TW202308980A - Resin composition, cured product, resin sheet, circuit substrate, and semiconductor chip package - Google Patents

Resin composition, cured product, resin sheet, circuit substrate, and semiconductor chip package Download PDF

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TW202308980A
TW202308980A TW111122346A TW111122346A TW202308980A TW 202308980 A TW202308980 A TW 202308980A TW 111122346 A TW111122346 A TW 111122346A TW 111122346 A TW111122346 A TW 111122346A TW 202308980 A TW202308980 A TW 202308980A
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resin composition
resin
mass
epoxy resin
inorganic filler
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阪內啓之
佐佐木成
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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
    • 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08K5/00—Use of organic ingredients
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    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium 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
    • 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
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • 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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

A resin composition with a stable viscosity life; a resin sheet that uses said resin composition; a circuit substrate; and a semiconductor chip package are provided. In this resin composition, which contains (A) a curable resin and (B) an inorganic filler, the average particle diameter of the (B) inorganic filler is in the range 0.5-12 [mu]m and the crystalline silica content in the inorganic filler material is greater than or equal to 0 mass% and less than 2.1 mass%.

Description

樹脂組成物、硬化物、樹脂薄片、電路基板及半導體晶片封裝Resin composition, cured product, resin sheet, circuit board and semiconductor chip package

本發明關於樹脂組成物。再者，關於使用該樹脂組成物而得之硬化物、樹脂薄片、電路基板及半導體晶片封裝。The present invention relates to resin compositions. Furthermore, it relates to a cured product obtained by using the resin composition, a resin sheet, a circuit board, and a semiconductor chip package.

近年來，智慧型手機、平板型裝置等小型的高功能電子機器之需求係增大，伴隨其，在此等小型的電子機器所用的半導體晶片封裝用絕緣材料(絕緣層)，亦要求更高功能化。為了形成如此的絕緣層，使用樹脂組成物(專利文獻1)。 [先前技術文獻] [專利文獻] In recent years, the demand for small and high-function electronic devices such as smart phones and tablet devices has increased. Along with this, the insulating materials (insulating layers) for semiconductor chip packaging used in such small electronic devices have also required higher requirements. Functional. In order to form such an insulating layer, a resin composition is used (Patent Document 1). [Prior Art Literature] [Patent Document]

[專利文獻1] 日本特開2006-037083號公報[Patent Document 1] Japanese Patent Laid-Open No. 2006-037083

[發明所欲解決的課題][Problems to be Solved by the Invention]

可是，於樹脂組成物，要求抑制在形成絕緣層時所發生的翹曲。此處，為了抑制翹曲，考慮使無機填充材成為高填充。為了使無機填充材成為高填充，考慮縮小無機填充材的粒徑之範圍。又，除了抑制翹曲以外，亦可能發生縮小無機填充材的粒徑之範圍之場面。However, in the resin composition, it is required to suppress the warpage which occurs when the insulating layer is formed. Here, in order to suppress warping, it is conceivable to make the inorganic filler highly filled. In order to make the inorganic filler highly filled, it is conceivable to narrow the range of the particle size of the inorganic filler. Also, in addition to suppressing warpage, there may also be a situation where the particle size range of the inorganic filler is reduced.

然而，發明者們之檢討的結果查明：僅縮小無機填充材的粒徑之範圍時，有得不到所欲的性質形狀，例如得不到具有安定的黏度壽命之樹脂組成物的情況。這樣的問題不限於液狀的樹脂組成物(亦稱為「油墨」或「樹脂糊」)而發生，於能形成薄膜的樹脂組成物(亦僅稱「薄膜品」或「薄片品」)中亦同樣地發生。而且，藉由使用具有安定的黏度壽命的樹脂組成物或樹脂薄片，可期待能提供：抑制流痕或埋入不良的發生等之良率良好的電路基板及半導體晶片封裝。However, as a result of the examination by the inventors, it was found that only narrowing the range of the particle size of the inorganic filler may not obtain desired properties, for example, a resin composition having a stable viscosity life may not be obtained. Such problems are not limited to liquid resin compositions (also called "ink" or "resin paste"), but occur in resin compositions capable of forming thin films (also called only "film products" or "sheet products") The same happens. Furthermore, by using a resin composition or a resin sheet having a stable viscosity life, it can be expected to provide a high-yield circuit board and semiconductor chip package that suppress the occurrence of flow marks and embedding defects.

本發明係鑒於上述問題而完成者，本發明之課題在於提供：帶來翹曲的發生被抑制之硬化物，同時至少黏度壽命安定的樹脂組成物；使用該樹脂組成物之樹脂薄片、電路基板及半導體晶片封裝。 [解決課題的手段] The present invention was made in view of the above-mentioned problems, and an object of the present invention is to provide: a cured product that causes warpage and is suppressed, and at the same time has a stable viscosity life; a resin sheet and a circuit board using the resin composition and semiconductor chip packaging. [means to solve the problem]

本發明者為了解決前述課題而專心致力地檢討。結果，本發明者發現藉由含有(A)硬化性樹脂與(B)無機填充材之樹脂組成物，無機填充材之平均粒徑在特定範圍內時，無機填充材中的結晶性二氧化矽含有率在特定範圍內，可解決前述課題，完成本發明。又，檢討本發明之樹脂組成物的硬化物時，查明與基材的密著性(例如聚醯亞胺樹脂之密著性)優異之傾向。 即，本發明包含下述者。 The inventors of the present invention have earnestly examined in order to solve the aforementioned problems. As a result, the present inventors have found that when the average particle diameter of the inorganic filler is within a specific range, the crystalline silica in the inorganic filler can When the content is within a specific range, the aforementioned problems can be solved, and the present invention has been completed. Also, when the cured product of the resin composition of the present invention was examined, it was found that the adhesion to the base material (for example, the adhesion of polyimide resin) tends to be excellent. That is, the present invention includes the following.

[1] 一種樹脂組成物其係含有(A)硬化性樹脂與(B)無機填充材之樹脂組成物，其特徵為：(B)無機填充材之平均粒徑在0.5μm～12μm之範圍內，無機填充材中的結晶性二氧化矽含有率在0質量%以上且未達2.1質量%之範圍內。 [2] 如[1]記載之樹脂組成物，其中前述結晶性二氧化矽含有率在0質量%以上且0.4質量%以下之範圍內。 [3] 如[1]或[2]記載之樹脂組成物，其中將樹脂組成物全體當作100體積%時，(B)無機填充材之含量為50體積%以上。 [4] 如[1]～[3]中任一項記載之樹脂組成物，其包含(C)硬化劑，(C)成分相對於(A)成分之質量比在1:0.01～1:10之範圍內。 [5] 如[1]～[4]中任一項記載之樹脂組成物，其中前述結晶性二氧化矽含有率係基於藉由X射線繞射測定所得之X射線繞射圖型而算出。 [6] 如[5]記載之樹脂組成物，其中前述結晶性二氧化矽含有率係將X射線繞射圖型進行裏特沃爾德(Rietveld)解析而算出。 [7] 如[1]～[6]中任一項記載之樹脂組成物，其係用於形成厚度50μm以上的樹脂組成物層。 [8] 如[1]～[7]中任一項記載之樹脂組成物，其係密封用。 [9] 一種如[1]～[8]中任一項記載之樹脂組成物的硬化物。 [10] 一種樹脂薄片，其具有支撐體與設於該支撐體上的包含如[1]～[8]中任一項記載之樹脂組成物的樹脂組成物層。 [11] 如[10]記載之樹脂薄片，其為半導體晶片封裝的絕緣層用樹脂薄片。 [12] 一種電路基板，其包含藉由如[1]～[8]中任一項記載之樹脂組成物的硬化物所形成的絕緣層。 [13] 一種半導體晶片封裝，其包含如[12]記載之電路基板與搭載於該電路基板上的半導體晶片。 [14] 一種半導體晶片封裝，其包含藉由如[1]～[8]中任一項記載之樹脂組成物所密封的半導體晶片。 [15] 一種半導體晶片封裝，其包含藉由如[10]記載之樹脂薄片所密封的半導體晶片。 [16] 一種半導體晶片封裝之製造方法，其包含使含有(A)與硬化性樹脂與(B)無機填充材之樹脂組成物硬化之步驟，其中(B)無機填充材之平均粒徑在0.5μm～12μm之範圍內，無機填充材中的結晶性二氧化矽含有率在0質量%以上且未達2.1質量%之範圍內。 [發明的效果] [1] A resin composition comprising (A) a curable resin and (B) an inorganic filler, characterized in that: (B) the average particle size of the inorganic filler is within the range of 0.5 μm to 12 μm , the content of crystalline silica in the inorganic filler is within the range of 0% by mass or more and less than 2.1% by mass. [2] The resin composition according to [1], wherein the crystalline silica content is in the range of 0% by mass to 0.4% by mass. [3] The resin composition according to [1] or [2], wherein the content of the (B) inorganic filler is 50% by volume or more when the entire resin composition is taken as 100% by volume. [4] The resin composition according to any one of [1] to [3], which contains (C) a curing agent, and the mass ratio of (C) component to (A) component is 1:0.01 to 1:10 within the range. [5] The resin composition according to any one of [1] to [4], wherein the crystalline silica content is calculated based on an X-ray diffraction pattern obtained by X-ray diffraction measurement. [6] The resin composition according to [5], wherein the crystalline silica content is calculated by performing Rietveld analysis on an X-ray diffraction pattern. [7] The resin composition according to any one of [1] to [6], which is used to form a resin composition layer having a thickness of 50 μm or more. [8] The resin composition according to any one of [1] to [7], which is used for sealing. [9] A cured product of the resin composition described in any one of [1] to [8]. [10] A resin sheet comprising a support and a resin composition layer provided on the support and comprising the resin composition according to any one of [1] to [8]. [11] The resin sheet according to [10], which is a resin sheet for an insulating layer of a semiconductor chip package. [12] A circuit board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [8]. [13] A semiconductor chip package comprising the circuit board described in [12] and a semiconductor chip mounted on the circuit board. [14] A semiconductor chip package including a semiconductor chip sealed with the resin composition according to any one of [1] to [8]. [15] A semiconductor chip package comprising a semiconductor chip sealed by the resin sheet as described in [10]. [16] A method of manufacturing a semiconductor chip package, which includes the step of curing a resin composition containing (A) a curable resin and (B) an inorganic filler, wherein the average particle size of the (B) inorganic filler is 0.5 Within the range of μm to 12 μm, the content of crystalline silica in the inorganic filler is within a range of 0% by mass or more and less than 2.1% by mass. [Effect of the invention]

依據本發明，可提供黏度壽命安定的樹脂組成物；使用該樹脂組成物之樹脂薄片、電路基板及半導體晶片封裝。According to the present invention, it is possible to provide a resin composition having a stable viscosity life, and a resin sheet, a circuit board, and a semiconductor chip package using the resin composition.

[實施發明的形態][Mode of Carrying Out the Invention]

以下，顯示本發明之實施形態及例示物而詳細地說明。惟，本發明不受下述實施形態及例示物所限定，在不脫離本發明之申請專利範圍及其均等範圍之範圍內，可任意地變更而實施。Hereinafter, embodiments and examples of the present invention are shown and described in detail. However, the present invention is not limited by the following embodiments and illustrations, and can be implemented with arbitrary changes within the scope not departing from the scope of claims and equivalents of the present invention.

[樹脂組成物] 本發明之樹脂組成物係含有(A)硬化性樹脂與(B)無機填充材之樹脂組成物，其特徵為：(B)無機填充材之平均粒徑在0.5μm～12μm之範圍內，無機填充材中的結晶性二氧化矽含有率在0質量%以上且未達2.1質量%之範圍內的樹脂組成物。而且，本發明係如由以下之說明亦可明知，至少達成能提供黏度壽命安定的樹脂組成物；使用該樹脂組成物之樹脂薄片、電路基板及半導體晶片封裝之效果。藉由本發明所達成的其他效果，只要是屬於本技術領域者，則可參照本說明書及圖式而掌握。 [Resin composition] The resin composition of the present invention is a resin composition containing (A) a curable resin and (B) an inorganic filler, and is characterized in that: (B) the average particle diameter of the inorganic filler is within the range of 0.5 μm to 12 μm, and the inorganic filler A resin composition in which the content of crystalline silica in the filler is in the range of 0% by mass to less than 2.1% by mass. Moreover, the present invention can at least achieve the effects of providing a resin composition with a stable viscosity life, and resin sheets, circuit boards, and semiconductor chip packages using the resin composition, as can be understood from the following description. Other effects achieved by the present invention can be grasped with reference to this specification and drawings as long as they belong to the technical field.

[樹脂組成物之組成] 本發明之樹脂組成物含有(A)硬化性樹脂與(B)無機填充材。本發明之樹脂組成物，只要不過度地妨礙上述效果，則除了(A)成分及(B)成分之外，例如還可包含(C)硬化劑、(D)其他添加劑、溶劑。 [Composition of resin composition] The resin composition of the present invention contains (A) curable resin and (B) inorganic filler. The resin composition of the present invention may contain, for example, (C) a curing agent, (D) other additives, and a solvent in addition to the (A) component and (B) component, as long as the above-mentioned effect is not excessively hindered.

[(A)硬化性樹脂] 本發明之樹脂組成物含有(A)硬化性樹脂。作為(A)硬化性樹脂，可使用由熱硬化性樹脂、光硬化性樹脂及自由基聚合性樹脂所選出的1種以上之樹脂。自由基聚合性樹脂係視情況地在聚合起始劑之存在下，藉由熱或光而自由基聚合進行之樹脂，可被分類為熱硬化性樹脂或光硬化性樹脂。(A)成分可單獨1種類使用，也可以任意的比率組合2種類以上而使用。 [(A) curable resin] The resin composition of the present invention contains (A) curable resin. As (A) curable resin, one or more resins selected from thermosetting resins, photocurable resins, and radical polymerizable resins can be used. Radical polymerizable resins are resins that radically polymerize by heat or light in the presence of a polymerization initiator as the case may be, and can be classified into thermosetting resins or photocurable resins. (A) The component may be used individually by 1 type, and may use it combining 2 or more types by arbitrary ratios.

作為熱硬化性樹脂，例如可舉出環氧樹脂、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、聚醯亞胺樹脂、苯并㗁𠯤樹脂、不飽和聚酯樹脂、酚樹脂、三聚氰胺樹脂、聚矽氧樹脂、苯氧基樹脂等。於一實施形態中，(A)硬化性樹脂包含環氧樹脂。樹脂組成物含有熱硬化性樹脂時，較佳為含有(C)硬化劑，再者更佳為含有後述的硬化促進劑。Examples of thermosetting resins include epoxy resins, epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, polyimide resins, benzo 𠯤resin, unsaturated polyester resin, phenolic resin, melamine resin, silicone resin, phenoxy resin, etc. In one embodiment, (A) curable resin contains epoxy resin. When a resin composition contains a thermosetting resin, it is preferable to contain (C) hardening|curing agent, and it is more preferable to contain the hardening accelerator mentioned later.

所謂環氧樹脂，就是指具有環氧基的樹脂。作為環氧樹脂，例如可舉出聯二甲酚型環氧樹脂、雙酚A型環氧樹脂；雙酚F型環氧樹脂；雙酚S型環氧樹脂；雙酚AF型環氧樹脂；二環戊二烯型環氧樹脂；三酚型環氧樹脂；苯酚酚醛清漆型環氧樹脂；環氧丙基胺型環氧樹脂；環氧丙基酯型環氧樹脂；甲酚酚醛清漆型環氧樹脂；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；脂環式環氧樹脂；具有酯骨架的脂環式環氧樹脂；雜環式環氧樹脂；含螺環的環氧樹脂；環己烷型環氧樹脂；環己烷二甲醇型環氧樹脂；三羥甲基型環氧樹脂；四苯基乙烷型環氧樹脂；伸萘基醚型環氧樹脂、第三丁基兒茶酚型環氧樹脂、萘型環氧樹脂、萘酚型環氧樹脂、蒽型環氧樹脂、萘酚酚醛清漆型環氧樹脂等之含有縮合環骨架的環氧樹脂；異氰脲酸酯型環氧樹脂；含有伸烷氧基骨架及丁二烯骨架的環氧樹脂；含有茀結構的環氧樹脂等。環氧樹脂可單獨1種類使用，也可組合2種類以上使用。The so-called epoxy resin refers to a resin with an epoxy group. Examples of the epoxy resin include bixylenol type epoxy resin, bisphenol A type epoxy resin; bisphenol F type epoxy resin; bisphenol S type epoxy resin; bisphenol AF type epoxy resin; Dicyclopentadiene type epoxy resin; triphenol type epoxy resin; phenol novolak type epoxy resin; glycidylamine type epoxy resin; glycidyl ester type epoxy resin; cresol novolac type Epoxy resin; biphenyl type epoxy resin; linear aliphatic epoxy resin; epoxy resin with butadiene structure; alicyclic epoxy resin; alicyclic epoxy resin with ester skeleton; heterocyclic type Epoxy resins; epoxy resins containing spiro rings; cyclohexane-type epoxy resins; cyclohexanedimethanol-type epoxy resins; trimethylol-type epoxy resins; tetraphenylethane-type epoxy resins; Containing naphthyl ether type epoxy resin, tertiary butylcatechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, naphthol novolak type epoxy resin, etc. Epoxy resin with condensed ring skeleton; isocyanurate epoxy resin; epoxy resin with alkoxyl skeleton and butadiene skeleton; epoxy resin with fennel structure, etc. Epoxy resins may be used alone or in combination of two or more.

從得到耐熱性優異的硬化物之觀點來看，環氧樹脂亦可包含含有芳香族結構的環氧樹脂。所謂芳香族結構，就是一般被定義為芳香族的化學結構，亦包含多環芳香族及芳香族雜環。作為含有芳香族結構的環氧樹脂，例如可舉出雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚AF型環氧樹脂、二環戊二烯型環氧樹脂、三酚型環氧樹脂、萘酚酚醛清漆型環氧樹脂、苯酚酚醛清漆型環氧樹脂、第三丁基兒茶酚型環氧樹脂、萘型環氧樹脂、萘酚型環氧樹脂、蒽型環氧樹脂、聯二甲酚型環氧樹脂、具有芳香族結構的環氧丙基胺型環氧樹脂、具有芳香族結構的環氧丙基酯型環氧樹脂、甲酚酚醛清漆型環氧樹脂、聯苯型環氧樹脂、具有芳香族結構的線狀脂肪族環氧樹脂、具有芳香族結構的具有丁二烯結構的環氧樹脂、具有芳香族結構的脂環式環氧樹脂、雜環式環氧樹脂、具有芳香族結構的含螺環的環氧樹脂、具有芳香族結構的環己烷二甲醇型環氧樹脂、伸萘基醚型環氧樹脂、具有芳香族結構的三羥甲基型環氧樹脂、具有芳香族結構的四苯基乙烷型環氧樹脂等。From the viewpoint of obtaining a cured product excellent in heat resistance, the epoxy resin may include epoxy resins containing an aromatic structure. The so-called aromatic structure refers to a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles. Examples of the epoxy resin containing an aromatic structure include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene Olefin-type epoxy resin, triphenol-type epoxy resin, naphthol novolac-type epoxy resin, phenol novolac-type epoxy resin, tert-butylcatechol-type epoxy resin, naphthalene-type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bixylenol type epoxy resin, glycidylamine type epoxy resin with aromatic structure, glycidyl ester type epoxy resin with aromatic structure, Cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin with aromatic structure, epoxy resin with butadiene structure with aromatic structure, aliphatic epoxy resin with aromatic structure Cyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin with aromatic structure, cyclohexanedimethanol epoxy resin with aromatic structure, naphthyl ether epoxy resin, Trimethylol-type epoxy resins having an aromatic structure, tetraphenylethane-type epoxy resins having an aromatic structure, and the like.

於含有芳香族結構的環氧樹脂之中，從得到耐熱性優異的硬化物之觀點來看，較佳為含有縮合環結構的環氧樹脂。作為含有縮合環結構的環氧樹脂中之縮合環，例如可舉出萘環、蒽環、菲環等，特佳為萘環。因此，環氧樹脂較佳為包含含有萘環結構的萘型環氧樹脂。相對於環氧樹脂之全量100質量%，萘型環氧樹脂之量較佳為10質量%以上，更佳為15質量%以上，特佳為20質量%以上，且較佳為50質量%以下，更佳為40質量%以下，尤佳為30質量%以下。Among epoxy resins containing an aromatic structure, epoxy resins containing a condensed ring structure are preferred from the viewpoint of obtaining a cured product excellent in heat resistance. As a condensed ring in the epoxy resin containing a condensed ring structure, a naphthalene ring, an anthracene ring, a phenanthrene ring, etc. are mentioned, for example, Naphthalene ring is especially preferable. Therefore, the epoxy resin is preferably a naphthalene-type epoxy resin containing a naphthalene ring structure. The amount of the naphthalene-type epoxy resin is preferably at least 10% by mass, more preferably at least 15% by mass, particularly preferably at least 20% by mass, and more preferably at most 50% by mass, based on 100% by mass of the total amount of the epoxy resin , more preferably 40% by mass or less, especially preferably 30% by mass or less.

從提高硬化物的耐熱性及金屬密著性之觀點來看，環氧樹脂可包含環氧丙基胺型環氧樹脂。From the viewpoint of improving the heat resistance and metal adhesion of the cured product, the epoxy resin may include a glycidylamine type epoxy resin.

環氧樹脂可包含具有丁二烯結構的環氧樹脂。The epoxy resin may include an epoxy resin having a butadiene structure.

樹脂組成物較佳為包含在1分子中具有2個以上環氧基的環氧樹脂作為環氧樹脂。相對於環氧樹脂的不揮發成分100質量%，在1分子中具有2個以上環氧基的環氧樹脂之比例較佳為50質量%以上，更佳為60質量%以上，特佳為70質量%以上。The resin composition preferably contains, as the epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. The ratio of the epoxy resin having two or more epoxy groups per molecule is preferably at least 50% by mass, more preferably at least 60% by mass, and most preferably at least 70% by mass, based on 100% by mass of the non-volatile components of the epoxy resin. Mass% or more.

於環氧樹脂中，有在溫度20℃下液狀的環氧樹脂(以下亦稱為「液狀環氧樹脂」)與在溫度20℃下固體狀的環氧樹脂(以下亦稱為「固體狀環氧樹脂」)。本實施形態之樹脂組成物係在作為環氧樹脂，可僅包含液狀環氧樹脂，或也可僅包含固體狀環氧樹脂，或可組合包含液狀環氧樹脂與固體狀環氧樹脂，但較佳為至少包含液狀環氧樹脂。於一實施形態中，本發明之樹脂組成物僅包含液狀環氧樹脂作為硬化性樹脂。於其他實施形態中，本發明之樹脂組成物可組合包含液狀環氧樹脂與固體狀環氧樹脂作為硬化性樹脂，也可組合包含液狀環氧樹脂與固體狀環氧樹脂，亦可僅包含液狀環氧樹脂。Among epoxy resins, there are epoxy resins that are liquid at a temperature of 20°C (hereinafter also referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter also referred to as "solid epoxy resins"). shaped epoxy resin"). The resin composition of the present embodiment may contain only liquid epoxy resin, or only solid epoxy resin, or a combination of liquid epoxy resin and solid epoxy resin, as epoxy resin. However, it is preferable to contain at least a liquid epoxy resin. In one embodiment, the resin composition of the present invention contains only a liquid epoxy resin as a curable resin. In other embodiments, the resin composition of the present invention may contain liquid epoxy resin and solid epoxy resin in combination as curable resin, may also contain liquid epoxy resin and solid epoxy resin in combination, or may only Contains liquid epoxy resin.

作為液狀環氧樹脂，較佳為在1分子中具有2個以上環氧基的液狀環氧樹脂。As a liquid epoxy resin, what has 2 or more epoxy groups in 1 molecule is preferable.

作為液狀環氧樹脂，較佳為雙酚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、環氧丙基酯型環氧樹脂、環氧丙基胺型環氧樹脂、苯酚酚醛清漆型環氧樹脂、具有酯骨架的脂環式環氧樹脂、環己烷型環氧樹脂、環己烷二甲醇型環氧樹脂、具有丁二烯結構的環氧樹脂、含有伸烷氧基骨架及丁二烯骨架的環氧樹脂、含有茀結構的環氧樹脂、二環戊二烯型環氧樹脂。其中，特佳為雙酚A型環氧樹脂、雙酚F型環氧樹脂、萘型環氧樹脂、環氧丙基胺型環氧樹脂、具有酯骨架的脂環式環氧樹脂、具有丁二烯結構的環氧樹脂、含有伸烷氧基骨架及丁二烯骨架的環氧樹脂、含有茀結構的環氧樹脂、二環戊二烯型環氧樹脂。As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, Glycidylamine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, Epoxy resins with alkene structure, epoxy resins with alkene structure and butadiene structure, epoxy resins with fennel structure, and dicyclopentadiene type epoxy resins. Among them, especially preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, alicyclic epoxy resin with ester skeleton, Epoxy resins with diene structure, epoxy resins with alkylene structure and butadiene structure, epoxy resins with terpene structure, and dicyclopentadiene type epoxy resins.

作為液狀環氧樹脂之具體例，可舉出DIC公司製之「HP4032」、「HP4032D」、「HP4032SS」(萘型環氧樹脂)；三菱化學公司製之「828US」、「828EL」、「jER828EL」、「825」、「Epikote 828EL」(雙酚A型環氧樹脂)；三菱化學公司製之「jER807」、「1750」(雙酚F型環氧樹脂)；三菱化學公司製之「jER152」(苯酚酚醛清漆型環氧樹脂)；三菱化學公司製之「630」、「630LSD」、「604」(環氧丙基胺型環氧樹脂)；ADEKA公司製之「ED-523T」(甘草醇型環氧樹脂)；ADEKA公司製之「EP-3950L」、「EP-3980S」(環氧丙基胺型環氧樹脂)；ADEKA公司製之「EP-4088S」(二環戊二烯型環氧樹脂)；日鐵化學&材料公司製之「ZX1059」(雙酚A型環氧樹脂與雙酚F型環氧樹脂之混合品)；Nagase ChemteX公司製之「EX-721」(環氧丙基酯型環氧樹脂)；Nagase ChemteX公司製之「EX-991L」(含有伸烷氧基骨架的環氧樹脂)、「EX-992L」(含有聚醚的環氧樹脂)；DAICEL公司製之「Celloxide 2021P」(具有酯骨架的脂環式環氧樹脂)；DAICEL公司製之「PB-3600」、日本曹達公司製之「JP-100」、「JP-200」(具有丁二烯結構的環氧樹脂)；日鐵化學&材料公司製之「ZX1658」、「ZX1658GS」(液狀1,4-環氧丙基環己烷型環氧樹脂)；大阪瓦斯化學公司製之「EG-280」(含有茀結構的環氧樹脂)等。Specific examples of liquid epoxy resins include "HP4032," "HP4032D," and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US," "828EL," and " jER828EL", "825", "Epikote 828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152 manufactured by Mitsubishi Chemical Corporation "(phenol novolak type epoxy resin); "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (licorice Alcohol type epoxy resin); "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA Corporation; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA Corporation Epoxy resin); "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd.; "EX-721" (epoxy resin) manufactured by Nagase ChemteX Co., Ltd. Propyl ester type epoxy resin); Nagase ChemteX Co., Ltd. "EX-991L" (epoxy resin containing an alkeneoxy group), "EX-992L" (polyether-containing epoxy resin); DAICEL Co., Ltd. "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton); "PB-3600" manufactured by DAICEL Corporation; "JP-100" and "JP-200" manufactured by Nippon Soda Corporation (having a butadiene structure epoxy resin); "ZX1658" and "ZX1658GS" (liquid 1,4-epoxypropylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd.; "EG- 280" (epoxy resin containing fenugreek structure), etc.

作為固體狀環氧樹脂，較佳為在1分子中具有3個以上環氧基的固體狀環氧樹脂，更佳為在1分子中具有3個以上環氧基的芳香族系的固體狀環氧樹脂。The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule. oxygen resin.

作為固體狀環氧樹脂，較佳為聯二甲酚型環氧樹脂、萘型環氧樹脂、萘型4官能環氧樹脂、甲酚酚醛清漆型環氧樹脂、二環戊二烯型環氧樹脂、三酚型環氧樹脂、萘酚型環氧樹脂、聯苯型環氧樹脂、伸萘基醚型環氧樹脂、蒽型環氧樹脂、雙酚A型環氧樹脂、雙酚AF型環氧樹脂、四苯基乙烷型環氧樹脂。As the solid epoxy resin, bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type 4 functional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin are preferable. Resin, triphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type Epoxy resin, tetraphenylethane type epoxy resin.

