TWI822828B - resin composition - Google Patents

resin composition Download PDF

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TWI822828B
TWI822828B TW108127984A TW108127984A TWI822828B TW I822828 B TWI822828 B TW I822828B TW 108127984 A TW108127984 A TW 108127984A TW 108127984 A TW108127984 A TW 108127984A TW I822828 B TWI822828 B TW I822828B
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resin
resin composition
mass
layer
epoxy resin
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TW108127984A
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TW202020043A (en
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阪內啓之
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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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
    • 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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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    • C08L2205/00—Polymer mixtures characterised by other features
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    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

本發明之課題在於提供能得到翹曲抑制及脆化抑制優異的硬化物之樹脂組成物。 An object of the present invention is to provide a resin composition capable of obtaining a cured product excellent in warpage suppression and embrittlement suppression.

本發明之解決手段為一種樹脂組成物，其係包含(A)環氧樹脂及(B)硬化劑之樹脂組成物，使上述樹脂組成物在180℃熱硬化90分鐘而得的硬化物之透氧係數為3cc/(atm‧m2‧天‧mm)以下，上述硬化物之線熱膨脹係數為4~15ppm/℃。 The solution of the present invention is a resin composition, which is a resin composition containing (A) epoxy resin and (B) hardener. The resin composition is thermally cured at 180° C. for 90 minutes. The oxygen coefficient is 3cc/(atm‧m 2 ‧day‧mm) or less, and the linear thermal expansion coefficient of the above-mentioned hardened product is 4~15ppm/℃.

Description

樹脂組成物 resin composition

本發明關於關於：包含環氧樹脂及硬化劑之樹脂組成物；包含上述樹脂組成物之樹脂油墨；由上述樹脂油墨所成之樹脂油墨層；具有包含上述樹脂組成物的樹脂組成物層之樹脂薄片；及包含上述樹脂組成物的硬化物之半導體晶片封裝。 The present invention relates to: a resin composition containing an epoxy resin and a hardener; a resin ink containing the above-mentioned resin composition; a resin ink layer formed from the above-mentioned resin ink; and a resin having a resin composition layer containing the above-mentioned resin composition. Sheet; and a semiconductor chip package containing a cured product of the above-mentioned resin composition.

近年來，智慧型手機、平板型裝置等小型的高機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，亦要求更高機能化。已知如此的絕緣層係將樹脂組成物硬化而形成者等(例如參照專利文獻1)。 In recent years, the demand for small, high-performance electronic devices such as smartphones and tablet devices has increased. Along with this, the insulating materials for semiconductor chip packaging used in these small electronic devices have also been required to have higher functionality. It is known that such an insulating layer is formed by hardening a resin composition (for example, see Patent Document 1).

[先前技術文獻] [Prior technical literature] [專利文獻] [Patent Document]

[專利文獻1]日本特開2017-008312號公報 [Patent Document 1] Japanese Patent Application Publication No. 2017-008312

半導體晶片封裝用絕緣材料係為了可靠性提高，要求即使暴露於高溫處理下也不易遭受不良影響，於今後的小型化‧薄膜化的愈來愈高的要求之中，以往的絕緣材料還有改良之餘地的情況多。特別地，由於小型化‧薄膜化之請求，為了提高微細配線形成或晶片組裝時之安定性‧良率，封裝的翹曲抑制之要求係升高，但為了提高翹曲抑制，若提高硬化物的柔軟性，則會造成暴露於高溫處理時的機械特性之變差，硬化物會變脆。因此，可知兼顧該翹曲抑制與脆化抑制者係困難。 Insulating materials for semiconductor chip packaging are required to be less susceptible to adverse effects even when exposed to high-temperature processing in order to improve reliability. In view of the increasingly high requirements for miniaturization and thinning in the future, conventional insulating materials need to be improved. There are many situations where there is room. In particular, due to the requirements for miniaturization and thinning, in order to improve the stability and yield during fine wiring formation or chip assembly, the requirements for package warpage suppression are increasing. However, in order to improve warpage suppression, if the hardened material is increased The softness will cause the mechanical properties to deteriorate when exposed to high temperature treatment, and the hardened material will become brittle. Therefore, it is understood that it is difficult to achieve both the warpage suppression and the embrittlement suppression.

本發明之課題在於提供能得到翹曲抑制及脆化抑制優異的硬化物之樹脂組成物。 An object of the present invention is to provide a resin composition capable of obtaining a cured product excellent in warpage suppression and embrittlement suppression.

為了達成本發明之課題，本發明者們專心致力地檢討，結果發現藉由將樹脂組成物的硬化物之透過係數及線熱膨脹係數調整至指定之範圍內，可得到翹曲抑制及脆化抑制優異的硬化物，終於完成本發明。 In order to achieve the object of the present invention, the inventors conducted intensive examinations and found that by adjusting the transmission coefficient and linear thermal expansion coefficient of the cured resin composition to within specified ranges, warpage and embrittlement suppression can be obtained. Excellent hardened product, the present invention was finally completed.

即，本發明包含以下之內容。 That is, the present invention includes the following contents.

[1]一種樹脂組成物，其係包含(A)環氧樹脂及(B)硬化劑之樹脂組成物，使上述樹脂組成物在180℃熱硬化90分鐘而得的硬化物之透氧係數為3cc/(atm‧m2‧天‧mm)以下，上述硬化物之線熱膨脹係數為4~15ppm/℃。 [1] A resin composition containing (A) epoxy resin and (B) hardener. The oxygen permeability coefficient of the cured product obtained by thermally curing the resin composition at 180° C. for 90 minutes is: 3cc/(atm‧m 2 ‧day‧mm) or less, the linear thermal expansion coefficient of the above-mentioned hardened material is 4~15ppm/℃.

[2]如[1]記載之樹脂組成物，其進一步包含(C)無機填 充材。 [2] The resin composition according to [1], further containing (C) an inorganic filler Filling material.

[3]如[2]記載之樹脂組成物，其中將樹脂組成物中的不揮發成分當作100質量%時，(C)成分之含量為83質量%以上。 [3] The resin composition according to [2], wherein the content of component (C) is 83 mass% or more when the non-volatile components in the resin composition are regarded as 100 mass%.

[4]如[2]或[3]記載之樹脂組成物，其中(C)成分之平均粒徑為2.5μm以上。 [4] The resin composition according to [2] or [3], wherein the average particle diameter of component (C) is 2.5 μm or more.

[5]如[1]~[4]中任一項記載之樹脂組成物，其中(A)成分包含固體狀環氧樹脂。 [5] The resin composition according to any one of [1] to [4], wherein the component (A) contains a solid epoxy resin.

[6]如[1]~[5]中任一項記載之樹脂組成物，其中(A)成分包含液狀環氧樹脂，且將樹脂組成物中的樹脂成分當作100質量%時，液狀環氧樹脂之含量為70質量%以下。 [6] The resin composition according to any one of [1] to [5], wherein the component (A) contains a liquid epoxy resin, and when the resin component in the resin composition is regarded as 100% by mass, the liquid The content of the epoxy resin is less than 70% by mass.

[7]如[1]~[6]中任一項記載之樹脂組成物，其中作為(A)成分包含的環氧樹脂之環氧當量為400g/eq.以下。 [7] The resin composition according to any one of [1] to [6], wherein the epoxy resin contained as the component (A) has an epoxy equivalent of 400 g/eq. or less.

[8]如[1]~[7]中任一項記載之樹脂組成物，其中(B)成分包含苯酚系硬化劑或酸酐系硬化劑。 [8] The resin composition according to any one of [1] to [7], wherein the component (B) contains a phenol-based hardener or an acid anhydride-based hardener.

[9]如[1]~[8]中任一項記載之樹脂組成物，其進一步包含(D)彈性體。 [9] The resin composition according to any one of [1] to [8], further containing (D) elastomer.

[10]如[9]記載之樹脂組成物，其中將樹脂組成物中的樹脂成分當作100質量%時，(D)成分之含量為30質量%以下。 [10] The resin composition according to [9], wherein the content of component (D) is 30 mass% or less when the resin component in the resin composition is regarded as 100 mass%.

[11]如[1]~[10]中任一項記載之樹脂組成物，其中使樹脂組成物在180℃熱硬化24小時而得的硬化物之依據JIS K7127測定的在23℃的伸長率相對於使樹脂組成物在180℃熱硬化90分鐘而得的硬化物之依據JIS K7127測定的在23 ℃的伸長率之比為0.7以上。 [11] The resin composition according to any one of [1] to [10], wherein the cured product obtained by thermally curing the resin composition at 180°C for 24 hours has an elongation at 23°C measured in accordance with JIS K7127. Compared to the cured product obtained by thermally curing the resin composition at 180°C for 90 minutes, the value measured in accordance with JIS K7127 is 23 The ratio of elongation to ℃ is 0.7 or more.

[12]如[1]~[11]中任一項記載之樹脂組成物，其係半導體晶片封裝之半導體晶片密封用。 [12] The resin composition according to any one of [1] to [11], which is used for sealing semiconductor wafers in semiconductor wafer packaging.

[13]一種樹脂油墨，其包含如[1]~[11]中任一項記載之樹脂組成物。 [13] A resin ink containing the resin composition according to any one of [1] to [11].

[14]一種樹脂油墨層，其係由如[13]記載之樹脂油墨所成的厚度100μm以上者。 [14] A resin ink layer made of the resin ink according to [13] and having a thickness of 100 μm or more.

[15]一種樹脂薄片，其具有支撐體與設於上述支撐體上之包含如[1]~[11]中任一項記載之樹脂組成物的樹脂組成物層。 [15] A resin sheet having a support and a resin composition layer provided on the support and including the resin composition according to any one of [1] to [11].

[16]如[15]記載之樹脂薄片，其中上述樹脂組成物層之厚度為100μm以上。 [16] The resin sheet according to [15], wherein the thickness of the resin composition layer is 100 μm or more.

[17]一種半導體晶片封裝，其包含如[1]~[11]中任一項記載之樹脂組成物的硬化物。 [17] A semiconductor chip package containing a cured product of the resin composition according to any one of [1] to [11].

依照本發明，可提供：能得到翹曲抑制及脆化抑制優異的硬化物之樹脂組成物；包含上述樹脂組成物之樹脂油墨；由上述樹脂油墨所成之樹脂油墨層；具有包含上述樹脂組成物的樹脂組成物層之樹脂薄片；及包含上述樹脂組成物的硬化物之半導體晶片封裝。 According to the present invention, it is possible to provide: a resin composition capable of obtaining a cured product excellent in warpage suppression and embrittlement suppression; a resin ink containing the above resin composition; a resin ink layer composed of the above resin ink; and a resin composition containing the above resin composition. A resin sheet having a resin composition layer; and a semiconductor chip package including a cured product of the above-mentioned resin composition.

[實施發明的形態] [Form of carrying out the invention]

以下，以合適的實施形態詳細地說明本發明。惟，本發明不受下述實施形態及例示物所限定，在不脫離本發明之發明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, the present invention will be described in detail with appropriate embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented within the scope of the invention and its equivalent range without departing from the patentable scope of the invention.

<樹脂組成物> <Resin composition>

本發明之樹脂組成物包含(A)環氧樹脂及(B)硬化劑。使本發明之樹脂組成物在180℃熱硬化90分鐘而得的硬化物之透過係數為3cc/(atm‧m2‧天‧mm)以下，且硬化物之線熱膨脹係數為4~15ppm/℃。 The resin composition of the present invention includes (A) epoxy resin and (B) hardener. The transmission coefficient of the cured product obtained by thermally curing the resin composition of the present invention at 180°C for 90 minutes is 3cc/(atm‧m 2 ‧day‧mm) or less, and the linear thermal expansion coefficient of the cured product is 4~15ppm/°C. .

藉由使用如此之樹脂組成物，可達成能得到翹曲抑制及脆化抑制優異的硬化物之本發明的所欲效果。 By using such a resin composition, the desired effect of the present invention can be achieved in that a cured product excellent in warpage suppression and embrittlement suppression can be obtained.

本發明之樹脂組成物係除了(A)環氧樹脂及(B)硬化劑之外，還可進一步包含任意的成分。作為任意的成分，例如可舉出(C)無機填充材、(D)彈性體、(E)橡膠粒子、(F)硬化促進劑、(G)有機溶劑及(H)其他添加劑。以下，詳細說明樹脂組成物中所包含的各成分。 The resin composition of the present invention may further contain optional components in addition to (A) epoxy resin and (B) hardener. Examples of optional components include (C) inorganic filler, (D) elastomer, (E) rubber particles, (F) hardening accelerator, (G) organic solvent, and (H) other additives. Each component contained in the resin composition will be described in detail below.

<(A)環氧樹脂> <(A)Epoxy resin>

本發明之樹脂組成物含有(A)環氧樹脂。 The resin composition of the present invention contains (A) epoxy resin.

作為(A)環氧樹脂，例如可舉出聯二甲苯酚型環氧樹脂、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、三苯酚型環氧樹脂、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、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、具有丁二烯構造的環氧樹脂、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、萘醚型環氧樹脂、三羥甲基型環氧樹脂、四苯基乙烷型環氧樹脂等。環氧樹脂係可單獨使用1種類，也可組合2種以上使用。 Examples of the (A) epoxy resin include dixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AF type epoxy resin. Oxygen resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, benzene Phenolic novolak type epoxy resin, tert-butylcatechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, epoxypropylamine type epoxy resin, ring Oxypropyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, Heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane epoxy resin, cyclohexanedimethanol epoxy resin, naphthyl ether type epoxy resin, trimethylol type epoxy resin, tetrahydroxymethyl epoxy resin, Phenylethane type epoxy resin, etc. One type of epoxy resin can be used alone, or two or more types can be used in combination.

樹脂組成物較佳為包含在1分子中具有2個以上的環氧基之環氧樹脂作為(A)環氧樹脂。從顯著地得到本發明之所欲效果之觀點來看，相對於(A)環氧樹脂的不揮發成分100質量%，在1分子中具有2個以上的環氧基之環氧樹脂之比例較佳為50質量%以上，更佳為60質量%以上，特佳為70質量%以上。 The resin composition preferably contains an epoxy resin having two or more epoxy groups per molecule as (A) epoxy resin. From the viewpoint of significantly obtaining the desired effect of the present invention, the proportion of the epoxy resin having two or more epoxy groups per molecule is relatively high relative to 100% by mass of the non-volatile content of the epoxy resin (A). Preferably, it is 50 mass % or more, more preferably, it is 60 mass % or more, and especially preferably, it is 70 mass % or more.

於環氧樹脂中，有在溫度20℃液狀的環氧樹脂(以下亦稱為「液狀環氧樹脂」)與在溫度20℃固體狀的環氧樹脂(以下亦稱為「固體狀環氧樹脂」)。於一實施形態中，本發明之樹脂組成物包含液狀環氧樹脂作為環氧樹脂。於一實施形態中，本發明之樹脂組成物包含固體狀環氧樹脂作為環氧樹脂。本發明之樹脂組成物係可僅包含液狀環氧樹脂作為環氧樹脂，或也可僅包含固體狀環氧樹脂作為環氧樹脂，但較佳為組合液狀環氧樹脂與固體狀環氧樹脂而含有。 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"). Oxygen resin"). In one embodiment, the resin composition of the present invention includes liquid epoxy resin as the epoxy resin. In one embodiment, the resin composition of the present invention includes a solid epoxy resin as the epoxy resin. The resin composition of the present invention may include only liquid epoxy resin as the epoxy resin, or may include only solid epoxy resin as the epoxy resin, but it is preferred to combine the liquid epoxy resin and the solid epoxy resin. Contains resin.

作為液狀環氧樹脂，較佳為在1分子中具有2個以上的環氧基之液狀環氧樹脂。 As the liquid epoxy resin, one having two or more epoxy groups per molecule is preferred.

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、環氧丙基胺型環氧樹脂及具有丁二烯構造的環氧樹脂，更佳為環氧丙基胺型環氧樹脂、雙酚A型環氧樹脂及雙酚F型環氧樹脂。 As the liquid epoxy resin, preferred are 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, glycidyl Amine-type epoxy resin and epoxy resin with butadiene structure, more preferably glycidylamine-type epoxy resin, bisphenol A-type epoxy resin and bisphenol F-type epoxy resin.

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」、「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」(環氧丙基胺型環氧樹脂)；新日鐵住金化學公司製之「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)；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」(具有丁二烯構造的環氧樹脂)；新日鐵住金化學公司製之 「ZX1658」、「ZX1658GS」(液狀1,4-環氧丙基環己烷型環氧樹脂)等。此等係可單獨使用1種類，也可組合2種以上使用。 Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; "828US", "jER828EL", and " 825", "Epikote 828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical Corporation's "jER807", "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical Corporation's "jER152" (phenol novolac Varnish type epoxy resin); "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (bisphenol A type epoxy resin manufactured by Nippon Steel and Sumitomo Metal Chemical Corporation) Mixed product with bisphenol F-type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "Celloxide 2021P" (alicyclic ester skeleton with ester skeleton) manufactured by DAICEL type epoxy resin); "PB-3600" made by DAICEL Co., Ltd., "JP-100" and "JP-200" made by Nippon Soda Co., Ltd. (epoxy resin with butadiene structure); Nippon Steel & Sumitomo Metal Chemical Co., Ltd. control it "ZX1658", "ZX1658GS" (liquid 1,4-epoxypropylcyclohexane type epoxy resin), etc. One type of these can be used alone, or two or more types can be used in combination.

作為固體狀環氧樹脂，較佳為在1分子中具有3個以上的環氧基之固體狀環氧樹脂，更佳為在1分子中具有3個以上的環氧基之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 per molecule, and more preferably an aromatic solid having three or more epoxy groups per molecule. epoxy resin.

作為固體狀環氧樹脂，較佳為聯二甲苯酚型環氧樹脂、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、三苯酚型環氧樹脂、萘酚型環氧樹脂、聯苯型環氧樹脂、萘醚型環氧樹脂、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, preferred are dixylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol novolac-type epoxy resin, and dicyclopentadiene-type epoxy resin. Resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin 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」(二環戊二烯型環氧樹脂)；DIC公司製之「HP-7200HH」、「HP-7200H」、「EXA-7311」、「EXA-7311-G3」、「EXA-7311-G4」、「EXA-7311-G4S」、「HP6000」(萘醚型環氧樹脂)；日本化藥公司製之「EPPN-502H」(三苯酚型環氧樹脂)；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)；新日鐵住金化學公司製之「ESN475V」(萘酚型環氧樹脂)；新日鐵住金化學公司製之「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」(聯二甲苯酚型環氧樹脂)；三菱化學公司製之「YX8800」(蒽型環氧樹脂)；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。此等係可單獨使用1種類，也可組合2種以上使用。 Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Resin); "N-690" (cresol novolak type epoxy resin) made by DIC; "N-695" (cresol novolak type epoxy resin) made by DIC; "HP- 7200" (dicyclopentadiene type epoxy resin); "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" manufactured by DIC Corporation ", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" manufactured by Nippon Kayaku Co., Ltd. ” (naphthol novolak type epoxy resin); “NC3000H”, “NC3000”, “NC3000L” manufactured by Nippon Kayaku Co., Ltd. "NC3100" (biphenyl-type epoxy resin); "ESN475V" (naphthol-type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.; "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. Oxygen resin); "YX4000H", "YX4000", "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical "YX8800" (anthracene type epoxy resin) manufactured by the company; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Company; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" manufactured by Mitsubishi Chemical Corporation (N-type epoxy resin); "jER1010" manufactured by Mitsubishi Chemical Corporation (solid bisphenol A-type epoxy resin); "jER1031S" (tetraphenyl ethane) manufactured by Mitsubishi Chemical Corporation type epoxy resin), etc. One type of these can be used alone, or two or more types can be used in combination.

作為(A)環氧樹脂，組合液狀環氧樹脂與固體狀環氧樹脂而使用時，彼等的量比(液狀環氧樹脂：固體狀環氧樹脂)以質量比表示，較佳為20：1~1：20，更佳為10：1~1：10，特佳為5：1~1：5。由於液狀環氧樹脂與固體狀環氧樹脂的量比在如此的範圍，可顯著得到本發明之所欲效果。 When the (A) epoxy resin is used in combination with a liquid epoxy resin and a solid epoxy resin, the quantitative ratio (liquid epoxy resin: solid epoxy resin) is expressed as a mass ratio, preferably 20:1~1:20, better is 10:1~1:10, especially best is 5:1~1:5. Since the quantity ratio of the liquid epoxy resin to the solid epoxy resin is in such a range, the desired effects of the present invention can be significantly obtained.

從顯著得到本發明之所欲效果之觀點來看，(A)環氧樹脂之環氧當量較佳為50g/eq.以上，更佳為70g/eq.以上。另一方面，從顯著得到本發明之所欲效果之觀點來看，環氧當量較佳為5000g/eq.以下，更佳2000g/eq.以下，尤佳為1000g/eq.以下，尤較佳為500g/eq.以下，尤更佳為400g/eq.以下，特佳為350g/eq.以下。環氧當量係包 含1當量的環氧基之環氧樹脂的質量。此環氧當量係可依照JIS K7236測定。 From the viewpoint of significantly obtaining the desired effect of the present invention, the epoxy equivalent of (A) the epoxy resin is preferably 50 g/eq. or more, more preferably 70 g/eq. or more. On the other hand, from the viewpoint of significantly obtaining the desired effect of the present invention, the epoxy equivalent is preferably 5000 g/eq. or less, more preferably 2000 g/eq. or less, even more preferably 1000 g/eq. or less, and even more preferably 500g/eq. or less, more preferably 400g/eq. or less, particularly preferably 350g/eq. or less. Epoxy equivalent system package The mass of epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured in accordance with JIS K7236.

從顯著得到本發明之所欲效果之觀點來看，(A)環氧樹脂之重量平均分子量(Mw)較佳為100~5000，更佳為250~3000，尤佳為400~1500。樹脂之重量平均分子量係可藉由凝膠滲透層析(GPC)法，作為聚苯乙烯換算之值測定。 From the viewpoint of significantly obtaining the desired effect of the present invention, the weight average molecular weight (Mw) of (A) the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and particularly preferably 400 to 1500. The weight average molecular weight of the resin can be measured as a polystyrene-converted value by gel permeation chromatography (GPC).

(A)環氧樹脂之含量係沒有特別的限定，但將樹脂組成物中的樹脂成分當作100質量%時，從顯著得到本發明之所欲效果之觀點來看，較佳為20質量%以上，更佳為30質量%以上，尤佳為40質量%以上，特佳為45質量%以上。從顯著得到本發明之所欲效果之觀點來看，其上限較佳為90質量%以下，更佳為80質量%以下，尤佳為70質量%以下，特佳為60質量%以下。 The content of (A) epoxy resin is not particularly limited. However, when the resin component in the resin composition is regarded as 100% by mass, from the viewpoint of significantly obtaining the desired effect of the present invention, 20% by mass is preferred. or above, more preferably 30% by mass or more, still more preferably 40% by mass or more, and particularly preferably 45% by mass or more. From the viewpoint of significantly obtaining the desired effect of the present invention, the upper limit is preferably 90 mass% or less, more preferably 80 mass% or less, particularly preferably 70 mass% or less, and particularly preferably 60 mass% or less.

還有，本說明書中所謂的「樹脂成分」，就是指在構成樹脂組成物的不揮發成分之中，去除後述的(C)無機填充材後之成分。 In addition, the "resin component" in this specification refers to the component excluding the (C) inorganic filler mentioned later among the non-volatile components constituting the resin composition.

