苄基(例如，乙烯基苄基(即4-乙烯基苄基、3-乙烯基苄基、2-乙烯基苄基)、異丙烯基苄基(即4-異丙烯基苄基、3-異丙烯基苄基、2-異丙烯基苄基)等)、(7)馬來醯亞胺基(2,5-二氫-2,5-二氧代-1H-吡咯-1-基)等。A radically polymerizable group refers to a group having a radically polymerizable ethylenically unsaturated bond. Examples thereof are not particularly limited, and include (1) acrylyl group, (2) methacrylyl group, ( 3) allyl, (4) metallyl, (5) phenyl substituted with a group selected from vinyl and isopropenyl and which may be further substituted with an alkyl group (for example, vinyl Phenyl (i.e. 4-vinylphenyl, 3-vinylphenyl, 2-vinylphenyl), isopropenylphenyl (i.e. 4-isopropenylphenyl, 3-isopropenylphenyl, 2 -isopropenylphenyl), etc.), (6) a benzyl group substituted with a group selected from vinyl and isopropenyl and which may be further substituted by an alkyl group (for example, vinylbenzyl (i.e., 4-vinyl Benzyl, 3-vinylbenzyl, 2-vinylbenzyl), isopropenylbenzyl (i.e. 4-isopropenylbenzyl, 3-isopropenylbenzyl, 2-isopropenylbenzyl), etc. ), (7) maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl), etc.

在第一實施方式中，(B)含有自由基聚合性基團的化合物較好是包含具有2個以上自由基聚合性基團的熱塑性樹脂(例如數量平均分子量800以上)。作為熱塑性樹脂，沒有特別限定，可舉出例如苯氧樹脂、聚乙烯醇縮醛樹脂、聚苯乙烯樹脂、聚乙烯樹脂、聚丙烯樹脂、聚丁二烯樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醚醯亞胺樹脂、聚碸樹脂、聚醚碸樹脂、聚苯醚樹脂、聚醚醚酮樹脂、聚酯樹脂等，在該實施方式中，(B)含有自由基聚合性基團的化合物包含這些樹脂的具有2個以上自由基聚合性基團的改性樹脂。In the first embodiment, (B) the radically polymerizable group-containing compound preferably contains a thermoplastic resin having two or more radically polymerizable groups (for example, the number average molecular weight is 800 or more). The thermoplastic resin is not particularly limited, and examples thereof include phenoxy resin, polyvinyl acetal resin, polystyrene resin, polyethylene resin, polypropylene resin, polybutadiene resin, polyimide resin, and polyamide resin. Amine imine resin, polyether imine resin, polystyrene resin, polyether styrene resin, polyphenylene ether resin, polyether ether ketone resin, polyester resin, etc. In this embodiment, (B) contains free radicals The polymerizable group compound includes modified resins having two or more radically polymerizable groups of these resins.

在第一實施方式中，(B)含有自由基聚合性基團的化合物更好是包含選自具有2個以上自由基聚合性基團的改性聚苯醚樹脂、以及具有2個以上自由基聚合性基團的改性聚苯乙烯樹脂中的樹脂，進一步較好是包含具有2個以上自由基聚合性基團的改性聚苯醚樹脂，特別好是在一個實施方式中，較好是包含式(B)所示的樹脂。In the first embodiment, (B) the compound containing a radically polymerizable group preferably contains a modified polyphenylene ether resin having two or more radically polymerizable groups, and a compound having two or more radically polymerizable groups. The resin in the modified polystyrene resin having a polymerizable group is further preferably a modified polyphenylene ether resin having two or more radically polymerizable groups. In one embodiment, it is particularly preferred that Includes resin represented by formula (B).

[式中， R 11和R 12分別獨立地表示烷基； R 13、R 14、R 21、R 22、R 23和R 24分別獨立地表示氫原子或烷基； R a和R b分別獨立地表示(1)丙烯醯基、(2)甲基丙烯醯基、(3)烯丙基、(4)甲基烯丙基、(5)被選自乙烯基和異丙烯基中的基團取代且可進一步被烷基取代的苯基，或(6)被選自乙烯基和異丙烯基中的基團取代且可進一步被烷基取代的苄基； A表示單鍵、-C(R c) 2-、-O-、-CO-、-S-、-SO-或    -SO 2-； R c分別獨立地表示氫原子或烷基； s表示0或1； t和u分別獨立地表示1以上的整數。]。分別對於t單元和u單元而言，各單元可以相同，也可以不同。 [In the formula, R 11 and R 12 each independently represent an alkyl group; R 13 , R 14 , R 21 , R 22 , R 23 and R 24 each independently represent a hydrogen atom or an alkyl group; R a and R b each independently represent means (1) acrylyl group, (2) methacrylyl group, (3) allyl group, (4) methallyl group, (5) a group selected from vinyl group and isopropenyl group A phenyl group that is substituted and may be further substituted by an alkyl group, or (6) a benzyl group that is substituted by a group selected from vinyl and isopropenyl groups and may be further substituted by an alkyl group; A represents a single bond, -C(R c ) 2- , -O-, -CO-, -S-, -SO- or -SO 2 -; R c independently represents a hydrogen atom or an alkyl group; s represents 0 or 1; t and u independently Represents an integer above 1. ]. For the t unit and u unit respectively, each unit may be the same or different.

R 11和R 12分別獨立地表示烷基，在一個實施方式中，較好是甲基。R 13和R 14分別獨立地表示氫原子或烷基，在一個實施方式中，較好是氫原子。R 21和R 22分別獨立地表示氫原子或烷基，在一個實施方式中，較好是氫原子或甲基，更好是甲基。R 23和R 24分別獨立地表示氫原子或烷基，在一個實施方式中，較好是氫原子或甲基。 R 11 and R 12 each independently represent an alkyl group, and in one embodiment, they are preferably a methyl group. R 13 and R 14 each independently represent a hydrogen atom or an alkyl group, and in one embodiment, a hydrogen atom is preferred. R 21 and R 22 each independently represent a hydrogen atom or an alkyl group. In one embodiment, a hydrogen atom or a methyl group is preferred, and a methyl group is more preferred. R 23 and R 24 each independently represent a hydrogen atom or an alkyl group, and in one embodiment, they are preferably a hydrogen atom or a methyl group.

烷基(基團)是指直鏈、支鏈和/或環狀的一價脂肪族飽和烴基。烷基(基團)只要沒有特別指定，就較好是碳數1~14的烷基(基團)，更好是碳數1~10的烷基(基團)，進一步較好是碳數1~6的烷基(基團)。作為烷基(基團)，可舉出例如甲基、乙基、丙基、異丙基、丁基、異丁基、仲丁基、叔丁基、戊基、異戊基、仲戊基、新戊基、叔戊基、己基、異己基、庚基、異庚基、辛基、異辛基、叔辛基、環戊基、環己基等。Alkyl (group) refers to a linear, branched and/or cyclic monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, the alkyl group (group) is preferably an alkyl group (group) having 1 to 14 carbon atoms, more preferably an alkyl group (group) having 1 to 10 carbon atoms, and further preferably an alkyl group (group) having 1 to 10 carbon atoms. Alkyl (group) of 1 to 6. Examples of the alkyl group (group) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and sec-pentyl , neopentyl, tert-pentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, tert-octyl, cyclopentyl, cyclohexyl, etc.

R a和R b分別獨立地表示(1)丙烯醯基、(2)甲基丙烯醯基、(3)烯丙基、(4)甲基烯丙基、(5)被選自乙烯基和異丙烯基中的基團取代且可進一步被烷基取代的苯基，或(6)被選自乙烯基和異丙烯基中的基團取代且可進一步被烷基取代的苄基。 R a and R b respectively independently represent (1) acrylyl group, (2) methacrylyl group, (3) allyl group, (4) methallyl group, (5) selected from vinyl group and A phenyl group substituted by a group in isopropenyl and which may be further substituted by an alkyl group, or (6) a benzyl group substituted by a group selected from vinyl and isopropenyl and which may be further substituted by an alkyl group.

在一個實施方式中，R a和R b分別獨立地較好是(1)被選自乙烯基和異丙烯基中的基團取代且可進一步被烷基取代的苯基，或(2)被選自乙烯基和異丙烯基中的基團取代且可進一步被烷基取代的苄基；更好是4-乙烯基苯基、3-乙烯基苯基、2-乙烯基苯基、4-異丙烯基苯基、3-異丙烯基苯基、2-異丙烯基苯基、4-乙烯基苄基、3-乙烯基苄基、2-乙烯基苄基、4-異丙烯基苄基、3-異丙烯基苄基或2-異丙烯基苄基；特別好是4-乙烯基苄基、3-乙烯基苄基或2-乙烯基苄基。 In one embodiment, R a and R b are each independently preferably (1) a phenyl group substituted with a group selected from vinyl and isopropenyl and which may be further substituted by an alkyl group, or (2) a phenyl group substituted with a group selected from vinyl and isopropenyl groups, or (2) A benzyl group substituted by a group selected from vinyl and isopropenyl and which may be further substituted by an alkyl group; more preferably, 4-vinylphenyl, 3-vinylphenyl, 2-vinylphenyl, 4- Isopropenylphenyl, 3-isopropenylphenyl, 2-isopropenylphenyl, 4-vinylbenzyl, 3-vinylbenzyl, 2-vinylbenzyl, 4-isopropenylbenzyl , 3-isopropenylbenzyl or 2-isopropenylbenzyl; particularly preferred is 4-vinylbenzyl, 3-vinylbenzyl or 2-vinylbenzyl.

A表示單鍵、-C(R c) 2-、-O-、-CO-、-S-、  -SO-或-SO 2-，在一個實施方式中，較好是單鍵、-C(R c) 2-或-O-。R c分別獨立地表示氫原子或烷基，在一個實施方式中，較好是氫原子或甲基。 A represents a single bond, -C(R c ) 2 -, -O-, -CO-, -S-, -SO- or -SO 2 -. In one embodiment, it is preferably a single bond, -C( R c ) 2 - or -O-. R c each independently represents a hydrogen atom or an alkyl group, and in one embodiment, it is preferably a hydrogen atom or a methyl group.

s表示0或1，在一個實施方式中，較好是1。t和u分別獨立地表示1以上的整數，在一個實施方式中，較好是1~200的整數，更好是1~100的整數。s represents 0 or 1, and in one embodiment, s is preferably 1. t and u each independently represent an integer of 1 or more. In one embodiment, it is preferably an integer of 1 to 200, more preferably an integer of 1 to 100.

第一實施方式中的(B)含有自由基聚合性基團的化合物的自由基聚合性基團當量較好是300g/eq.~ 2500g/eq.，更好是400g/eq.~2000g/eq.。自由基聚合性基團當量表示每1當量自由基聚合性基團對應的樹脂(化合物)的質量。The radical polymerizable group equivalent of (B) the radical polymerizable group-containing compound in the first embodiment is preferably 300 g/eq. to 2500 g/eq., more preferably 400 g/eq. to 2000 g/eq. .. The radically polymerizable group equivalent represents the mass of the resin (compound) per 1 equivalent of radically polymerizable group.

第一實施方式中的(B)含有自由基聚合性基團的化合物的數量平均分子量較好是800~10000，更好是900~5000。樹脂的數量平均分子量可以通過凝膠滲透層析(GPC)法、作為經聚苯乙烯換算的值而測定。The number average molecular weight of the radical polymerizable group-containing compound (B) in the first embodiment is preferably 800 to 10,000, more preferably 900 to 5,000. The number average molecular weight of the resin can be measured as a polystyrene-converted value by gel permeation chromatography (GPC).

作為第一實施方式中的(B)含有自由基聚合性基團的化合物的市售品，可舉出例如三菱瓦斯化學公司製的「OPE-2St 1200」、「OPE-2St 2200」(乙烯基苄基改性聚苯醚樹脂)；沙伯基礎創新塑料(SABIC Innovative Plastics)公司製的「SA9000」、「SA9000-111」(甲基丙烯酸改性聚苯醚樹脂)等。Examples of commercially available products of the radical polymerizable group-containing compound (B) in the first embodiment include "OPE-2St 1200" and "OPE-2St 2200" (vinyl Benzyl modified polyphenylene ether resin); "SA9000" and "SA9000-111" (methacrylic acid modified polyphenylene ether resin) manufactured by SABIC Innovative Plastics, etc.

在第二實施方式中，(B)含有自由基聚合性基團的化合物包含具有2個以上自由基聚合性基團的低分子量的化合物(例如分子量小於800)。作為這種化合物，可舉出例如分子量小於800的含有多官能(甲基)丙烯醯基的化合物、分子量小於800的含有多官能乙烯基苯基的化合物、分子量小於800的含有多官能烯丙基的化合物等。In the second embodiment, (B) the radical polymerizable group-containing compound includes a low molecular weight compound (eg, molecular weight less than 800) having two or more radical polymerizable groups. Examples of such compounds include polyfunctional (meth)acrylyl group-containing compounds with a molecular weight of less than 800, polyfunctional vinylphenyl group-containing compounds with a molecular weight of less than 800, and polyfunctional allyl group-containing compounds with a molecular weight of less than 800. compounds, etc.

分子量小於800的含有多官能(甲基)丙烯醯基的化合物是具有2個以上(甲基)丙烯醯基的化合物。作為分子量小於800的含有多官能(甲基)丙烯醯基的化合物，可舉出例如環己烷-1,4-二甲醇二(甲基)丙烯酸酯、環己烷-1,3-二甲醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,8-辛二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯等的脂肪族(甲基)丙烯酸酯化合物；二噁烷二醇二(甲基)丙烯酸酯、3,6-二氧雜-1,8-辛二醇二(甲基)丙烯酸酯、3,6,9-三氧雜十一烷-1,11-二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、9,9-雙[4-(2-丙烯醯氧基乙氧基)苯基]茀、乙氧基化雙酚A二(甲基)丙烯酸酯、丙氧基化雙酚A二(甲基)丙烯酸酯等的含醚(甲基)丙烯酸酯化合物；三(3-羥丙基)異氰脲酸酯三(甲基)丙烯酸酯、三(2-羥乙基)異氰脲酸酯三(甲基)丙烯酸酯、乙氧基化異氰脲酸三(甲基)丙烯酸酯等的含異氰脲酸酯的(甲基)丙烯酸酯化合物等。作為分子量小於800的含有多官能(甲基)丙烯醯基的化合物的市售品，可舉出例如：新中村化學工業公司製的「A-DOG」(二噁烷二醇二丙烯酸酯)、共榮社化學公司製的「DCP-A」(三環癸烷二甲醇二丙烯酸酯)、「DCP」(三環癸烷二甲醇二甲基丙烯酸酯)、日本化藥股份有限公司的「KAYARAD R-684」(三環癸烷二甲醇二丙烯酸酯)、「KAYARAD R-604」(二噁烷二醇二丙烯酸酯)等。A polyfunctional (meth)acrylyl group-containing compound with a molecular weight of less than 800 is a compound having two or more (meth)acrylyl groups. Examples of polyfunctional (meth)acrylyl group-containing compounds having a molecular weight of less than 800 include cyclohexane-1,4-dimethanol di(meth)acrylate and cyclohexane-1,3-dimethanol. Di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1 ,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol Alcohol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glyceryl tri(meth)acrylate, pentaerythritol tetra(meth)acrylate ) aliphatic (meth)acrylate compounds such as acrylate; dioxanediol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate , 3,6,9-trioxundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-propenyloxyethoxy)phenyl]fluoride, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate ) Ether-containing (meth)acrylate compounds such as acrylate; tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tris Isocyanurate-containing (meth)acrylate compounds such as (meth)acrylate and ethoxylated isocyanurate tri(meth)acrylate. Examples of commercial products of polyfunctional (meth)acryl group-containing compounds having a molecular weight of less than 800 include "A-DOG" (dioxanediol diacrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. "DCP-A" (tricyclodecane dimethanol diacrylate), "DCP" (tricyclodecane dimethanol dimethacrylate) manufactured by Kyeisha Chemical Co., Ltd., "KAYARAD" of Nippon Kayaku Co., Ltd. R-684" (tricyclodecane dimethanol diacrylate), "KAYARAD R-604" (dioxanediol diacrylate), etc.

分子量小於800的含有多官能乙烯基苯基的化合物是具有2個以上的乙烯基苯基的化合物。作為分子量小於800的含有多官能乙烯基苯基的化合物，可舉出例如4,4’-二乙烯基聯苯、1,2-雙(4-乙烯基苯基)乙烷、2,2-雙(4-乙烯基苯基)丙烷、雙(4-乙烯基苯基)醚等。A compound containing a polyfunctional vinylphenyl group with a molecular weight of less than 800 is a compound having two or more vinylphenyl groups. Examples of polyfunctional vinylphenyl-containing compounds having a molecular weight of less than 800 include 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2- Bis(4-vinylphenyl)propane, bis(4-vinylphenyl)ether, etc.

分子量小於800的含有多官能烯丙基的化合物是具有2個以上烯丙基的化合物。作為分子量小於800的含有多官能烯丙基的化合物，可舉出例如聯苯二甲酸二烯丙酯(Diallyl Diphenate)、偏苯三酸三烯丙酯、鄰苯二甲酸二烯丙酯、間苯二甲酸二烯丙酯、對苯二甲酸二烯丙酯、2,6-萘二甲酸二烯丙酯、2,3-萘甲酸二烯丙酯等的芳族羧酸烯丙酯化合物；異氰脲酸1,3,5-三烯丙酯、異氰脲酸1,3-二烯丙基-5-縮水甘油基酯等的異氰脲酸烯丙酯化合物；2,2-雙[3-烯丙基-4-(縮水甘油基氧基)苯基]丙烷等的含有環氧的芳族烯丙基化合物；雙[3-烯丙基-4-(3,4-二氫-2H-1,3-苯并噁嗪-3-基)苯基]甲烷等含有苯并噁嗪的芳族烯丙基化合物；1,3,5-三烯丙基醚苯等的含醚芳族烯丙基化合物；二烯丙基二苯基矽烷等的烯丙基矽烷化合物等。作為分子量小於800的含有多官能烯丙基的化合物的市售品，可舉出日本化成公司製的「TAIC」(異氰脲酸1,3,5-三烯丙酯)、Nisshoku Techno Fine Chemical公司製的「DAD」(聯苯二甲酸二烯丙酯)、和光純藥工業公司製的「TRIAM-705」(偏苯三酸三烯丙酯)、日本蒸餾工業公司製的商品名「DAND」(2,3-萘甲酸二烯丙酯)、四國化成工業公司製「ALP-d」(雙[3-烯丙基-4-(3,4-二氫-2H-1,3-苯并噁嗪-3-基)苯基]甲烷)、日本化藥公司製的「RE-810NM」(2,2-雙[3-烯丙基-4-(縮水甘油氧基)苯基]丙烷)、四國化成公司製的「DA-MGIC」(1,3-二烯丙基-5-縮水甘油基異氰脲酸酯)等。A compound containing a polyfunctional allyl group with a molecular weight of less than 800 is a compound having two or more allyl groups. Examples of the polyfunctional allyl group-containing compound having a molecular weight of less than 800 include diallyl diphenate, triallyl trimellitate, diallyl phthalate, m- Aromatic carboxylic acid allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl 2,6-naphthoate, and diallyl 2,3-naphthoate; Allyl isocyanurate compounds such as 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; 2,2-bis Epoxy-containing aromatic allyl compounds such as [3-allyl-4-(glycidyloxy)phenyl]propane; bis[3-allyl-4-(3,4-dihydro) -2H-1,3-Benzoxazin-3-yl)phenyl]methane and other benzoxazine-containing aromatic allyl compounds; 1,3,5-triallyl ether benzene and other ether-containing compounds Aromatic allyl compounds; allyl silane compounds such as diallyl diphenyl silane, etc. Commercially available products of polyfunctional allyl group-containing compounds having a molecular weight of less than 800 include "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Co., Ltd. and Nisshoku Techno Fine Chemical "DAD" (diallyl diphenyl dicarboxylate) manufactured by the company, "TRIAM-705" (triallyl trimellitate) manufactured by Wako Pure Chemical Industries, Ltd., and "DAND" manufactured by Nippon Distillation Industry Co., Ltd. "(2,3-Diallyl naphthoate), "ALP-d" manufactured by Shikoku Chemical Industry Co., Ltd. (Bis[3-allyl-4-(3,4-dihydro-2H-1,3- Benzoxazin-3-yl)phenyl]methane), "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)phenyl] manufactured by Nippon Kayaku Co., Ltd. Propane), "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Chemicals Co., Ltd., etc.

第二實施方式中的(B)含有自由基聚合性基團的化合物的自由基聚合性基團當量較好是30g/eq.~ 400g/eq.，更好是50g/eq.~300g/eq.，進一步較好是75g/eq.~200g/eq.。The radical polymerizable group equivalent of (B) the radical polymerizable group-containing compound in the second embodiment is preferably 30 g/eq. to 400 g/eq., more preferably 50 g/eq. to 300 g/eq. ., further preferably 75g/eq.~200g/eq.

第二實施方式中的(B)含有自由基聚合性基團的化合物的分子量較好是100~700，更好是200~400，進一步較好是250~500。The molecular weight of the radically polymerizable group-containing compound (B) in the second embodiment is preferably 100 to 700, more preferably 200 to 400, further preferably 250 to 500.

(B)含有自由基聚合性基團的化合物可以單獨包含第一實施方式的優選的樹脂，或第二實施方式的優選的化合物中的任一者，也可以將它們中的2種以上以任意的比率組合包含。(B) The radically polymerizable group-containing compound may contain either the preferred resin of the first embodiment or the preferred compound of the second embodiment alone, or two or more of them may be combined in any desired form. The ratio combination contains.

(B)含有自由基聚合性基團的化合物的自由基聚合性基團當量較好是30g/eq.~2500g/eq.，特別好是75g/eq.~2000g/eq.。(B) The radical polymerizable group equivalent of the radical polymerizable group-containing compound is preferably 30 g/eq. to 2500 g/eq., particularly preferably 75 g/eq. to 2000 g/eq.

樹脂組成物中的(B)含有自由基聚合性基團的化合物的含量沒有特別限定，將樹脂組成物中的不揮發成分設為100質量%時，較好是30質量%以下，更好是20質量%以下，進一步較好是10質量%以下，進一步更好是5質量%以下，特別好是2質量%以下。樹脂組成物中的(B)含有自由基聚合性基團的化合物的含量的下限沒有特別限定，將樹脂組成物中的不揮發成分設為100質量%時，較好是0.001質量%以上，更好是0.01質量%以上，進一步較好是0.05質量%以上，進一步更好是0.1質量%以上，特別好是0.5質量%以上。The content of (B) the radical polymerizable group-containing compound in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100 mass %, it is preferably 30 mass % or less, more preferably 20 mass% or less, more preferably 10 mass% or less, still more preferably 5 mass% or less, particularly preferably 2 mass% or less. The lower limit of the content of (B) the radically polymerizable group-containing compound in the resin composition is not particularly limited. When the nonvolatile component in the resin composition is 100% by mass, it is preferably 0.001% by mass or more, more preferably 0.001% by mass or more. It is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, still more preferably 0.1 mass % or more, particularly preferably 0.5 mass % or more.

＜(C)硬化促進劑＞ 本發明的樹脂組成物含有(C)硬化促進劑。(C)硬化促進劑具有作為促進(A)環氧樹脂的硬化的硬化催化劑的功能。 ＜(C) Hardening accelerator＞ The resin composition of the present invention contains (C) a hardening accelerator. (C) The hardening accelerator functions as a hardening catalyst that accelerates hardening of the (A) epoxy resin.