作為固體狀環氧樹脂之具體例，可舉出DIC公司製之「HP4032H」(萘型環氧樹脂)；DIC公司製之「HP-4700」、「HP-4710」(萘型4官能環氧樹脂)；DIC公司製之「N-690」(甲酚酚醛清漆型環氧樹脂)；DIC公司製之「N-695」(甲酚酚醛清漆型環氧樹脂)；DIC公司製之「HP-7200」、「HP-7200HH」、「HP-7200H」(二環戊二烯型環氧樹脂)；DIC公司製之「EXA-7311」、「EXA-7311-G3」、「EXA-7311-G4」、「EXA-7311-G4S」、「HP6000」(伸萘基醚型環氧樹脂)：日本化藥公司製之「EPPN-502H」(三酚型環氧樹脂)；日本化藥公司製之「NC7000L」(萘酚酚醛清漆型環氧樹脂)；日本化藥公司製之「NC3000H」、「NC3000」、「NC3000L」、「NC3100」(聯苯型環氧樹脂)；日鐵化學&材料公司製之「ESN475V」(萘酚型環氧樹脂)；日鐵化學&材料公司製之「ESN485」(萘酚酚醛清漆型環氧樹脂)；三菱化學公司製之「YX4000H」、「YX4000」、「YL6121」(聯苯型環氧樹脂)；三菱化學公司製之「YX4000HK」(聯二甲酚型環氧樹脂)；三菱化學公司製之「YX8800」(蒽型環氧樹脂)；三菱化學公司製之「YX7700」(含有二甲苯結構的酚醛清漆型環氧樹脂)；大阪瓦斯化學公司製之「PG-100」、「CG-500」；三菱化學公司製之「YL7760」(雙酚AF型環氧樹脂)；三菱化學公司製之「YL7800」(茀型環氧樹脂)；三菱化學公司製之「jER1010」(固體狀雙酚A型環氧樹脂)；三菱化學公司製之「jER1031S」(四苯基乙烷型環氧樹脂)等。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); DIC Corporation's "N-690" (cresol novolak type epoxy resin); DIC Corporation's "N-695" (cresol novolak type epoxy resin); DIC Corporation's "HP- 7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" manufactured by DIC Corporation ", "EXA-7311-G4S", "HP6000" (naphthyl ether-type epoxy resin): "EPPN-502H" (triphenol-type epoxy resin) manufactured by Nippon Kayaku Corporation; manufactured by Nippon Kayaku Corporation "NC7000L" (naphthol novolak type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; Nippon Steel Chemical & Materials Co., Ltd. "ESN475V" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd. "ESN485" (naphthol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation "YX4000H", "YX4000", " YL6121" (biphenyl type epoxy resin); "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; manufactured by Mitsubishi Chemical Corporation "YX7700" (novolak-type epoxy resin containing xylene structure); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF-type ring Oxygen Resin); Mitsubishi Chemical Corporation's "YL7800" (Chi-type epoxy resin); Mitsubishi Chemical Corporation's "jER1010" (solid bisphenol A epoxy resin); Mitsubishi Chemical Corporation's "jER1031S" (four Phenylethane type epoxy resin), etc.

相對於環氧樹脂之全量100質量%，液狀環氧樹脂之量係沒有特別的限定，但較佳為50質量%以上，更佳為70質量%以上，尤佳為80質量%以上，尤更佳為90質量%以上，特佳為100質量%。The amount of liquid epoxy resin is not particularly limited relative to 100% by mass of the total amount of epoxy resin, but it is preferably at least 50% by mass, more preferably at least 70% by mass, especially preferably at least 80% by mass, especially More preferably, it is at least 90% by mass, and most preferably, it is 100% by mass.

環氧樹脂之環氧當量較佳為50g/eq.~5000 g/eq.，更佳為50g/eq.~3000g/eq.，尤佳為80g/eq.~2000 g/eq.，尤更佳為110g/eq.~1000g/eq.。環氧當量為包含1當量的環氧基的樹脂之質量。該環氧當量可依照JIS K7236進行測定。The epoxy equivalent of epoxy resin is preferably 50g/eq.~5000 g/eq., more preferably 50g/eq.~3000g/eq., especially 80g/eq.~2000 g/eq., especially The best is 110g/eq.~1000g/eq. The epoxy equivalent is the mass of the resin containing 1 equivalent of epoxy group. This epoxy equivalent can be measured based on JISK7236.

環氧樹脂之重量平均分子量(Mw)較佳為100～5000，更佳為200～3000，尤佳為400～1500。樹脂之重量平均分子量可藉由凝膠滲透層析(GPC)法，作為聚苯乙烯換算之值測定。The weight average molecular weight (Mw) of the epoxy resin is preferably 100-5000, more preferably 200-3000, and especially preferably 400-1500. The weight average molecular weight of resin can be measured as the value of polystyrene conversion by the gel permeation chromatography (GPC) method.

相對於樹脂組成物中的不揮發成分100質量%，硬化性樹脂之量係沒有特別的限定，但較佳為0.5質量%以上，更佳為1質量%以上，特佳為1.5質量%以上，且較佳為45質量%以下，更佳為40質量%以下，特佳為35質量%以下。The amount of the curable resin is not particularly limited relative to 100% by mass of the non-volatile components in the resin composition, but is preferably at least 0.5% by mass, more preferably at least 1% by mass, and most preferably at least 1.5% by mass. And it is preferably at most 45% by mass, more preferably at most 40% by mass, and most preferably at most 35% by mass.

[(B)無機填充材] 本發明之樹脂組成物含有(B)無機填充材。含有(B)無機填充材的樹脂組成物之硬化物通常有抑制翹曲的發生之傾向。又，含有(B)無機填充材的樹脂組成物之硬化物通常可減小熱膨脹係數。 [(B) Inorganic filler] The resin composition of the present invention contains (B) an inorganic filler. The cured product of the resin composition containing the (B) inorganic filler generally tends to suppress the occurrence of warpage. Also, the cured product of the resin composition containing (B) the inorganic filler can generally reduce the coefficient of thermal expansion.

作為無機填充材，使用無機化合物。作為無機填充材之例，可舉出二氧化矽、氧化鋁、玻璃、堇青石、矽氧化物、硫酸鋇、碳酸鋇、滑石、黏土、雲母粉、氧化鋅、水滑石、水鋁石、氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、氧化鎂、氮化硼、氮化鋁、氮化錳、硼酸鋁、碳酸鍶、鈦酸鍶、鈦酸鈣、鈦酸鎂、鈦酸鉍、氧化鈦、氧化鋯、鈦酸鋇、鈦酸鋯酸鋇、鋯酸鋇、鋯酸鈣、磷酸鋯及磷酸鎢酸鋯等。於此等之中，較佳為二氧化矽、氧化鋁，特佳為二氧化矽。作為二氧化矽，例如可舉出無定形二氧化矽、熔融二氧化矽、結晶二氧化矽、合成二氧化矽、中空二氧化矽等。又，作為二氧化矽，較佳為球狀二氧化矽。(B)無機填充材可單獨1種類使用，也可組合2種類以上使用。As the inorganic filler, an inorganic compound is used. Examples of inorganic fillers include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, diaspore, hydrogen Aluminum oxide, 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 titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate, etc. Among them, silica and alumina are preferable, and silica is particularly preferable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as silica, spherical silica is preferable. (B) The inorganic filler may be used alone or in combination of two or more types.

(B)無機填充材，從提高耐濕性及分散性之觀點來看，較佳為被表面處理劑所處理。作為表面處理劑，例如可舉出含氟的矽烷偶合劑、胺基矽烷系偶合劑、環氧基矽烷系偶合劑、巰基矽烷系偶合劑、矽烷系偶合劑、烷氧基矽烷、有機矽氮烷化合物、鈦酸酯系偶合劑等。又，表面處理劑可單獨1種類使用，也可任意地組合2種類以上而使用。(B) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, and organosilanes. Alkane compounds, titanate coupling agents, etc. Moreover, a surface treatment agent may be used individually by 1 type, and may be used in combination of 2 or more types arbitrarily.

作為表面處理劑之市售品，例如可舉出信越化學工業公司製「KBM403」(3-環氧丙氧基丙基三甲氧基矽烷)、信越化學工業公司製「KBM803」(3-巰基丙基三甲氧基矽烷)、信越化學工業公司製「KBE903」(3-胺基丙基三乙氧基矽烷)、信越化學工業公司製「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 Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyl Trimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) , Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane) manufactured by the company, "KBM-4803" (long-chain epoxy-type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-7103" (3,3, 3-trifluoropropyltrimethoxysilane), etc.

表面處理劑所致的表面處理之程度，從無機填充材的分散性提升之觀點來看，較佳為收在特定之範圍內。具體而言，無機填充材100質量份較佳為被0.2質量份～5質量份的表面處理劑所表面處理，更佳為被0.2質量份～3質量份所表面處理，尤佳為被0.3質量份～2質量份所表面處理。The degree of surface treatment by the surface treatment agent is preferably within a specific range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated by 0.2 to 5 parts by mass of a surface treatment agent, more preferably by 0.2 to 3 parts by mass, and most preferably by 0.3 parts by mass. Parts to 2 parts by mass for surface treatment.

表面處理劑所致的表面處理之程度，係可藉由無機填充材的每單位表面積之碳量來評價。無機填充材的每單位表面積之碳量，從無機填充材的分散性提升之觀點來看，較佳為0.02mg/m 2以上，更佳為0.1mg/m 2以上，尤佳為0.2mg/m 2以上。另一方面，從抑制樹脂組成物的熔融黏度上升之觀點來看，較佳為1mg/m 2以下，更佳為0.8mg/m 2以下，尤佳為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 inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and most preferably 0.2 mg/m 2 from the viewpoint of improving the dispersibility of the inorganic filler. m2 or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin composition, it is preferably at most 1 mg/m 2 , more preferably at most 0.8 mg/m 2 , and most preferably at most 0.5 mg/m 2 .

無機填充材的每單位表面積之碳量，係可在藉由溶劑(例如甲基乙基酮(MEK))洗淨處理表面處理後的無機填充材後進行測定。具體而言，將作為溶劑的充分量之MEK加到經表面處理劑所表面處理之無機填充材中，在25℃下超音波洗淨5分鐘。去除上清液，使固體成分乾燥後，可使用碳分析計測定無機填充材的每單位表面積之碳量。作為碳分析計，可使用堀場製作所公司製「EMIA-320V」等。The amount of carbon per unit surface area of the inorganic filler can be measured after cleaning the surface-treated inorganic filler with a solvent (eg, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning was performed at 25° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA CO., LTD., etc. can be used.

本發明之樹脂組成物所含有的(B)無機填充材係其平均粒徑在0.5μm～12μm之範圍內，且結晶性二氧化矽含有率在0質量%以上且未達2.1質量%之範圍內的特定無機填充材(以下亦稱為「高非晶質小粒徑無機填充材」)。本發明之樹脂組成物含有2種以上的特定無機填充材，較佳至少1種為二氧化矽。本發明之樹脂組成物，只要不損害本發明的期望效果，則可包含高非晶質小粒徑無機填充材以外的無機填充材，但較佳為不含高非晶質小粒徑無機填充材以外的無機填充材。The (B) inorganic filler contained in the resin composition of the present invention has an average particle diameter in the range of 0.5 μm to 12 μm, and a crystalline silica content in the range of 0% by mass to less than 2.1% by mass Specific inorganic fillers (hereinafter also referred to as "highly amorphous and small particle size inorganic fillers"). The resin composition of the present invention contains two or more specific inorganic fillers, preferably at least one of which is silica. The resin composition of the present invention may contain inorganic fillers other than highly amorphous and small particle size inorganic fillers as long as the desired effect of the present invention is not impaired, but preferably does not contain high amorphous and small particle size inorganic fillers Inorganic fillers other than materials.

高非晶質小粒徑無機填充材係如前述，其平均粒徑在0.5μm～12μm之範圍內。高非晶質小粒徑無機填充材由於這樣地平均粒徑小，故可提高樹脂組成物中的填充度。The highly amorphous and small particle size inorganic filler is as mentioned above, and its average particle size is in the range of 0.5 μm to 12 μm. The highly amorphous and small-particle-diameter inorganic filler has such a small average particle diameter that it can increase the degree of filling in the resin composition.

無機填充材的平均粒徑之下限，只要不妨礙本發明之期望的效果，則可設為超過0.5μm、0.6μm以上、0.7μm以上、0.8μm以上、0.9μm以上或1.0μm以上。又，只要不妨礙本發明之期望的效果，則無機填充材的平均粒徑之上限可設為未達12μm、10μm以下、8μm以下、6μm以下、5μm以下或4.5μm以下，從降低後述結晶性二氧化矽含有率之觀點來看，無機填充材的平均粒徑之上限較佳為10μm以下，更佳為未達10μm，尤佳為9μm以下，特佳為8μm以下。The lower limit of the average particle size of the inorganic filler may be greater than 0.5 μm, 0.6 μm or greater, 0.7 μm or greater, 0.8 μm or greater, 0.9 μm or greater, or 1.0 μm or greater unless the desired effect of the present invention is hindered. In addition, as long as the desired effect of the present invention is not hindered, the upper limit of the average particle size of the inorganic filler may be set to less than 12 μm, 10 μm or less, 8 μm or less, 6 μm or less, 5 μm or less, or 4.5 μm or less, in order to reduce the crystallinity described later. From the viewpoint of the silica content, the upper limit of the average particle diameter of the inorganic filler is preferably 10 μm or less, more preferably less than 10 μm, particularly preferably 9 μm or less, particularly preferably 8 μm or less.

(B)成分之平均粒徑可藉由以米氏(Mie)散射理論為基礎的雷射繞射･散射法進行測定。具體而言，可藉由雷射繞射散射式粒徑分布測定裝置，以體積基準作成無機填充材之粒徑分布，將其中值粒徑當作平均粒徑而測定。測定樣品係可使用在小瓶中秤取無機填充材100mg、甲基乙基酮10g，以超音波使其分散10分鐘者。對於測定樣品，使用雷射繞射式粒徑分布測定裝置，將使用的光源波長設為藍色及紅色，以流通池(flow cell)方式測定(B)無機填充材的體積基準之粒徑分布，從所得之粒徑分布，算出平均粒徑作為中值粒徑。作為雷射繞射式粒徑分布測定裝置，例如可舉出堀場製作所公司製「LA-960」等。(B) The average particle diameter of the component can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis with a laser diffraction scattering type particle size distribution measuring device, and the median particle size can be measured as the average particle size. As a measurement sample, 100 mg of inorganic filler and 10 g of methyl ethyl ketone were weighed into a vial and dispersed by ultrasonic waves for 10 minutes. For the measurement sample, use a laser diffraction particle size distribution measuring device, set the wavelength of the light source used to blue and red, and measure the volume-based particle size distribution of (B) inorganic fillers in a flow cell method , from the obtained particle size distribution, the average particle size was calculated as the median particle size. As a laser diffraction type particle size distribution measuring device, "LA-960" etc. by Horiba Manufacturing Co., Ltd. are mentioned, for example.

(B)無機填充材之比表面積較佳為1m 2/g以上，更佳為1.5m 2/g以上，尤佳為2m 2/g以上，特佳為2.5m 2/g以上。上限係沒有特別的限制，但較佳為60m 2/g以下、50m 2/g以下或40m 2/g以下。比表面積係依照BET法，使用比表面積測定裝置(MOUNTECH公司製Macsorb HM-1210)，使氮氣吸附於試料表面，使用BET多點法算出比表面積而得。 (B) The specific surface area of the inorganic filler is preferably at least 1 m 2 /g, more preferably at least 1.5 m 2 /g, particularly preferably at least 2 m 2 /g, particularly preferably at least 2.5 m 2 /g. The upper limit is not particularly limited, but is preferably 60 m 2 /g or less, 50 m 2 /g or less, or 40 m 2 /g or less. The specific surface area was obtained by using a specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH Co., Ltd.) according to the BET method, allowing nitrogen gas to be adsorbed on the surface of the sample, and calculating the specific surface area using the BET multipoint method.

高非晶質小粒徑無機填充材係如前述，其結晶性二氧化矽含有率在0質量%以上且未達2.1質量%之範圍內。高非晶質小粒徑無機填充材由於這樣地結晶性二氧化矽含有率低，故可達成本發明之期望的效果。而且，如由後述實施例之欄中的例證亦可明知，結晶性二氧化矽含有率愈低，較佳為超過檢測極限而愈接近檢測極限，有黏度壽命的安定性愈優異之傾向，故可更顯著地得到本發明之期望的效果。又，無機填充材之填充度愈高，通常有黏度壽命的安定性愈降低之傾向，但依據本發明，由於黏度壽命的安定性優異，故可比通常更提高無機填充材的填充度。The highly amorphous and small particle size inorganic filler is as described above, and its crystalline silica content is within the range of 0% by mass or more and less than 2.1% by mass. The highly amorphous and small-particle-diameter inorganic filler achieves the desired effect of the present invention because of its low content of crystalline silica. Also, as can be seen from the examples in the Examples described later, the lower the content of crystalline silica, preferably exceeding the detection limit and the closer to the detection limit, the more excellent the stability of the viscosity life tends to be. The desired effect of the present invention can be more remarkably obtained. Also, the higher the filling degree of the inorganic filler, the lower the stability of the viscosity life usually tends to be. However, according to the present invention, since the stability of the viscosity life is excellent, the filling degree of the inorganic filler can be increased more than usual.

從黏度壽命的安定性更優異之觀點來看，結晶性二氧化矽含有率較佳為2.0質量%以下、1.9質量%以下、1.8質量%以下、1.7質量%以下或1.6質量%以下，更佳為1.5質量%以下、1.4質量%以下、1.3質量%以下、1.2質量%以下、1.1質量%以下或1.0質量%以下，尤佳為0.9質量%以下、0.8質量%以下、0.7質量%以下、0.6質量%以下、0.5質量%以下、0.4質量%以下、0.3質量%以下、0.2質量%以下或0.1質量%以下。結晶性二氧化矽含有率特佳為檢測極限量以下，也可為0質量%。另一方面，從得到藉由結晶性二氧化矽之存在而達成的效果(例如填充性提升或相溶性提升)之觀點來看，結晶性二氧化矽含有率較佳為超過0質量%，更佳為0.01質量%以上，尤佳為0.02質量%以上，也可為0.03質量%以上、0.04質量%以上、0.05質量%以上、0.06質量%以上、0.07質量%以上或0.08質量%以上。因此，結晶性二氧化矽含有率在超0質量%且未達2.1質量%之範圍內者亦在某實施態樣中較宜。From the viewpoint of better stability of viscosity life, the content of crystalline silica is preferably at most 2.0 mass %, 1.9 mass % or less, 1.8 mass % or less, 1.7 mass % or less, or 1.6 mass % or less, more preferably 1.5% by mass or less, 1.4% by mass or less, 1.3% by mass or less, 1.2% by mass or less, 1.1% by mass or less, or 1.0% by mass or less, preferably 0.9% by mass or less, 0.8% by mass or less, 0.7% by mass or less, 0.6% by mass or less Mass % or less, 0.5 mass % or less, 0.4 mass % or less, 0.3 mass % or less, 0.2 mass % or less, or 0.1 mass % or less. The content of crystalline silica is particularly preferably not more than the detection limit, and may be 0% by mass. On the other hand, from the viewpoint of obtaining the effects achieved by the presence of crystalline silica (such as improvement of filling property or improvement of compatibility), the content of crystalline silica is preferably more than 0% by mass, and more preferably It is preferably at least 0.01% by mass, particularly preferably at least 0.02% by mass, and may be at least 0.03% by mass, at least 0.04% by mass, at least 0.05% by mass, at least 0.06% by mass, at least 0.07% by mass, or at least 0.08% by mass. Therefore, it is also preferable in a certain embodiment that the crystalline silica content rate is in the range of exceeding 0% by mass and less than 2.1% by mass.

結晶性二氧化矽含有率係根據X射線繞射測定所得之X射線繞射圖型而算出。X射線繞射測定可使用市售的X射線繞射分析裝置，例如RIGAKU公司製的X射線繞射裝置「SmartLab(註冊商標)」而實施。X射線繞射測定之條件只要能檢測出結晶性二氧化矽，則沒有限定，X射線源、輸出、繞射角之測定範圍、掃描速度等係被適宜設定。結晶性二氧化矽含有率較佳為以裏特沃爾德解析來算出X射線繞射圖型。X射線繞射圖型的裏特沃爾德解析較佳為使用附屬於X射線繞射分析裝置的專用軟體，例如附屬於上述RIGAKU公司製的X射線繞射裝置「SmartLab (註冊商標)」的定性解析程式PDXL。於如此的專用軟體中，存放與結晶性二氧化矽(通常為α-石英或方石英)及非晶質二氧化矽(非晶質二氧化矽)有關的資訊。依據裏特沃爾德解析，在即使結晶性二氧化矽之含量為0.01質量%也可算出結晶性二氧化矽含有率之點上較宜。The content rate of crystalline silica was calculated from the X-ray diffraction pattern obtained by X-ray diffraction measurement. The X-ray diffraction measurement can be performed using a commercially available X-ray diffraction analysis device, for example, an X-ray diffraction device "SmartLab (registered trademark)" manufactured by RIGAKU Corporation. The conditions of X-ray diffraction measurement are not limited as long as crystalline silica can be detected, and the X-ray source, output, measurement range of diffraction angle, scanning speed, etc. are appropriately set. It is preferable to calculate the X-ray diffraction pattern by Rietveld analysis as a content rate of crystalline silica. The Rietwald analysis of the X-ray diffraction pattern is preferably performed using dedicated software attached to the X-ray diffraction analysis device, for example, the X-ray diffraction device "SmartLab (registered trademark)" attached to the above-mentioned RIGAKU company. Qualitative analysis program PDXL. In such dedicated software, information related to crystalline silica (usually α-quartz or cristobalite) and amorphous silica (amorphous silica) is stored. According to Rietwald's analysis, even if the content of crystalline silica is 0.01% by mass, the content of crystalline silica can be calculated.

結晶性二氧化矽含有率亦可藉由上述方法以外的方法來算出。惟，藉由這樣的方法所算出的結晶性二氧化矽含有率之數值與以上述方法(較佳為裏特沃爾德解析)所算出的結晶性二氧化矽含有率之數值大不相同時，不應採用這樣的方法。舉出上述方法以外的方法之例，可從藉由X射線繞射測定所得之X射線繞射圖型，由結晶性二氧化矽的波峰強度與非晶質二氧化矽的波峰強度(積分值)算出結晶性二氧化矽含有率，結晶性二氧化矽含有率可將已知的高非晶質小粒徑無機填充材之X射線繞射圖型當作校正曲線，算出結晶性二氧化矽含有率為未知的無機填充材中之結晶性二氧化矽含有率。The content rate of crystalline silica can also be calculated by the method other than the said method. However, when the value of the crystalline silica content calculated by such a method is significantly different from the value of the crystalline silica content calculated by the above method (preferably Rietwald analysis) , this approach should not be used. As an example of methods other than the above-mentioned methods, from the X-ray diffraction pattern obtained by X-ray diffraction measurement, the peak intensity of crystalline silica and the peak intensity of amorphous silica (integrated value ) to calculate the content of crystalline silica. The content of crystalline silica can be calculated by using the X-ray diffraction pattern of known high amorphous and small particle size inorganic fillers as a calibration curve. The content rate is the content rate of crystalline silica in the inorganic filler whose content is unknown.

作為高非晶質小粒徑無機填充材，可使用後述實施例之欄中的製造例1～4記載之無機填充材A、B、C、D、E、F或彼等的改變物(例如變更表面處理劑的種類者、不進行表面處理者)。高非晶質小粒徑無機填充材之製造方法係沒有限定。高非晶質小粒徑無機填充材可使用結晶質的無機填充材例如結晶性二氧化矽(例如日本特開2015-211086號公報中揭示的結晶二氧化矽)作為其原料，例如藉由在500℃～1100℃、1～12小時之範圍內變更熔融法中的熔融步驟之加熱溫度及加熱時間而獲得，較佳為以所得之熔融二氧化矽的密度成為2.4g/cm 3以下之方式調整加熱溫度及加熱時間(參照日本發明專利第6814906號)。從得到結晶性二氧化矽含有率低的無機填充材之觀點來看，較佳為複數次(例如2次)進行熔融法中的熔融處理。又，高非晶質小粒徑無機填充材亦可使用非晶質二氧化矽等之不含結晶成分的非晶質無機填充材作為原料。 As the highly amorphous and small-particle-diameter inorganic filler, the inorganic fillers A, B, C, D, E, and F described in Production Examples 1 to 4 in the column of Examples described later or their modifications (such as Those who change the type of surface treatment agent, those who do not perform surface treatment). The manufacturing method of the highly amorphous and small particle size inorganic filler is not limited. Highly amorphous and small particle size inorganic fillers can use crystalline inorganic fillers such as crystalline silica (such as the crystalline silica disclosed in Japanese Patent Application Laid-Open No. 2015-211086) as its raw material, for example, by It is obtained by changing the heating temperature and heating time of the melting step in the melting method within the range of 500°C to 1100°C for 1 to 12 hours, preferably in such a way that the density of the obtained fused silica becomes 2.4 g/cm 3 or less Adjust the heating temperature and heating time (refer to Japanese Patent No. 6814906). From the viewpoint of obtaining an inorganic filler with a low crystalline silica content, it is preferable to perform the melting treatment in the melting method multiple times (for example, twice). In addition, as the highly amorphous and small-particle-diameter inorganic filler, an amorphous inorganic filler that does not contain a crystalline component such as amorphous silica can also be used as a raw material.

本發明者們之檢討結果，查明無機填充材為二氧化矽時，若進行複數次的熔融處理之實施，則有得到結晶性二氧化矽含有率低的二氧化矽(以下亦稱為「高非晶質小粒徑二氧化矽」)之傾向，但不取決於二氧化矽之種類。而且，所得之無機填充材中的結晶性二氧化矽含有率是否在上述範圍內係可藉由上述方法算出這樣的結晶性二氧化矽含有率而容易地確認，結晶性二氧化矽含有率不在上述範圍內時，只要增加熔融步驟的次數等而得到初期的結晶性二氧化矽含有率即可。As a result of the examination by the present inventors, it was found that when the inorganic filler is silica, if the implementation of the melting treatment is performed multiple times, silica with a low content of crystalline silica (hereinafter also referred to as "silica") may be obtained. High amorphous small particle size silica") tends to, but does not depend on the type of silica. In addition, whether or not the crystalline silica content in the obtained inorganic filler is within the above-mentioned range can be easily confirmed by calculating such a crystalline silica content by the above-mentioned method. If it is within the above range, the initial crystalline silica content may be obtained by increasing the number of times of the melting step or the like.

相對於樹脂組成物中的不揮發成分100質量%，高非晶質小粒徑無機填充材之量係沒有特別的限定，但從得到翹曲經抑制的硬化物之觀點來看，為30質量%以上，較佳為40質量%以上，更佳為50質量%以上，尤佳為超過50質量%，也可為60質量%以上、65質量%以上、70質量%以上、75質量%以上或80質量%以上。高非晶質小粒徑無機填充材之量係沒有特別的限定，但相對於樹脂組成物中的不揮發成分100質量%，可設為96質量%以下、95質量%以下、94質量%以下或93質量%以下。包含如此範圍之量的高非晶質小粒徑無機填充材之樹脂組成物的硬化物，係抑制翹曲之發生。又，包含如此範圍之量的高非晶質小粒徑無機填充材之樹脂組成物的硬化物，係可有效地減小熱膨脹係數。With respect to 100% by mass of the non-volatile components in the resin composition, the amount of the highly amorphous and small particle size inorganic filler is not particularly limited, but it is 30% by mass from the viewpoint of obtaining a cured product with warpage suppressed % or more, preferably more than 40% by mass, more preferably more than 50% by mass, especially more than 50% by mass, or more than 60% by mass, more than 65% by mass, more than 70% by mass, or more than 75% by mass, or More than 80% by mass. The amount of the highly amorphous and small-particle-diameter inorganic filler is not particularly limited, but it can be set to 96% by mass or less, 95% by mass or less, or 94% by mass or less with respect to 100% by mass of the non-volatile components in the resin composition Or 93% by mass or less. The cured product of the resin composition containing the highly amorphous and small particle size inorganic filler in such an amount suppresses the occurrence of warpage. Also, the cured product of the resin composition containing the highly amorphous and small particle size inorganic filler in such an amount can effectively reduce the coefficient of thermal expansion.

相對於樹脂組成物中的不揮發成分100體積%，高非晶質小粒徑無機填充材之量係沒有特別的限定，但從得到翹曲經抑制的硬化物之觀點來看，為50體積%以上，較佳為55體積%以上，更佳為60體積%以上，尤佳為超過65體積%，亦可為66體積%以上、67體積%以上或68體積%以上。從提高本發明之期望的效果之觀點來看，高非晶質小粒徑無機填充材之量，相對於樹脂組成物中的不揮發成分100體積%，可設為95體積%以下、90體積%以下、85體積%以下或83體積%以下。包含如此範圍之量的高非晶質小粒徑無機填充材之樹脂組成物的硬化物，係可有效地減小熱膨脹係數。With respect to 100% by volume of the non-volatile components in the resin composition, the amount of the highly amorphous and small particle size inorganic filler is not particularly limited, but from the viewpoint of obtaining a cured product with suppressed warpage, it is 50% by volume % or more, preferably more than 55% by volume, more preferably more than 60% by volume, especially more than 65% by volume, or more than 66% by volume, more than 67% by volume or more than 68% by volume. From the viewpoint of improving the desired effect of the present invention, the amount of the highly amorphous and small-particle-diameter inorganic filler can be set to 95% by volume or less, 90% by volume relative to 100% by volume of the non-volatile components in the resin composition. % or less, less than 85% by volume or less than 83% by volume. The cured product of the resin composition containing the high amorphous and small particle size inorganic filler in such an amount can effectively reduce the coefficient of thermal expansion.

[(C)硬化劑] 本發明之樹脂組成物較佳為含有(C)硬化劑。(C)硬化劑通常具有與(A)硬化性樹脂反應而將樹脂組成物硬化之功能。作為該(C)硬化劑，可舉出活性酯系硬化劑、酚系硬化劑、苯并㗁𠯤系硬化劑、酸酐系硬化劑、胺系硬化劑、氰酸酯系硬化劑等。其中，於一實施形態中，使用選自由酸酐系硬化劑、胺系硬化劑及酚系硬化劑所成之群組的至少1種作為(C)硬化劑。使用酸酐系硬化劑、胺系硬化劑或酚系硬化劑時，通常可抑制硬化物的翹曲。硬化劑可單獨使用1種類，也可組合2種類以上使用。 [(C) Hardener] The resin composition of the present invention preferably contains (C) a curing agent. (C) The curing agent generally has a function of reacting with the (A) curable resin to harden the resin composition. Examples of the (C) curing agent include active ester-based curing agents, phenol-based curing agents, benzophenone-based curing agents, acid anhydride-based curing agents, amine-based curing agents, cyanate-based curing agents, and the like. However, in one embodiment, at least one selected from the group consisting of acid anhydride-based curing agents, amine-based curing agents, and phenol-based curing agents is used as the (C) curing agent. When an acid anhydride-based hardener, amine-based hardener, or phenolic hardener is used, warping of the cured product is generally suppressed. A curing agent may be used alone or in combination of two or more.