包含液狀環氧樹脂時，液狀環氧樹脂之含量係沒有特別的限定，但將樹脂組成物中的樹脂成分當作100質量%時，從顯著得到本發明之所欲效果之觀點來看，較佳為10質量%以上，更佳為20質量%以上，尤佳為25質量%以上，特佳為30質量%以上。從顯著得到本發明之所欲效果之觀點來看，其上限較佳為90質量%以下，更佳為80質量%以下，尤佳為70質量%以下，特佳為60質量 %以下。 When a liquid epoxy resin is included, the content of the liquid epoxy resin is not particularly limited. However, when the resin component in the resin composition is regarded as 100% by mass, the desired effect of the present invention is significantly obtained. , preferably 10 mass% or more, more preferably 20 mass% or more, particularly preferably 25 mass% or more, particularly preferably 30 mass% or more. From the viewpoint of significantly obtaining the desired effect of the present invention, the upper limit is preferably 90 mass% or less, more preferably 80 mass% or less, particularly preferably 70 mass% or less, and particularly preferably 60 mass%. %the following.

包含固體狀環氧樹脂時，固體狀環氧樹脂之含量係沒有特別的限定，但將樹脂組成物中的樹脂成分當作100質量%時，從顯著得到本發明之所欲效果之觀點來看，較佳為1質量%以上，更佳為5質量%以上，尤佳為10質量%以上，特佳為15質量%以上。從顯著得到本發明之所欲效果之觀點來看，其上限較佳為40質量%以下，更佳為30質量%以下，尤佳為25質量%以下，特佳為20質量%以下。 When a solid epoxy resin is included, the content of the solid epoxy resin is not particularly limited. However, when the resin component in the resin composition is regarded as 100% by mass, the desired effect of the present invention is significantly obtained. , preferably 1 mass% or more, more preferably 5 mass% or more, particularly preferably 10 mass% or more, particularly preferably 15 mass% or more. From the viewpoint of significantly obtaining the desired effect of the present invention, the upper limit is preferably 40 mass% or less, more preferably 30 mass% or less, particularly preferably 25 mass% or less, and particularly preferably 20 mass% or less.

<(B)硬化劑> <(B) Hardener>

本發明之樹脂組成物含有(B)硬化劑。 The resin composition of the present invention contains (B) hardener.

作為(B)硬化劑，只要具有使環氧樹脂硬化之機能，則沒有特別的限定，例如可舉出苯酚系硬化劑、萘酚系硬化劑、酸酐系硬化劑、活性酯系硬化劑、苯并

Figure 108127984-A0305-02-0013-2
Figure 108127984-A0305-02-0013-3
系硬化劑、氰酸酯系硬化劑及碳二亞胺系硬化劑。硬化劑係可單獨1種使用，也可組合2種以上使用。本發明之樹脂組成物的(B)硬化劑，從顯著得到本發明之所欲效果之觀點來看，較佳為包含苯酚系硬化劑或酸酐系硬化劑者。 The curing agent (B) is not particularly limited as long as it has the function of curing the epoxy resin. Examples thereof include phenol-based curing agents, naphthol-based curing agents, acid anhydride-based curing agents, active ester-based curing agents, and benzene-based curing agents. and
Figure 108127984-A0305-02-0013-2
Figure 108127984-A0305-02-0013-3
It is a hardener, cyanate ester hardener and carbodiimide hardener. The hardener system may be used individually by 1 type, or in combination of 2 or more types. The (B) hardener of the resin composition of the present invention preferably contains a phenol-based hardener or an acid anhydride-based hardener from the viewpoint of significantly obtaining the desired effects of the present invention.

作為苯酚系硬化劑及萘酚系硬化劑，從耐熱性及耐水性之觀點來看，較佳為具有酚醛清漆構造的苯酚系硬化劑或具有酚醛清漆構造的萘酚系硬化劑。又，從對於被附體的密著性之觀點來看，較佳為含氮苯酚系硬化劑或含氮萘酚系硬化劑，更佳為含三

Figure 108127984-A0305-02-0013-4
骨架的苯酚系硬化劑 或含三
Figure 108127984-A0305-02-0014-5
骨架的萘酚系硬化劑。其中，從高度滿足耐熱性、耐水性及密著性之觀點來看，較佳為含三
Figure 108127984-A0305-02-0014-6
骨架的苯酚酚醛清漆樹脂。作為苯酚系硬化劑及萘酚系硬化劑之具體例，例如可舉出明和化成公司製之「MEH-7700」、「MEH-7810」、「MEH-7851」、日本化藥公司製之「NHN」、「CBN」、「GPH」、新日鐵住金化學公司製之「SN-170」、「SN-180」、「SN-190」、「SN-475」、「SN-485」、「SN-495」、「SN-375」、「SN-395」、DIC公司製之「LA-7052」、「LA-7054」、「LA-3018」、「LA-3018-50P」、「LA-1356」、「TD2090」等。 As the phenol-based hardener and the naphthol-based hardener, from the viewpoint of heat resistance and water resistance, a phenol-based hardener having a novolac structure or a naphthol-based hardener having a novolac structure is preferred. Furthermore, from the viewpoint of adhesion to the adherend, a nitrogen-containing phenol-based hardening agent or a nitrogen-containing naphthol-based hardening agent is preferred, and a nitrogen-containing naphthol-based hardening agent is more preferred.
Figure 108127984-A0305-02-0013-4
The skeleton of phenol hardener may contain three
Figure 108127984-A0305-02-0014-5
Naphthol based hardener with skeleton. Among them, from the viewpoint of highly satisfying heat resistance, water resistance and adhesion, those containing the three
Figure 108127984-A0305-02-0014-6
Backbone of phenol novolac resin. Specific examples of phenol-based hardeners and naphthol-based hardeners include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN" manufactured by Nippon Kayaku Co., Ltd. ", "CBN", "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. -495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356" made by DIC Corporation ”, “TD2090”, etc.

作為酸酐系硬化劑，可舉出在1分子內中具有1個以上的酸酐基之硬化劑。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、甲基六氫鄰苯二甲酸酐、甲基納迪克酸酐、氫化甲基納迪克酸酐、三烷基四氫鄰苯二甲酸酐、十二烯基琥珀酸酐、5-(2,5-二氧代四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、偏苯三酸酐、苯均四酸酐、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之酸酐等。作為酸酐系硬化劑之市售品，可舉 出新日本理化公司製之「HNA-100」、「MH-700」等。 Examples of the acid anhydride-based curing agent include those having one or more acid anhydride groups per molecule. Specific examples of the acid anhydride-based hardener include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Dicarboxylic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3- Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, diphenyl ketone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene Tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyltetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydrogen -5-(Tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride), styrene and Polymer-type acid anhydrides such as styrene and maleic acid resin copolymerized with maleic acid. Commercially available acid anhydride hardeners include "HNA-100", "MH-700", etc. manufactured by Shin Nippon Rika Co., Ltd. are released.

作為活性酯系硬化劑，並沒有特別的限制，一般較宜使用苯酚酯類、硫苯酚酯類、N-羥基胺酯類、雜環羥基化合物之酯類等的反應活性高之在1分子中具有2個以上的酯基之化合物。該活性酯系硬化劑較佳為藉由羧酸化合物及/或硫代羧酸化合物與羥基化合物及/或硫醇化合物之縮合反應而獲得者。特別地從耐熱性提升之觀點來看，較佳為由羧酸化合物與羥基化合物所得之活性酯系硬化劑，更佳為由羧酸化合物與苯酚化合物及/或萘酚化合物所得之活性酯系硬化劑。作為羧酸化合物，例如可舉出苯甲酸、醋酸、琥珀酸、馬來酸、伊康酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、苯均四酸等。作為苯酚化合物或萘酚化合物，例如可舉出氫醌、間苯二酚、雙酚A、雙酚F、雙酚S、酚酞啉、甲基化雙酚A、甲基化雙酚F、甲基化雙酚S、苯酚、鄰甲酚、間甲酚、對甲酚、兒茶酚、α-萘酚、β-萘酚、1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基二苯基酮、三羥基二苯基酮、四羥基二苯基酮、間苯三酚、苯三酚、二環戊二烯型的二苯酚化合物、苯酚酚醛清漆等。此處所謂的「二環戊二烯型二苯酚化合物」，就是指苯酚2分子縮合於二環戊二烯1分子而得之二苯酚化合物。 There are no particular restrictions on the active ester hardener. Generally, it is preferable to use phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxyl compounds, etc., which have high reactivity per molecule. Compounds with two or more ester groups. The active ester hardener is preferably obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester hardener obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester system obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is more preferred. Hardener. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthaloline, methylated bisphenol A, methylated bisphenol F, and toluene. Sylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-Dihydroxynaphthalene, dihydroxydiphenylketone, trihydroxydiphenylketone, tetrahydroxydiphenylketone, phloroglucinol, phloroglucinol, dicyclopentadiene-type diphenol compounds, phenol Novolac, etc. The so-called "dicyclopentadiene-type diphenol compound" here refers to a diphenol compound obtained by condensing two molecules of phenol into one molecule of dicyclopentadiene.

具體而言，較佳為包含二環戊二烯型二苯酚構造的活性酯化合物、包含萘構造的活性酯化合物、包含苯酚酚醛清漆的乙醯化物之活性酯化合物、包含苯酚酚醛 清漆的苯甲醯化物之活性酯化合物，其中更佳為包含萘構造的活性酯化合物、包含二環戊二烯型二苯酚構造的活性酯化合物。所謂的「二環戊二烯型二苯酚構造」，就是表示由伸苯基-二環戊搭烯-伸苯基所成之2價的結構單元。 Specifically, preferred are active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetate of phenol novolac, and phenol novolacs. An active ester compound of a benzyl compound of a varnish, of which an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferred. The so-called "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene group-dicyclopentadienyl-phenylene group.

作為活性酯系硬化劑之市售品，於包含二環戊二烯型二苯酚構造的活性酯化合物中，可舉出「EXB9451」、「EXB9460」、「EXB9460S」、「HPC-8000」、「HPC-8000H」、「HPC-8000-65T」、「HPC-8000H-65TM」、「EXB-8000L」、「EXB-8000L-65TM」(DIC公司製)；於包含萘構造的活性酯化合物中，可舉出「EXB9416-70BK」、「EXB-8150-65T」(DIC公司製)；於包含苯酚酚醛清漆的乙醯化物之活性酯化合物中，可舉出「DC808」(三菱化學公司製)；於包含苯酚酚醛清漆的苯甲醯化物之活性酯化合物中，可舉出「YLH1026」(三菱化學公司製)；於苯酚酚醛清漆的乙醯化物之活性酯系硬化劑中，可舉出「DC808」(三菱化學公司製)；於苯酚酚醛清漆的苯甲醯化物之活性酯系硬化劑，可舉出「YLH1026」(三菱化學公司製)、「YLH1030」(三菱化學公司製)、「YLH1048」(三菱化學公司製)等。 As commercially available active ester hardeners, among active ester compounds containing a dicyclopentadiene-type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", " HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65TM" (manufactured by DIC Corporation); among active ester compounds containing a naphthalene structure, Examples include "EXB9416-70BK" and "EXB-8150-65T" (manufactured by DIC Corporation); among active ester compounds containing acetyl compounds of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation) can be cited; Among the active ester compounds containing the benzyl compound of phenol novolac, "YLH1026" (manufactured by Mitsubishi Chemical Corporation) can be cited; among the active ester hardeners of the acetyl compound of phenol novolak, "DC808" can be cited ” (manufactured by Mitsubishi Chemical Corporation); active ester-based hardeners for benzyl compounds of phenol novolaks include “YLH1026” (manufactured by Mitsubishi Chemical Corporation), “YLH1030” (manufactured by Mitsubishi Chemical Corporation), and “YLH1048” (Made by Mitsubishi Chemical Corporation), etc.

作為苯并

Figure 108127984-A0305-02-0016-7
系硬化劑之具體例，可舉出JFE化學公司製之「JBZ-OP100D」、「ODA-BOZ」；昭和高分子公司製之「HFB2006M」、四國化成工業公司製之「P-d」、「F-a」等。 as benzo
Figure 108127984-A0305-02-0016-7
Specific examples of the hardener include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd. "wait.

作為氰酸酯系硬化劑，例如可舉出雙酚A二 氰酸酯、多酚氰酸酯(寡聚(3-亞甲基-1,5-伸苯基氰酸酯))、4,4’-亞甲基雙(2,6-二甲基苯基氰酸酯)、4,4’-亞乙基二苯基二氰酸酯、六氟雙酚A二氰酸酯、2,2-雙(4-氰酸酯)苯基丙烷、1,1-雙(4-氰酸酯苯基甲烷)、雙(4-氰酸酯-3,5-二甲基苯基)甲烷、1,3-雙(4-氰酸酯苯基-1-(甲基亞乙基))苯、雙(4-氰酸酯苯基)硫醚，及雙(4-氰酸酯苯基)醚等之2官能氰酸酯樹脂、由苯酚酚醛清漆及甲酚酚醛清漆等所衍生之多官能氰酸酯樹脂、此等氰酸酯樹脂經一部分三

Figure 108127984-A0305-02-0017-8
化之預聚物等。作為氰酸酯系硬化劑之具體例，可舉LONZA日本公司製之「PT30」及「PT60」(皆苯酚酚醛清漆型多官能氰酸酯樹脂)、「BA230」、「BA230S75」(雙酚A二氰酸酯之一部分或全部經三
Figure 108127984-A0305-02-0017-9
化成三聚物之預聚)等。 Examples of the cyanate-based hardener include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4, 4'-methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2, 2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylene))benzene, bis(4-cyanatophenyl)sulfide, and bis(4-cyanatophenyl) Difunctional cyanate ester resins such as ethers, multifunctional cyanate ester resins derived from phenol novolaks and cresol novolaks, etc., these cyanate ester resins are treated with a portion of
Figure 108127984-A0305-02-0017-8
Chemical prepolymers, etc. Specific examples of cyanate ester hardeners include "PT30" and "PT60" (both phenol novolak type polyfunctional cyanate ester resins) manufactured by LONZA Japan, "BA230", and "BA230S75" (bisphenol A One part or all of the dicyanate has been treated with three
Figure 108127984-A0305-02-0017-9
Prepolymerization into trimer), etc.

作為碳二亞胺系硬化劑之具體例，可舉出日清紡化學公司製之「V-03」、「V-07」等。 Specific examples of carbodiimide-based hardeners include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

包含硬化劑時，環氧樹脂與硬化劑之量比，以[環氧樹脂的環氧基之合計數]：[硬化劑的反應基之合計數]之比率表示，較佳為1：0.2~1：2之範圍，更佳為1：0.3~1：1.5，尤佳為1：0.4~1：1.2。此處，所謂硬化劑之反應基，就是活性羥基、活性酯基等，取決於硬化劑之種類而不同。又，所謂環氧樹脂的環氧基之合計數，就是將各環氧樹脂的不揮發成分質量除以環氧當量而得之值，對於全部的環氧樹脂所合計之值，所謂硬化劑的反應基之合計數，就是將各硬化劑的不揮發成分質量除以反應基當 量而得之值，對於全部的硬化劑所合計之值。由於環氧樹脂與硬化劑之量比為如此的範圍，所得之硬化物的耐熱性係更升高。 When a hardener is included, the amount ratio of the epoxy resin to the hardener is expressed as the ratio of [the total number of epoxy groups of the epoxy resin]: [the total number of reactive groups of the hardener], preferably 1:0.2~ The range of 1:2 is preferably 1:0.3~1:1.5, and particularly preferably 1:0.4~1:1.2. Here, the so-called reactive groups of the hardener include active hydroxyl groups, active ester groups, etc., and vary depending on the type of hardener. In addition, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the mass of the non-volatile components of each epoxy resin by the epoxy equivalent. The total number of all epoxy resins is the so-called hardener. The total number of reactive groups is the mass of the non-volatile components of each hardener divided by the reactive groups. The measured value is the total value for all hardeners. Since the amount ratio of the epoxy resin and the hardener is in this range, the heat resistance of the obtained hardened product is further improved.

(B)硬化劑之含量係沒有特別的限定，但將樹脂組成物中的樹脂成分當作100質量%時，從顯著得到本發明之所欲效果之觀點來看，較佳為10質量%以上，更佳為15質量%以上，尤佳為20質量%以上，特佳為25質量%以上。從顯著得到本發明之所欲效果之觀點來看，其上限較佳為50質量%以下，更佳為45質量%以下，尤佳為40質量%以下，特佳為35質量%以下。 (B) The content of the hardener is not particularly limited. However, when the resin component in the resin composition is regarded as 100% by mass, from the viewpoint of significantly obtaining the desired effect of the present invention, it is preferably 10% by mass or more. , more preferably 15% by mass or more, still more preferably 20% by mass or more, and particularly preferably 25% by mass or more. From the viewpoint of significantly obtaining the desired effects of the present invention, the upper limit is preferably 50 mass% or less, more preferably 45 mass% or less, particularly preferably 40 mass% or less, and particularly preferably 35 mass% or less.

<(C)無機填充材> <(C) Inorganic filler>

本發明之樹脂組成物可進一步含有(C)無機填充材作為任意的成分。 The resin composition of the present invention may further contain (C) an inorganic filler as an optional component.

(C)無機填充材之材料係沒有特別的限定，例如可舉出二氧化矽、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，特佳為二氧化矽。作為二氧化矽，例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。無機填充材係可單獨使用1種，也可組合2種以上使用。 (C) The material of the inorganic filler is not particularly limited, and examples thereof include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, and zinc oxide. Hydrotalcite, diaspore, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, Magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc., especially silicon dioxide. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. Furthermore, as silica, spherical silica is preferred. Silicon. The inorganic filler system may be used individually by 1 type, or in combination of 2 or more types.

作為(C)無機填充材之市售品，例如可舉出電化化學工業公司製之「UFP-30」；新日鐵住金材料公司製之「SP60-05」、「SP507-05」；ADMATECHS公司製之「YC100C」、「YA050C」、「YA050C-MJE」、「YA010C」；DENKA公司製之「UFP-30」；TOKUYAMA公司製之「Silfill NSS-3N」、「Silfill NSS-4N」、「Silfill NSS-5N」；ADMATECHS公司製之「SC2500SQ」、「SO-C4」、「SO-C2」、「SO-C1」；等。 Examples of commercially available products of (C) inorganic fillers include "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd.; and ADMATECHS. "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by DENKA; "UFP-30" manufactured by DENKA; "Silfill NSS-3N", "Silfill NSS-4N", "Silfill" manufactured by TOKUYAMA NSS-5N"; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" made by ADMATECHS Co., Ltd.; etc.

(C)無機填充材之平均粒徑，從顯著得到本發明之所欲效果之觀點來看，較佳為30μm以下，更佳為20μm以下，尤佳為15μm以下，尤更佳為12μm以下，特佳為10μm以下。無機填充材之平均粒徑之下限，從顯著得到本發明之所欲效果之觀點來看，較佳為0.1μm以上，更佳為1μm以上，尤佳為2μm以上，特佳為2.5μm以上。特別地，用於樹脂薄片之形態時，較佳為2.5μm以上。無機填充劑之平均粒徑係可藉由以米氏(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，將其中值徑當作平均粒徑而測定。測定樣品係可在小瓶中秤取無機填充材100mg、甲基乙基酮10g，使用以超音波分散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，使用的光源波長為藍色及紅色，以流通池(flow cell)方式測定無機填充材的體積基準之粒徑分布，從所得之粒徑分布，作為中值徑算出平均粒徑。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。 (C) The average particle size of the inorganic filler is preferably 30 μm or less, more preferably 20 μm or less, particularly preferably 15 μm or less, and even more preferably 12 μm or less, from the viewpoint of significantly obtaining the desired effects of the present invention. Particularly preferred is 10 μm or less. From the viewpoint of significantly obtaining the desired effects of the present invention, the lower limit of the average particle size of the inorganic filler is preferably 0.1 μm or more, more preferably 1 μm or more, particularly preferably 2 μm or more, and particularly preferably 2.5 μm or more. In particular, when used in the form of a resin sheet, it is preferably 2.5 μm or more. The average particle size of the inorganic filler can be measured by the laser diffraction and scattering method based on the Mie scattering theory. Specifically, a laser diffraction and scattering particle size distribution measuring device can be used to prepare the particle size distribution of the inorganic filler on a volume basis, and the median diameter can be measured as the average particle size. For the measurement sample, 100 mg of inorganic filler and 10 g of methyl ethyl ketone can be weighed in a vial and dispersed with ultrasonic waves for 10 minutes. For measuring samples, use laser diffraction Type particle size distribution measuring device, using light source wavelengths of blue and red, measuring the volume-based particle size distribution of the inorganic filler using a flow cell method, and calculating the average diameter from the obtained particle size distribution as the median diameter particle size. Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

從提高耐濕性及分散性之觀點來看，(C)無機填充材較佳為被胺基矽烷系偶合劑、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、鈦酸酯系偶合劑等之1種以上的表面處理劑所處理。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「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。 From the viewpoint of improving moisture resistance and dispersibility, (C) the inorganic filler is preferably an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, an alkoxysilane compound, Treated with one or more surface treatment agents such as organosilazane compounds and titanate coupling agents. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd. and "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd. Trimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethyl Oxysilane), "SZ-31" (hexamethylsilazane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM-4803" manufactured by Shin-Etsu Chemical Industries, Ltd. ” (long-chain epoxy silane coupling agent), “KBM-7103” (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., 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，較佳為在指定之範圍內。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 specified 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 with 0.2 to 5 parts by mass of the surface treatment agent, more preferably 0.2 to 3 parts by mass, and most preferably 0.3 parts by mass. parts ~ 2 parts by mass 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而評價。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/m2以上，更佳為0.1mg/m2以上，尤佳為0.2mg/m2以上。另一方面，從防止樹脂清漆的熔融黏度及薄片形態之熔融黏度的上升之觀點來看，較佳為1mg/m2以下，更佳為0.8mg/m2以下，尤佳為0.5mg/m2以下。 The degree of surface treatment caused by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon amount 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 particularly preferably 0.2 mg/m 2 m 2 or more. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish and the melt viscosity of the flake form, it is preferably 1 mg/m 2 or less, more preferably 0.8 mg/m 2 or less, and particularly preferably 0.5 mg/m 2 or less.

(C)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而測定。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劑中，在25℃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。 (C) The carbon amount per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is 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 a carbon analyzer, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd., etc. can be used.

(C)無機填充材之比表面積，從更提高本發明之效果之觀點來看，較佳為1m2/g以上，更佳為1.5m2/g以上，特佳為2m2/g以上。上限係沒有特別的限制，但較佳為50m2/g以下、45m2/g以下或40m2/g以下。無機填充材之比表面積係依照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。 (C) The specific surface area of the inorganic filler is preferably 1 m 2 /g or more, more preferably 1.5 m 2 /g or more, and particularly preferably 2 m 2 /g or more, from the viewpoint of further improving the effect of the present invention. The upper limit is not particularly limited, but is preferably 50 m 2 /g or less, 45 m 2 /g or less, or 40 m 2 /g or less. The specific surface area of the inorganic filler material was calculated based on the BET method, using a specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH Corporation), adsorbing nitrogen gas on the sample surface, and calculating the specific surface area using the BET multi-point method.

含有(C)無機填充材時，(C)無機填充材之含量係沒有特別的限定，將樹脂組成物中的不揮發成分當作100質量%時，從顯著得到本發明之所欲效果之觀點來看，較佳為70質量%以上，更佳為80質量%以上，尤佳為83質量%以上，特佳為85質量%以上。從顯著得到本發明之所欲效果之觀點來看，其上限較佳為95質量%以下，更佳為90質量%以下，尤佳為88質量%以下。 When the (C) inorganic filler is contained, the content of the (C) inorganic filler is not particularly limited. When the non-volatile components in the resin composition are regarded as 100% by mass, the desired effects of the present invention are significantly obtained. From this point of view, 70 mass % or more is preferred, 80 mass % or more is more preferred, 83 mass % or more is particularly preferred, and 85 mass % or more is particularly preferred. From the viewpoint of significantly obtaining the desired effect of the present invention, the upper limit is preferably 95 mass% or less, more preferably 90 mass% or less, and particularly preferably 88 mass% or less.

