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CN113462276B - Resin composition, cured product of resin composition, resin sheet, printed wiring board, semiconductor chip package, and semiconductor device - Google Patents

Resin composition, cured product of resin composition, resin sheet, printed wiring board, semiconductor chip package, and semiconductor device Download PDF

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CN113462276B
CN113462276B CN202110339761.XA CN202110339761A CN113462276B CN 113462276 B CN113462276 B CN 113462276B CN 202110339761 A CN202110339761 A CN 202110339761A CN 113462276 B CN113462276 B CN 113462276B
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resin composition
mass
component
composition according
resin
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CN113462276A (en
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池平秀
阪内启之
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Ajinomoto Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • 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
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67121—Apparatus for making assemblies not otherwise provided for, e.g. package constructions
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/09—Shape and layout
    • H05K2201/09818—Shape or layout details not covered by a single group of H05K2201/09009 - H05K2201/09809
    • H05K2201/09872—Insulating conformal coating

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Laminated Bodies (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

The invention provides a resin composition capable of obtaining a cured product with suppressed warpage and excellent long-term reliability; and a cured product of the resin composition, a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor device. The solution of the present invention is that a resin composition comprising (A) an epoxy resin and (B) a curing agent, wherein the value Z f(ppm・cm3/mol K) obtained by dividing the average linear thermal expansion coefficient alpha of the cured product by the crosslink density n of the cured product satisfies 145 < Z f < 1300.

Description

树脂组合物、树脂组合物的固化物、树脂片材、印刷配线板、半 导体芯片封装和半导体装置Resin composition, cured product of resin composition, resin sheet, printed wiring board, semiconductor chip package and semiconductor device

技术领域Technical Field

本发明涉及树脂组合物。进一步涉及该树脂组合物的固化物、树脂片材、印刷配线板、半导体芯片封装和半导体装置。The present invention relates to a resin composition and further to a cured product of the resin composition, a resin sheet, a printed wiring board, a semiconductor chip package and a semiconductor device.

背景技术Background Art

半导体装置用的印刷配线板通常包含绝缘层。作为构成该绝缘层的绝缘材料，使用树脂组合物。专利文献1中，公开了包含热固性化合物、和固化剂的绝缘材料(参照权利要求1)。这样的树脂组合物有时被用于密封半导体芯片的情况。A printed wiring board for a semiconductor device generally includes an insulating layer. As an insulating material constituting the insulating layer, a resin composition is used. Patent Document 1 discloses an insulating material including a thermosetting compound and a curing agent (see Claim 1). Such a resin composition is sometimes used to seal a semiconductor chip.

现有技术文献Prior art literature

专利文献Patent Literature

专利文献1：日本特开2017-188667号公报。Patent document 1: Japanese Patent Application Publication No. 2017-188667.

发明内容Summary of the invention

发明要解决的课题Problems to be solved by the invention

在密封半导体芯片的情况(特别是密封半导体芯片的单面的情况)下，因应力的偏倚，有时产生翘曲。因此，要求抑制翘曲。When a semiconductor chip is sealed (particularly when one side of a semiconductor chip is sealed), warping may occur due to the bias of stress. Therefore, it is required to suppress the warping.

然而，有时在树脂组合物中包含热塑性树脂。并且，因树脂组合物包含热塑性树脂，导致该树脂组合物的固化物的弹性模量降低，其结果是，能够期待半导体芯片中产生的翘曲被抑制。然而，本发明人的研究结果表明，如果使用包含热塑性树脂的树脂组合物，则有时长期可靠性差。在此，长期可靠性可以通过例如对试验片实施HTS试验(High ThermalStorage test，高热储存测试)，比较试验前后的物性，其变化度小而确认。即表明，为了抑制翘曲、且使得长期可靠性优异，仅通过调整树脂组合物的固化物的弹性模量，是不充分的。因此，如果得到除了弹性模量之外的调整项目，则无论热塑性树脂的有无或热塑性树脂的含量如何，均期待能够提供树脂组合物，其可以得到翘曲被抑制、且长期可靠性优异的固化物。However, sometimes a thermoplastic resin is included in the resin composition. And, because the resin composition includes a thermoplastic resin, the elastic modulus of the cured product of the resin composition is reduced, as a result, it is expected that the warping generated in the semiconductor chip is suppressed. However, the research results of the inventors show that if a resin composition including a thermoplastic resin is used, sometimes the long-term reliability is poor. Here, the long-term reliability can be confirmed by, for example, performing an HTS test (High Thermal Storage test) on a test piece, comparing the physical properties before and after the test, and its degree of change is small. That is, it is shown that in order to suppress warping and make the long-term reliability excellent, it is insufficient to only adjust the elastic modulus of the cured product of the resin composition. Therefore, if an adjustment item other than the elastic modulus is obtained, regardless of the presence or absence of a thermoplastic resin or the content of the thermoplastic resin, it is expected that a resin composition can be provided, which can obtain a cured product with suppressed warping and excellent long-term reliability.

本发明的课题在于，提供可以得到翘曲被抑制、且长期可靠性优异的固化物的树脂组合物；以及该树脂组合物的固化物、树脂片材、印刷配线板、半导体芯片封装和半导体装置。An object of the present invention is to provide a resin composition that can provide a cured product having suppressed warping and excellent long-term reliability; and a cured product of the resin composition, a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor device.

用于解决问题的手段Means used to solve problems

本发明人等针对包含(A)环氧树脂和(B)固化剂的树脂组合物进行深入研究的结果发现，通过使用树脂组合物的固化物的平均线热膨胀系数α、和该固化物的交联密度n作为参数，平均线热膨胀系数α除以交联密度n而得到的值Zf(ppm・cm3/mol・K)满足145＜Zf＜1300，能够解决上述课题，从而完成了本发明。As a result of intensive studies on a resin composition comprising (A) an epoxy resin and (B) a curing agent, the present inventors have found that the above-mentioned problems can be solved by using the average linear thermal expansion coefficient α of a cured product of the resin composition and the crosslinking density n of the cured product as parameters, and that a value Z f (ppm・cm 3 /mol・K) obtained by dividing the average linear thermal expansion coefficient α by the crosslinking density n satisfies 145＜Z f ＜1300, thereby completing the present invention.

即，本发明包括以下的内容。That is, the present invention includes the following contents.

[1] 树脂组合物，其包含(A)环氧树脂和(B)固化剂，[1] A resin composition comprising (A) an epoxy resin and (B) a curing agent,

通过使该树脂组合物在180℃下固化90分钟而得到的固化物的平均线热膨胀系数α(ppm/K)除以该固化物的交联密度n(mol/cm3)而得到的值Zf(ppm・cm3/mol・K)满足下述式：The value Zf (ppm· cm3 /mol·K) obtained by dividing the average linear thermal expansion coefficient α (ppm/K) of the cured product obtained by curing the resin composition at 180°C for 90 minutes by the crosslinking density n (mol/ cm3 ) of the cured product satisfies the following formula:

145＜Zf＜1300。145＜Z f ＜1300.

[2] 根据[1]所述的树脂组合物，其进一步包含(C)无机填充剂。[2] The resin composition according to [1], further comprising (C) an inorganic filler.

[3] 根据[2]所述的树脂组合物，其中，(C)成分的含量在将树脂组合物中的不挥发成分设为100质量%的情况下为70质量%以上。[3] The resin composition according to [2], wherein the content of the component (C) is 70% by mass or more when the non-volatile component in the resin composition is 100% by mass.

[4] 根据[2]或[3]所述的树脂组合物，其中，(C)成分的平均粒径为10μm以下。[4] The resin composition according to [2] or [3], wherein the average particle size of the component (C) is 10 μm or less.

[5] 根据[1]~[4]中任一项所述的树脂组合物，其中，(B)成分包含在分子中具有任选具有取代基的碳原子数为5以上的烷基、和任选具有取代基的碳原子数为5以上的亚烷基中的至少任一烃链的马来酰亚胺化合物。[5] The resin composition according to any one of [1] to [4], wherein the component (B) contains a maleimide compound having a hydrocarbon chain of at least one of an alkyl group having 5 or more carbon atoms which may have a substituent and an alkylene group having 5 or more carbon atoms which may have a substituent in the molecule.

[6] 根据[1]~[5]中任一项所述的树脂组合物，其中，(B)成分的含量在将树脂组合物中的不挥发成分设为100质量%的情况下为0.5质量%以上。[6] The resin composition according to any one of [1] to [5], wherein the content of the component (B) is 0.5% by mass or more when the non-volatile component in the resin composition is 100% by mass.

[7] 根据[1]~[6]中任一项所述的树脂组合物，其进一步包含(D)热塑性树脂。[7] The resin composition according to any one of [1] to [6], further comprising (D) a thermoplastic resin.

[8] 根据[7]所述的树脂组合物，其中，(D)成分的含量在将树脂组合物中的不挥发成分设为100质量%的情况下为25质量%以下。[8] The resin composition according to [7], wherein the content of the component (D) is 25% by mass or less when the non-volatile component in the resin composition is 100% by mass.

[9] 根据[1]~[8]中任一项所述的树脂组合物，其中，前述固化物的玻璃化转变温度Tg处于150~240℃的范围内。[9] The resin composition according to any one of [1] to [8], wherein the glass transition temperature Tg of the cured product is within the range of 150 to 240°C.

[10] 根据[1]~[9]中任一项所述的树脂组合物，其中，前述固化物的平均线热膨胀系数α为25ppm/K以下。[10] The resin composition according to any one of [1] to [9], wherein the average linear thermal expansion coefficient α of the cured product is 25 ppm/K or less.

[11] 根据[1]~[10]中任一项所述的树脂组合物，其中，前述固化物的规定的温度T(K)下的储能模量E'低于1.50×109Pa，在此，规定的温度T(K)是表示该固化物的玻璃化转变温度Tg(℃)与353(K)之和的温度。[11] The resin composition according to any one of [1] to [10], wherein the storage modulus E' of the cured product at a predetermined temperature T (K) is less than 1.50×10 9 Pa, wherein the predetermined temperature T (K) is a temperature representing the sum of the glass transition temperature Tg (° C.) of the cured product and 353 (K).

[12] 根据[1]~[11]中任一项所述的树脂组合物，其中，前述固化物的交联密度n为0.15mol/cm3以下。[12] The resin composition according to any one of [1] to [11], wherein the crosslinking density n of the cured product is 0.15 mol/cm 3 or less.

[13] 根据[1]~[12]中任一项所述的树脂组合物，其中，前述值Zf满足下述式：[13] The resin composition according to any one of [1] to [12], wherein the value Z f satisfies the following formula:

150≤Zf≤1000。150≤Z f ≤1000.

[14] 根据[1]~[13]中任一项所述的树脂组合物，其用于形成绝缘层。[14] The resin composition according to any one of [1] to [13], which is used for forming an insulating layer.

[15] 根据[1]~[14]中任一项所述的树脂组合物，其用于形成阻焊剂层。[15] The resin composition according to any one of [1] to [14], which is used for forming a solder resist layer.

[16] [1]~[15]中任一项所述的树脂组合物的固化物。[16] A cured product of the resin composition according to any one of [1] to [15].

[17] 树脂片材，其包含支撑体、和在该支撑体上设置的包含[1]~[15]中任一项所述的树脂组合物的树脂组合物层。[17] A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of [1] to [15] provided on the support.

[18] 印刷配线板，其包含由[1]~[15]中任一项所述的树脂组合物的固化物或[16]所述的固化物形成的绝缘层。[18] A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [15] or a cured product according to [16].

[19] 半导体芯片封装，其包含[18]所述的印刷配线板、和在该印刷配线板上搭载的半导体芯片。[19] A semiconductor chip package comprising the printed wiring board described in [18] and a semiconductor chip mounted on the printed wiring board.

[20] 半导体芯片封装，其包含半导体芯片、和将该半导体芯片密封的[1]~[15]中任一项所述的树脂组合物的固化物或[16]所述的固化物。[20] A semiconductor chip package comprising a semiconductor chip and a cured product of the resin composition described in any one of [1] to [15] or the cured product described in [16], which seals the semiconductor chip.

[21] 半导体装置，其包含[18]所述的印刷配线板、或[19]或[20]所述的半导体芯片封装。[21] A semiconductor device comprising the printed wiring board described in [18], or the semiconductor chip package described in [19] or [20].

发明效果Effects of the Invention

根据本发明，能够提供可以得到翘曲被抑制、且长期可靠性优异的固化物的树脂组合物；以及该树脂组合物的固化物、树脂片材、印刷配线板、半导体芯片封装和半导体装置。According to the present invention, there can be provided a resin composition which can obtain a cured product having suppressed warpage and excellent long-term reliability; and a cured product of the resin composition, a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor device.

具体实施方式DETAILED DESCRIPTION

以下，针对本发明的树脂组合物、该树脂组合物的固化物、树脂片材、印刷配线板、半导体芯片封装和半导体装置进行详细说明。Hereinafter, the resin composition of the present invention, a cured product of the resin composition, a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor device will be described in detail.

[树脂组合物][Resin composition]

本发明的树脂组合物是包含(A)环氧树脂和(B)固化剂的树脂组合物，通过使该树脂组合物在180℃下固化90分钟而得到的固化物的平均线热膨胀系数α除以该固化物的交联密度n而得到的值Zf(ppm・cm3/mol・K)处于后述数值范围内。根据该树脂组合物，可以得到翘曲被抑制、且长期可靠性优异的固化物。如果使用这样的树脂组合物，能够提供树脂组合物的固化物、树脂片材、印刷配线板、半导体芯片封装和半导体装置。The resin composition of the present invention is a resin composition comprising (A) an epoxy resin and (B) a curing agent, wherein the value Zf (ppm・cm3 /mol・K) obtained by curing the resin composition at 180°C for 90 minutes and dividing the average linear thermal expansion coefficient α of the cured product by the crosslinking density n of the cured product is within the numerical range described below. According to the resin composition, a cured product having suppressed warping and excellent long-term reliability can be obtained. If such a resin composition is used, a cured product of the resin composition, a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor device can be provided.

本发明的树脂组合物与(A)成分和(B)成分组合，可以进一步包含任选的成分。作为任选的成分，可以举出例如(C)无机填充材料、(D)热塑性树脂、(E)固化促进剂和(F)其他添加剂(但是，(A)成分~(E)成分除外)等。以下，针对树脂组合物中包含的各成分进行详细说明。应予说明，本发明中，树脂组合物中的各成分的含量在没有另外明示的情况下，是将树脂组合物中的不挥发成分设为100质量%时的值。The resin composition of the present invention can further include optional components in combination with (A) component and (B) component. As optional components, for example (C) inorganic filler, (D) thermoplastic resin, (E) curing accelerator and (F) other additives (but, (A) component ~ (E) component are excluded) etc. can be cited. Hereinafter, each component included in the resin composition is described in detail. It should be noted that in the present invention, the content of each component in the resin composition is the value when the non-volatile component in the resin composition is set to 100% by mass without further explicit indication.

＜(A)环氧树脂＞＜(A) Epoxy resin＞

树脂组合物含有(A)环氧树脂。环氧树脂是指在分子中具有1个以上的环氧基的树脂。树脂组合物含有(A)环氧树脂，由此能够得到具有交联结构的固化物。The resin composition contains (A) an epoxy resin. An epoxy resin is a resin having one or more epoxy groups in a molecule. The resin composition contains (A) an epoxy resin, and thus a cured product having a crosslinked structure can be obtained.

作为环氧树脂，可以举出例如联二甲苯酚型环氧树脂、双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、双酚AF型环氧树脂、二环戊二烯型环氧树脂、三酚型环氧树脂、萘酚酚醛清漆型环氧树脂、苯酚酚醛清漆型环氧树脂、叔丁基-邻苯二酚型环氧树脂、萘型环氧树脂、萘酚型环氧树脂、蒽型环氧树脂、缩水甘油基胺型环氧树脂、缩水甘油基酯型环氧树脂、甲酚酚醛清漆型环氧树脂、联苯型环氧树脂、线状脂肪族环氧树脂、具有丁二烯结构的环氧树脂、脂环式环氧树脂、杂环式环氧树脂、含螺环的环氧树脂、环己烷型环氧树脂、环己烷二甲醇型环氧树脂、萘醚型环氧树脂、三羟甲基型环氧树脂、四苯基乙烷型环氧树脂等。环氧树脂可以单独使用1种，也可以组合使用2种以上。Examples of the epoxy resin include bixylenol-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, bisphenol AF-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol novolac-type epoxy resins, phenol novolac-type epoxy resins, tert-butyl-catechol-type epoxy resins, naphthalene-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, glycidylamine-type epoxy resins, glycidylester-type epoxy resins, cresol novolac-type epoxy resins, biphenyl-type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro-ring-containing epoxy resins, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, naphthyl ether-type epoxy resins, trimethylol-type epoxy resins, and tetraphenylethane-type epoxy resins. The epoxy resins may be used alone or in combination of two or more.

环氧树脂优选包含在分子中具有2个以上的环氧基的环氧树脂。在将环氧树脂的不挥发成分设为100质量%的情况下，优选50质量%以上为在分子中具有2个以上的环氧基的环氧树脂。The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in the molecule. When the nonvolatile component of the epoxy resin is 100% by mass, preferably 50% by mass or more is an epoxy resin having two or more epoxy groups in the molecule.

环氧树脂可以为(A-1)液体状环氧树脂，也可以为(A-2)固体状环氧树脂。树脂组合物可以组合包含(A-1)液体状环氧树脂、和(A-2)固体状环氧树脂。The epoxy resin may be (A-1) a liquid epoxy resin or (A-2) a solid epoxy resin. The resin composition may contain (A-1) a liquid epoxy resin and (A-2) a solid epoxy resin in combination.

((A-1)液体状环氧树脂)((A-1) Liquid epoxy resin)

(A-1)液体状环氧树脂是指温度20℃下为液体状的环氧树脂。树脂组合物优选包含(A-1)液体状环氧树脂。在此，液体状环氧树脂是具有降低树脂组合物的固化物的玻璃化转变温度的倾向的成分之一，但根据本发明，即使树脂组合物包含所述成分，也能够得到平均线热膨胀系数充分低且耐热性优异的固化物。(A-1) Liquid epoxy resin refers to an epoxy resin that is liquid at a temperature of 20° C. The resin composition preferably contains (A-1) liquid epoxy resin. Here, the liquid epoxy resin is one of the components that tends to lower the glass transition temperature of the cured product of the resin composition, but according to the present invention, even if the resin composition contains the above component, a cured product having a sufficiently low average linear thermal expansion coefficient and excellent heat resistance can be obtained.

作为液体状环氧树脂，优选为在分子中具有2个以上的环氧基的液体状环氧树脂，更优选为在分子中具有2个以上的环氧基的芳族系液体状环氧树脂。本发明中，芳族系的环氧树脂是指在其分子内具有芳香环的环氧树脂。The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in the molecule, and more preferably an aromatic liquid epoxy resin having two or more epoxy groups in the molecule. In the present invention, the aromatic epoxy resin refers to an epoxy resin having an aromatic ring in its molecule.

作为液体状环氧树脂，优选为双酚A型环氧树脂、双酚F型环氧树脂、双酚AF型环氧树脂、萘型环氧树脂、缩水甘油基酯型环氧树脂、缩水甘油基胺型环氧树脂、苯酚酚醛清漆型环氧树脂、具有酯骨架的脂环式环氧树脂、环己烷型环氧树脂、环己烷二甲醇型环氧树脂、缩水甘油基胺型环氧树脂、和具有丁二烯结构的环氧树脂，更优选为双酚A型环氧树脂。As liquid epoxy resins, preferred are bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure, and bisphenol A type epoxy resins are more preferred.

作为液体状环氧树脂的具体例，可以举出DIC公司制的“HP4032”、“HP4032D”、“HP-4032-SS”(萘型环氧树脂)；三菱化学公司制的“828US”、“jER828EL”、“825”、“828EL”(双酚A型环氧树脂)；三菱化学公司制的“YX7400”(可挠性环氧树脂)；三菱化学公司制的“jER807”、“1750”(双酚F型环氧树脂)；三菱化学公司制的“jER152”(苯酚酚醛清漆型环氧树脂)；三菱化学公司制的“630”、“630LSD”(缩水甘油基胺型环氧树脂)；新日铁住金化学公司制的“ZX1059”(双酚A型环氧树脂和双酚F型环氧树脂的混合品)；ナガセケムテックス公司制的“EX-721”(缩水甘油基酯型环氧树脂)；裸片セル公司制的“セロキサイド2021P”(具有酯骨架的脂环式环氧树脂)；裸片セル公司制的“PB-3600”(具有丁二烯结构的环氧树脂)；新日铁住金化学公司制的“ZX1658”、“ZX1658GS”(液体状1,4-缩水甘油基环己烷型环氧树脂)等。它们可以单独使用1种，也可以组合使用2种以上。Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP-4032-SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "828EL" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "YX7400" (flexible epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F-type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", " "630LSD" (glycidylamine type epoxy resin); "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; "EX-721" (glycidyl ester type epoxy resin) manufactured by Naga Sechem Tec Co., Ltd.; "Cellocid 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Cell Cell Co., Ltd.; "PB-3600" (epoxy resin with butadiene structure) manufactured by Cell Cell Co., Ltd.; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., etc. They can be used alone or in combination of two or more.

树脂组合物中的(A-1)成分的含量从得到利用包含(A-1)成分的效果(例如树脂清漆的处理性提高、相容性的提高)的观点出发，在将树脂组合物中的不挥发成分设为100质量%的情况下，优选为0.1质量%以上、更优选为0.5质量%以上、进一步优选为1质量%以上、特别优选为2质量%以上。(A-1)成分的含量的上限只要没有过度损害本发明的效果，则没有特别限定，可以设为40质量%以下、35质量%以下、30质量%以下或25质量%以下。The content of the component (A-1) in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and particularly preferably 2% by mass or more, from the viewpoint of obtaining the effect of including the component (A-1) (for example, improved handling of resin varnish, improved compatibility), when the non-volatile component in the resin composition is set to 100% by mass. The upper limit of the content of the component (A-1) is not particularly limited as long as it does not excessively impair the effect of the present invention, and can be set to 40% by mass or less, 35% by mass or less, 30% by mass or less, or 25% by mass or less.

((A-2)固体状环氧树脂)((A-2) Solid epoxy resin)

固体状环氧树脂是指温度20℃下为固体状的环氧树脂。树脂组合物作为(A)成分，仅包含(A-2)固体状环氧树脂，从降低平均线热膨胀系数的观点或提高交联密度的观点出发，优选与(A-1)液体状环氧树脂组合，包含(A-2)固体状环氧树脂。作为固体状环氧树脂，优选为在分子中具有3个以上的环氧基的固体状环氧树脂。A solid epoxy resin refers to an epoxy resin that is solid at a temperature of 20°C. The resin composition contains only the solid epoxy resin (A-2) as the (A) component, and preferably contains the solid epoxy resin (A-2) in combination with the liquid epoxy resin (A-1) from the viewpoint of reducing the average linear thermal expansion coefficient or increasing the crosslinking density. As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in the molecule is preferred.

作为固体状环氧树脂，优选为联二甲苯酚型环氧树脂、萘型环氧树脂、萘型4官能环氧树脂、甲酚酚醛清漆型环氧树脂、二环戊二烯型环氧树脂、三酚型环氧树脂、萘酚型环氧树脂、联苯型环氧树脂、萘醚型环氧树脂、蒽型环氧树脂、双酚A型环氧树脂、双酚AF型环氧树脂、四苯基乙烷型环氧树脂，更优选为萘酚型环氧树脂、双酚AF型环氧树脂、萘型环氧树脂、和联苯型环氧树脂。As solid epoxy resins, preferred are bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthyl ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins, and more preferred are naphthol-type epoxy resins, bisphenol AF-type epoxy resins, naphthalene-type epoxy resins, and biphenyl-type epoxy resins.

作为固体状环氧树脂的具体例，可以举出DIC公司制的“HP4032H”(萘型环氧树脂)；DIC公司制的“HP-4700”、“HP-4710”(萘型4官能环氧树脂)；DIC公司制的“N-690”(甲酚酚醛清漆型环氧树脂)；DIC公司制的“N-695”(甲酚酚醛清漆型环氧树脂)；DIC公司制的“HP-7200L”、“HP-7200”、“HP-7200HH”、“HP-7200H”(二环戊二烯型环氧树脂)；DIC公司制的“EXA-7311”、“EXA-7311-G3”、“EXA-7311-G4”、“EXA-7311-G4S”、“HP6000”、“HP6000L”(萘醚型环氧树脂)；日本化药公司制的“EPPN-502H”(三酚型环氧树脂)；日本化药公司制的“NC7000L”(萘酚酚醛清漆型环氧树脂)；日本化药公司制的“NC3000H”、“NC3000”、“NC3000L”、“NC3100”(联苯型环氧树脂)；新日铁住金化学公司制的“ESN475V”(萘酚型环氧树脂)；新日铁住金化学公司制的“ESN485”(萘酚酚醛清漆型环氧树脂)；三菱化学公司制的“YX4000H”、“YX4000”、“YL6121”(联苯型环氧树脂)；三菱化学公司制的“YX4000HK”(联二甲苯酚型环氧树脂)；三菱化学公司制的“YX8800”(蒽型环氧树脂)；大阪气体化学公司制的“PG-100”、“CG-500”；三菱化学公司制的“157S70”(双酚A酚醛清漆型环氧树脂)；三菱化学公司制的“YL7760”(双酚AF型环氧树脂)；三菱化学公司制的“YL7800”(芴型环氧树脂)；三菱化学公司制的“jER1010”(双酚A型环氧树脂)；三菱化学公司制的“jER1031S”(四苯基乙烷型环氧树脂)等。它们可以单独使用1种，也可以组合使用2种以上。Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolac-type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac-type epoxy resin) manufactured by DIC Corporation; "HP-7200L", "HP-7200", "HP-7200HH", "HP-7200" manufactured by DIC Corporation; H" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (naphthyl ether type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC 3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemicals; "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemicals; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical; "YX4000HK" (biphenylphenol type epoxy resin) manufactured by Mitsubishi Chemical; "YX8 "800" (anthracene type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "157S70" (bisphenol A novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. They can be used alone or in combination of two or more.

树脂组合物中的(A-2)成分的含量从得到利用包含(A-2)成分的效果(例如平均线热膨胀系数的降低、耐热性提高、或良好的交联密度)的观点出发，在将树脂组合物中的不挥发成分设为100质量%的情况下，优选为0.01质量%以上、更优选为0.05质量%以上、进一步优选为0.1质量%以上、特别优选为0.2质量%以上。(A-2)成分的含量的上限只要不过度损害本发明的效果，则没有特别限定，从适度抑制交联密度的观点出发，可以设为10质量%以下、8质量%以下、5质量%以下或3质量%以下。The content of the component (A-2) in the resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more, from the viewpoint of obtaining the effect of the component (A-2) (e.g., reduction in average linear thermal expansion coefficient, improvement in heat resistance, or good crosslinking density), when the non-volatile component in the resin composition is set to 100% by mass. The upper limit of the content of the component (A-2) is not particularly limited as long as it does not excessively damage the effect of the present invention, and can be set to 10% by mass or less, 8% by mass or less, 5% by mass or less, or 3% by mass or less, from the viewpoint of appropriately suppressing the crosslinking density.