作為(C)硬化劑，可使用由液狀硬化劑及固體狀硬化劑所選出的1種以上，較佳為使用液狀硬化劑。於一實施形態中，(C)硬化劑係由液狀硬化劑所構成。於其他實施形態中，(C)硬化劑係由固體狀硬化劑所構成。 所謂「液狀硬化劑」，就是指溫度20℃下液狀的硬化劑，所謂「固體狀硬化劑」，就是指溫度20℃下固體狀的硬化劑。 As the (C) curing agent, at least one selected from liquid curing agents and solid curing agents can be used, and it is preferable to use a liquid curing agent. In one embodiment, the (C) curing agent is composed of a liquid curing agent. In another embodiment, (C) curing agent consists of a solid curing agent. The term "liquid curing agent" refers to a liquid curing agent at a temperature of 20°C, and the so-called "solid curing agent" refers to a solid curing agent at a temperature of 20°C.

作為酸酐系硬化劑，例如可舉出在1分子內中具有1個以上酸酐基的硬化劑，較佳為在1分子內中具有2個以上酸酐基的硬化劑。作為酸酐系硬化劑，可舉出在1分子內中具有1個以上酸酐基的硬化劑。作為酸酐系硬化劑之具體例，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、4-甲基六氫鄰苯二甲酸酐、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、二苯基酮四羧酸二酐、聯苯基四羧酸二酐、萘四羧酸二酐、氧基二鄰苯二甲酸二酐、3,3’-4,4’-二苯基碸四羧酸二酐、1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二氧代-3-呋喃基)-萘并[1,2-C]呋喃-1,3-二酮、乙二醇雙(偏苯三酸酐)、苯乙烯與馬來酸共聚合成之苯乙烯・馬來酸樹脂等的聚合物型酸酐等。作為酸酐系硬化劑之市售品，例如可舉出新日本理化公司製之「HNA-100」、「MH-700」、「MTA-15」、「DDSA」。「OSA」；三菱化學公司製之「YH-306」、「YH-307」；日立化成公司製之「HN-2200」、「HN-5500」等。Examples of the acid anhydride curing agent include those having one or more acid anhydride groups in one molecule, preferably those having two or more acid anhydride groups in one molecule. Examples of the acid anhydride curing agent include those having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride hardeners include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydro Phthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-( 2,5-dioxotetrahydro-3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, diphenyl ketone tetracarboxylic acid di anhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyl tetracarboxylic 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(trimellitic anhydride), polymer anhydrides such as styrene-maleic acid resin produced by copolymerization of styrene and maleic acid, etc. Examples of commercially available acid anhydride curing agents include "HNA-100", "MH-700", "MTA-15" and "DDSA" manufactured by Nippon Chemical Co., Ltd. "OSA"; "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Corporation; "HN-2200" and "HN-5500" manufactured by Hitachi Chemical Co., Ltd., etc.

作為胺系硬化劑，例如可舉出在1分子內中具有1個以上、較佳2個以上的胺基之硬化劑。作為其具體例，可舉出脂肪族胺類、聚醚胺類、脂環式胺類、芳香族胺類等，其中較佳為芳香族胺類。胺系硬化劑較佳為一級胺或二級胺，更佳為一級胺。作為胺系硬化劑之具體例，可舉出4,4’-亞甲基雙(2,6-二甲基苯胺)、二苯基二胺基碸、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、間苯二甲基二胺、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。胺系硬化劑可使用市售品，例如可舉出SEIKA公司製「SEIKACURE-S」、日本化藥公司製之「KAYABOND C-200S」、「KAYABON DC-100」、「KAYAHARD A-A」、「KAYAHARD A-B」、「KAYAHARD A-S」、三菱化學公司製之「EPICURE W」、住友精化公司製「DTDA」等。Examples of the amine-based curing agent include those having one or more, preferably two or more, amine groups in one molecule. Specific examples thereof include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, among which aromatic amines are preferred. The amine-based hardener is preferably a primary amine or a secondary amine, more preferably a primary amine. Specific examples of amine-based hardeners include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminopyridine, 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenylene, 3,3'-diaminodiphenylene, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4 ,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl Benzene, 3,3'-dihydroxybenzidine, 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)pyridine, bis(4-(3-aminophenoxy)phenyl)pyridine, etc. Commercially available amine hardeners can be used, for example, "SEIKACURE-S" manufactured by SEIKA Corporation, "KAYABOND C-200S" manufactured by Nippon Kayaku Co., Ltd., "KAYABON DC-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S", "EPICURE W" manufactured by Mitsubishi Chemical Corporation, "DTDA" manufactured by Sumitomo Seika Co., Ltd., etc.

作為酚系硬化劑，可舉出在1分子中具有1個以上，較佳2個以上的鍵結於苯環、萘環等芳香環的羥基之硬化劑。其中，較佳為具有鍵結於苯環的羥基之化合物。又，從耐熱性及耐水性之觀點來看，較佳為具有酚醛清漆結構的酚系硬化劑。再者，從密著性之觀點來看，較佳為含氮酚系硬化劑，更佳為含有三𠯤骨架的酚系硬化劑。特別地，從高度滿足耐熱性、耐水性及密著性之觀點來看，較佳為含有三𠯤骨架的苯酚酚醛清漆硬化劑。Examples of the phenolic curing agent include those having one or more, preferably two or more, hydroxyl groups bonded to aromatic rings such as benzene rings and naphthalene rings in one molecule. Among them, a compound having a hydroxyl group bonded to a benzene ring is preferable. Also, from the viewpoint of heat resistance and water resistance, a phenolic hardener having a novolac structure is preferable. Furthermore, from the viewpoint of adhesiveness, a nitrogen-containing phenolic curing agent is preferred, and a phenolic curing agent containing a trioxane skeleton is more preferred. In particular, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesiveness, a phenol novolac hardener containing a three-skeleton skeleton is preferable.

作為酚系硬化劑之具體例，可舉出明和化成公司製的「MEH-7700」、「MEH-7810」、「MEH-7851」、「MEH-8000H」；日本化藥公司製的「NHN」、「CBN」、「GPH」；DIC公司製的「TD-2090」、「TD-2090-60M」、「LA-7052」、「LA-7054」、「LA-1356」、「LA-3018」、「LA-3018-50P」、「EXB-9500」、「HPC-9500」、「KA-1160」、「KA-1163」、「KA-1165」；群榮化學公司製的「GDP-6115L」、「GDP-6115H」、「ELPC75」；Sigma-Aldrich公司製的「2,2-二烯丙基雙酚A」等。Specific examples of phenolic curing agents include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd.; "NHN" manufactured by Nippon Kayaku Co., Ltd. , "CBN", "GPH"; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018" manufactured by DIC Corporation , "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165"; "GDP-6115L" manufactured by Qunyei Chemical Co., Ltd. , "GDP-6115H", "ELPC75"; "2,2-diallyl bisphenol A" manufactured by Sigma-Aldrich, etc.

(C)硬化劑的活性基當量較佳為50g/eq.～3000g/eq. ，更佳為100g/eq.～1000g/eq.，尤佳為100g/eq.～500g/eq.，特佳為100g/eq.～300g/eq.。活性基當量表示活性基每1當量的硬化劑之質量。(C) The active group equivalent weight of the hardener is preferably 50g/eq.～3000g/eq., more preferably 100g/eq.～1000g/eq., especially preferably 100g/eq.～500g/eq., especially preferred 100g/eq.～300g/eq. Active group equivalent means the mass of active group per 1 equivalent of hardener.

(C)硬化劑之量係其活性基數較佳為按照(A)硬化性樹脂的環氧基數而決定。例如，將(A)硬化性樹脂之環氧基數當作1時，(C)硬化劑之活性基數較佳為0.1以上，更佳為0.3以上，尤佳為0.5以上，且較佳為5.0以下，更佳為4.0以下，尤佳為3.0以下。此處，所謂「硬化性樹脂之環氧基數」，就是表示將樹脂組成物中存在之硬化性樹脂的不揮發成分之質量除以反應基當量而得之值全部合計後的值。又，所謂「(C)硬化劑之活性基數」，就是表示將樹脂組成物中存在之(C)硬化劑的不揮發成分之質量除以活性基當量而得之值全部合計後的值。(C) The amount of the curing agent is preferably determined according to the number of epoxy groups of (A) curable resin. For example, when the number of epoxy groups in (A) curable resin is taken as 1, the number of active groups in (C) curing agent is preferably 0.1 or more, more preferably 0.3 or more, especially preferably 0.5 or more, and more preferably 5.0 or less , more preferably less than 4.0, especially preferably less than 3.0. Here, the "number of epoxy groups in the curable resin" means the total of all the values obtained by dividing the mass of the non-volatile components of the curable resin present in the resin composition by the reactive group equivalent. In addition, "the active group number of (C) hardener" means the value obtained by dividing the mass of the non-volatile component of the (C) hardener present in the resin composition by the active group equivalent.

為了滿足上述(C)硬化劑之活性基數相對於(A)硬化性樹脂之反應基數的比值之範圍，(C)成分相對於(A)成分之質量比((A)：(C))較佳在1:0.01～1:10之範圍內。如此的質量比更佳為1:0.05～1:9之範圍內，尤佳為1:0.1～1:8之範圍內。In order to satisfy the above-mentioned range of the ratio of active radicals of (C) curing agent to reactive radicals of (A) curable resin, the mass ratio of (C) component to (A) component ((A):(C)) is relatively Preferably in the range of 1:0.01～1:10. Such a mass ratio is more preferably in the range of 1:0.05 to 1:9, especially preferably in the range of 1:0.1 to 1:8.

相對於樹脂組成物中的不揮發成分100質量%，(C)硬化劑之量較佳為0.05質量%以上，更佳為0.1質量%以上，特佳為0.2質量%以上，且較佳為25質量%以下，更佳為20質量%以下，尤佳為15質量%以下。The amount of the (C) curing agent is preferably at least 0.05% by mass, more preferably at least 0.1% by mass, particularly preferably at least 0.2% by mass, and more preferably 25% by mass relative to 100% by mass of the non-volatile components in the resin composition. Mass % or less, more preferably 20 mass % or less, especially preferably 15 mass % or less.

[(D)其他添加劑] 本發明之樹脂組成物可進一步含有(D)其他添加劑。作為其他添加劑之第1例，可舉出硬化促進劑、矽烷偶合劑、自由基聚合性化合物、自由基聚合起始劑、具有反應性官能基之含聚醚骨架的化合物、高分子量成分。 [(D) Other additives] The resin composition of the present invention may further contain (D) other additives. The first example of other additives includes hardening accelerators, silane coupling agents, radical polymerizable compounds, radical polymerization initiators, polyether skeleton-containing compounds having reactive functional groups, and high molecular weight components.

(硬化促進劑) 本發明之樹脂組成物可進一步包含硬化促進劑作為任意的成分。藉由硬化促進劑，可有效率地調整樹脂組成物之硬化時間。 (hardening accelerator) The resin composition of the present invention may further contain a curing accelerator as an optional component. The curing accelerator can effectively adjust the curing time of the resin composition.

作為硬化促進劑，例如可舉出磷系硬化促進劑、胺系硬化促進劑、咪唑系硬化促進劑、胍系硬化促進劑、金屬系硬化促進劑等。其中，較佳為咪唑系硬化促進劑。硬化促進劑可單獨使用1種類，也可組合2種類以上使用。Examples of the hardening accelerator include phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, and metal-based hardening accelerators. Among these, imidazole-based hardening accelerators are preferred. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

作為磷系硬化促進劑，例如可舉出三苯基膦、硼酸鏻化合物、四苯基鏻四苯基硼酸鹽、正丁基鏻四苯基硼酸鹽、四丁基鏻癸酸鹽、(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，較佳為三苯基膦、四丁基鏻癸酸鹽。Examples of phosphorus-based hardening accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4 -Methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., preferably triphenylphosphine, tetrabutylphosphonium decanoic acid Salt.

作為胺系硬化促進劑，例如可舉出三乙胺、三丁胺等之三烷基胺、4-二甲基胺基吡啶(DMAP)、苄基二甲基胺、2,4,6,-參(二甲基胺基甲基)苯酚、1,8-二氮雜雙環(5,4,0)-十一烯、1,8-二氮雜雙環[5,4,0]十一烯-7,4-二甲基胺基吡啶、2,4,6-參(二甲基胺基甲基)苯酚等，較佳為4-二甲基胺基吡啶、1,8-二氮雜雙環(5,4,0)-十一烯。Examples of amine-based hardening accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6, -Phenol(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, 1,8-diazabicyclo[5,4,0]undeca En-7,4-dimethylaminopyridine, 2,4,6-paraffin (dimethylaminomethyl)phenol, etc., preferably 4-dimethylaminopyridine, 1,8-diazo Heterobicyclo(5,4,0)-undecene.

作為咪唑系硬化促進劑，例如可舉出2-甲基咪唑、2-十一基咪唑、2-十七基咪唑、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-2-十一基咪唑鎓偏苯三酸酯、1-氰基乙基-2-苯基咪唑鎓偏苯三酸酯、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三𠯤、2,4-二胺基-6-[2’-十一基咪唑基-(1’)]-乙基-s-三𠯤、2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-s-三𠯤、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三𠯤異三聚氰酸加成物、2-苯基咪唑異三聚氰酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2,3-二氫-1H-吡咯并[1,2-a]苯并咪唑、1-十二基-2-甲基-3-苄基咪唑鎓氯化物、2-甲基咪唑啉、2-苯基咪唑啉等之咪唑化合物及咪唑化合物與環氧樹脂之加成物，較佳為2-乙基-4-甲基咪唑、1-苄基-2-苯基咪唑。Examples of imidazole-based hardening accelerators 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-2-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4 -Methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazole Onium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-trimethanium, 2,4-diamino-6- ( 1')]-Ethyl-s-trimethazolium, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-trimethazolium isocyanuric acid Adducts, 2-phenylimidazole isocyanuric acid adducts, 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-methylimidazoline, 2 -Imidazole compounds such as phenylimidazoline and adducts of imidazole compounds and epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

作為咪唑系硬化促進劑，可使用市售品，例如可舉出三菱化學公司製的「P200-H50」、四國化成工業公司製的「Curezol 2MZ」、「2E4MZ」、「Cl1Z」、「Cl1Z-CN」、「Cl1Z-CNS」、「Cl1Z-A」、「2MZ-OK」、「2MA-OK」、「2MA-OK-PW」、「2PHZ」等。As the imidazole-based hardening accelerator, commercially available products can be used, for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation, "Curezol 2MZ" manufactured by Shikoku Chemical Industry Co., Ltd., "2E4MZ", "Cl1Z", "Cl1Z -CN", "Cl1Z-CNS", "Cl1Z-A", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2PHZ", etc.

作為胍系硬化促進劑，例如可舉出氰胍、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，較佳為氰胍、1,5,7-三氮雜雙環[4.4.0]癸-5-烯。Examples of guanidine hardening accelerators include cyanoguanidine, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethyl Guanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1, 5,7-Triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1- Dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc., preferably cyanoguanidine, 1 ,5,7-Triazabicyclo[4.4.0]dec-5-ene.

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

相對於樹脂組成物中的不揮發成分100質量%，硬化促進劑之量係沒有特別的限定，但較佳為0.01質量%以上，更佳為0.05質量%以上，特佳為0.1質量%以上，且較佳為5質量%以下，更佳為4質量%以下，尤佳為3質量%以下。The amount of the hardening accelerator is not particularly limited relative to 100% by mass of the non-volatile components in the resin composition, but is preferably at least 0.01% by mass, more preferably at least 0.05% by mass, and most preferably at least 0.1% by mass. And preferably at most 5 mass %, more preferably at most 4 mass %, especially preferably at most 3 mass %.

(矽烷偶合劑) 本發明之樹脂組成物可進一步包含矽烷偶合劑作為任意的成分。惟，使用矽烷偶合劑作為無機填充材的表面處理劑時，經表面處理劑所處理的無機填充材係被分類為上述的(B)成分。藉由包含矽烷偶合劑作為任意的成分，可期待樹脂成分與無機填充材之鍵結。 (silane coupling agent) The resin composition of the present invention may further contain a silane coupling agent as an optional component. However, when a silane coupling agent is used as the surface treatment agent of the inorganic filler, the inorganic filler treated with the surface treatment agent is classified as the above-mentioned (B) component. By including a silane coupling agent as an optional component, the bond of a resin component and an inorganic filler can be expected.

作為矽烷偶合劑，例如可舉出胺基矽烷系偶合劑、環氧基矽烷系偶合劑、巰基矽烷系偶合劑、烷氧基矽烷化合物、有機矽氮烷化合物、鈦酸酯系偶合劑等。其中，較佳為含有環氧基的環氧基矽烷系偶合劑及含有巰基的巰基矽烷系偶合劑，特佳為環氧基矽烷系偶合劑。又，矽烷偶合劑可單獨使用1種類，也可組合2種類以上使用。於一實施形態中，作為任意的成分，包含單數種類的矽烷偶合劑。於其他實施形態中，作為任意的成分，包含複數種類，例如2種類的矽烷偶合劑。本發明之樹脂組成物較佳為包含複數種類的矽烷偶合劑，較佳為合併作為(B)成分的表面處理劑使用之矽烷偶合劑與作為該任意的成分使用的矽烷偶合劑，包含複數種類的矽烷偶合劑。Examples of the silane coupling agent include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanate coupling agents. Among them, epoxy silane coupling agents containing epoxy groups and mercapto silane coupling agents containing mercapto groups are preferred, and epoxy silane coupling agents are particularly preferred. Moreover, a silane coupling agent may be used individually by 1 type, and may use it in combination of 2 or more types. In one embodiment, a singular number of silane coupling agents is contained as an optional component. In another embodiment, plural types, for example, two types of silane coupling agents are included as optional components. The resin composition of the present invention preferably contains a plurality of types of silane coupling agents, preferably a combination of the silane coupling agent used as the surface treatment agent of component (B) and the silane coupling agent used as the optional component, including a plurality of types silane coupling agent.

作為矽烷偶合劑，例如可使用市售品。作為矽烷偶合劑的市售品，例如可舉出信越化學工業公司製「KBM403」(3-環氧丙氧基丙基三甲氧基矽烷)、信越化學工業公司製「KBM803」(3-巰基丙基三甲氧基矽烷)、信越化學工業公司製「KBE903」(3-胺基丙基三乙氧基矽烷)、信越化學工業公司製「KBM573」(N-苯基-3-胺基丙基三甲氧基矽烷)、信越化學工業公司製「SZ-31」(六甲基二矽氮烷)、信越化學工業公司製「KBM103」(苯基三甲氧基矽烷)、信越化學工業公司製「KBM-4803」(長鏈環氧型矽烷偶合劑)、信越化學工業公司製「KBM-7103」(3,3,3-三氟丙基三甲氧基矽烷)、信越化學工業公司製「KBM503」(3-甲基丙烯醯氧基丙基三甲氧基矽烷)、信越化學工業公司製「KBM5783」等。As a silane coupling agent, a commercial item can be used, for example. Examples of commercially available silane coupling agents include Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyl Trimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) oxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM- 4803” (long-chain epoxy silane coupling agent), “KBM-7103” (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM503” (3 -Methacryloxypropyltrimethoxysilane), "KBM5783" manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

相對於樹脂組成物中的不揮發成分100質量%，矽烷偶合劑之量為0質量%以上，較佳為0.01質量%以上、0.05質量%以上或0.1質量%以上，且較佳為10質量%以下、5質量%以下或3質量%以下。The amount of the silane coupling agent is 0% by mass or more, preferably 0.01% by mass or more, 0.05% by mass or more than 0.1% by mass, and more preferably 10% by mass relative to 100% by mass of the non-volatile components in the resin composition less than, 5% by mass or less than 3% by mass.

相對於樹脂組成物中的樹脂成分100質量%，矽烷偶合劑之量為0質量%以上，較佳為0.01質量%以上、0.1質量%以上或0.2質量%以上，且較佳為15質量%以下、10質量%以下或5質量%以下。The amount of the silane coupling agent is at least 0% by mass, preferably at least 0.01% by mass, at least 0.1% by mass, or at least 0.2% by mass relative to 100% by mass of the resin component in the resin composition, and is preferably at most 15% by mass , 10 mass % or less or 5 mass % or less.

(自由基聚合性化合物) 本發明之樹脂組成物可進一步包含自由基聚合性化合物任意的成分。可將自由基聚合性化合物分類為(A)成分。 (radical polymerizable compound) The resin composition of the present invention may further contain an optional component of a radical polymerizable compound. The radically polymerizable compound can be classified into (A) component.

作為自由基聚合性化合物，可使用具有乙烯性不飽和鍵的化合物。作為如此的自由基聚合性化合物，例如可舉出具有乙烯基、烯丙基、1-丁烯基、2-丁烯基、丙烯醯基、甲基丙烯醯基、富馬醯基、馬來醯基、乙烯基苯基、苯乙烯基、桂皮醯基及馬來醯亞胺基(2,5-二氫-2,5-二氧代-1H-吡咯-1-基)等之自由基聚合性基的化合物。自由基聚合性化合物可單獨使用1種類，也可組合2種類以上使用。As the radically polymerizable compound, a compound having an ethylenically unsaturated bond can be used. Examples of such radically polymerizable compounds include vinyl, allyl, 1-butenyl, 2-butenyl, acryl, methacryl, fumaryl, and maleyl , vinylphenyl, styryl, cinnamonyl and maleimide (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl) free radical polymerizability base compound. A radical polymerizable compound may be used individually by 1 type, and may use it in combination of 2 or more types.

作為自由基聚合性化合物之具體例，可舉出具有1個或2個以上丙烯醯基及/或甲基丙烯醯基的(甲基)丙烯酸系自由基聚合性化合物；具有直接鍵結於芳香族碳原子的1個或2個以上乙烯基的苯乙烯系自由基聚合性化合物；具有1個或2個以上烯丙基的烯丙基系自由基聚合性化合物；具有1個或2個以上馬來醯亞胺基的馬來醯亞胺系自由基聚合性化合物等。其中，較佳為(甲基)丙烯酸系自由基聚合性化合物。Specific examples of radical polymerizable compounds include (meth)acrylic radical polymerizable compounds having one or more acryl groups and/or methacryl groups; Styrenic radically polymerizable compounds with one or more vinyl groups of group carbon atoms; allyl-based radically polymerizable compounds with one or more allyl groups; with one or more allyl groups A maleimide-based radical polymerizable compound having a maleimide group, and the like. Among them, (meth)acrylic radical polymerizable compounds are preferable.

自由基聚合性化合物較佳為包含聚環氧烷結構。藉由使用包含聚環氧烷結構的自由基聚合性化合物，可提高樹脂組成物的硬化物之柔軟性。It is preferable that a radically polymerizable compound contains a polyalkylene oxide structure. By using a radically polymerizable compound containing a polyalkylene oxide structure, the flexibility of the cured product of the resin composition can be improved.

聚環氧烷結構可以式(1)：-(R f(O) n-表示。式(1)中，n通常表示2以上之整數。該整數n較佳為4以上，更佳為9以上，尤佳為11以上，且通常為101以下，較佳為90以下，更佳為68以下，尤佳為65以下。式(1)中，R f各自獨立地表示可具有取代基的伸烷基。前述伸烷基的碳原子數較佳為1以上，更佳為2以上，且較佳為6以下，更佳為5以下，尤佳為4以下，尤更佳為3以下，特佳為2。作為伸烷基可具有的取代基，例如可舉出鹵素原子、-OH、烷氧基、一級或二級胺基、芳基、-NH 2、-CN、-COOH、 -C(O)H、-NO 2等。惟，前述烷基較佳為不具有取代基。作為聚環氧烷結構之具體例，可舉出聚環氧乙烷結構、聚環氧丙烷結構、聚n-環氧丁烷結構、聚(環氧乙烷-co-環氧丙烷)結構、聚(環氧乙烷-ran-環氧丙烷)結構、聚(環氧乙烷-alt-環氧丙烷)結構及聚(環氧乙烷-block-環氧丙烷)結構。 The polyalkylene oxide structure can be represented by the formula (1): -(R f (O) n -. In the formula (1), n usually represents an integer of 2 or more. The integer n is preferably 4 or more, more preferably 9 or more , especially preferably 11 or more, and usually 101 or less, preferably 90 or less, more preferably 68 or less, especially preferably 65 or less. In formula (1), R f each independently represents an alkane that may have a substituent The number of carbon atoms in the aforementioned alkylene group is preferably 1 or more, more preferably 2 or more, and preferably 6 or less, more preferably 5 or less, especially preferably 4 or less, especially preferably 3 or less, especially preferably is 2. Examples of substituents that the alkylene group may have include halogen atoms, -OH, alkoxy groups, primary or secondary amino groups, aryl groups, -NH 2 , -CN, -COOH, -C( O) H, -NO 2 , etc. However, the above-mentioned alkyl group preferably has no substituent. As specific examples of the polyalkylene oxide structure, polyethylene oxide structure, polypropylene oxide structure, polyn -Butylene oxide structure, poly(ethylene oxide-co-propylene oxide) structure, poly(ethylene oxide-ran-propylene oxide) structure, poly(ethylene oxide-alt-propylene oxide) structure and poly(ethylene oxide-block-propylene oxide) structure.

自由基聚合性化合物係1分子中含有的聚環氧烷結構之數可為1，也可為2以上。自由基聚合性化合物係1分子中含有的聚環氧烷結構之數較佳為2以上，更佳為4以上，尤佳為9以上，特佳為11以上，且較佳為101以下，更佳為90以下，尤佳為68以下，特佳為65以下。自由基聚合性化合物係在1分子中含有2個以上聚環氧烷結構時，彼等之聚環氧烷結構可互相相同，也可相異。The number of polyalkylene oxide structures contained in 1 molecule of a radically polymerizable compound system may be 1, and may be 2 or more. The number of polyalkylene oxide structures contained in one molecule of the radically polymerizable compound is preferably 2 or more, more preferably 4 or more, especially preferably 9 or more, particularly preferably 11 or more, and preferably 101 or less, and more preferably The best is below 90, the best is below 68, and the best is below 65. When the radically polymerizable compound contains two or more polyalkylene oxide structures in one molecule, those polyalkylene oxide structures may be the same as or different from each other.

舉例包含聚環氧烷結構的自由基聚合性化合物之市售品之例，可舉出新中村化學工業公司製的單官能丙烯酸酯「AM-90G」、「AM-130G」、「AMP-20GY」；2官能丙烯酸酯「A-1000」、「A-B1206PE」、「A-BPE-20」、「A-BPE-30」；單官能甲基丙烯酸酯「M-20G」、「M-40G」、「M-90G」、「M-130G」、「M-230G」；以及，2官能甲基丙烯酸酯「23G」、「BPE-900」、「BPE-1300N」、「1206PE」。又，作為其他例，可舉出共榮公司化學公司製的「Light Ester BC」、「Light Ester 041MA」、「Light Acrylate EC-A」、「Light Acrylate EHDG-AT」；日立化成公司製的「FA-023M」；日油公司製的「Blemmer(註冊商標)PME-4000」、「Blemmer(註冊商標)50POEO-800B」、「Blemmer(註冊商標)PLE-200」、「Blemmer(註冊商標)PLE-1300」、「Blemmer(註冊商標)PSE-1300」、「Blemmer(註冊商標)43PAPE-600B」、「Blemmer(註冊商標)ANP-300」等。於一實施形態中，作為包含聚環氧烷結構的自由基聚合性化合物，可使用「M-130G」或「BPE-1300N」。Examples of commercially available radically polymerizable compounds containing a polyalkylene oxide structure include monofunctional acrylates "AM-90G", "AM-130G", and "AMP-20GY" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. "; bifunctional acrylate "A-1000", "A-B1206PE", "A-BPE-20", "A-BPE-30"; monofunctional methacrylate "M-20G", "M-40G ", "M-90G", "M-130G", "M-230G"; and, bifunctional methacrylate "23G", "BPE-900", "BPE-1300N", "1206PE". Also, as other examples, "Light Ester BC", "Light Ester 041MA", "Light Acrylate EC-A", "Light Acrylate EHDG-AT" manufactured by Kyoei Chemical Co., Ltd.; "Light Acrylate EHDG-AT" manufactured by Hitachi Chemical Co., Ltd. FA-023M"; "Blemmer (registered trademark) PME-4000", "Blemmer (registered trademark) 50POEO-800B", "Blemmer (registered trademark) PLE-200", "Blemmer (registered trademark) PLE -1300", "Blemmer (registered trademark) PSE-1300", "Blemmer (registered trademark) 43PAPE-600B", "Blemmer (registered trademark) ANP-300", etc. In one embodiment, "M-130G" or "BPE-1300N" can be used as a radically polymerizable compound containing a polyalkylene oxide structure.

自由基聚合性化合物之乙烯性不飽和鍵當量較佳為20g/eq.～3000g/eq.，更佳為50g/eq.～2500g/eq.，尤佳為70g/eq.～2000g/eq.，特佳為90g/eq.～1500g/eq.。乙烯性不飽和鍵當量表示乙烯性不飽和鍵每1當量的自由基聚合性化合物之質量。The ethylenically unsaturated bond equivalent of the radically polymerizable compound is preferably 20g/eq.～3000g/eq., more preferably 50g/eq.～2500g/eq., especially preferably 70g/eq.～2000g/eq. , especially 90g/eq.～1500g/eq. The ethylenically unsaturated bond equivalent represents the mass of the radical polymerizable compound per 1 equivalent of ethylenically unsaturated bond.

自由基聚合性化合物之重量平均分子量(Mw)較佳為150以上，更佳為250以上，尤佳為400以上，且較佳為40000以下，更佳為10000以下，尤佳為5000以下，特佳為3000以下。The weight average molecular weight (Mw) of the radically polymerizable compound is preferably at least 150, more preferably at least 250, particularly preferably at least 400, and preferably at most 40,000, more preferably at most 10,000, especially preferably at most 5,000, especially The best is below 3000.

相對於樹脂組成物中的不揮發成分100質量%，自由基聚合性化合物之量為0質量%以上，較佳為0.01質量%以上、0.05質量%以上或0.1質量%以上，且較佳為15質量%以下、10質量%以下或8質量%以下。With respect to 100% by mass of the non-volatile components in the resin composition, the amount of the radically polymerizable compound is 0% by mass or more, preferably 0.01% by mass or more, 0.05% by mass or more than 0.1% by mass, and preferably 15% by mass. Mass % or less, 10 mass % or less, or 8 mass % or less.