<(D)彈性體> <(D) Elastomer>

本發明之樹脂組成物可進一步含有(D)彈性體作為任意的成分。 The resin composition of the present invention may further contain (D) elastomer as an optional component.

於本發明中，(D)彈性體意指具有柔軟性的樹脂，為溶解於有機溶劑之不定形的樹脂成分，較佳為與具有橡膠彈性的樹脂或與其他成分聚合而顯示橡膠彈性之樹脂。橡膠彈性例如係依據日本工業規格(JIS K7161)，可舉出於溫度25℃、濕度40%RH下進行拉伸試驗時，顯示1GPa以下的彈性模數之樹脂。 In the present invention, (D) elastomer means a flexible resin, which is an amorphous resin component dissolved in an organic solvent. Preferably, it is a resin that is polymerized with a resin that has rubber elasticity or with other components to exhibit rubber elasticity. . Rubber elasticity is based on Japanese Industrial Standards (JIS K7161), for example, and is a resin that exhibits an elastic modulus of 1 GPa or less when a tensile test is performed at a temperature of 25° C. and a humidity of 40% RH.

於一實施形態中，(D)成分較佳為在分子內具有由聚丁二烯構造、聚矽氧烷構造、聚(甲基)丙烯酸酯構造、聚伸烷基構造、聚環氧烷構造、聚異戊二烯構造、聚異丁烯構造及聚碳酸酯構造所選出的1種以上之構造的樹脂，從更發揮本發明之所欲效果之觀點來看，更佳為具有由聚丁二烯構造及聚碳酸酯構造所選出的1種以上之構造的樹脂。還有，所謂的「(甲基)丙烯酸酯」，就是指甲 基丙烯酸酯及丙烯酸酯。 In one embodiment, component (D) preferably has a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, and a polyalkylene oxide structure in the molecule. , polyisoprene structure, polyisobutylene structure and polycarbonate structure. From the viewpoint of further exerting the desired effect of the present invention, it is more preferable to have a structure composed of polybutadiene. Resin with one or more structures selected from polycarbonate structure and polycarbonate structure. Also, the so-called "(meth)acrylate" is the nail acrylates and acrylates.

又，於另一實施形態中，(D)成分較佳為由玻璃轉移溫度(Tg)為25℃以下的樹脂及在25℃以下液狀的樹脂所選出的1種以上。玻璃轉移溫度(Tg)為25℃以下的樹脂之玻璃轉移溫度較佳為20℃以下，更佳為15℃以下。玻璃轉移溫度之下限係沒有特別的限定，通常可設為-15℃以上。又，作為在25℃液狀的樹脂，較佳為20℃以下液狀的樹脂，更佳為在15℃以下液狀的樹脂。 Moreover, in another embodiment, it is preferable that (D) component is one or more types selected from the resin whose glass transition temperature (Tg) is 25 degreeC or less, and the resin which is liquid at 25 degreeC or less. The glass transition temperature of the resin having a glass transition temperature (Tg) of 25°C or lower is preferably 20°C or lower, more preferably 15°C or lower. The lower limit of the glass transition temperature is not particularly limited, but it can usually be -15°C or higher. Moreover, as a resin which is liquid at 25 degreeC, resin which is liquid at 20 degreeC or less is preferable, and resin which is liquid at 15 degreeC or less is more preferable.

作為更合適的一實施形態，(D)成分較佳為由玻璃轉移溫度為25℃以下及在25℃液狀的樹脂所選出的1種以上，且在分子內具有由聚丁二烯構造、聚矽氧烷構造、聚(甲基)丙烯酸酯構造、聚伸烷基構造、聚環氧烷構造、聚異戊二烯構造、聚異丁烯構造及聚碳酸酯構造所選出的1種以上之構造的樹脂。 As a more suitable embodiment, the component (D) is preferably at least one selected from a resin having a glass transition temperature of 25°C or lower and a liquid state at 25°C, and having a polybutadiene structure in the molecule. One or more structures selected from polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkylene oxide structure, polyisoprene structure, polyisobutylene structure and polycarbonate structure of resin.

聚丁二烯構造係不僅將丁二烯聚合而形成的構造，而且亦包含在該構造進行氫化而形成的構造。又，丁二烯構造係可僅其一部分被氫化，也可其全部被氫化。再者，聚丁二烯構造係在(D)成分中，可含於主鏈中，也可含於側鏈中。 The polybutadiene structure includes not only a structure formed by polymerizing butadiene, but also a structure formed by hydrogenating the structure. In addition, only a part of the butadiene structure may be hydrogenated, or all of it may be hydrogenated. Furthermore, the polybutadiene structure is contained in the component (D), and may be contained in the main chain or in the side chain.

作為聚丁二烯樹脂之較佳例，可舉出含有氫化聚丁二烯骨架的樹脂、含有羥基的聚丁二烯樹脂、含有酚性羥基的聚丁二烯樹脂、含有羧基的聚丁二烯樹脂、含有酸酐基的聚丁二烯樹脂、含有環氧基的聚丁二烯樹脂、含有異氰酸酯基的聚丁二烯樹脂、含有胺基甲酸酯基的聚 丁二烯樹脂等。其中，更佳為含有酚性羥基的聚丁二烯樹脂。此處，所謂的「含有氫化聚丁二烯骨架的樹脂」，就是指聚丁二烯骨架的至少一部分經氫化的樹脂，不必要是聚丁二烯骨架完全地經氫化之樹脂。作為含有氫化聚丁二烯骨架的樹脂，例如可舉出含有氫化聚丁二烯骨架的環氧樹脂等。又，作為含有酚性羥基的聚丁二烯樹脂，可舉出具有聚丁二烯構造且具有酚性羥基之樹脂等。 Preferable examples of the polybutadiene resin include a hydrogenated polybutadiene skeleton-containing resin, a hydroxyl group-containing polybutadiene resin, a phenolic hydroxyl group-containing polybutadiene resin, and a carboxyl group-containing polybutadiene resin. Polyethylene resin, polybutadiene resin containing acid anhydride groups, polybutadiene resin containing epoxy groups, polybutadiene resin containing isocyanate groups, polybutadiene resin containing urethane groups Butadiene resin, etc. Among them, a polybutadiene resin containing a phenolic hydroxyl group is more preferred. Here, the so-called "resin containing a hydrogenated polybutadiene skeleton" refers to a resin in which at least part of the polybutadiene skeleton is hydrogenated, and does not necessarily mean a resin in which the polybutadiene skeleton is completely hydrogenated. Examples of the resin containing a hydrogenated polybutadiene skeleton include an epoxy resin containing a hydrogenated polybutadiene skeleton. Examples of the polybutadiene resin containing a phenolic hydroxyl group include a resin having a polybutadiene structure and a phenolic hydroxyl group.

作為在分子內具有聚丁二烯構造之樹脂的聚丁二烯樹脂之具體例，可舉出CRAY VALLEY公司製之「Ricon 657」(含有環氧基的聚丁二烯)、「Ricon 130MA8」、「Ricon 130MA13」、「Ricon 130MA20」、「Ricon 131MA5」、「Ricon 131MA10」、「Ricon 131MA17」、「Ricon 131MA20」、「Ricon 184MA6」(含有酸酐基的聚丁二烯)、「GQ-1000」(導入羥基、羧基的聚丁二烯)、「G-1000」、「G-2000」、「G-3000」(兩末端羥基聚丁二烯)、「GI-1000」、「GI-2000」、「GI-3000」(兩末端羥基氫化聚丁二烯)、DAICEL公司製之「PB3600」、「PB4700」(聚丁二烯骨架環氧化合物)、「Epofriend A1005」、「Epofriend A1010」、「Epofriend A1020」(苯乙烯與丁二烯與苯乙烯嵌段共聚物之環氧化合物)、Nagase ChemteX公司製之「FCA-061L」(氫化聚丁二烯骨架環氧化合物)、「R-45EPT」(聚丁二烯骨架環氧化合物)等。 Specific examples of the polybutadiene resin, which is a resin having a polybutadiene structure in the molecule, include "Ricon 657" (epoxy group-containing polybutadiene) and "Ricon 130MA8" manufactured by CRAY VALLEY Co., Ltd. , "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", "Ricon 184MA6" (polybutadiene containing acid anhydride groups), "GQ-1000 ” (polybutadiene with hydroxyl and carboxyl groups introduced), “G-1000”, “G-2000”, “G-3000” (polybutadiene with both terminal hydroxyl groups), “GI-1000”, “GI-2000” ", "GI-3000" (hydrogenated polybutadiene with both terminal hydroxyl groups), "PB3600", "PB4700" (polybutadiene skeleton epoxy compound) manufactured by DAICEL, "Epofriend A1005", "Epofriend A1010", "Epofriend A1020" (epoxy compound of block copolymer of styrene, butadiene and styrene), "FCA-061L" (hydrogenated polybutadiene skeleton epoxy compound) manufactured by Nagase ChemteX, "R-45EPT ” (polybutadiene skeleton epoxy compound), etc.

又，作為較佳的聚丁二烯樹脂之例，亦可舉 出以羥基末端聚丁二烯、二異氰酸酯化合物及多元酸或其酐為原料之線狀聚醯亞胺(日本特開2006-37083號公報、國際公開第2008/153208號中記載之聚醯亞胺)。該聚醯亞胺樹脂之聚丁二烯構造的含有率較佳為60質量%~95質量%，更佳為75質量%~85質量%。該聚醯亞胺樹脂之詳細係可參考日本特開2006-37083號公報、國際公開第2008/153208號之記載，其內容係併入本說明書中。 In addition, as a preferred example of polybutadiene resin, there can also be mentioned Linear polyimide using hydroxyl-terminated polybutadiene, diisocyanate compound and polybasic acid or its anhydride as raw materials (polyimide described in Japanese Patent Application Laid-Open No. 2006-37083 and International Publication No. 2008/153208) was developed. amine). The content rate of the polybutadiene structure of the polyimide resin is preferably 60 mass% to 95 mass%, and more preferably 75 mass% to 85 mass%. For details on the polyimide resin, please refer to Japanese Patent Application Laid-Open No. 2006-37083 and International Publication No. 2008/153208, the contents of which are incorporated into this specification.

羥基末端聚丁二烯之數量平均分子量，從發揮本發明之所欲效果之觀點來看，較佳為500~5,000，更佳為1,000~3,000。羥基末端聚丁二烯之羥基當量，從發揮本發明之所欲效果之觀點來看，較佳為250~1,250。 From the viewpoint of exerting the desired effect of the present invention, the number average molecular weight of the hydroxyl-terminated polybutadiene is preferably 500 to 5,000, and more preferably 1,000 to 3,000. The hydroxyl equivalent of the hydroxyl-terminated polybutadiene is preferably 250 to 1,250 from the viewpoint of exerting the desired effects of the present invention.

作為二異氰酸酯化合物，例如可舉出甲苯-2,4-二異氰酸酯、甲苯-2,6-二異氰酸酯、苯二甲基二異氰酸酯、二苯基甲烷二異氰酸酯等之芳香族二異氰酸酯；六亞甲基二異氰酸酯等之脂肪族二異氰酸酯；異佛爾酮二異氰酸酯等之脂環式二異氰酸酯。於此等之中，較佳為芳香族二異氰酸酯，更佳為甲苯-2,4-二異氰酸酯。 Examples of the diisocyanate compound include aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate; hexamethylene Aliphatic diisocyanates such as base diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate. Among these, aromatic diisocyanate is preferred, and toluene-2,4-diisocyanate is more preferred.

作為多元酸或其酐，例如可舉出乙二醇雙偏苯三酸、苯均四酸、二苯基酮四羧酸、聯苯基四羧酸、萘四羧酸、5-(2,5-二氧代四氫呋喃基)-3-甲基-環己烯-1,2-二羧酸、3,3’-4,4’-二苯基碸四羧酸等之四元酸及此等之酐、偏苯三酸、環己烷三羧酸等之三元酸及此等之酐、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-1,3-二酮等。 Examples of the polybasic acid or its anhydride include ethylene glycol bistrimellitic acid, pyromellitic acid, diphenylketotetracarboxylic acid, biphenyltetracarboxylic acid, naphthalenetetracarboxylic acid, 5-(2, Tetrabasic acids such as 5-dioxotetrahydrofuryl)-3-methyl-cyclohexene-1,2-dicarboxylic acid, 3,3'-4,4'-diphenyltetracarboxylic acid and the like Tribasic acids such as trimellitic acid, cyclohexanetricarboxylic acid and the like and their anhydrides, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5 -Dioxo-3-furyl)-naphtho(1,2-C)furan-1,3-dione, etc.

聚矽氧烷構造係包含矽氧烷鍵之構造，例如含於聚矽氧橡膠中。聚矽氧烷構造係在(D)成分中，可含於主鏈中，也可含於側鏈中。 The polysiloxane structure is a structure containing siloxane bonds, such as is contained in polysiloxane rubber. The polysiloxane structure is contained in component (D) and may be contained in the main chain or in the side chain.

作為在分子內具有聚矽氧烷構造之樹脂的聚矽氧烷樹脂之具體例，可舉出信越聚矽氧公司製之「SMP-2006」、「SMP-2003PGMEA」、「SMP-5005PGMEA」、以胺基末端聚矽氧烷、四元酸酐為原料之線狀聚醯亞胺(國際公開第2010/053185號)等。 Specific examples of the polysiloxane resin, which is a resin having a polysiloxane structure in the molecule, include "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" manufactured by Shin-Etsu Polysiloxane Co., Ltd. Linear polyimide (International Publication No. 2010/053185) using amino-terminated polysiloxane and tetrabasic acid anhydride as raw materials.

聚(甲基)丙烯酸酯構造係將丙烯酸或丙烯酸酯聚合而形成的構造，亦包含將甲基丙烯酸或甲基丙烯酸酯聚合而形成的構造。(甲基)丙烯酸酯構造係在(D)成分中，可含於主鏈中，也可含於側鏈中。 The poly(meth)acrylate structure is a structure formed by polymerizing acrylic acid or acrylate, and also includes a structure formed by polymerizing methacrylic acid or methacrylate. The (meth)acrylate structure is in component (D) and may be contained in the main chain or in the side chain.

作為在分子內具有聚(甲基)丙烯酸酯構造之樹脂的聚(甲基)丙烯酸酯樹脂之較佳例，可舉出含有羥基的聚(甲基)丙烯酸酯樹脂、含有酚性羥基的聚(甲基)丙烯酸酯樹脂、含有羧基的聚(甲基)丙烯酸酯樹脂、含有酸酐基的聚(甲基)丙烯酸酯樹脂、含有環氧基的聚(甲基)丙烯酸酯樹脂、含有異氰酸酯基的聚(甲基)丙烯酸酯樹脂、含有胺基甲酸酯基的聚(甲基)丙烯酸酯樹脂等。 Preferable examples of the poly(meth)acrylate resin, which is a resin having a poly(meth)acrylate structure in the molecule, include a hydroxyl-containing poly(meth)acrylate resin, a phenolic hydroxyl-containing poly(meth)acrylate resin, and a phenolic hydroxyl-containing poly(meth)acrylate resin. (Meth)acrylate resin, carboxyl group-containing poly(meth)acrylate resin, acid anhydride group-containing poly(meth)acrylate resin, epoxy group-containing poly(meth)acrylate resin, isocyanate group-containing Poly(meth)acrylate resin, poly(meth)acrylate resin containing urethane group, etc.

作為聚(甲基)丙烯酸酯樹脂之具體例，可舉出Nagase ChemteX公司製之TEISANRESIN「SG-70L」、「SG-708-6」、「WS-023」、「SG-700AS」、「SG-280TEA」(含有羧基的丙烯酸酯共聚物樹脂，酸價5~34mgKOH/g，重量平均分子量40萬~90萬、Tg-30℃~5 ℃)、「SG-80H」、「SG-80H-3」、「SG-P3」(含有環氧基的丙烯酸酯共聚物樹脂，環氧當量4761~14285g/eq，重量平均分子量35萬~85萬，Tg11℃~12℃)、「SG-600TEA」、「SG-790」」(含有羥基的丙烯酸酯共聚物樹脂，羥值20~40mgKOH/g，重量平均分子量50萬~120萬，Tg-37℃~-32℃)、根上工業公司製之「ME-2000」、「W-116.3」(含有羧基的丙烯酸酯共聚物樹脂)、「W-197C」(含有羥基的丙烯酸酯共聚物樹脂)、「KG-25」、「KG-3000」(含有環氧基的丙烯酸酯共聚物樹脂)等。 Specific examples of the poly(meth)acrylate resin include TEISANRESIN "SG-70L", "SG-708-6", "WS-023", "SG-700AS", and "SG" manufactured by Nagase ChemteX Corporation -280TEA" (acrylate copolymer resin containing carboxyl groups, acid value 5~34mgKOH/g, weight average molecular weight 400,000~900,000, Tg-30℃~5 ℃), "SG-80H", "SG-80H-3", "SG-P3" (epoxy group-containing acrylate copolymer resin, epoxy equivalent 4761~14285g/eq, weight average molecular weight 350,000~85 million, Tg11℃~12℃), "SG-600TEA", "SG-790" (hydroxyl-containing acrylate copolymer resin, hydroxyl value 20~40mgKOH/g, weight average molecular weight 500,000~1.2 million, Tg- 37℃~-32℃), "ME-2000", "W-116.3" (carboxyl group-containing acrylate copolymer resin), "W-197C" (hydroxyl group-containing acrylate copolymer resin) manufactured by Negami Industrial Co., Ltd. , "KG-25", "KG-3000" (epoxy group-containing acrylate copolymer resin), etc.

聚伸烷基構造較佳為具有特定的碳原子數。聚伸烷基構造之具體的碳原子數較佳為2以上，更佳為3以上，特佳為5以上，且較佳為15以下，更佳為10以下，特佳為6以下。又，聚伸烷基構造係在(D)成分中，可含於主鏈中，也可含於側鏈中。 The polyalkylene structure preferably has a specific number of carbon atoms. The specific number of carbon atoms in the polyalkylene structure is preferably 2 or more, more preferably 3 or more, particularly preferably 5 or more, and preferably 15 or less, more preferably 10 or less, and particularly preferably 6 or less. In addition, the polyalkylene structure is in the component (D), and may be contained in the main chain or in the side chain.

聚環氧烷構造較佳為具有特定的碳原子數。聚環氧烷構造之具體的碳原子數較佳為2以上，更佳為3以上，尤佳為5以上，且較佳為15以下，更佳為10以下，特佳為6以下。聚環氧烷構造係在(D)成分中，可含於主鏈中，也可含於側鏈中。 The polyalkylene oxide structure preferably has a specific number of carbon atoms. The specific number of carbon atoms in the polyalkylene oxide structure is preferably 2 or more, more preferably 3 or more, even more preferably 5 or more, and preferably 15 or less, more preferably 10 or less, and particularly preferably 6 or less. The polyalkylene oxide structure is contained in component (D) and may be contained in the main chain or in the side chain.

作為在分子內具有聚伸烷基構造之樹脂的聚伸烷基樹脂及在分子內具聚環氧烷構造之樹脂的聚環氧烷樹脂之具體例，可舉出旭化成纖維公司製之「PTXG-1000」、「PTXG-1800」、三菱化學公司製之「YX-7180」(含有具有醚鍵的伸烷基構造之樹脂)、DIC Corporation公司製之「EXA-4850-150」、「EXA-4816」、「EXA-4822」、ADEKA公司製之「EP-4000」、「EP-4003」、「EP-4010」、「EP-4011」、新日本理化公司製之「BEO-60E」、「BPO-20E」、三菱化學公司製之「YL7175」、「YL7410」等。 Specific examples of the polyalkylene resin, which is a resin having a polyalkylene structure in the molecule, and the polyalkylene oxide resin, which is a resin having a polyalkylene oxide structure in the molecule, include "PTXG" manufactured by Asahi Kasei Fibers Co., Ltd. -1000", "PTXG-1800", "YX-7180" manufactured by Mitsubishi Chemical Corporation (resin containing an alkylene structure having an ether bond), DIC "EXA-4850-150", "EXA-4816", "EXA-4822" made by Corporation, "EP-4000", "EP-4003", "EP-4010", "EP-4011" made by ADEKA ", "BEO-60E" and "BPO-20E" manufactured by New Nippon Rika Co., Ltd., "YL7175" and "YL7410" manufactured by Mitsubishi Chemical Corporation, etc.

聚異戊二烯構造係在(D)成分中，可含於主鏈中，也可含於側鏈中。作為在分子內具有聚異戊二烯構造之樹脂的聚異戊二烯樹脂之具體例，可舉出KURARAY公司製之「KL-610」、「KL-613」等。 The polyisoprene structure is contained in component (D) and may be contained in the main chain or in the side chain. Specific examples of the polyisoprene resin, which is a resin having a polyisoprene structure in the molecule, include "KL-610" and "KL-613" manufactured by KURARAY Corporation.

聚異丁烯構造係在(D)成分中，可含於主鏈中，也可含於側鏈中。作為在分子內具有聚異丁烯構造之樹脂的聚異丁烯樹脂之具體例，可舉出KANEKA公司製之「SIBSTAR-073T」(苯乙烯-異丁烯-苯乙烯三嵌段共聚物)、「SIBSTAR-042D」(苯乙烯-異丁烯二嵌段共聚物)等。 The polyisobutylene structure is contained in component (D), and may be contained in the main chain or in the side chain. Specific examples of the polyisobutylene resin, which is a resin having a polyisobutylene structure in the molecule, include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" manufactured by KANEKA Corporation. (Styrene-isobutylene diblock copolymer) etc.

聚碳酸酯構造係在(D)成分中，可含於主鏈中，也可含於側鏈中。 The polycarbonate structure is contained in component (D) and may be contained in the main chain or side chains.

作為在分子內具有聚碳酸酯構造之樹脂的聚碳酸酯樹脂之較佳例，可舉出含有羥基的聚碳酸酯樹脂、含有酚性羥基的聚碳酸酯樹脂、含有羧基的聚碳酸酯樹脂、含有酸酐基的聚碳酸酯樹脂、含有環氧基的聚碳酸酯樹脂、含有異氰酸酯基的聚碳酸酯樹脂、含有胺基甲酸酯基的聚碳酸酯樹脂等。 Preferable examples of the polycarbonate resin having a polycarbonate structure in the molecule include a hydroxyl group-containing polycarbonate resin, a phenolic hydroxyl group-containing polycarbonate resin, a carboxyl group-containing polycarbonate resin, Anhydride group-containing polycarbonate resin, epoxy group-containing polycarbonate resin, isocyanate group-containing polycarbonate resin, urethane group-containing polycarbonate resin, etc.

作為聚碳酸酯樹脂之具體例，可舉出旭化成 化學公司製之「T6002」、「T6001」(聚碳酸酯二醇)、KURARAY公司製之「C-1090」、「C-2090」、「C-3090」(聚碳酸酯二醇)等。 Specific examples of the polycarbonate resin include Asahi Kasei "T6002" and "T6001" (polycarbonate diol) made by Chemical Company, "C-1090", "C-2090", "C-3090" (polycarbonate diol) made by KURARAY Co., Ltd., etc.

又，作為較佳的聚碳酸酯樹脂之例，可舉出以羥基末端聚碳酸酯、二異氰酸酯化合物及多元酸或其酐為原料之線狀聚醯亞胺。該線狀聚醯亞胺具有胺基甲酸酯構造及聚碳酸酯構造。該聚醯亞胺樹脂的聚碳酸酯構造之含有率較佳為60質量%~95質量%，更佳為75質量%~85質量%。該聚醯亞胺樹脂之詳細係可參考國際公開第2016/129541號之記載，其內容係併入本說明書中。 Preferable examples of polycarbonate resins include linear polyimides using hydroxyl-terminated polycarbonate, diisocyanate compounds, and polybasic acids or anhydrides thereof as raw materials. The linear polyimide has a urethane structure and a polycarbonate structure. The content rate of the polycarbonate structure of the polyimide resin is preferably 60 mass% to 95 mass%, and more preferably 75 mass% to 85 mass%. For details of the polyimide resin, please refer to International Publication No. 2016/129541, the content of which is incorporated into this specification.