在作为(A)成分而组合使用(A-1)液体状环氧树脂和(A-2)固体状环氧树脂的情况下，它们的量比(液体状环氧树脂：固体状环氧树脂)以质量比计优选为1：0.01~1：20的范围。通过将(A-1)液体状环氧树脂与(A-2)固体状环氧树脂的量比设为所述范围，可以得到下述等效果：i)在以树脂片材的形态使用的情况下具有适度的粘合性，ii)在以树脂片材的形态使用的情况下得到充分的可挠性，处理性提高，以及iii)能够得到具有充分的断裂强度的固化物。从得到上述i)~iii)的效果的观点和适度抑制交联密度的观点出发，(A-1)液体状环氧树脂与(A-2)固体状环氧树脂的量比(液体状环氧树脂：固体状环氧树脂)以质量比计更优选为1：0.01~1：10的范围、进一步优选为1：0.01~1：8的范围。When (A-1) a liquid epoxy resin and (A-2) a solid epoxy resin are used in combination as the component (A), the mass ratio of these (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1:0.01 to 1:20. By setting the mass ratio of the liquid epoxy resin (A-1) to the solid epoxy resin (A-2) to the above range, the following effects can be obtained: i) when used in the form of a resin sheet, it has moderate adhesiveness, ii) when used in the form of a resin sheet, it has sufficient flexibility and improved handling properties, and iii) a cured product with sufficient breaking strength can be obtained. From the viewpoint of obtaining the above-mentioned effects i) to iii) and the viewpoint of moderately suppressing the crosslinking density, the mass ratio of the liquid epoxy resin (A-1) to the solid epoxy resin (A-2) (liquid epoxy resin: solid epoxy resin) is more preferably in the range of 1:0.01 to 1:10, and further preferably in the range of 1:0.01 to 1:8.

树脂组合物中的(A)成分的含量从实现本发明的期望效果的观点出发，在将树脂组合物中的不挥发成分设为100质量%的情况下，优选为0.5质量%以上、更优选为1质量%以上、进一步优选为2质量%以上、特别优选为3质量%以上。环氧树脂的含量的上限只要实现本发明的效果，则没有特别限定，可以设为70质量%以下、60质量%以下、50质量%或35质量%以下。The content of the component (A) in the resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and particularly preferably 3% by mass or more, from the viewpoint of achieving the desired effect of the present invention, when the non-volatile component in the resin composition is set to 100% by mass. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is achieved, and can be set to 70% by mass or less, 60% by mass or less, 50% by mass or less, or 35% by mass or less.

(A)成分的环氧当量优选为50g/eq.~5000g/eq.、更优选为50g/eq.~3000g/eq.、进一步优选为70g/eq.~2000g/eq.、进一步更优选为70g/eq.~1000g/eq.。通过达到该范围，能够得到固化物的交联密度充分、强度和耐热性优异的固化物。应予说明，环氧当量可以按照JIS K7236而测定，为包含1当量的环氧基的树脂的质量。The epoxy equivalent of component (A) is preferably 50 g/eq. to 5000 g/eq., more preferably 50 g/eq. to 3000 g/eq., further preferably 70 g/eq. to 2000 g/eq., and further more preferably 70 g/eq. to 1000 g/eq. By reaching this range, a cured product having a sufficient crosslinking density and excellent strength and heat resistance can be obtained. It should be noted that the epoxy equivalent can be measured according to JIS K7236 and is the mass of a resin containing 1 equivalent of epoxy groups.

(A)成分的重均分子量优选为100~5000、更优选为250~3000、进一步优选为400~1500。在此，环氧树脂的重均分子量是通过凝胶渗透色谱(GPC)法测定的聚苯乙烯换算的重均分子量。The weight average molecular weight of the component (A) is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

＜(B)固化剂＞＜(B) Curing agent＞

树脂组合物含有(B)固化剂。作为(B)成分，可以使用具有将(A)成分固化的功能。树脂组合物与(A)环氧树脂一起含有(B)固化剂，由此能够得到耐热性优异的固化物。The resin composition contains (B) a curing agent. As the (B) component, a component having the function of curing the (A) component can be used. The resin composition contains the (B) curing agent together with the (A) epoxy resin, thereby obtaining a cured product having excellent heat resistance.

作为(B)固化剂，可以举出例如(B-1)马来酰亚胺系固化剂、以及(B-2)除了马来酰亚胺系固化剂之外的固化剂。作为(B-2)除了马来酰亚胺系固化剂之外的固化剂，可以举出选自活性酯系固化剂、苯酚系固化剂、萘酚系固化剂、碳二亚胺系固化剂、苯并噁嗪系固化剂、酸酐系固化剂、胺系固化剂、和氰酸酯系固化剂中的1种以上的固化剂(但是，包含马来酰亚胺基的固化剂除外)等。固化剂可以单独使用1种，或可以组合使用2种以上。As (B) curing agent, for example, (B-1) maleimide curing agent and (B-2) curing agent other than maleimide curing agent can be cited. As (B-2) curing agent other than maleimide curing agent, curing agent selected from active ester curing agent, phenol curing agent, naphthol curing agent, carbodiimide curing agent, benzoxazine curing agent, anhydride curing agent, amine curing agent and cyanate curing agent can be cited. One or more curing agents selected from active ester curing agent, phenol curing agent, naphthol curing agent, carbodiimide curing agent, benzoxazine curing agent, anhydride curing agent, amine curing agent and cyanate curing agent (but, except for curing agent containing maleimide group) etc. can be cited. One curing agent can be used alone, or two or more can be used in combination.

其中，从实现本发明的期望效果的观点出发，(B)成分优选包含(B-1)马来酰亚胺系固化剂。此外，(B)成分优选包含(B-1)马来酰亚胺系固化剂、和选自(B-2)除了马来酰亚胺系固化剂之外的固化剂中的1种以上的固化剂。更优选地，(B)成分包含(B-1)马来酰亚胺系固化剂、和作为(B-2)成分的选自活性酯系固化剂和酚系固化剂中的1种以上的固化剂。Among them, from the viewpoint of achieving the desired effect of the present invention, component (B) preferably includes (B-1) a maleimide-based curing agent. In addition, component (B) preferably includes (B-1) a maleimide-based curing agent and one or more curing agents selected from (B-2) curing agents other than maleimide-based curing agents. More preferably, component (B) includes (B-1) a maleimide-based curing agent and one or more curing agents selected from active ester-based curing agents and phenol-based curing agents as component (B-2).

((B-1)马来酰亚胺系固化剂)((B-1) Maleimide-based curing agent)

作为马来酰亚胺系固化剂，可以举出(B-1a)在分子中具有任选具有取代基的碳原子数为5以上的烷基、和任选具有取代基的碳原子数为5以上的亚烷基中的至少任一烃链的马来酰亚胺化合物。此外，作为马来酰亚胺系固化剂，可以举出(B-1b)除了(B-1a)成分之外的马来酰亚胺系固化剂。马来酰亚胺系固化剂可以单独使用1种，也可以组合使用2种以上。马来酰亚胺系固化剂优选包含(B-1a)成分，也可以进一步组合包含(B-1b)成分。As the maleimide curing agent, there can be mentioned (B-1a) a maleimide compound having at least any hydrocarbon chain in an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms and optionally having a substituent in the molecule. In addition, as the maleimide curing agent, there can be mentioned (B-1b) a maleimide curing agent other than the component (B-1a). The maleimide curing agent can be used alone or in combination of two or more. The maleimide curing agent preferably includes the component (B-1a), and can also be further combined to include the component (B-1b).

(B-1)成分是在分子中含有至少1个下述式所示的马来酰亚胺基的化合物，优选为含脂肪族结构的马来酰亚胺化合物。下述式所示的结构中，氮原子的3个键合位之中未与其他原子键合的1个键合位是指单键。Component (B-1) is a compound containing at least one maleimide group represented by the following formula in the molecule, preferably a maleimide compound containing an aliphatic structure. In the structure represented by the following formula, one of the three bonding positions of the nitrogen atom that is not bonded to other atoms is a single bond.

【化1】【Chemistry 1】

(B-1)成分中的平均1分子的马来酰亚胺基的数量为1个以上，从提高本发明的期望效果的观点出发，优选为2个以上、更优选为3个以上，上限没有特别限定，可以设为10个以下、6个以下、4个以下、或3个以下。The number of maleimide groups per molecule in the component (B-1) is 1 or more, preferably 2 or more, more preferably 3 or more, from the viewpoint of improving the desired effect of the present invention, and the upper limit is not particularly limited, and can be 10 or less, 6 or less, 4 or less, or 3 or less.

含脂肪族结构的马来酰亚胺化合物所具有的碳原子数为5以上的烷基的碳原子数优选为6以上、更优选为8以上，优选为50以下、更优选为45以下、进一步优选为40以下。该烷基可以为直链状、支链状、环状中任一者，其中，优选为直链状。作为这样的烷基，可以举出例如戊基、己基、庚基、辛基、壬基、癸基等。碳原子数为5以上的烷基可以为碳原子数为5以上的亚烷基的取代基。碳原子数为5以上的烷基可以为烯基中的一部分或链多烯基(双键的数量优选为2)中的一部分。The carbon number of the alkyl group with more than 5 carbon atoms in the maleimide compound containing an aliphatic structure is preferably more than 6, more preferably more than 8, preferably less than 50, more preferably less than 45, and further preferably less than 40. The alkyl group can be any one of straight chain, branched chain, and cyclic, wherein a straight chain is preferred. As such an alkyl group, for example, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. can be cited. The alkyl group with more than 5 carbon atoms can be a substituent of an alkylene group with more than 5 carbon atoms. The alkyl group with more than 5 carbon atoms can be a part of an alkenyl group or a part of a chain polyene group (the number of double bonds is preferably 2).

碳原子数为5以上的亚烷基的碳原子数优选为6以上、更优选为8以上，优选为50以下、更优选为45以下、进一步优选为40以下。该亚烷基可以为直链状、支链状、环状中任一者，其中，优选为直链状。在此，环状的亚烷基是指包括仅由环状的亚烷基组成的情况、和包含直链状的亚烷基与环状的亚烷基两者的情况的概念。作为这样的亚烷基，可以举出例如亚戊基、亚己基、亚庚基、亚辛基、亚壬基、亚癸基、亚十一烷基、亚十二烷基、亚十三烷基、亚十七烷基、亚三十六烷基、具有亚辛基-亚环己基结构的基团、具有亚辛基-亚环己基-亚辛基结构的基团、具有亚丙基-亚环己基-亚辛基结构的基团等。碳原子数为5以上的亚烷基可以为亚烯基中的一部分或亚链多烯基(双键的数量优选为2)中的一部分。The carbon number of the alkylene group with a carbon number of 5 or more is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and further preferably 40 or less. The alkylene group can be any one of straight chain, branched chain, and cyclic, wherein a straight chain is preferred. Here, a cyclic alkylene group refers to a concept including a situation consisting only of a cyclic alkylene group and a situation containing both a straight chain alkylene group and a cyclic alkylene group. As such an alkylene group, for example, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, heptadecanylene, triheptadecylene, trihexadecylene, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, etc. The alkylene group with a carbon number of 5 or more can be a part of an alkenylene group or a part of a chain polyene group (the number of double bonds is preferably 2).

含脂肪族结构的马来酰亚胺化合物从提高本发明的期望效果的观点出发，为(B-1a)在分子中具有任选具有取代基的碳原子数为5以上的烷基、和任选具有取代基的碳原子数为5以上的亚烷基中的至少任一烃链的马来酰亚胺化合物，优选为具有碳原子数为5以上的烷基和碳原子数为5以上的亚烷基两者的马来酰亚胺化合物。From the viewpoint of improving the desired effect of the present invention, the maleimide compound containing an aliphatic structure is a maleimide compound (B-1a) having in the molecule at least one hydrocarbon chain of an alkyl group having 5 or more carbon atoms which may have a substituent and an alkylene group having 5 or more carbon atoms which may have a substituent, and preferably a maleimide compound having both an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms.

碳原子数为5以上的烷基和碳原子数为5以上的亚烷基可以为链状，也可以至少一部分碳原子彼此键合而形成环，环结构还包括螺环、稠环。作为彼此键合形成的环，可以举出例如环己烷环等。The alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms may be in a chain or at least part of the carbon atoms may be bonded to form a ring, and the ring structure may include a spiro ring and a condensed ring. Examples of the ring formed by bonding to each other include a cyclohexane ring.

碳原子数为5以上的烷基和碳原子数为5以上的亚烷基可以不具有取代基，也可以具有取代基。作为取代基，可以举出例如卤素原子、-OH、-O-C1-10烷基、-N(C1-10烷基)2、C1-10烷基、C6-10芳基、-NH2、-CN、-C(O)O-C1-10烷基、-COOH、-C(O)H、-NO2等。在此，“Cx-y”(x和y为正整数，满足x＜y)这一术语表示紧接该术语后记载的有机基团的碳原子数为x~y。例如，“C1-10烷基”这一表达表示碳原子数1~10的烷基。这些取代基可以彼此键合而形成环，环结构还包括螺环、稠环。在此，取代基的碳原子数不包括在碳原子数为5以上的烷基和碳原子数为5以上的亚烷基的碳原子数中。上述取代基可以进一步具有取代基(以下有时称为“二次取代基”)。作为二次取代基，在没有特别记载的情况下，可以使用与上述取代基相同的基团。Alkyl groups having 5 or more carbon atoms and alkylene groups having 5 or more carbon atoms may or may not have a substituent. Examples of substituents include halogen atoms, -OH, -OC 1-10 alkyl, -N(C 1-10 alkyl) 2 , C 1-10 alkyl, C 6-10 aryl, -NH 2 , -CN, -C(O)OC 1-10 alkyl, -COOH, -C(O)H, -NO 2 , etc. Here, the term "C xy " (x and y are positive integers, satisfying x＜y) means that the number of carbon atoms of the organic group recorded immediately after the term is x to y. For example, the expression "C 1-10 alkyl" means an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring. Here, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms. The above-mentioned substituent may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). As the secondary substituent, the same substituents as those described above can be used unless otherwise specified.

含脂肪族结构的马来酰亚胺化合物中，碳原子数为5以上的烷基和碳原子数为5以上的亚烷基优选与马来酰亚胺基的氮原子直接键合。In the maleimide compound containing an aliphatic structure, an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms are preferably directly bonded to the nitrogen atom of the maleimide group.

含脂肪族结构的马来酰亚胺化合物的平均1分子的马来酰亚胺基的数量可以为1个，优选为2个以上，优选为10个以下、更优选6个以下、特别优选为3个以下。含脂肪族结构的马来酰亚胺化合物平均1分子具有2个以上的马来酰亚胺基，由此能够提高本发明的期望效果。The number of maleimide groups per molecule of the aliphatic structure-containing maleimide compound may be 1, preferably 2 or more, preferably 10 or less, more preferably 6 or less, and particularly preferably 3 or less. The aliphatic structure-containing maleimide compound has 2 or more maleimide groups per molecule, thereby enhancing the desired effect of the present invention.

含脂肪族结构的马来酰亚胺化合物优选为下述通式(B1)所示的马来酰亚胺化合物。The maleimide compound containing an aliphatic structure is preferably a maleimide compound represented by the following general formula (B1).

【化2】【Chemistry 2】

通式(B1)中，M表示任选具有取代基的包含碳原子数为5以上的亚烷基的2价脂肪族烃基，L表示单键或2价连结基。In the general formula (B1), M represents a divalent aliphatic hydrocarbon group including an alkylene group having 5 or more carbon atoms which may have a substituent, and L represents a single bond or a divalent linking group.

M表示任选具有取代基的包含碳原子数为5以上的亚烷基的2价脂肪族烃基。优选地，M表示任选具有取代基的碳原子数为5以上的亚烷基、亚烯基或亚链多烯基(更优选为双键的数量为2)。M的亚烷基与上述碳原子数为5以上的亚烷基相同。作为M的取代基，可以举出例如卤素原子、-OH、-O-C1-10烷基、-N(C1-10烷基)2、C1-10烷基、C6-10芳基、-NH2、-CN、-C(O)O-C1-10烷基、-COOH、-C(O)H、-NO2等。在此，“Cx-y”(x和y为正整数，满足x＜y)这一术语表示紧接该术语后记载的有机基团的碳原子数为x~y。例如，“C1-10烷基”这一表达表示碳原子数1~10的烷基。这些取代基可以彼此键合而形成环，环结构还包括螺环、稠环。上述取代基可以进一步具有取代基(以下有时称为“二次取代基”)。作为二次取代基，在没有特别记载的情况下，可以使用与上述取代基相同的基团。M的取代基优选为碳原子数为5以上的烷基。在此，取代基的碳原子数不包括在碳原子数为5以上的亚烷基的碳原子数中。M represents a divalent aliphatic hydrocarbon group including an alkylene group having 5 or more carbon atoms and optionally having a substituent. Preferably, M represents an alkylene group, an alkenylene group or an alkenylene group having 5 or more carbon atoms and optionally having a substituent (more preferably, the number of double bonds is 2). The alkylene group of M is the same as the alkylene group having 5 or more carbon atoms described above. As the substituent of M, for example, a halogen atom, -OH, -OC 1-10 alkyl, -N(C 1-10 alkyl) 2 , C 1-10 alkyl, C 6-10 aryl, -NH 2 , -CN, -C(O)OC 1-10 alkyl, -COOH, -C(O)H, -NO 2 , etc. can be cited. Here, the term "C xy " (x and y are positive integers, satisfying x＜y) means that the number of carbon atoms of the organic group recorded immediately after the term is x to y. For example, the expression "C 1-10 alkyl" means an alkyl group having 1 to 10 carbon atoms. These substituents can be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring. The above-mentioned substituent may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). As a secondary substituent, in the absence of special records, the same group as the above-mentioned substituent can be used. The substituent of M is preferably an alkyl group with a carbon number of more than 5. Here, the carbon number of the substituent is not included in the carbon number of the alkylene group with a carbon number of more than 5.

L表示单键或2价连结基。作为2价连结基，可以举出亚烷基、亚烯基、亚炔基、亚芳基、-C(=O)-、-C(=O)-O-、-NR0-(R0为氢原子、碳原子数1~3的烷基)、氧原子、硫原子、C(=O)NR0-、源自邻苯二甲酰亚胺的2价基团、源自均苯四甲酸二酰亚胺的2价基团、和包含它们中2种以上的2价基团的组合的基团等。亚烷基、亚烯基、亚炔基、亚芳基、源自邻苯二甲酰亚胺的2价基团、源自均苯四甲酸二酰亚胺的2价基团、和包含2种以上的2价基团的组合的基团可以具有碳原子数为5以上的烷基作为取代基。L represents a single bond or a divalent linking group. As a divalent linking group, alkylene, alkenylene, alkynylene, arylene, -C(=O)-, -C(=O)-O-, -NR 0 -(R 0 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms), an oxygen atom, a sulfur atom, C(=O)NR 0 -, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, and a group comprising a combination of two or more divalent groups thereof, etc. Alkylene, alkenylene, alkynylene, arylene, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, and a group comprising a combination of two or more divalent groups thereof may have an alkyl group having 5 or more carbon atoms as a substituent.

源自邻苯二甲酰亚胺的2价基团是指表示由邻苯二甲酰亚胺衍生的2价基团，具体而言是以下的通式所示的基团。式中，“*”表示键合位。The divalent group derived from phthalimide refers to a divalent group derived from phthalimide, and specifically refers to a group represented by the following general formula: In the formula, "*" represents a bonding position.

【化3】【Chemistry 3】

源自均苯四甲酸二酰亚胺的2价基团是指表示由均苯四甲酸二酰亚胺衍生的2价基团，具体而言是以下的通式所示的基团。式中，“*”表示键合位。The divalent group derived from pyromellitic acid imide refers to a divalent group derived from pyromellitic acid imide, and specifically refers to a group represented by the following general formula: In the formula, "*" represents a bonding position.

【化4】【Chemistry 4】

作为L中的2价连结基的亚烷基优选为碳原子数1~50的亚烷基，更优选为碳原子数1~45的亚烷基，特别优选为碳原子数1~40的亚烷基。该亚烷基可以为直链状、支链状、环状中任一者。作为这样的亚烷基，可以举出例如甲基亚乙基、亚环己基、亚戊基、亚己基、亚庚基、亚辛基、亚壬基、亚癸基、亚十一烷基、亚十二烷基、亚十三烷基、亚十七烷基、亚三十六烷基、具有亚辛基-亚环己基结构的基团、具有亚辛基-亚环己基-亚辛基结构的基团、具有亚丙基-亚环己基-亚辛基结构的基团等。The alkylene group as the divalent linking group in L is preferably an alkylene group having 1 to 50 carbon atoms, more preferably an alkylene group having 1 to 45 carbon atoms, and particularly preferably an alkylene group having 1 to 40 carbon atoms. The alkylene group may be any of a linear, branched, or cyclic shape. Examples of such alkylene groups include methylethylene, cyclohexylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, heptadecylene, trihexadecylene, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, and the like.

作为L中的2价连结基的亚烯基优选为碳原子数2~20的亚烯基，更优选为碳原子数2~15的亚烯基，特别优选为碳原子数2~10的亚烯基。该亚烯基可以为直链状、支链状、环状中任一者。作为这样的亚烯基，可以举出例如甲基亚乙烯基、亚环己烯基、亚戊烯基、亚己烯基、亚庚烯基、亚辛烯基等。The alkenylene group as the divalent linking group in L is preferably an alkenylene group having 2 to 20 carbon atoms, more preferably an alkenylene group having 2 to 15 carbon atoms, and particularly preferably an alkenylene group having 2 to 10 carbon atoms. The alkenylene group may be any of a linear, branched, or cyclic group. Examples of such alkenylene groups include methylvinylene, cyclohexenylene, pentenylene, hexenylene, heptenylene, and octenylene.

作为L中的2价连结基的亚炔基优选为碳原子数2~20的亚炔基，更优选为碳原子数2~15的亚炔基，特别优选为碳原子数2~10的亚炔基。该亚炔基可以为直链状、支链状、环状中任一者。作为这样的亚炔基，可以举出例如甲基亚乙炔基、环亚己炔基、亚戊炔基、亚己炔基、亚庚炔基、亚辛炔基等。The alkynylene group as the divalent linking group in L is preferably an alkynylene group having 2 to 20 carbon atoms, more preferably an alkynylene group having 2 to 15 carbon atoms, and particularly preferably an alkynylene group having 2 to 10 carbon atoms. The alkynylene group may be any of a linear, branched, or cyclic group. Examples of such alkynylene groups include methylethynylene, cyclohexynylene, pentynylene, hexynylene, heptynylene, and octynylene.

作为L中的2价连结基的亚芳基优选为碳原子数6~24的亚芳基，更优选为碳原子数6~18的亚芳基，进一步优选为碳原子数6~14的亚芳基，进一步更优选为碳原子数6~10的亚芳基。作为亚芳基，可以举出例如亚苯基、亚萘基、亚蒽基等。The arylene group as the divalent linking group in L is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, further preferably an arylene group having 6 to 14 carbon atoms, and further more preferably an arylene group having 6 to 10 carbon atoms. Examples of the arylene group include phenylene, naphthylene, anthrylene, and the like.

作为L中的2价连结基的亚烷基、亚烯基、亚炔基、和亚芳基可以具有取代基。作为取代基，与通式(B1)中的M的取代基同样地，优选为碳原子数为5以上的烷基。The alkylene group, alkenylene group, alkynylene group, and arylene group as the divalent linking group in L may have a substituent. As the substituent, similar to the substituent of M in the general formula (B1), an alkyl group having 5 or more carbon atoms is preferred.

作为L中的包含2种以上的2价基团的组合的基团，可以举出例如包含亚烷基、源自邻苯二甲酰亚胺的2价基团和氧原子的组合的2价基团；包含源自邻苯二甲酰亚胺的2价基团、氧原子、亚芳基和亚烷基的组合的2价基团；包含亚烷基和源自均苯四甲酸二酰亚胺的2价基团的组合的2价基团等。包含2种以上的2价基团的组合的基团可以通过各个基团的组合而形成稠环等环。此外，包含2种以上的2价基团的组合的基团可以为重复单元数为1~10的重复单元。As the group containing two or more divalent groups in L, for example, a divalent group containing an alkylene group, a divalent group derived from phthalimide, and an oxygen atom; a divalent group containing a combination of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a divalent group containing an alkylene group and a divalent group derived from pyromellitic acid diimide, etc. The group containing a combination of two or more divalent groups can form a ring such as a condensed ring by combining the respective groups. In addition, the group containing a combination of two or more divalent groups can be a repeating unit having a repeating unit number of 1 to 10.

其中，作为通式(B1)中的L，优选为氧原子、任选具有取代基的碳原子数6~24的亚芳基、任选具有取代基的碳原子数为1~50的亚烷基、碳原子数为5以上的烷基、源自邻苯二甲酰亚胺的2价基团、源自均苯四甲酸二酰亚胺的2价基团、或包含这些基团中的2种以上的组合的2价基团。其中，作为L，更优选为亚烷基；具有亚烷基-源自邻苯二甲酰亚胺的2价基团-氧原子-源自邻苯二甲酰亚胺的2价基团的结构的2价基团；具有亚烷基-源自邻苯二甲酰亚胺的2价基团-氧原子-亚芳基-亚烷基-亚芳基-氧原子-源自邻苯二甲酰亚胺的2价基团的结构的2价基团；具有亚烷基-源自均苯四甲酸二酰亚胺的2价基团的结构的2价基团。Among them, L in the general formula (B1) is preferably an oxygen atom, an arylene group having 6 to 24 carbon atoms optionally having a substituent, an alkylene group having 1 to 50 carbon atoms optionally having a substituent, an alkyl group having 5 or more carbon atoms, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, or a divalent group comprising a combination of two or more of these groups. Among them, L is more preferably an alkylene group; a divalent group having a structure of an alkylene group-a divalent group derived from phthalimide-an oxygen atom-a divalent group derived from phthalimide; a divalent group having a structure of an alkylene group-a divalent group derived from phthalimide-an oxygen atom-arylene group-alkylene group-arylene group-oxygen atom-a divalent group derived from phthalimide; a divalent group having a structure of an alkylene group-a divalent group derived from phthalimide-an oxygen atom-arylene group-alkylene group-arylene group-oxygen atom-a divalent group derived from phthalimide; a divalent group having a structure of an alkylene group-a divalent group derived from pyromellitic acid diimide.