相對於樹脂組成物中的樹脂成分100質量%，自由基聚合性化合物之量為0質量%以上，較佳為0.01質量%以上、0.1質量%以上或0.2質量%以上，且較佳為25質量%以下、20質量%以下或15質量%以下。With respect to 100% by mass of the resin component in the resin composition, the amount of the radically polymerizable compound is 0% by mass or more, preferably 0.01% by mass or more, 0.1% by mass or more than 0.2% by mass, and preferably 25% by mass % or less, 20 mass % or less, or 15 mass % or less.

(自由基聚合起始劑) 本發明之樹脂組成物可進一步包含自由基聚合起始劑作為任意的成分。作為自由基聚合起始劑，較佳為在加熱時產生自由基的熱聚合起始劑。樹脂組成物包含自由基聚合性化合物時，通常該樹脂組成物包含自由基聚合起始劑。自由基聚合起始劑可單獨使用1種類，也可組合2種類以上使用。 (radical polymerization initiator) The resin composition of the present invention may further contain a radical polymerization initiator as an optional component. The radical polymerization initiator is preferably a thermal polymerization initiator that generates radicals when heated. When the resin composition contains a radical polymerizable compound, the resin composition usually contains a radical polymerization initiator. A radical polymerization initiator may be used individually by 1 type, and may use it in combination of 2 or more types.

作為自由基聚合起始劑，例如可舉出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。其中，較佳為過氧化物系自由基聚合起始劑。As a radical polymerization initiator, a peroxide type radical polymerization initiator, an azo type radical polymerization initiator, etc. are mentioned, for example. Among these, peroxide-based radical polymerization initiators are preferred.

作為過氧化物系自由基聚合起始劑，例如可舉出1,1,3,3-四甲基丁基氫過氧化物等之氫過氧化物化合物；第三丁基異丙苯基過氧化物、二第三丁基過氧化物、二第三己基過氧化物、二異丙苯基過氧化物、1,4-雙(1-第三丁基過氧-1-甲基乙基)苯、2,5-二甲基-2,5-雙(第三丁基過氧)己烷、2,5-二甲基-2,5-雙(第三丁基過氧)-3-己炔等之二烷基過氧化物化合物；二月桂醯基過氧化物、二癸醯基過氧化物、二環己基過氧二碳酸酯、雙(4-第三丁基環己基)過氧二碳酸酯等之二醯基過氧化物化合物；第三丁基過氧乙酸酯、第三丁基過氧苯甲酸酯、第三丁基過氧異丙基單碳酸酯、第三丁基過氧-2-乙基己酸酯、第三丁基過氧新癸酸酯、第三己基過氧異丙基單碳酸酯、第三丁基過氧月桂酸酯、(1,1-二甲基丙基)2-乙基過己酸酯、第三丁基2-乙基過己酸酯、第三丁基3,5,5-三甲基過己酸酯、第三丁基過氧-2-乙基己基單碳酸酯、第三丁基過氧馬來酸等之過氧酯化合物等。Examples of peroxide-based radical polymerization initiators include hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; tertiary butylcumyl peroxide; Oxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, dicumyl peroxide, 1,4-bis(1-tert-butylperoxy-1-methylethyl ) benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3 - dialkyl peroxide compounds of hexyne, etc.; Diacyl peroxide compounds such as oxydicarbonate; tertiary butyl peroxyacetate, tertiary butyl peroxybenzoate, tertiary butyl peroxyisopropyl monocarbonate, tertiary butyl peroxyisopropyl monocarbonate, Butylperoxy-2-ethylhexanoate, tert-butylperoxyneodecanoate, tert-hexylperoxyisopropyl monocarbonate, tert-butylperoxylaurate, (1,1 -Dimethylpropyl) 2-ethylperhexanoate, tert-butyl 2-ethylperhexanoate, tert-butyl 3,5,5-trimethylperhexanoate, tert-butyl Peroxyester compounds such as 2-ethylhexyl monocarbonate and tertiary butylperoxymaleic acid.

作為偶氮系自由基聚合起始劑，例如可舉出2,2’-偶氮雙(4-甲氧基-2,4-二甲基戊腈)、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2-甲基丁腈)、1,1’-偶氮雙(環己烷-1-碳腈)、1-[(1-氰基-1-甲基乙基)偶氮]甲醯胺、2-苯基偶氮-4-甲氧基-2,4-二甲基-戊腈等之偶氮腈化合物；2,2’-偶氮雙[2-甲基-N-[1,1-雙(羥基甲基)-2-羥基乙基]丙醯胺]、2,2’-偶氮雙[2-甲基-N-[1,1-雙(羥基甲基)乙基]丙醯胺]、2,2’-偶氮雙[2-甲基-N-[2-(1-羥基丁基)]-丙醯胺]、2,2’-偶氮雙[2-甲基-N-(2-羥基乙基)-丙醯胺]、2,2’-偶氮雙(2-甲基丙醯胺)二水合物、2,2’-偶氮雙[N-(2-丙烯基)-2-甲基丙醯胺]、2,2’-偶氮雙(N-丁基-2-甲基丙醯胺)、2,2’-偶氮雙(N-環己基-2-甲基丙醯胺)等之偶氮醯胺化合物；2,2’-偶氮雙(2,4,4-三甲基戊烷)、2,2’-偶氮雙(2-甲基丙烷)等之烷基偶氮化合物等。Examples of the azo radical polymerization initiator include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis( 2,4-Dimethylvaleronitrile), 2,2'-Azobisisobutyronitrile, 2,2'-Azobis(2-methylbutyronitrile), 1,1'-Azobis(cyclo Hexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, 2-phenylazo-4-methoxy-2,4-di Azonitrile compounds such as methyl-valeronitrile; 2,2'-Azobis[2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide] , 2,2'-Azobis[2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide], 2,2'-Azobis[2-methyl- N-[2-(1-hydroxybutyl)]-propionamide], 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2, 2'-Azobis(2-methylpropionamide) dihydrate, 2,2'-Azobis[N-(2-propenyl)-2-methylpropionamide], 2,2' -Azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide) and other azoamide compounds; 2 , 2'-Azobis(2,4,4-trimethylpentane), 2,2'-Azobis(2-methylpropane) and other alkyl azo compounds.

自由基聚合起始劑較佳為具有中溫活性。具體而言，自由基聚合起始劑係10小時半衰期溫度T10(℃)較佳在特定的低溫度範圍。前述10小時半衰期溫度T10較佳為50℃～110℃，更佳為50℃～100℃，尤佳為50℃～80℃。作為如此的自由基聚合起始劑之市售品，例如可舉出ARKEMA富士公司製「Luperox 531M80」、日油公司製「Perhexyl(註冊商標)O」及富士軟片和光純藥公司製「MAIB」。The radical polymerization initiator preferably has moderate temperature activity. Specifically, the 10-hour half-life temperature T10 (° C.) of the radical polymerization initiator is preferably in a specific low temperature range. The aforementioned 10-hour half-life temperature T10 is preferably from 50°C to 110°C, more preferably from 50°C to 100°C, especially preferably from 50°C to 80°C. Examples of such commercially available radical polymerization initiators include "Luperox 531M80" manufactured by ARKEMA Fuji Corporation, "Perhexyl (registered trademark) O" manufactured by NOF Corporation, and "MAIB" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. .

相對於樹脂組成物中的不揮發成分100質量%，自由基聚合起始劑之量係沒有特別的限定，但較佳為0.01質量%以上，更佳為0.02質量%以上，特佳為0.05質量%以上，且較佳為5質量%以下，更佳為2質量%以下，尤佳為1質量%以下。The amount of the radical polymerization initiator is not particularly limited relative to 100% by mass of the non-volatile components in the resin composition, but is preferably at least 0.01% by mass, more preferably at least 0.02% by mass, and most preferably at least 0.05% by mass % or more, and preferably less than 5% by mass, more preferably less than 2% by mass, especially preferably less than 1% by mass.

(具有反應性官能基之含聚醚骨架的化合物) 本發明之樹脂組成物可進一步包含具有反應性官能基之含聚醚骨架的化合物作為任意的成分。可將具有反應性官能基之含聚醚骨架的化合物分類為(A)成分。 (Compounds containing polyether skeleton with reactive functional groups) The resin composition of the present invention may further contain a polyether skeleton-containing compound having a reactive functional group as an optional component. The polyether skeleton-containing compound having a reactive functional group can be classified as the (A) component.

本發明之樹脂組成物可進一步包含具有反應性官能基之含聚醚骨架的化合物作為任意的成分。藉由具有反應性官能基之含聚醚骨架的化合物，可抑制樹脂組成物的硬化物之翹曲。具有反應性官能基之含聚醚骨架的化合物可單獨使用1種類，也可組合2種類以上使用。The resin composition of the present invention may further contain a polyether skeleton-containing compound having a reactive functional group as an optional component. The warpage of the cured product of the resin composition can be suppressed by the polyether skeleton-containing compound having a reactive functional group. The polyether skeleton-containing compound having a reactive functional group may be used alone or in combination of two or more.

具有反應性官能基之含聚醚骨架的化合物表示具有聚醚骨架的聚合物化合物。具有反應性官能基之含聚醚骨架的化合物所含有的聚醚骨架，較佳為以由環氧乙烷單元及環氧丙烷單元所選出的1種以上之單體單元所構成的聚氧化烯骨架。因此，具有反應性官能基之含聚醚骨架的化合物較佳為不包含環氧丁烷單元、苯醚單元等之包含碳數4以上的單體單元之聚醚骨架。又，具有反應性官能基之含聚醚骨架的化合物亦可含有羥基作為反應性官能基。The polyether skeleton-containing compound having a reactive functional group means a polymer compound having a polyether skeleton. The polyether skeleton contained in the polyether skeleton-containing compound having a reactive functional group is preferably a polyoxyalkylene composed of one or more monomer units selected from ethylene oxide units and propylene oxide units. skeleton. Therefore, the polyether skeleton-containing compound having a reactive functional group is preferably a polyether skeleton containing a monomer unit having 4 or more carbon atoms that does not contain a butylene oxide unit, a phenylene ether unit, or the like. Moreover, the polyether skeleton-containing compound which has a reactive functional group may contain a hydroxyl group as a reactive functional group.

具有反應性官能基之含聚醚骨架的化合物可含有聚矽氧骨架。作為聚矽氧骨架，例如可舉出聚二甲基矽氧烷骨架等之聚二烷基矽氧烷骨架；聚二苯基矽氧烷骨架等之聚二芳基矽氧烷骨架；聚甲基苯基矽氧烷骨架等之聚烷基芳基矽氧烷骨架；聚二甲基-二苯基矽氧烷骨架等之聚二烷基-二芳基矽氧烷骨架；聚二甲基-甲基苯基矽氧烷骨架等之聚二烷基-烷基芳基矽氧烷骨架；聚二苯基-甲基苯基矽氧烷骨架等之聚二芳基-烷基芳基矽氧烷骨架等，較佳為聚二烷基矽氧烷骨架，特佳為聚二甲基矽氧烷骨架。含有聚矽氧骨架之含聚醚骨架的化合物，例如可為聚氧化烯改質聚矽氧、烷基醚化聚氧化烯改質聚矽氧(聚醚骨架末端的至少一部分為烷氧基的聚氧化烯改質聚矽氧)等。The polyether skeleton-containing compound having a reactive functional group may contain a polysiloxane skeleton. Examples of the silicone skeleton include polydialkylsiloxane skeletons such as polydimethylsiloxane skeletons; polydiarylsiloxane skeletons such as polydiphenylsiloxane skeletons; polymethicone skeletons and the like; polyalkylarylsiloxane skeleton such as phenylsiloxane skeleton; polydialkyl-diarylsiloxane skeleton such as polydimethyl-diphenylsiloxane skeleton; polydimethyl -polydialkyl-alkylarylsiloxane skeleton such as methylphenylsiloxane skeleton; polydiaryl-alkylarylsiloxane skeleton such as polydiphenyl-methylphenylsiloxane skeleton Oxane skeleton etc., Preferably it is a polydialkylsiloxane skeleton, Especially preferably, it is a polydimethylsiloxane skeleton. Polyether-skeleton-containing compounds containing a polysiloxane skeleton, such as polyoxyalkylene-modified polysiloxane, alkyletherified polyoxyalkylene-modified polysiloxane (at least a part of the end of the polyether skeleton is an alkoxy group) Polyoxyalkylene modified polysiloxane), etc.

具有反應性官能基之含聚醚骨架的化合物可含有聚酯骨架。該聚酯骨架較佳為脂肪族聚酯骨架。脂肪族聚酯骨架所含有的烴鏈可為直鏈狀，也可為支鏈狀，較佳為支鏈狀。聚酯骨架所包含的碳原子數，例如可為4～16。聚酯骨架由於可源自多羧酸、內酯或彼等的酐而形成，故含有聚酯骨架的具有反應性官能基之含聚醚骨架的化合物，可在分子之末端具有羧基，但較佳為在分子之末端具有羥基作為反應性官能基。The polyether skeleton-containing compound having a reactive functional group may contain a polyester skeleton. The polyester backbone is preferably an aliphatic polyester backbone. The hydrocarbon chain contained in the aliphatic polyester skeleton may be linear or branched, preferably branched. The number of carbon atoms included in the polyester skeleton may be, for example, 4-16. Since the polyester skeleton can be formed from polycarboxylic acid, lactone or their anhydrides, the polyether skeleton-containing compound having a reactive functional group containing a polyester skeleton may have a carboxyl group at the end of the molecule, but is less It is preferable to have a hydroxyl group as a reactive functional group at the terminal of the molecule.

作為具有反應性官能基之含聚醚骨架的化合物，例如可舉出聚乙二醇、聚丙二醇、聚氧乙烯聚氧丙烯二醇等之直鏈型聚氧化烯二醇(直鏈型聚烷二醇)；聚氧乙烯甘油醚、聚氧丙烯甘油醚、聚氧乙烯聚氧丙烯甘油醚、聚氧乙烯三羥甲基丙烷醚、聚氧丙烯三羥甲基丙烷醚、聚氧乙烯聚氧丙烯三羥甲基丙烷醚、聚氧乙烯二甘油醚、聚氧丙烯二甘油醚、聚氧乙烯聚氧丙烯二甘油醚、聚氧乙烯季戊四醇醚、聚氧丙烯季戊四醇醚、聚氧乙烯聚氧丙烯季戊四醇醚、聚氧乙烯山梨糖醇、聚氧丙烯山梨糖醇、聚氧乙烯聚氧丙烯山梨糖醇等之多鏈型聚氧化烯二醇(多鏈型聚烷二醇)等之聚氧化烯二醇(聚烷二醇)；聚氧乙烯單烷基醚、聚氧乙烯二烷基醚、聚氧丙烯單烷基醚、聚氧丙烯二烷基醚、聚氧乙烯聚氧丙烯單烷基醚、聚氧乙烯聚氧丙烯二烷基醚等之聚氧化烯烷基醚；聚氧乙烯單酯、聚氧乙烯二酯、聚丙二醇單酯、聚丙二醇二酯、聚氧乙烯聚氧丙烯單酯、聚氧乙烯聚氧丙烯二酯等之聚氧化烯酯(包含乙酸酯、丙酸酯、丁酸酯、(甲基)丙烯酸酯等)；聚氧乙烯單酯、聚氧乙烯二酯、聚氧丙烯單酯、聚氧丙烯二酯、聚氧乙烯聚氧丙烯單酯、聚氧乙烯聚氧丙烯二酯、聚氧乙烯烷基醚酯、聚氧丙烯烷基醚酯、聚氧乙烯聚氧丙烯烷基醚酯等之聚氧化烯烷基醚酯(包含乙酸酯、丙酸酯、丁酸酯、(甲基)丙烯酸酯等)；聚氧乙烯烷基胺、聚氧丙烯烷基胺、聚氧乙烯聚氧丙烯烷基胺等之聚氧化烯烷基胺；聚氧乙烯烷基醯胺、聚氧丙烯烷基醯胺、聚氧乙烯聚氧丙烯烷基醯胺等之聚氧化烯烷基醯胺；聚氧乙烯二甲基矽氧烷、聚氧丙烯二甲基矽氧烷、聚氧乙烯聚氧丙烯二甲基矽氧烷、聚氧乙烯聚二甲基矽氧基烷基二甲基矽氧烷、聚氧丙烯聚二甲基矽氧基烷基二甲基矽氧烷、聚氧乙烯聚氧丙烯聚二甲基矽氧基烷基二甲基矽氧烷等之聚氧化烯改質聚矽氧；聚氧乙烯烷基醚二甲基矽氧烷、聚氧丙烯烷基醚二甲基矽氧烷、聚氧乙烯聚氧丙烯烷基醚二甲基矽氧烷、聚氧乙烯烷基醚聚二甲基矽氧基烷基二甲基矽氧烷、聚氧丙烯烷基醚聚二甲基矽氧基烷基二甲基矽氧烷、聚氧乙烯聚氧丙烯烷基醚聚二甲基矽氧基烷基二甲基矽氧烷等之烷基醚化聚氧化烯改質聚矽氧(聚醚骨架末端係至少一部分為烷氧基的聚氧化烯改質聚矽氧)等。Examples of polyether skeleton-containing compounds having reactive functional groups include linear polyoxyalkylene glycols (linear polyalkylene glycols) such as polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol. Diol); polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene glyceryl ether, polyoxyethylene trimethylolpropane ether, polyoxypropylene trimethylolpropane ether, polyoxyethylene polyoxyethylene Propylene trimethylol propane ether, polyoxyethylene diglyceryl ether, polyoxypropylene diglyceryl ether, polyoxyethylene polyoxypropylene diglyceryl ether, polyoxyethylene pentaerythritol ether, polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene Polyoxyalkylenes such as pentaerythritol ether, polyoxyethylene sorbitol, polyoxypropylene sorbitol, polyoxyethylene polyoxypropylene sorbitol, etc. Diol (polyalkylene glycol); polyoxyethylene monoalkyl ether, polyoxyethylene dialkyl ether, polyoxypropylene monoalkyl ether, polyoxypropylene dialkyl ether, polyoxyethylene polyoxypropylene monoalkyl Polyoxyalkylene alkyl ethers such as ethers, polyoxyethylene polyoxypropylene dialkyl ethers, etc.; polyoxyethylene monoesters, polyoxyethylene diesters, polypropylene glycol monoesters, polypropylene glycol diesters, polyoxyethylene polyoxypropylene monoesters Polyoxyalkylene esters of esters, polyoxyethylene polyoxypropylene diesters, etc. (including acetates, propionates, butyrates, (meth)acrylates, etc.); polyoxyethylene monoesters, polyoxyethylene diesters , polyoxypropylene monoester, polyoxypropylene diester, polyoxyethylene polyoxypropylene monoester, polyoxyethylene polyoxypropylene diester, polyoxyethylene alkyl ether ester, polyoxypropylene alkyl ether ester, polyoxyethylene Polyoxyalkylene alkyl ether esters such as polyoxypropylene alkyl ether esters (including acetates, propionates, butyrates, (meth)acrylates, etc.); polyoxyethylene alkylamines, polyoxypropylene alkane polyoxyalkylene alkylamines such as polyoxyethylene polyoxypropylene alkylamines; polyoxyethylene alkylamides, polyoxypropylene alkylamides, polyoxyethylene polyoxypropylene alkylamides, etc. Oxyalkylene Alkylamide; Polyoxyethylene Dimethicone, Polyoxypropylene Dimethicone, Polyoxyethylene Polyoxypropylene Dimethicone, Polyoxyethylene Dimethicone Alkyl Dimethicone, Polyoxypropylene Polydimethylsiloxyalkyl Dimethicone, Polyoxyethylene Polyoxypropylene Polydimethylsiloxyalkyl Dimethicone, etc. Polyoxyalkylene modified polysiloxane; polyoxyethylene alkyl ether dimethyl siloxane, polyoxypropylene alkyl ether dimethyl siloxane, polyoxyethylene polyoxypropylene alkyl ether dimethyl siloxane Alkane, polyoxyethylene alkyl ether polydimethylsiloxyalkyl dimethylsiloxane, polyoxypropylene alkyl ether polydimethylsiloxyalkyldimethylsiloxane, polyoxyethylene polydimethylsiloxane Alkyl etherified polyoxyalkylene modified polysiloxane such as oxypropylene alkyl ether polydimethylsiloxyalkyl dimethylsiloxane (polyoxyalkylene with at least a part of the end of the polyether skeleton being alkoxy) modified polysiloxane), etc.

具有反應性官能基之含聚醚骨架的化合物之數量平均分子量較佳為500～40000，更佳為500～20000，尤佳為500～10000。含聚醚骨架的化合物之重量平均分子量較佳為500～40000，更佳為500～20000，尤佳為500～10000。數量平均分子量及重量平均分子量可藉由凝膠滲透層析(GPC)法，作為聚苯乙烯換算之值測定。The number average molecular weight of the polyether skeleton-containing compound having a reactive functional group is preferably from 500 to 40,000, more preferably from 500 to 20,000, and especially preferably from 500 to 10,000. The weight average molecular weight of the polyether skeleton-containing compound is preferably from 500 to 40,000, more preferably from 500 to 20,000, and especially preferably from 500 to 10,000. The number average molecular weight and the weight average molecular weight can be measured as polystyrene conversion values by the gel permeation chromatography (GPC) method.

具有反應性官能基之含聚醚骨架的化合物較佳在25℃下為液狀。具有反應性官能基之含聚醚骨架的化合物在25℃下的黏度較佳為100000mPa･s以下，更佳為50000mPa･s以下，尤佳為30000mPa･s以下、10000mPa･s以下、5000mPa･s以下、4000mPa･s以下、3000mPa･s以下、2000mPa･s以下或1500mPa･s以下。具有反應性官能基之含聚醚骨架的化合物在25℃下的黏度之下限較佳為10mPa･s以上，更佳為20mPa･s以上，尤佳為30mPa･s以上、40mPa･s以上或50mPa･s以上。黏度可為藉由B型黏度計進行測定而得的黏度(mPa･s)。The polyether skeleton-containing compound having a reactive functional group is preferably liquid at 25°C. The viscosity of the polyether skeleton-containing compound having a reactive functional group at 25°C is preferably 100000mPa･s or less, more preferably 50000mPa･s or less, especially preferably 30000mPa･s or less, 10000mPa･s or less, 5000mPa･s or less Below, 4000mPa･s or less, 3000mPa･s or less, 2000mPa･s or less, or 1500mPa･s or less. The lower limit of the viscosity of the polyether skeleton-containing compound having a reactive functional group at 25°C is preferably at least 10mPa･s, more preferably at least 20mPa･s, especially preferably at least 30mPa･s, at least 40mPa･s, or 50mPa ･S or more. The viscosity may be a viscosity (mPa･s) measured by a B-type viscometer.

作為具有反應性官能基之含聚醚骨架的化合物之市售品，例如可舉出日油公司製的「Pronon #102」、「Pronon #104」、「Pronon #201」、「Pronon #202B」、「Pronon #204」、「Pronon #208」、「Unilub 70DP-600B」、「Unilub 70DP-950B」(聚氧乙烯聚氧丙烯二醇)；ADEKA公司製的「Pluronic(註冊商標)L-23」、「Pluronic L-31」、「Pluronic L-44」、「Pluronic L-61」、「Adeka Pluronic L-62」、「Pluronic L-64」、「Pluronic L-71」、「Pluronic L-72」、「Pluronic L-101」、「Pluronic L-121」、「Pluronic P-84」、「Pluronic P-85」、「Pluronic P-103」、「Pluronic F-68」、「Pluronic F-88」、「Pluronic F-108」、「Pluronic 25R-1」、「Pluronic 25R-2」、「Pluronic 17R-2」、「Pluronic 17R-3」、「Pluronic 17R-4」(聚氧乙烯聚氧丙烯二醇)；信越聚矽氧公司製的「KF-6011」、「KF-6011P」、「KF-6012」、「KF-6013」、「KF-6015」、「KF-6016」、「KF-6017」、「KF-6017P」、「KF-6043」、「KF-6004」、「KF351A」、「KF352A」、「KF353」、「KF354L」、「KF355A」、「KF615A」、「KF945」、「KF-640」、「KF-642」、「KF-643」、「KF-644」、「KF-6020」、「KF-6204」、「X22-4515」、「KF-6028」、「KF-6028P」、「KF-6038」、「KF-6048」、「KF-6025」(聚氧化烯改質聚矽氧)等。作為具有反應性官能基之含聚醚骨架的化合物，亦可使用藉由後述「聚酯多元醇A」之合成而合成的聚醚多元醇或其改良物。Examples of commercially available polyether skeleton-containing compounds having reactive functional groups include "Pronon #102", "Pronon #104", "Pronon #201", and "Pronon #202B" manufactured by NOF Corporation. , "Pronon #204", "Pronon #208", "Unilub 70DP-600B", "Unilub 70DP-950B" (polyoxyethylene polyoxypropylene glycol); "Pluronic (registered trademark) L-23" manufactured by ADEKA ", "Pluronic L-31", "Pluronic L-44", "Pluronic L-61", "Adeka Pluronic L-62", "Pluronic L-64", "Pluronic L-71", "Pluronic L-72 ", "Pluronic L-101", "Pluronic L-121", "Pluronic P-84", "Pluronic P-85", "Pluronic P-103", "Pluronic F-68", "Pluronic F-88" , "Pluronic F-108", "Pluronic 25R-1", "Pluronic 25R-2", "Pluronic 17R-2", "Pluronic 17R-3", "Pluronic 17R-4" (polyoxyethylene polyoxypropylene di Alcohol); "KF-6011", "KF-6011P", "KF-6012", "KF-6013", "KF-6015", "KF-6016", "KF-6017" manufactured by Shin-Etsu Silicone Co., Ltd. ", "KF-6017P", "KF-6043", "KF-6004", "KF351A", "KF352A", "KF353", "KF354L", "KF355A", "KF615A", "KF945", "KF -640", "KF-642", "KF-643", "KF-644", "KF-6020", "KF-6204", "X22-4515", "KF-6028", "KF-6028P ", "KF-6038", "KF-6048", "KF-6025" (polyoxyalkylene modified polysiloxane), etc. As the polyether skeleton-containing compound having a reactive functional group, a polyether polyol synthesized by synthesis of "polyester polyol A" described later or an improved product thereof can also be used.

相對於樹脂組成物中的不揮發成分100質量%，具有反應性官能基之含聚醚骨架的化合物之量為0質量%以上，較佳為0.01質量%以上、0.05質量%以上或0.1質量%以上，且較佳為15質量%以下、10質量%以下或8質量%以下，15質量%以下、10質量%以下或8質量%以下。The amount of the polyether skeleton-containing compound having a reactive functional group is 0% by mass or more, preferably 0.01% by mass or more, 0.05% by mass or 0.1% by mass relative to 100% by mass of the non-volatile components in the resin composition Above, and preferably 15% by mass or less, 10% by mass or less, or 8% by mass or less, 15% by mass or less, 10% by mass or less, or 8% by mass or less.

相對於樹脂組成物中的樹脂成分100質量%，具有反應性官能基之含聚醚骨架的化合物之量為0質量%以上，較佳為0.01質量%以上、0.1質量%以上或0.2質量%以上，且較佳為25質量%以下、20質量%以下或15質量%以下。The amount of the polyether skeleton-containing compound having a reactive functional group is 0% by mass or more, preferably 0.01% by mass or more, 0.1% by mass or more than 0.2% by mass relative to 100% by mass of the resin component in the resin composition , and preferably less than 25% by mass, less than 20% by mass or less than 15% by mass.

(高分子量成分) 本發明之樹脂組成物可包含高分子量成分。高分子量成分可發揮可塑劑的功能。作為高分子量成分之市售品，可舉出日本曹達公司製的丁二烯均聚物「B-1000」、「B-2000」、「B-3000」等。高分子量成分可單獨使用1種類，也可組合2種類以上使用。 (high molecular weight component) The resin composition of the present invention may contain high molecular weight components. High molecular weight components can function as plasticizers. As a commercial item of a high molecular weight component, the butadiene homopolymer "B-1000", "B-2000", "B-3000" etc. manufactured by Nippon Soda Co., Ltd. are mentioned. A high molecular weight component may be used individually by 1 type, and may use it in combination of 2 or more types.

高分子量成分之數量平均分子量較佳為500～40000，更佳為500～20000，尤佳為500～10000。高分子量成分之重量平均分子量較佳為500～40000，更佳為500～20000，尤佳為500～10000。數量平均分子量及重量平均分子量可藉由凝膠滲透層析(GPC)法，作為聚苯乙烯換算之值測定。The number average molecular weight of the high molecular weight component is preferably from 500 to 40,000, more preferably from 500 to 20,000, especially preferably from 500 to 10,000. The weight average molecular weight of the high molecular weight component is preferably from 500 to 40,000, more preferably from 500 to 20,000, especially preferably from 500 to 10,000. The number average molecular weight and the weight average molecular weight can be measured as polystyrene conversion values by the gel permeation chromatography (GPC) method.

高分子量成分在25℃為液狀，或者高分子量成分在45℃下的黏度較佳為100000mPa･s以下，更佳為50000mPa･s以下，尤佳為30000mPa･s以下、10000mPa･s以下、5000mPa･s以下、4000mPa･s以下、3000mPa･s以下、2000mPa･s以下、1500mPa･s以下或500mPa以下。具有反應性官能基之含聚醚骨架的化合物在25℃下的黏度之下限較佳為0.5mPa･s以上，更佳為1mPa･s以上，尤佳為2mPa･s以上、3mPa･s以上或4mPa･s以上。黏度可為藉由B型黏度計所測定而得的黏度(mPa･s)。The high molecular weight component is liquid at 25°C, or the viscosity of the high molecular weight component at 45°C is preferably 100000mPa･s or less, more preferably 50000mPa･s or less, especially preferably 30000mPa･s or less, 10000mPa･s or less, or 5000mPa ･s or less, 4000mPa･s or less, 3000mPa･s or less, 2000mPa･s or less, 1500mPa･s or less, or 500mPa or less. The lower limit of the viscosity of the polyether skeleton-containing compound having a reactive functional group at 25°C is preferably at least 0.5mPa･s, more preferably at least 1mPa･s, especially preferably at least 2mPa･s, or at least 3mPa･s, or 4mPa･s or more. The viscosity may be the viscosity (mPa･s) measured by a B-type viscometer.