在本發明的樹脂組成物中，(C)硬化促進劑包含(C1)具有被碳數7以上的烴基取代的含氮雜環的化合物。In the resin composition of the present invention, (C) the hardening accelerator includes (C1) a compound having a nitrogen-containing heterocyclic ring substituted with a hydrocarbon group having 7 or more carbon atoms.

含氮雜環是指至少將碳原子和氮原子這兩者作為成環原子、進而可具有氧原子和硫原子等除氮原子以外的雜原子作為成環原子的雜環。含氮雜環可以是環上的π電子體系所含的電子數為4p+2個(p為自然數)的遵循休克爾規則(Hückel’s rule)的含氮芳族雜環，也可以是環整體不具有芳族性的含氮非芳族雜環，在一個實施方式中，較好是含氮芳族雜環。含氮雜環可以是單環式含氮雜環，也可以是雙環式含氮雜環，還可以是三環式含氮雜環，在一個實施方式中，較好是單環式含氮雜環。在一個實施方式中，含氮雜環較好是4~14員，更好是5~10員。作為含氮雜環的優選的具體例，可舉出吡咯環、咪唑環、吡唑環、三唑環、噁唑環、異噁唑環、噻唑環、異噻唑環、吡啶環、吡嗪環、嘧啶環、噠嗪環、1,2,3-三嗪環、1,2,4-三嗪環、1,3,5-三嗪環等的單環式含氮芳族雜環；吲哚環、異吲哚環、苯并咪唑環、吲唑環等的雙環式含氮芳族雜環；吡咯烷環、咪唑烷環、咪唑啉環、吡唑烷環、吡唑啉環、噁唑烷環、噁唑啉環、噻唑烷環、噻唑啉環等的單環式含氮非芳族雜環；吲哚啉環、二氫苯并咪唑環等的雙環式含氮非芳族雜環，較好是咪唑環或咪唑啉環，特別好是咪唑環。A nitrogen-containing heterocyclic ring refers to a heterocyclic ring having at least two carbon atoms and nitrogen atoms as ring-forming atoms, and may further have heteroatoms other than nitrogen atoms such as oxygen atoms and sulfur atoms as ring-forming atoms. The nitrogen-containing heterocycle can be a nitrogen-containing aromatic heterocycle that follows 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), or it can be the entire ring. The non-aromatic nitrogen-containing non-aromatic heterocyclic ring is preferably a nitrogen-containing aromatic heterocyclic ring in one embodiment. The nitrogen-containing heterocycle may be a monocyclic nitrogen-containing heterocycle, a bicyclic nitrogen-containing heterocycle, or a tricyclic nitrogen-containing heterocycle. In one embodiment, it is preferably a monocyclic nitrogen-containing heterocycle. ring. In one embodiment, the nitrogen-containing heterocycle preferably has 4 to 14 members, more preferably 5 to 10 members. Preferable specific examples of nitrogen-containing heterocyclic rings include pyrrole ring, imidazole ring, pyrazole ring, triazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, pyridine ring, and pyrazine ring , pyrimidine ring, pyridazine ring, 1,2,3-triazine ring, 1,2,4-triazine ring, 1,3,5-triazine ring and other monocyclic nitrogen-containing aromatic heterocycles; indole Bicyclic nitrogen-containing aromatic heterocycles such as indole ring, isoindole ring, benzimidazole ring, indazole ring, etc.; pyrrolidine ring, imidazolidine ring, imidazoline ring, pyrazolidine ring, pyrazoline ring, oxazoline ring, etc. Monocyclic nitrogen-containing non-aromatic heterocycles such as oxazolidine ring, oxazoline ring, thiazolidine ring, thiazolidine ring, etc.; bicyclic nitrogen-containing non-aromatic heterocycles such as indoline ring, dihydrobenzimidazole ring, etc. The ring is preferably an imidazole ring or an imidazoline ring, and particularly preferably an imidazole ring.

烴基是指僅將碳原子和氫原子作為構成原子的一價基團，可包含直鏈結構、支鏈結構和/或環狀結構，可以是不含芳環的基團，也可以是包含芳環的基團。作為碳數7以上的烴基的例子，可舉出碳數7以上的烷基、碳數7以上的烯基等。A hydrocarbyl group refers to a monovalent group with only carbon atoms and hydrogen atoms as constituent atoms. It can include linear structures, branched chain structures, and/or cyclic structures. It can be a group that does not contain an aromatic ring, or it can contain an aromatic ring. ring group. Examples of the hydrocarbon group having 7 or more carbon atoms include an alkyl group having 7 or more carbon atoms, an alkenyl group having 7 or more carbon atoms, and the like.

碳數7以上的烷基是指直鏈、支鏈和/或環狀的碳數7以上的一價脂肪族飽和烴基。碳數7以上的烷基的碳數較好是7~30，更好是7~20，進一步較好是8~15，特別好是9~13。碳數7以上的烷基較好是碳數7以上的直鏈烷基。作為碳數7以上的烷基，可舉出例如庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基等。The alkyl group having 7 or more carbon atoms refers to a linear, branched and/or cyclic monovalent aliphatic saturated hydrocarbon group having 7 or more carbon atoms. The carbon number of the alkyl group having 7 or more carbon atoms is preferably 7 to 30, more preferably 7 to 20, further preferably 8 to 15, particularly preferably 9 to 13. The alkyl group having 7 or more carbon atoms is preferably a linear alkyl group having 7 or more carbon atoms. Examples of the alkyl group having 7 or more carbon atoms include heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, etc. .

碳數7以上的烯基是指具有至少1個碳-碳雙鍵的直鏈、支鏈和/或環狀的碳數7以上的一價脂肪族不飽和烴基。碳數7以上的烯基的碳數較好是7~30，更好是7~20，進一步較好是8~15，特別好是9~13。碳數7以上的烯基較好是碳數7以上的直鏈烯基。作為碳數7以上的烯基，可舉出庚烯基(6-庚烯基等)、辛烯基(7-辛烯基等)、壬烯基(8-壬烯基等)、癸烯基(9-癸烯基等)、十一烯基(10-十一烯基等)、十二烯基、十三烯基、十四烯基、十五烯基等。The alkenyl group having 7 or more carbon atoms refers to a linear, branched and/or cyclic monovalent aliphatic unsaturated hydrocarbon group having 7 or more carbon atoms and having at least one carbon-carbon double bond. The carbon number of the alkenyl group having 7 or more carbon atoms is preferably 7 to 30, more preferably 7 to 20, further preferably 8 to 15, particularly preferably 9 to 13. The alkenyl group having 7 or more carbon atoms is preferably a linear alkenyl group having 7 or more carbon atoms. Examples of the alkenyl group having 7 or more carbon atoms include heptenyl (6-heptenyl, etc.), octenyl (7-octenyl, etc.), nonenyl (8-nonenyl, etc.), and decene. Base (9-decenyl, etc.), undecenyl (10-undecenyl, etc.), dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, etc.

(C1)成分較好是含氮雜環上的碳原子被碳數7以上的烴基取代。含氮雜環上的碳數7以上的烴基較好是在1分子中為1或2個，特別好為1個。(C1)成分在含氮雜環上可具有除碳數7以上的烴基以外的進一步任意的取代基。The component (C1) preferably has a carbon atom in the nitrogen-containing heterocyclic ring substituted by a hydrocarbon group having 7 or more carbon atoms. The number of hydrocarbon groups having 7 or more carbon atoms on the nitrogen-containing heterocyclic ring is preferably 1 or 2 per molecule, and particularly preferably 1. The component (C1) may have further optional substituents other than a hydrocarbon group having 7 or more carbon atoms on the nitrogen-containing heterocyclic ring.

在一個實施方式中，(C1)成分較好是包含式(C)所示的化合物。In one embodiment, component (C1) preferably contains a compound represented by formula (C).

[式中， R 1表示碳數7以上的烷基或碳數7以上的烯基； R 2表示氫原子、可具有取代基的烷基、可具有取代基的烯基、可具有取代基的芳基，或可具有取代基的雜芳基； R 3和R 4分別獨立地表示氫原子或取代基，或者R 3和R 4一起鍵結而形成可具有取代基的芳環或可具有取代基的非芳環； 由虛線和實線組成的雙重線表示單鍵或雙鍵。]。 [In the formula, R 1 represents an alkyl group having 7 or more carbon atoms or an alkenyl group having 7 or more carbon atoms; R 2 represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an alkenyl group which may have a substituent. Aryl, or heteroaryl that may have a substituent; R 3 and R 4 independently represent a hydrogen atom or a substituent, or R 3 and R 4 are bonded together to form an aromatic ring that may have a substituent or may have a substitution The nonaromatic ring of the base; the double line consisting of a dashed and a solid line represents a single or double bond. ].

R 1表示碳數7以上的烷基或碳數7以上的烯基；在一個實施方式中，較好是碳數7~30的烷基，或碳數7~30的烯基；更好是碳數7~20的烷基，或碳數7~20的烯基；進一步較好是碳數8~15的烷基，或碳數8~15的烯基；進一步更好是碳數9~13的烷基，或碳數9~13的烯基；特別好是十一烷基。 R 1 represents an alkyl group with 7 or more carbon atoms or an alkenyl group with 7 or more carbon atoms; in one embodiment, it is preferably an alkyl group with 7 to 30 carbon atoms or an alkenyl group with 7 to 30 carbon atoms; more preferably An alkyl group having 7 to 20 carbon atoms, or an alkenyl group having 7 to 20 carbon atoms; more preferably, an alkyl group having 8 to 15 carbon atoms, or an alkenyl group having 8 to 15 carbon atoms; further more preferably, an alkyl group having 7 to 20 carbon atoms, or an alkenyl group having 9 to 15 carbon atoms. Alkyl group with 13 carbon atoms, or alkenyl group with 9 to 13 carbon atoms; undecyl group is particularly preferred.

R 2表示氫原子、可具有取代基的烷基、可具有取代基的烯基、可具有取代基的芳基，或可具有取代基的雜芳基。 R 2 represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.

烯基(基團)是指具有至少1個碳-碳雙鍵的直鏈、支鏈和/或環狀的一價脂肪族不飽和烴基。烯基(基團)只要沒有特別指定，就較好是碳數2~14的烯基(基團)，更好是碳數2~10的烯基(基團)，進一步較好是碳數2~6的烯基(基團)。作為烯基(基團)，可舉出例如乙烯基、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、異丁烯基等)、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 (group) refers to a linear, branched and/or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least 1 carbon-carbon double bond. Unless otherwise specified, the alkenyl group (group) is preferably an alkenyl group (group) having 2 to 14 carbon atoms, more preferably an alkenyl group (group) having 2 to 10 carbon atoms, and further preferably an alkenyl group (group) having 2 to 10 carbon atoms. Alkenyl (group) of 2 to 6. Examples of the alkenyl group (group) include vinyl, propenyl (allyl, 1-propenyl, isopropenyl), butenyl (1-butenyl, crotyl, methylallyl). , isobutenyl, etc.), pentenyl (1-pentenyl, etc.), hexenyl (1-hexenyl, etc.), heptenyl (1-heptenyl, etc.), octenyl (1-octenyl, etc.) base, etc.), cyclopentenyl (2-cyclopentenyl, etc.), cyclohexenyl (3-cyclohexenyl, etc.), etc.

芳基(基團)是指僅將碳原子作為成環原子的芳族碳環的1個氫原子被除去而成的一價基團。芳基(基團)只要沒有特別指定，就較好是碳數6~14的芳基(基團)，特別好是碳數6~10的芳基(基團)。作為芳基(基團)，可舉出例如苯基、1-萘基、2-萘基等。An aryl group (group) refers to a monovalent group in which one hydrogen atom of an aromatic carbocyclic ring having only a carbon atom as a ring atom is removed. Unless otherwise specified, the aryl group (group) is preferably an aryl group (group) having 6 to 14 carbon atoms, and particularly preferably an aryl group (group) having 6 to 10 carbon atoms. Examples of the aryl group (group) include phenyl, 1-naphthyl, 2-naphthyl, and the like.

雜芳基是指將除了具有碳原子以外、而且具有氧原子、氮原子、硫原子等雜原子作為成環原子的芳族雜環的1個氫原子被除去而成的一價基團。雜芳基只要沒有特別指定，就較好是5~14員的雜芳基，特別好是5~10員的雜芳基。作為雜芳基，可舉出例如呋喃基、噻吩基、吡咯基、吡唑基、噁唑基、異噁唑基、噻唑基、咪唑基、吡啶基、噠嗪基、嘧啶基、吡嗪基、三嗪基(例如1,3,5-三嗪-2-基等)等。A heteroaryl group refers to a monovalent group obtained by removing one hydrogen atom from an aromatic heterocyclic ring that has hetero atoms such as oxygen atoms, nitrogen atoms, and sulfur atoms as ring atoms in addition to carbon atoms. Unless otherwise specified, the heteroaryl group is preferably a heteroaryl group with 5 to 14 members, particularly preferably a heteroaryl group with 5 to 10 members. Examples of the heteroaryl group include furyl, thienyl, pyrrolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, imidazolyl, pyridyl, pyridazinyl, pyrimidinyl, and pyrazinyl. , triazinyl (such as 1,3,5-triazin-2-yl, etc.), etc.

作為R 2中的烷基和烯基的「取代基」，沒有特別限定，可舉出例如鹵素原子、硝基、氰基、羥基、胺基、-R’、-OR、-COR、-SR、-SOR、-SO 2R、-NHR、-NR 2、-COOR、-OCOR、-CONHR、-CONR 2、-NHCOR等，作為R 2中的芳基和雜芳基的「取代基」，沒有特別限定，可舉出例如鹵素原子、硝基、氰基、羥基、胺基、-R、-OR、-COR、-SR、-SOR、-SO 2R、-NHR、-NR 2、-COOR、  -OCOR、-CONHR、-CONR 2、-NHCOR等。R’表示(1)可被選自鹵素原子、硝基、氰基、羥基、胺基、烷基、烯基、芳基、芳基-烷基(被1個以上芳基取代的烷基)、烷基-芳基(被1個以上烷基取代的芳基)、烷基-氧基、烯基-氧基和芳基-氧基中的基團取代的芳基，或(2)可被選自鹵素原子、硝基、氰基、羥基、胺基、烷基、烯基、芳基、芳基-烷基、烷基-芳基、烷基-氧基、烯基-氧基和芳基-氧基中的基團取代的雜芳基，R表示R’中的上述(1)、R’中的上述(2)、(3)可被選自鹵素原子、硝基、氰基、羥基、胺基、芳基、烷基-芳基、烷基-氧基、烯基-氧基和芳基-氧基中的基團取代的烷基，或(4)可被選自鹵素原子、硝基、氰基、羥基、胺基、芳基、烷基-芳基、烷基-氧基、烯基-氧基和芳基-氧基中的基團取代的烯基。 The "substituent" of the alkyl group and alkenyl group in R 2 is not particularly limited, and examples thereof include a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, -R', -OR, -COR, and -SR. , -SOR, -SO 2 R, -NHR, -NR 2 , -COOR, -OCOR, -CONHR, -CONR 2 , -NHCOR, etc., as the "substituents" of the aryl and heteroaryl groups in R 2 , It is not particularly limited, and examples thereof include halogen atom, nitro group, cyano group, hydroxyl group, amino group, -R, -OR, -COR, -SR, -SOR, -SO 2 R, -NHR, -NR 2 , - COOR, -OCOR, -CONHR, -CONR2 , -NHCOR, etc. R' represents (1) which can be selected from halogen atom, nitro group, cyano group, hydroxyl group, amine group, alkyl group, alkenyl group, aryl group, aryl-alkyl group (alkyl group substituted by more than one aryl group) , alkyl-aryl (aryl substituted by more than 1 alkyl), alkyl-oxy, alkenyl-oxy and aryl-oxy, aryl substituted by a group, or (2) can Selected from halogen atom, nitro, cyano, hydroxyl, amine, alkyl, alkenyl, aryl, aryl-alkyl, alkyl-aryl, alkyl-oxy, alkenyl-oxy and A heteroaryl group substituted by a group in an aryl-oxy group, R represents the above (1) in R', the above (2), (3) in R' can be selected from a halogen atom, a nitro group, and a cyano group , hydroxyl, amine, aryl, alkyl-aryl, alkyl-oxy, alkenyl-oxy and aryl-oxy groups substituted alkyl, or (4) may be selected from halogen Alkenyl groups substituted by atom, nitro, cyano, hydroxyl, amine, aryl, alkyl-aryl, alkyl-oxy, alkenyl-oxy and aryl-oxy.

在一個實施方式中，R 2較好是可具有取代基的烷基，或可具有取代基的烯基；更好是可具有取代基的烷基；進一步較好是式(R2)所示的基團。 In one embodiment, R 2 is preferably an alkyl group which may have a substituent, or an alkenyl group which may have a substituent; more preferably it is an alkyl group which may have a substituent; further preferably it is represented by formula (R2) group.

[式中， X表示碳數1~6的伸烷基； Y表示單鍵、-O-、-CO-、-S-、-SO-、-SO 2-、-NH-、 -COO-、-OCO-、-CONH-或-NHCO-； ＊表示鍵結部位。]。通過使R 2為式(R2)所示的基團，能夠使樹脂組成物的pH升高、進而促進環氧樹脂的硬化。 [In the formula, X represents an alkylene group having 1 to 6 carbon atoms; Y represents a single bond, -O-, -CO-, -S-, -SO-, -SO 2 -, -NH-, -COO-, -OCO-, -CONH- or -NHCO-; * indicates the bonding site. ]. When R 2 is a group represented by the formula (R2), the pH of the resin composition can be increased and the hardening of the epoxy resin can be accelerated.

X表示碳數1~6的伸烷基：在一個實施方式中，較好是碳數1~3的伸烷基；特別好是-CH 2-CH 2-。 X represents an alkylene group having 1 to 6 carbon atoms: in one embodiment, it is preferably an alkylene group having 1 to 3 carbon atoms; particularly preferably, it is -CH 2 -CH 2 -.

伸烷基是指直鏈、支鏈，和/或環狀的二價脂肪族飽和烴基。碳數1~6的伸烷基較好是碳數1~3的伸烷基。作為碳數1~6的伸烷基，可舉出例如-CH 2-、 -CH 2-CH 2-、-CH(CH 3)-、-CH 2-CH 2-CH 2-、-CH 2-CH(CH 3)-、-CH(CH 3)-CH 2-、-C(CH 3) 2-等。 Alkylene refers to a linear, branched, and/or cyclic divalent aliphatic saturated hydrocarbon group. The alkylene group having 1 to 6 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group having 1 to 6 carbon atoms include -CH 2 -, -CH 2 -CH 2 -, -CH(CH 3 )-, -CH 2 -CH 2 -CH 2 -, -CH 2 -CH(CH 3 )-, -CH(CH 3 )-CH 2 -, -C(CH 3 ) 2 -, etc.

Y表示單鍵、-O-、-CO-、-S-、-SO-、-SO 2-、-NH-、-COO-、-OCO-、-CONH-或-NHCO-；在一個實施方式中，較好是單鍵。 Y represents a single bond, -O-, -CO-, -S-, -SO-, -SO 2 -, -NH-, -COO-, -OCO-, -CONH- or -NHCO-; in one embodiment Among them, single bond is preferred.

R 3和R 4分別獨立地表示氫原子或取代基，或者R 3和R 4一起鍵結而形成可具有取代基的芳環或可具有取代基的非芳環。 R 3 and R 4 each independently represent a hydrogen atom or a substituent, or R 3 and R 4 are bonded together to form an aromatic ring which may have a substituent or a non-aromatic ring which may have a substituent.

芳環是指環上的π電子體系所含的電子數為4p+2個(p為自然數)的遵循休克爾規則(Hückel’s rule)的環。芳環可以是僅以碳原子作為成環原子的芳族碳環；或者除了具有碳原子以外、而且具有氧原子、氮原子、硫原子等的雜原子作為成環原子的芳族雜環。在一個實施方式中，芳環較好是5~14員的芳環，更好是6~14員的芳環，進一步更好是6~10員的芳環。作為芳環的優選具體例，可舉出苯環、萘環、蒽環、菲環等，更好是苯環或萘環，特別好是苯環。An aromatic ring refers to a ring that follows 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). The aromatic ring may be an aromatic carbocyclic ring having only carbon atoms as ring-forming atoms; or an aromatic heterocyclic ring having, in addition to carbon atoms, heteroatoms such as oxygen atoms, nitrogen atoms, sulfur atoms, etc. as ring-forming atoms. In one embodiment, the aromatic ring is preferably an aromatic ring with 5 to 14 members, more preferably an aromatic ring with 6 to 14 members, and even more preferably an aromatic ring with 6 to 10 members. Preferable specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and the like. A benzene ring or a naphthalene ring is more preferred, and a benzene ring is particularly preferred.

非芳環是指環整體具有芳族性的芳環以外的環。非芳環可以是：僅將碳原子作為成環原子的非芳族碳環；或者除了具有碳原子以外、而且具有氧原子、氮原子、硫原子等雜原子作為成環原子的非芳族雜環。非芳環較好是3~21員的非芳環，更好是4~17員的非芳環，進一步較好是5~14員的非芳環。作為非芳環的優選的具體例，可舉出環丁烯環、環戊烯環、環己烯環、環戊二烯環、1,3-環己二烯環、1,4-環己二烯環等。A non-aromatic ring refers to a ring other than an aromatic ring in which the entire ring is aromatic. Non-aromatic rings can be: non-aromatic carbocyclic rings that only use carbon atoms as ring-forming atoms; or non-aromatic heterocyclic rings that have, in addition to carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms and other heteroatoms as ring-forming atoms. ring. The non-aromatic ring is preferably a non-aromatic ring with 3 to 21 members, more preferably a non-aromatic ring with 4 to 17 members, further preferably a non-aromatic ring with 5 to 14 members. Preferable specific examples of the non-aromatic ring include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cyclopentadiene ring, a 1,3-cyclohexadiene ring, and a 1,4-cyclohexane ring. Diene rings etc.

作為R 3和R 4的「取代基」以及R 3和R 4形成的芳環和非芳環的「取代基」，可舉出與R 2中的芳基和雜芳基的「取代基」同樣的基團。 Examples of "substituents" for R 3 and R 4 and "substituents" for the aromatic ring and non-aromatic ring formed by R 3 and R 4 include aryl groups and heteroaryl groups in R 2 Same group.

在一個實施方式中，R 3和R 4分別獨立地較好是氫原子或取代基；更好是氫原子或烷基；特別好是氫原子。 In one embodiment, R 3 and R 4 are each independently preferably a hydrogen atom or a substituent; more preferably a hydrogen atom or an alkyl group; particularly preferably a hydrogen atom.

由虛線和實線組成的雙重線表示單鍵或雙鍵；在一個實施方式中，較好是雙鍵。The double line consisting of a dashed line and a solid line represents a single bond or a double bond; in one embodiment, a double bond is preferred.

作為(C1)成分的具體例，可舉出2,4-二胺基-6-[2-(2-十一烷基-1H-咪唑-1-基)乙基]-1,3,5-三嗪等。Specific examples of the component (C1) include 2,4-diamino-6-[2-(2-undecyl-1H-imidazol-1-yl)ethyl]-1,3,5 -Triazines, etc.