含脂肪族结构的马来酰亚胺化合物优选为下述通式(B2)所示的马来酰亚胺化合物。The maleimide compound containing an aliphatic structure is preferably a maleimide compound represented by the following general formula (B2).

【化5】【Chemistry 5】

通式(B2)中，M1各自独立地表示任选具有取代基的包含碳原子数为5以上的亚烷基的2价脂肪族烃基，A各自独立地表示具有任选具有取代基的碳原子数为5以上的亚烷基或任选具有取代基的芳香环的2价基团。t表示1~10的整数。In the general formula (B2), M1 each independently represents a divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms which may have a substituent, and A each independently represents a divalent group containing an alkylene group having 5 or more carbon atoms which may have a substituent or an aromatic ring which may have a substituent. t represents an integer of 1 to 10.

M1各自独立地表示任选具有取代基的包含碳原子数为5以上的亚烷基的2价脂肪族烃基。优选地，M1各自独立地表示任选具有取代基的碳原子数为5以上的亚烷基、亚烯基或亚链多烯基(更优选为双键的数量为2)。M1更优选与通式(B1)中的M相同。M1 each independently represents a divalent aliphatic hydrocarbon group including an alkylene group having 5 or more carbon atoms and optionally having a substituent. Preferably, M1 each independently represents an alkylene group, an alkenylene group or an alkenylene group having 5 or more carbon atoms and optionally having a substituent (more preferably having 2 double bonds). M1 is more preferably the same as M in the general formula (B1).

A各自独立地表示具有任选具有取代基的碳原子数为5以上的亚烷基或任选具有取代基的芳香环的2价基团。作为A中的亚烷基，可以为链状、支链状、环状中任一者，其中，优选为环状、即任选具有取代基的碳原子数为5以上的环状的亚烷基。亚烷基的碳原子数优选为6以上、更优选为8以上，优选为50以下、更优选为45以下、进一步优选为40以下。作为这样的亚烷基，可以举出例如具有亚辛基-亚环己基结构的基团、具有亚辛基-亚环己基-亚辛基结构的基团、具有亚丙基-亚环己基-亚辛基结构的基团等。A each independently represents a divalent group having an alkylene group with 5 or more carbon atoms which may have a substituent or an aromatic ring which may have a substituent. As the alkylene group in A, any one of chain, branched, and cyclic may be used, and among them, a cyclic alkylene group, i.e., a cyclic alkylene group with 5 or more carbon atoms which may have a substituent, is preferred. The number of carbon atoms of the alkylene group is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and further preferably 40 or less. As such an alkylene group, for example, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, etc. can be cited.

作为A所表示的具有芳香环的2价基团中的芳香环，可以举出例如苯环、萘环、蒽环、邻苯二甲酰亚胺环、均苯四甲酸二酰亚胺环、芳族杂环等，优选为苯环、邻苯二甲酰亚胺环、均苯四甲酸二酰亚胺环。即，作为具有芳香环的2价基团，优选为具有任选具有取代基的苯环的2价基团、具有任选具有取代基的邻苯二甲酰亚胺环的2价基团、具有任选具有取代基的均苯四甲酸二酰亚胺环的2价基团。作为具有芳香环的2价基团，可以举出例如包含源自邻苯二甲酰亚胺的2价基团和氧原子的组合的基团；包含源自邻苯二甲酰亚胺的2价基团、氧原子、亚芳基和亚烷基的组合的基团；包含亚烷基和源自均苯四甲酸二酰亚胺的2价基团的组合的基团；包含源自均苯四甲酸二酰亚胺的2价基团；源自邻苯二甲酰亚胺的2价基团和亚烷基的组合的基团等。上述亚芳基和亚烷基与通式(B1)中的L所表示的2价连结基中的亚芳基和亚烷基相同。As the aromatic ring in the divalent group having an aromatic ring represented by A, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a pyromellitic acid diimide ring, an aromatic heterocyclic ring, etc., preferably a benzene ring, a phthalimide ring, and a pyromellitic acid diimide ring. That is, as the divalent group having an aromatic ring, preferably a divalent group having a benzene ring optionally having a substituent, a divalent group having a phthalimide ring optionally having a substituent, and a divalent group having a pyromellitic acid diimide ring optionally having a substituent. Examples of the divalent group having an aromatic ring include a group comprising a combination of a divalent group derived from phthalimide and an oxygen atom; a group comprising a combination of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a group comprising a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide; a group comprising a divalent group derived from pyromellitic acid diimide; a group comprising a combination of a divalent group derived from phthalimide and an alkylene group, etc. The above-mentioned arylene group and alkylene group are the same as the arylene group and alkylene group in the divalent linking group represented by L in the general formula (B1).

A所表示的亚烷基和具有芳香环的2价基团可以具有取代基。作为取代基，与通式(B1)中的M的取代基所表示的取代基相同。The alkylene group and the divalent group having an aromatic ring represented by A may have a substituent. The substituent is the same as the substituent represented by the substituent of M in the general formula (B1).

作为A所表示的基团的具体例，可以举出以下的基团。式中，“*”表示键合位。Specific examples of the group represented by A include the following groups: In the formula, "*" represents a bonding position.

【化6】【Chemistry 6】

【化7】【Chemistry 7】

通式(B2)所示的马来酰亚胺化合物优选为下述通式(B2-1)所示的马来酰亚胺化合物、和下述通式(B2-2)所示的马来酰亚胺化合物中任一者。The maleimide compound represented by the general formula (B2) is preferably any one of a maleimide compound represented by the following general formula (B2-1) and a maleimide compound represented by the following general formula (B2-2).

【化8】【Chemistry 8】

通式(B2-1)中，M2和M3各自独立地表示任选具有取代基的包含碳原子数为5以上的亚烷基的2价脂肪族烃基，R30各自独立地表示氧原子、亚芳基、亚烷基、或包含这些的基团中的2种以上的组合的2价基团。t1表示1~10的整数。In the general formula (B2-1), M2 and M3 each independently represent a divalent aliphatic hydrocarbon group optionally having a substituent and containing an alkylene group having 5 or more carbon atoms, and R30 each independently represents an oxygen atom, an arylene group, an alkylene group, or a divalent group of a combination of two or more of these groups. t1 represents an integer of 1 to 10.

【化9】【Chemistry 9】

通式(B2-2)中，M4、M6和M7各自独立地表示任选具有取代基的包含碳原子数为5以上的亚烷基的2价脂肪族烃基，M5各自独立地表示任选具有取代基的具有芳香环的2价基团，R31和R32各自独立地表示碳原子数为5以上的烷基。t2表示0~10的整数，u1和u2各自独立地表示0~4的整数。In the general formula (B2-2), M4 , M6 and M7 each independently represent a divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms which may have a substituent, M5 each independently represents a divalent group having an aromatic ring which may have a substituent, R31 and R32 each independently represent an alkyl group having 5 or more carbon atoms. t2 represents an integer of 0 to 10, and u1 and u2 each independently represent an integer of 0 to 4.

M2和M3各自独立地表示任选具有取代基的包含碳原子数为5以上的亚烷基的2价脂肪族烃基。优选地，M2和M3各自独立地表示任选具有取代基的碳原子数为5以上的亚烷基、亚烯基或亚链多烯基(更优选为双键的数量为2)。M2和M3更优选与通式(B1)中的M所表示的碳原子数为5以上的亚烷基相同，优选为亚三十六烷基。 M2 and M3 each independently represent a divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms and optionally having a substituent. Preferably, M2 and M3 each independently represent an alkylene group, an alkenylene group or an alkenylene group having 5 or more carbon atoms and optionally having a substituent (more preferably having 2 double bonds). M2 and M3 are more preferably the same as the alkylene group having 5 or more carbon atoms represented by M in the general formula (B1), and are preferably hexatriadecylene.

R30各自独立地表示氧原子、亚芳基、亚烷基、或包含这些中的2种以上的2价基团的组合的基团。亚芳基、亚烷基与通式(B1)中的L所表示的2价连结基中的亚芳基和亚烷基相同。作为R30，优选为包含2种以上的2价基团的组合的基团或氧原子。R 30 each independently represents an oxygen atom, an arylene group, an alkylene group, or a group comprising a combination of two or more divalent groups thereof. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (B1). R 30 is preferably a group comprising a combination of two or more divalent groups or an oxygen atom.

作为R30中的包含2种以上的2价基团的组合的基团，可以举出氧原子、亚芳基、和亚烷基的组合。作为包含2种以上的2价基团的组合的基团的具体例，可以举出以下的基团。式中，“*”表示键合位。As the group including two or more divalent groups in R 30 , a combination of an oxygen atom, an arylene group, and an alkylene group can be cited. As specific examples of the group including two or more divalent groups, the following groups can be cited. In the formula, "*" represents a bonding position.

【化10】【Chemistry 10】

M4、M6和M7各自独立地表示任选具有取代基的包含碳原子数为5以上的亚烷基的2价脂肪族烃基。优选地，M4、M6和M7各自独立地表示任选具有取代基的碳原子数为5以上的亚烷基、亚烯基或亚链多烯基(更优选为双键的数量为2)。M4、M6和M7与通式(B1)中的M所表示的任选具有取代基的碳原子数为5以上的亚烷基相同，优选为亚己基、亚庚基、亚辛基、亚壬基、亚癸基，更优选为亚辛基。 M4 , M6 and M7 each independently represent a divalent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms and optionally having a substituent. Preferably, M4 , M6 and M7 each independently represent an alkylene group, an alkenylene group or an alkadiene group having 5 or more carbon atoms and optionally having a substituent (more preferably having 2 double bonds). M4 , M6 and M7 are the same as the alkylene group having 5 or more carbon atoms and optionally having a substituent represented by M in the general formula (B1), preferably hexylene, heptylene, octylene, nonylene, decylene, more preferably octylene.

M5各自独立地表示任选具有取代基的具有芳香环的2价基团。M5与通式(B2)中的A所表示的任选具有取代基的具有芳香环的2价基团相同，优选为包含亚烷基和源自均苯四甲酸二酰亚胺的2价基团的组合的基团；包含源自邻苯二甲酰亚胺的2价基团和亚烷基的组合的基团，更优选为包含亚烷基和源自均苯四甲酸二酰亚胺的2价基团的组合的基团。 M5 each independently represents a divalent group having an aromatic ring which may have a substituent. M5 is the same as the divalent group having an aromatic ring which may have a substituent represented by A in the general formula (B2), preferably a group comprising a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide; a group comprising a combination of a divalent group derived from phthalimide and an alkylene group, and more preferably a group comprising a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide.

作为M5所表示的基团的具体例，可以举出例如以下的基团。式中，“*”表示键合位。Specific examples of the group represented by M5 include the following groups: wherein "*" represents a bonding position.

【化11】【Chemistry 11】

R31和R32各自独立地表示碳原子数为5以上的烷基。R31和R32与上述碳原子数为5以上的烷基相同，优选为己基、庚基、辛基、壬基、癸基，更优选为己基、辛基。 R31 and R32 each independently represent an alkyl group having at least 5 carbon atoms. R31 and R32 are the same as the above-mentioned alkyl group having at least 5 carbon atoms, and are preferably hexyl, heptyl, octyl, nonyl, or decyl, and more preferably hexyl or octyl.

u1和u2各自独立地表示1~15的整数，优选为1~10的整数。u1 and u2 each independently represent an integer of 1-15, and preferably an integer of 1-10.

作为含脂肪族结构的马来酰亚胺化合物的具体例，可以举出以下的(b1)、(b2)、(b3)、(b4)、(b5)和(b6)的化合物。但是，含脂肪族结构的马来酰亚胺化合物不限于这些具体例。式(b1)、(b2)、(b3)、(b5)和(b6)中，n9、n10、n11、n12和n13表示1~10的整数。Specific examples of maleimide compounds containing an aliphatic structure include the following compounds (b1), (b2), (b3), (b4), (b5) and (b6). However, maleimide compounds containing an aliphatic structure are not limited to these specific examples. In formulas (b1), (b2), (b3), (b5) and (b6), n9, n10, n11, n12 and n13 represent integers of 1 to 10.

【化12】【Chemistry 12】

【化13】【Chemistry 13】

【化14】【Chemistry 14】

【化15】【Chemistry 15】

【化16】【Chemistry 16】

【化17】【Chemistry 17】

作为含脂肪族结构的马来酰亚胺化合物((B-1)成分)的具体例，可以举出デザイナーモレキュールズ公司制的“BMI-1500”(式(b1)的化合物、式(b5)的化合物)、“BMI-1700”(式(b2)的化合物、式(b6)的化合物)、“BMI-3000J”(式(b3)的化合物)和“BMI-689”(式(b4)的化合物)等。Specific examples of maleimide compounds containing an aliphatic structure (component (B-1)) include "BMI-1500" (a compound of formula (b1), a compound of formula (b5)), "BMI-1700" (a compound of formula (b2), a compound of formula (b6)), "BMI-3000J" (a compound of formula (b3)), and "BMI-689" (a compound of formula (b4)) manufactured by Desinair Molecule Co., Ltd.

(B-1)成分的马来酰亚胺基当量从显著得到本发明的期望效果的观点出发，优选为50g/eq.~2000g/eq.、更优选为100g/eq.~1000g/eq.、进一步优选为150g/eq.~500g/eq.。马来酰亚胺基当量为包含1当量的马来酰亚胺基的马来酰亚胺化合物的质量。The maleimide group equivalent of the component (B-1) is preferably 50 g/eq. to 2000 g/eq., more preferably 100 g/eq. to 1000 g/eq., and even more preferably 150 g/eq. to 500 g/eq., from the viewpoint of significantly obtaining the desired effect of the present invention. The maleimide group equivalent is the mass of the maleimide compound containing 1 equivalent of maleimide groups.

(B-1)成分的含量在树脂组合物的不挥发成分设为100质量%的情况下，尽管取决于除了(A)成分和(B-1)成分之外的成分的含量，但从提高本发明的期望效果的观点出发，可以设为0.2质量%以上、0.5质量%以上、1.0质量%以上或2.0质量%以上。从提高本发明的期望效果的观点出发，上限优选为15质量%以下、更优选为13质量%以下、进一步优选为10质量%以下。(B-1)成分在(B)成分中所占的比例从提高本发明的期望效果的观点出发，优选为30质量%以上、40质量%以上或50质量%以上，上限为100质量%。The content of (B-1) component, when the non-volatile component of the resin composition is set to 100% by mass, may be set to 0.2% by mass or more, 0.5% by mass or more, 1.0% by mass or more, or 2.0% by mass or more from the viewpoint of improving the desired effect of the present invention, although it depends on the content of the components other than (A) component and (B-1) component. From the viewpoint of improving the desired effect of the present invention, the upper limit is preferably 15% by mass or less, more preferably 13% by mass or less, and further preferably 10% by mass or less. From the viewpoint of improving the desired effect of the present invention, the proportion of (B-1) component in (B) component is preferably 30% by mass or more, 40% by mass or more, or 50% by mass or more, and the upper limit is 100% by mass.

((B-2)除了马来酰亚胺系固化剂之外的固化剂)((B-2) Curing agent other than maleimide-based curing agent)

作为活性酯系固化剂，没有特别限制，一般而言，优选使用苯酚酯类、硫代苯酚酯类、N-羟基胺酯类、杂环羟基化合物的酯类等在1分子中具有2个以上的反应活性高的酯基的化合物。该活性酯系固化剂优选通过羧酸化合物和/或硫代羧酸化合物与羟基化合物和/或硫醇化合物的缩合反应而得到。特别是从耐热性提高的观点出发，优选由羧酸化合物与羟基化合物得到的活性酯系固化剂，更优选为由羧酸化合物与苯酚化合物和/或萘酚化合物得到的活性酯系固化剂。作为羧酸化合物，可以举出例如苯甲酸、乙酸、丁二酸、马来酸、衣康酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、均苯四甲酸等。作为苯酚化合物或萘酚化合物，可以举出例如氢醌、间苯二酚、双酚A、双酚F、双酚S、苯酚苯并吡咯烷酮、甲基化双酚A、甲基化双酚F、甲基化双酚S、苯酚、邻甲酚、间甲酚、对甲酚、邻苯二酚、α-萘酚、β-萘酚、1,5-二羟基萘、1,6-二羟基萘、2,6-二羟基萘、二羟基二苯甲酮、三羟基二苯甲酮、四羟基二苯甲酮、间苯三酚、苯三酚、二环戊二烯型二酚化合物、苯酚酚醛清漆等。在此，“二环戊二烯型二酚化合物”是指在二环戊二烯1分子上缩合苯酚2分子而得到的二酚化合物。As active ester curing agent, there is no particular restriction, generally speaking, preferably use phenol esters, thiophenol esters, N-hydroxylamine esters, heterocyclic hydroxy compounds and the like in 1 molecule have more than 2 reactive high ester groups of the compound. The active ester curing agent is preferably obtained by the condensation reaction of carboxylic acid compounds and/or thiocarboxylic acid compounds and hydroxy compounds and/or thiol compounds. Particularly from the viewpoint of heat resistance improvement, preferably the active ester curing agent obtained by carboxylic acid compounds and hydroxy compounds, more preferably the active ester curing agent obtained by carboxylic acid compounds and phenol compounds and/or naphthol compounds. As carboxylic acid compounds, for example benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid etc. can be enumerated. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenol benzopyrrolidone, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadiene-type diphenol compounds, phenol novolac, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol on one molecule of dicyclopentadiene.

具体而言，优选为包含二环戊二烯型二酚结构的活性酯化合物、包含萘结构的活性酯化合物、包含苯酚酚醛清漆的乙酰基化物的活性酯化合物、包含苯酚酚醛清漆的苯甲酰基化物的活性酯化合物，其中，更优选为包含萘结构的活性酯化合物、包含二环戊二烯型二酚结构的活性酯化合物。“二环戊二烯型二酚结构”是指表示包含亚苯基-二亚环戊基-亚苯基的2价结构单元。Specifically, active ester compounds containing a dicyclopentadiene diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing acetylated products of phenol novolac, and active ester compounds containing benzoylated products of phenol novolac are preferred, and active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene diphenol structure are more preferred. "Dicyclopentadiene diphenol structure" refers to a divalent structural unit containing phenylene-dicyclopentylene-phenylene.

作为活性酯系固化剂的市售品，作为包含二环戊二烯型二酚结构的活性酯化合物，可以举出“EXB―9451”、“EXB―9460”、“EXB―9460S”、“HPC-8000-65T”、“HPC-8000H-65TM”、“HPC-8000L-65TM”(DIC公司制)，作为包含萘结构的活性酯化合物，可以举出“EXB―9416-70BK”、“EXB-8100L-65T”、“EXB-8150-65T”、“EXB-8150L-65T”、“HPC-8150-60T”、“HPC-8150-62T”、“HP-B-8151-62T”(DIC公司制)，作为包含苯酚酚醛清漆的乙酰基化物的活性酯化合物，可以举出“DC808”(三菱化学公司制)，作为包含苯酚酚醛清漆的苯甲酰基化物的活性酯化合物，可以举出“YLH1026”(三菱化学公司制)，作为苯酚酚醛清漆的乙酰基化物的活性酯系固化剂，可以举出“DC808”(三菱化学公司制)，作为苯酚酚醛清漆的苯甲酰基化物的活性酯系固化剂，可以举出“YLH1026”(三菱化学公司制)、“YLH1030”(三菱化学公司制)、“YLH1048”(三菱化学公司制)，作为包含苯乙烯基的活性酯化合物，可以举出“PC1300-02-65MA”(エア・ウォーター公司制)等。As commercially available products of active ester curing agents, as active ester compounds containing a dicyclopentadiene type diphenol structure, there can be mentioned "EXB-9451", "EXB-9460", "EXB-9460S", "HPC-8000-65T", "HPC-8000H-65TM", "HPC-8000L-65TM" (manufactured by DIC Corporation); as active ester compounds containing a naphthalene structure, there can be mentioned "EXB-9416-70BK", "EXB-8100L-65T", "EXB-8150-65T", "EXB-8150L-65T", "HPC-8150-60T", "HPC-8150-62T", "HP-B-8151-62T" (manufactured by DIC Corporation); Examples of active ester compounds containing acetylated phenol novolacs include "DC808" (manufactured by Mitsubishi Chemical Corporation), examples of active ester compounds containing benzoylated phenol novolacs include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), examples of active ester curing agents for acetylated phenol novolacs include "DC808" (manufactured by Mitsubishi Chemical Corporation), examples of active ester curing agents for benzoylated phenol novolacs include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and examples of active ester compounds containing a styryl group include "PC1300-02-65MA" (manufactured by Aea World Corporation) and the like.

作为酚系固化剂(活性酯化合物除外)和萘酚系固化剂(活性酯化合物除外)，从耐热性和耐水性的观点出发，优选为具有酚醛清漆结构或甲酚酚醛清漆结构的酚系固化剂、或具有酚醛清漆结构的萘酚系固化剂。此外，从与导体层的密合性的观点出发，优选为含氮酚系固化剂，更优选为含三嗪骨架的酚系固化剂。As the phenolic curing agent (excluding active ester compounds) and the naphthol curing agent (excluding active ester compounds), from the viewpoint of heat resistance and water resistance, a phenolic curing agent having a novolac structure or a cresol novolac structure, or a naphthol curing agent having a novolac structure is preferred. In addition, from the viewpoint of adhesion with the conductor layer, a nitrogen-containing phenolic curing agent is preferred, and a phenolic curing agent containing a triazine skeleton is more preferred.

作为酚系固化剂和萘酚系固化剂的具体例，可以举出例如明和化成公司制的“MEH-7700”、“MEH-7810”、“MEH-7851”、日本化药公司制的“NHN”、“CBN”、“GPH”、新日铁住金化学公司制的“SN170”、“SN180”、“SN190”、“SN475”、“SN485”、“SN495”、“SN-495V”、“SN375”、“SN395”、DIC公司制的“TD-2090”、“LA-7052”、“LA-7054”、“LA-1356”、“LA-3018-50P”、“EXB-9500”、“KA-1160”等。Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemicals, "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", and "SN395" manufactured by Nippon Steel & Sumitomo Chemicals Corporation, and "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", and "KA-1160" manufactured by DIC Corporation.

作为碳二亚胺系固化剂的具体例，可以举出日清纺化学公司制的“V-03”、“V-05”、“V-07”、“V-09”、“Elastostab H01”等。Specific examples of the carbodiimide-based curing agent include "V-03", "V-05", "V-07", "V-09", and "Elastostab H01" manufactured by Nisshinbo Chemical Co., Ltd.

作为苯并噁嗪系固化剂的具体例，可以举出JFE化学公司制的“JBZ-OP100D”、“ODA-BOZ”、昭和高分子公司制的“HFB2006M”、四国化成工业公司制的“P-d”、“F-a”。苯并噁嗪系固化剂是具有苯并噁嗪结构的化合物。苯并噁嗪结构是指取代或非取代的苯并噁嗪环(例如1,2-苯并噁嗪环、1,3-苯并噁嗪环)、或部分双键被氢化的苯并噁嗪环(例如3,4-二氢-2H-1,3-苯并噁嗪环)。Specific examples of benzoxazine curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd., "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industry Co., Ltd. Benzoxazine curing agents are compounds having a benzoxazine structure. The benzoxazine structure refers to a substituted or unsubstituted benzoxazine ring (e.g., 1,2-benzoxazine ring, 1,3-benzoxazine ring), or a benzoxazine ring with a partially hydrogenated double bond (e.g., 3,4-dihydro-2H-1,3-benzoxazine ring).

作为酸酐系固化剂，可以举出在1分子内具有1个以上的酸酐基的固化剂，优选为在1分子内具有2个以上的酸酐基的固化剂。作为酸酐系固化剂的具体例，可以举出邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、甲基四氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、甲基纳迪克酸酐、氢化甲基纳迪克酸酐、三烷基四氢邻苯二甲酸酐、十二碳烯基丁二酸酐、5-(2,5-二氧代四氢-3-呋喃基)-3-甲基-3-环己烯-1,2-二甲酸酐、偏苯三甲酸酐、均苯四甲酸酐、二苯甲酮四甲酸二酐、联苯四甲酸二酐、萘四甲酸二酐、氧基二邻苯二甲酸二酐、3,3'-4,4'-二苯基砜四甲酸二酐、1,3,3a,4,5,9b-六氢-5-(四氢-2,5-二氧代-3-呋喃基)-萘并[1,2-C]呋喃-1,3-二酮、乙二醇双(无水偏苯三甲酸酯)、苯乙烯与马来酸共聚而得到的苯乙烯・马来酸树脂等聚合物型的酸酐等。作为酸酐系固化剂的市售品，可以举出新日本理化公司制的“HNA-100”、“MH-700”、“MTA-15”、“DDSA”、“OSA”、三菱化学公司制的“YH-306”、“YH-307”、日立化成公司制的“HN-2200”、“HN-5500”等。As the acid anhydride curing agent, there can be mentioned a curing agent having one or more acid anhydride groups in one molecule, preferably a curing agent having two or more acid anhydride groups in one molecule. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, dicarboxylic anhydride, and the like. Benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrous trimellitate), styrene-maleic acid resin obtained by copolymerization of styrene and maleic acid, and the like. Commercially available products of anhydride-based curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by Shin Nippon Chemical Co., Ltd., "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Corporation, and "HN-2200" and "HN-5500" manufactured by Hitachi Chemical Co., Ltd.

作为胺系固化剂，可以举出在1分子内具有1个以上、优选为2个以上的氨基的固化剂，可以举出例如脂肪族胺类、聚醚胺类、脂环式胺类、芳族胺类等，其中，从实现本发明的期望效果的观点出发，优选为芳族胺类。胺系固化剂优选为伯胺或仲胺，更优选为伯胺。作为胺系固化剂的具体例，可以举出4,4'-亚甲基双(2,6-二甲基苯胺)、二苯基二氨基砜、4,4'-二氨基二苯基甲烷、4,4'-二氨基二苯基砜、3,3'-二氨基二苯基砜、间苯二胺、间亚二甲苯基二胺、二乙基甲苯二胺、4,4'-二氨基二苯基醚、3,3'-二甲基-4,4'-二氨基联苯、2,2'-二甲基-4,4'-二氨基联苯、3,3'-二羟基联苯胺、2,2-双(3-氨基-4-羟基苯基)丙烷、3,3-二甲基-5,5-二乙基-4,4-二苯基甲烷二胺、2,2-双(4-氨基苯基)丙烷、2,2-双(4-(4-氨基苯氧基)苯基)丙烷、1,3-双(3-氨基苯氧基)苯、1,3-双(4-氨基苯氧基)苯、1,4-双(4-氨基苯氧基)苯、4,4'-双(4-氨基苯氧基)联苯、双(4-(4-氨基苯氧基)苯基)砜、双(4-(3-氨基苯氧基)苯基)砜等。胺系固化剂可以使用市售品，可以举出例如日本化药公司制的“KAYABONDC-200S”、“KAYABOND C-100”、“カヤハードA-A”、“カヤハードA-B”、“カヤハードA-S”、三菱化学公司制的“エピキュアW”等。As the amine curing agent, there can be mentioned a curing agent having one or more, preferably two or more, amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc., wherein, from the viewpoint of achieving the desired effect of the present invention, aromatic amines are preferred. The amine curing agent is preferably a primary amine or a secondary amine, more preferably a primary amine. As specific examples of the amine curing agent, there can be mentioned 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, metaphenylenediamine, metaxylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino bis(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone and the like. As the amine curing agent, commercially available products can be used, and examples thereof include "KAYABOND C-200S", "KAYABOND C-100", "KAYAHADO AA-A", "KAYAHADO AB", "KAYAHADO AA-S" manufactured by Nippon Kayaku Co., Ltd., and "EPICURA W" manufactured by Mitsubishi Chemical Corporation.