相對於樹脂組成物中的不揮發成分100質量%，高分子量成分之量係沒有限定，但為0質量%以上，較佳為0.01質量%以上、0.05質量%以上或0.1質量%以上，且較佳為15質量%以下、10質量%以下或8質量%以下。With respect to 100% by mass of non-volatile components in the resin composition, the amount of high molecular weight components is not limited, but it is 0% by mass or more, preferably 0.01% by mass or more, 0.05% by mass or more than 0.1% by mass, and more Preferably, it is 15 mass % or less, 10 mass % or less, or 8 mass % or less.

相對於樹脂組成物中的樹脂成分100質量%，高分子量成分之量係沒有限定，但為0質量%以上，較佳為0.01質量%以上、0.1質量%以上或0.2質量%以上，且較佳為15質量%以下、10質量%以下或8質量%以下。With respect to 100% by mass of the resin component in the resin composition, the amount of the high molecular weight component is not limited, but it is 0% by mass or more, preferably 0.01% by mass or more, 0.1% by mass or more than 0.2% by mass, and more preferably 15% by mass or less, 10% by mass or less, or 8% by mass or less.

作為其他添加劑之第2例，例如可舉出橡膠粒子、聚醯胺微粒子、聚矽氧粒子等之有機填充材；聚碳酸酯樹脂、苯氧基樹脂、聚乙烯縮醛樹脂、聚烯烴樹脂、聚碸樹脂、聚酯樹脂等之熱塑性樹脂；碳二亞胺化合物；有機銅化合物、有機鋅化合物、有機鈷化合物等之有機金屬化合物；酞菁藍、酞菁綠、碘綠、重氮黃、結晶紫、氧化鈦、碳黑等之著色劑；氫醌、兒茶酚、焦棓酚、吩噻𠯤等之聚合抑制劑；矽氧系調平劑、丙烯酸聚合物系調平劑等之調平劑；本頓(benton)、蒙脫石等之增黏劑；矽氧系消泡劑、丙烯酸系消泡劑、氟系消泡劑、乙烯基樹脂系消泡劑等之消泡劑；苯并三唑系紫外線吸收劑等之紫外線吸收劑；脲矽烷等之接著性提升劑；三唑系密著性賦予劑、四唑系密著性賦予劑、三𠯤系密著性賦予劑等之密著性賦予劑；受阻酚系抗氧化劑、受阻胺系抗氧化劑等之抗氧化劑；二苯乙烯衍生物等之螢光增白劑；氟系界面活性劑等之界面活性劑；磷系難燃劑(例如磷酸酯化合物、磷腈化合物、膦酸化合物、紅磷)、氮系難燃劑(例如硫酸三聚氰胺)、鹵素系難燃劑、無機系難燃劑(例如三氧化銻)等之難燃劑等。添加劑可單獨使用1種，也可以任意之比率組合2種類以上使用。As a second example of other additives, for example, organic fillers such as rubber particles, polyamide particles, and silicone particles; polycarbonate resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, Thermoplastic resins such as polyester resins and polyester resins; carbodiimide compounds; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, Colorants for crystal violet, titanium oxide, carbon black, etc.; polymerization inhibitors for hydroquinone, catechol, pyrogallol, phenothioneol, etc.; silicone-based leveling agents, acrylic polymer-based leveling agents, etc. Leveling agent; viscosifier of benton, montmorillonite, etc.; defoamer of silicone-based defoamer, acrylic defoamer, fluorine-based defoamer, vinyl resin-based defoamer, etc.; UV absorbers such as benzotriazole-based UV absorbers; Adhesive enhancers such as urea-silane; Triazole-based adhesive agents, tetrazole-based adhesive agents, triazole-based adhesive agents, etc. Adhesive imparting agents; hindered phenolic antioxidants, hindered amine antioxidants, etc.; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants; Flame retardants (such as phosphoric acid ester compounds, phosphazene compounds, phosphonic acid compounds, red phosphorus), nitrogen-based flame retardants (such as melamine sulfate), halogen-based flame retardants, inorganic flame retardants (such as antimony trioxide), etc. flame retardant etc. One kind of additive may be used alone, or two or more kinds may be used in combination at an arbitrary ratio.

[溶劑] 本發明之樹脂組成物可進一步含有任意的溶劑作為揮發性成分。作為溶劑，例如可舉出有機溶劑。又，溶劑可單獨使用1種，也可以任意比率組合2種類以上而使用。於一實施形態中，溶劑係量愈少愈佳。溶劑之含量，於樹脂組成物中的不揮發成分100質量%時，作為揮發性成分，較佳為3質量%以下，更佳為1質量%以下，尤佳為0.5質量%以下，尤佳為0.1質量%以下，尤佳為0.01質量%以下，特佳為不含(0質量%)。於其他實施形態中，包含溶劑。藉此，可提高作為樹脂清漆的操作性。 [solvent] The resin composition of the present invention may further contain an optional solvent as a volatile component. As a solvent, an organic solvent is mentioned, for example. Moreover, a solvent may be used individually by 1 type, and may use it combining 2 or more types by arbitrary ratios. In one embodiment, the less the amount of solvent, the better. The content of the solvent is preferably 3% by mass or less, more preferably 1% by mass or less, particularly preferably 0.5% by mass or less, and most preferably 0.5% by mass or less as a volatile component when the non-volatile components in the resin composition are 100% by mass. 0.1% by mass or less, preferably 0.01% by mass or less, particularly preferably not containing (0% by mass). In other embodiments, a solvent is included. Thereby, the handleability as a resin varnish can be improved.

[樹脂組成物之製造方法] 本發明之樹脂組成物例如可藉由混合上述成分而製造。上述成分係可同時混合一部分或全部，也可依順序混合。於混合各成分的過程中，可適宜設定溫度，因此，可一時地或始終地加熱及/或冷卻。又，於混合各成分的過程中，可進行攪拌或振盪。 [Manufacturing method of resin composition] The resin composition of this invention can be manufactured by mixing the above-mentioned components, for example. A part or all of the above-mentioned components may be mixed at the same time, or may be mixed sequentially. In the process of mixing the components, the temperature can be set appropriately, so heating and/or cooling can be done temporarily or constantly. Moreover, stirring or shaking may be performed in the process of mixing each component.

[樹脂組成物之特性] 本發明之樹脂組成物係於含有(A)硬化性樹脂與(B)無機填充材之樹脂組成物中，(B)無機填充材之平均粒徑在0.5μm～12μm之範圍內，無機填充材中的結晶性二氧化矽含有率在0質量%以上且未達2.1質量%之範圍內的樹脂組成物。藉此，本發明達成能提供黏度壽命安定的樹脂組成物；使用該樹脂組成物之樹脂薄片、電路基板及半導體晶片封裝之效果。本案發明係如於後述實施例之欄中所例證，於將無機填充材之平均粒徑縮小至小的範圍之情況中，查明結晶性二氧化矽之存在不損害黏度壽命的安定性，因此以應限制其上限的知識見解為基礎而完成者。 [Characteristics of resin composition] The resin composition of the present invention is a resin composition containing (A) curable resin and (B) inorganic filler, (B) the average particle size of the inorganic filler is in the range of 0.5 μm to 12 μm, and the inorganic filler A resin composition in which the content of crystalline silica is in the range of 0% by mass to less than 2.1% by mass. Thereby, the present invention achieves the effect of being able to provide a resin composition with a stable viscosity life; a resin sheet, a circuit substrate, and a semiconductor chip package using the resin composition. In the present invention, as exemplified in the column of Examples described later, in the case of reducing the average particle size of the inorganic filler to a small range, it was found that the presence of crystalline silica does not impair the stability of the viscosity life, so Those done on the basis of intellectual insights that should limit their upper limit.

本發明之樹脂組成物之黏度壽命的安定性，例如可藉由後述實施例之欄中記載之方法進行評價。具體而言，測定初期熔融黏度MV0及12小時後熔融黏度MV12，求出隨著12小時經過的增黏比作為12小時後熔融黏度MV12相對於初期熔融黏度MV0之比值(亦即，MV12/MV0)時，本發明之樹脂組成物的增黏比較佳為未達1.7，更佳為1.6以下，尤佳為1.5以下，特佳為1.4以下，通常超過1.0。The stability of the viscosity life of the resin composition of the present invention can be evaluated, for example, by the method described in the column of Examples described later. Specifically, the initial melt viscosity MV0 and the melt viscosity MV12 after 12 hours were measured, and the viscosity increase ratio as 12 hours passed was obtained as the ratio of the melt viscosity MV12 after 12 hours to the initial melt viscosity MV0 (that is, MV12/MV0 ), the thickening ratio of the resin composition of the present invention is preferably less than 1.7, more preferably less than 1.6, especially preferably less than 1.5, particularly preferably less than 1.4, and usually more than 1.0.

此時，本發明之一實施形態的不含溶劑之樹脂組成物(樹脂糊)的初期熔融黏度MV0較佳在20泊～800泊之範圍內，更佳在20泊～700泊之範圍內，尤佳在20泊～600泊之範圍內。又，本發明之一實施形態的不含溶劑之樹脂組成物(樹脂糊)的12小時後熔融黏度MV12較佳在超過20泊～未達1360泊之範圍內，更佳在21泊～1190泊之範圍內，尤佳在21泊～1020泊之範圍內。再者，依據本發明之一實施形態的樹脂糊，由於可以高填充無機填充材，有能得到翹曲的發生經抑制之硬化物的傾向。翹曲量可藉由後述方法進行測定，例如翹曲量未達1500μm，較佳為未達1300μm，更佳為未達1100μm。At this time, the initial melt viscosity MVO of the solvent-free resin composition (resin paste) according to one embodiment of the present invention is preferably in the range of 20 poise to 800 poise, more preferably in the range of 20 poise to 700 poise, Preferably it is within the range of 20 poises to 600 poises. In addition, the melt viscosity MV12 after 12 hours of the solvent-free resin composition (resin paste) according to an embodiment of the present invention is preferably in the range of more than 20 poises to less than 1360 poises, more preferably 21 poises to 1190 poises In the range of 21 poises to 1020 poises is especially preferable. Furthermore, since the resin paste according to one embodiment of the present invention can be highly filled with an inorganic filler, there is a tendency to obtain a cured product in which the occurrence of warpage is suppressed. The amount of warpage can be measured by the method described later. For example, the amount of warpage is less than 1500 μm, preferably less than 1300 μm, more preferably less than 1100 μm.

又，本發明之其他實施形態的使用包含溶劑的樹脂組成物(樹脂清漆)所形成之樹脂組成物層的初期熔融黏度MV0較佳在20泊～20000泊之範圍內，更佳在1000泊～19000泊之範圍內，尤佳在2000泊～18000泊之範圍內。另外，本發明之其他實施形態的使用包含溶劑的樹脂組成物(樹脂清漆)所形成之樹脂組成物層的12小時後熔融黏度MV12較佳在超過20泊～未達34000泊之範圍內，更佳在1100泊～30000泊之範圍內，尤佳在2200泊～25000泊之範圍內。再者，依據本發明之一實施形態的樹脂清漆，由於可高填充無機填充材，有能得到翹曲的發生經抑制之硬化物的傾向。翹曲量可藉由後述之方法進行測定，例如翹曲量未達2000μm，較佳為未達1800μm，更佳為未達1600 μm。In addition, the initial melt viscosity MV0 of the resin composition layer formed by using the resin composition (resin varnish) containing a solvent in other embodiments of the present invention is preferably in the range of 20 poises to 20000 poises, more preferably in the range of 1000 poises to 20000 poises. Within the range of 19,000 poises, preferably within the range of 2,000 poises to 18,000 poises. In addition, the melt viscosity MV12 after 12 hours of the resin composition layer formed using the resin composition (resin varnish) containing a solvent in another embodiment of the present invention is preferably in the range of more than 20 poises to less than 34000 poises, and more Preferably within the range of 1100 poises to 30000 poises, especially preferably within the range of 2200 poises to 25000 poises. Furthermore, since the resin varnish according to one embodiment of the present invention can be highly filled with an inorganic filler, there is a tendency to obtain a cured product in which occurrence of warpage is suppressed. The amount of warpage can be measured by the method described later, for example, the amount of warpage is less than 2000 μm, preferably less than 1800 μm, more preferably less than 1600 μm.

於一實施形態中，本發明之樹脂組成物為糊狀。如此地糊狀的樹脂組成物(亦稱為「樹脂糊」)可容易地進行壓縮模塑的成型。於其他實施形態中，本發明之樹脂組成物為在薄片狀基材(例如後述的支撐體)上能形成樹脂組成物層之樹脂清漆。藉此，可提高操作性。無論是一實施形態之糊狀的樹脂組成物，還是其他實施形態的樹脂組成物(樹脂清漆)，如上述，由於增黏比小，故即使增大厚度，也組成的不均勻所致的流痕發生或黏度不均勻所致的埋入不良之發生被抑制等，可提供良率良好的電路基板及半導體晶片封裝。因此，本發明之樹脂組成物亦適用於形成厚度50μm以上的樹脂組成物層。又，本發明之樹脂組成物由於可以高填充無機填充材，故有能提供翹曲的發生經抑制之電路基板及半導體晶片封裝的傾向。In one embodiment, the resin composition of the present invention is in a paste form. Such a pasty resin composition (also referred to as "resin paste") can be easily formed by compression molding. In other embodiments, the resin composition of the present invention is a resin varnish capable of forming a resin composition layer on a sheet-shaped substrate (for example, a support described later). Thereby, operability can be improved. Regardless of whether it is the paste-like resin composition of one embodiment or the resin composition (resin varnish) of another embodiment, as mentioned above, since the thickening ratio is small, even if the thickness is increased, the flow due to uneven composition It is possible to provide circuit boards and semiconductor chip packages with good yields by suppressing the occurrence of embedding defects caused by marks or uneven viscosity. Therefore, the resin composition of the present invention is also suitable for forming a resin composition layer having a thickness of 50 μm or more. Furthermore, since the resin composition of the present invention can be highly filled with an inorganic filler, it tends to provide a circuit board and a semiconductor chip package in which the occurrence of warpage is suppressed.

[樹脂組成物之用途] 本發明之樹脂組成物可適用作為用於密封有機EL裝置及半導體等之電子機器的樹脂組成物(密封用的樹脂組成物)，尤其可適用作為用於密封半導體的樹脂組成物(半導體密封用的樹脂組成物)，較佳可適用作為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)。又，樹脂組成物係在密封用途以外可用作為絕緣層用的絕緣用途之樹脂組成物。例如，前述樹脂組成物可適用作為用於形成半導體晶片封裝的絕緣層，例如再配線形成層的樹脂組成物(半導體晶片封裝的絕緣層用的樹脂組成物、再配線形成層用的樹脂組成物)及電路基板(包含印刷配線板)的絕緣層之樹脂組成物(電路基板的絕緣層用的樹脂組成物)。 [Applications of resin composition] The resin composition of the present invention can be suitably used as a resin composition (resin composition for sealing) for sealing electronic devices such as organic EL devices and semiconductors, especially as a resin composition for sealing semiconductors (resin composition for sealing semiconductors). resin composition) is preferably applicable as a resin composition for sealing a semiconductor wafer (resin composition for sealing a semiconductor wafer). Also, the resin composition is a resin composition for insulating use that can be used as an insulating layer other than sealing use. For example, the aforementioned resin composition can be suitably used as an insulating layer for forming a semiconductor chip package, such as a resin composition for rewiring forming layer (resin composition for insulating layer of semiconductor chip packaging, resin composition for rewiring forming layer ) and resin compositions for insulating layers of circuit boards (including printed wiring boards) (resin compositions for insulating layers of circuit boards).

本發明之樹脂組成物係如前述，可作為用於形成半導體晶片封裝的密封層或絕緣層之材料使用。作為半導體晶片封裝，例如可舉出FC-CSP、MIS-BGA封裝、ETS-BGA封裝、扇出型WLP(晶圓級封裝，Wafer Level Package)、扇入(Fan-in)型WLP、扇出型PLP(面板級封裝，Panel Level Package)、扇入型PLP。As mentioned above, the resin composition of the present invention can be used as a material for forming a sealing layer or an insulating layer of a semiconductor chip package. Examples of semiconductor chip packages include FC-CSP, MIS-BGA package, ETS-BGA package, fan-out WLP (Wafer Level Package), fan-in (Fan-in) WLP, fan-out Type PLP (Panel Level Package), fan-in PLP.

又，前述樹脂組成物可作為底部填充材使用，例如可作為在將半導體晶片連接至基板後所用之MUF(模塑底部填充，Molding Under Filling)的材料使用。In addition, the aforementioned resin composition can be used as an underfill material, for example, as a material for MUF (Molding Under Filling) used after connecting a semiconductor chip to a substrate.

再者，前述樹脂組成物可使用於樹脂薄片、預浸體等之薄片狀積層材料、阻焊劑、黏晶材、埋孔樹脂、零件埋入樹脂等採用樹脂組成物之廣泛用途。Furthermore, the above-mentioned resin composition can be used in a wide range of applications using resin compositions such as sheet-shaped laminate materials such as resin sheets and prepregs, solder resists, crystal bonding materials, buried hole resins, and parts embedding resins.

[樹脂薄片] 本發明之一實施形態的樹脂薄片至少具有支撐體與設於該支撐體上的樹脂組成物層，視需要具有保護膜。樹脂組成物層為包含本發明之樹脂組成物的層。樹脂組成物層之厚度及使該樹脂組成物層硬化而得的硬化物層之厚度為任意。樹脂薄片例如可依照眾所周知的方法來製造，作為支撐體使用的材料亦任意地選定。 [Resin flakes] A resin sheet according to an embodiment of the present invention has at least a support, a resin composition layer provided on the support, and optionally a protective film. The resin composition layer is a layer containing the resin composition of the present invention. The thickness of the resin composition layer and the thickness of the cured product layer obtained by curing the resin composition layer are arbitrary. The resin sheet can be produced, for example, according to a known method, and the material used as the support is also selected arbitrarily.

樹脂薄片之用途係與前述本發明之樹脂組成物之用途同樣。作為使用能適用的電路基板之封裝之例，可舉出FC-CSP、MIS-BGA封裝、ETS-BGA封裝。作為能適用的半導體晶片封裝，例如可舉出扇出型WLP、扇入型WLP、扇出型PLP、扇入型PLP等。又，可將樹脂薄片使用於在將半導體晶片連接至基板後所用之MUF的材料。再者，樹脂薄片係可使用於要求高絕緣可靠性的其他廣泛之用途。The use of the resin sheet is the same as that of the aforementioned resin composition of the present invention. Examples of packages using applicable circuit boards include FC-CSP, MIS-BGA packages, and ETS-BGA packages. Examples of applicable semiconductor chip packages include fan-out WLP, fan-in WLP, fan-out PLP, fan-in PLP, and the like. Also, a resin sheet can be used as a material of MUF used after connecting a semiconductor chip to a substrate. Furthermore, the resin sheet can be used in a wide range of other applications requiring high insulation reliability.

[電路基板] 本發明之一實施形態的電路基板可包含本發明之樹脂組成物的硬化物。電路基板例如可依照眾所周知的方法來製造，作為基材及可形成於基材上的導體層使用之材料亦被任意地選定。 [circuit substrate] A circuit board according to an embodiment of the present invention may contain a cured product of the resin composition of the present invention. The circuit board can be manufactured by, for example, a well-known method, and the materials used as the base material and the conductive layer that can be formed on the base material are also selected arbitrarily.

於製造電路基板時，在準備基材後，於基材上，例如依照眾所周知之方法形成樹脂組成物層，例如包含本發明之樹脂組成物的樹脂組成物層。例如，樹脂組成物層之形成可藉由壓縮成型法進行。於壓縮成型法中，通常將基材及樹脂組成物配置於模具，在該模具內將壓力及視需要的熱施加於樹脂組成物，而在基材上形成樹脂組成物層。When manufacturing a circuit board, after preparing a substrate, a resin composition layer, such as a resin composition layer comprising the resin composition of the present invention, is formed on the substrate, for example, according to a well-known method. For example, the resin composition layer can be formed by compression molding. In the compression molding method, a base material and a resin composition are generally placed in a mold, and pressure and, if necessary, heat are applied to the resin composition in the mold to form a resin composition layer on the base material.

壓縮成型法之具體的操作例如可如下述。作為壓縮成型用之模具，準備上模及下模。又，在基材上塗佈樹脂組成物。將塗佈有樹脂組成物的基材安裝於下模。然後，閉合上模與下模，將熱及壓力施加於樹脂組成物，進行壓縮成型。The specific operation of the compression molding method can be as follows, for example. As a mold for compression molding, prepare an upper mold and a lower mold. Also, the resin composition is coated on the substrate. The substrate coated with the resin composition is mounted on the lower mold. Then, the upper mold and the lower mold are closed, heat and pressure are applied to the resin composition, and compression molding is performed.

另外，壓縮成型法之具體的操作例如可如下述。作為壓縮成型用之模具，準備上模及下模。將樹脂組成物載置於下模。另外，將基材及視需要的脫模薄膜安裝於上模。然後，以在下模所載置的樹脂組成物接觸在上模所安裝的基材之方式，閉合上模與下模，施予熱及壓力，進行壓縮成型。In addition, the specific operation of the compression molding method can be as follows, for example. As a mold for compression molding, prepare an upper mold and a lower mold. The resin composition is placed on the lower mold. In addition, a substrate and, if necessary, a release film are attached to the upper mold. Then, the upper mold and the lower mold are closed so that the resin composition placed on the lower mold contacts the base material attached to the upper mold, and heat and pressure are applied to perform compression molding.

成型條件係隨著本發明之樹脂組成物之組成而不同，可採用適當的條件而達成良好的密封。例如，成型時的模具之溫度較佳為70℃以上，更佳為80℃以上，特佳為90℃以上，且較佳為200℃以下。又，成型時施加的壓力較佳為1MPa以上，更佳為3MPa以上，特佳為5MPa以上，且較佳為50MPa以下，更佳為30MPa以下，特佳為20MPa以下。硬化時間較佳為1分鐘以上，更佳為2分鐘以上，特佳為3分鐘以上，且較佳為100分鐘以下，更佳為90分鐘以下，於一實施形態中，可設為60分鐘以下、30分鐘以下或20分鐘以下。通常，於樹脂組成物層之形成後，拆卸模具。模具之拆卸係可在樹脂組成物層之熱硬化前進行，也可在熱硬化後進行。Molding conditions vary with the composition of the resin composition of the present invention, and good sealing can be achieved by adopting appropriate conditions. For example, the temperature of the mold during molding is preferably 70°C or higher, more preferably 80°C or higher, particularly preferably 90°C or higher, and more preferably 200°C or lower. Also, the pressure applied during molding is preferably at least 1 MPa, more preferably at least 3 MPa, particularly preferably at least 5 MPa, and more preferably at most 50 MPa, more preferably at most 30 MPa, most preferably at most 20 MPa. The hardening time is preferably at least 1 minute, more preferably at least 2 minutes, particularly preferably at least 3 minutes, and is preferably at most 100 minutes, more preferably at most 90 minutes, and in one embodiment, it can be set at less than 60 minutes , less than 30 minutes or less than 20 minutes. Usually, the mold is disassembled after the resin composition layer is formed. The removal of the mold can be performed before or after the thermal curing of the resin composition layer.

在基材上形成樹脂組成物層後，將樹脂組成物層熱硬化(後硬化)，形成硬化物層。樹脂組成物層之熱硬化條件亦隨著樹脂組成物的種類而不同，但硬化溫度通常為120℃～240℃之範圍(較佳為150℃～220℃之範圍，更佳為170℃～200之範圍)，硬化時間為5分鐘～120分鐘之範圍(較佳為10分鐘～100分鐘之範圍，更佳為15分鐘～90分鐘之範圍)。After the resin composition layer is formed on the substrate, the resin composition layer is thermally cured (post-cured) to form a cured product layer. The thermal curing conditions of the resin composition layer also vary with the type of resin composition, but the curing temperature is usually in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably in the range of 170°C to 200°C range), the curing time is in the range of 5 minutes to 120 minutes (preferably in the range of 10 minutes to 100 minutes, more preferably in the range of 15 minutes to 90 minutes).

於使樹脂組成物層熱硬化之前，對於樹脂組成物層，可施予在比硬化溫度更低的溫度下加熱之預備加熱處理。例如，於使樹脂組成物層熱硬化之前，可通常在50℃以上且未達120℃(較佳為60℃以上110℃以下，更佳為70℃以上100℃以下)之溫度下，將樹脂組成物層通常預備加熱5分鐘以上(較佳為5分鐘～150分鐘，更佳為15分鐘～120分鐘)。Before thermosetting the resin composition layer, the resin composition layer may be subjected to a preliminary heat treatment of heating at a temperature lower than the curing temperature. For example, before thermally hardening the resin composition layer, the resin can be heated at a temperature of above 50°C and below 120°C (preferably above 60°C and below 110°C, more preferably above 70°C and below 100°C). The composition layer is usually preheated for at least 5 minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

如以上，可製造具有以本發明之樹脂組成物的硬化物所形成的硬化物層之電路基板。又，電路基板之製造方法可進一步包含任意的步驟。As described above, a circuit board having a cured product layer formed of a cured product of the resin composition of the present invention can be produced. Moreover, the manufacturing method of a circuit board may further include arbitrary steps.

[半導體晶片封裝] 本發明之一實施形態的半導體晶片封裝包含本發明之樹脂組成物的硬化物。作為該半導體晶片封裝，例如可舉出下述者。 [Semiconductor Chip Package] A semiconductor chip package according to an embodiment of the present invention includes a cured product of the resin composition of the present invention. As this semiconductor chip package, the following are mentioned, for example.

第一例之半導體晶片封裝包含上述電路基板與搭載於此電路基板的半導體晶片。此半導體晶片封裝可藉由將半導體晶片接合至電路基板而製造。The semiconductor chip package of the first example includes the above-mentioned circuit substrate and a semiconductor chip mounted on the circuit substrate. This semiconductor chip package can be manufactured by bonding a semiconductor chip to a circuit substrate.

電路基板與半導體晶片之接合條件可採用半導體晶片之端子電極與電路基板之電路配線可導體連接的任意條件。例如，可採用半導體晶片之覆晶晶片安裝中使用的條件。又，例如可於半導體晶片與電路基板之間，透過絕緣性的接著劑進行接合。As the bonding condition of the circuit board and the semiconductor chip, any condition can be adopted in which the terminal electrodes of the semiconductor chip and the circuit wiring of the circuit board can be electrically connected. For example, conditions used in flip-chip mounting of semiconductor wafers can be employed. Also, for example, the semiconductor chip and the circuit board can be bonded through an insulating adhesive.

作為接合方法之例，可舉出將半導體晶片壓接於電路基板之方法。作為壓接條件，壓接溫度通常為120℃～240℃之範圍(較佳為130℃～200℃之範圍，更佳為140℃～180℃之範圍)，壓接時間通常為1秒～60秒之範圍(較佳為5秒～30秒之範圍)。As an example of the bonding method, a method of pressure-bonding a semiconductor wafer to a circuit board is mentioned. As crimping conditions, the crimping temperature is usually in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, more preferably in the range of 140°C to 180°C), and the crimping time is usually in the range of 1 second to 60 The range of seconds (preferably the range of 5 seconds to 30 seconds).

又，作為接合方法的其他例，可舉出將半導體晶片回焊至電路基板而接合之方法。回焊條件可設為120℃～300℃之範圍。Moreover, as another example of a bonding method, the method of rebonding a semiconductor wafer to a circuit board and bonding is mentioned. The reflow condition can be set in the range of 120°C to 300°C.

將半導體晶片接合於電路基板後，可以模塑底部填充材填充半導體晶片。作為該模塑底部填充材，可使用上述樹脂組成物。因此，包含使本發明之樹脂組成物硬化之步驟。After the semiconductor wafer is bonded to the circuit substrate, the semiconductor wafer may be filled with an underfill by molding. As the mold underfill material, the resin composition described above can be used. Therefore, the step of hardening the resin composition of this invention is included.

第二例之半導體晶片封裝包含半導體晶片與密封此半導體晶片的本發明之樹脂組成物的硬化物。於如此的半導體晶片封裝中，通常本發明之樹脂組成物的硬化物發揮密封層之功能。作為第二例之半導體晶片封裝，例如可舉出扇出型WLP。The semiconductor chip package of the second example includes a semiconductor chip and a cured product of the resin composition of the present invention that seals the semiconductor chip. In such a semiconductor chip package, usually the cured product of the resin composition of the present invention functions as a sealing layer. As a second example of a semiconductor chip package, for example, a fan-out type WLP is mentioned.

圖1係示意地顯示作為本實施形態的半導體晶片封裝之一例的扇出型WLP的構成之剖面圖。作為扇出型WLP的半導體晶片封裝100，例如像圖1所示，具備：半導體晶片110；以覆蓋半導體晶片110的周圍之方式所形成的密封層120；在半導體晶片110之與密封層120相反側之面所設置的作為絕緣層的再配線形成層130；作為導體層的再配線層140；阻焊劑層150；及，凸塊160。FIG. 1 is a cross-sectional view schematically showing the structure of a fan-out WLP as an example of a semiconductor chip package according to this embodiment. A semiconductor chip package 100 as a fan-out type WLP, for example, as shown in FIG. 1 , has: a semiconductor chip 110; The rewiring formation layer 130 as an insulating layer, the rewiring layer 140 as a conductor layer, the solder resist layer 150 , and the bump 160 provided on the side surface.