羥基末端聚碳酸酯之數量平均分子量，從發揮本發明之所欲效果之觀點來看，較佳為500~5,000，更佳為1,000~3,000。羥基末端聚碳酸酯之羥基當量，從發揮本發明之所欲效果之觀點來看，較佳為250~1,250。 From the viewpoint of exerting the desired effect of the present invention, the number average molecular weight of the hydroxyl-terminated polycarbonate is preferably 500 to 5,000, and more preferably 1,000 to 3,000. The hydroxyl equivalent of the hydroxyl-terminated polycarbonate is preferably 250 to 1,250 from the viewpoint of exerting the desired effect of the present invention.

(D)成分較佳為進一步具有醯亞胺構造。由於具有醯亞胺構造，而提高(D)成分之耐熱性，可有效果地提高抗龜裂性。 It is preferable that the component (D) further has an amide imine structure. Due to its imide structure, the heat resistance of component (D) can be improved, which can effectively improve the crack resistance.

(D)成分可為直鏈狀、分枝狀及環狀之任一構造，但從發揮本發明之所欲效果之觀點來看，較佳為直鏈狀。 Component (D) may have any structure of linear, branched or cyclic structure, but from the viewpoint of exerting the desired effect of the present invention, linear structure is preferred.

(D)成分較佳為進一步具有能與(A)成分反應的官能基。於此官能基中，亦包含因加熱而出現的反應基。由於(D)成分具有官能基，可提高樹脂組成物的硬化物之機械強度。 It is preferable that the component (D) further has a functional group capable of reacting with the component (A). This functional group also includes reactive groups that appear due to heating. Since component (D) has a functional group, the mechanical strength of the cured product of the resin composition can be improved.

作為官能基，可舉出羧基、羥基、酸酐基、酚性羥基、環氧基、異氰酸酯基及胺基甲酸酯基等。其中，從顯著得到本發明之效果之觀點來看，作為官能基，較佳為具有由羥基、酸酐基、酚性羥基、環氧基、異氰酸酯基及胺基甲酸酯基所選出的1種以上之官能基，特佳為酚性羥基。 Examples of the functional group include a carboxyl group, a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, a urethane group, and the like. Among them, from the viewpoint of significantly obtaining the effects of the present invention, the functional group is preferably one selected from the group consisting of a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group. The above functional groups are particularly preferably phenolic hydroxyl groups.

(D)成分係可單獨使用1種類，也可組合2種以上使用。 (D) Component system may be used individually by 1 type, or may be used in combination of 2 or more types.

從發揮本發明之所欲效果之觀點來看，(D)成分較佳為高分子量者。(D)成分之具體的數量平均分子量Mn較佳為4000以上，更佳為4500以上，尤佳為5000以上，特佳為5500以上，且較佳為100000以下，更佳為95000以下，特佳為90000以下。由於(D)成分之數量平均分子量Mn在前述之範圍，可顯著得到本發明之所欲效果。(D)成分之數量平均分子量Mn係使用GPC(凝膠滲透層析法)所測定的聚苯乙烯換算之數量平均分子量。 From the viewpoint of exerting the desired effects of the present invention, component (D) is preferably a high molecular weight component. The specific number average molecular weight Mn of the component (D) is preferably 4,000 or more, more preferably 4,500 or more, especially preferably 5,000 or more, particularly preferably 5,500 or more, and preferably 100,000 or less, more preferably 95,000 or less, and particularly preferably is below 90,000. Since the number average molecular weight Mn of component (D) is within the aforementioned range, the desired effects of the present invention can be significantly obtained. (D) The number average molecular weight Mn of the component is the number average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography).

又，(D)成分之具體的重量平均分子量，從顯著得到本發明之所欲效果之觀點來看，較佳為5500~100000，更佳為10000~90000，尤佳為15000~80000。(D)成分之重量平均分子量係藉由凝膠滲透層析法(GPC)法所測定的聚苯乙烯換算之重量平均分子量。 In addition, the specific weight average molecular weight of component (D) is preferably 5,500 to 100,000, more preferably 10,000 to 90,000, and particularly preferably 15,000 to 80,000, from the viewpoint of significantly obtaining the desired effects of the present invention. The weight average molecular weight of the component (D) is the weight average molecular weight in terms of polystyrene measured by the gel permeation chromatography (GPC) method.

於(D)成分具有官能基時，(D)成分之官能基當量較佳為100以上，更佳為200以上，尤佳為1000以上，特佳為2500以上，且較佳為50000以下，更佳為30000以 下，尤佳為10000以下，特佳為5000以下。官能基當量係包含1克當量的官能基之樹脂的克數。例如、環氧基當量係可依照JIS K7236測定。又，例如羥基當量係可將依照JIS K1557-1測定的羥值除以KOH的分子量而算出。 When component (D) has a functional group, the functional group equivalent of component (D) is preferably 100 or more, more preferably 200 or more, especially 1,000 or more, particularly preferably 2,500 or more, and more preferably 50,000 or less, more preferably Preferably more than 30,000 Below, the best value is below 10,000, and the best value is below 5,000. Functional group equivalent weight is the number of grams of resin containing 1 gram equivalent of functional group. For example, the epoxy group equivalent can be measured in accordance with JIS K7236. In addition, for example, the hydroxyl equivalent can be calculated by dividing the hydroxyl value measured in accordance with JIS K1557-1 by the molecular weight of KOH.

含有(D)彈性體時，(D)彈性體之含量係沒有特別的限定，但將樹脂組成物中的樹脂成分當作100質量%時，從顯著得到本發明之所欲效果之觀點來看，較佳為2質量%以上，更佳為5質量%以上，尤佳為8質量%以上，特佳為9質量%以上。從顯著得到本發明之所欲效果之觀點來看，其上限較佳為40質量%以下，更佳為35質量%以下，尤佳為30質量%以下，特佳為25質量%以下。 When (D) elastomer is contained, the content of (D) elastomer is not particularly limited. However, when the resin component in the resin composition is regarded as 100% by mass, the desired effect of the present invention is significantly obtained. , preferably 2 mass% or more, more preferably 5 mass% or more, particularly preferably 8 mass% or more, particularly preferably 9 mass% or more. From the viewpoint of significantly obtaining the desired effect of the present invention, the upper limit is preferably 40 mass% or less, more preferably 35 mass% or less, particularly preferably 30 mass% or less, and particularly preferably 25 mass% or less.

<(E)橡膠粒子> <(E)Rubber particles>

本發明之樹脂組成物可進一步含有(E)橡膠粒子作為任意的成分。 The resin composition of the present invention may further contain (E) rubber particles as an optional component.

樹脂組成物包含(E)橡膠粒子。本發明中的(E)橡膠粒子係可將橡膠成分的分子量增大到不溶解在有機溶劑及樹脂成分中的水準為止，作為粒子狀製造。因此不溶解於有機溶劑中，也不與環氧樹脂或硬化劑等的其他成分相溶，可在樹脂清漆中及樹脂組成物中以分散狀態存在。通常，作為具有橡膠彈性的有機填充材發揮機能。由於包含此(E)橡膠粒子，可改善樹脂組成物的硬化物在低溫時的密著性。又，由於在樹脂組成物中包含(E)成分，可減小沾黏性，可提高樹脂組成物的硬化物之操作性。再 者，藉由(E)成分，通常可降低絕緣層的彈性模數，提高對於伸長的耐性。 The resin composition contains (E) rubber particles. The (E) rubber particles in the present invention can be produced in the form of particles by increasing the molecular weight of the rubber component to a level that does not dissolve in the organic solvent and resin component. Therefore, it is not dissolved in organic solvents, nor is it compatible with other components such as epoxy resin or hardener, and can exist in a dispersed state in resin varnishes and resin compositions. Usually, it functions as an organic filler having rubber elasticity. By including the rubber particles (E), the adhesion of the cured product of the resin composition at low temperatures can be improved. In addition, since the resin composition contains the component (E), the stickiness can be reduced and the workability of the cured product of the resin composition can be improved. Again Furthermore, the (E) component can generally reduce the elastic modulus of the insulating layer and improve the resistance to elongation.

若舉(E)橡膠粒子之例，可舉出芯殼型橡膠粒子、交聯丙烯腈丁二烯橡膠粒子、交聯苯乙烯丁二烯橡膠粒子、丙烯酸橡膠粒子等。其中，從顯著得到本發明之所欲效果之觀點來看，較佳為芯殼型橡膠粒子。 Examples of (E) rubber particles include core-shell rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles. Among them, from the viewpoint of significantly obtaining the desired effects of the present invention, core-shell rubber particles are preferred.

芯殼型橡膠粒子係包含在該粒子的表面之殼層與在該殼層的內部之芯層的橡膠粒子。例如，可舉出以具有相對高的玻璃轉移溫度之聚合物所形成之殼層與具有以相對低的玻璃轉移溫度之聚合物所形成之芯層的芯殼型橡膠粒子。其中，較佳為殼層以玻璃狀聚合物形成，且芯層以橡膠狀聚合物形成之芯殼型橡膠粒子。如此的芯殼型橡膠粒子係可藉由殼層而抑制橡膠粒子之凝聚，提高橡膠粒子在樹脂成分中的分散性，且可藉由芯層而發揮優異的橡膠彈性。芯殼型橡膠粒子例如可藉由將對應於各層的1種類或2種類以上之單體，分成複數階段進行種子聚合而製造。 Core-shell rubber particles are rubber particles including a shell layer on the surface of the particle and a core layer inside the shell layer. For example, core-shell type rubber particles include a shell layer formed of a polymer having a relatively high glass transition temperature and a core layer formed of a polymer having a relatively low glass transition temperature. Among them, core-shell type rubber particles in which the shell layer is formed of a glassy polymer and the core layer is formed of a rubbery polymer are preferred. Such core-shell type rubber particles can suppress the aggregation of the rubber particles through the shell layer, improve the dispersibility of the rubber particles in the resin component, and can exert excellent rubber elasticity through the core layer. Core-shell rubber particles can be produced, for example, by dividing one type or two or more types of monomers corresponding to each layer into a plurality of stages and performing seed polymerization.

芯殼型橡膠粒子可具有僅包含殼層及芯層的2層構造，也可具有進一步包含任意之層的3層以上之構造。例如，芯殼型橡膠粒子係可在殼層與芯層之間包含任意之層，也可在芯層之內部包含任意之層。若舉出具體例，則芯殼型橡膠粒子可具有3層構造，其包含以玻璃狀聚合物形成之殼層、以橡膠狀聚合物形成之芯層及在芯層之內部以玻璃狀聚合物形成的任意之層。 The core-shell type rubber particles may have a two-layer structure including only a shell layer and a core layer, or may have a three- or more-layer structure including any further layers. For example, the core-shell rubber particle system may include any layer between the shell layer and the core layer, or may include any layer inside the core layer. As a specific example, core-shell rubber particles may have a three-layer structure including a shell layer made of a glassy polymer, a core layer made of a rubbery polymer, and a glassy polymer inside the core layer. Any layer formed.

於前述芯殼型橡膠粒子中，作為玻璃狀聚合物，可舉出聚甲基丙烯酸甲酯等之丙烯酸系聚合物；聚苯乙烯、聚甲基丙烯酸甲酯‧苯乙烯共聚合、苯乙烯‧二乙烯基苯共聚物等之苯乙烯系聚合物等。其中，較佳為丙烯酸系聚合物，特佳為聚甲基丙烯酸甲酯。另一方面，作為橡膠狀聚合物，可舉出丙烯酸丁酯等之丙烯酸單體的均聚物或共聚物等之丙烯酸橡膠；聚丁二烯、丁二烯‧苯乙烯共聚物等之丁二烯橡膠；異戊二烯橡膠；丁基橡膠；等。其中，較佳為丙烯酸橡膠及丁二烯橡膠，特佳為丙烯酸橡膠。此處，於前述用語「丙烯酸單體」中，包含丙烯酸酯、甲基丙烯酸酯及此等之組合。 Among the core-shell type rubber particles mentioned above, examples of glassy polymers include acrylic polymers such as polymethylmethacrylate; polystyrene, polymethylmethacrylate·styrene copolymer, styrene· Styrenic polymers such as divinylbenzene copolymer, etc. Among them, an acrylic polymer is preferred, and polymethylmethacrylate is particularly preferred. On the other hand, examples of rubber-like polymers include acrylic rubbers such as homopolymers or copolymers of acrylic monomers such as butyl acrylate; and butadiene such as polybutadiene and butadiene-styrene copolymers. Olefin rubber; isoprene rubber; butyl rubber; etc. Among them, acrylic rubber and butadiene rubber are preferred, and acrylic rubber is particularly preferred. Here, the aforementioned term "acrylic monomer" includes acrylate, methacrylate, and combinations thereof.

作為芯殼型橡膠粒子之具體例，可舉出AICA工業公司製之Stafroid「AC3832」、「AC3816N」、「IM401-改7-17」；三菱化學公司製之「Metablen KW-4426」；陶氏化學日本公司製之Paraloid「EXL-2655」等。 Specific examples of core-shell type rubber particles include Stafroid "AC3832", "AC3816N", and "IM401-modified 7-17" manufactured by AICA Industrial Co., Ltd.; "Metablen KW-4426" manufactured by Mitsubishi Chemical Corporation; Dow Chemical Co., Ltd. Paraloid "EXL-2655" manufactured by Chemical Nippon Co., Ltd., etc.

作為交聯丙烯腈丁二烯橡膠(NBR)粒子之具體例，可舉出JSR公司製「XER-91」(平均粒徑0.5μm)等。作為交聯苯乙烯丁二烯橡膠(SBR)粒子之具體例，可舉出JSR公司製「XSK-500」(平均粒徑0.5μm)等。作為丙烯酸橡膠粒子之具體例，可舉出三菱化學公司製之Metablen「W300A」(平均粒徑0.1μm)、「W450A」(平均粒徑0.2μm)等。 Specific examples of cross-linked acrylonitrile butadiene rubber (NBR) particles include "XER-91" (average particle diameter: 0.5 μm) manufactured by JSR Corporation. Specific examples of cross-linked styrene butadiene rubber (SBR) particles include "XSK-500" (average particle diameter: 0.5 μm) manufactured by JSR Corporation. Specific examples of acrylic rubber particles include Metablen "W300A" (average particle diameter: 0.1 μm) and "W450A" (average particle diameter: 0.2 μm) manufactured by Mitsubishi Chemical Corporation.

(E)橡膠粒子係可單獨使用1種類，也可組合 2種以上使用。 (E) Rubber particles can be used individually or in combination. Use 2 or more types.

(E)橡膠粒子通常具有提高樹脂組成物的硬化物之韌性的作用。因此，以包含(E)橡膠粒子的樹脂組成物的硬化物所形成之絕緣層，係機械強度更優異。又，(E)橡膠粒子通常具有應力緩和作用。因此，以包含(E)橡膠粒子的樹脂組成物的硬化物所形成之絕緣層，係其形成時所產生內部應力被(E)橡膠粒子所緩和。因此，可減小絕緣層的殘留應力，故藉此可更提高絕緣層的機械強度，可進一步抑制脆化。因此，即使在低溫下也可抑制絕緣層之剝離(脫層)。 (E) Rubber particles generally have the function of improving the toughness of the cured product of the resin composition. Therefore, the insulating layer formed of the cured product of the resin composition containing (E) rubber particles has better mechanical strength. Moreover, (E) rubber particles usually have a stress relaxing effect. Therefore, in the insulating layer formed of a cured product of a resin composition containing (E) rubber particles, the internal stress generated during its formation is relaxed by the (E) rubber particles. Therefore, the residual stress of the insulating layer can be reduced, thereby further improving the mechanical strength of the insulating layer and further suppressing embrittlement. Therefore, peeling (delamination) of the insulating layer can be suppressed even at low temperatures.

(E)橡膠粒子之平均粒徑較佳為0.005μm以上，更佳為0.01μm以上，且較佳為1μm以下，更佳為0.6μm以下。(E)橡膠粒子之平均粒徑係可使用動態光散射法測定。具體而言，藉由超音波等之方法使橡膠粒子均勻分散在適當的有機溶劑中，使用濃厚系粒徑分析器(大塚電子公司製「FPAR-1000」)，以質量基準作成橡膠粒子的粒度分布，將其中值徑當作平均粒徑測定。 (E) The average particle diameter of the rubber particles is preferably 0.005 μm or more, more preferably 0.01 μm or more, and preferably 1 μm or less, more preferably 0.6 μm or less. (E) The average particle size of rubber particles can be measured using the dynamic light scattering method. Specifically, the rubber particles are uniformly dispersed in an appropriate organic solvent by methods such as ultrasonic waves, and the particle size of the rubber particles is determined based on mass using a concentrated particle size analyzer ("FPAR-1000" manufactured by Otsuka Electronics Co., Ltd.) Distribution, the median diameter is measured as the average particle diameter.

含有(E)橡膠粒子時，(E)橡膠粒子之含量係沒有特別的限定，但將樹脂組成物中的樹脂成分當作100質量%時，從顯著得到本發明之所欲效果之觀點來看，較佳為40質量%以下，更佳為30質量%以下，尤佳為20質量%以下。 When (E) rubber particles are contained, the content of (E) rubber particles is not particularly limited. However, when the resin component in the resin composition is regarded as 100% by mass, the desired effect of the present invention is significantly obtained. , preferably 40 mass% or less, more preferably 30 mass% or less, especially 20 mass% or less.

<(F)硬化促進劑> <(F) Hardening accelerator>

本發明之樹脂組成物可進一步含有(F)硬化促進劑作為任意的成分。 The resin composition of the present invention may further contain (F) a hardening accelerator as an optional component.

作為(F)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，較佳為磷系硬化促進劑、胺系硬化促進劑、咪唑系硬化促進劑、金屬系硬化促進劑，更佳為磷系硬化促進劑、咪唑系硬化促進劑。硬化促進劑係可單獨使用1種類，也可組合2種以上使用。 Examples of the (F) 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 them, phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are preferred, and phosphorus-based hardening accelerators and imidazole-based hardening accelerators are more preferred. One type of hardening accelerator may be used alone, or two or more types may be used in combination.

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、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、甲基三丁基鏻二甲基磷酸鹽等。 Examples of the phosphorus-based hardening accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4- Methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, methyltributylphosphonium dimethylphosphate, etc.

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)-十一烯等。 Examples of amine-based hardening accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6, -Shen(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc.

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

Figure 108127984-A0305-02-0036-10
、2,4-二胺基-6-[2’-十一基咪唑基-(1’)]-乙基-s-三
Figure 108127984-A0305-02-0036-11
、2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-s-三
Figure 108127984-A0305-02-0036-12
、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三
Figure 108127984-A0305-02-0036-13
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。 Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecanylimidazole, 1,2-dimethylimidazole, and 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-tri
Figure 108127984-A0305-02-0036-10
, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-tri
Figure 108127984-A0305-02-0036-11
,2,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-tri
Figure 108127984-A0305-02-0036-12
, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-tri
Figure 108127984-A0305-02-0036-13
Isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methyl Imidazole compounds such as 2-phenylimidazoline and 2-phenylimidazoline and adducts of imidazole compounds and epoxy resins.

作為咪唑系硬化促進劑，亦可使用市售品，例如可舉出三菱化學公司製之「P200-H50」等。 As the imidazole-based hardening accelerator, commercially available products can also be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

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。 Examples of the guanidine-based hardening accelerator include cyanoguanidine, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, and dimethylguanidine. 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.

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 organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt acetyl acetonate (II), cobalt acetyl acetonate (III), and acetyl acetonate. Organic copper complexes such as copper (II), organic zinc complexes such as zinc acetyl acetonate (II), organic iron complexes such as iron acetyl acetonate (III), nickel acetyl acetonate (II), etc. Organic nickel complexes, acetyl acetonate manganese (II) and other organic manganese complexes. Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

含有(F)硬化促進劑時，(F)硬化促進劑之含量係沒有特別的限定，但將樹脂組成物中的樹脂成分當作100質量%時，從顯著得到本發明之所欲效果之觀點來看，較佳為0.001質量%以上，更佳為0.01質量%以上，尤佳為0.1質量%以上，特佳為0.4質量%以上。從顯著得到本發明之所欲效果之觀點來看，其上限較佳為10質量%以下，更佳為5質量%以下，尤佳為2質量%以下，特佳為1質量%以下。 When the (F) hardening accelerator is contained, the content of the (F) hardening accelerator is not particularly limited. However, when the resin component in the resin composition is regarded as 100% by mass, the desired effect of the present invention is significantly obtained. From this point of view, the content is preferably 0.001 mass% or more, more preferably 0.01 mass% or more, particularly preferably 0.1 mass% or more, and particularly preferably 0.4 mass% or more. From the viewpoint of significantly obtaining the desired effects of the present invention, the upper limit is preferably 10 mass% or less, more preferably 5 mass% or less, particularly preferably 2 mass% or less, and particularly preferably 1 mass% or less.

<(G)有機溶劑> <(G)Organic solvent>

本發明之樹脂組成物可進一步含有(G)有機溶劑作為任意的成分。 The resin composition of the present invention may further contain (G) an organic solvent as an optional component.

作為有機溶劑，例如可舉出丙酮、甲基乙基酮及環己酮等之酮系溶劑；乙酸乙酯、乙酸丁酯、賽珞蘇乙酸酯、丙二醇單甲基醚乙酸酯、卡必醇乙酸酯、乙基二甘醇乙酸酯等之酯系溶劑；賽珞蘇及丁基卡必醇等之卡必醇溶劑；苯、甲苯、二甲苯、乙苯、三甲苯等之芳香族烴系溶劑；二甲基甲醯胺、二甲基乙醯胺(DMAc)及N-甲基吡咯啶酮等之醯胺系溶劑等。有機溶劑係可單獨使用1 種，也可以任意之比率組合2種以上使用。 Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellulose acetate, propylene glycol monomethyl ether acetate, and carboxyl acetate. Ester solvents such as bitol acetate and ethyl diglycol acetate; carbitol solvents such as cellulose and butyl carbitol; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, etc. Aromatic hydrocarbon solvents; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. Organic solvent system can be used alone1 It can also be used in combination of two or more types in any ratio.

含有(G)有機溶劑時，(G)有機溶劑之含量係沒有特別的限定，但將樹脂組成物全體當作100質量%時，從得到本發明之所欲效果之觀點來看，較佳為50質量%以下，更佳為40質量%以下，尤佳為30質量%以下，特佳為20質量%以下。其下限係沒有特別的限定。 When (G) organic solvent is contained, the content of (G) organic solvent is not particularly limited. However, when the entire resin composition is regarded as 100% by mass, from the viewpoint of obtaining the desired effect of the present invention, it is preferably 50 mass % or less, more preferably 40 mass % or less, still more preferably 30 mass % or less, particularly preferably 20 mass % or less. The lower limit is not particularly limited.

<(H)其他添加劑> <(H)Other additives>

樹脂組成物係除了上述成分以外，還可進一步包含其他添加劑作為任意的成分。作為如此的添加劑，例如可舉出熱塑性樹脂、黏結劑、難燃劑、增黏劑、消泡劑、調平劑、有機金屬化合物、著色劑、密著性賦予劑等之樹脂添加劑；聚合起始劑等。此等添加劑係可單獨使用1種類，也可組合2種以上使用。各自之含量只要是本業者則可適宜設定。 In addition to the above-mentioned components, the resin composition may further contain other additives as optional components. Examples of such additives include resin additives such as thermoplastic resins, binders, flame retardants, tackifiers, defoaming agents, leveling agents, organic metal compounds, colorants, and adhesion-imparting agents; polymerized starter, etc. These additives may be used individually by 1 type, or in combination of 2 or more types. Each content can be appropriately set by the manufacturer.