作为氰酸酯系固化剂，可以举出例如双酚A二氰酸酯、聚苯酚氰酸酯、低聚(3-亚甲基-1,5-亚苯基氰酸酯)、4,4'-亚甲基双(2,6-二甲基苯基氰酸酯)、4,4'-乙叉基二苯基二氰酸酯、六氟双酚A二氰酸酯、2,2-双(4-氰酸酯)苯基丙烷、1,1-双(4-氰酸根合苯基甲烷)、双(4-氰酸酯-3,5-二甲基苯基)甲烷、1,3-双(4-氰酸根合苯基-1-(甲基乙叉基))苯、双(4-氰酸根合苯基)硫代醚、和双(4-氰酸根合苯基)醚等2官能氰酸酯树脂、由苯酚酚醛清漆和甲酚酚醛清漆等衍生的多官能氰酸酯树脂、这些氰酸酯树脂部分三嗪化而得到的预聚物等。作为氰酸酯系固化剂的具体例，可以举出ロンザジャパン公司制的“PT30”和“PT60”(苯酚酚醛清漆型多官能氰酸酯树脂)、“ULL-950S”(多官能氰酸酯树脂)、“BA230”、“BA230S75”(双酚A二氰酸酯中的一部分或全部三嗪化而形成三聚体的预聚物)等。Examples of the cyanate curing agent include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis(2,6-dimethylphenylcyanate), 4,4′-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers obtained by partially triazinizing these cyanate resins. Specific examples of cyanate curing agents include "PT30" and "PT60" (phenol novolac type multifunctional cyanate resins), "ULL-950S" (multifunctional cyanate resin), "BA230", "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate is triazine-formed to form a trimer) manufactured by Lonza Japan Co., Ltd.

(A)环氧树脂与(B)固化剂的量比以[环氧树脂的环氧基的总计数]：[固化剂的反应基的总计数]的比率计，优选为1：0.01~1：2的范围、更优选为1：0.05~1：3、进一步优选为1：0.1~1：1.5。在此，(B)固化剂的反应基是指活性酯基、活性羟基等，根据(B)固化剂的种类而不同。此外，(A)环氧树脂的环氧基的总计数是指将(A)环氧树脂的各个不挥发分质量除以环氧当量而得到的值针对全部环氧树脂总计的值，(B)固化剂的反应基的总计数是指将(B)固化剂的各个不挥发分质量除以反应基当量而得到的值针对全部固化剂总计的值。通过将(A)环氧树脂与(B)固化剂的量比设为所述范围，能够提高本发明的期望效果。The amount ratio of (A) epoxy resin to (B) curing agent is preferably in the range of 1:0.01 to 1:2, more preferably 1:0.05 to 1:3, and further preferably 1:0.1 to 1:1.5, based on the ratio of [total count of epoxy groups of epoxy resin]: [total count of reactive groups of curing agent]. Here, the reactive groups of (B) curing agent refer to active ester groups, active hydroxyl groups, etc., which vary depending on the type of (B) curing agent. In addition, the total count of epoxy groups of (A) epoxy resin refers to the value obtained by dividing the mass of each non-volatile component of (A) epoxy resin by the epoxy equivalent for the total value of all epoxy resins, and the total count of reactive groups of (B) curing agent refers to the value obtained by dividing the mass of each non-volatile component of (B) curing agent by the reactive group equivalent for the total value of all curing agents. By setting the amount ratio of (A) epoxy resin to (B) curing agent in the above range, the expected effect of the present invention can be improved.

(B)成分的含量优选以满足上述(A)环氧树脂与(B)固化剂的量比的范围的方式确定。从提高本发明的期望效果的观点出发，(B)成分的含量在将树脂组合物中的不挥发分设为100质量%的情况下，可以设为0.5质量%以上、1质量%以上、2质量%以上或3质量%以上、50质量%以下、40质量%以下、30质量%以下或25质量%以下。The content of component (B) is preferably determined in a manner that satisfies the range of the amount ratio of the above-mentioned (A) epoxy resin to the (B) curing agent. From the viewpoint of improving the desired effect of the present invention, the content of component (B) can be set to 0.5% by mass or more, 1% by mass or more, 2% by mass or more, 3% by mass or more, 50% by mass or less, 40% by mass or less, 30% by mass or less, or 25% by mass or less, when the non-volatile matter in the resin composition is set to 100% by mass.

＜(C)无机填充材料＞＜(C) Inorganic fillers＞

树脂组合物可以含有(C)无机填充材料。从减小树脂组合物的固化物的平均线热膨胀系数的观点出发，树脂组合物优选包含无机填充材料。The resin composition may contain (C) an inorganic filler. From the viewpoint of reducing the average linear thermal expansion coefficient of the cured product of the resin composition, the resin composition preferably contains an inorganic filler.

无机填充材料的材料只要是无机化合物，则没有特别限定，可以举出例如二氧化硅、氧化铝、玻璃、堇青石、硅氧化物、硫酸钡、碳酸钡、滑石、粘土、云母粉、氧化锌、水滑石、勃姆石、氢氧化铝、氢氧化镁、碳酸钙、碳酸镁、氧化镁、氮化硼、氮化铝、氮化锰、硼酸铝、碳酸锶、钛酸锶、钛酸钙、钛酸镁、钛酸铋、氧化钛、氧化锆、钛酸钡、钛酸锆酸钡、锆酸钡、锆酸钙、磷酸锆、和磷酸钨酸锆等。这些之中，特别适合为二氧化硅。作为二氧化硅，可以举出例如无定形二氧化硅、熔融二氧化硅、晶体二氧化硅、合成二氧化硅、中空二氧化硅等。此外，作为二氧化硅，优选为球状二氧化硅。无机填充材料可以单独使用1种，也可以组合使用2种以上。作为二氧化硅的市售品，可以举出アドマテックス公司制“SO-C2”、“SO-C1”、デンカ公司制“UFP-30”、“UFP-40”等。The material of the inorganic filler is not particularly limited as long as it is an inorganic compound, and can include, for example, silicon dioxide, aluminum oxide, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among these, silicon dioxide is particularly suitable. As silicon dioxide, amorphous silicon dioxide, fused silica, crystalline silicon dioxide, synthetic silicon dioxide, hollow silicon dioxide, etc. can be included. In addition, as silicon dioxide, spherical silicon dioxide is preferably used. One inorganic filler can be used alone, or two or more can be used in combination. Examples of commercially available silica include "SO-C2" and "SO-C1" manufactured by Admatex Corporation, and "UFP-30" and "UFP-40" manufactured by Denka Corporation.

无机填充材料的平均粒径通常为20μm以下，从提高本发明的期望效果的观点出发，优选为10μm以下、更优选为5.0μm以下、进一步优选为2.5μm以下、进一步优选为2.0μm以下。平均粒径的下限没有特别限定，可以设为1nm(0.001μm)以上、或5nm以上、或10nm以上等。The average particle size of the inorganic filler is usually 20 μm or less, preferably 10 μm or less, more preferably 5.0 μm or less, further preferably 2.5 μm or less, and further preferably 2.0 μm or less from the viewpoint of improving the desired effect of the present invention. The lower limit of the average particle size is not particularly limited, and can be set to 1 nm (0.001 μm) or more, or 5 nm or more, or 10 nm or more.

无机填充材料的平均粒径可以通过基于Mie散射理论的激光衍射・散射法而测定。具体而言，通过激光衍射散射式粒径分布测定装置，以体积基准制作无机填充材料的粒径分布，将其中值直径作为平均粒径，由此能够测定。测定样品可以优选使用将无机填充材料通过超声分散在甲基乙基酮中而得到的物质。作为激光衍射散射式粒径分布测定装置，可以使用堀场制作所公司制“LA-500”、岛津制作所公司制“SALD-2200”等。The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis by a laser diffraction scattering particle size distribution measuring device, and the median diameter thereof is used as the average particle size, thereby enabling measurement. The measurement sample can preferably be a substance obtained by ultrasonically dispersing the inorganic filler in methyl ethyl ketone. As a laser diffraction scattering particle size distribution measuring device, the "LA-500" manufactured by Horiba, Ltd., the "SALD-2200" manufactured by Shimadzu Corporation, etc. can be used.

无机填充材料从使埋设性达到良好的观点等出发，优选用表面处理剂进行处理，更优选用含氟的硅烷偶联剂、氨基硅烷系偶联剂、环氧硅烷系偶联剂、巯基硅烷系偶联剂、硅烷系偶联剂、烷氧基硅烷化合物、有机硅氮烷化合物、钛酸酯系偶联剂等中的1种以上的表面处理剂进行处理，进一步优选用氨基硅烷系硅烷偶联剂进行处理。表面处理剂优选具有其他成分、例如与树脂反应的官能团、例如具有环氧基、氨基或巯基，更优选该官能团与末端基团键合。作为表面处理剂的市售品，可以举出例如信越化学工业公司制硅烷系偶联剂“KBM403”(3-环氧丙氧基丙基三甲氧基硅烷)、信越化学工业公司制硅烷系偶联剂“KBM803”(3-巯基丙基三甲氧基硅烷)、信越化学工业公司制硅烷系偶联剂“KBE903”(3-氨基丙基三乙氧基硅烷)、信越化学工业公司制硅烷系偶联剂“KBM573”(N-苯基-3-氨基丙基三甲氧基硅烷)、信越化学工业公司制硅烷系偶联剂“SZ-31”(六甲基二硅氮烷)、信越化学工业公司制烷氧基硅烷化合物“KBM103”(苯基三甲氧基硅烷)、信越化学工业公司制硅烷系偶联剂“KBM-4803”(长链环氧型硅烷偶联剂)、信越化学工业公司制硅烷系偶联剂“KBM-7103”(3,3,3-三氟丙基三甲氧基硅烷)等。The inorganic filler material is preferably treated with a surface treatment agent from the viewpoint of achieving good embedding properties, and more preferably treated with one or more surface treatment agents selected from fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane compounds, organosilazane compounds, titanate coupling agents, etc., and further preferably treated with an aminosilane silane coupling agent. The surface treatment agent preferably has other components, such as a functional group that reacts with a resin, such as an epoxy group, an amino group or a mercapto group, and more preferably the functional group is bonded to a terminal group. Examples of commercially available surface treatment agents include silane coupling agent “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent “KBM573” (N-phenyl- 3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. silane coupling agent "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. alkoxysilane compound "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. silane coupling agent "KBM-4803" (long-chain epoxy silane coupling agent), Shin-Etsu Chemical Co., Ltd. silane coupling agent "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), etc.

利用表面处理剂的表面处理的程度从使埋设性达到良好的观点等出发，相对于(C)成分100质量份，优选用0.2质量份~5质量份的表面处理剂进行表面处理，优选用0.2质量份~4质量份进行表面处理，优选用0.3质量份~3质量份进行表面处理。The degree of surface treatment with a surface treatment agent is preferably 0.2 to 5 parts by mass of a surface treatment agent, preferably 0.2 to 4 parts by mass, and preferably 0.3 to 3 parts by mass, relative to 100 parts by mass of component (C), from the viewpoint of achieving good embedding properties.

利用表面处理剂的表面处理的程度可以通过无机填充材料的单位表面积的碳量而评价。无机填充材料的单位表面积的碳量从使埋设性达到良好的观点等出发，优选为0.02mg/m2以上，更优选为0.1mg/m2以上，进一步优选为0.2mg/m2以上。另一方面，从抑制树脂清漆的熔融粘度和片材形态下的熔融粘度的上升的观点出发，优选为1mg/m2以下、更优选为0.8mg/m2以下、进一步优选为0.5mg/m2以下。The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/ m2 or more, more preferably 0.1 mg/ m2 or more, and further preferably 0.2 mg/ m2 or more from the viewpoint of achieving good embedding properties. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, it is preferably 1 mg/ m2 or less, more preferably 0.8 mg/ m2 or less, and further preferably 0.5 mg/ m2 or less.

无机填充材料的单位表面积的碳量可以将表面处理后的无机填充材料通过溶剂(例如甲基乙基酮(MEK))进行洗涤处理后测定。具体而言，作为溶剂，将充分量的MEK添加至用表面处理剂进行了表面处理的无机填充材料，在25℃下进行5分钟超声洗涤。去除上清液，使不挥发成分干燥后，可以使用碳分析计而测定无机填充材料的单位表面积的碳量。作为碳分析计，可以使用堀场制作所公司制“EMIA-320V”等。The amount of carbon per unit surface area of the inorganic filler can be measured by washing the surface-treated inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, as a solvent, a sufficient amount of MEK is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic washing is performed for 5 minutes at 25°C. After removing the supernatant and drying the non-volatile components, 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, Ltd., etc. can be used.

作为(C)成分的比表面积，优选为1m2/g以上、更优选为2m2/g以上、特别优选为3m2/g以上。上限没有特别限制，优选为60m2/g以下、50m2/g以下或40m2/g以下。比表面积通过按照BET法，使用BET全自动比表面积测定装置(マウンテック公司制“Macsorb HM-1210”)，在试样表面上吸附氮气，使用BET多点法，算出比表面积，从而得到。The specific surface area of the component (C) is preferably 1 m 2 /g or more, more preferably 2 m 2 /g or more, and particularly preferably 3 m 2 /g or more. The upper limit is not particularly limited, but is preferably 60 m 2 /g or less, 50 m 2 /g or less, or 40 m 2 /g or less. The specific surface area is obtained by adsorbing nitrogen on the surface of the sample using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by MacTech) according to the BET method, and calculating the specific surface area using the BET multipoint method.

(C)成分的含量从减小树脂组合物的固化物的平均线热膨胀系数的观点等出发，将树脂组合物中的不挥发分设为100质量%的情况下，优选为40质量%以上、更优选为50质量%以上、进一步优选为60质量%以上、特别优选为70质量%以上或71质量%以上。上限没有特别限定，通常为95质量%以下，可以设为94质量%以下或93质量%以下。本发明中如实施例中例证那样，将树脂组合物中的不挥发成分设为100质量%的情况下，(C)成分的含量即使为70质量%以上，也确认得到翘曲被抑制、且长期可靠性优异的固化物。The content of (C) component is from the viewpoint of reducing the average linear thermal expansion coefficient of the cured product of the resin combination, when the non-volatile matter in the resin combination is set to 100 mass %, preferably more than 40 mass %, more preferably more than 50 mass %, further preferably more than 60 mass %, particularly preferably more than 70 mass % or more than 71 mass %. The upper limit is not particularly limited, usually below 95 mass %, and can be set to below 94 mass % or below 93 mass %. In the present invention, as exemplified in the embodiments, when the non-volatile matter in the resin combination is set to 100 mass %, even if the content of (C) component is more than 70 mass %, it is confirmed that the cured product with suppressed warping and excellent long-term reliability is obtained.

＜(D)热塑性树脂＞＜(D) Thermoplastic resin＞

树脂组合物作为任选的成分，可以含有(D)热塑性树脂。在将树脂组合物以树脂片材或膜形状处理的情况下，树脂组合物优选包含(D)成分。但是，只要后述值Zf处于规定的范围，则树脂组合物也可以不含(D)成分。The resin composition may contain (D) a thermoplastic resin as an optional component. When the resin composition is processed in the form of a resin sheet or a film, the resin composition preferably contains the (D) component. However, as long as the value Z f described below is within a specified range, the resin composition may not contain the (D) component.

(D)成分的聚苯乙烯换算的重均分子量(Mw)优选为1000以上、更优选为1500以上、进一步优选为2000以上、3000以上。上限优选为1000000以下、更优选为900000以下。(D)成分的聚苯乙烯换算的数均分子量(Mn)优选为1000以上、更优选为1500以上、进一步优选为2000以上、3000以上。上限优选为1000000以下、更优选为900000以下。(D)成分的聚苯乙烯换算的重均分子量(Mw)和数均分子量(Mn)通过凝胶渗透色谱(GPC)法测定。具体而言，(D)成分的聚苯乙烯换算的重均分子量(Mw)和数均分子量(Mn)可以作为测定装置而使用岛津制作所公司制LC-9A/RID-6A，作为柱而使用昭和电工公司制Shodex K-800P/K-804L/K-804L，作为流动相而使用氯仿等，将柱温度设为40℃而测定，使用标准聚苯乙烯的标准曲线算出。The polystyrene-equivalent weight average molecular weight (Mw) of the component (D) is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, 3000 or more. The upper limit is preferably 1000000 or less, more preferably 900000 or less. The polystyrene-equivalent number average molecular weight (Mn) of the component (D) is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, 3000 or more. The upper limit is preferably 1000000 or less, more preferably 900000 or less. The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the component (D) are measured by gel permeation chromatography (GPC). Specifically, the polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the component (D) can be measured using LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring apparatus, Shodex K-800P/K-804L/K-804L manufactured by Showa Denko K.K. as a column, chloroform or the like as a mobile phase, and the column temperature set to 40°C, and calculated using a standard curve of standard polystyrene.

作为(D)热塑性树脂，可以举出例如苯氧基树脂、聚乙烯醇缩醛树脂、聚烯烃树脂、聚酰亚胺树脂、聚酰胺酰亚胺树脂、聚醚酰亚胺树脂、聚砜树脂、聚醚砜树脂、聚苯醚树脂、聚醚醚酮树脂、聚酯树脂等，优选为苯氧基树脂。热塑性树脂可以单独使用1种，或也可以组合使用2种以上。(D) Thermoplastic resins include, for example, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polyimide resins, polyamide-imide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polyetheretherketone resins, polyester resins, etc., preferably phenoxy resins. Thermoplastic resins may be used alone or in combination of two or more.

作为苯氧基树脂，可以举出例如具有双酚A骨架、双酚F骨架、双酚S骨架、双酚苯乙酮骨架、酚醛清漆骨架、联苯骨架、芴骨架、二环戊二烯骨架、降冰片烯骨架、萘骨架、蒽骨架、金刚烷骨架、萜烯骨架、和三甲基环己烷骨架中的1种以上的骨架的苯氧基树脂。苯氧基树脂的末端可以为酚性羟基、环氧基等中任一官能团。苯氧基树脂可以单独使用1种，也可以组合使用2种以上。作为苯氧基树脂的具体例，可以举出三菱化学公司制的“1256”和“4250”(均为含双酚A骨架的苯氧基树脂)、“YX8100”(含双酚S骨架的苯氧基树脂)、和“YX6954”(含双酚苯乙酮骨架的苯氧基树脂)，除此之外，还可以举出日铁化学&マテリアル公司制的“FX280”和“FX293”、三菱化学公司制的“YX7200B35”、“YL7500BH30”、“YX6954BH30”、“YX7553”、“YX7553BH30”、“YL7769BH30”、“YL6794”、“YL7213”、“YL7290”和“YL7482”等。As the phenoxy resin, for example, a phenoxy resin having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton can be cited. The terminal of the phenoxy resin can be any functional group selected from the group consisting of phenolic hydroxyl group and epoxy group. The phenoxy resin can be used alone or in combination of two or more. Specific examples of phenoxy resins include "1256" and "4250" (both are phenoxy resins containing a bisphenol A skeleton), "YX8100" (a phenoxy resin containing a bisphenol S skeleton), and "YX6954" (a phenoxy resin containing a bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation. In addition, "FX280" and "FX293" manufactured by Nippon Steel Chemical & Material Corporation, "YX7200B35", "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482" manufactured by Mitsubishi Chemical Corporation can also be mentioned.

作为聚乙烯醇缩醛树脂，可以举出例如聚乙烯醇缩甲醛树脂、聚乙烯醇缩丁醛树脂，优选为聚乙烯醇缩丁醛树脂。作为聚乙烯醇缩醛树脂的具体例，可以举出例如电气化学工业公司制的“电化ブチラール4000-2”、“电化ブチラール5000-A”、“电化ブチラール6000-C”、“电化ブチラール6000-EP”、积水化学工业公司制的エスレックBH系列、BX系列(例如BX-5Z)、KS系列(例如KS-1)、BL系列、BM系列等。As the polyvinyl acetal resin, for example, polyvinyl formal resin and polyvinyl butyral resin can be mentioned, and polyvinyl butyral resin is preferred. As specific examples of the polyvinyl acetal resin, for example, "Denka Buchlal 4000-2", "Denka Buchlal 5000-A", "Denka Buchlal 6000-C", "Denka Buchlal 6000-EP" manufactured by Denki Kagaku Kogyo Co., Ltd., Eslake BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, BM series, etc. manufactured by Sekisui Chemical Co., Ltd. can be mentioned.

作为聚酰亚胺树脂的具体例，可以举出新日本理化公司制的“リカコートSN20”和“リカコートPN20”。Specific examples of the polyimide resin include "RICACOAT SN20" and "RICACOAT PN20" manufactured by Shin Nippon Chemical Industries, Ltd.

作为聚酰胺酰亚胺树脂的具体例，可以举出东洋纺公司制的“バイロマックスHR11NN”和“バイロマックスHR16NN”。作为聚酰胺酰亚胺树脂的具体例，此外可以举出日立化成工业公司制的“KS9100”、“KS9300”(含聚硅氧烷骨架的聚酰胺酰亚胺)等改性聚酰胺酰亚胺。Specific examples of polyamide-imide resins include "Biomac HR11NN" and "Biomac HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamide-imide resins include modified polyamide-imides such as "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd.

作为聚醚砜树脂的具体例，可以举出住友化学公司制的“PES5003P”等。作为聚苯醚树脂的具体例，可以举出三菱气体化学公司制的低聚苯醚・苯乙烯树脂“OPE-2St 1200”等。作为聚醚醚酮树脂的具体例，可以举出住友化学公司制的“スミプロイK”等。作为聚醚酰亚胺树脂的具体例，可以举出GE公司制的“ウルテム”等。Specific examples of polyethersulfone resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. Specific examples of polyphenylene ether resins include "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd. Specific examples of polyetheretherketone resins include "SUMIPROI K" manufactured by Sumitomo Chemical Co., Ltd. Specific examples of polyetherimide resins include "Ultime" manufactured by GE.

作为聚砜树脂的具体例，可以举出ソルベイアドバンストポリマーズ公司制的聚砜“P1700”、“P3500”等。Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Band Polymers.

作为聚烯烃树脂，可以举出例如低密度聚乙烯、超低密度聚乙烯、高密度聚乙烯、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸甲酯共聚物等乙烯基系共聚树脂；聚丙烯、乙烯-丙烯嵌段共聚物等聚烯烃系弹性体等。Examples of the polyolefin resin include vinyl copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, and ethylene-methyl acrylate copolymers; and polyolefin elastomers such as polypropylene and ethylene-propylene block copolymers.

作为聚酯树脂，可以举出例如聚对苯二甲酸乙二醇酯树脂、聚萘二甲酸乙二醇酯树脂、聚对苯二甲酸丁二醇酯树脂、聚萘二甲酸丁二醇酯树脂、聚对苯二甲酸三亚甲基酯树脂、聚萘二甲酸三亚甲基酯树脂、聚环己烷对苯二甲酸二甲酯树脂等。Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexane dimethyl terephthalate resin.

作为(D)成分，优选为在分子内具有选自聚丁二烯结构、聚硅氧烷结构、聚(甲基)丙烯酸酯结构、聚亚烷基结构、聚亚烷基氧基结构、聚异戊二烯结构、聚异丁烯结构、和聚碳酸酯结构中的1种以上的结构的树脂，更优选为具有选自聚丁二烯结构、聚(甲基)丙烯酸酯结构、聚亚烷基氧基结构、聚异戊二烯结构、聚异丁烯结构和聚碳酸酯结构中的1种或2种以上的结构的树脂，进一步优选为具有选自聚丁二烯结构和聚碳酸酯结构中的1种以上的结构的树脂。应予说明，“(甲基)丙烯酸酯”是指包含甲基丙烯酸酯和丙烯酸酯以及它们的组合的术语。这些的结构可以包含在主链中，也可以包含在侧链中。As component (D), it is preferred that the resin has one or more structures selected from polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkyleneoxy structure, polyisoprene structure, polyisobutylene structure, and polycarbonate structure in the molecule, and more preferably has one or more structures selected from polybutadiene structure, poly(meth)acrylate structure, polyalkyleneoxy structure, polyisoprene structure, polyisobutylene structure, and polycarbonate structure, and further preferably has one or more structures selected from polybutadiene structure and polycarbonate structure. It should be noted that "(meth)acrylate" refers to a term including methacrylate and acrylate and combinations thereof. These structures may be contained in the main chain or in the side chain.

(D)成分优选具有具备反应性的官能团(以下也称为“反应性官能团”)，由此能够并入由(A)成分和(B)成分构成的交联结构中。应予说明，反应性官能团中，也可以是通过加热或光照射而表现出反应性的物质。The component (D) preferably has a reactive functional group (hereinafter also referred to as a "reactive functional group") so that it can be incorporated into the crosslinked structure composed of the components (A) and (B). The reactive functional group may be a substance that becomes reactive by heating or light irradiation.

作为(D)成分所具有的反应性基团，可以举出羟基、羧基、氨基、乙烯基、丙烯酰基、甲基丙烯酰基。替代乙烯基，也可以是在碳-碳间具有双键的基团。羟基从提高交联结构的耐热性的观点出发，优选为酚性羟基。As the reactive group possessed by the component (D), hydroxyl, carboxyl, amino, vinyl, acryloyl, and methacryloyl can be cited. Instead of vinyl, a group having a double bond between carbon and carbon can also be used. From the viewpoint of improving the heat resistance of the crosslinked structure, the hydroxyl group is preferably a phenolic hydroxyl group.