如此的半導體晶片封裝之製造方法包含： (A)將暫時固定薄膜層合於基材之步驟， (B)將半導體晶片暫時固定於暫時固定薄膜上之步驟， (C)在半導體晶片上形成密封層步驟， (D)將基材及暫時固定薄膜從半導體晶片剝離之步驟， (E)於半導體晶片之剝離了基材及暫時固定薄膜之面上，形成再配線形成層之步驟， (F)於再配線形成層上，形成作為導體層的再配線層之步驟，以及 (G)於再配線層上形成阻焊劑層之步驟。 又，前述半導體晶片封裝之製造方法亦可包含： (H)將複數的半導體晶片封裝切割成各個半導體晶片封裝，進行單片化之步驟。 A method of manufacturing such a semiconductor chip package includes: (A) the step of laminating the temporary fixing film on the substrate, (B) The step of temporarily fixing the semiconductor wafer on the temporary fixing film, (C) a step of forming a sealing layer on the semiconductor wafer, (D) the step of peeling the base material and the temporary fixing film from the semiconductor wafer, (E) A step of forming a rewiring formation layer on the surface of the semiconductor wafer from which the base material and the temporarily fixed film are removed, (F) a step of forming a rewiring layer as a conductor layer on the rewiring forming layer, and (G) A step of forming a solder resist layer on the rewiring layer. Moreover, the manufacturing method of the aforementioned semiconductor chip package may also include: (H) A step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and performing singulation.

(步驟(A)) 步驟(A)為將暫時固定薄膜層合於基材之步驟。基材與暫時固定薄膜的層合條件可與電路基板之製造方法中的基材與樹脂薄片之層合條件同樣。 (step (A)) Step (A) is a step of laminating the temporary fixing film on the substrate. The lamination conditions of the base material and the temporary fixing film can be the same as the lamination conditions of the base material and the resin sheet in the manufacturing method of the circuit board.

作為基材，例如可舉出矽晶圓；玻璃晶圓；玻璃基板；銅、鈦、不鏽鋼、冷軋鋼板(SPCC)等之金屬基板；FR-4基板等之使環氧樹脂等滲入玻璃纖維並進行熱硬化處理的基板；BT樹脂等之由雙馬來醯亞胺三𠯤樹脂所成之基板等。Examples of base materials include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel plate (SPCC); Substrates that undergo thermal hardening treatment; substrates made of bismaleimide tri-maleimide resin such as BT resin, etc.

暫時固定薄膜可使用能從半導體晶片剝離，且能將半導體晶片暫時固定之任意的材料。作為市售品，可舉出日東電工公司製「Revalpha」等。Any material that can be peeled off from the semiconductor wafer and temporarily fix the semiconductor wafer can be used for the temporary fixing film. As a commercially available item, "Revalpha" manufactured by Nitto Denko Co., Ltd. and the like may be mentioned.

(步驟(B)) 步驟(B)為將半導體晶片暫時固定於暫時固定薄膜上之步驟。半導體晶片之暫時固定，例如可使用覆晶黏合機、黏晶機等之裝置來進行。半導體晶片之配置的佈局及配置數，可按照暫時固定薄膜之形狀、大小、目的之半導體晶片封裝之生產數等來適當地設定。例如，可使半導體晶片排列成複數行且複數列之矩陣狀，進行暫時固定。 (step (B)) Step (B) is a step of temporarily fixing the semiconductor wafer on the temporary fixing film. Temporary fixation of semiconductor wafers can be carried out using devices such as flip chip bonding machines and die bonding machines, for example. The layout and the number of placements of semiconductor chips can be appropriately set in accordance with the shape and size of the temporary fixing film, the number of production of the intended semiconductor chip package, and the like. For example, semiconductor wafers can be arranged in a matrix of plural rows and plural columns, and temporarily fixed.

(步驟(C)) 步驟(C)為在半導體晶片上形成密封層之步驟。密封層可藉由本發明之樹脂組成物的硬化物而形成。密封層通常以包含在導體晶片上形成樹脂組成物層之步驟，與使此樹脂組成物層熱硬化而形成作為密封層的硬化物層之步驟之方法來形成。樹脂組成物層在半導體晶片上之形成，例如除了使用半導體晶片代替基板以外，以與在前述[電路基板]所說明的在基板上形成樹脂組成物層之方法相同的方法來進行。 (step (C)) Step (C) is a step of forming a sealing layer on the semiconductor wafer. The sealing layer can be formed from a cured product of the resin composition of the present invention. The sealing layer is generally formed by a method including the steps of forming a resin composition layer on the conductor wafer, and thermally curing the resin composition layer to form a hardened layer as the sealing layer. Formation of the resin composition layer on the semiconductor wafer is carried out in the same manner as the method of forming the resin composition layer on the substrate described above in [Circuit Board], for example, except that a semiconductor wafer is used instead of the substrate.

在半導體晶片上形成樹脂組成物層後，使此樹脂組成物層熱硬化，可得到覆蓋半導體晶片的密封層。因此，包含使本發明之樹脂組成物硬化之步驟。藉此，進行藉由樹脂組成物的硬化物密封半導體晶片。樹脂組成物層之熱硬化條件，可採用與電路基板之製造方法中的樹脂組成物層之熱硬化條件相同的條件。再者，於使樹脂組成物層熱硬化之前，對於樹脂組成物層，可施予在比硬化溫度更低的溫度下加熱之預備加熱處理。此預備加熱處理之處理條件，可採用與電路基板之製造方法中的預備加熱處理相同的條件。After forming a resin composition layer on a semiconductor wafer, the resin composition layer is thermally cured to obtain a sealing layer covering the semiconductor wafer. Therefore, the step of hardening the resin composition of this invention is included. Thereby, sealing of the semiconductor wafer with the cured product of the resin composition is performed. The thermosetting conditions of the resin composition layer can be the same conditions as the thermosetting conditions of the resin composition layer in the production method of the circuit board. Furthermore, before thermally curing the resin composition layer, a preheating treatment of heating at a temperature lower than the curing temperature may be given to the resin composition layer. The treatment conditions of this preliminary heat treatment can be the same conditions as those of the preliminary heat treatment in the production method of the circuit board.

(步驟(D)) 步驟(D)為從半導體晶片剝離基材及暫時固定薄膜之步驟。剝離方法宜採用對應於暫時固定薄膜的材質之適當方法。作為剝離方法，例如可舉出使暫時固定薄膜加熱、發泡或膨脹而剝離之方法。又，作為剝離方法，例如可舉出通過基材將紫外線照射至暫時固定薄膜，使暫時固定薄膜的黏著力降低而剝離之方法。 (step (D)) The step (D) is a step of peeling the substrate from the semiconductor wafer and temporarily fixing the film. The method of peeling should adopt an appropriate method corresponding to the material of the temporarily fixed film. As a peeling method, the method of peeling off by heating, foaming, or expanding a temporarily fixed film is mentioned, for example. Moreover, as a peeling method, the method of peeling off by reducing the adhesive force of a temporarily fixed film by irradiating ultraviolet-ray to a temporarily fixed film through a base material is mentioned, for example.

於使暫時固定薄膜加熱、發泡或膨脹而剝離之方法中，加熱條件通常為100℃～250℃下1秒～90秒或5分鐘～15分鐘。又，於照射紫外線使暫時固定薄膜的黏著力降低而剝離之方法中，紫外線的照射量通常10mJ/cm 2～1000mJ/cm 2。 In the method of peeling off the temporarily fixed film by heating, foaming or expanding, the heating conditions are usually 100°C to 250°C for 1 second to 90 seconds or 5 minutes to 15 minutes. In addition, in the method of irradiating ultraviolet rays to lower the adhesive force of the temporarily fixed film and peel it off, the irradiation amount of ultraviolet rays is usually 10 mJ/cm 2 to 1000 mJ/cm 2 .

如前述，若將基材及暫時固定薄膜從半導體晶片剝離，則密封層之面露出。半導體晶片封裝之製造方法可包含研磨該露出的密封層之面。藉由研磨，可提高密封層的表面平滑性。作為研磨方法，可採用與在電路基板之製造方法所說明者相同的方法。As described above, when the base material and the temporary fixing film are peeled off from the semiconductor wafer, the surface of the sealing layer is exposed. The method of manufacturing a semiconductor chip package may include grinding the exposed surface of the sealing layer. By grinding, the surface smoothness of the sealing layer can be improved. As a polishing method, the same method as that described in the method of manufacturing a circuit board can be used.

(步驟(E)) 步驟(E)為於半導體晶片之剝離了基材及暫時固定薄膜之面上，形成作為絕緣層的再配線形成層之步驟。通常，此再配線形成層係形成在半導體晶片及密封層上。 (step (E)) The step (E) is a step of forming a rewiring forming layer as an insulating layer on the surface of the semiconductor wafer from which the base material and the temporarily fixed film have been peeled off. Usually, the redistribution forming layer is formed on the semiconductor wafer and the sealing layer.

再配線形成層之材料可使用具有絕緣性之任意的材料。藉由本發明之樹脂組成物的硬化物形成密封層時，在該密封層上所形成的再配線形成層可藉由感光性樹脂組成物來形成。Any material having insulating properties can be used as the material of the rewiring formation layer. When the sealing layer is formed from a cured product of the resin composition of the present invention, the rewiring formation layer formed on the sealing layer can be formed from a photosensitive resin composition.

形成再配線形成層後，為了將半導體晶片與再配線層進行層間連接，通常於再配線形成層中形成通孔。再配線形成層以感光性樹脂組成物形成時，通孔之形成方法通常包含通過遮罩將再配線形成層之表面進行曝光。作為活性能量線，例如可舉出紫外線、可見光線、電子線、X射線等，特佳為紫外線。作為曝光方法，例如可舉出使遮罩密著於再配線形成層而進行曝光之接觸曝光法、不使遮罩密著於再配線形成層而使用平行光線進行曝光之非接觸曝光法等。After the rewiring formation layer is formed, via holes are usually formed in the rewiring formation layer for interlayer connection between the semiconductor wafer and the rewiring layer. When the rewiring formation layer is formed with a photosensitive resin composition, the method of forming the through hole generally includes exposing the surface of the rewiring formation layer through a mask. Examples of active energy rays include ultraviolet rays, visible rays, electron beams, X-rays, and the like, particularly preferably ultraviolet rays. Examples of the exposure method include a contact exposure method of exposing with a mask attached to the rewiring formation layer, and a non-contact exposure method of exposing with parallel rays without a mask attached to the rewiring formation layer.

藉由前述曝光，由於可在再配線形成層中潛像，故其後藉由進行顯像，去除再配線形成層的一部分，可形成通孔作為貫穿再配線形成層的開口部分。顯像可進行濕式顯像、乾式顯像之任一者。作為顯像之方式，例如可舉出浸漬方式、覆液方式、噴霧方式、刷洗方式、刮刷方式等，從解析性之觀點來看，宜為覆液方式。By the above-mentioned exposure, since a latent image can be formed in the rewiring formation layer, a part of the rewiring formation layer can be removed by developing thereafter, and via holes can be formed as openings penetrating the rewiring formation layer. For the image development, either wet image development or dry image image may be performed. Examples of image development methods include immersion methods, liquid covering methods, spray methods, brushing methods, and wiper methods, and liquid covering methods are preferred from the viewpoint of resolution.

通孔之形狀係沒有特別的限定，但一般而言為圓形(略圓形)。通孔之頂徑例如為50μm以下、30μm以下、20μm以下、10μm以下。此處，所謂通孔之頂徑，就是指再配線形成層之表面的通孔之開口直徑。The shape of the through hole is not particularly limited, but generally it is circular (slightly circular). The top diameter of the through hole is, for example, 50 μm or less, 30 μm or less, 20 μm or less, or 10 μm or less. Here, the top diameter of the via hole refers to the opening diameter of the via hole on the surface of the rewiring formation layer.

(步驟(F)) 步驟(F)為於再配線形成層上，形成作為導體層的再配線層之步驟。於再配線形成層上形成再配線層之方法，可與電路基板之製造方法中的於硬化物層上形成導體層之方法相同。又，可重複進行步驟(E)及步驟(F)，交替堆疊(增建)再配線層及再配線形成層。 (step (F)) Step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring formation layer. The method of forming the rewiring layer on the rewiring formation layer may be the same as the method of forming the conductor layer on the hardened material layer in the method of manufacturing the circuit board. Also, step (E) and step (F) may be repeated to alternately stack (build up) the rewiring layer and the rewiring formation layer.

(步驟(G)) 步驟(G)為於再配線層上形成阻焊劑層之步驟。阻焊劑層之材料可使用具有絕緣性之任意的材料。其中，從半導體晶片封裝的製造容易度之觀點來看，較佳為感光性樹脂及熱硬化性樹脂。又，作為熱硬化性樹脂，可使用本發明之樹脂組成物。因此，可包含使本發明之樹脂組成物硬化之步驟。 (step (G)) Step (G) is a step of forming a solder resist layer on the rewiring layer. As the material of the solder resist layer, any material having insulating properties can be used. Among these, photosensitive resins and thermosetting resins are preferable from the viewpoint of the ease of manufacture of semiconductor chip packages. Moreover, the resin composition of this invention can be used as a thermosetting resin. Therefore, a step of hardening the resin composition of the present invention may be included.

又，於步驟(G)中，視需要可進行形成凸塊之凸塊加工。凸塊加工可藉由焊球、鍍焊料等之方法來進行。又，凸塊加工中的通孔之形成可與步驟(E)同樣地進行。In addition, in the step (G), if necessary, bump processing for forming bumps may be performed. Bumping can be done by means of solder balls, solder plating, and the like. Moreover, the formation of the via hole in bump processing can be performed similarly to step (E).

(步驟(H)) 半導體晶片封裝之製造方法係除了步驟(A)～(G)之外，還可包含步驟(H)。步驟(H)為將複數的半導體晶片封裝切割成各個半導體晶片封裝，進行單片化之步驟。將半導體晶片封裝切割成各個半導體晶片封裝之方法係沒有特別的限定。 (step (H)) The method for manufacturing a semiconductor chip package may further include step (H) in addition to steps (A) to (G). The step (H) is a step of cutting the plurality of semiconductor chip packages into individual semiconductor chip packages and performing singulation. The method of dicing the semiconductor chip package into individual semiconductor chip packages is not particularly limited.

作為第三例之半導體晶片封裝，可舉出於如圖1所示的一例之半導體晶片封裝100中，以本發明之樹脂組成物的硬化物形成再配線形成層130或阻焊劑層150而成之半導體晶片封裝。As a third example of the semiconductor chip package, in the semiconductor chip package 100 shown in FIG. Semiconductor chip packaging.

[半導體裝置] 半導體裝置具備半導體晶片封裝。作為半導體裝置，例如舉出供電氣製品(例如電腦、行動電話、智慧型手機、平板型裝置、可穿戴裝置、數位相機、醫療機器及電視等)及交通工具(例如機車、汽車、電車、船舶及航空機等)等之各種半導體裝置。 [實施例] [semiconductor device] The semiconductor device includes a semiconductor chip package. Examples of semiconductor devices include electrical products (such as computers, mobile phones, smart phones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions, etc.) and vehicles (such as motorcycles, automobiles, trains, ships, etc.) and aircraft, etc.) and other semiconductor devices. [Example]

以下，藉由實施例來具體地說明本發明。本發明不受此等實施例所限定。尚且，以下中，表示量的「份」及「%」，只要沒有另外明示，則分別意指「質量份」及「質量%」。尤其沒有溫度指定時的溫度條件及壓力條件為室溫(25℃)及大氣壓(1atm)。Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited by these examples. In addition, in the following, "parts" and "%" indicating amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. In particular, the temperature conditions and pressure conditions when no temperature is specified are room temperature (25° C.) and atmospheric pressure (1 atm).

首先，說明樹脂組成物。First, the resin composition will be described.

＜製造例1：無機填充材A之製造＞ 使用結晶性二氧化矽作為原料，將藉由實施2次的熔融法中的熔融步驟而得之高非晶質小粒徑二氧化矽B1，以信越化學工業公司製的表面處理劑「KBM573」(N-苯基-3-胺基丙基三甲氧基矽烷)進行表面處理而得到無機填充材A。 無機填充材A之平均粒徑為3.1μm，比表面積為5.1m 2/g。平均粒徑及比表面積係依照前述方法進行測定。 基於藉由X射線繞射測定所得之X射線繞射圖型，算出無機填充材A的結晶性二氧化矽含有率。為了X射線繞射測定，使用RIGAKU公司製的X射線繞射分析裝置「SmartLab(註冊商標)」。具體而言，作為結晶性二氧化矽含有率，採用由X射線繞射分析裝置(及附屬的定性解析程式PDXL)對於X射線繞射圖型進行裏特沃爾德解析而算出的結果所得之數值0.3%。 <Manufacturing Example 1: Manufacture of Inorganic Filler A> Using crystalline silica as a raw material, the highly amorphous and small-diameter silica B1 obtained by performing the melting step in the melting method twice was Inorganic filler A was obtained by surface treatment with surface treatment agent "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. The average particle diameter of the inorganic filler A was 3.1 μm, and the specific surface area was 5.1 m 2 /g. The average particle diameter and specific surface area are measured according to the aforementioned methods. Based on the X-ray diffraction pattern obtained by the X-ray diffraction measurement, the crystalline silica content of the inorganic filler A was calculated. For the X-ray diffraction measurement, an X-ray diffraction analyzer "SmartLab (registered trademark)" manufactured by RIGAKU Corporation was used. Specifically, as the content rate of crystalline silica, the result obtained by performing Rietwald analysis on the X-ray diffraction pattern by an X-ray diffraction analyzer (and the attached qualitative analysis program PDXL) is used. Value 0.3%.

＜製造例2、3：無機填充材B、C之製造＞ 使用結晶性二氧化矽作為原料，將藉由實施2次的熔融法中的熔融步驟而得之高非晶質小粒徑二氧化矽B2、藉由實施1次的熔融法中的熔融步驟而得之高非晶質小粒徑二氧化矽B3，各自與製造例1同樣地進行表面處理，得到無機填充材B、C。 無機填充材B之平均粒徑為10μm，比表面積為3.4m 2/g，結晶性二氧化矽含有率為0.3%。 無機填充材C之平均粒徑為9.8μm，比表面積為3.5m 2/g，結晶性二氧化矽含有率為0.09%。 <Production Examples 2 and 3: Production of Inorganic Fillers B and C> Using crystalline silica as a raw material, highly amorphous and small particle size silica obtained by performing the melting step in the melting method twice Silicon B2 and high amorphous small particle diameter silicon dioxide B3 obtained by carrying out the melting step in the melting method once were each subjected to surface treatment in the same manner as in Production Example 1 to obtain inorganic fillers B and C. The average particle diameter of the inorganic filler B was 10 μm, the specific surface area was 3.4 m 2 /g, and the content of crystalline silica was 0.3%. The inorganic filler C has an average particle diameter of 9.8 μm, a specific surface area of 3.5 m 2 /g, and a crystalline silica content of 0.09%.

＜製造例4：無機填充材D之製造＞ 使用非晶質二氧化矽作為原料，與製造例1同樣地藉由表面處理，得到無機填充材D。 無機填充材D之平均粒徑為3.2μm，比表面積為3.8m 2/g，結晶性二氧化矽含有率為檢測極限以下(檢測極限約0.01質量%)。 <Manufacture example 4: Manufacture of the inorganic filler D> Using amorphous silica as a raw material, it carried out surface treatment similarly to manufacture example 1, and obtained the inorganic filler D. Inorganic filler D has an average particle diameter of 3.2 μm, a specific surface area of 3.8 m 2 /g, and a content rate of crystalline silica below the detection limit (the detection limit is about 0.01% by mass).

＜製造例5、6：無機填充材E、F之製造＞ 使用結晶性二氧化矽作為原料，將藉由實施1次的熔融法中的熔融步驟而得之高非晶質小粒徑二氧化矽B4、藉由實施1次的熔融法中的熔融步驟而得之高非晶質小粒徑二氧化矽B5，各自與製造例1同樣地進行表面處理，得到無機填充材E、F。 無機填充材E之平均粒徑為3.4μm，比表面積為5.0m 2/g，結晶性二氧化矽含有率為2.1%。 無機填充材F之平均粒徑為9.5μm，比表面積為3.2m 2/g，結晶性二氧化矽含有率為5%。 <Production Examples 5 and 6: Production of Inorganic Fillers E and F> Using crystalline silica as a raw material, highly amorphous and small particle size silica obtained by performing one melting step in the melting method Silicon B4 and high amorphous small particle diameter silica B5 obtained by carrying out the melting step in the melting method once were each subjected to surface treatment in the same manner as in Production Example 1 to obtain inorganic fillers E and F. The average particle diameter of the inorganic filler E was 3.4 μm, the specific surface area was 5.0 m 2 /g, and the content of crystalline silica was 2.1%. The average particle diameter of the inorganic filler F was 9.5 μm, the specific surface area was 3.2 m 2 /g, and the content of crystalline silica was 5%.

＜實施例1-1＞ 使用混合器，均勻地分散作為(C)成分的硬化劑(新日本理化公司製的酸酐系硬化劑「MH-700」，酸酐基當量：164g/eq.)8份、作為(A)成分的環氧樹脂(日鐵化學&材料公司製的液狀環氧樹脂「ZX1059」，雙酚A型環氧樹脂與雙酚F型環氧樹脂之1：1混合品(質量比)，環氧當量：169g/eq.)2份、作為(A)成分的環氧樹脂(DAICEL公司製的脂環型環氧樹脂「Celloxide 2021P」，環氧當量：136g/eq.)2份、作為(A)成分的環氧樹脂(DIC公司製的萘型環氧樹脂「HP4032D」，環氧當量：143g/eq.)2份、作為(D)成分的硬化促進劑(四國化成工業公司製的咪唑系硬化促進劑「2MA-OK-PW」)0.4份、作為(A)成分的環氧樹脂(ADEKA公司製的環氧丙基胺型環氧樹脂「EP-3950L」，環氧當量：95g/eq.)2份、作為(A)成分的環氧樹脂(ADEKA公司製的二環戊二烯二甲醇型環氧樹脂「EP-4088S」，環氧當量：170g/eq.)2份、作為(D)成分的甲基丙烯酸酯(新中村化學工業公司製的具有甲基丙烯醯基與聚環氧乙烷結構的化合物「M-130G」)3份、作為(D)成分的自由基聚合起始劑(日油公司製「Perhexyl(註冊商標)O」，10小時半衰期溫度T10：69.9℃)0.1份、作為(B)成分的無機填充材A 110份、作為(D)成分的矽烷偶合劑(信越化學工業公司製「KBM403」(3-環氧丙氧基丙基三甲氧基矽烷))0.2份，調製糊狀的樹脂組成物(樹脂糊)。將樹脂糊全體當作100體積%時，無機填充材A之含量為71.7體積%。表1中顯示樹脂組成物糊中的無機填充材之含量。 所調製的樹脂糊係迅速地供後述初期熔融黏度MV0之測定。 <Example 1-1> Using a mixer, uniformly disperse 8 parts of the hardener (anhydride-based hardener "MH-700" manufactured by Shin Nippon Physical and Chemical Co., Ltd., acid anhydride group equivalent: 164g/eq.) as component (C), and 8 parts as component (A) Epoxy resin (liquid epoxy resin "ZX1059" manufactured by Nippon Steel Chemical & Materials Co., Ltd., a 1:1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent : 169g/eq.) 2 parts, epoxy resin (Alicyclic epoxy resin "Celloxide 2021P" manufactured by DAICEL Co., Ltd., epoxy equivalent: 136g/eq.) 2 parts as (A) component, as (A) 2 parts of epoxy resin (Naphthalene-type epoxy resin "HP4032D" manufactured by DIC Corporation, epoxy equivalent: 143g/eq.) Hardening accelerator "2MA-OK-PW") 0.4 parts, epoxy resin (glycidylamine type epoxy resin "EP-3950L" manufactured by ADEKA Co., Ltd.) as component (A), epoxy equivalent: 95g/eq .) 2 parts, epoxy resin (dicyclopentadiene dimethanol type epoxy resin "EP-4088S" manufactured by ADEKA company, epoxy equivalent: 170g/eq.) as (A) component 2 parts, as ( D) 3 parts of methacrylate (compound "M-130G" having a methacryl group and polyethylene oxide structure manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), radical polymerization as (D) component Primer ("Perhexyl (registered trademark) O" manufactured by NOF Corporation, 10-hour half-life temperature T10: 69.9°C) 0.1 part, 110 parts of inorganic filler A as component (B), silane coupling agent as component (D) ("KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.) 0.2 part, and the paste-like resin composition (resin paste) was prepared. The content of the inorganic filler A was 71.7% by volume when the entire resin paste was taken as 100% by volume. Table 1 shows the content of the inorganic filler in the resin composition paste. The prepared resin paste was quickly used for the measurement of the initial melt viscosity MVO described later.

＜實施例1-2＞ 於實施例1-1中，變更以下之事項。 關於(A)成分，代替分別摻合2份的環氧樹脂(「ZX1059」、「Celloxide 2021P」、「HP4032D、「EP-3950L」及「EP-4088S」)，改成摻合2份的環氧樹脂(「ZX1059」)、2份的環氧樹脂(「HP4032D」)、2份的環氧樹脂(Nagase ChemteX公司製的聚醚含有環氧樹脂「EX-992L」，環氧當量：680g/eq.)、2份的環氧樹脂(大阪瓦斯化學公司製的含有茀結構的環氧樹脂「EG-280」，環氧當量：460g/eq.)及2份的環氧樹脂(ADEKA公司製的環氧丙基胺型環氧樹脂「EP-3980S」，環氧當量：115g/eq.)。 關於(D)成分，代替摻合3份的甲基丙烯酸酯(「M-130G」)，改成摻合4份的甲基丙烯酸酯(新中村化學工業公司製的2官能甲基丙烯酸酯「M-230G」)。再者，將硬化促進劑(「2MA-OK-PW」)之摻合量從0.4份變更成0.5份。 上述事項以外，與實施例1-1同樣地，調製實施例1-2之樹脂糊。 <Example 1-2> In Example 1-1, the following matters were changed. Regarding component (A), instead of mixing 2 parts of epoxy resin (“ZX1059”, “Celloxide 2021P”, “HP4032D, “EP-3950L” and “EP-4088S”), mix 2 parts of epoxy resin Oxygen resin ("ZX1059"), 2 parts of epoxy resin ("HP4032D"), 2 parts of epoxy resin (polyether-containing epoxy resin "EX-992L" manufactured by Nagase ChemteX Co., Ltd., epoxy equivalent: 680g/ eq.), 2 parts of epoxy resin (Epoxy resin "EG-280" containing fennel structure produced by Osaka Gas Chemical Co., Ltd., epoxy equivalent: 460g/eq.) and 2 parts of epoxy resin (manufactured by ADEKA Co., Ltd. Glycidylamine type epoxy resin "EP-3980S", epoxy equivalent: 115g/eq.). For component (D), instead of blending 3 parts of methacrylate ("M-130G"), 4 parts of methacrylate (bifunctional methacrylate manufactured by Shin-Nakamura Chemical Co., Ltd. " M-230G"). Furthermore, the blending amount of the hardening accelerator ("2MA-OK-PW") was changed from 0.4 part to 0.5 part. Except for the above matters, the resin paste of Example 1-2 was prepared in the same manner as in Example 1-1.

＜實施例1-3＞ 於實施例1-1中，變更以下之事項。 關於(A)成分，將環氧樹脂(「ZX1059」、「Celloxide 2021P」、「HP4032D、「EP-3950L」及「EP-4088S」)之摻合量分別從2份各自變更成3份。 關於(C)成分，代替摻合8份的硬化劑(「MH-700」)，改成摻合3份的硬化劑(日本化藥公司製的胺系硬化劑「Kayahard A-A」(4,4’-二胺基-3,3’-二乙基二苯基甲烷))。 關於(D)成分，代替摻合0.4份的硬化促進劑(「2MA-OK-PW」)，改成摻合0.4份的硬化促進劑(四國化成公司製的咪唑系硬化促進劑「2E4MZ」)。 上述事項以外，與實施例1-1同樣地，調製實施例1-3之樹脂糊。 <Example 1-3> In Example 1-1, the following matters were changed. About (A) component, the compounding quantity of epoxy resin ("ZX1059", "Celloxide 2021P", "HP4032D, "EP-3950L", and "EP-4088S") was changed from 2 parts to 3 parts respectively. For component (C), instead of blending 8 parts of hardener (“MH-700”), 3 parts of hardener (amine-based hardener “Kayahard A-A” manufactured by Nippon Kayaku Co., Ltd. (4,4 '-diamino-3,3'-diethyldiphenylmethane)). For component (D), instead of blending 0.4 parts of hardening accelerator (“2MA-OK-PW”), 0.4 parts of hardening accelerator (imidazole-based hardening accelerator “2E4MZ” manufactured by Shikoku Chemicals Co., Ltd. ). Except for the above matters, the resin paste of Example 1-3 was prepared in the same manner as in Example 1-1.

＜實施例1-4＞ 於實施例1-1中，變更以下之事項。 關於(A)成分，代替分別摻合2份的環氧樹脂(「ZX1059」、「Celloxide 2021P」、「HP4032D、「EP-3950L」及「EP-4088S」)，改成摻合3份的環氧樹脂(「ZX1059」)、2份的環氧樹脂(「HP4032D」)及1份的環氧樹脂(日本曹達公司製的環氧化聚丁二烯樹脂「JP-100」)。 關於(B)成分，代替摻合110份的無機填充材A，改成摻合120份的無機填充材B。 關於(C)成分，將硬化劑(「MH-700」)之摻合量從8份變更成9份。 關於(D)成分，將矽烷偶合劑(「KBM403」)之摻合量從0.2份變更成0.1份。又，將硬化促進劑(「2MA-OK-PW」)之摻合量從0.4份變更成0.5份，不使用自由基聚合起始劑(「Perhexyl(註冊商標)O」)。 上述事項以外，與實施例1-1同樣地，調製實施例1-4之樹脂糊。 <Example 1-4> In Example 1-1, the following matters were changed. Regarding component (A), instead of blending 2 parts of epoxy resin ("ZX1059", "Celloxide 2021P", "HP4032D, "EP-3950L" and "EP-4088S"), mix 3 parts of epoxy resin epoxy resin ("ZX1059"), 2 parts of epoxy resin ("HP4032D"), and 1 part of epoxy resin (epoxidized polybutadiene resin "JP-100" manufactured by Nippon Soda Co., Ltd.). About (B) component, instead of mixing the inorganic filler A of 110 parts, it changed to mixing the inorganic filler B of 120 parts. Regarding component (C), the blending amount of the curing agent ("MH-700") was changed from 8 parts to 9 parts. About (D) component, the compounding quantity of a silane coupling agent ("KBM403") was changed from 0.2 part to 0.1 part. Also, the compounding amount of the curing accelerator ("2MA-OK-PW") was changed from 0.4 part to 0.5 part, and the radical polymerization initiator ("Perhexyl (registered trademark) O") was not used. Except for the above matters, the resin paste of Example 1-4 was prepared in the same manner as in Example 1-1.