樹脂組成物中的(C1)成分的含量沒有特別限定，將樹脂組成物中的不揮發成分設為100質量%時，較好是0.0001質量%以上，更好是0.001質量%以上，進一步較好是0.01質量%以上，特別好是0.03質量%以上。樹脂組成物中的(C1)成分的含量的上限沒有特別限定，將樹脂組成物中的不揮發成分設為100質量%時，較好是5質量%以下，更好是1質量%以下，進一步較好是0.5質量%以下，特別好是0.1質量%以下。將樹脂組成物中的(C)硬化促進劑的總量設為100質量%時，樹脂組成物中的(C1)成分的含量較好是10質量%以上，更好是30質量%以上，進一步較好是40質量%以上，特別好是50質量%以上。The content of the (C1) component in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100 mass %, it is preferably 0.0001 mass % or more, more preferably 0.001 mass % or more, and still more preferably The content is 0.01 mass% or more, particularly preferably 0.03 mass% or more. The upper limit of the content of the (C1) component in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100% by mass, it is preferably 5% by mass or less, more preferably 1% by mass or less. Further, The content is preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less. When the total amount of (C) hardening accelerator in the resin composition is 100% by mass, the content of the component (C1) in the resin composition is preferably 10% by mass or more, more preferably 30% by mass or more, and further The content is preferably 40 mass% or more, and particularly preferably 50 mass% or more.

在本發明的樹脂組成物中，(C)硬化促進劑可包含(C2)除(C1)成分以外的硬化促進劑。In the resin composition of the present invention, (C) the curing accelerator may contain (C2) a curing accelerator other than the component (C1).

作為(C2)成分，可舉出例如除(C1)成分以外的咪唑系硬化促進劑、除(C1)成分以外的胺系硬化促進劑、除(C1)成分以外的磷系硬化促進劑、除(C1)成分以外的脲系硬化促進劑、除(C1)成分以外的胍系硬化促進劑、除(C1)成分以外的金屬系硬化促進劑等。(C)硬化促進劑較好是包含選自除(C1)成分以外的咪唑系硬化促進劑和除(C1)成分以外的胺系硬化促進劑中的硬化促進劑，特別好是包含除(C1)成分以外的胺系硬化促進劑。(C)硬化促進劑可以單獨使用1種，也可以將2種以上組合使用。Examples of the component (C2) include imidazole-based curing accelerators other than the component (C1), amine-based curing accelerators other than the component (C1), phosphorus-based curing accelerators other than the component (C1), Urea-based hardening accelerators other than the component (C1), guanidine-based hardening accelerators other than the component (C1), metal-based hardening accelerators other than the component (C1), etc. (C) The hardening accelerator preferably contains a hardening accelerator selected from the group consisting of imidazole-based hardening accelerators other than the component (C1) and amine-based hardening accelerators other than the component (C1). Particularly preferably, it contains a hardening accelerator other than the component (C1). ) ingredients other than amine-based hardening accelerators. (C) The hardening accelerator may be used individually by 1 type, or in combination of 2 or more types.

作為除(C1)成分以外的咪唑系硬化促進劑，可舉出例如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-均三嗪、2,4-二胺基-6-[2’-十一烷基咪唑基-(1’)]-乙基-均三嗪、2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-均三嗪、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-均三嗪異氰脲酸加成物、2-苯基咪唑異氰脲酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2,3-二氫-1H-吡咯并[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-苯基咪唑啉等咪唑化合物及咪唑化合物與環氧樹脂的加合物。Examples of the imidazole-based hardening accelerator other than the component (C1) include 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 Base-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl Ethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1 -Cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-Diamino-6-[2'-Undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-Diamino-6-[2'-ethyl -4'-Methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl- s-Triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 -Hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2 -Imidazole compounds such as methyl imidazoline and 2-phenylimidazoline and adducts of imidazole compounds and epoxy resins.

作為除(C1)成分以外的咪唑系硬化促進劑，可使用市售品，可舉出例如四國化成工業公司製的「1B2PZ」、「2MZA-PW」、「2PHZ-PW」、三菱化學公司製的「P200-H50」等。As the imidazole-based hardening accelerator other than the component (C1), commercially available products can be used, and examples thereof include "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Shikoku Chemical Industry Co., Ltd., and Mitsubishi Chemical Corporation Made of "P200-H50", etc.

作為除(C1)成分以外的胺系硬化促進劑，可舉出例如三乙胺、三丁胺等的三烷基胺、4-二甲基胺基吡啶、苄基二甲基胺、2,4,6-三(二甲基胺基甲基)苯酚、1,8-二氮雜雙環(5,4,0)-十一烯等。Examples of amine-based hardening accelerators other than component (C1) include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2, 4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc.

作為除(C1)成分以外的胺系硬化促進劑，可使用市售品，可舉出例如味之素精細化學公司製的「MY-25」等。As the amine-based hardening accelerator other than the component (C1), commercially available products can be used, and examples include "MY-25" manufactured by Ajinomoto Fine Chemicals Co., Ltd.

作為除(C1)成分以外的磷系硬化促進劑，可舉出例如四丁基鏻溴化物、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)均苯四酸鹽、四丁基鏻氫六氫化鄰苯二甲酸鹽、四丁基鏻2,6-雙[(2-羥基-5-甲基苯基)甲基]-4-甲基苯酚鹽、二叔丁基甲基鏻四苯基硼酸鹽等的脂肪族鏻鹽；甲基三苯基鏻溴化物、乙基三苯基鏻溴化物、丙基三苯基鏻溴化物、丁基三苯基鏻溴化物、苄基三苯基鏻氯化物、四苯基鏻溴化物、對甲苯基三苯基鏻四-對甲苯基硼酸鹽、四苯基鏻四苯基硼酸鹽、四苯基鏻四對甲苯基硼酸鹽、三苯基乙基鏻四苯基硼酸鹽、三(3-甲基苯基)乙基鏻四苯基硼酸鹽、三(2-甲氧基苯基)乙基鏻四苯基硼酸鹽、(4-甲基苯基)三苯基鏻硫氰酸鹽、四苯基鏻硫氰酸鹽、丁基三苯基鏻硫氰酸鹽等的芳族鏻鹽；三苯基膦/三苯基硼烷等的芳族膦-硼烷複合物；三苯基膦/對苯醌加成反應物等的芳族膦/醌加成反應物；三丁基膦、三叔丁基膦、三辛基膦、二叔丁基(2-丁烯基)膦、二叔丁基(3-甲基-2-丁烯基)膦、三環己基膦等的脂肪族膦；二丁基苯基膦、二叔丁基苯基膦、甲基二苯基膦、乙基二苯基膦、丁基二苯基膦、二苯基環己基膦、三苯基膦、三鄰甲苯基膦、三間甲苯基膦、三對甲苯基膦、三(4-乙基苯基)膦、三(4-丙基苯基)膦、三(4-異丙基苯基)膦、三(4-丁基苯基)膦、三(4-叔丁基苯基)膦、三(2,4-二甲基苯基)膦、三(2,5-二甲基苯基)膦、三(2,6-二甲基苯基)膦、三(3,5-二甲基苯基)膦、三(2,4,6-三甲基苯基)膦、三(2,6-二甲基-4-乙氧基苯基)膦、三(2-甲氧基苯基)膦、三(4-甲氧基苯基)膦、三(4-乙氧基苯基)膦、三(4-叔丁氧基苯基)膦、二苯基-2-吡啶基膦、1,2-雙(二苯基膦)乙烷、1,3-雙(二苯基膦)丙烷、1,4-雙(二苯基膦)丁烷、1,2-雙(二苯基膦)乙炔、2,2’-雙(二苯基膦)二苯醚等的芳族膦等。Examples of the phosphorus-based hardening accelerator other than the component (C1) include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, and tetrabutylphosphonium decanoate. Phosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hydrohexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methyl Aliphatic phosphonium salts such as phenyl)methyl]-4-methylphenolate, di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, Propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetrakisylborate Phenylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, Tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenyl Aromatic phosphonium salts such as phosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine/triphenylborane; aromatic phosphines such as triphenylphosphine/p-benzoquinone addition reactants /Quinone addition reactant; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butene aliphatic phosphines such as methyl)phosphine, tricyclohexylphosphine, etc.; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, Diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine , tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, Tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6- Trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl) Phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphine)ethane , 1,3-bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)butane, 1,2-bis(diphenylphosphine)acetylene, 2,2'-bis(diphenylphosphine) Phosphines) aromatic phosphines such as diphenyl ether, etc.

作為除(C1)成分以外的脲系硬化促進劑，可舉出例如1,1-二甲基脲；1,1,3-三甲基脲、3-乙基-1,1-二甲基脲、3-環己基-1,1-二甲基脲、3-環辛基-1,1-二甲基脲等的脂肪族二甲基脲；3-苯基-1,1-二甲基脲、3-(4-氯苯基)-1,1-二甲基脲、3-(3,4-二氯苯基)-1,1-二甲基脲、3-(3-氯-4-甲基苯基)-1,1-二甲基脲、3-(2-甲基苯基)-1,1-二甲基脲、3-(4-甲基苯基)-1,1-二甲基脲、3-(3,4-二甲基苯基)-1,1-二甲基脲、3-(4-異丙基苯基)-1,1-二甲基脲、3-(4-甲氧基苯基)-1,1-二甲基脲、3-(4-硝基苯基)-1,1-二甲基脲、3-[4-(4-甲氧基苯氧基)苯基]-1,1-二甲基脲、3-[4-(4-氯苯氧基)苯基]-1,1-二甲基脲、3-[3-(三氟甲基)苯基]-1,1-二甲基脲、N,N-(1,4-伸苯基)雙(N’,N’-二甲基脲)、N,N-(4-甲基-1,3-伸苯基)雙(N’,N’-二甲基脲)〔甲苯雙二甲基脲〕等的芳族二甲基脲等。Examples of urea-based hardening accelerators other than component (C1) include 1,1-dimethylurea; 1,1,3-trimethylurea, and 3-ethyl-1,1-dimethyl Aliphatic dimethylureas such as urea, 3-cyclohexyl-1,1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea urea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro -4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1 ,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethyl Urea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4 -Methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[ 3-(Trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N, Aromatic dimethylureas such as N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea], etc.

作為除(C1)成分以外的胍系硬化促進劑，可舉出例如雙氰胺、1-甲基胍、1-乙基胍、1-環己基胍、1-苯基胍、1-(鄰甲苯基)胍、二甲基胍、二苯基胍、三甲基胍、四甲基胍、五甲基胍、1,5,7-三氮雜雙環[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-正丁基雙胍、1-正十八烷基雙胍、1,1-二甲基雙胍、1,1-二乙基雙胍、1-環己基雙胍、1-烯丙基雙胍、1-苯基雙胍、1-(鄰甲苯基)雙胍等。Examples of the guanidine-based hardening accelerator other than the component (C1) include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(ortho)guanidine, Tolyl)guanidine, dimethylguanidine, 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-deca Octalkyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide wait.

作為除(C1)成分以外的金屬系硬化促進劑，可舉出例如鈷、銅、鋅、鐵、鎳、錳、錫等金屬的、有機金屬錯合物或有機金屬鹽。作為有機金屬錯合物的具體例，可舉出乙醯丙酮鈷(II)、乙醯丙酮鈷(III)等有機鈷錯合物、乙醯丙酮銅(II)等有機銅錯合物、乙醯丙酮鋅(II)等有機鋅錯合物、乙醯丙酮鐵(III)等有機鐵錯合物、乙醯丙酮鎳(II)等有機鎳錯合物、乙醯丙酮錳(II)等有機錳錯合物等。作為有機金屬鹽，可舉出例如辛酸鋅、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 other than the component (C1) include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt acetyl acetonate (II) and cobalt acetyl acetonate (III), organic copper complexes such as copper acetyl acetonate (II), ethanol acetonate, etc. Organic zinc complexes such as zinc acetyl acetonate (II), organic iron complexes such as iron acetyl acetonate (III), organic nickel complexes such as nickel acetyl acetonate (II), and organic manganese acetyl acetonate (II). Manganese complexes, etc. Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

樹脂組成物中的(C)硬化促進劑的含量沒有特別限定，將樹脂組成物中的不揮發成分設為100質量%時，較好是0.0001質量%以上，更好是0.001質量%以上，進一步較好是0.01質量%以上，特別好是0.05質量%以上。樹脂組成物中的(C)硬化促進劑的含量的上限沒有特別限定，將樹脂組成物中的不揮發成分設為100質量%時，較好是5質量%以下，更好是1質量%以下，進一步較好是0.5質量%以下，特別好是0.2質量%以下。The content of (C) hardening accelerator in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100 mass %, it is preferably 0.0001 mass % or more, more preferably 0.001 mass % or more. Further, The content is preferably 0.01 mass% or more, particularly preferably 0.05 mass% or more. The upper limit of the content of (C) the hardening accelerator in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100% by mass, it is preferably 5% by mass or less, more preferably 1% by mass or less. , further preferably 0.5% by mass or less, particularly preferably 0.2% by mass or less.

＜(D)無機填充材料＞ 本發明的樹脂組成物也可以包含(D)無機填充材料作為任意的成分。(D)無機填充材料以粒子的狀態包含在樹脂組成物中。 ＜(D) Inorganic filler＞ The resin composition of the present invention may contain (D) an inorganic filler as an optional component. (D) The inorganic filler is contained in the resin composition in the form of particles.

作為(D)無機填充材料的材料，使用無機化合物。作為(D)無機填充材料的材料，可舉出例如二氧化矽、氧化鋁、鋁矽酸鹽、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、勃姆石、氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、氧化鎂、氮化硼、氮化鋁、氮化錳、硼酸鋁、碳酸鍶、鈦酸鍶、鈦酸鈣、鈦酸鎂、鈦酸鉍、氧化鈦、氧化鋯、鈦酸鋇、鋯鈦酸鋇、鋯酸鋇、鋯酸鈣、磷酸鋯和磷鎢酸鋯等。(D)無機填充材料的材料較好是包含選自二氧化矽、氧化鋁和鋁矽酸鹽中的材料，特別好是包含二氧化矽作為材料。(D)無機填充材料的材料可以為單獨1種，也可以為將2種以上以任意的比率組合。As the material of (D) the inorganic filler, an inorganic compound is used. (D) Examples of the inorganic filler material include silica, alumina, aluminosilicate, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, and zinc oxide. , hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate , magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium phosphotungstate, etc. (D) The inorganic filler material preferably contains a material selected from silica, alumina, and aluminosilicates, and particularly preferably contains silica as the material. (D) The material of the inorganic filler may be one type alone, or two or more types may be combined in an arbitrary ratio.

(D)無機填充材料可以僅由(D1)中空無機填充材料構成，也可以僅由(D2)實心無機填充材料構成，還可以由(D1)中空無機填充材料和(D2)實心無機填充材料這兩者構成。(D)無機填充材料較好是由(D1)中空無機填充材料和(D2)實心無機填充材料這兩者構成。(D) The inorganic filler material may be composed of only (D1) hollow inorganic filler material, or may be composed of only (D2) solid inorganic filler material, or may be composed of (D1) hollow inorganic filler material and (D2) solid inorganic filler material. Made up of both. (D) The inorganic filler material is preferably composed of both (D1) hollow inorganic filler material and (D2) solid inorganic filler material.

(D1)中空無機填充材料可以包含在粒子內部僅具有1個空孔的單中空粒子的無機填充材料，也可以包含在粒子內部具有多個空孔的多中空粒子的無機填充材料，還可以包含這兩者。(D1) The hollow inorganic filler may include an inorganic filler of a single hollow particle having only one pore inside the particle, or an inorganic filler of multiple hollow particles having a plurality of pores inside the particle. Both.

對於(D1)中空無機填充材料而言，平均空孔率大於0體積%，平均空孔率較好是1體積%以上，更好是5體積%以上，進一步較好是10體積%以上，特別好是15體積%以上。(D1)中空無機填充材料的平均空孔率的上限沒有特別限定，較好是90體積%以下，更好是85體積%以下。(D1) The hollow inorganic filler material has an average porosity greater than 0% by volume. The average porosity is preferably at least 1% by volume, more preferably at least 5% by volume, and further preferably at least 10% by volume, especially Preferably it is 15% by volume or more. (D1) The upper limit of the average porosity of the hollow inorganic filling material is not particularly limited, but it is preferably 90 volume % or less, more preferably 85 volume % or less.

無機填充材料的平均空孔率P(體積%)以在粒子內部存在的1個或2個以上的空孔的合計體積相對於以粒子的外表面為基準的粒子整體的體積的體積基準比例(空孔的合計體積/粒子的體積)的形式來定義，例如可以使用無機填充材料的實際的密度的測定值D M(g/cm 3)，和形成無機填充材料的材料的物質密度的理論值D T(g/cm 3)，通過下述式(I)算出。 The average porosity P (volume %) of the inorganic filler material is the volume basis ratio of the total volume of one or more pores present inside the particle to the volume of the entire particle based on the outer surface of the particle ( It can be defined in the form of the total volume of pores/volume of particles). For example, the measured value D M (g/cm 3 ) of the actual density of the inorganic filler material and the theoretical value of the material density of the material forming the inorganic filler material can be used. D T (g/cm 3 ) is calculated from the following formula (I).

無機填充材料的實際的密度例如可以使用真密度測定裝置進行測定。作為真密度測定裝置，可舉出例如QUANTACHROME公司製的ULTRAPYCNOMETER1000等。作為測定氣體，例如使用氮氣。The actual density of the inorganic filler material can be measured using a true density measuring device, for example. Examples of true density measuring devices include ULTRAPYCNOMETER 1000 manufactured by QUANTACHROME Co., Ltd. As a measurement gas, nitrogen gas is used, for example.

(D1)中空無機填充材料較好是選自球形中空二氧化矽、球形中空氧化鋁和球形中空鋁矽酸鹽中的中空無機填充材料。(D1)中空無機填充材料可以單獨使用1種，也可以將2種以上以任意的比率組合使用。(D1) The hollow inorganic filler material is preferably a hollow inorganic filler material selected from spherical hollow silica, spherical hollow alumina and spherical hollow aluminosilicate. (D1) The hollow inorganic filler material may be used individually by 1 type, or in combination of 2 or more types at arbitrary ratios.

(D1)中空無機填充材料的平均粒徑較好是10μm以下，更好是5μm以下，進一步較好是3μm以下。(D1)中空無機填充材料的平均粒徑的下限沒有特別限定，較好是0.01μm以上，更好是0.05μm以上，進一步較好是0.1μm以上，特別好是0.2μm以上。(D1) The average particle diameter of the hollow inorganic filler is preferably 10 μm or less, more preferably 5 μm or less, further preferably 3 μm or less. (D1) The lower limit of the average particle diameter of the hollow inorganic filler is not particularly limited, but it is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, particularly preferably 0.2 μm or more.

無機填充材料的平均粒徑可通過基於米氏(Mie)散射理論的雷射繞射-散射法進行測定。具體來說，可通過雷射繞射散射式粒徑分佈測定裝置，以體積基準製成無機填充材料的粒徑分佈，將其中值粒徑作為平均粒徑來進行測定。測定樣品可使用將無機填充材料100mg、甲基乙基酮10g稱量至管瓶(vial)中並通過超音波分散10分鐘而得的樣品。對於測定樣品，使用雷射繞射式粒徑分佈測定裝置，將使用光源波長設為藍色和紅色，以流動池(flow cell)方式測定無機填充材料的體積基準的粒徑分佈，根據所得的粒徑分佈作為中值粒徑而算出平均粒徑。作為雷射繞射式粒徑分佈測定裝置，可舉出例如堀場製作所製「LA-960」等。The average particle size of the inorganic filler material can be measured by a laser diffraction-scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis using a laser diffraction and scattering particle size distribution measuring device, and the median particle size can be measured as the average particle size. As a measurement sample, a sample obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing it with ultrasonic waves for 10 minutes can be used. For the measurement sample, a laser diffraction particle size distribution measuring device was used, and the wavelength of the light source was set to blue and red, and the volume-based particle size distribution of the inorganic filler was measured in a flow cell method. The particle size distribution was used to calculate the average particle size as the median particle size. Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

(D1)中空無機填充材料的比表面積沒有特別限定，較好是0.1m 2/g以上，更好是0.5m 2/g以上，進一步較好是1m 2/g以上，特別好是3m 2/g以上。(D1)中空無機填充材料的比表面積的上限沒有特別限定，較好是100m 2/g以下，更好是70m 2/g以下，進一步較好是50m 2/g以下，特別好是40m 2/g以下。對於無機填充材料的比表面積而言，可根據BET法使用比表面積測定裝置(Mountech製Macsorb HM-1210)使氮氣吸附於試樣表面，用BET多點法算出比表面積來獲得。 (D1) The specific surface area of the hollow inorganic filler material is not particularly limited, but is preferably 0.1 m 2 /g or more, more preferably 0.5 m 2 /g or more, further preferably 1 m 2 /g or more, particularly preferably 3 m 2 / g and above. (D1) The upper limit of the specific surface area of the hollow inorganic filler material is not particularly limited, but it is preferably 100 m 2 /g or less, more preferably 70 m 2 /g or less, further preferably 50 m 2 /g or less, and particularly preferably 40 m 2 /g. g below. The specific surface area of the inorganic filler material can be obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mounttech) according to the BET method, and calculating the specific surface area using the BET multi-point method.

作為(D1)中空無機填充材料的市售品，可舉出例如日揮觸媒化成公司製的「BA-S」(平均粒徑2.6μm，空孔率25體積%)、Ube Exsymo公司製的「LHP-208」(平均粒徑0.5μm，空孔率50體積%)、大研化學公司製的「DLSB-001」(平均粒徑0.23μm，空孔率20體積%)、太平洋水泥(Taiheiyo-Cement)公司製的「MG-005」(平均粒徑1.6μm，空孔率80體積%)等。Examples of commercially available hollow inorganic fillers (D1) include "BA-S" manufactured by Nikko Catalysts Co., Ltd. (average particle diameter: 2.6 μm, porosity: 25% by volume), and "BA-S" manufactured by Ube Exsymo Co., Ltd. LHP-208" (average particle size 0.5 μm, porosity 50% by volume), "DLSB-001" manufactured by Taihe Chemical Co., Ltd. (average particle size 0.23 μm, porosity 20% by volume), Pacific Cement (Taiheiyo- Cement) company's "MG-005" (average particle size 1.6 μm, porosity 80 volume %), etc.

從提高耐濕性和分散性的觀點來看，(D1)中空無機填充材料較好是用表面處理劑進行了處理。作為表面處理劑，可舉出例如：含氟矽烷偶合劑、胺基矽烷系偶合劑、環氧矽烷系偶合劑、巰基矽烷系偶合劑、矽烷系偶合劑、烷氧基矽烷、有機矽氮烷化合物、鈦酸酯系偶合劑等。此外，表面處理劑可以單獨使用1種，也可以將2種以上任意組合使用。From the viewpoint of improving moisture resistance and dispersibility, (D1) the hollow inorganic filler material is preferably treated with a surface treatment agent. Examples of surface treatment agents include fluorinated silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane, and organosilazane. compounds, titanate coupling agents, etc. In addition, one type of surface treatment agent may be used alone, or two or more types may be used in any combination.

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

從(D1)中空無機填充材料的分散性提高的觀點來看，用表面處理劑進行的表面處理的程度較好是在規定的範圍內。具體來說，(D1)中空無機填充材料100質量%較好是用0.2質量%~5質量%的表面處理劑進行了表面處理，更好是用0.2質量%~3質量%的表面處理劑進行了表面處理，進一步較好是用0.3質量%~2質量%的表面處理劑進行了表面處理。(D1) From the viewpoint of improving the dispersibility of the hollow inorganic filler, the degree of surface treatment with the surface treatment agent is preferably within a predetermined range. Specifically, (D1) 100% by mass of the hollow inorganic filler is preferably surface-treated with a surface treatment agent of 0.2% to 5% by mass, more preferably 0.2% to 3% by mass of a surface treatment agent. Surface treatment is required, and more preferably, surface treatment is carried out with a surface treatment agent of 0.3% by mass to 2% by mass.