(D)成分的适合的一个实施方式是含有聚丁二烯结构的树脂，聚丁二烯结构可以包含在主链中，也可以包含在侧链中。应予说明，聚丁二烯结构可以部分或全部被加氢。含有聚丁二烯结构的树脂被称为聚丁二烯树脂。One suitable embodiment of the component (D) is a resin containing a polybutadiene structure, and the polybutadiene structure may be contained in the main chain or in the side chain. It should be noted that the polybutadiene structure may be partially or completely hydrogenated. The resin containing a polybutadiene structure is called a polybutadiene resin.

作为聚丁二烯树脂的具体例，可以举出クレイバレー公司制的“Ricon 130MA8”、“Ricon 130MA13”、“Ricon 130MA20”、“Ricon 131MA5”、“Ricon 131MA10”、“Ricon131MA17”、“Ricon 131MA20”、“Ricon 184MA6”(含酸酐基的聚丁二烯)、日本曹达公司制的“GQ-1000”(导入羟基、羧基的聚丁二烯)、“G-1000”、“G-2000”、“G-3000”(两末端羟基聚丁二烯)、“GI-1000”、“GI-2000”、“GI-3000”(两末端羟基氢化聚丁二烯)、ナガセケムテックス公司制的“FCA-061L”(氢化聚丁二烯骨架环氧树脂)等。此外，作为聚丁二烯树脂，可以使用后述＜热塑性树脂溶液A的制备＞中制备的热塑性树脂溶液A中包含的具有反应性官能团的热塑性树脂A或其改性物。此外，作为聚丁二烯树脂，可以使用日本特开2006-037083号公报中公开的去除了2官能性羟基末端聚丁二烯的羟基而具有残基的树脂或其改性物，其中，从得到柔软性优异的固化物的观点出发，优选使用去除平均分子量800~1000的2官能性羟基末端聚丁二烯的羟基而具有残基的树脂或其改性物、或聚丁二烯结构的含有率为45质量%以上的树脂或其改性物。此外，作为聚丁二烯树脂，可以使用国际公开第2008/153208号中公开的在1分子中具有2个以上的醇性羟基的聚丁二烯多元醇化合物作为原料的具有聚丁二烯结构的树脂或其改性物，其中，从得到柔软性优异的固化物的观点出发，优选使用数均分子量为300~5000的聚丁二烯多元醇化合物作为原料的具有聚丁二烯结构的树脂或其改性物。聚丁二烯树脂中的丁二烯结构的含有率优选为40质量%以上、更优选为50质量%以上、进一步优选为60质量%以上、65质量%以上或70质量%以上，丁二烯结构的含有率的上限根据分子中的其他结构部位而大概确定。Specific examples of the polybutadiene resin include "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131 ... 184MA6" (polybutadiene containing anhydride groups), "GQ-1000" (polybutadiene introduced with hydroxyl groups and carboxyl groups) manufactured by Nippon Soda Co., Ltd., "G-1000", "G-2000", "G-3000" (polybutadiene containing hydroxyl groups at both ends), "GI-1000", "GI-2000", "GI-3000" (hydrogenated polybutadiene containing hydroxyl groups at both ends), "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin) manufactured by Nagase Chemtex Co., Ltd., etc. As the polybutadiene resin, the thermoplastic resin A having a reactive functional group contained in the thermoplastic resin solution A prepared in the "Preparation of Thermoplastic Resin Solution A" described later or a modified product thereof can be used. In addition, as the polybutadiene resin, a resin or a modified product thereof having a residue by removing the hydroxyl group of a bifunctional hydroxyl-terminated polybutadiene disclosed in Japanese Patent Application Laid-Open No. 2006-037083 or a modified product thereof can be used, wherein, from the viewpoint of obtaining a cured product with excellent flexibility, a resin or a modified product thereof having a residue by removing the hydroxyl group of a bifunctional hydroxyl-terminated polybutadiene with an average molecular weight of 800 to 1000 or a resin or a modified product thereof having a polybutadiene structure content of 45% by mass or more can be preferably used. In addition, as the polybutadiene resin, a resin or a modified product thereof having a polybutadiene structure as a raw material using a polybutadiene polyol compound having two or more alcoholic hydroxyl groups in one molecule disclosed in International Publication No. 2008/153208 can be used, wherein, from the viewpoint of obtaining a cured product with excellent flexibility, a resin or a modified product thereof having a polybutadiene structure as a raw material using a polybutadiene polyol compound having a number average molecular weight of 300 to 5000 can be preferably used. The content of the butadiene structure in the polybutadiene resin is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, 65% by mass or more, or 70% by mass or more, and the upper limit of the content of the butadiene structure is roughly determined by other structural parts in the molecule.

(D)成分的适合的一个实施方式是含有聚(甲基)丙烯酸酯结构的树脂。含有聚(甲基)丙烯酸酯结构的树脂被称为聚(甲基)丙烯酸树脂。作为聚(甲基)丙烯酸树脂，可以举出ナガセケムテックス公司制的テイサン树脂、根上工业公司制的“ME-2000”、“W-116.3”、“W-197C”、“KG-25”、“KG-3000”等。(D) component is suitable for a resin containing a poly (meth) acrylate structure. The resin containing a poly (meth) acrylate structure is called a poly (meth) acrylic acid resin. As the poly (meth) acrylic acid resin, there can be cited Teisan resin made by Nagasechemtex, "ME-2000", "W-116.3", "W-197C", "KG-25", "KG-3000" made by Gengaku Kogyo Co., Ltd., etc.

(D)成分的适合的实施方式是含有聚碳酸酯结构的树脂。含有聚碳酸酯结构的树脂被称为聚碳酸酯树脂。作为聚碳酸酯树脂，可以使用旭化成化学ズ公司制的“T6002”、“T6001”(聚碳酸酯二醇)、クラレ公司制的“C-1090”、“C-2090”、“C-3090”(聚碳酸酯二醇)等。此外，作为聚碳酸酯树脂，可以使用后述＜热塑性树脂溶液B的制备＞中制备的热塑性树脂溶液B中包含的具有反应性官能团的热塑性树脂B或其改性物。此外，作为聚碳酸酯树脂，可以使用国际公开第2016/129541号中公开的去除聚碳酸酯二醇的羟基的具有残基的树脂或其改性物，其中，从得到柔软性和耐药品性优异的固化物的观点出发，优选使用去除羟基当量为250~1250的聚碳酸酯二醇的羟基而具有残基的树脂或其改性物。此外，作为聚碳酸酯树脂，可以使用去除聚碳酸酯多元醇的羟基而具有残基的树脂或其改性物。聚碳酸酯树脂中的碳酸酯结构的含有率优选为60质量%以上、更优选为65质量%以上、进一步优选为75质量%以上，碳酸酯结构的含有率的上限根据分子中的其他结构部位而大概确定。A suitable embodiment of the component (D) is a resin containing a polycarbonate structure. A resin containing a polycarbonate structure is called a polycarbonate resin. As the polycarbonate resin, "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, "C-1090", "C-2090", "C-3090" (polycarbonate diol) manufactured by Kurara Co., Ltd., etc. can be used. In addition, as the polycarbonate resin, a thermoplastic resin B having a reactive functional group contained in the thermoplastic resin solution B prepared in the <Preparation of Thermoplastic Resin Solution B> described later can be used, or a modified product thereof. In addition, as the polycarbonate resin, a resin having a residue in which the hydroxyl group of the polycarbonate diol is removed as disclosed in International Publication No. 2016/129541, or a modified product thereof, can be used, wherein, from the viewpoint of obtaining a cured product having excellent flexibility and chemical resistance, it is preferred to use a resin having a residue in which the hydroxyl group of the polycarbonate diol having a hydroxyl equivalent of 250 to 1250 is removed, or a modified product thereof. In addition, as polycarbonate resin, the hydroxyl group of polycarbonate polyol can be removed and the resin or its modified product having residue can be used. The content of carbonate structure in polycarbonate resin is preferably more than 60 mass %, more preferably more than 65 mass %, further preferably more than 75 mass %, and the upper limit of the content of carbonate structure is roughly determined according to other structural parts in the molecule.

此外，作为(D)成分的其他实施方式，是含有硅氧烷结构的树脂。含有硅氧烷结构的树脂被称为硅氧烷树脂。作为硅氧烷树脂，可以举出例如信越硅酮公司制的“SMP-2006”、“SMP-2003PGMEA”、“SMP-5005PGMEA”、胺基末端聚硅氧烷和四元酸酐作为原料的线状聚酰亚胺(国际公开第2010/053185号公报、日本特开2002-012667号公报和日本特开2000-319386号公报等)等。In addition, as another embodiment of component (D), it is a resin containing a siloxane structure. The resin containing a siloxane structure is called a siloxane resin. As the siloxane resin, for example, "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" made by Shin-Etsu Silicone Co., Ltd., amino-terminated polysiloxane and linear polyimide (International Publication No. 2010/053185, Japanese Patent Publication No. 2002-012667 and Japanese Patent Publication No. 2000-319386, etc.) made of tetrabasic acid anhydride can be cited.

作为(D)成分的其他实施方式，是含有亚烷基结构、亚烷基氧基结构的树脂。含有亚烷基结构的树脂被称为亚烷基树脂，含有亚烷基氧基结构的树脂被称为亚烷基氧基树脂。聚亚烷基氧基结构优选为碳原子数2~15的聚亚烷基氧基结构，更优选为碳原子数3~10的聚亚烷基氧基结构，进一步优选为碳原子数5~6的聚亚烷基氧基结构。作为亚烷基树脂、亚烷基氧基树脂的具体例，可以举出旭化成せんい公司制的“PTXG-1000”、“PTXG-1800”等。As other embodiments of the component (D), it is a resin containing an alkylene structure and an alkyleneoxy structure. The resin containing an alkylene structure is called an alkylene resin, and the resin containing an alkyleneoxy structure is called an alkyleneoxy resin. The polyalkyleneoxy structure is preferably a polyalkyleneoxy structure having 2 to 15 carbon atoms, more preferably a polyalkyleneoxy structure having 3 to 10 carbon atoms, and further preferably a polyalkyleneoxy structure having 5 to 6 carbon atoms. As specific examples of alkylene resins and alkyleneoxy resins, "PTXG-1000", "PTXG-1800" and the like manufactured by Asahi Kasei Corporation can be cited.

作为(D)成分的其他实施方式，是含有异戊二烯结构的树脂。含有异戊二烯结构的树脂被称为异戊二烯树脂。作为异戊二烯树脂的具体例，可以举出クラレ公司制的“KL-610”、“KL613”等。Another embodiment of the component (D) is a resin containing an isoprene structure. A resin containing an isoprene structure is called an isoprene resin. Specific examples of the isoprene resin include "KL-610" and "KL613" manufactured by Kuraray Corporation.

作为(D)成分的其他实施方式，是含有异丁烯结构的树脂。含有异丁烯结构的树脂被称为异丁烯树脂。作为异丁烯树脂的具体例，可以举出カネカ公司制的“SIBSTAR-073T”(苯乙烯-异丁烯-苯乙烯三嵌段共聚物)、“SIBSTAR-042D”(苯乙烯-异丁烯二嵌段共聚物)等。Another embodiment of the component (D) is a resin containing an isobutylene structure. A resin containing an isobutylene structure is called an isobutylene resin. Specific examples of isobutylene resins include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation.

(D)成分的含量在将树脂组合物中的树脂成分设为100质量%的情况下，可以设为0.1质量%以上、0.3质量%以上或0.5质量%以上。下限从实现含有(D)成分的期望效果的观点出发，优选为10质量%以上、更优选为20质量%以上、进一步优选为30质量%以上。上限从得到长期可靠性优异的固化物的观点出发，优选为65质量%以下、更优选为60质量%以下、进一步优选为55质量%以下。树脂成分是指从树脂组合物中包含的全部成分中排除(C)无机填充材料和(F)其他添加剂的成分。The content of (D) component can be set to more than 0.1 mass %, more than 0.3 mass % or more than 0.5 mass % when the resin component in the resin combination is set to 100 mass %. The lower limit is preferably more than 10 mass %, more preferably more than 20 mass %, and more preferably more than 30 mass % from the viewpoint of realizing the desired effect containing (D) component. The upper limit is preferably less than 65 mass %, more preferably less than 60 mass %, and more preferably less than 55 mass % from the viewpoint of obtaining a cured product with excellent long-term reliability. Resin component refers to the component excluding (C) inorganic filler and (F) other additives from all the components included in the resin combination.

(D)成分的含量在将树脂组合物中的不挥发成分设为100质量%的情况下，可以设为0.1质量%以上、0.3质量%以上或0.5质量%以上。下限从实现含有(D)成分的期望效果的观点出发，优选为1质量%以上、更优选为3质量%以上、进一步优选为5质量%以上。上限从得到长期可靠性优异的固化物的观点出发，优选为25质量%以下、更优选为20质量%以下、进一步优选为15质量%以下。The content of (D) component can be set to more than 0.1 mass %, more than 0.3 mass % or more than 0.5 mass % when the non-volatile component in the resin combination is set to 100 mass %. The lower limit is preferably more than 1 mass %, more preferably more than 3 mass %, and more preferably more than 5 mass % from the viewpoint of realizing the desired effect containing (D) component. The upper limit is preferably less than 25 mass %, more preferably less than 20 mass %, and more preferably less than 15 mass % from the viewpoint of obtaining a cured product with excellent long-term reliability.

＜(E)固化促进剂＞＜(E) Curing accelerator＞

树脂组合物可以含有(E)固化促进剂。作为固化促进剂，可以举出例如磷系固化促进剂、胺系固化促进剂、咪唑系固化促进剂、胍系固化促进剂、金属系固化促进剂等，优选为磷系固化促进剂、胺系固化促进剂、咪唑系固化促进剂、金属系固化促进剂，更优选为胺系固化促进剂。固化促进剂可以单独使用1种，也可以组合使用2种以上。The resin composition may contain (E) a curing accelerator. Examples of the curing accelerator include phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, guanidine curing accelerators, and metal curing accelerators. Preferably, phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, and metal curing accelerators are used. More preferably, amine curing accelerators are used. One curing accelerator may be used alone, or two or more may be used in combination.

作为磷系固化促进剂，可以举出例如三苯基膦、磷鎓硼酸盐化合物、四苯基磷鎓四苯基硼酸盐、正丁基磷鎓四苯基硼酸盐、四丁基磷鎓癸酸盐、(4-甲基苯基)三苯基磷鎓硫氰酸酯、四苯基磷鎓硫氰酸酯、丁基三苯基磷鎓硫氰酸酯等，优选为三苯基膦、四丁基磷鎓癸酸盐。Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, and preferably triphenylphosphine and tetrabutylphosphonium decanoate.

作为胺系固化促进剂，可以举出例如三乙基胺、三丁基胺等三烷基胺、4-二甲基氨基吡啶(DMAP)、苯甲基二甲基胺、2,4,6,-三(二甲基氨基甲基)苯酚、1,8-二氮杂双环(5,4,0)-十一碳烯等，优选为4-二甲基氨基吡啶、1,8-二氮杂双环(5,4,0)-十一碳烯。Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferred.

作为咪唑系固化促进剂，可以举出例如2-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苯甲基-2-甲基咪唑、1-苯甲基-2-苯基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-十一烷基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-十一烷基咪唑鎓偏苯三甲酸盐、1-氰基乙基-2-苯基咪唑鎓偏苯三甲酸盐、2,4-二氨基-6-[2'-甲基咪唑基-(1')]-乙基-均三嗪、2,4-二氨基-6-[2'-十一烷基咪唑基-(1')]-乙基-均三嗪、2,4-二氨基-6-[2'-乙基-4'-甲基咪唑基-(1')]-乙基-均三嗪、2,4-二氨基-6-[2'-甲基咪唑基-(1')]-乙基-均三嗪异氰脲酸加成物、2-苯基咪唑异氰脲酸加成物、2-苯基-4,5-二羟基甲基咪唑、2-苯基-4-甲基-5-羟基甲基咪唑、2,3-二氢-1H-吡咯并[1,2-a]苯并咪唑、1-十二烷基-2-甲基-3-苯甲基咪唑鎓氯化物、2-甲基咪唑啉、2-苯基咪唑啉等咪唑化合物和咪唑化合物与环氧树脂的加合物体，优选为2-乙基-4-甲基咪唑、1-苯甲基-2-苯基咪唑。Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4- Imidazole compounds such as diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins are preferred, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

作为咪唑系固化促进剂，可以使用市售品，可以举出例如四国化成公司制咪唑化合物“1B2PZ”、三菱化学公司制的“P200-H50”等。As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include an imidazole compound "1B2PZ" manufactured by Shikoku Chemicals Co., Ltd. and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

作为胍系固化促进剂，可以举出例如二氰二胺、1-甲基胍、1-乙基胍、1-环己基胍、1-苯基胍、1-(邻甲苯基)胍、二甲基胍、二苯基胍、三甲基胍、四甲基胍、五甲基胍、1,5,7-三氮杂双环[4.4.0]癸-5-烯、7-甲基-1,5,7-三氮杂双环[4.4.0]癸-5-烯、1-甲基双胍、1-乙基双胍、1-正丁基双胍、1-正十八烷基双胍、1,1-二甲基双胍、1,1-二乙基双胍、1-环己基双胍、1-烯丙基双胍、1-苯基双胍、1-(邻甲苯基)双胍等，优选为二氰二胺、1,5,7-三氮杂双环[4.4.0]癸-5-烯。Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine. Preferred examples include dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

作为金属系固化促进剂，可以举出例如钴、铜、锌、铁、镍、锰、锡等金属的有机金属络合物或有机金属盐。作为有机金属络合物的具体例，可以举出乙酰丙酮合钴(II)、乙酰丙酮合钴(III)等有机钴络合物、乙酰丙酮合铜(II)等有机铜络合物、乙酰丙酮合锌(II)等有机锌络合物、乙酰丙酮合铁(III)等有机铁络合物、乙酰丙酮合镍(II)等有机镍络合物、乙酰丙酮合锰(II)等有机锰络合物等。作为有机金属盐，可以举出例如辛酸锌、辛酸锡、环烷酸锌、环烷酸钴、硬脂酸锡、硬脂酸锌等。As metal curing accelerators, organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin can be cited. As specific examples of organic metal complexes, organic cobalt complexes such as acetylacetonate cobalt (II), acetylacetonate cobalt (III), organic copper complexes such as acetylacetonate copper (II), organic zinc complexes such as acetylacetonate zinc (II), organic iron complexes such as acetylacetonate iron (III), organic nickel complexes such as acetylacetonate nickel (II), organic manganese complexes such as acetylacetonate manganese (II), etc. can be cited. As organic metal salts, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc. can be cited.

树脂组合物含有(E)成分的情况下，(E)成分的含量在将树脂组合物中的不挥发分设为100质量%的情况下，通常为0.001质量%以上，优选为0.01质量%以上、更优选为0.02质量%以上。上限优选为3质量%以下、更优选为2质量%以下、进一步优选为1质量%以下。由此，能够切实促进树脂组合物的固化。When the resin composition contains (E) component, the content of (E) component is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.02% by mass or more, when the non-volatile matter in the resin composition is set to 100% by mass. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less. Thus, the curing of the resin composition can be effectively promoted.

＜(F)任选的添加剂＞<(F) Optional additives>

一个实施方式中，树脂组合物进一步根据需要，可以包含(F)其他添加剂(但是，(A)成分~(E)成分除外)，作为所述其他添加剂，可以举出例如有机填充材料、有机铜化合物、有机锌化合物和有机钴化合物等有机金属化合物、以及增稠剂、消泡剂、流平剂、密合性赋予剂、和着色剂等树脂添加剂等。In one embodiment, the resin composition may further contain (F) other additives (however, excluding components (A) to (E)) as needed. Examples of the other additives include organic fillers, organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, and resin additives such as thickeners, defoamers, leveling agents, adhesion-imparting agents, and colorants.

作为有机填充材料，可以使用在形成印刷配线板的绝缘层时能够使用的任意的有机填充材料，可以举出例如橡胶颗粒、聚酰胺微粒、硅酮颗粒等。作为橡胶颗粒，可以使用市售品，可以举出例如ダウ・化学日本公司制的“EXL2655”、アイカ工业公司制的“AC3401N”、“AC3816N”等。As the organic filler, any organic filler that can be used when forming the insulating layer of the printed wiring board can be used, and examples thereof include rubber particles, polyamide microparticles, silicone particles, etc. As the rubber particles, commercially available products can be used, and examples thereof include "EXL2655" manufactured by Dai Chemical Japan Co., Ltd., "AC3401N" and "AC3816N" manufactured by Ika Industries Co., Ltd., etc.

(F)成分的含量只要不过度损害本发明的期望效果，则是任意的，在将树脂组合物中的不挥发成分设为100质量%的情况下，可以设为例如0.1质量%以上、0.3质量%以上或0.5质量%以上、例如15质量%以下、13质量%以下或10质量%以下。The content of the component (F) is arbitrary as long as it does not excessively impair the desired effect of the present invention, and can be, for example, 0.1% by mass or more, 0.3% by mass or more, or 0.5% by mass or more, for example, 15% by mass or less, 13% by mass or less, or 10% by mass or less, when the non-volatile component in the resin composition is set to 100% by mass.

＜树脂组合物的特性＞＜Characteristics of resin composition＞

(值Zf)(Value Z f )

本发明的树脂组合物针对在180℃下固化90分钟而得到的固化物，满足平均线热膨胀系数α除以交联密度n而得到的值Zf(ppm・cm3/mol・K)为145＜Zf＜1300，优选满足150≤Zf≤1000。由此，本发明的树脂组合物如实施例一栏中例示性证实那样，与比较例相比，可以得到翘曲被抑制、且长期可靠性优异的固化物。优选地，在此，Zf可以按照后述＜值Zf的获取＞而获取。Zf通常大于145(ppm・cm3/mol・K)、优选为150(ppm・cm3/mol・K)以上，从提高本发明的期望效果(翘曲的抑制和长期可靠性)的观点出发，优选为155(ppm・cm3/mol・K)以上、更优选为160(ppm・cm3/mol・K)以上，通常低于1300(ppm・cm3/mol・K)、优选为1000(ppm・cm3/mol・K)以下，从提高本发明的期望效果的观点出发，优选为700(ppm・cm3/mol・K)以下、更优选为500(ppm・cm3/mol・K)以下。在此，值Zf可以通过例如树脂组合物所包含的(A)成分和(B)成分等成分的种类和量而调整。值Zf是平均线热膨胀系数α与交联密度n的关系式所示的参数，是翘曲的抑制和长期可靠性相关的参数，因此可以把握为已经反映与下述相关的参数的指标之一：(i)一般而言降低平均线热膨胀系数α的成分、即(C)成分的有无和其含量；(ii)能够抑制由环氧树脂和固化剂形成的交联结构的形成、或能够抑制交联密度的提高的成分或部位(例如(C)成分和(D)成分)的有无和其含量；和(iii)能够促进前述交联结构的形成的成分(例如(E)成分)的有无和其含量。The resin composition of the present invention satisfies the value Z f (ppm・cm 3 /mol・K) obtained by dividing the average linear thermal expansion coefficient α by the crosslinking density n of 145＜Z f ＜1300, preferably 150≤Z f ≤1000 for the cured product obtained by curing at 180°C for 90 minutes. Therefore, the resin composition of the present invention can obtain a cured product with suppressed warpage and excellent long-term reliability compared with the comparative example, as exemplarily demonstrated in the first column of the examples. Preferably, Z f can be obtained according to the <Obtaining the value Z f > described later. Zf is usually greater than 145 (ppm・cm 3 /mol・K), preferably 150 (ppm・cm 3 /mol・K) or more, preferably 155 (ppm・cm 3 /mol・K) or more, more preferably 160 (ppm・cm 3 /mol・K) or more from the viewpoint of enhancing the desired effect of the present invention (suppression of warpage and long-term reliability), and is usually less than 1300 (ppm・cm 3 /mol・K), preferably 1000 (ppm・cm 3 /mol・K) or less, and preferably 700 (ppm・cm 3 /mol・K) or less, more preferably 500 (ppm・cm 3 /mol・K) or less from the viewpoint of enhancing the desired effect of the present invention. Here, the value Zf can be adjusted by, for example, the types and amounts of components such as the (A) component and the (B) component contained in the resin composition. The value Zf is a parameter represented by the relationship between the average linear thermal expansion coefficient α and the crosslinking density n, and is a parameter related to the suppression of warpage and long-term reliability. Therefore, it can be understood as one of the indicators that reflects the following related parameters: (i) the presence and content of a component that generally reduces the average linear thermal expansion coefficient α, that is, the (C) component; (ii) the presence and content of components or parts that can suppress the formation of a crosslinked structure formed by an epoxy resin and a curing agent, or can suppress the increase in crosslinking density (for example, the (C) component and the (D) component); and (iii) the presence and content of a component that can promote the formation of the aforementioned crosslinked structure (for example, the (E) component).

(玻璃化转变温度Tg)(Glass transition temperature Tg)

本发明的树脂组合物从得到耐热性优异的固化物的观点出发，在180℃下固化90分钟而得到的固化物的玻璃化转变温度Tg(℃)优选处于150~240℃的范围内。玻璃化转变温度Tg(℃)可以在后述＜动态弹性模量的测定＞时获取。玻璃化转变温度Tg(℃)通常为150℃以上，从得到耐热性优异的固化物的观点出发，优选大于165℃、更优选为176℃以上。玻璃化转变温度Tg(℃)的上限通常为240℃以下，例如从得到处理性优异的固化物的观点出发，可以设为210℃以下、209℃以下、或205℃以下。The resin composition of the present invention preferably has a glass transition temperature Tg (°C) of a cured product obtained by curing at 180°C for 90 minutes in the range of 150 to 240°C from the viewpoint of obtaining a cured product having excellent heat resistance. The glass transition temperature Tg (°C) can be obtained in the <Determination of dynamic elastic modulus> described later. The glass transition temperature Tg (°C) is usually 150°C or higher, and is preferably greater than 165°C, more preferably 176°C or higher from the viewpoint of obtaining a cured product having excellent heat resistance. The upper limit of the glass transition temperature Tg (°C) is usually 240°C or lower, and can be set to 210°C or lower, 209°C or lower, or 205°C or lower, for example, from the viewpoint of obtaining a cured product having excellent handleability.