＜實施例1-5＞ 於實施例1-4中，變更以下之事項。 關於(A)成分，代替摻合3份的環氧樹脂(「ZX1059」)、2份的環氧樹脂(「HP4032D」)及1份的環氧樹脂(「JP-100」)，改成摻合3份的環氧樹脂(「ZX1059」)、1份的環氧樹脂(「HP4032D」)及1份的環氧樹脂(「EG-280」)。 關於(D)成分，代替摻合0.1份的矽烷偶合劑(「KBM403」)，改成摻合0.1份的矽烷偶合劑(「KBM403」)及0.1份的矽烷偶合劑(信越化學工業公司製「KBM803」(3-巰基丙基三甲氧基矽烷)))。亦即，於實施例1-5中，摻合複數種類的矽烷偶合劑。 再者，摻合1份作為(D)成分的聚矽氧樹脂(信越聚矽氧公司製的聚氧化烯改質聚矽氧樹脂「KF-6012」，黏度(25℃)：1500mm 2/s)。 上述事項以外，與實施例1-4同樣地，調製實施例1-5之樹脂糊。 <Example 1-5> In Example 1-4, the following matters were changed. Regarding component (A), instead of blending 3 parts of epoxy resin ("ZX1059"), 2 parts of epoxy resin ("HP4032D"), and 1 part of epoxy resin ("JP-100"), Combine 3 parts of epoxy resin (“ZX1059”), 1 part of epoxy resin (“HP4032D”) and 1 part of epoxy resin (“EG-280”). For component (D), instead of blending 0.1 part of silane coupling agent ("KBM403"), 0.1 part of silane coupling agent ("KBM403") and 0.1 part of silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane))). That is, in Examples 1-5, several types of silane coupling agents were blended. Furthermore, 1 part of silicone resin (polyoxyalkylene-modified silicone resin "KF-6012" manufactured by Shin-Etsu Silicone Co., Ltd., viscosity (25°C): 1500 mm 2 /s) was blended as component (D) ). Except the above matters, the resin paste of Example 1-5 was prepared similarly to Example 1-4.

＜實施例1-6＞ 於實施例1-5中，關於(D)成分，代替摻合1份的聚矽氧樹脂(「KF-6012」)，改成摻合1份的聚氧乙烯聚氧丙烯二醇化合物(ADEKA公司製的聚氧乙烯聚氧丙烯二醇「L-64」)。 上述事項以外，與實施例1-5同樣地，調製實施例1-6之樹脂糊。 <Example 1-6> In Examples 1-5, regarding (D) component, instead of blending 1 part of polysiloxane resin (“KF-6012”), 1 part of polyoxyethylene polyoxypropylene glycol compound (ADEKA Polyoxyethylene polyoxypropylene glycol "L-64" manufactured by the company). Except the above matters, the resin paste of Example 1-6 was prepared similarly to Example 1-5.

＜實施例1-7＞ 於實施例1-5中，關於(A)成分，代替摻合3份的環氧樹脂(「ZX1059」)、1份的環氧樹脂(「HP4032D」)及1份的環氧樹脂(「EG-280」)，改成摻合3份的環氧樹脂(「ZX1059」)、1份的環氧樹脂(「HP4032D」)及2份的環氧樹脂(「EP-3950L」)。 又，於實施例1-5中，關於(D)成分，代替摻合1份的聚矽氧樹脂(「KF-6012」)，改成摻合1份的如下述所合成的聚酯多元醇A。 <Example 1-7> In Examples 1-5, regarding (A) component, instead of blending 3 parts of epoxy resin ("ZX1059"), 1 part of epoxy resin ("HP4032D") and 1 part of epoxy resin ("EG -280"), instead of blending 3 parts of epoxy resin ("ZX1059"), 1 part of epoxy resin ("HP4032D") and 2 parts of epoxy resin ("EP-3950L"). Also, in Examples 1-5, regarding component (D), instead of blending 1 part of silicone resin ("KF-6012"), 1 part of polyester polyol synthesized as follows was blended a.

-「聚酯多元醇A」之合成- 於反應容器中加入ε-己內酯單體(DAICEL公司製「Placcel M」)22.6g、聚丙二醇(富士軟片和光純藥公司製「聚丙二醇，二醇型，3,000」)10g、2-乙基己酸錫(II)(富士軟片和光純藥製)1.62g，於氮環境下升溫至130℃，攪拌約16小時而使其反應。將反應後的生成物溶於氯仿中，以甲醇使該生成物再沉澱後進行乾燥。藉此，作為「聚酯多元醇A」，得到具有脂肪族骨架，且羥基末端的聚酯多元醇。根據GPC分析，Mn=9000。 上述事項以外，與實施例1-5同樣地，調製實施例1-7之樹脂糊。 -Synthesis of "polyester polyol A"- 22.6 g of ε-caprolactone monomer ("Placcel M" manufactured by DAICEL Co., Ltd.), 10 g of polypropylene glycol ("Polypropylene glycol, diol type, 3,000" manufactured by Fujisoft Wako Pure Chemical Industries, Ltd.), 2-ethylene glycol were added to the reaction vessel. 1.62 g of tin(II) phenylhexanoate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was heated up to 130° C. under a nitrogen atmosphere, stirred for about 16 hours, and reacted. The product after the reaction was dissolved in chloroform, reprecipitated with methanol, and dried. Thereby, as "polyester polyol A", the polyester polyol which has an aliphatic frame|skeleton and terminated with a hydroxyl group was obtained. According to GPC analysis, Mn=9000. Except for the above matter, the resin paste of Example 1-7 was prepared similarly to Example 1-5.

＜實施例1-8＞ 於實施例1-3中，變更以下之事項。 關於(A)成分，代替分別摻合3份的環氧樹脂(「ZX1059」、「Celloxide 2021P」、「HP4032D、「EP-3950L」及「EP-4088S」)，改成摻合3份的環氧樹脂(「ZX1059」)、3份的環氧樹脂(「Celloxide 2021P」)、3份的環氧樹脂(「HP4032D」)、2份的環氧樹脂(「EP-3950L」)及1份的環氧樹脂(「EP-4088S」)。 關於(B)成分，代替摻合110份的無機填充材A，改成摻合120份的無機填充材B。 關於(D)成分，將矽烷偶合劑(「KBM403」)之摻合量從0.2份變更成0.3份。又，代替摻合3份的甲基丙烯酸酯(「M-130G」)，改成摻合1份的聚酯多元醇A。又，將自由基聚合起始劑(「Perhexyl(註冊商標)O」)之摻合量從0.1份變更成0份。亦即，於實施例1-8中，不使用自由基聚合起始劑。 上述事項以外，與實施例1-3同樣地，調製實施例1-8之樹脂糊。 <Example 1-8> In Examples 1-3, the following matters were changed. Regarding component (A), instead of blending 3 parts of epoxy resin ("ZX1059", "Celloxide 2021P", "HP4032D, "EP-3950L" and "EP-4088S"), mix 3 parts of epoxy resin Oxygen resin ("ZX1059"), 3 parts of epoxy resin ("Celloxide 2021P"), 3 parts of epoxy resin ("HP4032D"), 2 parts of epoxy resin ("EP-3950L") and 1 part of Epoxy resin ("EP-4088S"). About (B) component, instead of mixing the inorganic filler A of 110 parts, it changed to mixing the inorganic filler B of 120 parts. About (D) component, the compounding quantity of a silane coupling agent ("KBM403") was changed from 0.2 part to 0.3 part. Also, instead of blending 3 parts of methacrylate ("M-130G"), 1 part of polyester polyol A was blended. Moreover, the compounding quantity of the radical polymerization initiator ("Perhexyl (registered trademark) O") was changed from 0.1 part to 0 part. That is, in Examples 1-8, no radical polymerization initiator was used. Except the above matters, the resin paste of Example 1-8 was prepared similarly to Example 1-3.

＜實施例1-9＞ 於實施例1-8中，變更以下之事項。 關於(A)成分，代替摻合3份的氧樹脂(「ZX1059」)、3份的環氧樹脂(「Celloxide 2021P」)、3份的環氧樹脂(「HP4032D」)、2份的環氧樹脂(「EP-3950L」)及1份的環氧樹脂(「EP-4088S」)，改成摻合3份的環氧樹脂(「ZX1059」)、3份的環氧樹脂(「Celloxide 2021P」)、3份的環氧樹脂(「HP4032D」)、2份的環氧樹脂(「EP-3950L」)及1份的環氧樹脂(「EX-992L」)。 關於(C)成分，代替摻合3份的硬化劑(「Kayahard A-A」)，改成摻合3份的硬化劑(Sigma-Aldrich公司製的酚系硬化劑「2,2-二烯丙基雙酚A」)。 關於(B)成分，將無機填充材B之摻合量從120份變更成100份。 關於(D)成分，代替摻合1份的聚酯多元醇A，改成摻合2份的聚矽氧樹脂(「KF-6012」)。 上述事項以外，與實施例1-8同樣地，調製實施例1-9之樹脂糊。 <Example 1-9> In Examples 1-8, the following matters were changed. Regarding (A) component, instead of blending 3 parts of epoxy resin ("ZX1059"), 3 parts of epoxy resin ("Celloxide 2021P"), 3 parts of epoxy resin ("HP4032D"), 2 parts of epoxy Resin ("EP-3950L") and 1 part of epoxy resin ("EP-4088S"), changed to blending 3 parts of epoxy resin ("ZX1059"), 3 parts of epoxy resin ("Celloxide 2021P" ), 3 parts of epoxy resin ("HP4032D"), 2 parts of epoxy resin ("EP-3950L") and 1 part of epoxy resin ("EX-992L"). Regarding component (C), instead of blending 3 parts of hardener (“Kayahard A-A”), 3 parts of hardener (phenolic hardener “2,2-diallyl Bisphenol A"). About (B) component, the compounding quantity of the inorganic filler B was changed into 100 parts from 120 parts. Regarding the component (D), instead of blending 1 part of polyester polyol A, 2 parts of silicone resin ("KF-6012") were blended. Except the above matters, the resin paste of Example 1-9 was prepared similarly to Example 1-8.

＜實施例1-10＞ 於實施例1-7中，將(B)成分的無機填充材B 120份變更為無機填充材C 120份。 上述事項以外，與實施例1-7同樣地，調製實施例1-10之樹脂糊。 <Example 1-10> In Examples 1-7, 120 parts of the inorganic filler B of the (B) component was changed to 120 parts of the inorganic filler C. Except the above matters, the resin paste of Example 1-10 was prepared similarly to Example 1-7.

＜實施例1-11＞ 於實施例1-2中，將作為(B)成分的無機填充材A 110份變更為無機填充材D 110份。 上述事項以外，與實施例1-2同樣地，調製實施例1-11之樹脂糊。 <Example 1-11> In Example 1-2, 110 parts of inorganic filler A as (B) component was changed to 110 parts of inorganic filler D. Except for the above matters, the resin paste of Example 1-11 was prepared in the same manner as in Example 1-2.

＜實施例2-1＞ ＜樹脂清漆之製作＞ 以高速旋轉混合器，均勻地分散作為(D)成分如下述所合成的聚醯亞胺樹脂A溶液2份、作為(A)成分的環氧樹脂(日鐵化學&材料公司製的萘型環氧樹脂「ESN-475V」，環氧當量：約332g/eq.)2.4份、作為(A)成分的環氧樹脂(「HP4032D」)6份、作為(C)成分的硬化劑(DIC(股)製「LA-3018-50P」，羥基當量：151g/eq.，固體成分50%的2-甲氧基丙醇溶液)7份、作為(B)成分的無機填充材B 85份、甲基乙基酮(MEK)10份、環己酮8份，調製樹脂清漆。 <Example 2-1> ＜Production of resin varnish＞ With a high-speed rotary mixer, uniformly disperse 2 parts of polyimide resin A solution synthesized as follows as (D) component, epoxy resin (Nippon Steel Chemical & Materials Co., Ltd. Epoxy resin "ESN-475V", epoxy equivalent: about 332g/eq.) 2.4 parts, epoxy resin ("HP4032D") as component (A) 6 parts, hardener (DIC (stock) ) "LA-3018-50P", hydroxyl equivalent: 151g/eq., 2-methoxy propanol solution with 50% solid content) 7 parts, 85 parts of inorganic filler B as component (B), methyl Prepare a resin varnish with 10 parts of ethyl ketone (MEK) and 8 parts of cyclohexanone.

-聚醯亞胺樹脂A溶液之調製- 於安裝有攪拌裝置、溫度計及冷凝器之燒瓶中，加入作為溶劑的乙基二甘醇乙酸酯368.41g及Exxon Mobil公司製的芳香族系溶劑「Solvesso 150(註冊商標)」(芳香族系溶劑)368.41g。再者，於前述燒瓶中，加入二苯基甲烷二異氰酸酯100.1g(0.4莫耳)、聚碳酸酯二醇(KURARAY公司製「C-2015N」，數量平均分子量：約2000，羥基當量：1000g/eq.，不揮發成分：100質量%)400g(0.2莫耳)，在70℃下進行4小時反應。藉此，得到第1反應溶液。 -Preparation of Polyimide Resin A Solution- In a flask equipped with a stirring device, a thermometer and a condenser, 368.41 g of ethyl diglycol acetate and an aromatic solvent "Solvesso 150 (registered trademark)" (aromatic system solvent) 368.41 g. Furthermore, 100.1 g (0.4 mol) of diphenylmethane diisocyanate, polycarbonate diol (manufactured by KURARAY "C-2015N", number average molecular weight: about 2000, hydroxyl equivalent: 1000 g/ eq., non-volatile matter: 100% by mass) 400 g (0.2 mol), and reacted at 70° C. for 4 hours. Thereby, the 1st reaction solution was obtained.

接著，於前述燒瓶中，更添加壬基酚酚醛清漆樹脂(羥基當量：229.4g/eq，平均4.27官能，平均計算分子量：979.5g/莫耳)195.9g(0.2莫耳)與乙二醇雙偏苯三酸酐41.0g(0.1莫耳)，費2小時升溫至150℃，反應12小時。藉此，得到第2反應溶液。藉由FT-IR，進行2250cm -1的NCO波峰之消失的確認。以NCO波峰消失之確認，視為反應之終點，將第2反應溶液降溫至室溫。然後，以100網目的濾布過濾第2反應溶液。藉此，得到包含具有聚碳酸酯結構的聚醯亞胺樹脂A作為不揮發成分之聚醯亞胺樹脂A溶液(不揮發成分50質量%)作為濾液。聚醯亞胺樹脂A的數量平均分子量為6100。 Next, in the aforementioned flask, 195.9 g (0.2 moles) of nonylphenol novolak resin (hydroxyl equivalent: 229.4 g/eq, average 4.27 functions, average calculated molecular weight: 979.5 g/mole) and ethylene glycol bis 41.0 g (0.1 mol) of trimellitic anhydride was heated up to 150° C. over 2 hours, and reacted for 12 hours. Thereby, the 2nd reaction solution was obtained. The disappearance of the NCO peak at 2250 cm −1 was confirmed by FT-IR. The confirmation of the disappearance of the NCO peak was regarded as the end of the reaction, and the temperature of the second reaction solution was lowered to room temperature. Then, the second reaction solution was filtered through a 100-mesh filter cloth. Thereby, the polyimide resin A solution (50 mass % of non-volatile components) containing the polyimide resin A which has a polycarbonate structure as a nonvolatile component was obtained as a filtrate. The number average molecular weight of the polyimide resin A was 6100.

所調製的樹脂清漆之一部分係迅速地供以下說明的樹脂薄片St0之製作。 又，將樹脂清漆的另一部分在23℃、濕度50%之環境下保管12小時，供以下說明的樹脂薄片St12之製作。 A part of the prepared resin varnish was quickly used for the preparation of the resin sheet St0 described below. Also, the other part of the resin varnish was stored at 23° C. and a humidity of 50% for 12 hours to prepare the resin sheet St12 described below.

＜樹脂薄片St0之製作＞ 作為支撐體，準備以醇酸樹脂系脫模劑(LINTEC公司製「AL-5」)在表面施予脫模處理後之PET薄膜(厚度38μm、軟化點130℃)。 ＜Production of resin sheet St0＞ As a support, a PET film (thickness 38 μm, softening point 130° C.) whose surface was subjected to release treatment with an alkyd resin-based release agent (“AL-5” manufactured by Lintec Corporation) was prepared.

將調製不久的樹脂清漆，以乾燥後的樹脂組成物層之厚度成為200μm之方式，用模塗機均勻地塗佈於支撐體上，藉由在100℃下乾燥6分鐘，而在支撐體上得到樹脂組成物層。其次，於樹脂組成物層之未與支撐體接合之面，層合作為保護膜的聚丙烯薄膜(王子F-TEX公司製「Arufun MA411」、厚度15μm)之粗面，而使其與樹脂組成物層接合。藉此，得到由依支撐體、樹脂組成物層及保護膜之順序所構成的樹脂薄片St0。 將樹脂薄片St0的樹脂組成物層全體當作100體積%時，無機填充材B之含量為76.7體積%。又，加熱及乾燥之結果，將樹脂薄片St0的樹脂組成物層全體當作100質量%時，溶劑之含量被估計為5質量%以下。 將所製作的樹脂薄片St0之樹脂組成物層迅速地供後述的初期熔融黏度MV0之測定。 The newly prepared resin varnish was uniformly coated on the support with a die coater in such a way that the thickness of the dried resin composition layer became 200 μm, and dried at 100°C for 6 minutes. A resin composition layer was obtained. Next, on the surface of the resin composition layer that is not bonded to the support, the rough surface of a polypropylene film ("Arufun MA411" manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) is laminated as a protective film, and it is combined with the resin. layer bonding. Thereby, a resin sheet St0 composed of a support, a resin composition layer, and a protective film in this order was obtained. The content of the inorganic filler B was 76.7% by volume when the entire resin composition layer of the resin sheet St0 was taken as 100% by volume. Also, as a result of heating and drying, when the entire resin composition layer of the resin sheet St0 is taken as 100% by mass, the content of the solvent is estimated to be 5% by mass or less. The resin composition layer of the prepared resin sheet St0 was quickly subjected to the measurement of the initial melt viscosity MV0 described later.

＜樹脂薄片St12之製作＞ 作為支撐體，準備以醇酸樹脂系脫模劑(LINTEC公司製「AL-5」)在表面施予脫模處理後之PET薄膜(厚度38μm、軟化點130℃)。 ＜Production of resin sheet St12＞ As a support, a PET film (thickness 38 μm, softening point 130° C.) whose surface was subjected to release treatment with an alkyd resin-based release agent (“AL-5” manufactured by Lintec Corporation) was prepared.

將12小時保管後的樹脂清漆，以乾燥後的樹脂組成物層之厚度成為200μm之方式，用模塗機均勻地塗佈於支撐體上，藉由在100℃下乾燥6分鐘，而在支撐體上得到樹脂組成物層。其次，於樹脂組成物層之未與支撐體接合之面，層合作為保護膜的聚丙烯薄膜(王子F-TEX公司製「Arufun MA411」、厚度15μm)之粗面，而使其與樹脂組成物層接合。藉此，得到由依支撐體、樹脂組成物層及保護膜之順序所構成的樹脂薄片St12。 將樹脂薄片St12的樹脂組成物層全體當作100體積%時，無機填充材B之含量為76.7體積%。又，加熱及乾燥之結果，將樹脂薄片St12的樹脂組成物層全體當作100質量%時，溶劑之含量被估計為5質量%以下。 將所製作的樹脂薄片St12的樹脂組成物層之樹脂組成物層迅速地供後述的12小時後熔融黏度MV12之測定。 The resin varnish stored for 12 hours was uniformly coated on the support with a die coater in such a way that the thickness of the dried resin composition layer became 200 μm, and dried at 100°C for 6 minutes. A resin composition layer was obtained on the body. Next, on the surface of the resin composition layer that is not bonded to the support, the rough surface of a polypropylene film ("Arufun MA411" manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) is laminated as a protective film, and it is combined with the resin. layer bonding. Thereby, the resin sheet St12 which consists of a support body, a resin composition layer, and a protective film in this order is obtained. When the entire resin composition layer of the resin sheet St12 is taken as 100% by volume, the content of the inorganic filler B is 76.7% by volume. Also, as a result of heating and drying, when the entire resin composition layer of the resin sheet St12 is taken as 100% by mass, the content of the solvent is estimated to be 5% by mass or less. The resin composition layer of the resin composition layer of the produced resin sheet St12 was quickly subjected to the measurement of the melt viscosity MV12 after 12 hours described later.

＜實施例2-2＞ 以高速旋轉混合器，均勻地分散作為(A)成分的環氧樹脂(DAICEL公司製的脂環型環氧樹脂「Celloxide 2021P」，環氧當量：136g/eq.)2份、作為(A)成分的環氧樹脂(DIC公司製的萘醚型環氧樹脂「HP6000L」，環氧當量：215g/eq.)4份、作為(A)成分的環氧樹脂(日鐵化學&材料公司製的液狀1,4-環氧丙基環己烷型環氧樹脂「ZX1658GS」(環氧當量：135g/eq.)2份、作為(C)成分的硬化劑(DIC公司製的活性酯樹脂「EXB-8150-60T」，活性基當量：230g/eq.，不揮發分60%的甲苯溶液)10份、作為(D)成分的碳二亞胺化合物(日清紡化學公司製「V-03」，固體成分50質量%的甲苯溶液)2份、作為(B)成分的無機填充材B 85份、作為(D)成分的胺系硬化促進劑(4-二甲基胺基吡啶：DMAP)0.1份、甲基乙基酮(MEK)9份、環己酮6份，調製樹脂清漆。 上述事項以外，與實施例2-1同樣地，調製實施例2-2之樹脂清漆，且製作樹脂薄片St0及樹脂薄片St12。 <Example 2-2> With a high-speed rotary mixer, 2 parts of epoxy resin (alicyclic epoxy resin "Celloxide 2021P" manufactured by DAICEL Co., Ltd., epoxy equivalent: 136g/eq.) as (A) component was uniformly dispersed, and as (A) 4 parts of epoxy resin (Naphthyl ether type epoxy resin "HP6000L" manufactured by DIC Corporation, epoxy equivalent: 215g/eq.), 4 parts of epoxy resin (Nippon Steel Chemical & Materials Co., Ltd. Liquid 1,4-epoxypropylcyclohexane type epoxy resin "ZX1658GS" (epoxy equivalent: 135g/eq.) 2 parts, hardener (active ester resin manufactured by DIC Corporation " EXB-8150-60T", active group equivalent: 230g/eq., non-volatile 60% toluene solution) 10 parts, carbodiimide compound (Nisshinbo Chemical Co., Ltd. "V-03" as the component (D), Toluene solution with a solid content of 50% by mass) 2 parts, 85 parts of inorganic filler B as component (B), 0.1 part of amine-based hardening accelerator (4-dimethylaminopyridine: DMAP) as component (D) , 9 parts of methyl ethyl ketone (MEK), and 6 parts of cyclohexanone to prepare a resin varnish. Except for the above matters, the resin varnish of Example 2-2 was prepared in the same manner as in Example 2-1, and the resin sheet St0 and the resin sheet St12 were produced.

＜實施例2-3＞ 以高速旋轉混合器，均勻地分散作為(A)成分的環氧樹脂(ADEKA公司製的環氧丙基胺型環氧樹脂「EP-3950L」，環氧當量：95g/eq.)2份、作為(A)成分的環氧樹脂(日鐵化學&材料公司製的萘型環氧樹脂「ESN-475V」，環氧當量：約332g/eq.)4份、作為(A)成分的環氧樹脂(「HP4032D」)4份、作為(A)成分的環氧樹脂(日鐵化學&材料公司製的液狀1,4-環氧丙基環己烷型環氧樹脂「ZX1658GS」(環氧當量：135g/eq.)2份、作為(C)成分的硬化劑(DIC公司製「LA-3018-50P」，羥基當量：151g/eq.，固體成分50%的2-甲氧基丙醇溶液)7份、作為(B)成分的無機填充材B 85份、甲基乙基酮(MEK)10份、環己酮8份，調製樹脂清漆。 上述事項以外，與實施例2-1同樣地，調製實施例2-3之樹脂清漆，且製作樹脂薄片St0及樹脂薄片St12。 <Example 2-3> With a high-speed rotary mixer, 2 parts of epoxy resin (glycidylamine type epoxy resin "EP-3950L" manufactured by ADEKA Co., Ltd., epoxy equivalent: 95g/eq.) as component (A) were uniformly dispersed, Epoxy resin (Nippon Steel Chemical & Materials Co., Ltd. naphthalene-type epoxy resin "ESN-475V", epoxy equivalent: about 332g/eq.) 4 parts of (A) component, epoxy resin as (A) component Resin ("HP4032D") 4 parts, epoxy resin (Nippon Steel Chemical & Materials Co., Ltd. liquid 1,4-epoxypropylcyclohexane type epoxy resin "ZX1658GS" (epoxy Equivalent: 135g/eq.) 2 parts, 2-methoxypropanol as component (C) hardener ("LA-3018-50P" manufactured by DIC Corporation, hydroxyl equivalent: 151g/eq., solid content 50% 7 parts of solution), 85 parts of inorganic filler B as component (B), 10 parts of methyl ethyl ketone (MEK), and 8 parts of cyclohexanone were used to prepare a resin varnish. Except for the above matters, the resin varnish of Example 2-3 was prepared in the same manner as in Example 2-1, and the resin sheet St0 and the resin sheet St12 were produced.

＜比較例1-1＞ 於實施例1-3中，代替摻合110份作為(B)成分的無機填充材A，改成摻合110份作為(B’)成分的無機填充材E。 上述事項以外，與實施例1-3同樣地，調製比較例1-1之樹脂糊。 <Comparative example 1-1> In Examples 1-3, instead of blending 110 parts of inorganic filler A as component (B), 110 parts of inorganic filler E as component (B') were blended. Except for the above matters, the resin paste of Comparative Example 1-1 was prepared in the same manner as in Example 1-3.

＜比較例1-2＞ 於實施例1-7中，代替摻合120份作為(B)成分的無機填充材B，改成摻合120份作為(B’)成分的無機填充材F。 上述事項以外，與實施例1-7同樣地，調製比較例1-2之樹脂糊。 <Comparative example 1-2> In Examples 1-7, instead of blending 120 parts of inorganic filler B as component (B), 120 parts of inorganic filler F as component (B') was blended. Except for the above matters, the resin paste of Comparative Example 1-2 was prepared in the same manner as in Example 1-7.

接著，說明樹脂組成物之測定方法・評價方法。Next, the measurement method and evaluation method of the resin composition will be described.

＜黏度壽命的安定性之評價：增黏比之判定＞ 藉由測定初期熔融黏度及12小時後熔融黏度，求出增黏比，而評價黏度壽命的安定性。 ＜＜初期熔融黏度MV0之測定＞＞ 對於實施例1-1～1-11及比較例1-1～1-2所調製的樹脂糊(調製後30分鐘以內者)以及實施例2-1～2-3所製作的樹脂薄片St0(製作後30分鐘以內者)之樹脂組成物層各自，使用動態黏彈性測定裝置(UBM公司製「Rheosol-G3000」)測定動態黏彈性模數。作為測定條件，對於樹脂糊或樹脂組成物層1g，使用直徑18mm的平行板，從開始溫度60℃起以5℃/分鐘的升溫速度升溫到200℃為止，採用測定溫度間隔2.5℃、振動數1Hz、應變1deg。從測定結果所得之動態黏彈性模數，求出最低熔融黏度(泊)。將如此所求出的最低熔融黏度當作「初期熔融黏度MV0」。 ＜＜12小時後熔融黏度MV12之測定＞＞ 將實施例1-1～1-11及比較例1-1～1-2所調製的樹脂糊，在23℃、濕度50%之環境下保管12小時。對於12小時經過後的樹脂糊以及實施例2-1～2-3所製作的樹脂薄片St12(製作後30分鐘以內者)之樹脂組成物層各自，與上述初期熔融黏度MV0之測定同樣地，測定動態黏彈性模數，求出最低熔融黏度(泊)。將如此所求出的最低熔融黏度當作「12小時後熔融黏度MV12」。 ＜＜增黏比＞＞ 將隨著12小時經過的增黏比當作12小時後熔融黏度MV12相對於初期熔融黏度MV0之比值(亦即，MV12/MV0)。用下述基準評價增黏比。 「○」：增黏比未達1.7 「×」：增黏比為1.7以上 ＜Evaluation of stability of viscosity life: Judgment of viscosity increase ratio＞ By measuring the initial melt viscosity and the melt viscosity after 12 hours, the viscosity increase ratio is obtained to evaluate the stability of the viscosity life. ＜＜Determination of initial melt viscosity MV0＞＞ For the resin paste (within 30 minutes after preparation) prepared in Examples 1-1 to 1-11 and Comparative Examples 1-1 to 1-2 and the resin sheet St0 prepared in Examples 2-1 to 2-3 ( The dynamic viscoelastic modulus of each resin composition layer within 30 minutes after production was measured using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM Corporation). As the measurement conditions, for 1 g of the resin paste or resin composition layer, using a parallel plate with a diameter of 18 mm, the temperature was raised from the starting temperature of 60 ° C to 200 ° C at a temperature increase rate of 5 ° C / min, and the measurement temperature interval was 2.5 ° C. 1Hz, strain 1deg. From the dynamic viscoelastic modulus obtained from the measurement results, the minimum melt viscosity (poise) was obtained. The lowest melt viscosity obtained in this way is referred to as "initial melt viscosity MV0". ＜＜Determination of melt viscosity MV12 after 12 hours＞＞ The resin pastes prepared in Examples 1-1 to 1-11 and Comparative Examples 1-1 to 1-2 were stored at 23° C. and in an environment with a humidity of 50% for 12 hours. For each of the resin composition layers of the resin paste after 12 hours and the resin sheet St12 (within 30 minutes after production) produced in Examples 2-1 to 2-3, the same as the measurement of the above-mentioned initial melt viscosity MV0, The dynamic viscoelastic modulus was measured, and the minimum melt viscosity (Poise) was obtained. The lowest melt viscosity obtained in this way was regarded as "melt viscosity MV12 after 12 hours". ＜＜Viscosity ratio＞＞ The viscosity increasing ratio with the elapse of 12 hours was taken as the ratio of the melt viscosity MV12 after 12 hours to the initial melt viscosity MV0 (that is, MV12/MV0). The thickening ratio was evaluated on the basis of the following criteria. "○": Viscosity ratio is less than 1.7 "×": Viscosity ratio is 1.7 or more

表1中顯示實施例1-1～1-11及比較例1-1～1-2之樹脂組成物之組成及評價結果。表2中顯示實施例2-1～2-3之樹脂組成物之組成及評價結果。Table 1 shows the compositions and evaluation results of the resin compositions of Examples 1-1 to 1-11 and Comparative Examples 1-1 to 1-2. Table 2 shows the compositions and evaluation results of the resin compositions of Examples 2-1 to 2-3.