用表面處理劑進行的表面處理的程度，可通過(D1)中空無機填充材料的每單位表面積的碳量進行評價。從(D1)中空無機填充材料的分散性提高的觀點來看，(D1)中空無機填充材料的每單位表面積的碳量較好是0.02mg/m 2以上，更好是0.1mg/m 2以上，進一步更好是0.2mg/m 2以上。另一方面，從抑制樹脂組成物的熔融黏度、片材形態下的熔融黏度的上升的觀點來看，較好是1.0mg/m 2以下，更好是0.8mg/m 2以下，進一步較好是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 hollow inorganic filler material (D1). From the viewpoint of improving the dispersibility of the hollow inorganic filler (D1), the carbon amount per unit surface area of the hollow inorganic filler (D1) is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more , further preferably 0.2 mg/m 2 or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin composition and the melt viscosity in the sheet form, it is preferably 1.0 mg/m 2 or less, more preferably 0.8 mg/m 2 or less, and still more preferably It is 0.5mg/ m2 or less.

從將相對介電常數抑制為更低的觀點來看，將樹脂組成物中的不揮發成分設為100質量%時，(D)無機填充材料中的(D1)中空無機填充材料的含量(質量%)較好是10質量%以上，更好是20質量%以上，進一步較好是30質量%以上。(D)無機填充材料中的(D1)中空無機填充材料的含量(質量%)的上限沒有特別限定，將樹脂組成物中的不揮發成分設為100質量%時，較好可以是90質量%以下，更好可以是80質量%以下，進一步較好可以是75質量%以下，進一步更好可以是70質量%以下，特別好可以是60質量%以下。From the viewpoint of suppressing the relative dielectric constant to a lower level, when the non-volatile component in the resin composition is set to 100 mass %, the content (mass) of (D1) hollow inorganic filler in (D) inorganic filler %) is preferably 10 mass% or more, more preferably 20 mass% or more, further preferably 30 mass% or more. (D) The upper limit of the content (mass %) of the (D1) hollow inorganic filler in the inorganic filler is not particularly limited. When the non-volatile component in the resin composition is 100 mass %, it is preferably 90 mass %. below, more preferably 80 mass % or less, still more preferably 75 mass % or less, still more preferably 70 mass % or less, particularly preferably 60 mass % or less.

(D2)實心無機填充材料的平均空孔率為0體積%。(D2) The average porosity of the solid inorganic filler material is 0% by volume.

(D2)實心無機填充材料較好是選自球形實心二氧化矽、球形實心氧化鋁，和球形實心鋁矽酸鹽中的實心無機填充材料。(D2)實心無機填充材料可以單獨使用1種，也可以將2種以上以任意的比率組合使用。(D2) The solid inorganic filler material is preferably a solid inorganic filler material selected from spherical solid silica, spherical solid alumina, and spherical solid aluminosilicate. (D2) The solid inorganic filler material may be used individually by 1 type, or in combination of 2 or more types at arbitrary ratios.

(D2)實心無機填充材料的平均粒徑較好是5μm以下，更好是3μm以下，進一步較好是2μm以下，進一步更好是1μm以下，特別好是0.6μm以下。(D2)實心無機填充材料的平均粒徑的下限沒有特別限定，較好是0.01μm以上，更好是0.05μm以上，進一步較好是0.1μm以上，特別好是0.2μm以上。(D2) The average particle diameter of the solid inorganic filler is preferably 5 μm or less, more preferably 3 μm or less, further preferably 2 μm or less, still more preferably 1 μm or less, particularly preferably 0.6 μm or less. (D2) The lower limit of the average particle diameter of the solid inorganic filler is not particularly limited, but it is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, particularly preferably 0.2 μm or more.

(D2)實心無機填充材料的比表面積沒有特別限定，較好是0.1m 2/g以上，更好是0.5m 2/g以上，進一步較好是1m 2/g以上，特別好是3m 2/g以上。(D2)實心無機填充材料的比表面積的上限沒有特別限定，較好是100m 2/g以下，更好是70m 2/g以下，進一步較好是50m 2/g以下，特別好是40m 2/g以下。 (D2) The specific surface area of the solid inorganic filler material is not particularly limited, but is preferably 0.1 m 2 /g or more, more preferably 0.5 m 2 /g or more, further preferably 1 m 2 /g or more, particularly preferably 3 m 2 / g and above. (D2) The upper limit of the specific surface area of the solid inorganic filler is not particularly limited, but it is preferably 100 m 2 /g or less, more preferably 70 m 2 /g or less, further preferably 50 m 2 /g or less, particularly preferably 40 m 2 /g. g below.

作為(D2)實心無機填充材料的市售品，可舉出例如日鐵化學材料公司製的「SP60-05」、「SP507-05」；雅都瑪公司製的「YC100C」、「YA050C」、「YA050C-MJE」、「YA010C」；DENKA公司製的「UFP-30」；德山公司製的「Silfil NSS-3N」、「Silfil NSS-4N」、「Silfil NSS-5N」；雅都瑪公司製的「SC2500SQ」、「SO-C4」、「SO-C2」、「SO-C1」；DENKA公司製的「DAW-03」、「FB-105FD」等。Examples of commercially available solid inorganic fillers (D2) include "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical Materials Co., Ltd.; "YC100C" and "YA050C" manufactured by Yaduma Corporation; "YA050C-MJE", "YA010C"; "UFP-30" made by DENKA Co., Ltd.; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" made by Tokuyama Co., Ltd.; Yaduma Co., Ltd. "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by DENKA; "DAW-03", "FB-105FD" manufactured by DENKA, etc.

從提高耐濕性和分散性的觀點來看，(D2)實心無機填充材料較好是用表面處理劑進行了處理。From the viewpoint of improving moisture resistance and dispersibility, (D2) the solid inorganic filler material is preferably treated with a surface treatment agent.

從提高(D2)實心無機填充材料的分散性的觀點來看，通過表面處理劑進行的表面處理的程度較好是在規定的範圍內。具體來說，相對於(D2)實心無機填充材料100質量%，較好是通過0.2質量%~5質量%的表面處理劑進行了表面處理，更好是通過0.2質量%~3質量%的表面處理劑進行了表面處理，進一步較好是通過0.3質量%~2質量%的表面處理劑進行了表面處理。From the viewpoint of improving the dispersibility of the solid inorganic filler (D2), the degree of surface treatment by the surface treatment agent is preferably within a predetermined range. Specifically, relative to 100% by mass of the (D2) solid inorganic filler material, it is preferably surface treated with a surface treatment agent of 0.2% to 5% by mass, and more preferably 0.2% to 3% by mass of the surface treatment agent. The surface is treated with a treatment agent, and more preferably, the surface is treated with a surface treatment agent of 0.3% by mass to 2% by mass.

通過表面處理劑進行的表面處理的程度可通過(D2)實心無機填充材料的每單位表面積的碳量進行評價。從提高(D2)實心無機填充材料的分散性的觀點來看，(D2)實心無機填充材料的每單位表面積的碳量較好是0.02mg/m 2以上，更好是0.1mg/m 2以上，進一步較好是0.2mg/m 2以上。另一方面，從防止樹脂組成物的熔融黏度、片材形態下的熔融黏度的上升的觀點來看，較好是1.0mg/m 2以下，更好是0.8mg/m 2以下，進一步較好是0.5mg/m 2以下。 The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the (D2) solid inorganic filler material. From the viewpoint of improving the dispersibility of the solid inorganic filler (D2), the carbon amount per unit surface area of the solid inorganic filler (D2) is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more , further preferably 0.2 mg/m 2 or more. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition and the melt viscosity in the sheet form, it is preferably 1.0 mg/m 2 or less, more preferably 0.8 mg/m 2 or less, and still more preferably It is 0.5mg/ m2 or less.

將樹脂組成物中的不揮發成分設為100質量%時，樹脂組成物中的(D)無機填充材料的含量(質量%)例如是0質量%以上、10質量%以上、20質量%以上、30質量%以上，較好是40質量%以上，更好是50質量%以上，進一步較好是60質量%以上，進一步更好是65質量%以上，特別好是70質量%以上。樹脂組成物中的(D)無機填充材料的含量(質量%)的上限沒有特別限定，將樹脂組成物中的不揮發成分設為100質量%時，較好可以為90質量%以下，更好可以為85質量%以下，進一步較好可以為80質量%以下。When the nonvolatile component in the resin composition is 100% by mass, the content (% by mass) of the (D) inorganic filler in the resin composition is, for example, 0% by mass or more, 10% by mass or more, 20% by mass or more, 30 mass% or more, preferably 40 mass% or more, more preferably 50 mass% or more, still more preferably 60 mass% or more, still more preferably 65 mass% or more, particularly preferably 70 mass% or more. The upper limit of the content (mass %) of (D) inorganic filler in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100 mass %, it is preferably 90 mass % or less, more preferably The content may be 85 mass% or less, and more preferably, it may be 80 mass% or less.

將樹脂組成物中的不揮發成分設為100體積%時，樹脂組成物中的(D)無機填充材料的含量(體積%)例如是0體積%以上、10體積%以上，較好是20體積%以上，更好是30體積%以上，進一步較好是40體積%以上，進一步更好是50體積%以上，特別好是60體積%以上。樹脂組成物中的(D)無機填充材料的含量(體積%)的上限沒有特別限定，將樹脂組成物中的不揮發成分設為100體積%時，較好可以為80體積%以下，更好可以為75體積%以下，進一步較好可以為70體積%以下。When the nonvolatile component in the resin composition is 100 volume %, the content (volume %) of (D) the inorganic filler in the resin composition is, for example, 0 volume % or more, 10 volume % or more, preferably 20 volume % % or more, more preferably 30 volume % or more, still more preferably 40 volume % or more, still more preferably 50 volume % or more, particularly preferably 60 volume % or more. The upper limit of the content (volume %) of (D) inorganic filler in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100 volume %, it is preferably 80 volume % or less, more preferably The content may be 75% by volume or less, more preferably 70% by volume or less.

＜(E)環氧樹脂硬化劑＞ 本發明的樹脂組成物可以包含(E)環氧樹脂硬化劑作為任意的成分。(E)環氧樹脂硬化劑可具有與(A)環氧樹脂反應而使其硬化的功能。(E)環氧樹脂硬化劑可以單獨使用1種，也可以將2種以上任意地組合使用。此處說明的(E)環氧樹脂硬化劑是除屬下述說明的(F)熱塑性樹脂的物質以外的成分。 ＜(E) Epoxy resin hardener＞ The resin composition of the present invention may contain (E) an epoxy resin hardener as an optional component. (E) The epoxy resin hardener may react with (A) epoxy resin to harden it. (E) The epoxy resin hardener may be used alone or in combination of two or more types. The (E) epoxy resin hardener described here is a component other than the (F) thermoplastic resin described below.

作為(E)環氧樹脂硬化劑，沒有特別限定，可舉出例如活性酯系硬化劑、酚系硬化劑、碳二亞胺系硬化劑、酸酐系硬化劑、胺系硬化劑、苯并噁嗪系硬化劑、氰酸酯系硬化劑和硫醇系硬化劑等。在一個實施方式中，(E)環氧樹脂硬化劑較好是包含選自活性酯系硬化劑、酚系硬化劑和氰酸酯酯系硬化劑中的1種以上的環氧樹脂硬化劑，更好是包含選自活性酯系硬化劑和酚系硬化劑中的1種以上的環氧樹脂硬化劑。在一個實施方式中，從將介電損耗角正切控制為更低的值的觀點來看，(E)環氧樹脂硬化劑特別好是包含活性酯系硬化劑。另外，在一個實施方式中，從更為提高硬化性的觀點來看，(E)環氧樹脂硬化劑特別好是包含酚系硬化劑。(E) The epoxy resin hardener is not particularly limited, and examples thereof include active ester-based hardeners, phenol-based hardeners, carbodiimide-based hardeners, acid anhydride-based hardeners, amine-based hardeners, benzox Azine-based hardeners, cyanate ester-based hardeners, thiol-based hardeners, etc. In one embodiment, (E) the epoxy resin hardener preferably contains one or more epoxy resin hardeners selected from the group consisting of active ester hardeners, phenol hardeners, and cyanate ester hardeners, More preferably, it contains one or more epoxy resin hardeners selected from active ester hardeners and phenol hardeners. In one embodiment, from the viewpoint of controlling the dielectric loss tangent to a lower value, the (E) epoxy resin curing agent preferably contains an active ester-based curing agent. In one embodiment, the (E) epoxy resin curing agent preferably contains a phenolic curing agent from the viewpoint of further improving curability.

作為活性酯系硬化劑，一般較好是使用酚酯類、硫酚酯類、N-羥基胺酯類、雜環羥基化合物的酯類等的在1分子中具有2個以上的反應活性高的酯基的化合物。該活性酯化合物較好是通過羧酸化合物和/或硫代羧酸化合物與羥基化合物和/或硫醇化合物的縮合反應獲得的化合物。特別是從耐熱性提高的觀點來看，較好是由羧酸化合物和羥基化合物獲得的活性酯化合物，更好是由羧酸化合物與苯酚化合物和/或萘酚化合物獲得的活性酯化合物。作為羧酸化合物，可舉出例如苯甲酸、乙酸、琥珀酸、馬來酸、衣康酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、均苯四酸等。作為苯酚化合物或萘酚化合物，可舉出例如氫醌、間苯二酚、雙酚A、雙酚F、雙酚S、酚酞啉、甲基化雙酚A、甲基化雙酚F、甲基化雙酚S、苯酚、鄰甲酚、間甲酚、對甲酚、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、二羥基二苯酮、三羥基二苯酮、四羥基二苯酮、間苯三酚、苯三酚、雙環戊二烯型二苯酚化合物、線型酚醛樹脂(phenol novolac)等。在此，「雙環戊二烯型二苯酚化合物」是指1分子雙環戊二烯縮合2分子苯酚而得的二苯酚化合物。As the active ester-based hardener, it is generally preferable to use phenolic esters, thiophenol esters, N-hydroxylamine esters, esters of heterocyclic hydroxyl compounds, etc., which have two or more reactive properties per molecule and are highly reactive. Ester-based compounds. The active ester compound is preferably a compound obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. 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, a phenol compound and/or a naphthol compound is more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthaloline, methylated bisphenol A, methylated bisphenol F, and toluene. Sylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, phloroglucinol, dicyclopentadiene-type diphenol compound, phenol novolac )wait. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound in which one molecule of dicyclopentadiene condenses two molecules of phenol.

作為活性酯系硬化劑，具體地，較好是雙環戊二烯型活性酯化合物、包含萘結構的萘型活性酯化合物、包含線型酚醛樹脂的乙醯基化物的活性酯化合物、包含線型酚醛樹脂的苯甲醯基化物的活性酯化合物，其中，更好是選自雙環戊二烯型活性酯化合物和萘型活性酯化合物中的至少一種。作為雙環戊二烯型活性酯化合物，較好是包含雙環戊二烯型二苯酚結構的活性酯化合物。As the active ester-based hardener, specifically, dicyclopentadiene-type active ester compounds, naphthalene-type active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated product of a novolac resin, and novolac-containing phenolic resins are preferred. An active ester compound of a benzyl compound, preferably at least one selected from the group consisting of a dicyclopentadiene-type active ester compound and a naphthalene-type active ester compound. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferred.

作為活性酯系硬化劑的市售品，包含雙環戊二烯型二苯酚結構的活性酯化合物可舉出「EXB9451」、「EXB9460」、「EXB9460S」、「HPC-8000L-65TM」、「HPC-8000-65T」、「HPC-8000H」、「HPC-8000H-65TM」(DIC公司製)；包含萘結構的活性酯化合物可舉出「HP-B-8151-62T」、「EXB-8100L-65T」、「EXB-9416-70BK」、「HPC-8150-62T」、「EXB-8」(DIC公司製)；含磷活性酯化合物可舉出「EXB9401」(DIC公司製)；作為線型酚醛樹脂的乙醯基化物的活性酯化合物可舉出「DC808」(三菱化學公司製)；作為線型酚醛樹脂的苯甲醯基化物的活性酯化合物可舉出「YLH1026」、「YLH1030」、「YLH1048」(三菱化學公司製)；包含苯乙烯基及萘結構的活性酯化合物可舉出「PC1300-02-65MA」(AIR&WATER公司製)等。As commercially available active ester hardeners, active ester compounds containing a dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000L-65TM", "HPC- 8000-65T", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC Corporation); active ester compounds containing a naphthalene structure include "HP-B-8151-62T" and "EXB-8100L-65T" ", "EXB-9416-70BK", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); examples of the phosphorus-containing active ester compound include "EXB9401" (manufactured by DIC Corporation); as a novolac resin Examples of the active ester compound of the acetyl compound include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of the active ester compound of the benzyl compound of the novolak resin include "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); examples of active ester compounds containing a styrene group and a naphthalene structure include "PC1300-02-65MA" (manufactured by AIR & WATER Corporation).

作為酚系硬化劑，從耐熱性及耐水性的觀點來看，較好具有酚醛結構(novolac structure)的酚系硬化劑。另外，從與被黏接物的密合性的觀點來看，較好是含氮酚系硬化劑，更好是含有三嗪骨架的酚系硬化劑。其中，從高度滿足耐熱性、耐水性和密合性的觀點來看，較好是含有三嗪骨架的線型酚醛樹脂(phenol novolac resin)。作為酚系硬化劑的具體例，可舉出例如明和化成公司製的「MEH-7700」、「MEH-7810」、「MEH-7851」、日本化藥公司製的「NHN」、「CBN」、「GPH」、日鐵化學材料公司製的「SN-170」、「SN-180」、「SN-190」、「SN-475」、「SN-485」、「SN-495」、「SN-375」、「SN-395」、DIC公司製的「LA-7052」、「LA-7054」、「LA-3018」、「LA-3018-50P」、「LA-1356」、「TD2090」、「KA-1160」等。As a phenol-based hardener, a phenol-based hardener having a novolac structure is preferred from the viewpoint of heat resistance and water resistance. In addition, from the viewpoint of adhesion to the adherend, a nitrogen-containing phenol-based hardening agent is preferred, and a phenol-based hardening agent containing a triazine skeleton is more preferred. Among them, a phenol novolac resin containing a triazine skeleton is preferred from the viewpoint of highly satisfying heat resistance, water resistance and adhesion. Specific examples of the phenolic hardener include "MEH-7700", "MEH-7810" and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN" and "CBN" manufactured by Nippon Kayaku Co., Ltd. "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-" manufactured by Nippon Steel Chemical Materials Co., Ltd. 375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", " KA-1160" etc.

作為碳二亞胺系硬化劑，可舉出在1分子中具有1個以上、較好是2個以上碳二亞胺結構的硬化劑，可舉出例如：四亞甲基-雙(叔丁基碳二亞胺)、環己烷雙(亞甲基-叔丁基碳二亞胺)等脂肪族雙碳二亞胺；伸苯基-雙(二甲苯基碳二亞胺)等芳族雙碳二亞胺等雙碳二亞胺；聚六亞甲基碳二亞胺、聚三甲基六亞甲基碳二亞胺、聚伸環己基碳二亞胺、聚(亞甲基雙伸環己基碳二亞胺)、聚(異佛爾酮碳二亞胺)等脂肪族聚碳二亞胺；聚(伸苯基碳二亞胺)、聚(伸萘基碳二亞胺)、聚(伸甲苯基碳二亞胺)、聚(甲基二異丙基伸苯基碳二亞胺)、聚(三乙基伸苯基碳二亞胺)、聚(二乙基伸苯基碳二亞胺)、聚(三異丙基伸苯基碳二亞胺)、聚(二異丙基伸苯基碳二亞胺)、聚(伸二甲苯基碳二亞胺)、聚(四甲基伸二甲苯基碳二亞胺)、聚(亞甲基二伸苯基碳二亞胺)、聚[亞甲基雙(甲基伸苯基)碳二亞胺]等芳族聚碳二亞胺等聚碳二亞胺。Examples of carbodiimide-based curing agents include those having one or more, preferably two or more carbodiimide structures per molecule. Examples include tetramethylene-bis(tert-butyl). Aliphatic biscarbodiimides such as cyclohexane bis(methylene-tert-butylcarbodiimide) and cyclohexane bis(methylene-tert-butylcarbodiimide); aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide) Biscarbodiimides such as biscarbodiimide; polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylcarbodiimide, poly(methylenebis) Aliphatic polycarbodiimides such as cyclohexylenecarbodiimide) and poly(isophoronecarbodiimide); poly(phenylenecarbodiimide) and poly(naphthylenecarbodiimide) , poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide) imine), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylene) aromatic polycarbodiimide), poly(methylene diphenylene carbodiimide), poly[methylene bis(methylphenylene) carbodiimide] and other aromatic polycarbodiimides. Carbodiimide.

作為碳二亞胺系硬化劑的市售品，可舉出例如：日清紡化學公司製的「CARBODILITE V-02B」、「CARBODILITE V-03」、「CARBODILITE V-04K」、「CARBODILITE V-07」和「CARBODILITE V-09」；Rhein-Chemie公司製的「Stabaxol P」、「Stabaxol P400」、「Hycasyl 510」等。Examples of commercially available carbodiimide hardeners include "CARBODILITE V-02B", "CARBODILITE V-03", "CARBODILITE V-04K", and "CARBODILITE V-07" manufactured by Nisshinbo Chemical Co., Ltd. and "CARBODILITE V-09"; "Stabaxol P", "Stabaxol P400", "Hycasyl 510" manufactured by Rhein-Chemie, etc.

作為酸酐系硬化劑，可舉出1分子中具有1個以上酸酐基的硬化劑，較好是1分子中具有2個以上酸酐基的硬化劑。作為酸酐系硬化劑的具體例，可舉出鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、甲基納迪克酸酐、氫化甲基納迪克酸酐、三烷基四氫鄰苯二甲酸酐、十二烯基琥珀酸酐、5-(2,5-二氧代四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、偏苯三酸酐、均苯四酸酐、二苯甲酮四羧酸二酐、聯苯四羧酸二酐、萘四羧酸二酐、氧雙鄰苯二甲酸二酐、3,3’-4,4’-二苯基碸四羧酸二酐、1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二氧代-3-呋喃基)-萘并[1,2-C]呋喃-1,3-二酮、乙二醇雙(脫水偏苯三酸酯)、苯乙烯和馬來酸共聚而成的苯乙烯-馬來酸樹脂等聚合物型的酸酐等。作為酸酐系硬化劑的市售品，可舉出新日本理化公司製的「HNA-100」、「MH-700」、「MTA-15」、「DDSA」、「OSA」、三菱化學公司製的「YH-306」、「YH-307」、日立化成公司製的「HN-2200」、「HN-5500」、Cray Valley公司製「EF-30」、「EF-40」「EF-60」、「EF-80」等。Examples of the acid anhydride-based curing agent include those having one or more acid anhydride groups per molecule, and preferably those having two or more acid anhydride groups per molecule. Specific examples of the acid anhydride-based hardener include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Dicarboxylic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3- Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic anhydride Carboxylic dianhydride, oxybisphthalic dianhydride, 3,3'-4,4'-diphenyltetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5 -(Tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(dehydrated trimellitate), Polymer-type acid anhydrides such as styrene-maleic acid resin copolymerized with styrene and maleic acid. Examples of commercially available acid anhydride-based hardeners include "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by New Nippon Rika Co., Ltd., and Mitsubishi Chemical Corporation's "YH-306", "YH-307", "HN-2200" and "HN-5500" made by Hitachi Chemical Co., Ltd., "EF-30", "EF-40" and "EF-60" made by Cray Valley Co., Ltd. "EF-80" etc.