<樹脂組成物之製造方法> <Manufacturing method of resin composition>

本發明之樹脂組成物例如可藉由使用旋轉混合器等之攪拌裝置，攪拌摻合成分，使其均勻地分散而製造。 The resin composition of the present invention can be produced by, for example, using a stirring device such as a rotary mixer to stir the blended ingredients and disperse them uniformly.

<樹脂組成物之特性> <Characteristics of resin composition>

本發明之樹脂組成物具有特徵為使其在180℃熱硬化90分鐘而得的硬化物之透氧係數為3cc/(atm‧m2‧天‧mm)以下。透氧係數係藉由測定使本發明之樹脂組成物在 180℃熱硬化90分鐘而得的硬化物之透氧率，將其值除以硬化物之厚度而進行算出。測定透氧率之方法及透氧係數之算出方法，具體而言可使用實施例中記載之方法。在180℃熱硬化90分鐘而得的硬化物之透氧係數較佳為2.5cc/(atm‧m2‧天‧mm)以下，更佳為2.0cc/(atm‧m2‧天‧mm)以下，尤佳為1.5cc/(atm‧m2‧天‧mm)以下。下限係沒有特別的限制，通常較佳為0.01cc/(atm‧m2‧天‧mm)以上，更佳為0.2cc/(atm‧m2‧天‧mm)以上。 The resin composition of the present invention is characterized in that the cured product obtained by thermal curing at 180° C. for 90 minutes has an oxygen permeability coefficient of 3cc/(atm‧m 2 ‧day‧mm) or less. The oxygen permeability coefficient is calculated by measuring the oxygen permeability of a cured product obtained by thermally curing the resin composition of the present invention at 180° C. for 90 minutes, and dividing the value by the thickness of the cured product. As for the method of measuring the oxygen permeability and the method of calculating the oxygen permeability coefficient, specifically, the methods described in the Examples can be used. The oxygen permeability coefficient of the cured product obtained by heat curing at 180°C for 90 minutes is preferably 2.5cc/(atm‧m 2 ‧day‧mm) or less, more preferably 2.0cc/(atm‧m 2 ‧day‧mm) or less, preferably 1.5cc/(atm‧m 2 ‧day‧mm) or less. The lower limit is not particularly limited, but it is usually preferably 0.01cc/(atm‧m 2 ‧day‧mm) or more, and more preferably 0.2cc/(atm‧m 2 ‧day‧mm) or more.

本發明之樹脂組成物具有特徵為使其在180℃熱硬化90分鐘而得的的硬化物之線熱膨脹係數為4~15ppm/℃。作為測定方法，具體而言可使用實施例中記載之方法。使本發明之樹脂組成物在180℃熱硬化90分鐘而得的硬化物之線熱膨脹係數較佳為12ppm/℃以下，更佳為10ppm/℃以下，尤佳為8.5ppm/℃以下。下限較佳為3.5ppm/℃以上，更佳為4.5ppm/℃以上，尤佳為5.5ppm/℃以上。 The resin composition of the present invention is characterized in that the linear thermal expansion coefficient of the cured product obtained by thermal curing at 180°C for 90 minutes is 4 to 15 ppm/°C. As the measurement method, specifically, the method described in the Examples can be used. The linear thermal expansion coefficient of the cured product obtained by thermally curing the resin composition of the present invention at 180°C for 90 minutes is preferably 12 ppm/°C or less, more preferably 10 ppm/°C or less, and particularly preferably 8.5 ppm/°C or less. The lower limit is preferably 3.5 ppm/°C or more, more preferably 4.5 ppm/°C or more, and particularly preferably 5.5 ppm/°C or more.

線熱膨脹係數及透氧係數各自係可一般地藉由樹脂組成物中可含有的各成分之種類或摻合量進行調節，此為本業者所已知。 Each of the linear thermal expansion coefficient and the oxygen permeability coefficient can generally be adjusted by the type or blending amount of each component that can be contained in the resin composition, and this is known in the art.

本發明之樹脂組成物係藉由使透氧係數及線熱膨脹係數成為上述之指定範圍，而可得到脆化抑制及翹曲經抑制之硬化物。此處，脆化係高溫下的伸長率降低作為指標。 In the resin composition of the present invention, by setting the oxygen permeability coefficient and linear thermal expansion coefficient within the above-mentioned specified ranges, a cured product with suppressed embrittlement and suppressed warpage can be obtained. Here, the decrease in elongation at high temperatures in the embrittlement system is used as an index.

具體而言，依照本發明之樹脂組成物，使用 其，根據實施例中記載之方法，在12吋晶圓上形成樹脂組成物的硬化物，製作試料基板，將試料基板以35℃、260℃及35℃之順序加熱及冷卻時，可使以實施例中記載之方法所測的翹曲量較佳成為未達2.0mm，更佳成為未達1.5mm，尤佳成為未達1.0mm。 Specifically, according to the resin composition of the present invention, use According to the method described in the examples, a hardened product of the resin composition is formed on a 12-inch wafer to prepare a sample substrate. When the sample substrate is heated and cooled in order of 35°C, 260°C and 35°C, it is possible to use The amount of warpage measured by the method described in the Examples is preferably less than 2.0 mm, more preferably less than 1.5 mm, still more preferably less than 1.0 mm.

又，依照本發明之樹脂組成物，可使其在180℃熱硬化24小時而得的硬化物之依據JIS K7127測定的在23℃的伸長率相對於使其在180℃熱硬化90分鐘而得的硬化物之依據JIS K7127測定的在23℃的伸長率之比較佳成為0.70以上，更佳成為0.73以上，尤佳成為0.75以上。 Furthermore, according to the resin composition of the present invention, the elongation at 23°C measured in accordance with JIS K7127 of the cured product obtained by thermally curing it at 180°C for 24 hours is compared to that obtained by thermally curing it at 180°C for 90 minutes. The ratio of the elongation at 23°C of the hardened material measured in accordance with JIS K7127 is preferably 0.70 or more, more preferably 0.73 or more, and still more preferably 0.75 or more.

<樹脂組成物之用途> <Use of resin composition>

本發明之樹脂組成物的硬化物係因上述優點，而有用於半導體的密封層及絕緣層。因此，此樹脂組成物係可作為半導體密封用或絕緣層用的樹脂組成物使用。 The cured product of the resin composition of the present invention is useful for sealing layers and insulating layers of semiconductors due to the above advantages. Therefore, this resin composition can be used as a resin composition for semiconductor sealing or insulating layers.

例如，本發明之樹脂組成物係可適用作為用於形成半導體晶片封裝的絕緣層之樹脂組成物(半導體晶片封裝的絕緣層用之樹脂組成物)及用於形成電路基板(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之樹脂組成物)。 For example, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a semiconductor chip package (a resin composition for an insulating layer of a semiconductor chip package) and for forming a circuit board (including a printed wiring board). Resin composition for the insulating layer (resin composition for the insulating layer of the circuit board).

又，例如本發明之樹脂組成物係可適用作為用於密封半導體晶片封裝的半導體晶片之樹脂組成物(半導體晶片密封用之樹脂組成物)。 Furthermore, for example, the resin composition of the present invention can be suitably used as a resin composition for sealing a semiconductor wafer in a semiconductor wafer package (resin composition for semiconductor wafer sealing).

作為採用以本發明之樹脂組成物的硬化物所 形成的密封層或絕緣層之半導體晶片封裝，例如可舉出FC-CSP、MIS-BGA封裝、ETS-BGA封裝、扇出(Fan-out)型WLP(晶圓級封裝)、扇入(Fan-in)型WLP、扇出型PLP(面板級封裝)、扇入型PLP。 As a cured product using the resin composition of the present invention, Semiconductor chip packages with a sealing layer or insulating layer formed include, for example, FC-CSP, MIS-BGA packaging, ETS-BGA packaging, fan-out type WLP (wafer level packaging), fan-in (Fan) -in) type WLP, fan-out PLP (panel level packaging), fan-in PLP.

又，本發明之樹脂組成物係可作為底部填充材使用，例如可使用作為將半導體晶片連接於基板後所用之MUF(模塑底部填充)的材料。 Furthermore, the resin composition of the present invention can be used as an underfill material, for example, as a material for MUF (molding underfill) used to connect a semiconductor chip to a substrate.

再者，本發明之樹脂組成物係可使用於樹脂薄片、預浸體等的薄片狀層合材料、阻焊劑等用的樹脂油墨等之液狀材料、黏晶材、埋孔樹脂、零件埋入樹脂等使用樹脂組成物的廣泛用途。 Furthermore, the resin composition of the present invention can be used in sheet-like laminates such as resin sheets and prepregs, liquid materials such as resin inks for solder resists, etc., die bonding materials, buried hole resins, and component embedding materials. A wide range of uses using resin compositions, such as resin injection.

<樹脂油墨(樹脂清漆)> <Resin ink (resin varnish)>

本發明之樹脂油墨包含樹脂組成物，藉由使樹脂組成物之成分中含有有機溶劑，可調整黏度，提高塗佈性。 The resin ink of the present invention contains a resin composition, and by adding an organic solvent to the components of the resin composition, the viscosity can be adjusted and the coating property can be improved.

本發明之樹脂油墨例如可作為阻焊劑油墨，塗佈在印刷配線板等之電路基板上而使用。於塗佈時，可使用模塗機等的塗佈裝置。塗佈所形成的樹脂油墨層之厚度較佳為600μm以下，更佳為500μm以下。樹脂油墨層之厚度之下限較佳可為1μm以上、5μm以上，更佳可為10μm以上，尤佳可為50μm以上，特佳可為100μm以上。 The resin ink of the present invention can be used as a solder resist ink, for example, by coating it on a circuit substrate such as a printed wiring board. For coating, a coating device such as a die coater can be used. The thickness of the resin ink layer formed by coating is preferably 600 μm or less, more preferably 500 μm or less. The lower limit of the thickness of the resin ink layer is preferably 1 μm or more and 5 μm or more, more preferably 10 μm or more, particularly preferably 50 μm or more, and particularly preferably 100 μm or more.

又，本發明之樹脂油墨可用於得到較佳為1μm以上、5μm以上，更佳為10μm以上，尤佳為50μm以上，特佳為100μm以上之厚度的硬化物。 Furthermore, the resin ink of the present invention can be used to obtain a cured product having a thickness of preferably 1 μm or more, 5 μm or more, more preferably 10 μm or more, particularly preferably 50 μm or more, particularly preferably 100 μm or more.

<樹脂薄片> <Resin sheet>

本發明之樹脂薄片具有支撐體與設於該支撐體上的樹脂組成物層。樹脂組成物層係包含本發明之樹脂組成物的層，通常以樹脂組成物形成。 The resin sheet of the present invention has a support body and a resin composition layer provided on the support body. The resin composition layer is a layer containing the resin composition of the present invention, and is usually formed of the resin composition.

樹脂組成物層之厚度，從薄型化之觀點來看，較佳為600μm以下，更佳為500μm以下。樹脂組成物層之厚度之下限較佳可為1μm以上、5μm以上，更佳可為10μm以上，尤佳可為50μm以上，特佳可為100μm以上。 From the viewpoint of thinning, the thickness of the resin composition layer is preferably 600 μm or less, more preferably 500 μm or less. The lower limit of the thickness of the resin composition layer is preferably 1 μm or more and 5 μm or more, more preferably 10 μm or more, particularly preferably 50 μm or more, and particularly preferably 100 μm or more.

又，使樹脂組成物層硬化而得的硬化物之厚度較佳可為1μm以上、5μm以上，更佳可為10μm以上，尤佳可為50μm以上，特佳可為100μm以上。 Moreover, the thickness of the hardened material obtained by hardening the resin composition layer is preferably 1 μm or more, 5 μm or more, more preferably 10 μm or more, particularly preferably 50 μm or more, particularly preferably 100 μm or more.

作為支撐體，例如可舉出由塑膠材料所成之薄膜、金屬箔、離型紙、由塑膠材料所成之薄膜、金屬箔。 Examples of the support include a film made of a plastic material, a metal foil, a release paper, a film made of a plastic material, and a metal foil.

使用由塑膠材料所成的薄膜作為支撐體時，作為塑膠材料，例如可舉出聚對苯二甲酸乙二酯(以下「亦簡稱PET」)、聚萘二甲酸乙二酯(以下亦簡稱「PEN」)等之聚酯；聚碳酸酯(以下亦簡稱「PC」)；聚甲基丙烯酸甲酯(以下亦簡稱「PMMA」)等之丙烯酸聚合物；環狀聚烯烴；三乙醯纖維素(以下亦簡稱「TAC」)；聚醚硫化物(以下亦簡稱「PES」)；聚醚酮；聚醯亞胺等。其中，較佳聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯，特佳為便宜的聚對苯二甲酸乙二酯。 When a film made of a plastic material is used as a support, examples of the plastic material include polyethylene terephthalate (hereinafter also referred to as "PET"), polyethylene naphthalate (hereinafter also referred to as "PET") and polyethylene naphthalate (hereinafter also referred to as "PET"). PEN") and other polyesters; polycarbonate (hereinafter also referred to as "PC"); polymethylmethacrylate (hereinafter also referred to as "PMMA") and other acrylic polymers; cyclic polyolefins; triacetyl cellulose (hereinafter also referred to as "TAC"); polyether sulfide (hereinafter also referred to as "PES"); polyetherketone; polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and cheap polyethylene terephthalate is especially preferred.

使用金屬箔作為支撐體時，作為金屬箔，例如可舉出銅箔、鋁箔等。其中，較佳為銅箔。作為銅箔，可使用由銅的單金屬所成之箔，也可使用由銅與其他金屬(例如，錫、鉻、銀、鎂、鎳、鋯、矽、鈦等)的合金所成之箔。 When a metal foil is used as a support, examples of the metal foil include copper foil, aluminum foil, and the like. Among them, copper foil is preferred. As the copper foil, a foil made of copper as a single metal may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. .

支撐體係可對於與樹脂組成物層接合之面施予消光處理、電暈處理、抗靜電處理。 The support system can be subjected to matting treatment, corona treatment, and antistatic treatment on the surface bonded to the resin composition layer.

又，作為支撐體，亦可使用在與樹脂組成物層接合之面具有脫模層的附脫模層之支撐體。作為使用於附脫模層之支撐體的脫模層之脫模劑，例如可舉出選自由醇酸樹脂、聚烯烴樹脂、胺基甲酸酯樹脂及聚矽氧樹脂所成之群組的1種以上之脫模劑。作為脫模劑之市售品，例如可舉出醇酸樹脂系脫模劑之LINTEC公司製的「SK-1」、「AL-5」、「AL-7」等。又，作為附脫模層之支撐體，例如可舉出東麗(股)製「Lumirror T60」；帝人公司製的「Purex」；UNITIKA公司製的「Unipeel」等 Moreover, as a support body, the support body with a release layer which has a release layer on the surface joined to a resin composition layer can also be used. Examples of the release agent used for the release layer of the support with a release layer include those selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and polysiloxane resins. More than 1 type of release agent. Examples of commercially available release agents include "SK-1", "AL-5", and "AL-7" of alkyd resin release agents manufactured by LINTEC Corporation. Examples of the support with a mold release layer include "Lumirror T60" manufactured by Toray Industries, Ltd.; "Purex" manufactured by Teijin Corporation; and "Unipeel" manufactured by UNITIKA Corporation, etc.

支撐體之厚度較佳為5μm~75μm之範圍，更佳為10μm~60μm之範圍。還有，使用附有脫模層的支撐體時，附有脫模層的支撐體全體之厚度較佳為上述範圍。 The thickness of the support body is preferably in the range of 5 μm ~ 75 μm, more preferably in the range of 10 μm ~ 60 μm. When using a support with a release layer, the thickness of the entire support with a release layer is preferably within the above range.

樹脂薄片例如係可使用模塗機等的塗佈裝置，將樹脂組成物塗佈於支撐體上而製造。又，視需要可將樹脂組成物溶解於有機溶劑中而調製樹脂清漆，塗佈該樹脂清漆而製造樹脂薄片。藉由使用溶劑，調整黏度，可提高塗佈性。使用樹脂清漆時，通常在塗佈後使樹脂清漆 乾燥，形成樹脂組成物層。 The resin sheet can be produced by applying a resin composition to a support using a coating device such as a die coater. If necessary, the resin composition may be dissolved in an organic solvent to prepare a resin varnish, and the resin varnish may be applied to produce a resin sheet. By using solvents and adjusting the viscosity, the coating properties can be improved. When using resin varnish, the resin varnish is usually applied after application Dry to form a resin composition layer.

乾燥係可藉由加熱、熱風噴吹等眾所周知之方法而實施。乾燥條件係以樹脂組成物層中的有機溶劑之含量通常成為10質量%以下，較佳成為5質量%以下之方式使其乾燥。雖然亦隨著樹脂清漆中的有機溶劑之沸點而不同，但例如當使用含有30質量%~60質量%的有機溶劑之樹脂清漆時，藉由在50℃~150℃乾燥3分鐘~10分鐘，可形成樹脂組成物層。 Drying can be implemented by well-known methods such as heating and hot air blowing. The drying conditions are such that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although it also varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% to 60% by mass of organic solvent, by drying at 50°C to 150°C for 3 minutes to 10 minutes, A resin composition layer can be formed.

樹脂薄片係視需要可包含支撐體及樹脂組成物層以外的任意之層。例如，於樹脂薄片中，在樹脂組成物層之未與支撐體接合的面(即與支撐體相反側之面)，可設置符合支撐體的保護膜。保護膜之厚度例如為1μm~40μm。藉由保護膜，可防止灰塵等對樹脂組成物層的表面之附著或損傷。當樹脂薄片具有保護膜時，可藉由剝離保護膜而使用樹脂薄片。又，樹脂薄片係可捲繞成捲筒狀而保存。 The resin sheet may include any layer other than the support and the resin composition layer if necessary. For example, in the resin sheet, a protective film conforming to the support may be provided on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support). The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film can prevent dust and the like from adhering to or damaging the surface of the resin composition layer. When the resin sheet has a protective film, the resin sheet can be used by peeling off the protective film. In addition, the resin sheet can be wound into a roll shape and stored.

樹脂薄片係可適用於在半導體晶片封裝之製造中形成絕緣層(半導體晶片封裝的絕緣用樹脂薄片)。例如，樹脂薄片係可使用於形成電路基板的絕緣層(電路基板的絕緣層用樹脂薄片)。作為使用如此的基板之封裝之例，可舉出FC-CSP、MIS-BGA封裝、ETS-BGA封裝。 The resin sheet can be suitably used to form an insulating layer in the manufacture of semiconductor chip packages (resin sheet for insulation of semiconductor chip packages). For example, the resin sheet can be used to form an insulating layer of a circuit board (a resin sheet for an insulating layer of a circuit board). Examples of packages using such a substrate include FC-CSP, MIS-BGA packages, and ETS-BGA packages.

又，樹脂薄片係可適用於用於密封半導體晶片(半導體晶片密封用樹脂薄片)。作為可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。 Furthermore, the resin sheet can be suitably used for sealing semiconductor wafers (resin sheet for semiconductor wafer sealing). Examples of applicable semiconductor chip packages include fan-out WLP, fan-in WLP, and fan-out WLP. PLP, fan-in PLP, etc.

另外，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。 In addition, a resin sheet can be used as a material for the MUF used after connecting the semiconductor chip to the substrate.

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。例如，樹脂薄片係可適用於形成印刷配線板等的電路基板之絕緣層。 Furthermore, the resin sheet can be used in a wide range of other applications requiring high insulation reliability. For example, the resin sheet can be suitably used to form an insulating layer of a circuit board such as a printed wiring board.

<電路基板> <Circuit board>

本發明中的電路基板包含藉由本發明之樹脂組成物的硬化物所形成之絕緣層。此電路基板例如係可藉由包含下述步驟(1)及步驟(2)之製造方法而製造。 The circuit board in the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention. This circuit substrate can be manufactured, for example, by a manufacturing method including the following steps (1) and (2).

(1)於基材上，形成樹脂組成物層之步驟。 (1) The step of forming a resin composition layer on a substrate.

(2)使樹脂組成物層熱硬化，形成絕緣層之步驟。 (2) The step of thermally hardening the resin composition layer to form an insulating layer.

於步驟(1)中，準備基材。作為基材，例如可舉出玻璃環氧基板、金屬基板(不銹鋼或冷軋鋼板(SPCC)等)、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚伸苯基醚基板等之基板。又，基材係在作為該基材的一部分，亦可在表面具有銅箔等的金屬層。例如，可使用在兩表面具有能剝離的第一金屬層及第二金屬層之基材。使用如此的基材時，通常具有可作為電路配線之機能的配線層之導體層，係形成在第二金屬層之與第一金屬層相反側之面。作為具有如此的金屬層之基材，例如可舉出三井金屬礦業公司製之附載體銅箔的極薄銅箔「Micro Thin」。 In step (1), prepare the substrate. Examples of the base material include glass epoxy substrate, metal substrate (stainless steel, cold-rolled steel plate (SPCC), etc.), polyester substrate, polyimide substrate, BT resin substrate, and thermosetting polyphenylene ether substrate. And so on the substrate. In addition, the base material may have a metal layer such as copper foil on the surface as a part of the base material. For example, a substrate having a peelable first metal layer and a second metal layer on both surfaces can be used. When such a base material is used, a conductor layer having a function as a wiring layer for circuit wiring is usually formed on the surface of the second metal layer opposite to the first metal layer. An example of a base material having such a metal layer is an ultra-thin copper foil with a carrier copper foil "Micro Thin" manufactured by Mitsui Mining & Metals Co., Ltd.

又，於基材之一或兩表面上，可形成導體層。於以下之說明中，將包含基材與在該基材表面所形成的導體層之構件適宜地亦稱為「附配線層的基材」。作為導體層所包含的導體材料，例如可舉出包含選自由金、鉑、鈀、銀、銅、鋁、鈷、鉻、鋅、鎳、鈦、鎢、鐵、錫及銦所成之群組的1種以上之金屬的材料。作為導體材料，可使用單金屬，也可使用合金。作為合金，例如可舉出由選自上述之群組的2種以上之金屬的合金(例如，鎳-鉻合金、銅-鎳合金及銅-鈦合金)。其中，從導體層形成的通用性、成本、圖型化的容易性等之觀點來看，較佳係作為單金屬的鉻、鎳、鈦、鋁、鋅、金、鈀、銀或銅；及作為合金之鎳-鉻合金、銅-鎳合金、銅-鈦合金之合金。其中，更佳為鉻、鎳、鈦、鋁、鋅、金、鈀、銀或銅之單金屬；及，鎳-鉻合金，特佳為銅的單金屬。 In addition, a conductor layer can be formed on one or both surfaces of the substrate. In the following description, a member including a base material and a conductor layer formed on the surface of the base material is also appropriately referred to as a "base material with a wiring layer." Examples of the conductor material included in the conductor layer include a material selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. A material made of more than one metal. As the conductor material, a single metal or an alloy can be used. Examples of the alloy include alloys of two or more metals selected from the group described above (for example, nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper as a single metal is preferred; and As alloys, they are nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys. Among them, a single metal of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper is more preferred; and, for a nickel-chromium alloy, a single metal of copper is particularly preferred.

導體層例如係為了具有配線層之機能，可被圖型加工。此時，導體層之線(電路寬度)/間隔(電路間的寬度)比係沒有特別的限制，但較佳為20/20μm以下(即間距為40μm以下)，更佳為10/10μm以下，尤佳為5/5μm以下，尤更佳為1/1μm以下，特佳為0.5/0.5μm以上。間距未必要在導體層之全體中為相同。導體層的最小間距例如可為40μm以下、36μm以下或30μm以下。 The conductive layer can be patterned, for example, in order to function as a wiring layer. At this time, the line (circuit width)/space (width between circuits) ratio of the conductor layer is not particularly limited, but it is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), and more preferably 10/10 μm or less. Particularly preferably, it is 5/5 μm or less, particularly preferably 1/1 μm or less, and particularly preferably 0.5/0.5 μm or more. The spacing does not necessarily have to be the same throughout the conductor layers. The minimum pitch of the conductor layer may be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.