(平均线热膨胀系数α)(Average linear thermal expansion coefficient α)

本发明的树脂组合物从提高本发明的期望效果的观点出发，在180℃下固化90分钟而得到的固化物的平均线热膨胀系数α优选小。在此，平均线热膨胀系数α的值可以例如通过树脂组合物所包含的(A)成分和(B)成分等成分的种类和量而进行降低的调整。平均线热膨胀系数α可以按照后述＜平均线热膨胀系数(CTE)α的测定＞来测定。所述固化物的平均线热膨胀系数α通常低于30ppm/K、优选为25ppm/K以下、更优选为20ppm/K以下，下限没有特别限定，可以设为例如1ppm/K以上或2ppm/K以上。所述固化物的平均线热膨胀系数α从上述值Zf满足上述数值范围的观点出发，可以设为例如5ppm/K以上或7ppm/K以上。The resin composition of the present invention preferably has a small average linear thermal expansion coefficient α of a cured product obtained by curing at 180° C. for 90 minutes from the viewpoint of improving the desired effect of the present invention. Here, the value of the average linear thermal expansion coefficient α can be adjusted to be lowered, for example, by adjusting the type and amount of components such as the (A) component and the (B) component contained in the resin composition. The average linear thermal expansion coefficient α can be measured according to the <Measurement of the average linear thermal expansion coefficient (CTE) α> described later. The average linear thermal expansion coefficient α of the cured product is usually lower than 30 ppm/K, preferably lower than 25 ppm/K, and more preferably lower than 20 ppm/K. The lower limit is not particularly limited and can be set to, for example, 1 ppm/K or more or 2 ppm/K or more. From the viewpoint that the above-mentioned value Z f satisfies the above-mentioned numerical range, the average linear thermal expansion coefficient α of the cured product can be set to, for example, 5 ppm/K or more or 7 ppm/K or more.

(规定的温度T(K)下的储能模量E')(Storage modulus E' at a specified temperature T (K))

本发明的树脂组合物针对在180℃下固化90分钟而得到的固化物，规定的温度T(K)下的储能模量E'通常为2.00×109Pa以下。规定的温度T(K)是表示该固化物的玻璃化转变温度Tg(℃)与353(K)之和的温度(即，应当将玻璃化转变温度Tg(℃)换算为单位K而加算273K，且加算80K的值)。在此，规定的温度T(K)下的储能模量E'的值可以通过例如树脂组合物所包含的(A)成分和(B)成分等成分的种类和量而调整。从提高本发明的期望效果的观点出发，所述储能模量E'优选低于1.50×109Pa、更优选为1.40×109Pa以下、进一步优选为1.30×109Pa以下或1.20×109Pa以下，通常为0.10×109Pa以上，从提高本发明的期望效果的观点出发，优选大于0.30×109Pa、更优选为0.35×109Pa以上、进一步优选为0.40×109Pa以上。所述固化物从上述值Zf满足上述数值范围而提高本发明的期望效果的观点出发，优选平均线热膨胀系数α为25ppm/K以下、且规定的温度T(K)下的储能模量E'低于1.50×109Pa，或优选平均线热膨胀系数α为25ppm/K以下、且规定的温度T(K)下的储能模量E'大于0.30×109Pa。规定的温度T(K)处于例如473K~673K的范围内。The storage modulus E' at a predetermined temperature T (K) of the resin composition of the present invention for a cured product obtained by curing at 180°C for 90 minutes is usually 2.00×10 9 Pa or less. The predetermined temperature T (K) is a temperature representing the sum of the glass transition temperature Tg (°C) of the cured product and 353 (K) (i.e., the value obtained by converting the glass transition temperature Tg (°C) into a unit of K and adding 273K and 80K). Here, the value of the storage modulus E' at the predetermined temperature T (K) can be adjusted by, for example, the types and amounts of components such as the (A) component and the (B) component contained in the resin composition. From the viewpoint of improving the desired effect of the present invention, the storage modulus E' is preferably less than 1.50×10 9 Pa, more preferably 1.40×10 9 Pa or less, further preferably 1.30×10 9 Pa or less or 1.20×10 9 Pa or less, and is usually 0.10×10 9 Pa or more. From the viewpoint of improving the desired effect of the present invention, it is preferably greater than 0.30×10 9 Pa, more preferably 0.35×10 9 Pa or more, and further preferably 0.40×10 9 Pa or more. From the viewpoint of improving the desired effect of the present invention by satisfying the above numerical range, the cured product preferably has an average linear thermal expansion coefficient α of 25 ppm/K or less and a storage modulus E' at a predetermined temperature T (K) of less than 1.50×10 9 Pa, or has an average linear thermal expansion coefficient α of 25 ppm/K or less and a storage modulus E' at a predetermined temperature T (K) of more than 0.30×10 9 Pa. The predetermined temperature T (K) is within the range of 473K to 673K, for example.

(交联密度n)(crosslink density n)

本发明的树脂组合物从提高本发明的期望效果的观点出发，在180℃下固化90分钟而得到的固化物的交联密度n优选为0.15mol/cm3以下。在此，交联密度n的值可以通过例如树脂组合物所包含的(A)成分和(B)成分等成分的种类和量而调整。交联密度n可以通过使用后述＜动态弹性模量的测定＞中的测定结果而获取。从提高本发明的期望效果的观点出发，所述交联密度n优选为0.15mol/cm3以下、更优选为0.07mol/cm3以下、进一步优选为0.05mol/cm3以下或0.04mol/cm3以下，通常为0.01mol/cm3以上，从提高本发明的期望效果的观点出发，优选为0.02mol/cm3以上、更优选为0.03mol/cm3以上。The resin composition of the present invention preferably has a crosslinking density n of a cured product obtained by curing at 180° C. for 90 minutes, from the viewpoint of improving the desired effect of the present invention, which is preferably 0.15 mol/cm 3 or less. Here, the value of the crosslinking density n can be adjusted by, for example, the type and amount of components such as the (A) component and the (B) component contained in the resin composition. The crosslinking density n can be obtained by using the measurement results in the <Determination of dynamic elastic modulus> described later. From the viewpoint of improving the desired effect of the present invention, the crosslinking density n is preferably 0.15 mol/cm 3 or less, more preferably 0.07 mol/cm 3 or less, further preferably 0.05 mol/cm 3 or less or 0.04 mol/cm 3 or less, and is usually 0.01 mol/cm 3 or more, and from the viewpoint of improving the desired effect of the present invention, it is preferably 0.02 mol/cm 3 or more, and more preferably 0.03 mol/cm 3 or more.

本发明的树脂组合物可以得到由翘曲被抑制、且长期可靠性优异的固化物形成的绝缘层。因此，本发明的树脂组合物可以适合用作用于形成印刷配线板的绝缘层的树脂组合物(印刷配线板的绝缘层形成用树脂组合物)，可以更适合用作用于形成印刷配线板的层间绝缘层的树脂组合物(印刷配线板的层间绝缘层形成用树脂组合物)。此外，本发明的树脂组合物具有由翘曲被抑制、且长期可靠性优异的固化物形成的绝缘层，因此也可以适合用于印刷配线板为部件内藏电路板的情况。进一步，本发明的树脂组合物具有由翘曲被抑制、且长期可靠性优异的固化物形成的绝缘层，因此可以更适合用作用于形成阻焊剂层的树脂组合物(印刷配线板的阻焊剂层形成用树脂组合物)。此外，本发明的树脂组合物具有由翘曲被抑制的固化物形成的绝缘层，因此可以适合用作用于形成将半导体芯片封装用的半导体芯片密封的密封层的树脂组合物(半导体芯片封装的密封层形成用树脂组合物)。此外，本发明的树脂组合物可以适合用作用于形成半导体芯片封装的再配线形成层的树脂组合物(半导体芯片封装用的再配线形成层形成用的树脂组合物)。The resin composition of the present invention can obtain an insulating layer formed by a cured product having excellent long-term reliability and suppressed warping. Therefore, the resin composition of the present invention can be suitable as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board), and can be more suitable as a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for forming an interlayer insulating layer of a printed wiring board). In addition, the resin composition of the present invention has an insulating layer formed by a cured product having excellent long-term reliability and suppressed warping, so it can also be suitable for the case where a printed wiring board is a component built-in circuit board. Further, the resin composition of the present invention has an insulating layer formed by a cured product having excellent long-term reliability and suppressed warping, so it can be more suitable as a resin composition for forming a solder resist layer (resin composition for forming a solder resist layer of a printed wiring board). In addition, the resin composition of the present invention has an insulating layer formed by a cured product having suppressed warping, so it can be suitable as a resin composition for forming a sealing layer for sealing a semiconductor chip for semiconductor chip encapsulation (resin composition for forming a sealing layer of semiconductor chip encapsulation). Furthermore, the resin composition of the present invention can be suitably used as a resin composition for forming a redistribution forming layer of a semiconductor chip package (resin composition for forming a redistribution forming layer for a semiconductor chip package).

包含再配线形成层的半导体芯片封装经过例如以下的(1)~(6)步骤而制造。A semiconductor chip package including a redistribution forming layer is manufactured through, for example, the following steps (1) to (6).

(1)在基材上层叠预固定膜的步骤，(1) a step of laminating a pre-fixed film on a substrate,

(2)将半导体芯片在预固定膜上预固定的步骤，(2) a step of pre-fixing the semiconductor chip on the pre-fixing film,

(3)在半导体芯片上形成密封层的步骤，(3) a step of forming a sealing layer on the semiconductor chip,

(4)将基材和预固定膜从半导体芯片上剥离的步骤，(4) a step of peeling the substrate and the pre-fixed film from the semiconductor chip,

(5)在将半导体芯片的基材和预固定膜剥离的面上形成作为绝缘层的再配线形成层的步骤，和(5) forming a redistribution wiring forming layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film are peeled off, and

(6)在再配线形成层上形成作为导体层的再配线层的步骤(6) Step of forming a redistribution layer as a conductor layer on the redistribution formation layer

此外，在制造包含密封层的半导体芯片封装时，可以在密封层上进一步形成再配线层。Furthermore, when manufacturing a semiconductor chip package including a sealing layer, a redistribution layer may be further formed on the sealing layer.

＜树脂组合物的制造方法＞<Method for producing resin composition>

本发明的树脂组合物的制造方法没有特别限定，可以举出例如将配合成分与根据需要的溶剂等混合，使用旋转混合机等分散的方法等。在制造本发明的树脂组合物时，通过调整(A)成分和(B)成分的选择、以及(A)成分的含量和(B)成分的含量，能够使上述值Zf落入上述范围内。The method for producing the resin composition of the present invention is not particularly limited, and examples thereof include a method of mixing the compounding components with a solvent as required, and dispersing using a rotary mixer, etc. When producing the resin composition of the present invention, the value Zf can be made to fall within the above range by adjusting the selection of the component (A) and the component (B), and the content of the component (A) and the content of the component (B).

树脂组合物通过包含例如溶剂，能够制成树脂清漆。此外，从实现本发明的期望效果的观点出发，使树脂清漆干燥，优选将树脂组合物以B台的状态下或膜形状而使用。The resin composition can be made into a resin varnish by including, for example, a solvent. In addition, from the viewpoint of achieving the desired effect of the present invention, the resin varnish is dried and the resin composition is preferably used in a B stage state or in a film shape.

＜树脂组合物的固化物的物性、用途＞<Physical properties and uses of cured products of resin compositions>

(长期可靠性)(Long-term reliability)

将本发明的树脂组合物热固化而得到的固化物通常长期可靠性优异。长期可靠性可以按照后述＜长期可靠性的评价＞的记载而评价。例如，将树脂组合物在180℃下90分钟的条件下热固化而得到的固化物优选HTS试验的前后的拉伸断裂点强度的变化度的绝对值小(例如低于20%或10%以下)。The cured product obtained by thermally curing the resin composition of the present invention generally has excellent long-term reliability. The long-term reliability can be evaluated according to the description of "Evaluation of Long-term Reliability" described later. For example, the cured product obtained by thermally curing the resin composition at 180°C for 90 minutes preferably has a small absolute value of the change in tensile breaking point strength before and after the HTS test (for example, less than 20% or less than 10%).

(翘曲的抑制)(Warping Suppression)

将本发明的树脂组合物热固化而得到的固化物在基板上形成的情况下，通常基板的翘曲被抑制。翘曲可以按照后述＜翘曲的评价＞的记载而评价。例如，将树脂组合物在180℃下90分钟的条件下热固化而得到的形成有厚度300μm的固化物的基板中可产生的最大翘曲量可以为2000μm以下。When a cured product obtained by thermally curing the resin composition of the present invention is formed on a substrate, the warping of the substrate is usually suppressed. The warping can be evaluated according to the description of "Evaluation of Warping" described later. For example, the maximum warping amount that can be generated in a substrate having a cured product having a thickness of 300 μm obtained by thermally curing the resin composition at 180° C. for 90 minutes can be 2000 μm or less.

(耐药品性)(Chemical resistance)

将本发明的树脂组合物热固化而得到的固化物通常示出耐药品性优异这一特性。耐药品性可以按照后述＜耐药品性的评价＞的记载而评价。例如，将树脂组合物在180℃下90分钟的条件下热固化而得到的厚度100μm的固化物即使在强碱水溶液(例如氢氧化钾水溶液、氢氧化四甲基铵溶液、氢氧化钠水溶液或碳酸钠水溶液)中浸渍，其前后的质量减少率可以为1质量%以下。The cured product obtained by thermally curing the resin composition of the present invention generally shows the characteristic of excellent chemical resistance. Chemical resistance can be evaluated according to the description of <Evaluation of Chemical Resistance> described later. For example, a cured product with a thickness of 100 μm obtained by thermally curing the resin composition at 180° C. for 90 minutes can have a mass reduction rate of less than 1% by mass before and after being immersed in a strong alkali aqueous solution (e.g., an aqueous potassium hydroxide solution, a tetramethylammonium hydroxide solution, an aqueous sodium hydroxide solution, or an aqueous sodium carbonate solution).

(玻璃化转变温度Tg)(Glass transition temperature Tg)

将本发明的树脂组合物热固化而得到的固化物从耐热性优异的观点出发，玻璃化转变温度Tg(℃)优选处于150~240℃的范围内。更优选的范围等针对树脂组合物如前所述。The cured product obtained by thermally curing the resin composition of the present invention preferably has a glass transition temperature Tg (° C.) in the range of 150 to 240° C. from the viewpoint of excellent heat resistance. The more preferred ranges are as described above for the resin composition.

(平均线热膨胀系数α)(Average linear thermal expansion coefficient α)

将本发明的树脂组合物热固化而得到的固化物从提高本发明的期望效果的观点出发，平均线热膨胀系数α优选小。更优选的范围等针对树脂组合物如前所述。The cured product obtained by thermally curing the resin composition of the present invention preferably has a small average linear thermal expansion coefficient α from the viewpoint of enhancing the desired effects of the present invention. The more preferred ranges are as described above for the resin composition.

(规定的温度T(K)下的储能模量E')(Storage modulus E' at a specified temperature T (K))

将本发明的树脂组合物热固化而得到的固化物的规定的温度T(K)下的储能模量E'通常为2.00×109Pa以下。优选的范围等针对树脂组合物如前所述。The storage modulus E' of a cured product obtained by thermally curing the resin composition of the present invention at a predetermined temperature T (K) is usually not more than 2.00×10 9 Pa. The preferred ranges and the like are as described above for the resin composition.

(交联密度n)(crosslink density n)

将本发明的树脂组合物热固化而得到的固化物从提高本发明的期望效果的观点出发，交联密度n优选为0.15mol/cm3以下。更优选的范围等针对树脂组合物如前所述。The crosslink density n of the cured product obtained by thermally curing the resin composition of the present invention is preferably 0.15 mol/cm 3 or less from the viewpoint of enhancing the desired effect of the present invention. The more preferred ranges are as described above for the resin composition.

(值Zf)(Value Z f )

将本发明的树脂组合物热固化而得到的固化物优选满足前述平均线热膨胀系数α除以前述交联密度n而得到的值Zf(ppm・cm3/mol・K)为145＜Zf＜1300，更优选满足150≤Zf≤1000。这样的固化物如实施例一栏中例示性证实那样，翘曲被抑制，且长期可靠性优异。更优选的范围等针对树脂组合物如前所述。The cured product obtained by thermally curing the resin composition of the present invention preferably satisfies the value Zf (ppm・cm3 /mol・K) obtained by dividing the above average linear thermal expansion coefficient α by the above crosslinking density n of 145＜ Zf ＜1300, and more preferably satisfies 150≤Zf≤1000. Such a cured product has suppressed warpage and excellent long-term reliability as exemplarily demonstrated in the first embodiment. The more preferred ranges, etc., are as described above for the resin composition.

本发明的树脂组合物的固化物的翘曲被抑制、且长期可靠性优异。因此，本发明的树脂组合物的固化物可以适合用作印刷配线板的绝缘层，可以更适合用作印刷配线板的层间绝缘层。此外，本发明的树脂组合物的固化物具有翘曲被抑制、且长期可靠性优异的绝缘层，因此还可以适合用于印刷配线板为部件内藏电路板的情况。进一步，本发明的树脂组合物的固化物具有由翘曲被抑制、且长期可靠性优异的固化物形成的绝缘层，因此可以更适合用作阻焊剂层。此外，本发明的树脂组合物的固化物具有由翘曲被抑制的固化物形成的绝缘层，因此可以适合用作将半导体芯片封装用的半导体芯片密封的密封层。此外，本发明的树脂组合物的固化物可以适合用作用于形成半导体芯片封装的再配线层的再配线形成层(绝缘层)。The curing material of the resin composition of the present invention is suppressed in warpage and has excellent long-term reliability. Therefore, the curing material of the resin composition of the present invention can be suitable for use as the insulating layer of a printed wiring board, and can be more suitable for use as the interlayer insulating layer of a printed wiring board. In addition, the curing material of the resin composition of the present invention has an insulating layer in which warpage is suppressed and has excellent long-term reliability, so it can also be suitable for use in the case where a printed wiring board is a component with a built-in circuit board. Further, the curing material of the resin composition of the present invention has an insulating layer formed by a cured material in which warpage is suppressed and has excellent long-term reliability, so it can be more suitable for use as a solder resist layer. In addition, the curing material of the resin composition of the present invention has an insulating layer formed by a cured material in which warpage is suppressed, so it can be suitable for use as a sealing layer for sealing a semiconductor chip for semiconductor chip encapsulation. In addition, the curing material of the resin composition of the present invention can be suitable for use as a redistribution forming layer (insulating layer) for forming a redistribution layer for semiconductor chip encapsulation.

[树脂片材][Resin sheet]

本发明的树脂片材包含支撑体、和在该支撑体上设置的包含本发明的树脂组合物的树脂组合物层。树脂组合物层可以为B台的状态。The resin sheet of the present invention comprises a support and a resin composition layer comprising the resin composition of the present invention provided on the support. The resin composition layer may be in a B stage state.

树脂片材的树脂组合物层的厚度通常为 150μm以下、优选为110μm以下，从印刷配线板的薄型化的观点出发，可以设为50μm以下或40μm以下。进一步可以减小厚度。树脂组合物层的厚度的下限没有特别限定，通常可以设为1μm以上、1.5μm以上、2μm以上等。The thickness of the resin composition layer of the resin sheet is usually 150 μm or less, preferably 110 μm or less, and can be 50 μm or less or 40 μm or less from the viewpoint of thinning the printed wiring board. The thickness can be further reduced. The lower limit of the thickness of the resin composition layer is not particularly limited, and can usually be 1 μm or more, 1.5 μm or more, 2 μm or more, etc.

作为支撑体，可以举出例如包含塑料材料的膜、金属箔、脱模纸，优选为包含塑料材料的膜、金属箔。Examples of the support include films made of plastic materials, metal foils, and release papers, and films made of plastic materials and metal foils are preferred.

作为支撑体而使用包含塑料材料的膜的情况下，作为塑料材料，可以举出例如聚对苯二甲酸乙二醇酯(以下有时简称为“PET”)、聚萘二甲酸乙二醇酯(以下有时简称为“PEN”)等聚酯、聚碳酸酯(以下有时简称为“PC”)、聚甲基丙烯酸甲酯(PMMA)等丙烯酸酯、环状聚烯烃、三乙酰基纤维素(TAC)、聚醚硫醚(PES)、聚醚酮、聚酰亚胺等。其中，优选为聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯，特别优选为廉价的聚对苯二甲酸乙二醇酯。When a film made of a plastic material is used as a support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate (hereinafter sometimes referred to as "PEN"), polycarbonate (hereinafter sometimes referred to as "PC"), acrylates such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

作为支撑体而使用金属箔的情况下，作为金属箔，可以举出例如铜箔、铝箔等，优选为铜箔。作为铜箔，可以使用包含铜的单金属的箔，也可以使用包含铜与其他金属(例如锡、铬、银、镁、镍、锆、硅、钛等)的合金的箔。When a metal foil is used as a support, examples of the metal foil include copper foil, aluminum foil, etc., preferably copper foil. As the copper foil, a foil of a single metal including copper can be used, or a foil of an alloy including copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

支撑体可以对与树脂组合物层接合的面实施哑光处理、电晕处理、抗静电处理。The surface of the support to be in contact with the resin composition layer may be subjected to matte treatment, corona treatment, or antistatic treatment.

此外，作为支撑体，可以使用在与树脂组合物层接合的面上具有脱模层的带脱模层的支撑体。作为带脱模层的支撑体的脱模层中使用的脱模剂，可以举出例如选自醇酸树脂、聚烯烃树脂、氨基甲酸酯树脂、和硅酮树脂中的1种以上的脱模剂。带脱模层的支撑体可以使用市售品，可以举出例如具有以醇酸树脂系脱模剂作为主成分的脱模层的PET膜的リンテック公司制的“SK-1”、“AL-5”、“AL-7”、东レ公司制的“ルミラーT60”、帝人公司制的“ピューレックス”、ユニチカ公司制的“ユニピール”等。In addition, as a support, a support with a release layer having a release layer on the surface bonded to the resin composition layer can be used. As a release agent used in the release layer of the support with a release layer, for example, one or more release agents selected from alkyd resins, polyolefin resins, urethane resins, and silicone resins can be cited. The support with a release layer can use commercial products, for example, "SK-1", "AL-5", "AL-7" made by Lintech Co., Ltd., "Lumira T60" made by Toray Co., Ltd., "Purex" made by Teijin Co., Ltd., "Unipiru" made by Unichika Co., Ltd., etc.

作为支撑体的厚度，没有特别限定，优选为5μm~75μm的范围，更优选为10μm~60μm的范围。应予说明，在使用带脱模层的支撑体的情况下，带脱模层的支撑体全体的厚度优选为上述范围。The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

一个实施方式中，树脂片材进一步根据需要，可以包含其他层。作为所述其他层，可以举出例如在未与树脂组合物层的支撑体接合的面(即与支撑体相对侧的面)上设置的按照支撑体的保护膜等。保护膜的厚度没有特别限定，例如为1μm~40μm。通过层叠保护膜，可以抑制在树脂组合物层的表面上的污物等的附着、伤痕。In one embodiment, the resin sheet may further include other layers as needed. As the other layers, for example, a protective film according to the support provided on the surface not bonded to the support of the resin composition layer (i.e., the surface on the opposite side of the support) can be cited. The thickness of the protective film is not particularly limited, for example, 1 μm to 40 μm. By laminating the protective film, the attachment and scratches of dirt on the surface of the resin composition layer can be suppressed.

树脂片材可以通过例如制备在溶剂中溶解有树脂组合物的树脂清漆，将该树脂清漆使用模涂机等而在支撑体上涂布，进一步干燥而形成树脂组合物层，从而制造。The resin sheet can be produced by, for example, preparing a resin varnish in which a resin composition is dissolved in a solvent, applying the resin varnish on a support using a die coater or the like, and further drying to form a resin composition layer.

作为有机溶剂，可以举出例如丙酮、甲基乙基酮(MEK)和环己酮等酮类；乙酸乙酯、乙酸丁酯、溶纤剂乙酸酯、丙二醇单甲基醚乙酸酯和卡必醇乙酸酯等乙酸酯类；溶纤剂和丁基卡必醇等卡必醇类；甲苯和二甲苯等芳族烃类；二甲基甲酰胺、二甲基乙酰胺(DMAc)和N-甲基吡咯烷酮等酰胺系溶剂等。有机溶剂可以单独使用1种，也可以组合使用2种以上。Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone, etc. The organic solvent may be used alone or in combination of two or more.

干燥可以通过加热、吹附热风等公知的方法而实施。干燥条件没有特别限定，以树脂组合物层中的有机溶剂的含量达到10质量%以下、优选达到5质量%以下的方式干燥。根据树脂清漆中的有机溶剂的沸点而不同，在使用例如包含30质量%~60质量%的有机溶剂的树脂清漆的情况下，通过在50℃~150℃下干燥3分钟~10分钟，能够形成树脂组合物层。Drying can be carried out by known methods such as heating and blowing hot air. The drying conditions are not particularly limited, and the resin composition layer is dried in a manner such that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin varnish, when using a resin varnish containing, for example, 30% by mass to 60% by mass of an organic solvent, the resin composition layer can be formed by drying at 50° C. to 150° C. for 3 minutes to 10 minutes.

树脂片材可以卷取为辊状而保存。在树脂片材具有保护膜的情况下，可以通过剥离保护膜而使用。The resin sheet can be stored by winding it up in a roll shape. When the resin sheet has a protective film, it can be used by peeling off the protective film.

本发明的树脂片材具有由翘曲被抑制、且长期可靠性优异的固化物形成的绝缘层。因此，本发明的树脂片材可以适合用作用于形成印刷配线板的绝缘层的树脂片材(印刷配线板的绝缘层形成用树脂片材)，可以更适合用作用于形成印刷配线板的层间绝缘层的树脂片材(印刷配线板的层间绝缘层用树脂片材)。此外，本发明的树脂片材可以适合用作用于形成印刷配线板的阻焊剂层的树脂片材(印刷配线板的阻焊剂层形成用树脂片材)。此外，本发明的树脂片材具有由翘曲被抑制固化物形成的绝缘层，因此可以适合用作用于形成将半导体芯片封装用的半导体芯片密封的密封层的树脂组合物(半导体芯片封装的密封层形成用树脂片材)。此外，本发明的树脂片材可以适合用作用于形成半导体芯片封装的再配线形成层(绝缘层)的树脂片材(半导体芯片封装用的再配线形成层形成用树脂片材)。The resin sheet of the present invention has an insulating layer formed by a cured product that is suppressed from warping and has excellent long-term reliability. Therefore, the resin sheet of the present invention can be suitable as a resin sheet (resin sheet for forming the insulating layer of a printed wiring board) for forming the insulating layer of a printed wiring board, and can be more suitable as a resin sheet (resin sheet for forming the interlayer insulating layer of a printed wiring board) for forming the interlayer insulating layer of a printed wiring board. In addition, the resin sheet of the present invention can be suitable as a resin sheet (resin sheet for forming the solder resist layer of a printed wiring board) for forming the solder resist layer of a printed wiring board. In addition, the resin sheet of the present invention has an insulating layer formed by a cured product that is suppressed from warping, so it can be suitable as a resin composition (resin sheet for forming the sealing layer of a semiconductor chip package) for forming a semiconductor chip for semiconductor chip packaging. In addition, the resin sheet of the present invention can be suitable as a resin sheet (resin sheet for forming the redistribution layer for semiconductor chip packaging) for forming the redistribution formation layer (insulating layer) of a semiconductor chip package.