作為胺系硬化劑，可舉出在1分子中具有1個以上、較好是2個以上胺基的硬化劑，可舉出例如脂肪族胺類、聚醚胺類、脂環族胺類、芳族胺類等，其中，從實現本發明所期望的效果的觀點來看，較好是芳族胺類。胺系硬化劑較好是伯胺或仲胺，更好是伯胺。作為胺系硬化劑的具體例，可舉出4,4’-亞甲基雙(2,6-二甲基苯胺)、4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基碸、3,3’-二胺基二苯基碸、間苯二胺、間二甲苯二胺、二乙基甲苯二胺、4,4’-二胺基二苯基醚、3,3’-二甲基-4,4’-二胺基聯苯、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。胺系硬化劑可以使用市售品，可舉出例如，SEIKA公司製「SEIKACURE-S」、日本化藥公司製的「KAYABOND C-200S」、「KAYABOND C-100」、「KAYAHARD A-A」、「KAYAHARD A-B」、「KAYAHARD A-S」、三菱化學公司製的「Epicure W」等。Examples of the amine-based curing agent include those having one or more, preferably two or more amine groups per molecule, and examples include aliphatic amines, polyether amines, alicyclic amines, Aromatic amines, etc. Among them, aromatic amines are preferred from the viewpoint of achieving 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 the amine-based hardener include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, and 4,4'- Diaminodiphenyl terine, 3,3'-diaminodiphenyl terine, m-phenylenediamine, m-xylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyldiamine 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-aminophenyl)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)sine, bis(4-(3-aminophenoxy)phenyl)sine, etc. Commercially available amine hardeners can be used, and examples thereof include "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.

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

作為氰酸酯系硬化劑，可舉出例如，雙酚A二氰酸酯、多酚氰酸酯(低聚(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，和雙(4-氰酸酯苯基)醚等2官能氰酸酯樹脂、由苯酚酚醛清漆樹脂和甲酚酚醛清漆樹脂等衍生的多官能氰酸酯樹脂、這些氰酸酯樹脂一部分三嗪化的預聚物等。作為氰酸酯系硬化劑的具體例，可舉出Lonza日本公司製的「PT30」和「PT60」(均為苯酚酚醛清漆型多官能氰酸酯樹脂)、「BA230」、「BA230S75」(雙酚A二氰酸酯的一部分或全部三嗪化而成為三聚物的預聚物)等。Examples of the cyanate-based hardener include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4 ,4'-methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2 ,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane , 1,3-bis(4-cyanatophenyl-1-(methylethylene))benzene, bis(4-cyanatophenyl)sulfide, and bis(4-cyanatophenyl) ) ether and other bifunctional cyanate ester resins, multifunctional cyanate ester resins derived from phenol novolac resin and cresol novolac resin, etc., prepolymers of a part of these cyanate ester resins that are triazinized, etc. Specific examples of cyanate-based hardeners include "PT30" and "PT60" manufactured by Lonza Japan Co., Ltd. (both are phenol novolac-type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (dual Prepolymers in which part or all of phenol A dicyanate is triazinized to form a terpolymer), etc.

作為硫醇系硬化劑，可舉出例如：三羥甲基丙烷三(3-巰基丙酸酯)、季戊四醇四(3-巰基丁酸酯)、三(3-巰基丙基)異氰脲酸酯等。Examples of thiol-based hardeners include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanuric acid. Ester etc.

(E)環氧樹脂硬化劑的反應基當量較好是50g/eq.~3000g/eq.，更好是100g/eq.~1000g/eq.，進一步較好是100g/eq.~500g/eq.，特別好是100g/eq.~300g/eq.。反應基當量是每1當量反應基對應的(E)環氧樹脂硬化劑的質量。(E) The reactive group equivalent of the epoxy resin hardener is preferably 50g/eq.~3000g/eq., more preferably 100g/eq.~1000g/eq., further preferably 100g/eq.~500g/eq. ., especially good is 100g/eq.~300g/eq. The reactive group equivalent is the mass of (E) epoxy resin hardener corresponding to 1 equivalent of reactive group.

作為(E)環氧樹脂硬化劑，包含活性酯系硬化劑的情況下，從將介電損耗角正切抑制為更低的觀點來看，將樹脂組成物中的不揮發成分設為100質量%時，樹脂組成物中的活性酯系硬化劑的含量較好是1質量%以上，更好是3質量%以上，進一步較好是5質量%以上，特別好是8質量%以上。另外，從將介電損耗角正切抑制為更低的觀點來看，將樹脂組成物中的(E)環氧樹脂硬化劑的總量設為100質量%時，(E)環氧樹脂硬化劑中的活性酯系硬化劑的含量較好是10質量%以上，更好是30質量%以上，進一步較好是40質量%以上，特別好是50質量%以上。When the (E) epoxy resin curing agent contains an active ester-based curing agent, from the viewpoint of suppressing the dielectric loss tangent to a lower level, the nonvolatile component in the resin composition is set to 100 mass %. When the content of the active ester hardener in the resin composition is preferably 1 mass% or more, more preferably 3 mass% or more, further preferably 5 mass% or more, particularly preferably 8 mass% or more. In addition, from the viewpoint of suppressing the dielectric loss tangent to a lower level, when the total amount of the (E) epoxy resin hardener in the resin composition is 100% by mass, the (E) epoxy resin hardener The content of the active ester hardener in the composition is preferably 10 mass% or more, more preferably 30 mass% or more, further preferably 40 mass% or more, particularly preferably 50 mass% or more.

作為(E)環氧樹脂硬化劑，包含酚系硬化劑的情況下，從更為提高硬化性的觀點來看，將樹脂組成物中的不揮發成分設為100質量%時，樹脂組成物中的酚系硬化劑的含量較好是0.5質量%以上，更好是1質量%以上，進一步較好是1.5質量%以上，特別好是1.7質量%以上。When the (E) epoxy resin hardener contains a phenolic hardener, from the viewpoint of further improving the curability, when the non-volatile component in the resin composition is 100% by mass, The content of the phenolic hardener is preferably 0.5 mass% or more, more preferably 1 mass% or more, further preferably 1.5 mass% or more, particularly preferably 1.7 mass% or more.

樹脂組成物中的(E)環氧樹脂硬化劑的含量沒有特別限定，將樹脂組成物中的不揮發成分設為100質量%時，較好是30質量%以下，更好是25質量%以下，進一步較好是20質量%以下，進一步較好是15質量%以下，特別好是13質量%以下。樹脂組成物中的(E)環氧樹脂硬化劑的含量的下限沒有特別限定，將樹脂組成物中的不揮發成分設為100質量%時，較好可以是0.5質量%以上，更好可以是1質量%以上，進一步較好可以是5質量%以上，進一步更好可以是8質量%以上，特別好可以是10質量%以上。The content of (E) epoxy resin hardener in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100% by mass, it is preferably 30% by mass or less, more preferably 25% by mass or less. , further preferably 20 mass% or less, still more preferably 15 mass% or less, particularly preferably 13 mass% or less. The lower limit of the content of (E) epoxy resin hardener in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100% by mass, it is preferably 0.5% by mass or more, more preferably 0.5% by mass or more. 1% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, particularly preferably 10% by mass or more.

＜(F)熱塑性樹脂＞ 本發明的樹脂組成物可以包含(F)熱塑性樹脂作為任意成分。(F)熱塑性樹脂是不屬上述說明的(A)環氧樹脂的成分。 ＜(F)Thermoplastic resin＞ The resin composition of the present invention may contain (F) thermoplastic resin as an optional component. (F) Thermoplastic resin is a component that is not included in (A) epoxy resin described above.

作為(F)熱塑性樹脂，可舉出例如：聚醯亞胺樹脂、苯氧樹脂、聚乙烯醇縮醛樹脂、聚烯烴樹脂、聚丁二烯樹脂、聚醯胺醯亞胺樹脂、聚醚醯亞胺樹脂、聚碸樹脂、聚醚碸樹脂、聚苯醚樹脂、聚碳酸酯樹脂、聚醚醚酮樹脂、聚酯樹脂等。在一個實施方式中，(F)熱塑性樹脂較好是包含選自由聚醯亞胺樹脂和苯氧樹脂所成群組中的熱塑性樹脂，更好是包含苯氧樹脂。(F)熱塑性樹脂可以單獨使用1種，或者也可以組合2種以上使用。Examples of (F) thermoplastic resin include polyamide resin, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamide imine resin, and polyether resin. Imine resin, polyester resin, polyether resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc. In one embodiment, (F) the thermoplastic resin preferably includes a thermoplastic resin selected from the group consisting of polyimide resin and phenoxy resin, and more preferably includes a phenoxy resin. (F) Thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more types.

作為聚醯亞胺樹脂的具體例，可舉出信越化學工業公司製「SLK-6100」、新日本理化公司製的「RIKACOAT SN20」和「RIKACOAT PN20」等。Specific examples of the polyimide resin include "SLK-6100" manufactured by Shin-Etsu Chemical Industry Co., Ltd., "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Shin-Nippon Rika Co., Ltd., and the like.

作為苯氧樹脂，可舉出例如具有選自由雙酚A骨架、雙酚F骨架、雙酚S骨架、雙酚苯乙酮骨架、酚醛骨架、聯苯骨架、茀骨架、雙環戊二烯骨架、降冰片烯骨架、萘骨架、蒽骨架、金剛烷骨架、萜烯骨架和三甲基環己烷骨架所成群組中的1種以上的骨架的苯氧樹脂。苯氧樹脂的末端可以是酚式羥基、環氧基等的任一官能團。Examples of the phenoxy resin include those having a skeleton selected from a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a phenolic skeleton, a biphenyl skeleton, a fluorine skeleton, and a dicyclopentadiene skeleton. Phenoxy resin having one or more skeletons from the group consisting of norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

作為苯氧樹脂的具體例，可舉出：三菱化學公司製的「1256」及「4250」(均為含雙酚A骨架的苯氧樹脂)；三菱化學公司製的「YX8100」(含雙酚S骨架的苯氧樹脂)；三菱化學公司製的「YX6954」(含雙酚苯乙酮骨架的苯氧樹脂)；日鐵化學材料公司製的「FX280」及「FX293」；三菱化學公司製的「YX7200B35」、「YL7500BH30」、「YX6954BH30」、「YX7553BH30」、「YL7769BH30」、「YL6794」、「YL7213」、「YL7290」和「YL7482」等。Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (containing bisphenol A skeleton) Phenoxy resin with S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel Chemical Materials Corporation; manufactured by Mitsubishi Chemical Corporation "YX7200B35", "YL7500BH30", "YX6954BH30", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482", etc.

作為聚乙烯醇縮醛樹脂，可舉出例如聚乙烯醇縮甲醛樹脂、聚乙烯醇縮丁醛樹脂，較好是聚乙烯醇縮丁醛樹脂。作為聚乙烯醇縮醛樹脂的具體例，可舉出：電氣化學工業公司製的「電化縮丁醛4000-2」、「電化縮丁醛5000-A」、「電化縮丁醛6000-C」、「電化縮丁醛6000-EP」；積水化學工業公司製的S-LEC BH系列、BX系列(例如BX-5Z)、KS系列(例如KS-1)、BL系列、BM系列；等。Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, with polyvinyl butyral resin being preferred. Specific examples of the polyvinyl acetal resin include "Electric Butyral 4000-2", "Electric Butyral 5000-A" and "Electric Butyral 6000-C" manufactured by Denki Chemical Industry Co., Ltd. , "Electrochemical Butyral 6000-EP"; S-LEC BH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series manufactured by Sekisui Chemical Industry Co., Ltd.; etc.

作為聚烯烴樹脂，可舉出例如低密度聚乙烯、超低密度聚乙烯、高密度聚乙烯、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸甲酯共聚物等乙烯系共聚樹脂；聚丙烯、乙烯-丙烯嵌段共聚物等聚烯烴系聚合物等。Examples of the polyolefin resin include ethylene such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer. Copolymer resin; polyolefin polymers such as polypropylene, ethylene-propylene block copolymer, etc.

作為聚丁二烯樹脂，可舉出例如：含氫化聚丁二烯骨架的樹脂、含羥基的聚丁二烯樹脂、含酚式羥基的聚丁二烯樹脂、含羧基的聚丁二烯樹脂、含酸酐基的聚丁二烯樹脂、含環氧基的聚丁二烯樹脂、含異氰酸酯基的聚丁二烯樹脂、含胺基甲酸酯基的聚丁二烯樹脂、聚苯醚-聚丁二烯樹脂等。Examples of the polybutadiene resin include hydrogenated polybutadiene skeleton-containing resin, hydroxyl group-containing polybutadiene resin, phenolic hydroxyl group-containing polybutadiene resin, and carboxyl group-containing polybutadiene resin. , Anhydride group-containing polybutadiene resin, epoxy group-containing polybutadiene resin, isocyanate group-containing polybutadiene resin, urethane group-containing polybutadiene resin, polyphenylene ether - Polybutadiene resin, etc.

作為聚醯胺醯亞胺樹脂的具體例，可舉出東洋紡公司製的「VYLOMAX HR11NN」和「VYLOMAX HR16NN」。作為聚醯胺醯亞胺樹脂的具體例，還可舉出日立化成公司製的「KS9100」、「KS9300」(含聚矽氧烷骨架的聚醯胺醯亞胺)等改性聚醯胺醯亞胺。Specific examples of the polyamide imide resin include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamide imine resins include modified polyamide imines such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide imine) manufactured by Hitachi Chemical Co., Ltd. imine.

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

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

作為聚苯醚樹脂的具體例，可舉出SABIC製「NORYL SA90」等。作為聚醚醯亞胺樹脂的具體例，可舉出GE公司製的「ULTEM」等。Specific examples of the polyphenylene ether resin include "NORYL SA90" manufactured by SABIC. Specific examples of the polyetherimide resin include "ULTEM" manufactured by GE Corporation, and the like.

作為聚碳酸酯樹脂，可舉出：含羥基的碳酸酯樹脂、含酚式羥基的碳酸酯樹脂、含羧基的碳酸酯樹脂、含酸酐基的碳酸酯樹脂、含異氰酸酯基的碳酸酯樹脂、含胺基甲酸酯基的碳酸酯樹脂等。作為聚碳酸酯樹脂的具體例，可舉出三菱瓦斯化學公司製的「FPC0220」、旭化成化學公司製的「T6002」、「T6001」(聚碳酸酯二醇)、可樂麗公司製的「C-1090」、「C-2090」、「C-3090」(聚碳酸酯二醇)等。作為聚醚醚酮樹脂的具體例，可舉出住友化學公司製的「SUMIPLOY K」等。Examples of the polycarbonate resin include hydroxyl group-containing carbonate resin, phenolic hydroxyl group-containing carbonate resin, carboxyl group-containing carbonate resin, acid anhydride group-containing carbonate resin, isocyanate group-containing carbonate resin, Urethane-based carbonate resin, etc. Specific examples of the polycarbonate resin include "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemical Co., Ltd., and "C-" manufactured by Kuraray Co., Ltd. 1090", "C-2090", "C-3090" (polycarbonate diol), etc. Specific examples of the polyetheretherketone resin include "SUMIPLOY K" manufactured by Sumitomo Chemical Corporation.

作為聚酯樹脂，可舉出例如聚對苯二甲酸乙二醇酯樹脂、聚萘二甲酸乙二醇酯樹脂、聚對苯二甲酸丁二醇酯樹脂、聚萘二甲酸丁二醇酯樹脂、聚對苯二甲酸丙二醇酯樹脂、聚萘二甲酸丙二醇酯樹脂、聚對苯二甲酸環己烷二甲酯樹脂等。Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, and polybutylene naphthalate resin. , polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexane dimethyl terephthalate resin, etc.

從更為提高膜製膜性的觀點來看，(F)熱塑性樹脂的重量平均分子量(Mw)較好是5000以上，更好是8000以上，進一步較好是10000以上，特別好是20000以上，較好是100000以下，更好是70000以下，進一步較好是60000以下，特別好是50000以下。From the viewpoint of further improving film-forming properties, the weight average molecular weight (Mw) of (F) the thermoplastic resin is preferably at least 5,000, more preferably at least 8,000, further preferably at least 10,000, and particularly preferably at least 20,000. The price is preferably 100,000 or less, more preferably 70,000 or less, further preferably 60,000 or less, and particularly preferably 50,000 or less.

樹脂組成物中的(F)熱塑性樹脂的含量沒有特別限定，將樹脂組成物中的不揮發成分設為100質量%時，較好可以是20質量%以下，更好可以是15質量%以下，進一步較好可以是10質量%以下，進一步更好可以是5質量%以下，特別好可以是2質量%以下。樹脂組成物中的(F)熱塑性樹脂的含量的下限沒有特別限定，將樹脂組成物中的不揮發成分設為100質量%時，例如是0質量%以上、0.01質量%以上，較好是0.05質量%以上，更好是0.1質量%以上，進一步較好是0.5質量%以上，特別好是0.7質量%以上。The content of (F) thermoplastic resin in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100% by mass, it is preferably 20% by mass or less, more preferably 15% by mass or less. More preferably, it may be 10% by mass or less, still more preferably, it may be 5% by mass or less, and particularly preferably, it may be 2% by mass or less. The lower limit of the content of (F) thermoplastic resin in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100 mass %, it is, for example, 0 mass % or more, 0.01 mass % or more, preferably 0.05 It is 0.1 mass % or more, more preferably 0.1 mass % or more, 0.5 mass % or more is more preferable, and it is especially preferably 0.7 mass % or more.

＜(G)其他添加劑＞ 本發明的樹脂組成物也可以還包含任意的添加劑。作為這種添加劑，可舉出例如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的自由基聚合起始劑；環氧丙烯酸酯樹脂、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、酚醛樹脂、三聚氰胺樹脂、聚矽氧樹脂等的除環氧樹脂以外的熱硬化性樹脂；橡膠粒子等的有機填充材料；有機銅化合物、有機鋅化合物、有機鈷化合物等的有機金屬化合物；酞菁藍、酞菁綠、碘綠、重氮黃、結晶紫、氧化鈦、炭黑等的著色劑；對苯二酚、鄰苯二酚、連苯三酚、吩噻嗪等的阻聚劑；聚矽氧系調平劑、丙烯酸聚合物系調平劑等的調平劑；Benton、蒙脫石等增稠劑；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的消泡劑；苯并三唑系紫外線吸收劑等的紫外線吸收劑；脲矽烷等的黏接性提高劑；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的密合性賦予劑；受阻酚系抗氧化劑等的抗氧化劑；茋衍生物等的螢光增白劑；氟系界面活性劑、聚矽氧系界面活性劑等的界面活性劑；磷系阻燃劑(例如磷酸酯化合物、磷腈化合物、次膦酸化合物、紅磷)、氮系阻燃劑(例如硫酸三聚氰胺)、鹵素系阻燃劑、無機系阻燃劑(例如三氧化銻)等的阻燃劑；磷酸酯系分散劑、聚氧化烯系分散劑、炔系分散劑、聚矽氧系分散劑、陰離子性分散劑、陽離子性分散劑等的分散劑；硼酸酯系穩定劑、鈦酸酯系穩定劑、鋁酸酯系穩定劑、鋯酸酯系穩定劑、異氰酸酯系穩定劑、羧酸系穩定劑、羧酸酐系穩定劑等的穩定劑等。(G)其他添加劑可以單獨使用一種，也可以將兩種以上以任意的比率組合使用。若為本領域技術人員，則可適當設定(G)其他添加劑的含量。 ＜(G)Other additives＞ The resin composition of the present invention may further contain optional additives. Examples of such additives include radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; epoxy acrylate resins and urethane acrylic resins; Thermosetting resins other than epoxy resins such as ester resins, urethane resins, cyanate ester resins, benzoxazine resins, unsaturated polyester resins, phenolic resins, melamine resins, and polysiloxane resins; Organic fillers such as rubber particles; organic metal compounds such as organic copper compounds, organic zinc compounds, organic cobalt compounds, etc.; phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, etc. Colorants; polymerization inhibitors for hydroquinone, catechol, pyrogallol, phenothiazine, etc.; leveling agents for polysiloxane-based leveling agents, acrylic polymer-based leveling agents, etc.; Benton, Thickeners such as montmorillonite; defoamer such as polysilicone defoamer, acrylic defoamer, fluorine defoamer, vinyl resin defoamer, etc.; benzotriazole ultraviolet absorber, etc. UV absorbers; adhesion improving agents such as urea silane; adhesion imparting agents such as triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, triazine-based adhesion-imparting agents, etc.; hindered Antioxidants such as phenolic antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and polysiloxane-based surfactants; phosphorus-based flame retardants (such as phosphate ester compounds, Flame retardants such as phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (such as melamine sulfate), halogen-based flame retardants, inorganic-based flame retardants (such as antimony trioxide); phosphate ester series Dispersants, polyoxyalkylene dispersants, acetylenic dispersants, polysiloxane dispersants, anionic dispersants, cationic dispersants, etc.; borate ester stabilizers, titanate ester stabilizers, Stabilizers such as aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers, etc. (G) Other additives may be used alone or in combination of two or more at any ratio. Those skilled in the art can appropriately set the content of (G) other additives.

＜(H)有機溶劑＞ 本發明的樹脂組成物有時還包含任意的有機溶劑。作為(H)有機溶劑，可以適當使用公知的溶劑，其種類沒有特別限定。作為(H)有機溶劑，可舉出例如丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮系溶劑；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-丁內酯等酯系溶劑；四氫吡喃、四氫呋喃、1,4-二噁烷、二乙醚、二異丙醚、二丁醚、二苯醚、苯甲醚等的醚系溶劑；甲醇、乙醇、丙醇、丁醇、乙二醇等醇系溶劑；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、二乙二醇單乙基醚乙酸酯(ethyl diglycol acetate)、γ-丁內酯、甲氧基丙酸甲酯等醚酯系溶劑；乳酸甲酯、乳酸乙酯、2-羥基異丁酸甲酯等酯醇系溶劑；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-吡咯烷酮等醯胺系溶劑；二甲基亞碸等的亞碸系溶劑；乙腈、丙腈等的腈系溶劑；己烷、環戊烷、環己烷、甲基環己烷等脂肪族烴系溶劑；苯、甲苯、二甲苯、乙基苯、三甲基苯等芳烴系溶劑等。(H)有機溶劑可以單獨使用一種，也可以將兩種以上以任意的比率組合使用。 ＜(H) Organic solvent＞ The resin composition of the present invention may further contain an optional organic solvent. As (H) the organic solvent, a known solvent can be used appropriately, and the type thereof is not particularly limited. Examples of (H) organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate. , isoamyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone and other ester solvents; tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, diisopropyl ether, etc. Ether solvents such as butyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether, acetic acid Ether ester solvents such as ester, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate (ethyl diglycol acetate), γ-butyrolactone, methyl methoxypropionate; Methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate and other ester alcohol solvents; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, Ether alcohol solvents such as diethylene glycol monobutyl ether (butylcarbitol); N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2- Amide solvents such as pyrrolidone; terine solvents such as dimethyl styrene; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon systems such as hexane, cyclopentane, cyclohexane, and methylcyclohexane Solvents; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (H) The organic solvent may be used alone or in combination of two or more at an arbitrary ratio.

乾燥前的塗料狀的樹脂組成物中的(H)有機溶劑的含量沒有特別限定，將樹脂組成物中的全部成分設為100質量%時，例如是40質量%以下、30質量%以下，較好是20質量%以下，更好是10質量%以下，進一步較好是8質量%以下，特別好是6質量%以下。形成樹脂片材中的樹脂組成物層的乾燥後的樹脂組成物中的(H)有機溶劑的含量沒有特別限定，將樹脂組成物中的全部成分設為100質量%時，較好是5質量%以下，更好是3質量%以下，進一步較好是2質量%以下，特別好是1質量%以下。The content of the (H) organic solvent in the paint-like resin composition before drying is not particularly limited. When all the components in the resin composition are taken as 100 mass %, it is, for example, 40 mass % or less, 30 mass % or less, or less. It is preferably 20 mass% or less, more preferably 10 mass% or less, still more preferably 8 mass% or less, particularly preferably 6 mass% or less. The content of the (H) organic solvent in the dried resin composition that forms the resin composition layer in the resin sheet is not particularly limited. When all the components in the resin composition are taken as 100 mass %, it is preferably 5 mass %. % or less, more preferably 3 mass% or less, further preferably 2 mass% or less, particularly preferably 1 mass% or less.