導體層之厚度係取決於電路基板之設計，但較佳為3μm~35μm，更佳為5μm~30μm，尤佳為10μm~20μm，特佳為15μm~20μm。 The thickness of the conductor layer depends on the design of the circuit substrate, but is preferably 3 μm ~ 35 μm, more preferably 5 μm ~ 30 μm, particularly preferably 10 μm ~ 20 μm, particularly preferably 15 μm ~ 20 μm.

導體層例如可藉由包含下步驟之方法而形成：在基材上層合乾薄膜(感光性阻劑薄膜)之步驟，使用光罩，對於乾薄膜，於指定之條件下進行曝光及顯像而形成圖型，得到圖型乾薄膜之步驟，將經顯像的圖型乾薄膜當作鍍敷遮罩，藉由電解鍍敷法等之鍍敷法形成導體層之步驟，及剝離圖型乾薄膜之步驟。作為乾薄膜，可使用由光阻組成物所成之感光性的乾薄膜，例如可使用以酚醛清漆樹脂、丙烯酸樹脂等樹脂所形成之乾薄膜。基材與乾薄膜之層合條件係可與後述之基材與樹脂薄片之層合條件同樣。乾薄膜之剝離例如可使用氫氧化鈉溶液等之鹼性剝離液實施。 The conductor layer can be formed, for example, by a method including the following steps: laminating a dry film (photoresist film) on a base material, using a photomask, and exposing and developing the dry film under specified conditions. The steps of forming a pattern and obtaining a pattern dry film, using the developed pattern dry film as a plating mask, forming a conductor layer by plating methods such as electrolytic plating, and peeling off the pattern dry film. Film steps. As the dry film, a photosensitive dry film made of a photoresist composition can be used. For example, a dry film formed of a resin such as novolac resin or acrylic resin can be used. The lamination conditions of the base material and the dry film can be the same as the lamination conditions of the base material and the resin sheet described later. The dry film can be peeled off using an alkaline peeling liquid such as sodium hydroxide solution, for example.

準備基材後，在基材上形成樹脂組成物層。在基材之表面上形有導體層時，樹脂組成物層之形成較佳為以導體層被埋入樹脂組成物層中之方式進行。 After preparing the base material, a resin composition layer is formed on the base material. When a conductor layer is formed on the surface of the base material, the resin composition layer is preferably formed in such a manner that the conductor layer is embedded in the resin composition layer.

樹脂組成物層之形成例如係藉由層合樹脂薄片與基材而進行。此層合例如係可藉由從支撐體側，將樹脂薄片加熱壓接於基材，使樹脂組成物層貼合於基材而進行。作為將樹脂薄片加熱壓接於基材的構件(以下，亦稱為「加熱壓接構件」)，例如可舉出經加熱的金屬板(SUS鏡板等)或金屬輥(SUS輥)等。再者，較佳為不將加熱壓接構件直接加壓於樹脂薄片，而是以樹脂薄片充分追隨基材的表面凹凸之方式，隔著耐熱橡膠等的彈性材來加壓。 The resin composition layer is formed, for example, by laminating a resin sheet and a base material. This lamination can be performed, for example, by heating and press-bonding the resin sheet to the base material from the support side to bond the resin composition layer to the base material. Examples of a member for thermally and press-bonding a resin sheet to a base material (hereinafter also referred to as a "heat-compression bonding member") include a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller). Furthermore, it is preferable not to directly pressurize the resin sheet with the heating and pressing member, but to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet fully follows the surface irregularities of the base material.

基材與樹脂薄片之層合係可藉由真空層合法實施。於真空層合法中，加熱壓接溫度較佳為60℃~160 ℃，更佳為80℃~140℃之範圍，加熱壓接壓力較佳為0.098MPa~1.77MPa，更佳為0.29MPa~1.47MPa之範圍，加熱壓接時間較佳為20秒~400秒，更佳為30秒~300秒之範圍。層合較佳為在壓力13hPa以下之減壓條件下實施。 The lamination system of the base material and the resin sheet can be implemented by vacuum lamination. In the vacuum lamination method, the preferred heating and crimping temperature is 60°C~160°C ℃, preferably in the range of 80℃~140℃, the heating and crimping pressure is preferably in the range of 0.098MPa~1.77MPa, and more preferably in the range of 0.29MPa~1.47MPa, and the heating and crimping time is preferably in the range of 20 seconds to 400 seconds. It is better to be in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions of 13 hPa or less.

於層合之後，藉由在常壓下(大氣壓下)，例如亦可從支撐體側將加熱壓接構件予以加壓，進行所層合之樹脂薄片的平滑化處理。平滑化處理的加壓條件係可與上述層合的加熱壓接條件同樣之條件。再者，層合與平滑化處理亦可使用真空層合機連續地進行。 After lamination, the laminated resin sheets can be smoothed by applying pressure to the heating and crimping member from the support side under normal pressure (atmospheric pressure), for example. The pressure conditions for the smoothing treatment may be the same as the conditions for heat and pressure bonding of the above-mentioned lamination. Furthermore, lamination and smoothing can also be performed continuously using a vacuum laminator.

又，樹脂組成物層之形成例如係可藉由壓縮成型法進行。成型條件係可採用與後述之形成半導體晶片封裝的密封層之步驟中的樹脂組成物層之形成方法同樣的條件。 In addition, the resin composition layer can be formed by, for example, a compression molding method. The molding conditions may be the same as the formation method of the resin composition layer in the step of forming the sealing layer of the semiconductor chip package described later.

於基材上形成樹脂組成物層後，使樹脂組成物層熱硬化，形成絕緣層。雖然樹脂組成物層之熱硬化條件亦取決於樹脂組成物之種類等而不同，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，更佳為15分鐘~90分鐘)。 After the resin composition layer is formed on the base material, the resin composition layer is thermally hardened to form an insulating layer. Although the thermal hardening conditions of the resin composition layer vary depending on the type of the resin composition, etc., 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 170°C ~200°C), and the hardening time is in the range of 5 minutes to 120 minutes (preferably 10 minutes ~ 100 minutes, more preferably 15 minutes ~ 90 minutes).

於使樹脂組成物層熱硬化之前，亦可在比硬化溫度更低的溫度下，對於樹脂組成物層，施予加熱之預備加熱處理。例如，於使樹脂組成物層熱硬化之前，亦可通常在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，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 thermally hardening the resin composition layer, a preliminary heat treatment of heating the resin composition layer may also be performed at a temperature lower than the curing temperature. For example, before thermally hardening the resin composition layer, the temperature may be usually 50°C or higher and less than 120°C (preferably 60°C or more and 110°C or less). (preferably above 70°C and below 100°C), the resin composition layer is usually preheated for more than 5 minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

如以上，可製造具有絕緣層的電路基板。又，電路基板之製造方法係可進一步包含任意之步驟。 As described above, a circuit board having an insulating layer can be manufactured. In addition, the manufacturing method of the circuit board may further include arbitrary steps.

例如，使用樹脂薄片來製造電路基板時，電路基板之製造方法可包含剝離樹脂薄片的支撐體之步驟。支撐體係可在樹脂組成物層的熱硬化之前剝離，也可在樹脂組成物層的熱硬化之後剝離。 For example, when a resin sheet is used to manufacture a circuit substrate, the manufacturing method of the circuit substrate may include a step of peeling off the support body of the resin sheet. The support system may be peeled off before the thermal hardening of the resin composition layer, or may be peeled off after the thermal hardening of the resin composition layer.

電路基板之製造方法例如係在形成絕緣層之後，可包含研磨該絕緣層的表面之步驟。研磨方法係沒有特別的限定，例如可使用平面研削盤，研磨絕緣層之表面。 For example, the manufacturing method of the circuit substrate may include the step of grinding the surface of the insulating layer after forming the insulating layer. The grinding method is not particularly limited. For example, a flat grinding disc can be used to grind the surface of the insulating layer.

電路基板之製造方法例如可包含層間連接導體層之步驟(3)，所謂的在絕緣層中開孔之步驟。藉此可在絕緣層中形成通孔、貫穿孔等之孔。作為通孔之形成方法，例如可舉出雷射照射、蝕刻、機械打孔等。通孔之尺法或形狀宜按照電路基板之設計而適宜決定。再者，步驟(3)亦可藉由絕緣層之研磨或研削而進行層間連接。 The manufacturing method of the circuit substrate may include, for example, step (3) of connecting the conductor layers between layers, a so-called step of opening holes in the insulating layer. Through this, holes such as through holes and through holes can be formed in the insulating layer. Examples of methods for forming through holes include laser irradiation, etching, mechanical drilling, and the like. The size or shape of the through hole should be appropriately determined according to the design of the circuit board. Furthermore, step (3) can also perform interlayer connection by grinding or grinding the insulating layer.

於通孔之形成後，較佳為進行去除通孔內的膠渣之步驟。此步驟亦稱為除膠渣步驟。例如，藉由鍍敷步驟進行在絕緣層上形成導體層時，對於通孔，可進行濕式的除膠渣處理。又，藉由濺鍍步驟進行在絕緣層上形成導體層時，可進行電漿處理步驟等之乾除膠渣步驟。再 者，藉由除膠渣步驟，亦可對於絕緣層施予粗化處理。 After the through hole is formed, it is preferable to perform a step of removing the slag in the through hole. This step is also called the desmear step. For example, when a conductor layer is formed on an insulating layer through a plating step, a wet desmear process can be performed on the through hole. In addition, when the conductor layer is formed on the insulating layer by a sputtering step, a dry desmear step such as a plasma treatment step may be performed. Again Alternatively, through the desmearing step, the insulation layer can also be roughened.

又，於絕緣層上形成導體層之前，對於絕緣層，可進行粗化處理。藉由此粗化處理，通常可將包含通孔內的絕緣層之表面予以粗化。作為粗化處理，可進行乾式及濕式之任一種粗化處理。作為乾式的粗化處理之例，可舉出電漿處理等。另外，作為濕式的粗化處理之例，可舉出依順序進行膨潤液的膨潤處理、氧化劑的粗化處理及中和液的中和處理之方法。 In addition, before forming the conductor layer on the insulating layer, the insulating layer may be roughened. Through this roughening process, the surface including the insulating layer within the through hole can generally be roughened. As roughening treatment, either dry type or wet type roughening treatment can be performed. Examples of dry roughening treatment include plasma treatment and the like. Examples of wet roughening treatment include a method of sequentially performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid.

於形成通孔後，在絕緣層上形成導體層。藉由在形成有通孔的位置形成導體層，新形成的導體層與基材表面的導體層係導通，進行層間連接。導體層之形成方法例如可舉出鍍敷法、濺鍍法、蒸鍍法等，其中較佳為鍍敷法。於合適的實施形態中，藉由半加成法、全加成法等之適當的方法，鍍敷於絕緣層之表面，形成具有所欲的配線圖型之導體層。又，當樹脂薄片中的支撐體為金屬箔時，可藉由減成法，形成具有所欲的配線圖型之導體層。所形成的導體層之材料可為單金屬，也可為合金。另外，此導體層係可具有單層構造，也可具有包含2層以上的不同種類的材料之層的複層構造。 After forming the through hole, a conductor layer is formed on the insulating layer. By forming a conductor layer at the position where the through hole is formed, the newly formed conductor layer is electrically connected to the conductor layer on the surface of the base material, thereby performing interlayer connection. Examples of methods for forming the conductor layer include plating, sputtering, and evaporation. Among them, the plating method is preferred. In a suitable embodiment, the surface of the insulating layer is plated by an appropriate method such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern. In addition, when the support in the resin sheet is a metal foil, a conductor layer with a desired wiring pattern can be formed by the subtractive method. The material of the formed conductor layer can be a single metal or an alloy. In addition, the conductor layer may have a single-layer structure or a multi-layer structure including two or more layers of different types of materials.

此處，詳細地說明在絕緣層上形成導體層之實施形態之例。於絕緣層之表面上，藉由無電解鍍敷，形成鍍敷種子層。接著，於所形成的鍍敷種子層上，對應於所欲的配線圖型，形成使鍍敷種子層的一部分露出之遮罩圖型。於所露出的鍍敷種子層上，藉由電解鍍敷形成電解 鍍敷層後，去除遮罩圖型。然後，藉由蝕刻等之處理而去除不要的鍍敷種子層，可形成具有所欲的配線圖型之導體層。再者，於形成導體層之際，遮罩圖型之形成中所用的乾薄膜係與上述乾薄膜同樣。 Here, an example of an embodiment in which a conductor layer is formed on an insulating layer will be described in detail. On the surface of the insulating layer, a plating seed layer is formed by electroless plating. Next, on the formed plating seed layer, a mask pattern is formed corresponding to a desired wiring pattern to expose a part of the plating seed layer. On the exposed plating seed layer, electrolytic plating is used to form electrolytic After plating the layer, remove the mask pattern. Then, the unnecessary plating seed layer is removed by processing such as etching, and a conductor layer having a desired wiring pattern can be formed. Furthermore, when forming the conductor layer, the dry film used for forming the mask pattern is the same as the dry film described above.

電路基板之製造方法可包含去除基材之步驟(4)。藉由去除基材，得到絕緣層與具有被埋入該絕緣層中的導體層之電路基板。此步驟(4)例如係在使用具有能剝離的金屬層之情況中可進行。 The manufacturing method of the circuit substrate may include the step (4) of removing the base material. By removing the base material, an insulating layer and a circuit substrate having a conductor layer embedded in the insulating layer are obtained. This step (4) can be performed, for example, when using a metal layer with a peelable metal layer.

<半導體晶片封裝> <Semiconductor chip packaging>

本發明之第一實施形態的半導體晶片封裝包含上述之電路基板與在該電路基板上所搭載的半導體晶片。此半導體晶片封裝係可藉由將半導體晶片接合至電路基板而製造。 A semiconductor chip package according to a first embodiment of the present invention includes the above-mentioned circuit substrate and a semiconductor chip mounted on the circuit substrate. The semiconductor chip package can be manufactured by bonding the semiconductor chip to the circuit substrate.

電路基板與半導體晶片之接合條件係可採用能導體連接半導體晶片的端子電極與電路基板的電路配線之任意條件。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，隔著絕緣性的接著劑進行接合。 The bonding conditions between the circuit board and the semiconductor chip can be any conditions that can conductively connect the terminal electrodes of the semiconductor chip and the circuit wiring of the circuit board. For example, conditions used in flip-chip mounting of semiconductor wafers may be adopted. Furthermore, for example, the semiconductor chip and the circuit board can be bonded via 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)。 An example of the bonding method is a method of press-bonding a semiconductor wafer to a circuit board. As the 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 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。 Another example of the bonding method is a method of bonding the semiconductor wafer to the circuit board by reflow soldering. Reflow conditions can be set within the range of 120℃~300℃.

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。作為此模塑底部填充材，可使用上述之樹脂組成物，而且也可使用上述之樹脂薄片。 After the semiconductor wafer is bonded to the circuit substrate, the underfill material may be molded to fill the semiconductor wafer. As the molding underfill material, the above-mentioned resin composition can be used, and the above-mentioned resin sheet can also be used.

本發明之第二實施形態的半導體晶片封裝包含半導體晶片與密封該半導體晶片之前述樹脂組成物的硬化物。於如此的半導體晶片封裝中，通常樹脂組成物的硬化物具有作為密封層之機能。作為第二實施形態的半導體晶片封裝，例如可舉出扇出型WLP。 A semiconductor chip package according to a second embodiment of the present invention includes a semiconductor wafer and a cured product of the resin composition that seals the semiconductor wafer. In such a semiconductor chip package, the cured product of the resin composition usually functions as a sealing layer. An example of the semiconductor chip package according to the second embodiment is a fan-out WLP.

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至基材之步驟，(B)將半導體晶片暫時固定於暫時固定薄膜上之步驟，(C)於半導體晶片上形成密封層之步驟，(D)從半導體晶片剝離基材及暫時固定薄膜之步驟，(E)於半導體晶片之已剝離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，(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。 The manufacturing method of such a semiconductor chip package includes: (A) the step of laminating the temporary fixing film to the base material, (B) the step of temporarily fixing the semiconductor chip on the temporary fixing film, (C) forming a seal on the semiconductor wafer The step of layering, (D) the step of peeling off the base material and the temporarily fixed film from the semiconductor wafer, (E) the step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor wafer from which the base material and temporarily fixed film have been peeled off , (F) the step of forming a rewiring layer as a conductor layer on the rewiring formation layer, and (G) the step of forming a solder resist layer on the rewiring layer.

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。 In addition, the aforementioned manufacturing method of semiconductor chip packages may also include: (H) cutting a plurality of semiconductor chip packages into individual semiconductor wafers. Encapsulation, the step of monolithicization.

(步驟(A)) (Step (A))

步驟(A)係將暫時固定薄膜層合至基材之步驟。基材與暫時固定薄膜之層合條件係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) is the step of laminating the temporary fixing film to 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、不銹鋼、冷軋鋼板(SPCC)等之金屬基板；FR-4基板等之於玻璃纖維中摻混有環氧樹脂等之經熱硬化處理的基板；由BT樹脂等之雙馬來醯亞胺三

Figure 108127984-A0305-02-0053-14
樹脂所成之基板等。 Examples of the base material include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel plates (SPCC); FR-4 substrates in which glass fibers are mixed with rings. Heat-hardened substrates made of oxy resin, etc.; Bismaleimide trisulfide made of BT resin, etc.
Figure 108127984-A0305-02-0053-14
Substrates made of resin, etc.

暫時固定薄膜係可使用能從半導體晶片剝離，且能暫時固定半導體晶片之任意的材料。作為市售品，可舉出日東電工公司製「Livalpha」等。 As the temporary fixing film, any material that can be peeled off from the semiconductor wafer and can temporarily fix the semiconductor wafer can be used. Examples of commercially available products include "Livalpha" manufactured by Nitto Denko Co., Ltd.

(步驟(B)) (Step (B))

步驟(B)係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晶片接合機、晶粒接合機等之裝置進行。半導體晶片之配置的佈局及配置數係可按照暫時固定薄膜之形狀、大小、目的之半導體晶片封裝的生產數等而適當地設定。例如，亦可使半導體晶片整齊排列成複數行且複數列的矩陣狀並暫時固定。 Step (B) is a step of temporarily fixing the semiconductor wafer on the temporary fixing film. The semiconductor chip can be temporarily fixed using, for example, a flip-chip wafer bonding machine, a die bonding machine, or the like. The layout and arrangement number of semiconductor wafers can be appropriately set according to the shape and size of the temporary fixation film, the intended production number of semiconductor wafer packages, and the like. For example, the semiconductor wafers may be arranged in a matrix with a plurality of rows and a plurality of columns and temporarily fixed.

(步驟(C)) (Step (C))

步驟(C)係於半導體晶片上形成密封層之步驟。密封層係藉由上述樹脂組成物的硬化物而形成。密封層通常係以包含以下步驟之方法形成：於半導體晶片上形成樹脂組成物層之步驟，及使此樹脂組成物層熱硬化而形成密封層之步驟。 Step (C) is a step of forming a sealing layer on the semiconductor wafer. The sealing layer is formed from a cured product of the above-mentioned resin composition. The sealing layer is usually formed by a method that includes the following steps: forming a resin composition layer on the semiconductor wafer, and thermally hardening the resin composition layer to form the sealing layer.

利用樹脂組成物之優異的壓縮成型性，樹脂組成物層之形成較佳為藉由壓縮成型法進行。於壓縮成型法中，通常將半導體晶片及樹脂組成物配置於模具，於該模具內對於樹脂組成物施加壓力及視需要的熱，形成覆蓋半導體晶片之樹脂組成物層。 Taking advantage of the excellent compression moldability of the resin composition, the formation of the resin composition layer is preferably performed by a compression molding method. In the compression molding method, a semiconductor wafer and a resin composition are usually placed in a mold, and pressure and optional heat are applied to the resin composition in the mold to form a resin composition layer covering the semiconductor wafer.

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，如前述，於暫時固定薄膜上所暫時固定的半導體晶片，塗佈樹脂組成物。將塗佈有樹脂組成物的半導體晶片與基材及暫時固定薄膜一起安裝於下模。然後，閉合上模與下模，將熱及壓力施予樹脂組成物，進行壓縮成型。 Specific operations of the compression molding method are as follows, for example. As a mold for compression molding, prepare an upper mold and a lower mold. Furthermore, as described above, the resin composition is applied to the semiconductor wafer temporarily fixed on the temporary fixing film. The semiconductor wafer coated with the resin composition is mounted on the lower mold together with the base material and the temporary fixing film. Then, the upper mold and the lower mold are closed, heat and pressure are applied to the resin composition, and compression molding is performed.

又，壓縮成型法之具體的操作例如係可如下述。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，將半導體晶片與基材及暫時固定薄膜一起安裝於上模。然後，以在下模所載置的樹脂組成物接觸在上模所安裝的半導體晶片之方式，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, the semiconductor wafer is mounted on the upper mold together with the base material and the temporary fixing film. Then, the upper mold and the lower mold are closed so that the resin composition placed on the lower mold contacts the semiconductor chip mounted on the upper mold, heat and pressure are applied, and compression molding is performed.

成型條件係隨著樹脂組成物之組成而不同， 可以達成良好的密封之方式採用適當的條件。例如，成型時之模具的溫度較佳為能發揮樹脂組成物優異的壓縮成型性之溫度，較佳為80℃以上，更佳為100℃以上，特佳為120℃以上，較佳為200℃以下，更佳為170℃以下，特佳為150℃以下。又，在成形時所施加的壓力較佳為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5分鐘以上，且較佳為60分鐘以下，更佳為30分鐘以下，特佳為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 depending on the composition of the resin composition. A good seal can be achieved by using appropriate conditions. For example, the temperature of the mold during molding is preferably a temperature that can exert the excellent compression moldability of the resin composition. It is preferably 80°C or higher, more preferably 100°C or higher, particularly preferably 120°C or higher, and more preferably 200°C. below, more preferably below 170°C, particularly preferably below 150°C. Moreover, the pressure applied during molding is preferably 1 MPa or more, more preferably 3 MPa or more, particularly preferably 5 MPa or more, and preferably 50 MPa or less, more preferably 30 MPa or less, particularly preferably 20 MPa or less. The hardening time is preferably at least 1 minute, more preferably at least 2 minutes, particularly preferably at least 5 minutes, and preferably at most 60 minutes, more preferably at most 30 minutes, and particularly preferably at most 20 minutes. Usually, after the resin composition layer is formed, the mold is disassembled. The mold can be disassembled before the resin composition layer is thermally hardened, or after the thermal hardening.

樹脂組成物層之形成係可藉由層合樹脂薄片與半導體晶片而進行。例如，藉由加熱壓接樹脂薄片的樹脂組成物層與半導體晶片，可在半導體晶片上形成樹脂組成物層。樹脂薄片與半導體晶片之層合通常係可使用半導體晶片代替基材，與電路基板之製造方法中的樹脂薄片與基材之層合同樣地進行。 The resin composition layer can be formed by laminating a resin sheet and a semiconductor wafer. For example, by heating and pressing the resin composition layer of the resin sheet and the semiconductor wafer, the resin composition layer can be formed on the semiconductor wafer. The lamination of the resin sheet and the semiconductor wafer can generally be performed in the same manner as the lamination of the resin sheet and the base material in the circuit board manufacturing method using the semiconductor wafer instead of the base material.