＜印刷配线板＞＜Printed wiring board＞

本发明的印刷配线板包括包含本发明的树脂组合物的固化物而形成的绝缘层。该印刷配线板可以通过例如包括下述步骤(1)和步骤(2)的制造方法而制造。The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention. The printed wiring board can be produced by a production method including the following steps (1) and (2), for example.

(1)在基材上，使用本发明的树脂组合物，形成包含树脂组合物的树脂组合物层的步骤。(1) A step of forming a resin composition layer containing a resin composition on a substrate using the resin composition of the present invention.

(2)将树脂组合物层热固化而形成绝缘层的步骤。(2) A step of thermally curing the resin composition layer to form an insulating layer.

步骤(1)中，准备基材。作为基材，可以举出例如玻璃环氧基板、金属基板(不锈钢、冷轧钢板(SPCC)等)、聚酯基板、聚酰亚胺基板、BT树脂基板、热固型聚苯醚基板等基板。此外，基材可以作为该基材中的一部分而在表面上具有铜箔等金属层。例如，可以使用在两个表面上具有可剥离的第一金属层和第二金属层的基材。在使用这样的基材的情况下，通常作为能够作为电路配线而发挥功能的配线层的导体层在第二金属层与第一金属层相反侧的面上形成。作为具有这样的金属层的基材，可以举出例如三井金属矿业公司制的带载体铜箔的极薄铜箔“Micro Thin”。In step (1), a substrate is prepared. Examples of the substrate include glass epoxy substrates, metal substrates (stainless steel, cold-rolled steel sheets (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. In addition, the substrate may have a metal layer such as copper foil on the surface as a part of the substrate. For example, a substrate having a peelable first metal layer and a second metal layer on both surfaces may be used. When such a substrate is used, a conductor layer, which is a wiring layer capable of functioning as circuit wiring, is usually formed on the surface opposite to the second metal layer and the first metal layer. Examples of the substrate having such a metal layer include, for example, the ultra-thin copper foil "Micro Thin" with a carrier copper foil manufactured by Mitsui Mining & Smelting Co., Ltd.

此外，在基材的一个或两个表面上，可以形成导体层。以下的说明中，包含基材、和在该基材表面上形成的导体层的构件有时适当称为“带配线层的基材”。作为导体层中包含的导体材料，可以举出包含例如选自金、铂、钯、银、铜、铝、钴、铬、锌、镍、钛、钨、铁、锡和铟中的1种以上的金属的材料。作为导体材料，可以使用单金属，也可以使用合金。作为合金，可以举出例如选自上述组中的2种以上的金属的合金(例如镍・铬合金、铜・镍合金和铜・钛合金)。其中，从导体层形成的通用性、成本、图案形成的容易性的观点出发，优选为作为单金属的铬、镍、钛、铝、锌、金、钯、银或铜；和作为合金的镍・铬合金、铜・镍合金、铜・钛合金的合金。其中，更优选为铬、镍、钛、铝、锌、金、钯、银或铜的单金属；和、镍・铬合金，特别优选为铜的单金属。In addition, a conductor layer may be formed on one or both surfaces of the substrate. In the following description, a member including a substrate and a conductor layer formed on the surface of the substrate is sometimes appropriately referred to as a "substrate with a wiring layer". Examples of the conductor material contained in the conductor layer include materials containing one or more metals selected from, for example, gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. As the conductor material, a single metal may be used, or an alloy may be used. Examples of the alloy include, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, from the viewpoint of versatility, cost, and ease of pattern formation in the formation of the conductor layer, a single metal of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper is preferred; and an alloy of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferred. Among them, a single metal of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper is more preferred; and a nickel-chromium alloy, and a single metal of copper is particularly preferred.

导体层为了例如作为配线层而发挥功能，可以进行图案加工。此时，导体层的线(电路宽度)/间距(电路间的宽度)比没有特别限制，优选为20/20μm以下(即间距为40μm以下)、更优选为10/10μm以下、进一步优选为5/5μm以下、更进一步优选为1/1μm以下、特别优选为0.5/0.5μm以上。间距不需要跨导体层的整体相同。导体层的最小间距可以为例如40μm以下、36μm以下、或30μm以下。The conductor layer may be patterned in order to function as a wiring layer, for example. In this case, the line (circuit width)/spacing (width between circuits) ratio of the conductor layer is not particularly limited, and is preferably 20/20 μm or less (i.e., the spacing is 40 μm or less), more preferably 10/10 μm or less, further preferably 5/5 μm or less, further preferably 1/1 μm or less, and particularly preferably 0.5/0.5 μm or more. The spacing does not need to be the same across the entire conductor layer. The minimum spacing of the conductor layer may be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.

导体层的厚度根据印刷配线板的设计而不同，优选为3μm~35μm、更优选为5μm~30μm、进一步优选为10μm~20μm、特别优选为15μm~20μm。The thickness of the conductor layer varies depending on the design of the printed wiring board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, further preferably 10 μm to 20 μm, and particularly preferably 15 μm to 20 μm.

导体层可以例如通过包括下述的方法而形成：在基材上层叠干膜(光敏性阻蚀剂膜)的步骤；使用光掩模对干膜在规定的条件下进行曝光和显影从而形成图案，得到图案干膜的步骤；以经显影的图案干膜作为镀敷掩模，通过电解镀敷法等镀敷法，形成导体层的步骤；和将图案干膜剥离的步骤。作为干膜，可以使用包含光刻胶组合物的光敏性的干膜，可以使用例如由酚醛清漆树脂、丙烯酸树脂等树脂形成的干膜。基材与干膜的层叠条件可以与后述基材和树脂片材的层叠的条件相同。干膜的剥离可以使用例如氢氧化钠溶液等碱性的剥离液而实施。The conductor layer can be formed, for example, by a method including the following: a step of laminating a dry film (photosensitive resist film) on a substrate; a step of exposing and developing the dry film under prescribed conditions using a photomask to form a pattern to obtain a pattern dry film; a step of forming a conductor layer by a plating method such as an electrolytic plating method using the developed pattern dry film as a plating mask; and a step of stripping the pattern dry film. As the dry film, a photosensitive dry film containing a photoresist composition can be used, and a dry film formed of a resin such as a novolac resin or an acrylic resin can be used. The lamination conditions of the substrate and the dry film can be the same as the lamination conditions of the substrate and the resin sheet described later. The stripping of the dry film can be carried out using an alkaline stripping solution such as a sodium hydroxide solution.

在准备基材后，在基材上形成树脂组合物层。在基材的表面上形成导体层的情况下，树脂组合物层的形成优选以导体层埋入树脂组合物层中的方式而进行。After preparing a substrate, a resin composition layer is formed on the substrate. When a conductor layer is formed on the surface of the substrate, the resin composition layer is preferably formed so that the conductor layer is buried in the resin composition layer.

树脂组合物层的形成通过例如将树脂片材和基材层叠而进行。该层叠可以通过例如从支撑体侧将树脂片材在基材上加热压接，在基材上贴合树脂组合物层，由此进行。作为将树脂片材在基材上加热压接的构件(以下有时称为“加热压接构件”)，可以举出例如经加热的金属板(SUS镜面板等)或金属辊(SUS辊等)等。应予说明，优选不将加热压接构件在树脂片材上直接加压，以对基材的表面凹凸树脂片材充分追随的方式，经由耐热橡胶等弹性材料而加压。The formation of the resin composition layer is carried out by, for example, stacking a resin sheet and a substrate. The stacking can be carried out by, for example, heating and pressing the resin sheet on the substrate from the support body side, and laminating the resin composition layer on the substrate. As a member (hereinafter sometimes referred to as "heating and pressing member") for heating and pressing the resin sheet on the substrate, for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller, etc.) can be cited. It should be noted that it is preferred that the heating and pressing member is not directly pressurized on the resin sheet, so that the surface concavo-convex resin sheet of the substrate is fully followed, and pressurized via elastic materials such as heat-resistant rubber.

基材与树脂片材的层叠可以例如通过真空层压法而实施。真空层压法中，加热压接温度优选为60℃~160℃、更优选为80℃~140℃的范围。加热压接压力优选为0.098MPa~1.77MPa、更优选为0.29MPa~1.47MPa的范围。加热压接时间优选为20秒~400秒、更优选为30秒~300秒的范围。层叠优选在压力13hPa以下的减压条件下实施。The lamination of the substrate and the resin sheet can be implemented, for example, by vacuum lamination. In the vacuum lamination method, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C. The heating and pressing pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa. The heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably implemented under reduced pressure conditions of 13hPa or less.

层叠后，可以在常压下(大气压下)，通过例如将加热压接构件从支撑体侧加压，进行经层叠的树脂片材的平滑化处理。平滑化处理的加压条件可以设为与上述层叠的加热压接条件相同的条件。应予说明，层叠和平滑化处理可以使用真空层压机而连续进行。After lamination, the laminated resin sheet can be smoothed under normal pressure (atmospheric pressure) by, for example, applying pressure to the heating and pressing member from the support side. The pressurizing conditions for the smoothing treatment can be set to the same conditions as the heating and pressing conditions for the above-mentioned lamination. It should be noted that lamination and smoothing treatment can be performed continuously using a vacuum laminator.

此外，树脂组合物层的形成可以通过例如压缩成型法进行。成型条件可以采用与在形成后述半导体芯片封装的密封层的步骤中的树脂组合物层的形成方法相同的条件。The resin composition layer can be formed by, for example, compression molding. The molding conditions can be the same as those in the method for forming the resin composition layer in the step of forming the sealing layer of the semiconductor chip package described later.

在基材上形成树脂组合物层后，将树脂组合物层热固化而形成绝缘层。树脂组合物层的热固化条件根据树脂组合物的种类而不同，固化温度通常为120℃~240℃的范围(优选为150℃~220℃的范围、更优选为170℃~200℃的范围)，固化时间为5分钟~120分钟的范围(优选为10分钟~100分钟、更优选为15分钟~90分钟)。After forming the resin composition layer on the substrate, the resin composition layer is thermally cured to form an insulating layer. The thermal curing conditions of the resin composition layer vary depending on the type of the resin composition, and the curing temperature is generally in the range of 120° C. to 240° C. (preferably in the range of 150° C. to 220° C., more preferably in the range of 170° C. to 200° C.), and the curing time is in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

在使树脂组合物层热固化前，可以对树脂组合物层，实施在与固化温度相比更低的温度下加热的预加热处理。例如，可以在使树脂组合物层热固化之前，在通常50℃以上且低于120℃(优选为60℃以上且110℃以下、更优选为70℃以上且100℃以下)的温度下，将树脂组合物层进行通常5分钟以上(优选为5分钟~150分钟、更优选为15分钟~120分钟)预加热。Before the resin composition layer is thermally cured, the resin composition layer may be subjected to a preheating treatment of heating at a temperature lower than the curing temperature. For example, before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature generally above 50° C. and below 120° C. (preferably above 60° C. and below 110° C., more preferably above 70° C. and below 100° C.) for generally 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

以上述的方式，可以制造具有绝缘层的印刷配线板。此外，印刷配线板的制造方法可以进一步包含任意的步骤。In the above-described manner, a printed wiring board having an insulating layer can be manufactured. In addition, the method for manufacturing a printed wiring board may further include an arbitrary step.

例如，在使用树脂片材而制造印刷配线板的情况下，印刷配线板的制造方法可以包括将树脂片材的支撑体剥离的步骤。支撑体可以在树脂组合物层的热固化前剥离，也可以在树脂组合物层的热固化后剥离。For example, when a printed wiring board is manufactured using a resin sheet, the method for manufacturing the printed wiring board may include the step of peeling off the support of the resin sheet. The support may be peeled off before or after the resin composition layer is thermally cured.

印刷配线板的制造方法可以例如在形成绝缘层后，可以包括对其绝缘层的表面进行研磨的步骤。研磨方法没有特别限定。例如，可以使用平面研削盘，对绝缘层的表面进行研磨。The method for manufacturing a printed wiring board may include, for example, a step of grinding the surface of the insulating layer after forming the insulating layer. The grinding method is not particularly limited. For example, the surface of the insulating layer may be ground using a flat grinding disc.

印刷配线板的制造方法可以包括例如将导体层进行层间连接的步骤(3)、例如在绝缘层中开孔的步骤。由此，可以在绝缘层中形成导通孔、通孔等孔。作为导通孔的形成方法，可以举出例如激光照射、蚀刻、机械钻孔等。导通孔的尺寸、形状可以根据印刷配线板的设计而适当决定。应予说明，步骤(3)可以通过绝缘层的研磨或研削而进行层间连接。The method for manufacturing a printed wiring board may include, for example, a step (3) of connecting the conductor layer to an interlayer, and a step of, for example, opening a hole in the insulating layer. Thus, holes such as via holes and through holes can be formed in the insulating layer. Examples of methods for forming the via holes include laser irradiation, etching, mechanical drilling, and the like. The size and shape of the via holes can be appropriately determined according to the design of the printed wiring board. It should be noted that step (3) can be performed by grinding or grinding the insulating layer to achieve interlayer connection.

导通孔的形成后，优选进行去除导通孔内的钻污的步骤。该步骤有时被称为去钻污步骤。例如，在通过镀敷步骤而进行在绝缘层上的导体层的形成的情况下，可以对导通孔，进行湿式的去钻污处理。此外，在通过溅射步骤进行在绝缘层上的导体层的形成的情况下，可以进行等离子体处理步骤等干式去钻污步骤。进一步，通过去钻污步骤，可以对绝缘层实施粗糙化处理。After the formation of the via hole, it is preferred to perform a step of removing the drill smear in the via hole. This step is sometimes referred to as a desmearing step. For example, in the case where the conductor layer is formed on the insulating layer by a plating step, the via hole can be subjected to a wet desmearing treatment. In addition, in the case where the conductor layer is formed on the insulating layer by a sputtering step, a dry desmearing step such as a plasma treatment step can be performed. Furthermore, the desmearing step can be used to roughen the insulating layer.

此外，在绝缘层上形成导体层前，可以对绝缘层进行粗糙化处理。根据该粗糙化处理，通常，将包含导通孔内的绝缘层的表面进行粗糙化。作为粗糙化处理，可以进行干式和湿式中任一粗糙化处理。作为干式的粗糙化处理的例子，可以举出等离子体处理等。此外，作为湿式的粗糙化处理的例子，可以举出按顺序进行利用溶胀液的溶胀处理、利用氧化剂的粗糙化处理、和利用中和液的中和处理的方法。In addition, before forming the conductor layer on the insulating layer, the insulating layer may be subjected to a roughening treatment. According to the roughening treatment, the surface of the insulating layer including the via hole is usually roughened. As the roughening treatment, any of dry and wet roughening treatments may be performed. As an example of dry roughening treatment, plasma treatment and the like may be cited. In addition, as an example of wet roughening treatment, a method of sequentially performing swelling treatment using a swelling solution, roughening treatment using an oxidant, and neutralization treatment using a neutralizing solution may be cited.

在形成导通孔后，可以在绝缘层上形成导体层。通过在形成导通孔的位置处形成导体层，新形成的导体层与基材表面的导体层导通，进行层间连接。导体层的形成方法可以举出例如镀敷法、溅射法、蒸镀法等，其中，优选为镀敷法。适合的实施方式中，通过半加成法、全加成法等适当的方法而在绝缘层的表面上镀敷，形成具有期望的配线图案的导体层。此外，在树脂片材中的支撑体为金属箔的情况下，通过减成法，可以形成具有期望的配线图案的导体层。所形成的导体层的材料可以为单金属，也可以为合金。此外，该导体层可以具有单层结构，也可以具有包含2层以上的不同种类的材料的层的多层结构。After forming the via hole, a conductor layer can be formed on the insulating layer. By forming the conductor layer at the position where the via hole is formed, the newly formed conductor layer is connected to the conductor layer on the surface of the substrate to perform interlayer connection. The method for forming the conductor layer can include, for example, plating, sputtering, evaporation, etc., among which plating is preferred. In a suitable embodiment, a conductor layer having a desired wiring pattern is formed by plating on the surface of the insulating layer by an appropriate method such as a semi-additive method and a full-additive method. In addition, in the case where the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by a subtractive method. The material of the conductor layer formed can be a single metal or an alloy. In addition, the conductor layer can have a single-layer structure or a multilayer structure including layers of two or more different types of materials.

在此，详细说明在绝缘层上形成导体层的实施方式的例子。在绝缘层的表面上，通过无电解镀敷而形成镀敷籽晶层。接着，在所形成的镀敷籽晶层上，根据期望的配线图案，形成使镀敷籽晶层中的一部分露出的掩模图案。露出的镀敷籽晶层上，通过电解镀敷形成电镀层后，去除掩模图案。其后，通过蚀刻等处理去除不需要的镀敷籽晶层，能够形成具有期望的配线图案的导体层。应予说明，形成导体层时，掩模图案的形成中使用的干膜与上述干膜相同。Here, an example of an implementation method for forming a conductor layer on an insulating layer is described in detail. On the surface of the insulating layer, a plating seed layer is formed by electroless plating. Then, on the formed plating seed layer, a mask pattern is formed to expose a portion of the plating seed layer according to a desired wiring pattern. After forming an electroplated layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or other treatments, so that a conductor layer having a desired wiring pattern can be formed. It should be noted that when forming the conductor layer, the dry film used in forming the mask pattern is the same as the above-mentioned dry film.

印刷配线板的制造方法可以包括去除基材的步骤(4)。通过去除基材，得到具有绝缘层、和在该绝缘层中埋入的导体层的印刷配线板。该步骤(4)可以例如在使用具有能够剥离的金属层的基材的情况下进行。The method for manufacturing a printed wiring board may include a step (4) of removing a substrate. By removing the substrate, a printed wiring board having an insulating layer and a conductor layer embedded in the insulating layer is obtained. This step (4) can be performed, for example, when a substrate having a strippable metal layer is used.

＜半导体芯片封装＞＜Semiconductor chip packaging＞

本发明的第一个实施方式所涉及的半导体芯片封装包含上述印刷配线板、和在该印刷配线板上搭载的半导体芯片。该半导体芯片封装可以通过在印刷配线板上接合半导体芯片，从而制造。A semiconductor chip package according to a first embodiment of the present invention includes the printed wiring board and a semiconductor chip mounted on the printed wiring board. The semiconductor chip package can be manufactured by bonding the semiconductor chip to the printed wiring board.

印刷配线板与半导体芯片的接合条件可以采用能够将半导体芯片的端子电极与印刷配线板的电路配线导体连接的任意的条件。例如，可以采用半导体芯片的倒装芯片安装中使用的条件。此外，例如在半导体芯片与印刷配线板之间，可以经由绝缘性的粘接剂而接合。The bonding conditions between the printed wiring board and the semiconductor chip can be any conditions that can connect the terminal electrodes of the semiconductor chip to the circuit wiring conductors of the printed wiring board. For example, the conditions used in the flip chip mounting of the semiconductor chip can be used. In addition, for example, the semiconductor chip and the printed wiring board can be bonded via an insulating adhesive.

作为接合方法的例子，可以举出将半导体芯片在印刷配线板上压接的方法。作为压接条件，压接温度通常为120℃~240℃的范围(优选为130℃~200℃的范围、更优选为140℃~180℃的范围)，压接时间通常为 1秒~60秒的范围(优选为5秒~30秒)。As an example of a joining method, a method of crimping a semiconductor chip on a printed wiring board can be cited. As crimping conditions, the crimping temperature is usually in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, more preferably in the range of 140°C to 180°C), and the crimping time is usually in the range of 1 second to 60 seconds (preferably 5 seconds to 30 seconds).

此外，作为接合方法的另一例，可以举出将半导体芯片在印刷配线板上回流而接合的方法。回流条件可以设为120℃~300℃的范围。Another example of the bonding method is a method of bonding the semiconductor chip to the printed wiring board by reflowing. The reflow conditions can be set to a range of 120°C to 300°C.

在将半导体芯片在印刷配线板上接合后，可以将半导体芯片用模具底部填充材料填充。作为该模具底部填充材料，可以使用上述树脂组合物，此外也可以使用上述树脂片材。After the semiconductor chip is bonded to the printed wiring board, the semiconductor chip may be filled with a mold underfill material. As the mold underfill material, the above-mentioned resin composition may be used, and the above-mentioned resin sheet may also be used.

本发明的第二实施方式所涉及的半导体芯片封装包含半导体芯片、和将该半导体芯片密封的前述树脂组合物的固化物。这样的半导体芯片封装中，通常树脂组合物的固化物作为密封层而发挥功能。作为第二实施方式所涉及的半导体芯片封装，可以举出例如Fan-out(扇出)型WLP。The semiconductor chip package involved in the second embodiment of the present invention comprises a semiconductor chip and a cured product of the aforementioned resin composition that seals the semiconductor chip. In such a semiconductor chip package, the cured product of the resin composition usually functions as a sealing layer. As the semiconductor chip package involved in the second embodiment, for example, a Fan-out type WLP can be cited.

这样的半导体芯片封装的制造方法可以包括：Such a method for manufacturing a semiconductor chip package may include:

(A)在基材上层叠预固定膜的步骤；(A) a step of laminating a pre-fixed film on a substrate;

(B)将半导体芯片在预固定膜上预固定的步骤；(B) a step of pre-fixing a semiconductor chip on a pre-fixing film;

(C)在半导体芯片上形成密封层的步骤；(C) forming a sealing layer on the semiconductor chip;

(D)将基材和预固定膜从半导体芯片上剥离的步骤；(D) a step of peeling the substrate and the pre-fixed film from the semiconductor chip;

(E)在将半导体芯片的基材和预固定膜剥离的面上形成作为绝缘层的再配线形成层的步骤；(E) forming a redistribution wiring forming layer as an insulating layer on the surface from which the substrate and the preliminary fixing film of the semiconductor chip are peeled off;

(F)在再配线形成层上形成作为导体层的再配线层的步骤；以及(F) a step of forming a redistribution layer as a conductor layer on the redistribution formation layer; and

(G)在再配线层上形成阻焊剂层的步骤。(G) A step of forming a solder resist layer on the redistribution layer.

此外，前述的半导体芯片封装的制造方法可以包括：In addition, the aforementioned method for manufacturing the semiconductor chip package may include:

(H)将多个半导体芯片封装切割为各个半导体芯片封装而单片化的步骤。(H) A step of cutting a plurality of semiconductor chip packages into individual semiconductor chip packages.

(步骤(A))(Step (A))

步骤(A)是在基材上层叠预固定膜的步骤。基材与预固定膜的层叠条件可以与印刷配线板的制造方法中的基材与树脂片材的层叠条件相同。Step (A) is a step of laminating the preliminary fixing film on the substrate. The lamination conditions of the substrate and the preliminary fixing film may be the same as the lamination conditions of the substrate and the resin sheet in the method for producing a printed wiring board.

作为基材，可以举出例如硅晶片；玻璃晶片；玻璃基板；铜、钛、不锈钢、冷轧钢板(SPCC)等金属基板；FR-4基板等在玻璃纤维中渗入环氧树脂等而进行热固化处理的基板；包含BT树脂等双马来酰亚胺三嗪树脂的基板等。As the substrate, for example, there can be cited silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, cold-rolled steel sheets (SPCC); substrates such as FR-4 substrates in which epoxy resins or the like are infiltrated into glass fibers and then heat-cured; substrates containing bismaleimide triazine resins such as BT resin, etc., etc.

预固定膜能够使用可以从半导体芯片上剥离，且可以将半导体芯片预固定的任意的材料。作为市售品，可以举出日东电工公司制“リヴァα”等。The temporary fixing film may be any material that can be peeled off from the semiconductor chip and can temporarily fix the semiconductor chip. Examples of commercially available products include "LIVA α" manufactured by Nitto Denko Corporation.

(步骤(B))(Step (B))

步骤(B)是将半导体芯片在预固定膜上预固定的步骤。半导体芯片的预固定可以使用例如倒装芯片焊接机、裸片焊接机等装置而进行。半导体芯片的配置的布局和配置数可以根据预固定膜的形状、大小、目标半导体芯片封装的生产数等而适当设定。例如，可以以多行且多列的矩阵状排列半导体芯片，进行预固定。Step (B) is a step of pre-fixing the semiconductor chip on the pre-fixing film. The pre-fixing of the semiconductor chip can be performed using a device such as a flip chip bonding machine, a bare die bonding machine, etc. The layout and number of configurations of the semiconductor chip can be appropriately set according to the shape and size of the pre-fixing film, the production number of the target semiconductor chip package, etc. For example, the semiconductor chips can be arranged in a matrix of multiple rows and columns for pre-fixing.

(步骤(C))(Step (C))

步骤(C)是在半导体芯片上形成密封层的步骤。密封层通过上述树脂组合物的固化物而形成。密封层通常通过包括：在半导体芯片上形成树脂组合物层的步骤、和使该树脂组合物层热固化而形成密封层的步骤的方法而形成。Step (C) is a step of forming a sealing layer on the semiconductor chip. The sealing layer is formed by a cured product of the resin composition. The sealing layer is usually formed by a method comprising: forming a resin composition layer on the semiconductor chip, and thermally curing the resin composition layer to form the sealing layer.

树脂组合物层的形成优选通过压缩成型法而进行。压缩成型法中，通常将半导体芯片和树脂组合物配置在模具中，在该模具内对树脂组合物施加压力和根据需要的热，形成覆盖半导体芯片的树脂组合物层。The resin composition layer is preferably formed by compression molding. In compression molding, a semiconductor chip and a resin composition are generally placed in a mold, and pressure and, if necessary, heat are applied to the resin composition in the mold to form a resin composition layer covering the semiconductor chip.

压缩成型法的具体操作可以例如如下述进行。作为压缩成型用的模具，准备上模和下模。此外，如前述那样在预固定膜上预固定的半导体芯片上，涂布树脂组合物。将涂布有树脂组合物的半导体芯片与基材和预固定膜一起，安装在下模中。其后，将上模和下模合模，对树脂组合物施加热和压力，进行压缩成型。The specific operation of the compression molding method can be performed, for example, as follows. As a mold for compression molding, an upper mold and a lower mold are prepared. In addition, a resin composition is applied to the semiconductor chip pre-fixed on the pre-fixed film as described above. The semiconductor chip coated with the resin composition is installed in the lower mold together with the substrate and the pre-fixed film. Thereafter, the upper mold and the lower mold are molded together, and heat and pressure are applied to the resin composition to perform compression molding.

此外，压缩成型法的具体操作可以例如如下述那样进行。作为压缩成型用的模具，准备上模和下模。在下模中载置树脂组合物。此外，在上模中将半导体芯片与基材和预固定膜一起安装。其后，以在下模中载置的树脂组合物与在上模中安装的半导体芯片接触的方式，将上模和下模合模，施加热和压力，进行压缩成型。In addition, the specific operation of the compression molding method can be carried out, for example, as follows. As a mold for compression molding, an upper mold and a lower mold are prepared. A resin composition is placed in the lower mold. In addition, a semiconductor chip is installed in the upper mold together with a substrate and a pre-fixed film. Thereafter, the upper mold and the lower mold are molded together in a manner such that the resin composition placed in the lower mold contacts the semiconductor chip installed in the upper mold, and heat and pressure are applied to perform compression molding.