＜樹脂組成物的製造方法＞ 本發明的樹脂組成物例如可以通過以下方式進行製造：在任意的製備容器中，將(A)環氧樹脂、(B)含有自由基聚合性基團的化合物、(C)硬化促進劑、根據需要的(D)無機填充材料、根據需要的(E)環氧樹脂硬化劑、根據需要的(F)熱塑性樹脂、根據需要的(G)其他添加劑，和根據需要的(H)有機溶劑以任意的順序加入和/或同時加入一部分或全部並混合。另外，在加入各成分並混合的過程中，可以適當設定溫度，可暫時或始終進行加熱和/或冷卻。另外，在加入並混合的過程中，或者該過程之後，可以例如使用混合機等的攪拌裝置或振盪裝置將樹脂組成物進行攪拌或振盪，使其均勻地分散。另外，可在攪拌或振盪的同時在真空下等的低壓條件下進行脫泡。 ＜Manufacturing method of resin composition＞ The resin composition of the present invention can be produced, for example, by adding (A) epoxy resin, (B) radically polymerizable group-containing compound, (C) curing accelerator, and (D) inorganic filler material as needed, (E) epoxy resin hardener as needed, (F) thermoplastic resin as needed, (G) other additives as needed, and (H) organic solvent as needed. Add them sequentially and/or add some or all at the same time and mix. In addition, during the process of adding each component and mixing, the temperature can be appropriately set, and heating and/or cooling can be performed temporarily or continuously. In addition, during the process of adding and mixing, or after the process, the resin composition can be stirred or shaken using a stirring device or an oscillating device such as a mixer to uniformly disperse it. In addition, defoaming can be performed under low-pressure conditions such as under vacuum while stirring or shaking.

＜樹脂組成物的特性＞ 本發明的樹脂組成物包含(A)環氧樹脂、(B)含有自由基聚合性基團的化合物和(C)硬化促進劑，(C)硬化促進劑包含(C1)具有被碳數7以上的烴基取代的含氮雜環的化合物。根據這種樹脂組成物，可以得到耐裂紋性優異的硬化物。 ＜Characteristics of resin composition＞ The resin composition of the present invention contains (A) epoxy resin, (B) a compound containing a radically polymerizable group, and (C) a curing accelerator, and the (C) curing accelerator contains (C1) having a carbon number of 7 or more Hydrocarbyl-substituted nitrogen-containing heterocyclic compounds. According to this resin composition, a cured product excellent in crack resistance can be obtained.

本發明的樹脂組成物的硬化物可具有能夠抑制除膠渣處理(粗糙化處理)後的裂紋的產生這樣的特徵。因此，在一個實施方式中，如下述試驗例3這樣將電路基板進行製作和除膠渣處理後，觀察電路基板的銅墊部100個時，裂紋較好可以是小於15%(15%以下)，特別好可以是小於5%(5%以下)。The cured product of the resin composition of the present invention may have the characteristic of being able to suppress the occurrence of cracks after the desmearing process (roughening process). Therefore, in one embodiment, after the circuit board is manufactured and desmeared as in Test Example 3 below, when 100 copper pad portions of the circuit board are observed, the cracks are preferably less than 15% (less than 15%). , particularly preferably less than 5% (below 5%).

在一個實施方式中，本發明的樹脂組成物的硬化物可具有線熱膨脹係數(CTE)低這樣的特徵。因此，在一個實施方式中，如下述試驗例1這樣測定的硬化物的線熱膨脹係數(CTE)在從25℃至150℃為止的範圍，較好是40ppm/K以下，更好是35ppm/K以下，進一步較好是30ppm/K以下，進一步更好是25ppm/K以下，特別好是22ppm/K以下。對於線熱膨脹係數(CTE)的下限，沒有特別限定，可設為1ppm/K以上等。In one embodiment, the cured product of the resin composition of the present invention may have a low linear thermal expansion coefficient (CTE). Therefore, in one embodiment, the linear thermal expansion coefficient (CTE) of the hardened material measured as in Test Example 1 below is in the range from 25°C to 150°C, preferably 40 ppm/K or less, more preferably 35 ppm/K. or less, more preferably 30 ppm/K or less, still more preferably 25 ppm/K or less, particularly preferably 22 ppm/K or less. The lower limit of the linear thermal expansion coefficient (CTE) is not particularly limited, but may be 1 ppm/K or more.

在一個實施方式中，本發明的樹脂組成物的硬化物可具有玻璃轉移溫度(Tg)更高這樣的特徵。因此，在一個實施方式中，如下述試驗例1這樣測定時的玻璃轉移溫度(Tg)較好可成為120℃以上，更好可成為130℃以上，進一步較好可成為140℃以上，進一步更好可成為145℃以上，特別好可成為150℃以上。In one embodiment, the cured product of the resin composition of the present invention may have a higher glass transition temperature (Tg). Therefore, in one embodiment, the glass transition temperature (Tg) when measured as in Test Example 1 below is preferably 120°C or higher, more preferably 130°C or higher, still more preferably 140°C or higher, and still more preferably The best temperature can be above 145℃, and the best temperature can be above 150℃.

在一個實施方式中，本發明的樹脂組成物的硬化物可具有介電損耗角正切(Df)更低的特徵。因此，在一個實施方式中，如下述試驗例2這樣在5.8GHz、23℃的條件下進行測定時的樹脂組成物的硬化物的介電損耗角正切(Df)較好可成為0.010以下，更好可成為0.009以下，進一步較好可成為0.008以下，進一步更好可成為0.007以下、再進一步較好可成為0.006以下或0.0055以下，特別好可成為0.005以下或0.0045以下。In one embodiment, the cured product of the resin composition of the present invention may have a lower dielectric loss tangent (Df). Therefore, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition when measured under the conditions of 5.8 GHz and 23°C as in Test Example 2 below is preferably 0.010 or less, more preferably 0.010 or less. Good may be 0.009 or less, further better may be 0.008 or less, further better may be 0.007 or less, still further better may be 0.006 or less or 0.0055 or less, and particularly good may be 0.005 or less or 0.0045 or less.

在一個實施方式中，本發明的樹脂組成物的硬化物可具有相對介電常數(Dk)更低的特徵。因此，在一個實施方式中，如下述試驗例2這樣在5.8GHz、23℃的條件下進行測定時的樹脂組成物的硬化物的相對介電常數(Dk)沒有特別限定，較好可成為5.0以下，更好可成為4.0以下，進一步較好可成為3.7以下，進一步更好可成為3.5以下，特別好可成為3.3以下。In one embodiment, the cured product of the resin composition of the present invention may have a lower relative dielectric constant (Dk). Therefore, in one embodiment, the relative dielectric constant (Dk) of the cured product of the resin composition when measured under the conditions of 5.8 GHz and 23°C as in Test Example 2 below is not particularly limited, but it is preferably 5.0. below, preferably 4.0 or below, more preferably 3.7 or below, further still better 3.5 or below, and particularly good 3.3 or below.

＜樹脂組成物的用途＞ 本發明的樹脂組成物可作為絕緣用途的樹脂組成物、特別是用於形成絕緣層的樹脂組成物而合適地使用。具體而言，可作為用於形成「供形成導體層(所述導體層形成於絕緣層上，所述導體層包括再配線層)用的該絕緣層」的樹脂組成物(供形成導體層用的絕緣層形成用樹脂組成物)而合適地使用。另外，後述的印刷配線板中，可作為用於形成印刷配線板的絕緣層的樹脂組成物(印刷配線板的絕緣層形成用樹脂組成物)而合適地使用。本發明的樹脂組成物還可用於樹脂片材、預浸料等片狀疊層材料、阻焊劑、底部填充材料、晶粒接合材料、半導體密封材料、填孔樹脂、部件埋入樹脂等需要樹脂組成物的廣泛的用途。 ＜Applications of resin composition＞ The resin composition of the present invention can be suitably used as a resin composition for insulating purposes, particularly a resin composition for forming an insulating layer. Specifically, it can be used as a resin composition (for forming a conductor layer) for forming "the insulating layer for forming a conductor layer (the conductor layer is formed on an insulating layer, and the conductor layer includes a rewiring layer)" resin composition for forming an insulating layer) is suitably used. In addition, in the printed wiring board described below, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for forming an insulating layer of a printed wiring board). The resin composition of the present invention can also be used in sheet-like laminated materials such as resin sheets and prepregs, solder resists, underfill materials, grain bonding materials, semiconductor sealing materials, hole-filling resins, component embedding resins, etc. Wide range of uses of the composition.

另外，例如，經過以下的(1)~(6)步驟來製造半導體晶片封裝的情況下，本發明的樹脂組成物也可合適地用作：作為供形成再配線層用的絕緣層的再配線形成層用的樹脂組成物(再配線形成層形成用的樹脂組成物)、及用於密封半導體晶片的樹脂組成物(半導體晶片密封用的樹脂組成物)。在製造半導體晶片封裝時，可以在密封層上進一步形成再配線層。 (1)在基材上疊層臨時固定膜的步驟， (2)將半導體晶片臨時固定在臨時固定膜上的步驟， (3)在半導體晶片上形成密封層的步驟， (4)將基材和臨時固定膜從半導體晶片剝離的步驟， (5)在半導體晶片的剝離了基材和臨時固定膜的面上，形成作為絕緣層的再配線形成層的步驟，和 (6)在再配線形成層上形成作為導體層的再配線層的步驟 In addition, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can also be suitably used as a rewiring as an insulating layer for forming a rewiring layer. A resin composition for forming a layer (a resin composition for forming a rewiring forming layer), and a resin composition for sealing a semiconductor wafer (a resin composition for sealing a semiconductor wafer). When manufacturing a semiconductor wafer package, a rewiring layer may be further formed on the sealing layer. (1) The step of laminating a temporary fixing film on the base material, (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 base material and the temporary fixing film from the semiconductor wafer, (5) The step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor wafer from which the base material and the temporary fixing film are peeled off, and (6) Step of forming a rewiring layer as a conductor layer on the rewiring formation layer

另外，對於本發明的樹脂組成物而言，由於形成部件埋入性良好的絕緣層，因此，也可合適地用於印刷配線板為部件內置電路板的情況。In addition, since the resin composition of the present invention forms an insulating layer with good component embedability, it can also be suitably used when a printed wiring board is a circuit board with built-in components.

＜片狀疊層材料＞ 本發明的樹脂組成物也可以以塗料狀態進行塗布而使用，但在工業上，優選一般以含有該樹脂組成物的片狀疊層材料的形態使用。 ＜Sheet laminated materials＞ The resin composition of the present invention may be applied and used in a paint state, but industrially, it is generally preferably used in the form of a sheet-like laminated material containing the resin composition.

作為片狀疊層材料，較好是以下所示的樹脂片材、預浸料。As the sheet-like laminated material, the following resin sheets and prepregs are preferred.

在一個實施方式中，樹脂片材包含支承體，和設置於該支承體上的樹脂組成物層，樹脂組成物層由本發明的樹脂組成物形成。In one embodiment, the resin sheet includes a support body and a resin composition layer provided on the support body, and the resin composition layer is formed of the resin composition of the present invention.

從印刷配線板的薄型化，和可提供即使該樹脂組成物的硬化物為薄膜而絕緣性也優異的硬化物這樣的觀點來看，樹脂組成物層的厚度較好是50μm以下，更好是40μm以下。樹脂組成物層的厚度的下限沒有特別限制，通常可以設為5μm以上、10μm以上等。From the viewpoint of thinning the printed wiring board and providing a cured product of the resin composition that has excellent insulation properties even if it is a thin film, the thickness of the resin composition layer is preferably 50 μm or less, more preferably Below 40μm. The lower limit of the thickness of the resin composition layer is not particularly limited, but can generally be set to 5 μm or more, 10 μm or more, or the like.

作為支承體，可舉出例如由塑膠材料形成的膜、金屬箔、脫模紙，較好是由塑膠材料形成的膜、金屬箔。Examples of the support include films, metal foils, and release papers made of plastic materials, and films and metal foils made of plastic materials are preferred.

使用由塑膠材料形成的膜作為支承體的情況下，作為塑膠材料，可舉出例如：聚對苯二甲酸乙二醇酯(以下有時簡稱為「PET」)、聚萘二甲酸乙二醇酯(以下有時簡稱為「PEN」)等聚酯、聚碳酸酯(以下有時簡稱為「PC」)、聚甲基丙烯酸甲酯(PMMA)等丙烯酸系聚合物、環狀聚烯烴、三乙醯纖維素(TAC)、聚醚硫化物(PES)、聚醚酮、聚醯亞胺等。其中，較好是聚對苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯，特別好是廉價的聚對苯二甲酸乙二醇酯。When using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate Polyesters such as ester (hereinafter sometimes referred to as "PEN"), polycarbonate (hereinafter sometimes referred to as "PC"), acrylic polymers such as polymethylmethacrylate (PMMA), cyclic polyolefins, tris Acetylcellulose (TAC), polyether sulfide (PES), polyetherketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

使用金屬箔作為支承體的情況下，作為金屬箔，可舉出例如銅箔、鋁箔等，較好是銅箔。作為銅箔，可使用由銅的單金屬形成的箔，也可使用由銅與其他金屬(例如錫、鉻、銀、鎂、鎳、鋯、矽、鈦等)的合金形成的箔。When a metal foil is used as a support, examples of the metal foil include copper foil, aluminum foil, and the like, and copper foil is preferred. As the copper foil, a foil formed of copper as a single metal may be used, or a foil formed of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

對於支承體而言，可以在與樹脂組成物層接合的面實施啞光處理、電暈處理、防靜電處理。The support may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface bonded to the resin composition layer.

此外，作為支承體，可使用在與樹脂組成物層接合的面具有脫模層的帶脫模層的支承體。作為用於帶脫模層的支承體的脫模層的脫模劑，可舉出例如選自由醇酸樹脂、聚烯烴樹脂、胺基甲酸酯樹脂和聚矽氧樹脂所成群組中的1種以上的脫模劑。帶脫模層的支承體可使用市售品，可舉出例如作為具有以醇酸樹脂系脫模劑為主要成分的脫模層的PET膜、即琳得科公司製的「SK-1」、「AL-5」、「AL-7」、東麗公司製的「LUMIRROR T60」、帝人公司製的「Purex」、UNITIKA公司製的「Unipeel」等。Moreover, as a support body, the support body with a release layer which has a release layer on the surface joined to a resin composition layer can be used. Examples of the release agent used for the release layer of the support with a release layer include those selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and polysiloxane resins. More than 1 type of release agent. A commercially available product can be used as a support with a release layer. For example, "SK-1" manufactured by Lintec Corporation, which is a PET film having a release layer containing an alkyd resin release agent as a main component, can be used. , "AL-5", "AL-7", "LUMIRROR T60" made by Toray, "Purex" made by Teijin, "Unipeel" made by UNITIKA, etc.

作為支承體的厚度，無特別限定，較好是在5μm~75μm的範圍內，更好是在10μm~60μm的範圍內。應予說明，在使用帶脫模層的支承體的情況下，較好是帶脫模層的支承體整體的厚度在上述範圍內。The thickness of the support is not particularly limited, but it is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. In addition, when using the support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is in the said range.

在一個實施方式中，樹脂片材根據需要可以進一步包含任意的層。作為所述任意的層，可舉出例如，在樹脂組成物層的不與支承體接合的面(即與支承體相反一側的面)上設置的按照支承體選用的保護膜等。保護膜的厚度沒有特別的限定，例如為1μm~40μm。通過疊層保護膜，可以抑制在樹脂組成物層的表面附著垃圾等或形成損傷。In one embodiment, the resin sheet may further include any layer as necessary. Examples of the optional layer include, for example, a protective film selected according 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, but is, for example, 1 μm to 40 μm. By laminating a protective film, it is possible to prevent dirt and the like from adhering to or causing damage to the surface of the resin composition layer.

樹脂片材例如可通過以下方式製造：使用模塗機等將液態(塗料狀)的樹脂組成物直接塗布於支承體上，或在有機溶劑中溶解樹脂組成物而製備液態(塗料狀)的樹脂組成物，並使用模塗機等將其塗布於支承體上，進而使其乾燥，從而形成樹脂組成物層。The resin sheet can be produced, for example, by directly applying a liquid (paint-like) resin composition onto a support using a die coater or the like, or by dissolving the resin composition in an organic solvent to prepare a liquid (paint-like) resin. The composition is applied on the support using a die coater, and then dried to form a resin composition layer.

作為有機溶劑，可舉出與作為樹脂組成物的成分所說明的有機溶劑相同的溶劑。有機溶劑可以單獨使用1種，也可組合使用2種以上。Examples of the organic solvent include the same organic solvents described as components of the resin composition. One type of organic solvent may be used alone, or two or more types may be used in combination.

乾燥可利用加熱、吹熱風等公知的方法實施。乾燥條件沒有特別限制，以樹脂組成物層中的有機溶劑的含量成為10質量%以下、較好是5質量%以下的方式進行乾燥。根據樹脂組成物中的有機溶劑的沸點而不同，例如使用包含30質量%~60質量%的有機溶劑的樹脂組成物時，通過在50℃~150℃乾燥3分鐘~10分鐘，可形成樹脂組成物層。Drying can be performed by known methods such as heating and blowing hot air. Drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer becomes 10 mass% or less, preferably 5 mass% or less. It depends on the boiling point of the organic solvent in the resin composition. For example, when using a resin composition containing 30% to 60% by mass of an organic solvent, the resin composition can be formed by drying at 50°C to 150°C for 3 to 10 minutes. object layer.

樹脂片材可以捲繞成卷狀而進行保存。樹脂片材具有保護膜時，可通過將保護膜剝離來使用。The resin sheet can be wound into a roll shape and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

在一個實施方式中，預浸料是通過使本發明的樹脂組成物浸滲在片狀纖維基材中而形成的。In one embodiment, a prepreg is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.

預浸料中使用的片狀纖維基材沒有特別限制，可使用玻璃布、芳族聚醯胺不織布、液晶聚合物不織布等作為預浸料用基材而常用的材料。從印刷配線板的薄型化的觀點來看，片狀纖維基材的厚度較好是50μm以下，更好是40μm以下，進一步較好是30μm以下，特別好是20μm以下。片狀纖維基材的厚度的下限沒有特別限制。通常為10μm以上。The sheet-like fiber base material used in the prepreg is not particularly limited, and materials commonly used as base materials for prepregs, such as glass cloth, aromatic polyamide nonwoven fabric, and liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-like fiber base material is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited. Usually above 10μm.

預浸料可利用熱熔法、溶劑法等公知的方法來製造。Prepregs can be produced by known methods such as hot melt method and solvent method.

預浸料的厚度可以是與上述的樹脂片材中的樹脂組成物層同樣的範圍。The thickness of the prepreg may be in the same range as the resin composition layer in the above-mentioned resin sheet.

本發明的片狀疊層材料可合適地用於形成印刷配線板的絕緣層(印刷配線板的絕緣層用)，可更合適地用於形成印刷配線板的層間絕緣層(印刷配線板的層間絕緣層用)。The sheet-like laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and can be more suitably used for forming an interlayer insulating layer of a printed wiring board (for an interlayer of a printed wiring board). for insulation).

＜印刷配線板＞ 本發明的印刷配線板包含由將本發明的樹脂組成物硬化而得到的硬化物形成的絕緣層。 ＜Printed wiring board＞ The printed wiring board of the present invention includes an insulating layer formed 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的樹脂片材，利用包括下述(I)和(II)的步驟的方法來製造。 (I)以樹脂片材的樹脂組成物層與內層基板接合的方式，在內層基板上疊層樹脂片材的步驟 (II)將樹脂組成物層硬化(例如熱硬化)而形成絕緣層的步驟 The printed wiring board can be produced by a method including the following steps (I) and (II) using, for example, the above-mentioned resin sheet. (I) The step of laminating the resin sheet on the inner substrate in such a manner that the resin composition layer of the resin sheet is bonded to the inner substrate. (II) The step of hardening (for example, thermal hardening) the resin composition layer to form an insulating layer

步驟(I)中使用的「內層基板」，是指成為印刷配線板的基板的構件，可舉出例如玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚苯醚基板等。此外，該基板可在其一面或兩面具有導體層，該導體層可以被進行了圖案加工。有時將在基板的一面或兩面形成有導體層(電路)的內層基板稱為「內層電路基板」。此外，在製造印刷配線板時待進一步形成絕緣層和/或導體層的中間製造物也被包含在本發明中所謂的「內層基板」中。印刷配線板為部件內置電路板時，可使用內置有部件的內層基板。The "inner layer substrate" used in step (I) refers to a member that becomes the substrate of a printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, and BT resin substrates. Thermosetting polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner-layer substrate in which a conductor layer (circuit) is formed on one or both sides of the substrate is sometimes called an "inner-layer circuit substrate." In addition, an intermediate product on which an insulating layer and/or a conductor layer is further formed when manufacturing a printed wiring board is also included in the so-called "inner layer substrate" in the present invention. When the printed wiring board is a circuit board with built-in components, an inner substrate with built-in components can be used.

內層基板與樹脂片材的疊層例如可通過從支承體側將樹脂片材向內層基板加熱壓接而進行。作為將樹脂片材加熱壓接於內層基板的構件(以下也稱為「加熱壓接構件」。)，可舉出例如經加熱的金屬板(SUS端板等)或金屬輥(SUS輥)等。應予說明，較好是並非直接將加熱壓接構件向樹脂片材壓製，而是隔著耐熱橡膠等彈性材料進行壓製，以使樹脂片材充分追隨內層基板的表面凹凸。The lamination of the inner-layer substrate and the resin sheet can be performed, for example, by thermally and press-bonding the resin sheet to the inner-layer substrate from the support side. Examples of a member for heat and pressure bonding the resin sheet to the inner substrate (hereinafter also referred to as "heat and pressure bonding member") include a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller) wait. It should be noted that it is preferable not to directly press the heat-pressing bonding member onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet can fully follow the surface irregularities of the inner substrate.

內層基板與樹脂片材的疊層可通過真空層壓法實施。真空層壓法中，加熱壓接溫度較好是60℃~160℃，更好是80℃~140℃的範圍，加熱壓接壓力較好是0.098MPa~1.77MPa，更好是0.29MPa~1.47MPa的範圍，加熱壓接時間較好是20秒~400秒，更好是30秒~300秒的範圍。疊層可較好在壓力為26.7hPa以下的減壓條件下實施。The inner substrate and the resin sheet can be laminated by a vacuum lamination method. In the vacuum lamination method, the heating and crimping temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heating and crimping pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47 In the range of MPa, the heating and crimping time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination can preferably be carried out under reduced pressure conditions of 26.7 hPa or less.

疊層可通過市售的真空層壓機進行。作為市售的真空層壓機，可舉出例如名機製作所製的真空加壓式層壓機、Nikko-Materials公司製的真空敷料器(vacuum applicator)、間歇式真空加壓層壓機等。Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko-Materials, and an intermittent vacuum pressure laminator.