於半導體晶片上形成樹脂組成物層後，使該樹脂組成物層熱硬化，得到覆蓋半導體晶片之密封層。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係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，可對於樹脂組成物層，施予以比 硬化溫度更低的溫度進行加熱之預備加熱處理。此預備加熱處理之處理條件係可採用與電路基板之製造方法中的預備加熱處理相同之條件。 After the resin composition layer is formed on the semiconductor wafer, the resin composition layer is thermally hardened to obtain a sealing layer covering the semiconductor wafer. Thereby, the semiconductor wafer is sealed with the hardened material of the resin composition. The thermal hardening conditions of the resin composition layer may be the same as the thermal hardening conditions of the resin composition layer in the manufacturing method of the circuit board. Furthermore, before thermally hardening the resin composition layer, the resin composition layer may be subjected to a specific treatment. Preparatory heat treatment for heating at a lower hardening temperature. The processing conditions of this preliminary heat treatment can be the same as those of the preliminary heat treatment in the manufacturing method of the circuit board.

(步驟(D)) (Step (D))

步驟(D)係從半導體晶片剝離基材及暫時固定薄膜之步驟。剝離方法宜採用符合暫時固定薄膜的材質之適切方法。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) is a step of peeling off the base material from the semiconductor wafer and temporarily fixing the film. The peeling method should be appropriate to the material used to temporarily fix the film. Examples of the peeling method include a method of heating, foaming or expanding the temporarily fixed film to peel it off. As a peeling method, for example, the temporarily fixed film is irradiated with ultraviolet rays through the base material to reduce the adhesive force of the temporarily fixed film and peel it off.

於使暫時固定薄膜加熱、發泡或膨脹而剝離之方法中，加熱條件通常在100℃~250℃為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，紫外線之照射量通常為10mJ/cm2~1000mJ/cm2。 In the method of heating, foaming or expanding the temporarily fixed film to peel off, the heating conditions are usually 1 second to 90 seconds or 5 minutes to 15 minutes at 100°C to 250°C. In addition, in the method of irradiating ultraviolet rays to reduce the adhesive force of the temporarily fixed film and peel it off, the irradiation amount of ultraviolet rays is usually 10mJ/cm 2 ~1000mJ/cm 2 .

(步驟(E)) (Step (E))

步驟(E)係於半導體晶片之已剝離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。 Step (E) is a step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor wafer from which the base material and the temporarily fixed film have been peeled off.

再配線形成層之材料係可使用具有絕緣性的任意材料。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，作為該熱硬化性樹脂，亦可使用本發明之樹脂組成物。 As the material of the rewiring forming layer, any material having insulating properties can be used. Among these, photosensitive resins and thermosetting resins are preferred from the viewpoint of ease of manufacturing semiconductor chip packages. Moreover, as this thermosetting resin, the resin composition of this invention can also be used.

形成再配線形成層後，為了層間連接半導體晶片與再配線層，可在再配線形成層中形成通孔。 After the rewiring forming layer is formed, a through hole may be formed in the rewiring forming layer in order to connect the semiconductor wafer and the rewiring layer between layers.

於再配線形成層之材料為感光性樹脂時的通孔之形成方法中，通常通過遮罩圖型，將活性能量線照射至再配線形成層之表面，而使照射部的再配線形成層進行光硬化。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。紫外線之照射量及照射時間係可按照感光性樹脂而適當地設定。作為曝光方法，例如可舉出使遮罩圖型緊貼於再配線形成層，進行曝光之接觸曝光法，不使遮罩圖型緊貼於再配線形成層，使用平行光線進行曝光之非接觸曝光法等。 In the formation method of the through hole when the material of the rewiring forming layer is a photosensitive resin, the active energy ray is usually irradiated to the surface of the rewiring forming layer through a mask pattern, so that the rewiring forming layer in the irradiated part is formed. Light hardening. Examples of active energy rays include ultraviolet rays, visible rays, electron rays, X-rays, etc., and ultraviolet rays are particularly preferred. The irradiation amount and irradiation time of ultraviolet rays can be appropriately set according to the photosensitive resin. Examples of the exposure method include a contact exposure method in which the mask pattern is brought into close contact with the rewiring forming layer and exposed, and a non-contact method in which parallel light is used for exposure without bringing the mask pattern into close contact with the rewiring forming layer. Exposure method etc.

於使再配線形成層進行光硬化後，將再配線形成層顯像，去除未曝光部，形成通孔。顯像係可進行濕顯像、乾顯像之任一者。作為顯像之方式，例如可舉出浸漬方式、覆液方式、噴霧方式、塗刷方式、刮塗方式等，從解析性之觀點來看，宜為覆液方式。 After the rewiring forming layer is photocured, the rewiring forming layer is developed to remove unexposed portions and form through holes. The imaging system can perform either wet imaging or dry imaging. Examples of the development method include a immersion method, a liquid coating method, a spray method, a brushing method, a blade coating method, and the like. From an analytical viewpoint, the liquid coating method is preferable.

作為再配線形成層之材料為熱硬化性樹脂時的通孔之形成方法，例如可舉出雷射照射、蝕刻、機械打孔等。其中，較佳為雷射照射。雷射照射係可使用採用二氧化碳雷射、UV-YAG雷射、準分子雷射等光源之適當之雷射加工機進行。 When the material of the rewiring formation layer is a thermosetting resin, examples of the method for forming the through hole include laser irradiation, etching, and mechanical drilling. Among them, laser irradiation is preferred. Laser irradiation can be performed using an appropriate laser processing machine using light sources such as carbon dioxide laser, UV-YAG laser, and excimer laser.

通孔之形狀係沒有特別的限定，但一般而言為圓形(略圓形)。通孔之頂徑較佳為50μm以下，更佳為30μm以下，尤佳為20μm以下，且較佳為3μm以上，更佳 為10μm以上，尤佳為15μm以上。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的直徑。 The shape of the through hole is not particularly limited, but is generally circular (slightly circular). The top diameter of the through hole is preferably 50 μm or less, more preferably 30 μm or less, especially 20 μm or less, and preferably 3 μm or more, still more preferably The thickness is 10 μm or more, preferably 15 μm or more. Here, the top diameter of the through hole refers to the diameter of the opening of the through hole on the surface of the wiring formation layer.

(步驟(F)) (Step (F))

步驟(F)係於再配線形成層上，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，係可與電路基板之製造方法中的在絕緣層上形成導體層之方法同樣。又，亦可重複進行步驟(E)及步驟(F)，交替地堆積(增建)再配線層及再配線形成層。 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 can be the same as the method of forming the conductor layer on the insulating layer in the manufacturing method of the circuit board. Alternatively, steps (E) and (F) may be repeated to alternately deposit (build up) rewiring layers and rewiring forming layers.

(步驟(G)) (Step (G))

步驟(G)係於再配線層上形成阻焊劑層之步驟。阻焊劑層之材料係可使用具有絕緣性的任意材料。其中，從半導體晶片封裝之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。 Step (G) is a step of forming a solder resist layer on the rewiring layer. The solder resist layer may be made of any insulating material. Among these, photosensitive resins and thermosetting resins are preferred from the viewpoint of ease of manufacturing of semiconductor chip packages. Moreover, as a thermosetting resin, the resin composition of this invention can be used.

又，於步驟(G)中，視需要亦可進行形成凸塊的凸塊加工。凸塊加工係可用焊球、焊料鍍敷等之方法進行。又，凸塊加工中的通孔之形成係可與步驟(E)同樣地進行。 Furthermore, in step (G), bump processing may be performed to form bumps if necessary. Bump processing can be performed by methods such as solder balls and solder plating. In addition, the formation of the through hole in the bump processing can be performed in the same manner as in step (E).

(步驟(H)) (Step (H))

半導體晶片封裝之製造方法係除了步驟(A)~(G)以外，亦可包含步驟(H)。步驟(H)係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。 In addition to steps (A) to (G), the manufacturing method of semiconductor chip packaging may also include step (H). Step (H) is to package a plurality of semiconductor wafers The process of cutting the package into individual semiconductor wafers and performing monolithization. The method of cutting the semiconductor wafer package into individual semiconductor wafer packages is not particularly limited.

<半導體裝置> <Semiconductor device>

半導體裝置具備半導體晶片封裝。作為半導體裝置，例如可舉出供電氣製品(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。 The semiconductor device includes a semiconductor chip package. Examples of semiconductor devices include electrically powered products (for example, computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, televisions, etc.) and vehicles (for example, motorcycles, automobiles, Various semiconductor devices such as trains, ships, and aircraft, etc.

[實施例] [Example]

以下，藉由實施例更具體地說明本發明。本發明係不受此等之實施例所限定。再者，於以下中，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%」。 Hereinafter, the present invention will be described in more detail using examples. The present invention is not limited by these examples. In addition, in the following, "parts" and "%" indicating amounts mean "mass parts" and "mass %" respectively, unless otherwise stated.

<合成例1：彈性體之合成> <Synthesis Example 1: Synthesis of Elastomer>

於具備攪拌裝置、溫度計及冷凝器之燒瓶中，加入作為溶劑之368.41g的乙基二甘醇乙酸酯、368.41g的Solvesso 150(註冊商標)(芳香族系溶劑，Exxon Mobil公司製)、100.1g(0.4莫耳)的二苯基甲烷二異氰酸酯與400g(0.2莫耳)的聚碳酸酯二醇(數量平均分子量：約2000，羥基當量：1000，不揮發分：100%，KURARAY(股)製「C- 2015N」)，在70℃進行4小時反應。接著，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，將反應物降溫至室溫後，以100網目的濾布進行過濾，得到具有聚碳酸酯構造的樹脂(不揮發成分50質量%)。所得之樹脂(彈性體)之數量平均分子量為6,100。 In a flask equipped with a stirring device, a thermometer and a condenser, 368.41g of ethyl diglycol acetate as a solvent, 368.41g of Solvesso 150 (registered trademark) (aromatic solvent, manufactured by Exxon Mobil Corporation), 100.1g (0.4 mol) of diphenylmethane diisocyanate and 400g (0.2 mol) of polycarbonate diol (number average molecular weight: about 2000, hydroxyl equivalent: 1000, non-volatile matter: 100%, KURARAY (stock) ) to prepare "C-2015N") and react at 70°C for 4 hours. Next, 195.9g (0.2 mole) of nonylphenol novolac resin (hydroxyl equivalent 229.4g/eq, average 4.27 functionality, average calculated molecular weight 979.5g/mol) and ethylene glycol bistrimellitic anhydride 41.0g (0.1 mole) were added. , it takes 2 hours to heat up to 150°C and react for 12 hours. The disappearance of the NCO peak at 2250 cm -1 was confirmed by FT-IR. Confirmation that the NCO peak disappeared was regarded as the end point of the reaction. After cooling the reaction product to room temperature, it was filtered with a 100-mesh filter cloth to obtain a resin with a polycarbonate structure (non-volatile content 50% by mass). The number average molecular weight of the obtained resin (elastomer) was 6,100.

<實施例1> <Example 1>

混合合成例1所合成之彈性體(不揮發成分50質量%)4份、橡膠粒子(陶氏化學公司製「PARALOID EXL-2655」)2份、萘型環氧樹脂(新日鐵住金化學(股)製「ESN-475V」，環氧當量約332g/eq.)3份、液狀環氧樹脂(新日鐵住金化學(股)製「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.)6份、含三

Figure 108127984-A0305-02-0060-15
骨架的苯酚酚醛清漆系硬化劑(DIC(股)製「LA-7054」，羥基當量125，不揮發成分60%之MEK溶液)8.3份、二氧化矽A(平均粒徑3μm，比表面積4m2/g，經KBM573所表面處理者)125份、硬化促進劑(2-苯基-4-甲基咪唑，四國化成工業(股)製「2P4MZ」)0.1份、甲基乙基酮(MEK)10份、環己酮8份，以高速旋轉混合器均均地分散，調製樹脂清漆1。 Mix 4 parts of the elastomer synthesized in Synthesis Example 1 (non-volatile content 50% by mass), 2 parts of rubber particles ("PARALOID EXL-2655" manufactured by Dow Chemical Company), and naphthalene-type epoxy resin (Nippon Steel & Sumitomo Metal Chemical Co., Ltd. "ESN-475V" manufactured by Nippon Steel Co., Ltd., epoxy equivalent of approximately 332g/eq.) 3 parts, liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., bisphenol A type epoxy resin and bisphenol F type epoxy resin 1:1 mixture (mass ratio), epoxy equivalent 169g/eq.) 6 parts, containing three
Figure 108127984-A0305-02-0060-15
8.3 parts of skeleton phenol novolac hardener ("LA-7054" manufactured by DIC Co., Ltd., hydroxyl equivalent 125, non-volatile content 60% MEK solution), silicon dioxide A (average particle size 3 μm, specific surface area 4 m 2 /g, surface treated by KBM573) 125 parts, hardening accelerator (2-phenyl-4-methylimidazole, "2P4MZ" manufactured by Shikoku Chemical Industry Co., Ltd.), 0.1 part methyl ethyl ketone (MEK ) and 8 parts of cyclohexanone, disperse them evenly with a high-speed rotating mixer to prepare resin varnish 1.

<實施例2> <Example 2>

混合合成例1所合成之彈性體(不揮發成分50質量%)8份、萘型環氧樹脂(新日鐵住金化學(股)製「ESN-475V」，環氧當量約332g/eq.)3份、液狀環氧樹脂(新日鐵住金化學(股)製「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.)6份、含三

Figure 108127984-A0305-02-0061-16
骨架的苯酚酚醛清漆系硬化劑(DIC(股)製「LA-7054」，羥基當量125，不揮發成分60%之MEK溶液)8.3份、二氧化矽A(平均粒徑3μm，比表面積4m2/g，經KBM573所表面處理者)125份、硬化促進劑(2-苯基-4-甲基咪唑，四國化成工業(股)製「2P4MZ」)0.1份、甲基乙基酮(MEK)10份、環己酮8份，以高速旋轉混合器均均地分散，調製樹脂清漆2。 Mix 8 parts of the elastomer synthesized in Synthesis Example 1 (non-volatile content 50% by mass) and naphthalene-type epoxy resin ("ESN-475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent: approximately 332g/eq.) 3 parts, liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1:1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy Equivalent: 169g/eq.) 6 servings, containing three
Figure 108127984-A0305-02-0061-16
8.3 parts of skeleton phenol novolac hardener ("LA-7054" manufactured by DIC Co., Ltd., hydroxyl equivalent 125, non-volatile content 60% MEK solution), silicon dioxide A (average particle size 3 μm, specific surface area 4 m 2 /g, surface treated by KBM573) 125 parts, hardening accelerator (2-phenyl-4-methylimidazole, "2P4MZ" manufactured by Shikoku Chemical Industry Co., Ltd.), 0.1 part methyl ethyl ketone (MEK ) and 8 parts of cyclohexanone were evenly dispersed with a high-speed rotating mixer to prepare resin varnish 2.

<實施例3> <Example 3>

混合合成例1所合成之彈性體(不揮發成分50質量%)4份、液狀環氧樹脂(新日鐵住金化學(股)製「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.)6份、環氧丙基胺型環氧樹脂(三菱化學公司製「630」，環氧當量90~105g/eq.)6份、酸酐系硬化劑(新日本理化公司製「MH-700」，4-甲基六氫鄰苯二甲酸酐/六氫鄰苯二甲酸酐=70/30)7份、二氧化矽B(平均粒徑9μm，比表面積5m2/g，經KBM573所表面處理 者)140份、硬化促進劑(甲基三正丁基鏻二甲基磷酸鹽，日本化學工業公司製「Hishicolin PX-4MP」)0.1份、甲基乙基酮(MEK)10份、環己酮8份，以高速旋轉混合器均均地分散，調製樹脂清漆3。 Mix 4 parts of the elastomer synthesized in Synthesis Example 1 (non-volatile content 50% by mass), liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., bisphenol A type epoxy resin and bisphenol F 1:1 mixture (mass ratio) of type epoxy resin, epoxy equivalent 169g/eq.) 6 parts, epoxypropylamine type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 90~105g /eq.) 6 parts, acid anhydride-based hardener ("MH-700" manufactured by Shinnippon Rika Co., Ltd., 4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride = 70/30) 7 parts, 140 parts of silicon dioxide B (average particle size 9 μm, specific surface area 5 m 2 /g, surface treated by KBM573), hardening accelerator (methyltri-n-butylphosphonium dimethylphosphate, manufactured by Nippon Chemical Industry Co., Ltd. " Disperse 0.1 part of Hishicolin PX-4MP"), 10 parts of methyl ethyl ketone (MEK), and 8 parts of cyclohexanone with a high-speed rotating mixer to prepare resin varnish 3.

<比較例1> <Comparative example 1>

混合合成例1所合成之彈性體(不揮發成分50質量%)14份、橡膠粒子(陶氏化學公司製「PARALOID EXL-2655」)2份、萘型環氧樹脂(新日鐵住金化學(股)製「ESN-475V」，環氧當量約332g/eq.)2份、液狀環氧樹脂(新日鐵住金化學(股)製「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.)4份、含三

Figure 108127984-A0305-02-0062-17
骨架的苯酚酚醛清漆系硬化劑(DIC(股)製「LA-7054」，羥基當量125，不揮發成分60%之MEK溶液)5份、二氧化矽A(平均粒徑3μm，比表面積4m2/g，經KBM573所表面處理者)125份、硬化促進劑(2-苯基-4-甲基咪唑，四國化成工業(股)製「2P4MZ」)0.1份、甲基乙基酮(MEK)10份、環己酮8份，以高速旋轉混合器均均地分散，調製樹脂清漆4。 Mix 14 parts of the elastomer synthesized in Synthesis Example 1 (non-volatile content 50% by mass), 2 parts of rubber particles ("PARALOID EXL-2655" manufactured by Dow Chemical Company), and naphthalene-type epoxy resin (Nippon Steel & Sumitomo Metal Chemical Co., Ltd. "ESN-475V" manufactured by Nippon Steel Co., Ltd., 2 parts of epoxy equivalent (approximately 332g/eq.), liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., bisphenol A type epoxy resin and bisphenol F type epoxy resin 1:1 mixture (mass ratio), epoxy equivalent 169g/eq.) 4 parts, containing three
Figure 108127984-A0305-02-0062-17
5 parts of skeleton phenol novolac hardener ("LA-7054" manufactured by DIC Co., Ltd., hydroxyl equivalent 125, non-volatile content 60% MEK solution), silica A (average particle size 3 μm, specific surface area 4 m 2 /g, surface treated by KBM573) 125 parts, hardening accelerator (2-phenyl-4-methylimidazole, "2P4MZ" manufactured by Shikoku Chemical Industry Co., Ltd.), 0.1 part methyl ethyl ketone (MEK ) and 8 parts of cyclohexanone are evenly dispersed with a high-speed rotating mixer to prepare resin varnish 4.

<比較例2> <Comparative example 2>

混合合成例1所合成之彈性體(不揮發成分50質量%)4份、橡膠粒子(陶氏化學公司製「PARALOID EXL-2655」)2份、液狀環氧樹脂(新日鐵住金化學(股)製 「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.)6份、在分子內具聚環氧烷構造之樹脂的聚環氧烷樹脂(DIC公司製「EXA-4816」，環氧當量403g/eq.)3份、含三

Figure 108127984-A0305-02-0063-18
骨架的苯酚酚醛清漆系硬化劑(DIC(股)製「LA-7054」，羥基當量125，不揮發成分60%之MEK溶液)8.3份、二氧化矽A(平均粒徑3μm，比表面積4m2/g，經KBM573所表面處理者)125份、硬化促進劑(2-苯基-4-甲基咪唑，四國化成工業(股)製「2P4MZ」)0.1份、甲基乙基酮(MEK)10份、環己酮8份，以高速旋轉混合器均均地分散，調製樹脂清漆5。 Mix 4 parts of the elastomer synthesized in Synthesis Example 1 (non-volatile content 50% by mass), 2 parts of rubber particles ("PARALOID EXL-2655" manufactured by Dow Chemical Company), and liquid epoxy resin (Nippon Steel & Sumitomo Metal Chemical Co., Ltd. "ZX1059" manufactured by Zhejiang Co., Ltd., a 1:1 mixture (mass ratio) of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin, epoxy equivalent 169g/eq.) 6 parts, with polycyclic rings in the molecule 3 parts of polyalkylene oxide resin ("EXA-4816" manufactured by DIC Corporation, epoxy equivalent 403g/eq.), a resin with an oxyalkane structure, containing three
Figure 108127984-A0305-02-0063-18
8.3 parts of skeleton phenol novolac hardener ("LA-7054" manufactured by DIC Co., Ltd., hydroxyl equivalent 125, non-volatile content 60% MEK solution), silicon dioxide A (average particle size 3 μm, specific surface area 4 m 2 /g, surface treated by KBM573) 125 parts, hardening accelerator (2-phenyl-4-methylimidazole, "2P4MZ" manufactured by Shikoku Chemical Industry Co., Ltd.), 0.1 part methyl ethyl ketone (MEK ) and 8 parts of cyclohexanone, disperse them evenly with a high-speed rotating mixer to prepare resin varnish 5.

<比較例3> <Comparative Example 3>

混合萘型環氧樹脂(新日鐵住金化學(股)製「ESN-475V」，環氧當量約332g/eq.)2份、液狀環氧樹脂(日本曹達公司製「JP-100」，環氧當量190~210g/eq.)7份、液狀環氧樹脂(新日鐵住金化學(股)製「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.)8份、含三

Figure 108127984-A0305-02-0063-19
骨架的苯酚酚醛清漆系硬化劑(DIC(股)製「LA-7054」，羥基當量125，不揮發成分60%之MEK溶液)5份、二氧化矽A(平均粒徑3μm，比表面積4m2/g，經KBM573所表面處理者)125份、硬化促進劑(2-苯基-4-甲基咪唑，四國化成工業(股)製「2P4MZ」)0.1份、甲基乙基酮(MEK)10份、環己酮8份，以高速旋轉混合器均均地分散，調製樹脂清漆6。 Mix 2 parts of naphthalene-type epoxy resin ("ESN-475V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent weight is about 332g/eq.), and liquid epoxy resin ("JP-100" manufactured by Nippon Soda Corporation, Epoxy equivalent: 190~210g/eq.) 7 parts, liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., bisphenol A type epoxy resin and bisphenol F type epoxy resin: 1: 1 mixture (mass ratio), epoxy equivalent 169g/eq.) 8 parts, containing three
Figure 108127984-A0305-02-0063-19
5 parts of skeleton phenol novolac hardener ("LA-7054" manufactured by DIC Co., Ltd., hydroxyl equivalent 125, non-volatile content 60% MEK solution), silica A (average particle size 3 μm, specific surface area 4 m 2 /g, surface treated by KBM573) 125 parts, hardening accelerator (2-phenyl-4-methylimidazole, "2P4MZ" manufactured by Shikoku Chemical Industry Co., Ltd.), 0.1 part methyl ethyl ketone (MEK ) and 8 parts of cyclohexanone were evenly dispersed with a high-speed rotating mixer to prepare resin varnish 6.

<試驗例1：透氧率> <Test example 1: Oxygen permeability>

對於實施例及比較例所製造的樹脂清漆各自，藉由形成樹脂組成物層之步驟，與以180℃ 90分鐘之加熱使該樹脂組成物層熱硬化之步驟，而準備用於測定透氧率之硬化薄片A或B。具體而言如下述。 Each of the resin varnishes produced in the Examples and Comparative Examples was prepared for measuring the oxygen permeability by a step of forming a resin composition layer and a step of thermally hardening the resin composition layer by heating at 180°C for 90 minutes. Hardened sheet A or B. The details are as follows.

(樹脂薄片A之製作) (Preparation of resin sheet A)

作為支撐體，準備經醇酸樹脂系脫模劑(LINTEC公司製「AL-5」)所脫模處理之PET薄膜(東麗公司製「Lumirror R80」，厚度38μm，軟化點130℃，「脫模PET」)。 As a support, a PET film ("Lumirror R80" manufactured by Toray) that has been released from an alkyd resin release agent ("AL-5" manufactured by LINTEC) was prepared. The thickness is 38 μm, the softening point is 130°C, and the "release" "PET").