Figure 02_image001
Figure 02_image001

Figure 02_image003
Figure 02_image003

接著，對於實施例之樹脂組成物的硬化物，說明其評價結果。Next, the evaluation results of cured products of the resin compositions of Examples will be described.

[實施例1-1～1-11之樹脂組成物的硬化物] ＜良率性之評價：有無流痕之判定＞ 在12吋矽晶圓上，將實施例1-1～1-11所製作的樹脂組成物，使用壓縮模塑裝置(模具溫度：130℃，壓力：6MPa，硬化時間：10分鐘)進行壓縮成型，形成厚度300μm的樹脂組成物層。然後，在150℃下加熱60分鐘後，目視樹脂組成物層(硬化物)之表面而確認流痕，用以下基準進行評價。 「○」：無流痕。 「×」：有流痕。 [Cured products of the resin compositions of Examples 1-1 to 1-11] ＜Evaluation of Yield: Judgment of whether there are flow marks or not＞ On a 12-inch silicon wafer, the resin compositions produced in Examples 1-1 to 1-11 were compression-molded using a compression molding device (mold temperature: 130°C, pressure: 6MPa, curing time: 10 minutes) , forming a resin composition layer with a thickness of 300 μm. Then, after heating at 150° C. for 60 minutes, the surface of the resin composition layer (cured product) was visually observed to confirm flow marks, and the following criteria were used for evaluation. "○": No flow marks. "×": There are flow marks.

＜密著性之評價：與聚醯亞胺樹脂之界面的剪切強度之測定＞ (準備在表面上形成有聚醯亞胺樹脂之矽晶圓) 於4吋矽晶圓上，塗佈後述製造例3所得之第一特定組成物(後述製造例1、2為製造例3之第一特定組成物的材料之製造例)。為了塗佈，使用旋轉塗佈機(MIKASA公司製「MS-A150」)，進行旋轉塗佈。此旋轉塗佈的旋轉數係最大旋轉數收在1000rpm～3000rpm的旋轉數範圍之範圍，以熱硬化後得到所欲厚度的試驗層之方式設定。然後，在加熱板上於120℃5分鐘之條件下進行加熱之預烘烤處理，在研磨面上形成中央的厚度10μm之第一特定組成物的層。然後，對於第一特定組成物的層，進行在250℃2小時之條件下熱硬化之全硬化處理，得到中央的厚度8μm之試驗層。此處，於全硬化之結果所得的第一特定組成物的層之硬化物中，包含聚醯亞胺樹脂。如此地，準備在表面上形成有聚醯亞胺樹脂之矽晶圓。再者，將該矽晶圓切割成1cm見方(亦即1cm×1cm)之尺寸。 <Evaluation of Adhesion: Measurement of Shear Strength of Interface with Polyimide Resin> (Prepare silicon wafer with polyimide resin formed on the surface) On a 4-inch silicon wafer, the first specific composition obtained in Manufacturing Example 3 described later was coated (Manufacturing Examples 1 and 2 described later are manufacturing examples of the material of the first specific composition in Manufacturing Example 3). For coating, spin coating was performed using a spin coater ("MS-A150" manufactured by MIKASA Corporation). The rotation speed of this spin coating is set so that the maximum rotation speed falls within the range of 1000 rpm to 3000 rpm so that a test layer with a desired thickness can be obtained after thermosetting. Then, a prebaking treatment was performed by heating at 120° C. for 5 minutes on a hot plate to form a central layer of the first specific composition with a thickness of 10 μm on the polished surface. Then, the layer of the first specific composition was subjected to a full curing treatment of thermal curing at 250° C. for 2 hours to obtain a test layer with a thickness of 8 μm in the center. Here, polyimide resin is contained in the cured product of the layer of the first specific composition obtained as a result of total curing. In this way, a silicon wafer having polyimide resin formed on the surface was prepared. Furthermore, the silicon wafer is cut into a size of 1 cm square (that is, 1 cm×1 cm).

(試驗片之製作) 在表面上形成有聚醯亞胺樹脂的經切割成1cm見方的矽晶圓上，設置經挖空直徑4mm的圓柱狀之矽橡膠框。於矽橡膠框之圓柱狀空洞，填充實施例1-1～1-11所製作的各樹脂糊直到在矽晶圓所形成的聚醯亞胺樹脂上高度5mm為止。在180℃下加熱90分鐘後，卸下矽橡膠框，製作由矽晶圓與在該矽晶圓所形成的聚醯亞胺樹脂上形成的實心圓柱狀樹脂組成物的硬化物所構成之試驗片。 (production of test piece) On a silicon wafer cut into 1 cm squares with polyimide resin formed on the surface, a cylindrical silicon rubber frame with a hollowed-out diameter of 4 mm was set. Fill the cylindrical cavity of the silicone rubber frame with the resin pastes prepared in Examples 1-1 to 1-11 until the height of the polyimide resin formed on the silicon wafer is 5 mm. After heating at 180°C for 90 minutes, remove the silicone rubber frame, and make a test consisting of a silicon wafer and a solid cylindrical resin composition formed on the polyimide resin formed on the silicon wafer. piece.

(測定) 以接合試驗機(Dage公司製系統4000)，於頭位置離矽晶圓1mm、頭速率700μm/s之條件下，測定聚醯亞胺樹脂與樹脂組成物的硬化物之界面的剪切強度[kgf/mm 2]。實施5次的試驗。使用5次的測定值之平均值，用以下基準評價作為基材的聚醯亞胺樹脂與樹脂糊的硬化物之密著性。 「◎」：剪切強度為2.5kgf/mm 2以上。 「○」：剪切強度為2.0kgf/mm 2以上、未達2.5kgf/mm 2。 「×」：剪切強度未達2.0kgf/mm 2。 (Measurement) Using a bonding tester (system 4000 manufactured by Dage Co., Ltd.), the shear at the interface between the polyimide resin and the hardened resin composition was measured under the conditions that the head position was 1 mm away from the silicon wafer and the head speed was 700 μm/s. Shear strength [kgf/mm 2 ]. The experiment was carried out 5 times. Using the average value of the measured values five times, the adhesiveness between the polyimide resin as the base material and the cured product of the resin paste was evaluated on the basis of the following criteria. "◎": The shear strength is 2.5 kgf/mm 2 or more. "○": The shear strength is 2.0 kgf/mm 2 or more and less than 2.5 kgf/mm 2 . "×": The shear strength is less than 2.0 kgf/mm 2 .

[製造例1. 作為第一聚合物的感光性聚醯亞胺前驅物(聚合物A-1)之製造] 將4,4’-氧基二鄰苯二甲酸二酐(ODPA)155.1g置入2公升容量的可分離式燒瓶內，添加甲基丙烯酸2-羥基乙酯(HEMA)134.0g及γ-丁內酯400ml。藉由在室溫下邊攪拌邊添加吡啶79.1g，而得到反應混合物。於反應所致的放熱之結束後，冷卻到室溫，進一步靜置16小時。 [Production example 1. Production of photosensitive polyimide precursor (polymer A-1) as the first polymer] Put 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) into a 2-liter separable flask, add 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and γ-butyl Lactone 400ml. A reaction mixture was obtained by adding 79.1 g of pyridine while stirring at room temperature. After the exothermic heat due to the reaction ended, it was cooled to room temperature and left still for 16 hours.

準備在γ-丁內酯180ml中溶解有二環己基碳二亞胺(DCC)206.3g之溶液。將該溶液在冰冷下，邊攪拌前述反應混合物邊費40分鐘添加至前述反應混合物中。 接著，將在γ-丁內酯350ml中懸浮有4,4’-二胺基二苯基醚(DADPE)93.0g的懸浮液，邊攪拌前述反應混合物邊費60分鐘添加至前述反應混合物中。 再者，將反應混合物在室溫下攪拌2小時後，於該反應混合物中添加乙醇30ml，進一步攪拌1小時。 然後，於反應混合物中添加γ-丁內酯400ml。藉由過濾去除反應混合物中生成的沉澱物，得到反應液。 A solution in which 206.3 g of dicyclohexylcarbodiimide (DCC) was dissolved in 180 ml of γ-butyrolactone was prepared. This solution was added to the above reaction mixture over 40 minutes while stirring the above reaction mixture under ice-cooling. Next, a suspension in which 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) was suspended in 350 ml of γ-butyrolactone was added to the reaction mixture over 60 minutes while stirring the reaction mixture. Furthermore, after stirring the reaction mixture at room temperature for 2 hours, 30 ml of ethanol was added to this reaction mixture, and it stirred for further 1 hour. Then, 400 ml of γ-butyrolactone was added to the reaction mixture. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

將所得之反應液加到3公升的乙醇中，生成由粗聚合物所構成的沉澱物。過濾取得所生成的粗聚合物，溶解於四氫呋喃1.5公升中，得到粗聚合物溶液。將所得之粗聚合物溶液滴下至28公升的水中，而使聚合物沉澱。過濾取得所得之沉澱物後，藉由真空乾燥，得到作為第一聚合物的粉末狀聚合物A-1。 測定該聚合物A-1之重量平均分子量(Mw)，結果為20,000。 The resulting reaction solution was added to 3 liters of ethanol to form a precipitate consisting of a crude polymer. The generated crude polymer was collected by filtration, and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was dropped into 28 liters of water to precipitate the polymer. After the obtained precipitate was obtained by filtration, it was vacuum-dried to obtain powdery polymer A-1 as the first polymer. When the weight average molecular weight (Mw) of this polymer A-1 was measured, it was 20,000.

[製造例2. 作為第二聚合物的感光性聚醯亞胺前驅物(聚合物A-2)之製造] 除了代替4,4’-氧基二鄰苯二甲酸二酐155.1g，使用3,3’4,4’-聯苯基四羧酸二酐147.1g以外，藉由與製造例1同樣的方法，製造作為第二聚合物的聚合物A-2。 測定該聚合物A-2的重量平均分子量(Mw)，結果為22,000。 [Production example 2. Production of photosensitive polyimide precursor (polymer A-2) as the second polymer] By the same method as in Production Example 1, except that 147.1 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride , Polymer A-2 was produced as the second polymer. When the weight average molecular weight (Mw) of this polymer A-2 was measured, it was 22,000.

[製造例3. 作為第一特定組成物的負型感光性樹脂組成物之製造] 將聚合物A-1 50g、聚合物A-2 50g、式(1)所表示的化合物2g、四乙二醇二甲基丙烯酸酯8g、2-亞硝基-1-萘酚0.05g、N-苯基二乙醇胺4g、N-(3-(三乙氧基矽烷基)丙基)鄰苯二甲醯胺酸0.5g與二苯甲酮-3,3’-雙(N-(3-三乙氧基矽烷基)丙基醯胺)-4,4’-二羧酸0.5g溶解於由N-甲基吡咯啶酮及乳酸乙酯所成之混合溶劑(重量比為N-甲基吡咯啶酮：乳酸乙酯=8：2)中，得到作為第一特定組成物的負型感光性樹脂組成物。混合溶劑之量係以所得之負型感光性樹脂組成物的黏度成為35泊之方式調整。 [Manufacture example 3. Manufacture of negative photosensitive resin composition as the first specific composition] Polymer A-1 50g, polymer A-2 50g, compound 2g represented by formula (1), tetraethylene glycol dimethacrylate 8g, 2-nitroso-1-naphthol 0.05g, N -Phenyldiethanolamine 4g, N-(3-(triethoxysilyl)propyl)phthalic acid 0.5g and benzophenone-3,3'-bis(N-(3- Triethoxysilyl) propylamide) -4,4'-dicarboxylic acid 0.5g dissolved in a mixed solvent made of N-methylpyrrolidone and ethyl lactate (the weight ratio is N-methyl Pyrrolidone:ethyl lactate=8:2), the negative photosensitive resin composition which is a 1st specific composition was obtained. The quantity of the mixed solvent was adjusted so that the viscosity of the obtained negative photosensitive resin composition might become 35 poises.

Figure 02_image005
Figure 02_image005

＜低翹曲性之評價：翹曲量之測定＞ 於12吋矽晶圓上，將實施例1-1～1-11所調製的各樹脂糊(調製後30分鐘以內者)，使用壓縮模塑裝置(模具溫度：120℃，壓力：6MPa，硬化時間：12分鐘)進行壓縮成型，形成厚度250μm的樹脂組成物層。然後，在180℃下加熱90分鐘，而使樹脂組成物層熱硬化。藉此，得到含有矽晶圓與樹脂組成物的硬化物層之試料基板。使用陰影疊紋測定裝置(Akorometrix公司製「Thermoire AXP」)，對於前述試料基板，測定25℃下的翹曲量。測定係依據電子資訊技術產業協會規格的JEITA EDX-7311-24進行。具體而言，將測定區域之基板面的全部數據之藉由最小平方法所求出的假想平面當作基準面，從該基準面求出垂直方向的最小值與最大值之差當作翹曲量[μm]，用以下基準評價翹曲量。 「○」：翹曲量未達1500μm 「×」：翹曲量為1500μm以上 ＜Evaluation of low warpage: measurement of warpage＞ On a 12-inch silicon wafer, apply the resin pastes prepared in Examples 1-1 to 1-11 (within 30 minutes after preparation), using a compression molding device (mold temperature: 120°C, pressure: 6MPa, harden Time: 12 minutes) compression molding was performed to form a resin composition layer with a thickness of 250 μm. Then, the resin composition layer was thermally cured by heating at 180° C. for 90 minutes. Thereby, a sample substrate including a cured product layer of a silicon wafer and a resin composition was obtained. The amount of warping at 25° C. was measured with respect to the aforementioned sample substrate using a shadow moiré measuring device (“Thermoire AXP” manufactured by Akorometrix Corporation). The measurement was performed in accordance with JEITA EDX-7311-24 of the Electronics and Information Technology Industries Association standard. Specifically, the virtual plane obtained by the least square method of all the data on the substrate surface in the measurement area is used as a reference plane, and the difference between the minimum value and the maximum value in the vertical direction is obtained from the reference plane as the warpage. amount [μm], and the amount of warpage was evaluated using the following criteria. "○": The amount of warpage is less than 1500 μm "×": The amount of warping is 1500 μm or more

表3中顯示實施例1-1～1-11之樹脂組成物的硬化物之評價結果。Table 3 shows the evaluation results of the cured products of the resin compositions of Examples 1-1 to 1-11.

Figure 02_image007
Figure 02_image007

[實施例2-1～2-3之樹脂組成物的硬化物] 對於實施例2-1～2-3之樹脂組成物的硬化物，說明其評價結果。 ＜密著性之評價：與聚醯亞胺樹脂之界面的剪切強度之測定＞ (準備在表面上形成有聚醯亞胺樹脂之矽晶圓) 於4吋矽晶圓上，塗佈上述之製造例3所得之第一特定組成物。為了塗佈，使用旋轉塗佈機(MIKASA公司製「MS-A150」)，進行旋轉塗佈。此旋轉塗佈的旋轉數係最大旋轉數收在1000rpm～3000rpm的旋轉數範圍之範圍，以熱硬化後得到所欲厚度的試驗層之方式設定。然後，在加熱板上於120℃5分鐘之條件下進行加熱之預烘烤處理，在研磨面上形成中央的厚度10μm之第一特定組成物的層。然後，對於第一特定組成物的層，進行在250℃2小時之條件下熱硬化之全硬化處理，得到中央的厚度8μm之試驗層。此處，於全硬化之結果所得的第一特定組成物的層之硬化物中，包含聚醯亞胺樹脂。如此地，準備在表面上形成有聚醯亞胺樹脂之矽晶圓。 [Cured products of the resin compositions of Examples 2-1 to 2-3] The evaluation results of the cured products of the resin compositions of Examples 2-1 to 2-3 will be described. <Evaluation of Adhesion: Measurement of Shear Strength of Interface with Polyimide Resin> (Prepare silicon wafer with polyimide resin formed on the surface) On a 4-inch silicon wafer, the first specific composition obtained in Manufacturing Example 3 above was coated. For coating, spin coating was performed using a spin coater ("MS-A150" manufactured by MIKASA Corporation). The rotation speed of this spin coating is set so that the maximum rotation speed falls within the range of 1000 rpm to 3000 rpm so that a test layer with a desired thickness can be obtained after thermosetting. Then, a prebaking treatment was performed by heating at 120° C. for 5 minutes on a hot plate to form a central layer of the first specific composition with a thickness of 10 μm on the polished surface. Then, the layer of the first specific composition was subjected to a full curing treatment of thermal curing at 250° C. for 2 hours to obtain a test layer with a thickness of 8 μm in the center. Here, polyimide resin is contained in the cured product of the layer of the first specific composition obtained as a result of total curing. In this way, a silicon wafer having polyimide resin formed on the surface was prepared.

(試料基板之製作) 對於實施例2-1～2-3所製作之樹脂薄片St0(200μm厚度)，使用分批式真空加壓層合機(NIKKO材料公司製2階增建層合機「CVP700」)，層合在表面上形成有聚醯亞胺樹脂之4吋矽晶圓上。各層合係減壓30秒而使氣壓成為13hPa以下後，藉由在溫度100℃、壓力0.74MPa下壓接30秒而實施。接著，重複支撐體的剝離及樹脂組成物層的積層(同條件下的層合)，使樹脂組成物層的積層體之總厚度成為5mm。再者，將該矽晶圓切割成1cm見方的尺寸。 然後，將矽晶圓上的總厚度為5mm的樹脂組成物層之積層體加工成直徑4mm的實心圓柱狀。藉此，得到包含矽晶圓與樹脂組成物層的積層體之硬化物的試料基板。然後，與上述同樣地測定剪切強度[kgf/mm 2]。實施5次的試驗。使用5次的測定值之平均值，用以下基準評價作為基材的聚醯亞胺樹脂與樹脂組成物層之積層體的硬化物之密著性。 「◎」：剪切強度為2.5kgf/mm 2以上。 「○」：剪切強度為2.0kgf/mm 2以上、未達2.5kgf/mm 2。 「×」：剪切強度未達2.0kgf/mm 2。 (Preparation of sample substrate) For the resin sheet St0 (200 μm thickness) produced in Examples 2-1 to 2-3, a batch-type vacuum pressure laminator (2-stage build-up laminator manufactured by NIKKO Material Co., Ltd. CVP700"), laminated on a 4-inch silicon wafer with polyimide resin formed on the surface. After each lamination system was depressurized for 30 seconds so that the air pressure became 13 hPa or less, it implemented by pressure-bonding at a temperature of 100° C. and a pressure of 0.74 MPa for 30 seconds. Next, peeling of the support and lamination of the resin composition layer (lamination under the same conditions) were repeated so that the total thickness of the laminate of the resin composition layers became 5 mm. Furthermore, the silicon wafer was cut into a size of 1 cm square. Then, the laminate of the resin composition layers with a total thickness of 5 mm on the silicon wafer was processed into a solid cylindrical shape with a diameter of 4 mm. Thus, a sample substrate including a cured product of a laminate of a silicon wafer and a resin composition layer was obtained. Then, the shear strength [kgf/mm 2 ] was measured in the same manner as above. The experiment was carried out 5 times. Using the average value of the measured values five times, the adhesiveness of the cured product of the laminate of the polyimide resin as the base material and the resin composition layer was evaluated according to the following criteria. "◎": The shear strength is 2.5 kgf/mm 2 or more. "○": The shear strength is 2.0 kgf/mm 2 or more and less than 2.5 kgf/mm 2 . "×": The shear strength is less than 2.0 kgf/mm 2 .

＜低翹曲性之評價：翹曲量之測定＞ 於12吋矽晶圓(厚度775μm)之單面全體上，使用分批式真空加壓層合機(NIKKO材料公司製2階增建層合機「CVP700」)，層合上述實施例2-1～2-3所得之各樹脂薄片St0，剝離支撐體。在層合於12吋矽晶圓的樹脂組成物層上，進一步層合樹脂薄片St0而2層積層樹脂組成物層，形成厚度400μm的樹脂組成物層。將所得之附有樹脂組成物層的矽晶圓在烘箱中於180℃及90分鐘之條件下進行熱處理，形成附有硬化的樹脂組成物層(亦即絕緣層)之矽晶圓。使用陰影疊紋測定裝置(Akorometrix公司製「Thermoire AXP」)，對於前述試料基板，測定25℃下的翹曲量。測定係依據電子資訊技術產業協會規格的JEITA EDX-7311-24進行。具體而言，將測定區域之基板面的全部數據之藉由最小平方法所求出的假想平面當作基準面，從該基準面求出垂直方向的最小值與最大值之差當作翹曲量[μm]。用以下基準評價翹曲量。 「○」：翹曲量未達2000μm 「×」：翹曲量為2000μm以上 ＜Evaluation of low warpage: measurement of warpage＞ On the whole of one side of a 12-inch silicon wafer (thickness 775 μm), using a batch-type vacuum pressure laminator (Nikko Material Co., Ltd. 2-stage build-up laminator "CVP700"), the above-mentioned Example 2- 1-2-3 Each of the obtained resin sheets St0 is peeled off the support body. On the resin composition layer laminated on the 12-inch silicon wafer, a resin sheet St0 was further laminated to form a resin composition layer with a thickness of 400 μm. The obtained silicon wafer with the resin composition layer is heat-treated in an oven at 180° C. for 90 minutes to form a silicon wafer with a hardened resin composition layer (ie an insulating layer). The amount of warping at 25° C. was measured with respect to the aforementioned sample substrate using a shadow moiré measuring device (“Thermoire AXP” manufactured by Akorometrix Corporation). The measurement was performed in accordance with JEITA EDX-7311-24 of the Electronics and Information Technology Industries Association standard. Specifically, the virtual plane obtained by the least square method of all the data on the substrate surface in the measurement area is used as a reference plane, and the difference between the minimum value and the maximum value in the vertical direction is obtained from the reference plane as the warpage. Amount [μm]. The amount of warpage was evaluated on the following criteria. "○": The amount of warpage is less than 2000 μm "×": The amount of warping is 2000 μm or more

表4中顯示實施例2-1～2-3之樹脂組成物的硬化物之評價結果。Table 4 shows the evaluation results of the cured products of the resin compositions of Examples 2-1 to 2-3.

Figure 02_image009
Figure 02_image009

＜探討＞ 根據表1，比較例之樹脂組成物係黏度壽命的安定性差，因此有因為長期保存而發生組成的不均勻之傾向。另一方面，根據表1，實施例之樹脂糊係黏度壽命的安定性良好。藉由使用那樣的樹脂糊，如由表3可知，確認可造成具有優異的特性之硬化物。藉此，例如可提供與基材(例如聚醯亞胺樹脂)的密著性優異之硬化物、包含該硬化物之電路基板及半導體晶片封裝。又，實施例之樹脂薄片的樹脂組成物層係如表2所示，黏度壽命的安定性良好。又，藉由從那樣的樹脂清漆或樹脂組成物層來形成，如由表4可知，確認可造成具有優異的特性之硬化物。藉此，可知例如能提供與基材(例如聚醯亞胺樹脂)的密著性優異之硬化物、包含該硬化物之電路基板及半導體晶片封裝。 ＜Discussion＞ According to Table 1, the resin composition of the comparative example has poor stability of viscosity life, so there is a tendency for the composition to be non-uniform due to long-term storage. On the other hand, according to Table 1, the stability of the viscosity life of the resin paste system of the examples is good. By using such a resin paste, as can be seen from Table 3, it was confirmed that a cured product having excellent characteristics can be obtained. Thereby, for example, a cured product excellent in adhesion to a base material (for example, polyimide resin), a circuit board and a semiconductor chip package including the cured product can be provided. Moreover, the resin composition layer system of the resin sheet of the example is shown in Table 2, and the stability of the viscosity life is good. Also, by forming from such a resin varnish or resin composition layer, as can be seen from Table 4, it was confirmed that a cured product having excellent characteristics can be obtained. Thereby, it can be seen that, for example, a cured product excellent in adhesion to a base material (for example, polyimide resin), a circuit board and a semiconductor chip package including the cured product can be provided.

100:半導體晶片封裝 110:半導體晶片 120:密封層 130:再配線形成層 140:再配線層 150:阻焊劑層 160:凸塊 100: Semiconductor chip packaging 110: Semiconductor wafer 120: sealing layer 130: Rewiring formation layer 140: Redistribution layer 150: Solder resist layer 160: Bump

[圖1]係示意地顯示作為本發明之一實施形態的半導體晶片封裝之一例的扇出(Fan-out)型WLP之構成的剖面圖。[ Fig. 1] Fig. 1 is a cross-sectional view schematically showing the structure of a fan-out type WLP as an example of a semiconductor chip package according to an embodiment of the present invention.

Claims (16)

一種樹脂組成物，其係含有(A)硬化性樹脂與(B)無機填充材之樹脂組成物，其特徵為， (B)無機填充材之平均粒徑在0.5μm～12μm之範圍內， 無機填充材中的結晶性二氧化矽含有率在0質量%以上且未達2.1質量%之範圍內。 A resin composition comprising (A) a curable resin and (B) an inorganic filler, characterized in that, (B) The average particle size of the inorganic filler is within the range of 0.5 μm to 12 μm, The content of crystalline silica in the inorganic filler is within the range of 0% by mass or more and less than 2.1% by mass. 如請求項1之樹脂組成物，其中前述結晶性二氧化矽含有率在0質量%以上且0.4質量%以下之範圍內。The resin composition according to claim 1, wherein the crystalline silica content is in the range of 0% by mass to 0.4% by mass. 如請求項1之樹脂組成物，其中將樹脂組成物全體當作100體積%時，(B)無機填充材之含量為50體積%以上。The resin composition according to claim 1, wherein the content of (B) the inorganic filler is 50% by volume or more when the entire resin composition is taken as 100% by volume. 如請求項1之樹脂組成物，其包含(C)硬化劑， (C)成分相對於(A)成分之質量比在1:0.01～1:10之範圍內。 The resin composition as claimed in item 1, which comprises (C) hardener, (C) The mass ratio of a component with respect to (A) component exists in the range of 1:0.01-1:10. 如請求項1之樹脂組成物，其中前述結晶性二氧化矽含有率係基於藉由X射線繞射測定所得之X射線繞射圖型而算出。The resin composition according to claim 1, wherein the crystalline silica content is calculated based on an X-ray diffraction pattern obtained by X-ray diffraction measurement. 如請求項5之樹脂組成物，其中前述結晶性二氧化矽含有率係將X射線繞射圖型進行裏特沃爾德(Rietveld)解析而算出。The resin composition according to claim 5, wherein the crystalline silica content is calculated by performing Rietveld analysis on the X-ray diffraction pattern. 如請求項1之樹脂組成物，其係用於形成厚度50μm以上的樹脂組成物層。The resin composition according to claim 1, which is used to form a resin composition layer with a thickness of 50 μm or more. 如請求項1之樹脂組成物，其係密封用。The resin composition as claimed in item 1 is used for sealing. 一種如請求項1～8中任一項之樹脂組成物的硬化物。A cured product of the resin composition according to any one of claims 1-8. 一種樹脂薄片，其具有支撐體與設於該支撐體上的包含如請求項1～8中任一項之樹脂組成物的樹脂組成物層。A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of claims 1-8 provided on the support. 如請求項10之樹脂薄片，其為半導體晶片封裝的絕緣層用樹脂薄片。The resin sheet according to claim 10, which is a resin sheet for an insulating layer of a semiconductor chip package. 一種電路基板，其包含藉由如請求項1～8中任一項之樹脂組成物的硬化物所形成的絕緣層。A circuit board comprising an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 8. 一種半導體晶片封裝，其包含如請求項12之電路基板與搭載於該電路基板上的半導體晶片。A semiconductor chip package, which includes the circuit substrate as claimed in claim 12 and a semiconductor chip mounted on the circuit substrate. 一種半導體晶片封裝，其包含藉由如請求項1～8中任一項之樹脂組成物所密封的半導體晶片。A semiconductor chip package comprising a semiconductor chip sealed by the resin composition according to any one of claims 1-8. 一種半導體晶片封裝，其包含藉由如請求項10之樹脂薄片所密封的半導體晶片。A semiconductor chip package comprising a semiconductor chip sealed by the resin sheet according to claim 10. 一種半導體晶片封裝之製造方法，其包含使含有(A)與硬化性樹脂與(B)無機填充材之樹脂組成物硬化之步驟，其中(B)無機填充材之平均粒徑在0.5μm～12μm之範圍內，無機填充材中的結晶性二氧化矽含有率在0質量%以上且未達2.1質量%之範圍內。A method for manufacturing a semiconductor chip package, comprising the step of curing a resin composition containing (A) a curable resin and (B) an inorganic filler, wherein (B) the average particle size of the inorganic filler is 0.5 μm to 12 μm Within the range, the content of crystalline silica in the inorganic filler is within the range of 0% by mass or more and less than 2.1% by mass.
TW111122346A 2021-06-22 2022-06-16 Resin composition, cured product, resin sheet, circuit substrate, and semiconductor chip package TW202308980A (en)

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