在疊層後，在常壓下(大氣壓下)，例如，從支承體側對加熱壓接構件進行壓製，由此，可進行疊層的樹脂片材的平滑化處理。平滑化處理的壓製條件可設定為與上述疊層的加熱壓接條件同樣的條件。平滑化處理可通過市售的層壓機進行。應予說明，疊層與平滑化處理可使用上述的市售的真空層壓機連續地進行。After lamination, the laminated resin sheets can be smoothed by pressing the heat-compression bonding member under normal pressure (atmospheric pressure), for example, from the support side. The pressing conditions for the smoothing treatment can be set to the same conditions as those for the heat and pressure bonding of the above-described laminate. Smoothing can be performed with a commercially available laminator. In addition, lamination and smoothing processing can be performed continuously using the above-mentioned commercially available vacuum laminator.

支承體可在步驟(I)與步驟(II)之間除去，也可在步驟(II)之後除去。The support may be removed between steps (I) and (II), or may be removed after step (II).

在步驟(II)中，將樹脂組成物層硬化(例如熱硬化)，形成由樹脂組成物的硬化物形成的絕緣層。樹脂組成物層的硬化條件沒有特別限制，可使用在形成印刷配線板的絕緣層時通常採用的條件。In step (II), the resin composition layer is hardened (for example, thermally hardened) to form an insulating layer formed of a hardened product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and conditions generally used when forming an insulating layer of a printed wiring board can be used.

例如，樹脂組成物層的熱硬化條件根據樹脂組成物的種類等而不同，在一個實施方式中，硬化溫度較好是120℃~240℃，更好是150℃~220℃，進一步較好是170℃~210℃。硬化時間可以較好設為5分鐘~120分鐘，更好設為10分鐘~100分鐘，進一步較好設為15分鐘~100分鐘。For example, the thermal hardening 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 further preferably 170℃~210℃. The hardening time can be preferably set to 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and further preferably 15 minutes to 100 minutes.

可在使樹脂組成物層熱硬化之前，在低於硬化溫度的溫度下對樹脂組成物層進行預加熱。例如，可在使樹脂組成物層熱硬化之前，在50℃~120℃、較好是60℃~115℃、更好是70℃~110℃的溫度下對樹脂組成物層進行5分鐘以上、較好是5分鐘~150分鐘、更好是15分鐘~120分鐘、進一步較好是15分鐘~100分鐘的預加熱。Before thermally hardening 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 be heated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, and more preferably 70°C to 110°C for 5 minutes or more. Preheating is preferably from 5 minutes to 150 minutes, more preferably from 15 minutes to 120 minutes, and further preferably from 15 minutes to 100 minutes.

在製造印刷配線板時，可以進一步實施(III)在絕緣層上開孔的步驟、(IV)對絕緣層進行粗糙化處理的步驟、(V)形成導體層的步驟。這些步驟(III)~步驟(V)可根據印刷配線板的製造中可使用的、本領域技術人員公知的各種方法實施。應予說明，在步驟(II)之後除去支承體時，該支承體的除去可在步驟(II)與步驟(III)之間、步驟(III)與步驟(IV)之間，或步驟(IV)與步驟(V)之間實施。另外，根據需要，也可反復實施步驟(II)~步驟(V)的絕緣層和導體層的形成，而形成多層配線板。When manufacturing the printed wiring board, the steps of (III) opening holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming the conductor layer may be further performed. These steps (III) to (V) can be implemented according to various methods that can be used for manufacturing printed wiring boards and are known to those skilled in the art. It should be noted that when the support is removed after step (II), the removal of the support may be between step (II) and step (III), between step (III) and step (IV), or between step (IV). ) and step (V). In addition, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board.

在其他實施方式中，本發明的印刷配線板可使用上述的預浸料來製造。製造方法基本上與使用樹脂片材的情況同樣。In other embodiments, the printed wiring board of the present invention can be produced using the prepreg described above. The manufacturing method is basically the same as when using a resin sheet.

步驟(III)為在絕緣層上開孔的步驟，由此，可在絕緣層上形成通孔、透孔等孔。對於步驟(III)而言，可根據絕緣層的形成中使用的樹脂組成物的組成等，使用例如鑽頭、雷射、電漿等來實施。孔的尺寸、形狀可根據印刷配線板的設計適當確定。Step (III) is a step of opening holes on the insulating layer, thereby forming holes such as through holes and through holes on the insulating layer. Step (III) can be implemented using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used in forming the insulating layer. The size and shape of the hole can be appropriately determined according to the design of the printed wiring board.

步驟(IV)是對絕緣層進行粗糙化處理的步驟。通常，在該步驟(IV)中，還進行膠渣的除去。粗糙化處理的步驟、條件沒有特別限制，可採用在形成印刷配線板的絕緣層時通常使用的公知的步驟、條件。例如，可通過依次實施基於膨潤液的膨潤處理、基於氧化劑的粗糙化處理、基於中和液的中和處理，從而對絕緣層進行粗糙化處理。Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), the slag is also removed. The steps and conditions of the roughening treatment are not particularly limited, and known steps and conditions generally used when forming an insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by sequentially performing swelling treatment using a swelling liquid, roughening treatment using an oxidizing agent, and neutralization treatment using a neutralizing liquid.

作為粗糙化處理中使用的膨潤液，沒有特別限制，可舉出鹼溶液、界面活性劑溶液等，較好是鹼溶液，作為該鹼溶液，更好是氫氧化鈉溶液、氫氧化鉀溶液。作為市售的膨潤液，可舉出例如安美特日本(ATOTECH JAPAN)公司製的「Swelling Dip Securiganth P」、「Swelling Dip Securiganth SBU」等。基於膨潤液的膨潤處理沒有特別限制，例如，可通過將絕緣層浸漬於30℃~90℃的膨潤液中1分鐘~20分鐘而進行。從將絕緣層的樹脂的膨潤抑制為適度的水平的觀點來看，較好是將絕緣層浸漬於40℃~80℃的膨潤液中5分鐘~15分鐘。The swelling liquid used in the roughening treatment is not particularly limited, and examples thereof include alkaline solutions, surfactant solutions, and the like. Alkaline solutions are preferred, and sodium hydroxide solutions and potassium hydroxide solutions are more preferred as the alkaline solution. Examples of commercially available swelling solutions include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by ATOTECH JAPAN. The swelling treatment based on the swelling liquid is not particularly limited. For example, the insulation layer can be immersed in a swelling liquid of 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid of 40°C to 80°C for 5 minutes to 15 minutes.

作為粗糙化處理中使用的氧化劑，沒有特別限制，可舉出例如在氫氧化鈉的水溶液中溶解過錳酸鉀或過錳酸鈉而成的鹼性過錳酸溶液。基於鹼性過錳酸溶液等氧化劑的粗糙化處理較好是通過將絕緣層浸漬於已加熱至60℃~100℃的氧化劑溶液中10分鐘~30分鐘而進行。此外，鹼性過錳酸溶液中的過錳酸鹽的濃度較好是5質量%~10質量%。作為市售的氧化劑，可舉出例如安美特日本公司製的「Concentrate Compact CP」、「Dosing Solution Securiganth P」等鹼性過錳酸溶液。The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment based on an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. In addition, 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 permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan.

此外，作為粗糙化處理中使用的中和液，較好是酸性的水溶液，作為市售品，可舉出例如安美特日本公司製的「Reduction Solution Securiganth P」。In addition, the neutralizing liquid used in the roughening treatment is preferably an acidic aqueous solution. An example of a commercially available product is "Reduction Solution Securiganth P" manufactured by Atotech Japan Co., Ltd.

基於中和液的處理可通過將完成了基於氧化劑的粗糙化處理的處理面浸漬於30℃~80℃的中和液中5分鐘~30分鐘而進行。從操作性等方面考慮，較好是將完成了基於氧化劑的粗糙化處理的對象物浸漬於40℃~70℃的中和液中5分鐘~20分鐘的方法。The treatment by the neutralizing liquid can be performed by immersing the treated surface that has completed the roughening treatment by the oxidizing agent in a neutralizing liquid of 30°C to 80°C for 5 to 30 minutes. From the viewpoint of workability, etc., it is preferable to immerse the object that has been roughened by an oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

在一個實施方式中，粗糙化處理後的絕緣層表面的算術平均粗糙度(Ra)沒有特別限定，較好是500nm以下，更好是400nm以下，進一步較好是300nm以下。對於下限，沒有特別限定，可設為例如1nm以上、2nm以上等。另外，粗糙化處理後的絕緣層表面的均方根粗糙度(Rq)較好是500nm以下，更好是400nm以下，進一步較好是300nm以下。對於下限沒有特別限制，例如可以設為1nm以上、2nm以上等。絕緣層表面的算術平均粗糙度(Ra)和均方根粗糙度(Rq)可使用非接觸型表面粗糙度計來測定。In one embodiment, the arithmetic mean roughness (Ra) of the roughened insulating layer surface is not particularly limited, but is preferably 500 nm or less, more preferably 400 nm or less, and further preferably 300 nm or less. The lower limit is not particularly limited, but may be, for example, 1 nm or more, 2 nm or more, or the like. In addition, the root mean square roughness (Rq) of the roughened insulating layer surface is preferably 500 nm or less, more preferably 400 nm or less, further 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, or the like. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

步驟(V)是形成導體層的步驟，在絕緣層上形成導體層。導體層中使用的導體材料沒有特別限制。在優選的實施方式中，導體層包含選自由金、鉑、鈀、銀、銅、鋁、鈷、鉻、鋅、鎳、鈦、鎢、鐵、錫和銦所成群組中的1種以上的金屬。導體層可以為單金屬層，也可以為合金層，作為合金層，可舉出例如由選自上述群組中的2種以上的金屬的合金(例如，鎳-鉻合金、銅-鎳合金和銅-鈦合金)形成的層。其中，從導體層形成的通用性、成本、圖案化的容易性等的觀點來看，較好是鉻、鎳、鈦、鋁、鋅、金、鈀、銀或銅的單金屬層，或鎳-鉻合金、銅-鎳合金、銅-鈦合金的合金層，更好是鉻、鎳、鈦、鋁、鋅、金、鈀、銀或銅的單金屬層，或鎳-鉻合金的合金層，進一步較好是銅的單金屬層。Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains at least one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. of metal. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include alloys of two or more metals selected from the above group (for example, 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 a nickel - an alloy layer of a chromium alloy, a copper-nickel alloy, a copper-titanium alloy, preferably a monometallic layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy , further preferably a single metal layer of copper.

導體層可以為單層結構，也可以為由不同種類的金屬或合金形成的單金屬層或合金層層合2層以上而成的多層結構。導體層為多層結構時，與絕緣層接觸的層較好是鉻、鋅或鈦的單金屬層，或鎳-鉻合金的合金層。The conductor layer may have a single-layer structure, or may have a multi-layer structure in which a single metal layer made of different types of metals or alloys or two or more alloy layers are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

導體層的厚度取決於所期望的印刷配線板的設計，通常為3μm~35μm，較好是5μm~30μm。The thickness of the conductor layer depends on the desired design of the printed wiring board, but is usually 3 μm to 35 μm, preferably 5 μm to 30 μm.

在一個實施方式中，導體層可通過鍍覆形成。例如，可利用半加成法、全加成法等現有公知的技術，在絕緣層的表面進行鍍覆，形成具有所期望的配線圖案的導體層，從製造的簡便性的觀點來看，較好是利用半加成法形成。以下，示出利用半加成法形成導體層的例子。In one embodiment, the conductor layer may be formed by plating. For example, the surface of the insulating layer can be plated using conventionally known techniques such as the semi-additive method and the full-additive method to form a conductor layer having a desired wiring pattern. From the viewpoint of ease of manufacturing, this method is relatively simple. It is best to use the semi-additive method. Hereinafter, an example of forming a conductor layer using a semi-additive method is shown.

首先，利用無電解鍍覆在絕緣層的表面上形成鍍敷種子層。接下來，在形成的鍍敷種子層上，對應於所期望的配線圖案，形成使鍍敷種子層的一部分露出的遮罩圖案。在露出的鍍敷種子層上，利用電解鍍覆形成金屬層，然後將遮罩圖案除去。然後，利用蝕刻等將不需要的鍍敷種子層除去，可形成具有所期望的配線圖案的導體層。First, a plating seed layer is formed on the surface of the insulating layer using electroless plating. Next, on the formed plating seed layer, a mask pattern is formed to expose a part of the plating seed layer in accordance with a desired wiring pattern. On the exposed plating seed layer, a metal layer is formed by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

在其他實施方式中，導體層可使用金屬箔形成。在使用金屬箔形成導體層的情況下，步驟(V)優選在步驟(I)與步驟(II)之間實施。例如，在步驟(I)之後，將支承體除去，在露出的樹脂組成物層的表面上疊層金屬箔。樹脂組成物層與金屬箔的疊層可利用真空層壓法實施。疊層的條件可與針對步驟(I)說明的條件同樣。接下來，實施步驟(II)，形成絕緣層。然後，利用絕緣層上的金屬箔，利用減成法(subtractive)法、改良的半加成法等現有公知的技術，可形成具有所期望的配線圖案的導體層。In other embodiments, the conductor layer may be formed using metal foil. In the case where a metal foil is used to form the conductor layer, step (V) is preferably performed between step (I) and step (II). For example, after step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. The resin composition layer and the metal foil can be laminated using a vacuum lamination method. The conditions for lamination may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Then, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed using conventionally known techniques such as the subtractive method and the improved semi-additive method.

金屬箔例如可利用電解法、軋製法等公知的方法來製造。作為金屬箔的市售品，可舉出例如JX日礦日石金屬公司製的HLP箔、JXUT-III箔、三井金屬礦山公司製的3EC-III箔、TP-III箔等。The metal foil can be produced by known methods such as electrolysis and rolling. Examples of commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Metals Co., Ltd., and the like.

＜半導體裝置＞ 本發明的半導體裝置包含本發明的印刷配線板。本發明的半導體裝置可以使用本發明的印刷配線板製造。 ＜Semiconductor Device＞ 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，可舉出供於電氣製品(例如電腦、手機、數位相機和電視機等)和交通工具(例如機車、汽車、電車、船舶和航空器等)等的各種半導體裝置。 [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 motorcycles, automobiles, trains, ships, and aircraft). [Example]

以下，通過實施例具體地說明本發明。本發明不受這些實施例的限定。應予說明，在下文中，只要沒有另外明確說明，表示量的「份」及「%」分別是指「質量份」及「質量%」。在沒有特別指定溫度的情況下的溫度條件是室溫(23℃)下，在沒有特別指定壓力的情況下的壓力條件是大氣壓(1atm)下。Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to these examples. It should be noted that in the following, unless otherwise specified, "parts" and "%" indicating amounts refer to "parts by mass" and "% by mass" respectively. When the temperature is not specified, the temperature condition is room temperature (23° C.), and when the pressure is not specified, the pressure condition is atmospheric pressure (1 atm).

＜實施例1＞ 一邊攪拌一邊使雙酚A型環氧樹脂(三菱化學股份有限公司製「828US」、環氧當量約180g/eq.)30份、聯苯型環氧樹脂(日本化藥股份有限公司製「NC3000H」，環氧當量約269g/eq.)30份加熱溶解於溶劑石腦油55份中，然後冷卻至室溫。在該混合溶液中，混合用胺基矽烷系偶合劑(信越化學工業股份有限公司製「KBM573」)進行了表面處理的球形二氧化矽(雅都瑪股份有限公司製「SO-C2」，平均粒徑0.5μm)280份、含有三嗪骨架的酚系硬化劑(DIC股份有限公司製「LA-3018-50P」，羥基當量約151，固體成分50%的2-甲氧基丙醇溶液)14份、活性酯化合物(DIC股份有限公司製「HPC-8000-65T」，活性基當量約223，不揮發成分65質量%的甲苯溶液)55份、苯氧樹脂(三菱化學股份有限公司製「YX6954BH30」，將不揮發成分30質量%的MEK與環己酮以1：1混合的溶液)10份、乙烯基化合物(新中村化學工業股份有限公司製「A-DOG」，二噁烷二醇二丙烯酸酯)3份、硬化促進劑A(2,4-二胺基-6-[2-(2-十一烷基-1H-咪唑-1-基)乙基]-1,3,5-三嗪，固體成分5質量%的2-甲氧基丙醇溶液)6份，用高速旋轉混合機均勻地分散，製備塗料狀的樹脂組成物。 <Example 1> While stirring, 30 parts of bisphenol A-type epoxy resin ("828US" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent weight is about 180g/eq.) and biphenyl-type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd. ”, the epoxy equivalent is about 269g/eq.) 30 parts are heated and dissolved in 55 parts of solvent naphtha, and then cooled to room temperature. In this mixed solution, spherical silica ("SO-C2" manufactured by Yaduma Co., Ltd.) surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was mixed, and the average 280 parts of a phenolic hardener containing a triazine skeleton (particle size: 0.5 μm) ("LA-3018-50P" manufactured by DIC Co., Ltd., 2-methoxypropanol solution with a hydroxyl equivalent of approximately 151 and a solid content of 50%) 14 parts, active ester compound ("HPC-8000-65T" manufactured by DIC Co., Ltd., toluene solution with an active group equivalent of approximately 223 and 65% non-volatile content by mass), 55 parts of phenoxy resin ("HPC-8000-65T" manufactured by Mitsubishi Chemical Co., Ltd. YX6954BH30", 10 parts of a solution of a 1:1 mixture of MEK and cyclohexanone with a non-volatile content of 30% by mass, vinyl compound ("A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., dioxanediol Diacrylate) 3 parts, hardening accelerator A (2,4-diamino-6-[2-(2-undecyl-1H-imidazol-1-yl)ethyl]-1,3,5 - 6 parts of a triazine, a 2-methoxypropanol solution with a solid content of 5% by mass) was uniformly dispersed with a high-speed rotary mixer to prepare a paint-like resin composition.

(無機填充材料的平均粒徑的測定方法) 將無機填充材料100mg和甲基乙基酮10g稱量至管瓶中並通過超音波分散10分鐘。使用雷射繞射式粒徑分佈測定裝置(堀場製作所製「LA-960」)，將使用光源波長設為藍色和紅色，利用流動池方式以體積基準測定無機填充材料的粒徑分佈。根據所得的粒徑分佈作為中值粒徑而算出無機填充材料的平均粒徑。 (Measurement method of average particle size of inorganic filler materials) 100 mg of inorganic filler material and 10 g of methyl ethyl ketone were weighed into a vial and dispersed by ultrasonic waves for 10 minutes. Using a laser diffraction particle size distribution measuring device ("LA-960" manufactured by Horiba Manufacturing Co., Ltd.), the wavelength of the light source used was set to blue and red, and the particle size distribution of the inorganic filler material was measured on a volume basis using a flow cell method. The average particle diameter of the inorganic filler was calculated as the median particle diameter based on the obtained particle diameter distribution.

＜實施例2＞ 將硬化促進劑A(2,4-二胺基-6-[2-(2-十一烷基-1H-咪唑-1-基)乙基]-1,3,5-三嗪，固體成分5質量%的2-甲氧基丙醇溶液)的使用量從6份改變為4份，進而混合硬化促進劑(「DMAP」，4-二甲基胺基吡啶，固體成分5質量%的MEK溶液)2份，除此以外，與實施例1同樣地製備塗料狀的樹脂組成物。 <Example 2> Hardening accelerator A (2,4-diamino-6-[2-(2-undecyl-1H-imidazol-1-yl)ethyl]-1,3,5-triazine, solid content The usage amount of 5 mass% 2-methoxypropanol solution) was changed from 6 parts to 4 parts, and a hardening accelerator ("DMAP", 4-dimethylaminopyridine, and solid content of 5 mass% MEK was mixed solution), a paint-like resin composition was prepared in the same manner as in Example 1, except for this.

＜實施例3＞ 代替聯苯型環氧樹脂(日本化藥股份有限公司製「NC3000H」、環氧當量約269g/eq.)30份而使用萘酚型環氧樹脂(日鐵化學材料股份有限公司製「ESN475V」、環氧當量332g/eq.)30份，除此以外，與實施例2同樣地製備塗料狀的樹脂組成物。 <Example 3> Instead of 30 parts of biphenyl-type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: approximately 269g/eq.), use naphthol-type epoxy resin ("ESN475V" manufactured by Nippon Steel Chemical Materials Co., Ltd. , epoxy equivalent (332 g/eq.) 30 parts, a paint-like resin composition was prepared in the same manner as in Example 2.

＜實施例4＞ 代替聯苯型環氧樹脂(日本化藥股份有限公司製「NC3000H」、環氧當量約269g/eq.)30份而使用聯二甲酚型環氧樹脂(三菱化學股份有限公司製「YX4000HK」、環氧當量約185g/eq.)30份，除此以外，與實施例2同樣地製備塗料狀的樹脂組成物。 <Example 4> Instead of 30 parts of biphenyl-type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: approximately 269g/eq.), dixylenol-type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd.) was used , epoxy equivalent (approximately 185 g/eq.) 30 parts, a paint-like resin composition was prepared in the same manner as in Example 2.

＜實施例5＞ 不使用活性酯化合物(DIC股份有限公司製「HPC-8000-65T」、活性基當量約223、不揮發成分65質量%的甲苯溶液)55份，將含有三嗪骨架的酚系硬化劑(DIC股份有限公司製「LA-3018-50P」、羥基當量約151、固體成分50%的2-甲氧基丙醇溶液)的使用量從14份改變為40份，將用胺基矽烷系偶合劑(信越化學工業股份有限公司製「KBM573」)進行了表面處理的球形二氧化矽(雅都瑪股份有限公司製「SO-C2」、平均粒徑0.5μm)的使用量從280份改變為220份，除此以外，與實施例2同樣地製備塗料狀的樹脂組成物。 <Example 5> Instead of using 55 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC Co., Ltd., a toluene solution with an active group equivalent of approximately 223 and a non-volatile content of 65% by mass), a phenolic hardener containing a triazine skeleton (DIC Co., Ltd.'s "LA-3018-50P", a 2-methoxypropanol solution with a hydroxyl equivalent of about 151 and a solid content of 50%) has been changed from 14 parts to 40 parts, and an aminosilane coupling agent will be used ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) The usage amount of surface-treated spherical silica ("SO-C2" manufactured by Yaduma Co., Ltd., average particle size 0.5 μm) was changed from 280 parts to 220 parts parts, except that a paint-like resin composition was prepared in the same manner as in Example 2.

＜實施例6＞ 代替丙烯酸酯化合物(新中村化學工業股份有限公司製「A-DOG」，二噁烷二醇二丙烯酸酯)3份而使用含有烯丙基的苯并噁嗪化合物(四國化成工業股份有限公司製「ALP-d」)3份，除此以外，與實施例2同樣地製備塗料狀的樹脂組成物。 <Example 6> Instead of 3 parts of an acrylate compound ("A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., dioxanediol diacrylate), an allyl-containing benzoxazine compound (Shikoku Chemical Industry Co., Ltd. A paint-like resin composition was prepared in the same manner as in Example 2, except that 3 parts of "ALP-d") were prepared.

＜實施例7＞ 代替丙烯酸酯化合物(新中村化學工業股份有限公司製「A-DOG」、二噁烷二醇二丙烯酸酯)3份而使用低聚苯醚-苯乙烯樹脂(三菱瓦斯化學公司製「OPE-2St 1200」，不揮發成分65%的甲苯溶液)4.6份，除此以外，與實施例2同樣地製備塗料狀的樹脂組成物。 <Example 7> Instead of 3 parts of an acrylate compound ("A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., dioxanediol diacrylate), an oligophenylene ether-styrene resin ("OPE-2St manufactured by Mitsubishi Gas Chemical Co., Ltd." was used) 1200", 4.6 parts of toluene solution with 65% non-volatile content), except that a paint-like resin composition was prepared in the same manner as in Example 2.