將實施例1及2以及比較例1~3所製造之樹脂清漆1、2及4~6各自，以乾燥後的樹脂組成物層之厚度成為150μm之方式，用模塗機均勻地塗佈於脫模PET上，在70℃至95℃進行2分鐘乾燥，而得到在脫模PET上具備樹脂組成物層之薄片。接著，於該薄片之不與支撐體接合的面上，層合作為保護膜的聚丙烯薄膜(王子F-TEX公司製「Arufun MA-411」，厚度15μm)，該聚丙烯薄膜之粗面係與樹脂組成物層接合。藉此，得到由脫模PET(支撐體)、樹脂組成物層及保護膜之順序所成的5種樹脂薄片A。 The resin varnishes 1, 2 and 4 to 6 produced in Examples 1 and 2 and Comparative Examples 1 to 3 were each uniformly coated using a die coater so that the thickness of the dried resin composition layer became 150 μm. On the release PET, drying is performed at 70°C to 95°C for 2 minutes to obtain a sheet having a resin composition layer on the release PET. Next, a polypropylene film ("Arufun MA-411" manufactured by Oji F-TEX Co., Ltd., thickness 15 μm) as a protective film was laminated on the surface of the sheet that was not bonded to the support. The rough surface of the polypropylene film was Bonded to the resin composition layer. In this way, five types of resin sheets A were obtained, which were composed of release PET (support), a resin composition layer, and a protective film in this order.

(硬化薄片A之製作) (Preparation of hardened sheet A)

從5種樹脂薄片A各自來剝離保護膜，使用分批式真空 加壓層合機(NICHIGO材料公司製，2階增建層合機，CVP700)，以樹脂組成物層相接之方式層合2片的樹脂薄片A。層合係藉由在30秒減壓而使氣壓成為13hPa以下，在130℃、壓力0.74MPa下壓接45秒而實施。然後，剝離一面的脫模PET，在180℃、90分鐘之硬化條件下將樹脂組成物層硬化後，剝離另一面的脫模PET，製作5種硬化薄片A。 Peel off the protective film from each of the five types of resin sheets A, using a batch vacuum A pressure laminator (manufactured by NICHIGO Materials Co., Ltd., 2-stage additional laminator, CVP700) laminates two resin sheets A in such a manner that the resin composition layers are connected. Lamination was performed by reducing the pressure for 30 seconds to bring the air pressure to 13 hPa or less, and then performing pressure bonding at 130° C. and a pressure of 0.74 MPa for 45 seconds. Then, the release PET on one side was peeled off, and the resin composition layer was cured under hardening conditions of 180° C. and 90 minutes. Then, the release PET on the other side was peeled off, and five types of cured sheets A were produced.

(硬化薄片B之製作) (Preparation of hardened sheet B)

於表面施有脫模處理的SUS板上，使用壓縮模塑裝置(模具溫度：130℃，壓力：6MPa，硬化時間：10分鐘)，將實施例3所製造之樹脂清漆3壓縮成型，形成厚度300μm的樹脂組成物層。剝離SUS板，藉由將樹脂組成物層在180℃加熱90分鐘而使其熱硬化，得到樹脂組成物之硬化薄片B。 On the SUS board with release treatment on the surface, use a compression molding device (mold temperature: 130°C, pressure: 6MPa, hardening time: 10 minutes) to compress the resin varnish 3 produced in Example 3 to form a thickness 300μm resin composition layer. The SUS board was peeled off, and the resin composition layer was thermally cured by heating it at 180° C. for 90 minutes to obtain a cured sheet B of the resin composition.

(透氧率之測定及透氧係數之算出) (Measurement of oxygen permeability and calculation of oxygen permeability coefficient)

使用透氧率測定裝置(MOCON公司製，OX-TRAN2/21)，依據JIS-K7126(等壓法)，在23℃、0%RH之環境下測定5種硬化薄片A及硬化薄片B各自的透氧率。還有，RH表示相對濕度。又，以在5種硬化薄片A及硬化薄片B各自所得之透氧率為基礎，藉由除以厚度而算出透氧係數(cc/(atm‧m2‧天‧mm))。下述表1中顯示結果。 Using an oxygen permeability measuring device (made by MOCON, OX-TRAN2/21), in accordance with JIS-K7126 (isobaric method), the five types of cured sheets A and cured sheets B were measured in an environment of 23°C and 0% RH. Oxygen permeability. Also, RH means relative humidity. Furthermore, the oxygen permeability coefficient (cc/(atm·m 2 ·day·mm)) was calculated by dividing the thickness by the oxygen permeability obtained for each of the five types of cured sheet A and cured sheet B. The results are shown in Table 1 below.

<試驗例2：線熱膨脹係數(CTE)> <Test Example 2: Coefficient of Linear Thermal Expansion (CTE)>

對於實施例及比較例所製造的樹脂清漆各自，藉由形成樹脂組成物層之步驟，與使該樹脂組成物層在180℃加熱90分鐘而使其熱硬化之步驟，準備用於測定線熱膨脹係數之評價用硬化物A或B。具體而言如下述。 Each of the resin varnishes produced in Examples and Comparative Examples was prepared for measurement of linear thermal expansion by a step of forming a resin composition layer and a step of thermally hardening the resin composition layer by heating it at 180° C. for 90 minutes. Use hardened material A or B to evaluate the coefficient. The details are as follows.

(評價用硬化物A之製作) (Preparation of hardened material A for evaluation)

於表面施有脫模處理的SUS板上，使用壓縮模塑裝置(模具溫度：130℃，壓力：6MPa，硬化時間：10分鐘)，將實施例3所製造之樹脂清漆3壓縮成型，形成厚度300μm的樹脂組成物層。剝離SUS板，藉由將樹脂組成物層在180℃加熱90分鐘而使其熱硬化，得到樹脂組成物之評價用硬化物A。 On the SUS board with release treatment on the surface, use a compression molding device (mold temperature: 130°C, pressure: 6MPa, hardening time: 10 minutes) to compress the resin varnish 3 produced in Example 3 to form a thickness 300μm resin composition layer. The SUS board was peeled off, and the resin composition layer was thermally cured by heating it at 180° C. for 90 minutes to obtain a cured product A for evaluation of the resin composition.

(樹脂薄片B之製作) (Preparation of resin sheet B)

於經脫模劑處理的PET薄膜(LINTEC公司製「501010」，厚度38μm，240mm見方)之脫模劑未處理面，重疊玻璃布基材環氧樹脂兩面覆銅層合板(PANASONIC公司製「R5715ES」，厚度0.7mm，255mm見方)，以聚醯亞胺接著膠帶(寬度10mm)固定四邊(以下，亦稱為「固定PET薄膜」)。 On the release agent-untreated side of a release agent-treated PET film ("501010" manufactured by LINTEC Corporation, thickness 38 μm, 240 mm square), a glass cloth base material epoxy resin double-sided copper-clad laminate ("R5715ES" manufactured by PANASONIC Corporation) was laminated ", thickness 0.7mm, 255mm square), fixed on the four sides with polyimide adhesive tape (width 10mm) (hereinafter also referred to as "fixed PET film").

將實施例1及2以及比較例1~3所製造之樹脂清漆1、2及4~6各自，以乾燥後的樹脂組成物層之厚度成為100μm之方式，用模塗機塗佈在上述「固定PET薄膜」 之脫模處理面上，在80℃~120℃(平均100℃)乾燥10分鐘而得到5種樹脂薄片B。 The resin varnishes 1, 2 and 4 to 6 produced in Examples 1 and 2 and Comparative Examples 1 to 3 were each coated on the above " Fixed PET film On the release-treated surface, dry at 80°C to 120°C (average 100°C) for 10 minutes to obtain 5 kinds of resin sheets B.

(評價用硬化物B之製作) (Preparation of hardened material B for evaluation)

將5種樹脂薄片B分別投入180℃的烘箱後，於90分鐘的硬化條件下使樹脂組成物層熱硬化。 After putting the five types of resin sheets B into an oven at 180° C., the resin composition layer was thermally cured under curing conditions for 90 minutes.

熱硬化後，剝離聚醯亞胺接著膠帶，從玻璃布基材環氧樹脂兩面覆銅層合板拆卸硬化物，亦更剝離PET薄膜(LINTEC公司製「501010」)，得到5種薄片狀的評價用硬化物B。 After thermal curing, the polyimide adhesive tape was peeled off, and the cured product was removed from the glass cloth-based epoxy resin double-sided copper-clad laminate. The PET film ("501010" manufactured by LINTEC Corporation) was also peeled off, and five types of flaky evaluations were obtained. Use hardener B.

(線熱膨脹係數之測定) (Measurement of linear thermal expansion coefficient)

將評價用硬化物A及5種的評價用硬化物B分別切斷成寬度5mm、長度15mm，得到試驗片。對於該試驗片，使用熱機械分析裝置(RIGAKU公司製「Thermo Plus TMA8310」)，以拉伸加重法進行熱機械分析。詳細而言，將試驗片安裝於前述熱機械分析裝置後，於荷重1g、升溫速度5℃/分鐘之測定條件下連續進行2次測定。然後，於第2次之測定中，算出25℃至150℃的範圍中之平面方向的線熱膨脹係數(ppm/℃)。下述表1中顯示結果。 The hardened material A for evaluation and the five types of hardened materials B for evaluation were cut into a width of 5 mm and a length of 15 mm, respectively, to obtain test pieces. This test piece was subjected to thermomechanical analysis by the tensile weighting method using a thermomechanical analysis device ("Thermo Plus TMA8310" manufactured by RIGAKU Corporation). Specifically, after the test piece was mounted on the aforementioned thermomechanical analysis device, the measurement was performed twice continuously under the measurement conditions of a load of 1 g and a temperature rise rate of 5° C./min. Then, in the second measurement, the linear thermal expansion coefficient (ppm/°C) in the plane direction in the range of 25°C to 150°C was calculated. The results are shown in Table 1 below.

<試驗例3：翹曲評價> <Test example 3: Warpage evaluation>

對於實施例及比較例所製造之樹脂清漆各自，藉由在矽晶圓上形成樹脂組成物層之步驟，與使該樹脂組成物層 在180℃加熱90分鐘而使其熱硬化之步驟，準備用於翹曲評價之試料基板A或B。具體而言如下述。 For each of the resin varnishes produced in Examples and Comparative Examples, the steps of forming a resin composition layer on a silicon wafer were performed, and the resin composition layer was In the step of thermal hardening by heating at 180° C. for 90 minutes, sample substrate A or B for warpage evaluation is prepared. The details are as follows.

(試料基板A之製作) (Preparation of sample substrate A)

使用分批式真空加壓層合機((股)名機製作所製「MVLP-500」)，將試驗例1所製作之5種樹脂薄片A各自，以樹脂組成物層的第1主面與12吋矽晶圓(厚度775μm)接合之方式，層合於12吋矽晶圓上。層合係減壓30秒而使氣壓成為13hPa以下後，藉由在100℃、壓力0.74MPa下壓接30秒而實施。實施2次的層合，形成厚度300μm的樹脂組成物層。然後，在180℃加熱90分鐘，而使樹脂組成物層熱硬化。藉此，得到包含矽晶圓與樹脂組成物層的硬化物之5種試料基板A。 Using a batch-type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.), each of the five types of resin sheets A produced in Test Example 1 was placed with the first main surface of the resin composition layer and The 12-inch silicon wafer (thickness 775μm) is bonded and laminated on the 12-inch silicon wafer. Lamination was performed by depressurizing for 30 seconds to bring the air pressure to 13 hPa or less, and then performing pressure bonding at 100° C. and a pressure of 0.74 MPa for 30 seconds. Lamination was performed twice to form a resin composition layer with a thickness of 300 μm. Then, the resin composition layer was heated at 180° C. for 90 minutes to thermally harden. Thereby, five types of sample substrates A including a silicon wafer and a cured product of a resin composition layer were obtained.

(試料基板B之製作) (Preparation of sample substrate B)

關於實施例3，使用壓縮模塑裝置(模具溫度：130℃，壓力：6MPa，硬化時間：10分鐘)，將樹脂清漆3壓縮成型於12吋矽晶圓(厚度775μm)上。然後，在180℃加熱90分鐘而使樹脂組成物層熱硬化。藉此，得到包含矽晶圓與樹脂組成物層(300μm)的硬化物之試料基板B。 Regarding Example 3, a compression molding device (mold temperature: 130° C., pressure: 6 MPa, hardening time: 10 minutes) was used to compress the resin varnish 3 onto a 12-inch silicon wafer (thickness: 775 μm). Then, the resin composition layer was heated at 180° C. for 90 minutes to thermally harden. Thereby, a sample substrate B including a cured product of a silicon wafer and a resin composition layer (300 μm) was obtained.

(翹曲評價) (Warp evaluation)

將5種試料基板A及試料基板B各自以35℃、260℃、35℃之順序加熱‧冷卻，使用陰影疊紋(Shadow Moire)裝 置(Akrometrix製「TherMoire AXP」)測定因其所產生的翹曲量。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，對於測定區域之試料基板面的全部數據，將使用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。將翹曲量未達2mm者當作「○」，將2mm以上者當作「×」，評價「翹曲」。 Five types of sample substrate A and sample substrate B were heated and cooled in order of 35°C, 260°C, and 35°C, using a shadow moire installation. A device ("TherMoire AXP" manufactured by Akrometrix) was used to measure the amount of warpage produced. The measurement was performed in accordance with the JEITA EDX-7311-24 standard of the Electronics and Information Technology Industries Association. Specifically, for all the data on the sample substrate surface in the measurement area, an imaginary plane calculated using the least squares method is used as the reference plane, and the difference between the minimum value and the maximum value in the vertical direction is calculated from the reference plane as the warp. Quantity. If the amount of warpage is less than 2 mm, it is regarded as "○", and if the amount of warpage is more than 2 mm, it is regarded as "×", and "warp" is evaluated.

<試驗例4：伸長率評價> <Test Example 4: Elongation Evaluation>

對於實施例及比較例所製造之樹脂清漆各自，藉由形成樹脂組成物層之步驟，使該樹脂組成物層在180℃加熱90分鐘而使其熱硬化之步驟，與切出使其熱硬化而得的硬化物層之步驟，準備用於評價伸長率之試驗片A或B。具體而言如下述。 For each of the resin varnishes produced in the Examples and Comparative Examples, the steps of forming a resin composition layer, the step of heating the resin composition layer at 180° C. for 90 minutes to thermally harden it, and the step of cutting out and thermally curing the resin composition layer were performed. In the step of obtaining the hardened material layer, test piece A or B for evaluation of elongation is prepared. The details are as follows.

(試驗片A之製作) (Preparation of test piece A)

於表面施有脫模處理的SUS板上，使用壓縮模塑裝置(模具溫度：130℃，壓力：6MPa，硬化時間：10分鐘)，將實施例3所製造之樹脂清漆3壓縮成型，形成厚度100μm的樹脂組成物層。剝離SUS板，藉由將樹脂組成物層在180℃加熱90分鐘或在180℃加熱24小時而使其熱硬化，得到樹脂組成物的硬化物層。從此硬化物層切出啞鈴狀1號型，對於1個樹脂組成物，得到2種(硬化條件：180℃ 90分鐘及180℃ 24小時)的試驗片A。 On the SUS board with release treatment on the surface, use a compression molding device (mold temperature: 130°C, pressure: 6MPa, hardening time: 10 minutes) to compress the resin varnish 3 produced in Example 3 to form a thickness 100μm resin composition layer. The SUS board is peeled off, and the resin composition layer is thermally cured by heating at 180° C. for 90 minutes or 180° C. for 24 hours, thereby obtaining a hardened material layer of the resin composition. A dumbbell-shaped No. 1 shape was cut out from the hardened material layer, and two types of test pieces A (hardening conditions: 180° C. for 90 minutes and 180° C. for 24 hours) were obtained for one resin composition.

(試驗片B之製作) (Preparation of test piece B)

將試驗例2所得之樹脂薄片B投入180℃的烘箱後，在90分鐘或24小時之硬化條件下使樹脂組成物層熱硬化。 After putting the resin sheet B obtained in Test Example 2 into an oven at 180° C., the resin composition layer was thermally cured under curing conditions of 90 minutes or 24 hours.

熱硬化後，剝離聚醯亞胺接著膠帶，從玻璃布基材環氧樹脂兩面覆銅層合板拆卸硬化物，亦更剝離PET薄膜(LINTEC公司製「501010」)，得到薄片狀的硬化物。從所得之硬化物切出啞鈴狀1號型，對於1個樹脂薄片B，得到2種(硬化條件：180℃ 90分鐘及180℃ 24小時)的試驗片B。 After thermal curing, the polyimide adhesive tape was peeled off, and the cured product was removed from the copper-clad laminate on both sides of the glass cloth-based epoxy resin. The PET film ("501010" manufactured by LINTEC Corporation) was also peeled off to obtain a thin sheet-like cured product. A dumbbell-shaped No. 1 shape was cut out from the obtained hardened material, and two types of test pieces B (hardening conditions: 180° C. for 90 minutes and 180° C. for 24 hours) were obtained from one resin sheet B.

(伸長率評價) (elongation evaluation)

對於試驗片A及B各2種(硬化條件：180℃ 90分鐘及180℃ 24小時)，分別使用ORIENTEC公司製拉伸試驗機「RTC-1250A」進行延伸度測定，求出在23℃下的伸長率。測定係依據JIS K7127實施。進行3次的此操作，算出伸長率的平均值(%)。 For each of two types of test pieces A and B (hardening conditions: 180°C for 90 minutes and 180°C for 24 hours), the elongation was measured using a tensile testing machine "RTC-1250A" manufactured by ORIENTEC Corporation, and the elongation at 23°C was determined. Elongation. The measurement system is carried out in accordance with JIS K7127. This operation was performed three times, and the average value (%) of the elongation was calculated.

再者，從所得之伸長率之值，算出180℃ 24小時硬化後的伸長率相對於180℃ 90分硬化後的伸長率之比。再者，將所得之伸長率之比未達0.70者當作「×」，將0.70以上者當作「○」，評價「脆性」。所得之伸長率之比值愈高，意指愈抑制脆化。下述表1中顯示結果。 Furthermore, from the obtained elongation value, the ratio of the elongation after hardening at 180° C. for 24 hours to the elongation after hardening at 180° C. for 90 minutes was calculated. In addition, the obtained elongation ratio was regarded as "×" if it was less than 0.70, and "○" was regarded as if it was 0.70 or more, and "brittleness" was evaluated. The higher the obtained elongation ratio, the more embrittlement is suppressed. The results are shown in Table 1 below.

Figure 108127984-A0305-02-0071-1
Figure 108127984-A0305-02-0071-1

由以上之結果可知，包含(A)環氧樹脂及(B)硬化劑之樹脂組成物，只要使樹脂組成物成為在180℃熱硬化90分鐘而得的硬化物之透氧係數為3cc/(atm‧m2‧天‧mm)以下，硬化物之線熱膨脹係數為4~15ppm/℃之樹脂組成物，則得到本發明之所欲效果。 From the above results, it can be seen that the oxygen permeability coefficient of a resin composition containing (A) epoxy resin and (B) hardener is 3cc/( Atm‧m 2 ‧day‧mm) or less, a resin composition with a linear thermal expansion coefficient of the cured product of 4 to 15 ppm/℃ can achieve the desired effects of the present invention.

Claims (15)

一種樹脂組成物，其係包含(A)環氧樹脂(惟，不包含(D)成分)、(B)硬化劑及(D)彈性體之樹脂組成物，將樹脂組成物中的樹脂成分當作100質量%時，(D)彈性體之含量為2~25質量%，使上述樹脂組成物在180℃熱硬化90分鐘而得的硬化物之透氧係數為3cc/(atm‧m2‧天‧mm)以下，上述硬化物之線熱膨脹係數為4~15ppm/℃。 A resin composition, which is a resin composition containing (A) epoxy resin (excluding (D) component), (B) hardener and (D) elastomer, and the resin component in the resin composition shall be When taken as 100 mass%, the content of (D) elastomer is 2 to 25 mass%, and the oxygen permeability coefficient of the cured product obtained by thermally curing the above resin composition at 180°C for 90 minutes is 3cc/(atm‧m 2 ‧ days ‧mm) or less, the linear thermal expansion coefficient of the above-mentioned hardened material is 4~15ppm/℃. 如請求項1之樹脂組成物，其進一步包含(C)無機填充材。 The resin composition of claim 1, further comprising (C) an inorganic filler. 如請求項2之樹脂組成物，其中將樹脂組成物中的不揮發成分當作100質量%時，(C)成分之含量為83質量%以上。 For example, in the resin composition of Claim 2, when the non-volatile components in the resin composition are regarded as 100 mass%, the content of component (C) is 83 mass% or more. 如請求項2或3之樹脂組成物，其中(C)成分之平均粒徑為2.5μm以上。 The resin composition of claim 2 or 3, wherein the average particle size of component (C) is 2.5 μm or more. 如請求項1之樹脂組成物，其中(A)成分包含固體狀環氧樹脂。 The resin composition of claim 1, wherein the component (A) contains a solid epoxy resin. 如請求項1之樹脂組成物，其中(A)成分包含液狀環氧 樹脂，且將樹脂組成物中的樹脂成分當作100質量%時，液狀環氧樹脂之含量為70質量%以下。 The resin composition of claim 1, wherein component (A) contains liquid epoxy Resin, and when the resin component in the resin composition is regarded as 100 mass%, the content of the liquid epoxy resin is 70 mass% or less. 如請求項1之樹脂組成物，其中作為(A)成分包含的環氧樹脂之環氧當量為400g/eq.以下。 The resin composition of Claim 1, wherein the epoxy resin contained as the component (A) has an epoxy equivalent of 400 g/eq. or less. 如請求項1之樹脂組成物，其中(B)成分包含苯酚系硬化劑或酸酐系硬化劑。 The resin composition of claim 1, wherein the component (B) contains a phenol-based hardener or an acid anhydride-based hardener. 如請求項1之樹脂組成物，其中使樹脂組成物在180℃熱硬化24小時而得的硬化物之依據JIS K7127測定的在23℃的伸長率相對於使樹脂組成物在180℃熱硬化90分鐘而得的硬化物之依據JIS K7127測定的在23℃的伸長率之比為0.7以上。 The resin composition of claim 1, wherein the elongation of the cured product obtained by thermally curing the resin composition at 180°C for 24 hours at 23°C measured in accordance with JIS K7127 is 90% by thermally curing the resin composition at 180°C. The ratio of the elongation at 23°C measured in accordance with JIS K7127 of the hardened material obtained in 10 minutes was 0.7 or more. 如請求項1之樹脂組成物，其係半導體晶片封裝之半導體晶片密封用。 The resin composition of claim 1 is used for sealing semiconductor wafers in semiconductor wafer packaging. 一種樹脂油墨，其包含如請求項1之樹脂組成物。 A resin ink comprising the resin composition of claim 1. 一種樹脂油墨層，其係由如請求項11之樹脂油墨所成的厚度100μm以上者。 A resin ink layer made of the resin ink of claim 11 and having a thickness of 100 μm or more. 一種樹脂薄片，其具有支撐體與設於上述支撐體上之 包含如請求項1之樹脂組成物的樹脂組成物層。 A resin sheet having a support body and a A resin composition layer including the resin composition of claim 1. 如請求項13之樹脂薄片，其中上述樹脂組成物層之厚度為100μm以上。 The resin sheet of claim 13, wherein the thickness of the resin composition layer is 100 μm or more. 一種半導體晶片封裝，其包含如請求項1之樹脂組成物的硬化物。 A semiconductor chip package including a cured product of the resin composition of claim 1.
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