＜實施例8＞ 將用胺基矽烷系偶合劑(信越化學工業股份有限公司製「KBM573」)進行了表面處理的球形二氧化矽(雅都瑪股份有限公司製「SO-C2」，平均粒徑0.5μm)的使用量從280份改變為160份，進而混合用胺基矽烷系偶合劑(信越化學工業股份有限公司製「KBM573」)進行了表面處理的中空二氧化矽(日揮觸媒化成股份有限公司製「BA-S」，平均粒徑2.6μm，空孔率25體積%)96份，除此以外，與實施例2同樣地製備塗料狀的樹脂組成物。 <Example 8> Spherical silica ("SO-C2" manufactured by Yaduma Co., Ltd., average particle diameter: 0.5 μm) surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) The usage amount was changed from 280 parts to 160 parts, and hollow silica (manufactured by Nikki Catalyst Chemicals Co., Ltd.) that was surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was mixed. BA-S", average particle diameter: 2.6 μm, porosity: 25 volume %), a paint-like resin composition was prepared in the same manner as in Example 2, except that 96 parts were used.

(無機填充材料的平均空孔率的測定方法) 使用真密度測定裝置(QUANTACHROME公司製「ULTRAPYCNOMETER1000」)測定無機填充材料的密度。在該測定中，使用氮氣作為測定氣體。然後，使用測定的密度(測定值)D M(g/cm 3)，和形成無機填充材料的無機材料(二氧化矽)的物質密度(理論值)D T(g/cm 3)，根據上述式(I)，測定無機填充材料的平均空孔率。在上述式(I)中，作為無機材料的二氧化矽的物質密度(理論值)設為2.2g/cm 3。 (Measurement method of average porosity of inorganic filler material) The density of the inorganic filler material was measured using a true density measuring device ("ULTRAPYCNOMETER1000" manufactured by QUANTACHROME Corporation). In this measurement, nitrogen is used as the measurement gas. Then, using the measured density (measured value) D M (g/cm 3 ) and the material density (theoretical value) D T (g/cm 3 ) of the inorganic material (silica) forming the inorganic filler material, according to the above Formula (I) determines the average porosity of the inorganic filler material. In the above formula (I), the material density (theoretical value) of silica as the inorganic material is 2.2 g/cm 3 .

＜比較例1＞ 代替硬化促進劑A(2,4-二胺基-6-[2-(2-十一烷基-1H-咪唑-1-基)乙基]-1,3,5-三嗪，固體成分5質量%的2-甲氧基丙醇溶液)6份，而使用硬化促進劑(四國化成工業股份有限公司製「1B2PZ」，1-苄基-2-苯基咪唑，固體成分5質量%的MEK溶液)6份，除此以外，與實施例1同樣地製備塗料狀的樹脂組成物。 ＜Comparative example 1＞ Substitute hardening accelerator A (2,4-diamino-6-[2-(2-undecyl-1H-imidazol-1-yl)ethyl]-1,3,5-triazine, solid content 5 mass% 2-methoxypropanol solution) 6 parts, and use a hardening accelerator ("1B2PZ" manufactured by Shikoku Chemical Industry Co., Ltd., 1-benzyl-2-phenylimidazole, solid content 5 mass% MEK solution) 6 parts, a paint-like resin composition was prepared in the same manner as in Example 1, except for this.

＜比較例2＞ 代替硬化促進劑A(2,4-二胺基-6-[2-(2-十一烷基-1H-咪唑-1-基)乙基]-1,3,5-三嗪，固體成分5質量%的2-甲氧基丙醇溶液)6份，而使用硬化促進劑(四國化成工業股份有限公司製「2P4MZ」，2-苯基-4-甲基咪唑，固體成分5質量%的2-甲氧基丙醇溶液)6份，除此以外，與實施例1同樣地製備塗料狀的樹脂組成物。 ＜Comparative example 2＞ Substitute hardening accelerator A (2,4-diamino-6-[2-(2-undecyl-1H-imidazol-1-yl)ethyl]-1,3,5-triazine, solid content 5 mass% 2-methoxypropanol solution) 6 parts, and use a hardening accelerator ("2P4MZ" manufactured by Shikoku Chemical Industry Co., Ltd., 2-phenyl-4-methylimidazole, solid content 5 mass% A paint-like resin composition was prepared in the same manner as in Example 1, except that 6 parts of 2-methoxypropanol solution was added.

＜比較例3＞ 代替硬化促進劑A(2,4-二胺基-6-[2-(2-十一烷基-1H-咪唑-1-基)乙基]-1,3,5-三嗪，固體成分5質量%的2-甲氧基丙醇溶液)6份，而使用硬化促進劑(四國化成工業股份有限公司製「TBP-DA」，四丁基鏻癸酸鹽、固體成分5質量%的MEK溶液)6份，除此以外，與實施例1同樣地製備塗料狀的樹脂組成物。 ＜Comparative Example 3＞ Substitute hardening accelerator A (2,4-diamino-6-[2-(2-undecyl-1H-imidazol-1-yl)ethyl]-1,3,5-triazine, solid content 5 mass% 2-methoxypropanol solution) 6 parts, and use a hardening accelerator (Shikoku Chemical Industry Co., Ltd. "TBP-DA", tetrabutylphosphonium decanoate, solid content 5 mass% MEK solution), a paint-like resin composition was prepared in the same manner as in Example 1, except for this.

＜比較例4＞ 代替硬化促進劑A(2,4-二胺基-6-[2-(2-十一烷基-1H-咪唑-1-基)乙基]-1,3,5-三嗪，固體成分5質量%的2-甲氧基丙醇溶液)6份，而使用硬化促進劑(「DMAP」，4-二甲基胺基吡啶，固體成分5質量%的MEK溶液)6份，除此以外，與實施例1同樣地製備塗料狀的樹脂組成物。 ＜Comparative Example 4＞ Substitute hardening accelerator A (2,4-diamino-6-[2-(2-undecyl-1H-imidazol-1-yl)ethyl]-1,3,5-triazine, solid content 5 mass% 2-methoxypropanol solution) 6 parts, and use a hardening accelerator ("DMAP", 4-dimethylaminopyridine, solid content 5 mass% MEK solution) 6 parts, in addition to , a paint-like resin composition was prepared in the same manner as in Example 1.

＜比較例5＞ 除了不使用硬化促進劑A(2,4-二胺基-6-[2-(2-十一烷基-1H-咪唑-1-基)乙基]-1,3,5-三嗪，固體成分5質量%的2-甲氧基丙醇溶液)6份以外，與實施例1同樣地製備塗料狀的樹脂組成物。 ＜Comparative Example 5＞ In addition to not using the hardening accelerator A (2,4-diamino-6-[2-(2-undecyl-1H-imidazol-1-yl)ethyl]-1,3,5-triazine, A paint-like resin composition was prepared in the same manner as in Example 1 except for 6 parts of a 2-methoxypropanol solution with a solid content of 5% by mass.

＜比較例6＞ 除了不使用乙烯基化合物(新中村化學工業股份有限公司製「A-DOG」，二噁烷二醇二丙烯酸酯)3份以外，與實施例2同樣地製備塗料狀的樹脂組成物。 <Comparative Example 6> A paint-like resin composition was prepared in the same manner as in Example 2, except that 3 parts of a vinyl compound ("A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., dioxanediol diacrylate) was not used.

＜試驗例1：硬化物的玻璃轉移溫度和線熱膨脹係數的測定＞ 作為支承體，準備帶醇酸樹脂系脫模層的PET膜(琳得科公司製「AL5」，厚度38μm)。在該支承體的脫模層上以乾燥後的樹脂組成物層的厚度達到40μm的方式均勻地塗布實施例和比較例中製備的塗料狀的樹脂組成物，在80℃~120℃(平均100℃)乾燥5分鐘，製作樹脂片材。 <Test Example 1: Measurement of glass transition temperature and linear thermal expansion coefficient of hardened material> As a support, a PET film with an alkyd resin release layer ("AL5" manufactured by Lintec, thickness 38 μm) was prepared. The paint-like resin composition prepared in the Examples and Comparative Examples was evenly coated on the release layer of the support so that the thickness of the dried resin composition layer reached 40 μm. ℃) and dry for 5 minutes to prepare a resin sheet.

將製作的樹脂組成物層的厚度為40μm的樹脂片材在200℃加熱90分鐘，使樹脂組成物層熱硬化後，將支承體剝離，得到評價用硬化物。將評價用硬化物切割成寬度5mm、長度15mm的試片。對於該試片，使用熱機械分析裝置(理學(Rigaku)股份有限公司製「Thermo Plus TMA8310」)，利用拉伸載荷法進行熱機械分析。詳細而言，將試片裝配於上述熱機械分析裝置後，在負荷1g、升溫速度5℃/分鐘的測定條件下連續地測定2次。並且，在2次的測定中，算出玻璃轉移溫度(℃)，和從25℃至150℃的範圍的平面方向的線熱膨脹係數(ppm/K)。The prepared resin sheet with a thickness of 40 μm in the resin composition layer was heated at 200° C. for 90 minutes to thermally harden the resin composition layer, and then the support was peeled off to obtain a cured product for evaluation. The hardened material for evaluation was cut into test pieces with a width of 5 mm and a length of 15 mm. This test piece was subjected to thermomechanical analysis using a tensile load method using a thermomechanical analysis device ("Thermo Plus TMA8310" manufactured by Rigaku Co., Ltd.). Specifically, after the test piece was installed in the above-mentioned thermomechanical analysis device, the measurement was performed twice continuously under the measurement conditions of a load of 1 g and a temperature increase rate of 5° C./min. Furthermore, in the second measurement, the glass transition temperature (°C) and the linear thermal expansion coefficient (ppm/K) in the plane direction in the range from 25°C to 150°C were calculated.

＜試驗例2：硬化物的相對介電常數和介電損耗角正切的測定＞ 將用與試驗例1同樣的方法得到的評價用硬化物切割成寬度2mm、長度80mm的試片。對於該試片，使用安捷倫科技公司製「HP8362B」，利用諧振腔微擾法在測定頻率5.8GHz、測定溫度23℃的條件下測定相對介電常數和介電損耗角正切。對於2個試片進行測定，算出平均值。 <Test Example 2: Measurement of relative permittivity and dielectric loss tangent of hardened material> The hardened material for evaluation obtained by the same method as Test Example 1 was cut into test pieces with a width of 2 mm and a length of 80 mm. For this test piece, the relative dielectric constant and dielectric loss tangent were measured using the resonant cavity perturbation method using "HP8362B" manufactured by Agilent Technologies under the conditions of a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Measurement was performed on two test pieces, and the average value was calculated.

＜試驗例3：耐裂紋性的評價＞ (1)內層基板的準備 將形成有內層電路的玻璃布基材環氧樹脂兩面覆銅疊層板(銅箔的厚度18μm，基板的厚度0.4mm，松下公司製「R1515A」)的兩面通過微蝕刻劑(美格(MEC)公司製「CZ8101」)蝕刻1μm而進行銅表面的粗糙化處理。 <Test Example 3: Evaluation of crack resistance> (1) Preparation of inner substrate Pass both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, "R1515A" manufactured by Panasonic Corporation) with an inner circuit formed thereon through a micro-etching agent (Meg( "CZ8101" (manufactured by MEC) Co., Ltd.) was etched to 1 μm to roughen the copper surface.

(2)樹脂片材的層壓 使用間歇式真空加壓層壓機(Nikko-Materials公司製，2級堆疊層壓機「CVP700」)，以樹脂組成物層與內層基板相接的方式，將用與試驗例1同樣的方法得到的樹脂片材層壓在內層基板的兩面。層壓通過以下方式實施：進行30秒減壓，將氣壓調整為13hPa以下，然後，在120℃以0.74MPa的壓力壓接30秒。接下來，在100℃以0.5MPa的壓力，進行60秒熱壓。 (2)Lamination of resin sheets An intermittent vacuum pressure laminator (2-stage stacking laminator "CVP700" manufactured by Nikko-Materials Co., Ltd.) was used to connect the resin composition layer to the inner substrate in the same manner as in Test Example 1. The obtained resin sheet was laminated on both sides of the inner substrate. Lamination was performed by reducing pressure for 30 seconds, adjusting the air pressure to 13 hPa or less, and then performing pressure bonding at 120° C. for 30 seconds at a pressure of 0.74 MPa. Next, hot pressing was performed at 100° C. and a pressure of 0.5 MPa for 60 seconds.

(3)樹脂組成物層的熱硬化 將層壓有樹脂片材的內層基板投入至130℃的烘箱中加熱30分鐘、接下來移至170℃的烘箱中加熱30分鐘，使樹脂組成物層熱硬化，形成了絕緣層。然後，剝離支承體，得到依次具有絕緣層、內層基板和絕緣層的硬化基板。 (3) Thermal hardening of the resin composition layer The inner substrate with the resin sheet laminated thereon was put into an oven at 130° C. and heated for 30 minutes, and then moved to an oven at 170° C. for 30 minutes to heat the resin composition layer to form an insulating layer. Then, the support body is peeled off to obtain a cured substrate having an insulating layer, an inner layer substrate, and an insulating layer in this order.

(4)粗糙化處理 對於硬化基板，進行作為粗糙化處理的除膠渣處理。作為除膠渣處理，實施下述的濕式除膠渣處理。 (4) Roughening treatment The hardened substrate is subjected to a desmearing process as a roughening process. As desmearing treatment, the following wet desmearing treatment is carried out.

(濕式除膠渣處理) 將硬化基板在膨潤液(安美特日本公司製「Swelling Dip Securiganth P」，二乙二醇單丁醚和氫氧化鈉的水溶液)中於60℃浸漬5分鐘，接著在氧化劑溶液(安美特日本公司製「Concentrate Compact CP」，過錳酸鉀濃度約6%、氫氧化鈉濃度約4%的水溶液)中於80℃浸漬20分鐘。接著，在中和液(安美特日本公司製「Reduction Solution Securiganth P」，硫酸水溶液)中於40℃浸漬5分鐘後，於80℃乾燥15分鐘。 (Wet desmear treatment) The hardened substrate was immersed in a swelling solution ("Swelling Dip Securiganth P" manufactured by Atotech Japan Co., Ltd., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 5 minutes, and then immersed in an oxidizing agent solution (Atotech Japan Co., Ltd. To prepare "Concentrate Compact CP", immerse it in an aqueous solution with a potassium permanganate concentration of approximately 6% and a sodium hydroxide concentration of approximately 4%) at 80°C for 20 minutes. Next, it was immersed in a neutralizing solution ("Reduction Solution Securiganth P" manufactured by Atotech Japan Co., Ltd., sulfuric acid aqueous solution) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

根據JIS K 5600-5-6，通過濕式除膠渣處理在粗糙化處理後的評價基板上以棋盤網狀引入切痕，用光學顯微鏡觀察並評價硬化塗膜的裂紋的有無。具體而言，在評價基板的硬化塗膜上以1mm的間隔、以格子狀引入切痕，形成在縱向為10個、橫向為10個、總計100個的塗膜片。此處，塗膜片表示用切痕區劃的硬化塗膜的各部分。用光學顯微鏡觀察這些100個的塗膜片，計數有裂紋的塗膜片的數目。基於有裂紋的塗膜片的數目相對於塗膜片的總數100個的比例，按照下述的評價基準評價耐裂紋性。In accordance with JIS K 5600-5-6, cuts were made in a checkerboard pattern on the roughened evaluation substrate through wet desmear treatment, and the presence or absence of cracks in the hardened coating film was observed and evaluated with an optical microscope. Specifically, cuts were introduced in a grid pattern at intervals of 1 mm on the cured coating film of the evaluation substrate to form 10 coating film pieces in the longitudinal direction and 10 in the transverse direction, for a total of 100 pieces. Here, the coated film sheet represents each part of the cured coating film divided by cuts. Observe these 100 coating pieces with an optical microscope, and count the number of cracked coating pieces. Based on the ratio of the number of cracked coating films to the total number of 100 coating films, the crack resistance was evaluated according to the following evaluation criteria.

評價基準 「○」：在硬化塗膜上幾乎沒有裂紋(小於5%) 「△」：在硬化塗膜上有少許裂紋(5%以上且小於15%) 「×」：在硬化塗膜上有較多的裂紋(15%以上) Evaluation benchmark "○": There are almost no cracks in the hardened coating film (less than 5%) "△": There are some cracks in the hardened coating film (more than 5% and less than 15%) "×": There are many cracks in the hardened coating film (more than 15%)

將各實施例和比較例的樹脂組成物中包含的不揮發成分的含量、試驗例的測定結果和評價結果匯總於下述表1。The content of nonvolatile components contained in the resin compositions of each Example and Comparative Example, and the measurement results and evaluation results of the test examples are summarized in Table 1 below.

由上述表1所示的結果可知，通過使用下述的樹脂組成物，可以得到耐裂紋性優異的硬化物，所述樹脂組成物包含(A)環氧樹脂、(B)含有自由基聚合性基團的化合物和(C)硬化促進劑，其中，(C)成分包含(C1)具有被碳數7以上的烴基取代的含氮雜環的化合物。From the results shown in Table 1 above, it can be seen that a cured product with excellent crack resistance can be obtained by using a resin composition containing (A) an epoxy resin and (B) a radical polymerizable resin. Group compound and (C) a hardening accelerator, wherein the component (C) includes (C1) a compound having a nitrogen-containing heterocyclic ring substituted by a hydrocarbon group having 7 or more carbon atoms.

本申請以在日本國專利局申請的日本特願2022-001258(申請日2022年1月6日)作為基礎，其內容全部包含在本說明書中。This application is based on Japanese Patent Application No. 2022-001258 (application date: January 6, 2022) filed with the Japan Patent Office, and the entire content is included in this specification.

Claims (20)

一種樹脂組成物，其是包含(A)環氧樹脂、(B)含有自由基聚合性基團的化合物和(C)硬化促進劑的樹脂組成物， 其中(C)成分包含：(C1)具有被碳數7以上的烴基取代的含氮雜環的化合物。 A resin composition containing (A) epoxy resin, (B) a compound containing a radically polymerizable group, and (C) a hardening accelerator, The component (C) includes: (C1) a compound having a nitrogen-containing heterocyclic ring substituted by a hydrocarbon group having 7 or more carbon atoms. 如請求項1之樹脂組成物，其中 (C1)成分包含式(C)所示的化合物， 式(C)中， R 1表示碳數7以上的烷基或碳數7以上的烯基； R 2表示氫原子、可具有取代基的烷基、可具有取代基的烯基、可具有取代基的芳基，或可具有取代基的雜芳基； R 3和R 4分別獨立地表示氫原子或取代基，或者R 3和R 4一起鍵結而形成可具有取代基的芳環或可具有取代基的非芳環； 由虛線和實線組成的雙重線表示單鍵或雙鍵。 The resin composition of claim 1, wherein the component (C1) includes a compound represented by formula (C), In formula (C), R 1 represents an alkyl group having 7 or more carbon atoms or an alkenyl group having 7 or more carbon atoms; R 2 represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an alkenyl group which may have a substituent. an aryl group, or a heteroaryl group that may have a substituent; R 3 and R 4 independently represent a hydrogen atom or a substituent, or R 3 and R 4 are bonded together to form an aromatic ring that may have a substituent or may Nonaromatic rings with substituents; a double line consisting of a dashed and a solid line represents a single or double bond. 如請求項2之樹脂組成物，其中 R 2為式(R2)所示的基團， 式(R2)中， X表示碳數1~6的伸烷基； Y表示單鍵、-O-、-CO-、-S-、-SO-、-SO 2-、-NH-、 -COO-、-OCO-、-CONH-或-NHCO-； *表示鍵結部位。 The resin composition of claim 2, wherein R 2 is a group represented by formula (R2), In formula (R2), X represents an alkylene group having 1 to 6 carbon atoms; Y represents a single bond, -O-, -CO-, -S-, -SO-, -SO 2 -, -NH-, -COO -, -OCO-, -CONH- or -NHCO-; * indicates the bonding site. 如請求項1之樹脂組成物，其中將樹脂組成物中的不揮發成分設為100質量%時，(C1)成分的含量為0.001質量%~1質量%。For example, in the resin composition of claim 1, when the non-volatile component in the resin composition is 100% by mass, the content of component (C1) is 0.001% by mass to 1% by mass. 如請求項1之樹脂組成物，其中將樹脂組成物中的不揮發成分設為100質量%時，(A)成分的含量為10質量%~30質量%。For example, in the resin composition of claim 1, when the non-volatile component in the resin composition is 100% by mass, the content of component (A) is 10% to 30% by mass. 如請求項1之樹脂組成物，其中進一步包含(D)無機填充材料。The resin composition of claim 1, further comprising (D) an inorganic filler material. 如請求項6之樹脂組成物，其中(D)成分的材料包含選自二氧化矽、氧化鋁和鋁矽酸鹽中的材料。The resin composition of claim 6, wherein the material of component (D) includes a material selected from the group consisting of silica, alumina and aluminosilicates. 如請求項6之樹脂組成物，其中將樹脂組成物中的不揮發成分設為100質量%時，(D)成分的含量為70質量%以上。For example, the resin composition of claim 6, wherein the content of component (D) is 70 mass% or more when the non-volatile components in the resin composition are 100 mass%. 如請求項1之樹脂組成物，其中進一步包含(E)環氧樹脂硬化劑。The resin composition of claim 1, further comprising (E) an epoxy resin hardener. 如請求項9之樹脂組成物，其中(E)成分包含活性酯系硬化劑。The resin composition of claim 9, wherein the component (E) contains an active ester hardener. 如請求項9之樹脂組成物，其中(E)成分包含酚系硬化劑。The resin composition according to claim 9, wherein the component (E) contains a phenolic hardener. 如請求項1之樹脂組成物，其中在5.8GHz、23℃的條件下進行測定時，樹脂組成物的硬化物的相對介電常數(Dk)為3.5以下。The resin composition of Claim 1, wherein when measured under conditions of 5.8 GHz and 23°C, the relative dielectric constant (Dk) of the cured product of the resin composition is 3.5 or less. 如請求項1之樹脂組成物，其中在5.8GHz、23℃的條件下進行測定時，樹脂組成物的硬化物的介電損耗角正切(Df)為0.005以下。The resin composition of Claim 1, wherein when measured under conditions of 5.8 GHz and 23°C, the dielectric loss tangent (Df) of a cured product of the resin composition is 0.005 or less. 如請求項1之樹脂組成物，其中樹脂組成物的硬化物的線熱膨脹係數(CTE)在25℃~150℃的範圍內為25ppm/K以下。The resin composition of claim 1, wherein the linear thermal expansion coefficient (CTE) of the cured product of the resin composition is 25 ppm/K or less in the range of 25°C to 150°C. 如請求項1之樹脂組成物，其中樹脂組成物的硬化物的玻璃轉移溫度(Tg)為150℃以上。The resin composition according to claim 1, wherein the glass transition temperature (Tg) of the cured product of the resin composition is 150°C or higher. 一種硬化物，其是如請求項1~15中任一項之樹脂組成物的硬化物。A cured product, which is a cured product of the resin composition according to any one of claims 1 to 15. 一種片狀疊層材料，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 to 15. 一種樹脂片材，其具有： 支承體，和 設置於該支承體上的由如請求項1~15中任一項之樹脂組成物形成的樹脂組成物層。 A resin sheet having: support, and A resin composition layer formed of the resin composition according to any one of claims 1 to 15 is provided on the support. 一種印刷配線板，其具備絕緣層， 所述絕緣層包含如請求項1~15中任一項之樹脂組成物的硬化物。 A printed wiring board with an insulating layer, The insulating layer includes a cured product of the 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 including the printed wiring board according to claim 19.
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