成型条件根据树脂组合物的组成而不同，可以以实现良好的密封的方式采用适当的条件。例如，成型时的模具的温度优选为70℃以上、更优选为80℃以上、特别优选为90℃以上、优选为200℃以下、更优选为170℃以下、特别优选为150℃以下。此外，成型时施加的压力优选为1MPa以上、更优选为3MPa以上、特别优选为5MPa以上、优选为50MPa以下、更优选为30MPa以下、特别优选为20MPa以下。固化时间优选为1分钟以上、更优选为2分钟以上、特别优选为3分钟以上、优选为60分钟以下、更优选为30分钟以下、特别优选为20分钟以下。通常，在树脂组合物层的形成后，拆卸模具。模具的拆卸可以在树脂组合物层的热固化前进行，也可以在热固化后进行。The molding conditions vary according to the composition of the resin composition, and appropriate conditions can be adopted in a manner to achieve good sealing. For example, the temperature of the mold during molding is preferably 70°C or more, more preferably 80°C or more, particularly preferably 90°C or more, preferably 200°C or less, more preferably 170°C or less, and particularly preferably 150°C or less. In addition, the pressure applied during molding is preferably 1MPa or more, more preferably 3MPa or more, particularly preferably 5MPa or more, preferably 50MPa or less, more preferably 30MPa or less, and particularly preferably 20MPa or less. The curing time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 3 minutes or more, preferably 60 minutes or less, more preferably 30 minutes or less, and particularly preferably 20 minutes or less. Usually, after the formation of the resin composition layer, the mold is disassembled. The disassembly of the mold can be performed before the thermal curing of the resin composition layer, or after the thermal curing.

树脂组合物层的形成可以通过将树脂片材与半导体芯片层叠而进行。例如，通过将树脂片材的树脂组合物层与半导体芯片加热压接，能够在半导体芯片上形成树脂组合物层。树脂片材与半导体芯片的层叠通常替代基材而使用半导体芯片，能够以与印刷配线板的制造方法中的树脂片材与基材的层叠相同的方式进行。The formation of the resin composition layer can be carried out by laminating a resin sheet with a semiconductor chip. For example, by thermally pressing the resin composition layer of the resin sheet with the semiconductor chip, a resin composition layer can be formed on the semiconductor chip. The lamination of the resin sheet and the semiconductor chip usually replaces the substrate and uses the semiconductor chip, and can be carried out in the same manner as the lamination of the resin sheet and the substrate in the manufacturing method of the printed wiring board.

在半导体芯片上形成树脂组合物层后，使该树脂组合物层热固化，得到覆盖半导体芯片的密封层。由此，利用树脂组合物的固化物进行半导体芯片的密封。树脂组合物层的热固化条件可以采用与印刷配线板的制造方法中的树脂组合物层的热固化条件相同的条件。进一步，在使树脂组合物层热固化前，对树脂组合物层，可以实施在与固化温度相比更低的温度下加热的预加热处理。该预加热处理的处理条件可以采用与印刷配线板的制造方法中的预加热处理相同的条件。After forming a resin composition layer on the semiconductor chip, the resin composition layer is thermally cured to obtain a sealing layer covering the semiconductor chip. Thus, the semiconductor chip is sealed using a cured product of the resin composition. The thermal curing conditions of the resin composition layer can be the same as the thermal curing conditions of the resin composition layer in the method for manufacturing a printed wiring board. Further, before the resin composition layer is thermally cured, a preheating treatment of heating at a lower temperature than the curing temperature can be implemented for the resin composition layer. The processing conditions of the preheating treatment can be the same as the preheating treatment in the method for manufacturing a printed wiring board.

(步骤(D))(Step (D))

步骤(D)是将基材和预固定膜从半导体芯片上剥离的步骤。剥离方法期望采用与、预固定膜的材质对应的适当的方法。作为剥离方法，可以举出例如将预固定膜加热、发泡或膨胀而剥离的方法。此外，作为剥离方法，可以举出例如通过基材而对预固定膜照射紫外线，降低预固定膜的粘合力而剥离的方法。Step (D) is a step of peeling the substrate and the pre-fixed film from the semiconductor chip. The peeling method is expected to adopt an appropriate method corresponding to the material of the pre-fixed film. As the peeling method, for example, a method of peeling the pre-fixed film by heating, foaming or expanding the pre-fixed film can be cited. In addition, as the peeling method, for example, a method of peeling the pre-fixed film by irradiating ultraviolet rays through the substrate to reduce the adhesive force of the pre-fixed film can be cited.

将预固定膜加热、发泡或膨胀而剥离的方法中，加热条件通常在100℃~250℃下为1秒~90秒或5分钟~15分钟。此外，照射紫外线降低预固定膜的粘合力而剥离的方法中，紫外线的照射量通常为10mJ/cm2~1000mJ/cm2。In the method of peeling off by heating, foaming or expanding the pre-fixing film, the heating conditions are usually 100°C to 250°C for 1 second to 90 seconds or 5 minutes to 15 minutes. In the method of peeling off by irradiating ultraviolet rays to reduce the adhesive force of the pre-fixing film, the irradiation amount of ultraviolet rays is usually 10mJ/ cm2 to 1000mJ/ cm2 .

(步骤(E))(Step (E))

步骤(E)是在将半导体芯片的基材和预固定膜剥离的面上形成作为绝缘层的再配线形成层的步骤。Step (E) is a step of forming a redistribution wiring forming layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film are peeled off.

再配线形成层的材料可以使用具有绝缘性的任意的材料。其中，从半导体芯片封装的制造容易性的观点出发，优选为光敏性树脂和热固性树脂。此外，作为该热固性树脂，可以使用本发明的树脂组合物。Any material having insulating properties can be used as the material of the redistribution forming layer. Among them, photosensitive resins and thermosetting resins are preferred from the viewpoint of ease of manufacturing of semiconductor chip packaging. In addition, as the thermosetting resin, the resin composition of the present invention can be used.

形成再配线形成层后，为了将半导体芯片与再配线层进行层间连接，可以在再配线形成层中形成导通孔。After the redistribution forming layer is formed, via holes may be formed in the redistribution forming layer in order to establish interlayer connection between the semiconductor chip and the redistribution forming layer.

再配线形成层的材料为光敏性树脂的情况的导通孔的形成方法中，通常对再配线形成层的表面，通过掩模图案而照射活性能量射线，使照射部的再配线形成层光固化。作为活性能量射线，可以举出例如紫外线、可见光线、电子射线、X射线等，特别优选为紫外线。紫外线的照射量和照射时间可以根据光敏性树脂而适当设定。作为曝光方法，可以举出例如将掩模图案与再配线形成层密合而曝光的接触曝光法、将掩模图案不与再配线形成层密合而使用平行光线曝光的非接触曝光法等。In the method for forming a via hole in the case where the material of the redistribution forming layer is a photosensitive resin, active energy rays are usually irradiated to the surface of the redistribution forming layer through a mask pattern to photocure the redistribution forming layer of the irradiated portion. As active energy rays, for example, ultraviolet rays, visible rays, electron rays, X-rays, etc. can be cited, and ultraviolet rays are particularly preferred. The irradiation amount and irradiation time of ultraviolet rays can be appropriately set according to the photosensitive resin. As exposure methods, for example, a contact exposure method in which a mask pattern is closely fitted to the redistribution forming layer and exposed, a non-contact exposure method in which a mask pattern is not closely fitted to the redistribution forming layer and exposed using parallel light, etc. can be cited.

使再配线形成层光固化后，将再配线形成层显影，去除未曝光部，形成导通孔。显影可以进行湿式显影、干式显影中任一者。作为显影的方式，可以举出例如浸渍方式、桨式方式、喷雾方式、刷拭方式、擦洗方式等，从分辨率的观点出发，适合为桨式方式。After the redistribution forming layer is photocured, the redistribution forming layer is developed to remove the unexposed portion and form a via hole. The development may be performed by either wet development or dry development. As the development method, for example, an immersion method, a paddle method, a spray method, a brush method, a scrubbing method, etc. may be cited. From the viewpoint of resolution, a paddle method is suitable.

作为再配线形成层的材料为热固性树脂的情况的导通孔的形成方法，可以举出例如激光照射、蚀刻、机械钻孔等。其中，优选为激光照射。激光照射可以使用利用二氧化碳激光、UV-YAG激光、准分子激光等光源的适当的激光加工机来进行。As a method for forming the via hole when the material of the redistribution forming layer is a thermosetting resin, for example, laser irradiation, etching, mechanical drilling, etc. can be cited. Among them, laser irradiation is preferred. Laser irradiation can be performed using an appropriate laser processing machine using a light source such as a carbon dioxide laser, a UV-YAG laser, an excimer laser, etc.

导通孔的形状没有特别限定，一般而言设为圆形(近似圆形)。导通孔的顶部直径优选为50μm以下、更优选为30μm以下、进一步优选为20μm以下。在此，导通孔的顶部直径是指再配线形成层的表面处的导通孔的开口的直径。The shape of the via hole is not particularly limited, and is generally a circle (approximately a circle). The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, and further preferably 20 μm or less. Here, the top diameter of the via hole refers to the diameter of the opening of the via hole at the surface of the redistribution formation layer.

(步骤(F))(Step (F))

步骤(F)是在再配线形成层上形成作为导体层的再配线层的步骤。在再配线形成层上形成再配线层的方法可以与印刷配线板的制造方法中的在绝缘层上的导体层的形成方法相同。此外，也可以反复进行步骤(E)和步骤(F)，交替堆叠再配线层和再配线形成层(积层)。Step (F) is a step of forming a redistribution layer as a conductor layer on the redistribution formation layer. The method of forming the redistribution layer on the redistribution formation layer may be the same as the method of forming the conductor layer on the insulating layer in the method of manufacturing a printed wiring board. In addition, steps (E) and (F) may be repeated to alternately stack the redistribution layer and the redistribution formation layer (build-up layer).

(步骤(G))(Step (G))

步骤(G)是在再配线层上形成阻焊剂层的步骤。阻焊剂层的材料可以使用具有绝缘性的任意的材料。其中，从半导体芯片封装的制造容易性的观点出发，优选为光敏性树脂和热固性树脂。此外，作为热固性树脂，可以使用本发明的树脂组合物。Step (G) is a step of forming a solder resist layer on the redistribution layer. The material of the solder resist layer can use any material with insulating properties. Among them, from the viewpoint of ease of manufacture of semiconductor chip packaging, photosensitive resins and thermosetting resins are preferred. In addition, as a thermosetting resin, the resin composition of the present invention can be used.

此外，步骤(G)中，根据需要，可以进行形成凸块的凸块加工。凸块加工可以通过焊球、焊接镀敷等方法而进行。此外，凸块加工中的导通孔的形成可以与步骤(E)同样地进行。In step (G), bump processing for forming bumps may be performed as needed. The bump processing may be performed by methods such as solder balls and solder plating. In addition, the formation of via holes in the bump processing may be performed in the same manner as in step (E).

(步骤(H))(Step (H))

半导体芯片封装的制造方法除了步骤(A)~(G)之外，还可以包括步骤(H)。步骤(H)是将多个半导体芯片封装切割为各个半导体芯片封装而单片化的步骤。将半导体芯片封装切割为各个半导体芯片封装的方法没有特别限定。The method for manufacturing a semiconductor chip package may further include step (H) in addition to steps (A) to (G). Step (H) is a step of cutting a plurality of semiconductor chip packages into individual semiconductor chip packages for singulation. The method for cutting a semiconductor chip package into individual semiconductor chip packages is not particularly limited.

＜半导体装置＞＜Semiconductor devices＞

半导体装置具有半导体芯片封装。作为半导体装置，可以举出例如供于电气制品(例如计算机、移动电话、智能手机、平板电脑型设备、可穿戴设备、数字相机、医疗器械、和电视等)和乘用工具(例如自动二轮车、汽车、列车、船舶和飞机等)等的各种半导体装置。The semiconductor device has a semiconductor chip package. Examples of the semiconductor device include various semiconductor devices for electrical products (such as computers, mobile phones, smart phones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions) and passenger vehicles (such as motorcycles, cars, trains, ships, and airplanes).

实施例Example

以下，针对本发明，示出实施例而具体说明。但是，本发明不限于以下的实施例。以下的说明中，表示量的“份”和“%”在没有另外明确说明的情况下，各自是指“质量份”和“质量%”。此外，以下说明的操作在没有另外明确说明的情况下，在常温常压的环境下进行。Hereinafter, the present invention will be specifically described by showing examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" indicating amounts refer to "parts by mass" and "% by mass" respectively unless otherwise clearly stated. In addition, the operations described below are performed under normal temperature and pressure unless otherwise clearly stated.

＜热塑性树脂溶液A的制备＞<Preparation of Thermoplastic Resin Solution A>

在反应容器中，加入2官能性羟基末端聚丁二烯(日本曹达公司制“G-3000”、数均分子量：3000、羟基当量：1800g/eq.)69g、芳族烃系混合溶剂(出光石油化学公司制“イプゾール150”)40g、和二丁基锡月桂酸盐0.005g，混合而均匀溶解。由此，得到溶液。将溶液升温至60℃，进一步在搅拌的同时添加异氟尔酮二异氰酸酯(エボニックデグサジャパン公司制“IPDI”、异氰酸酯基当量：113g/eq.)8g，进行约3小时反应。由此，得到第1反应溶液。In a reaction vessel, 69 g of a bifunctional hydroxy-terminated polybutadiene ("G-3000" manufactured by Nippon Soda Co., Ltd., number average molecular weight: 3000, hydroxyl equivalent: 1800 g/eq.), 40 g of an aromatic hydrocarbon mixed solvent ("IPSOL 150" manufactured by Idemitsu Petrochemical Co., Ltd.), and 0.005 g of dibutyltin laurate were added, mixed and uniformly dissolved. Thus, a solution was obtained. The solution was heated to 60° C., and 8 g of isophorone diisocyanate ("IPDI" manufactured by Ebony Degussapan Co., Ltd., isocyanate equivalent: 113 g/eq.) was further added while stirring, and the reaction was carried out for about 3 hours. Thus, a first reaction solution was obtained.

接着，向第1反应溶液中，添加甲酚酚醛清漆树脂(DIC公司制“KA-1160”、羟基当量：117g/eq.)23g、和乙基二乙二醇乙酸酯(ダイセル公司制)60g，在搅拌的同时升温至150℃，进行约10小时反应。由此，得到第2反应溶液。通过FT-IR，进行2250cm-1的NCO峰的消失的确认。根据NCO峰的消失的确认而视为反应的终点，将第2反应溶液降温至室温。并且，将第2反应溶液用100目的滤布过滤。由此，作为滤液，得到包含具有反应性官能团的热塑性树脂A(含酚性羟基的聚丁二烯树脂)作为不挥发成分的溶液(不挥发成分50质量%；以下记作“热塑性树脂溶液A”)。热塑性树脂A的数均分子量为5900，玻璃化转变温度为-7℃。Next, 23 g of cresol novolac resin ("KA-1160" manufactured by DIC Corporation, hydroxyl equivalent: 117 g/eq.) and 60 g of ethyl diglycol acetate (manufactured by Dicel Corporation) were added to the first reaction solution, and the temperature was raised to 150°C while stirring, and the reaction was carried out for about 10 hours. Thus, the second reaction solution was obtained. The disappearance of the NCO peak at 2250 cm -1 was confirmed by FT-IR. The disappearance of the NCO peak was considered as the end point of the reaction, and the second reaction solution was cooled to room temperature. In addition, the second reaction solution was filtered with a 100-mesh filter cloth. Thus, as a filtrate, a solution containing a thermoplastic resin A (polybutadiene resin containing phenolic hydroxyl groups) having a reactive functional group as a non-volatile component was obtained (non-volatile component 50% by mass; hereinafter referred to as "thermoplastic resin solution A"). The number average molecular weight of thermoplastic resin A is 5900, and the glass transition temperature is -7°C.

＜热塑性树脂溶液B的制备＞<Preparation of thermoplastic resin solution B>

向安装了搅拌装置、温度计和电容器的烧瓶中，作为溶剂，投入乙基二乙二醇乙酸酯368.41g和エクソンモービル公司制“ソルベッソ150(注册商标)”(芳族系溶剂)368.41g。进一步，向前述的烧瓶中，投入二苯基甲烷二异氰酸酯100.1g(0.4摩尔)、和聚碳酸酯二醇(クラレ公司制“C-2015N”、数均分子量：约2000、羟基当量：1000g/eq.、不挥发成分：100质量%)400g(0.2摩尔)，在70℃下进行4小时反应。由此，得到第1反应溶液。Into a flask equipped with a stirring device, a thermometer, and a capacitor, 368.41 g of ethyl diethylene glycol acetate and 368.41 g of "Solbeso 150 (registered trademark)" (aromatic solvent) manufactured by Ecoson Mobil Corporation were added as solvents. Furthermore, 100.1 g (0.4 mol) of diphenylmethane diisocyanate and 400 g (0.2 mol) of polycarbonate diol ("C-2015N" manufactured by Kuraray Corporation, number average molecular weight: about 2000, hydroxyl equivalent: 1000 g/eq., non-volatile component: 100% by mass) were added to the aforementioned flask, and the mixture was reacted at 70° C. for 4 hours. Thus, a first reaction solution was obtained.

接着，向前述的烧瓶中，进一步投入壬基苯酚酚醛清漆树脂(羟基当量：229.4g/eq、平均4.27官能、平均计算分子量：979.5g/摩尔)195.9g(0.2摩尔)、和乙二醇双无水偏苯三甲酸酯41.0g(0.1摩尔)，耗费2小时，升温至150℃，进行12小时反应。由此，得到第2反应溶液。通过FT-IR而进行2250cm-1的NCO峰的消失的确认。根据NCO峰的消失的确认，视为反应的终点，将第2反应溶液降温至室温。并且，将第2反应溶液用100目的滤布过滤。由此，作为滤液，得到包含具有反应性官能团的热塑性树脂B(含酚性羟基的聚碳酸酯树脂)作为不挥发成分的溶液(不挥发成分50质量%；以下记作“热塑性树脂溶液B”)。热塑性树脂B的数均分子量为6100，玻璃化转变温度为5℃。Next, 195.9 g (0.2 mol) of nonylphenol novolac resin (hydroxyl equivalent: 229.4 g/eq, average 4.27 functional groups, average calculated molecular weight: 979.5 g/mol) and 41.0 g (0.1 mol) of ethylene glycol dianhydrous trimellitate were further added to the aforementioned flask, and the temperature was raised to 150°C for 2 hours to react for 12 hours. Thus, a second reaction solution was obtained. The disappearance of the NCO peak of 2250 cm -1 was confirmed by FT-IR. Based on the confirmation of the disappearance of the NCO peak, the reaction was regarded as the end point, and the second reaction solution was cooled to room temperature. In addition, the second reaction solution was filtered with a 100-mesh filter cloth. Thus, as a filtrate, a solution containing a thermoplastic resin B (a polycarbonate resin containing phenolic hydroxyl groups) having a reactive functional group as a non-volatile component was obtained (non-volatile component 50% by mass; hereinafter referred to as "thermoplastic resin solution B"). The number average molecular weight of the thermoplastic resin B was 6100, and the glass transition temperature was 5°C.

[实施例1][Example 1]

＜树脂清漆A的制备＞<Preparation of resin varnish A>

将作为(A)成分的双酚A型环氧树脂(三菱化学公司制“jER828EL”、环氧当量：184~194g/eq.)3份、作为(A)成分的联苯型环氧树脂(日本化药公司制“NC3000L”、环氧当量：276g/eq.)1份、作为(A)成分的缩水甘油基胺型环氧树脂(三菱化学公司制“630”、环氧当量：95g/eq.)2份、作为(B-2)成分的甲酚酚醛清漆树脂(DIC公司制“KA-1160”、酚性羟基当量：117g/eq.)2份、作为(B-2)成分的活性酯树脂(DIC公司制、“HPC-8000-65T”、活性基当量：约223、不挥发成分65质量%的甲苯溶液)1.54份、作为(B-1)成分的马来酰亚胺化合物(デザイナーモレキュールズ制“BMI-689”)4份、作为(C)成分的无机填充材料A70份、作为(D)成分的热塑性树脂溶液A(不挥发成分：50%)20份、作为(E)成分的固化促进剂(四国化成工业公司制、“1B2PZ”)0.05份、和作为溶剂的甲基乙基酮15份混合，用高速旋转混合机均匀分散。以这样的方式，制备树脂清漆。以下，也将如下所述制备的树脂清漆总称，称为“树脂清漆A”。3 parts of bisphenol A type epoxy resin ("jER828EL" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 184 to 194 g/eq.) as component (A), 1 part of biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 276 g/eq.) as component (A), 2 parts of glycidylamine type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95 g/eq.) as component (A), 2 parts of cresol novolac resin ("KA-1160" manufactured by DIC Corporation, phenolic hydroxyl equivalent: 117 g/eq.) as component (B-2), and 1 part of active 1.54 parts of ester resin (made by DIC Corporation, "HPC-8000-65T", active group equivalent: about 223, toluene solution of 65% by mass of non-volatile components), 4 parts of maleimide compound (made by Desinair Moleculars "BMI-689") as component (B-1), 70 parts of inorganic filler A as component (C), 20 parts of thermoplastic resin solution A (non-volatile components: 50%) as component (D), 0.05 parts of curing accelerator (made by Shikoku Chemical Industry Co., Ltd., "1B2PZ") as component (E), and 15 parts of methyl ethyl ketone as solvent were mixed and uniformly dispersed with a high-speed rotary mixer. In this way, a resin varnish was prepared. Hereinafter, the resin varnish prepared as described below will also be collectively referred to as "resin varnish A".

在此，无机填充材料A是用氨基硅烷系偶联剂(信越化学工业公司制“KBM573”)进行表面处理的球形二氧化硅(アドマテックス公司制“SO-C2”)，测定其平均粒径的结果是0.5μm，测定其比表面积的结果是5.8m2/g。Here, the inorganic filler A is spherical silica (SO-C2 manufactured by Advantex Corporation) surface-treated with an aminosilane coupling agent (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.), and its average particle size was measured to be 0.5 μm and its specific surface area was measured to be 5.8 m 2 /g.

＜树脂片材B的制作＞<Production of resin sheet B>

作为支撑体，准备将一个主面用醇酸树脂系脱模剂(リンテック公司制“AL-5”)进行脱模处理的PET膜(东レ公司制“ルミラーR80”；厚度：38μm、软化点：130℃、以下有时称为“脱模PET”)。As a support, a PET film ("Lumira R80" manufactured by Toray Co., Ltd.; thickness: 38 μm, softening point: 130° C., hereinafter sometimes referred to as "release PET") was prepared, one main surface of which was release-treated with an alkyd resin-based release agent ("AL-5" manufactured by Lintech Co., Ltd.).

将树脂清漆A以干燥后的树脂组合物层的厚度达到100μm的方式，在脱模PET的脱模处理面上通过该膜涂机均匀涂布。其后，将树脂清漆A在80℃~120℃(平均100℃)下干燥6分钟。由此，得到包含支撑体、和在该支撑体上设置的包含树脂组合物的包含树脂组合物层的树脂片材。以下，也将以这样的方式制作的树脂片材称为“树脂片材B”。The resin varnish A was evenly applied on the release treated surface of the release PET by the film coater in such a manner that the thickness of the resin composition layer after drying reached 100 μm. Thereafter, the resin varnish A was dried at 80° C. to 120° C. (average 100° C.) for 6 minutes. Thus, a resin sheet including a support and a resin composition layer provided on the support was obtained. Hereinafter, the resin sheet prepared in this manner will also be referred to as "resin sheet B".

＜评价用固化物C的制作＞<Preparation of Cured Material C for Evaluation>

切出树脂片材B中的一部分，在180℃下进行90分钟加热，使树脂组合物层热固化。其后，将支撑体剥离，得到评价用固化物。以下，也将以这样的方式制作的评价用固化物称为“评价用固化物C”。A portion of the resin sheet B was cut out and heated at 180° C. for 90 minutes to thermally cure the resin composition layer. Thereafter, the support was peeled off to obtain a cured product for evaluation. Hereinafter, the cured product for evaluation prepared in this manner will also be referred to as “cured product for evaluation C”.

＜树脂组合物的固化物的各种参数的获取和评价＞<Acquisition and evaluation of various parameters of cured products of resin compositions>

使用树脂片材B的树脂组合物层或评价用固化物C，针对树脂组合物的固化物，获取各种参数，同时从翘曲和长期可靠性的观点出发，按照后述评价方法而评价。进一步，使用评价用固化物C，从耐药品性的观点出发，按照后述评价方法而评价。The resin composition layer of the resin sheet B or the evaluation cured product C was used to obtain various parameters for the cured product of the resin composition, and the evaluation was performed from the viewpoints of warpage and long-term reliability according to the evaluation method described below. Furthermore, the evaluation cured product C was used to perform the evaluation from the viewpoint of chemical resistance according to the evaluation method described below.

[实施例2][Example 2]

实施例1中，作为(A)成分的无机填充材料A70份变更为无机填充材料B115份。在此，作为无机填充材料B，为用信越化学工业公司制“KBM573”(N-苯基-3-氨基丙基三甲氧基硅烷)进行处理的球状氧化铝，使用最大切割直径为5μm的物质。测定的结果是，无机填充材料B的平均粒径为1.5μm，比表面积为2.0m2/g。In Example 1, 70 parts of the inorganic filler A as the component (A) was replaced with 115 parts of the inorganic filler B. Here, the inorganic filler B was spherical alumina treated with "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the one with a maximum cutting diameter of 5 μm was used. The results of the measurement showed that the average particle size of the inorganic filler B was 1.5 μm and the specific surface area was 2.0 m 2 /g.

除了以上的事项之外，以与实施例1相同的方式，制备包含树脂组合物的树脂清漆A。并且，使用树脂清漆A，以与实施例1相同的方式，得到树脂片材B和评价用固化物C，使用树脂片材B的树脂组合物层和评价用固化物C，以与实施例1相同的方式，供于对树脂组合物的固化物进行评价。Except for the above matters, a resin varnish A containing a resin composition was prepared in the same manner as in Example 1. Furthermore, a resin sheet B and a cured product C for evaluation were obtained using the resin varnish A in the same manner as in Example 1, and the resin composition layer of the resin sheet B and the cured product C for evaluation were used in the same manner as in Example 1 to evaluate the cured product of the resin composition.

[实施例3][Example 3]

实施例1中，变更为作为(A)成分的双酚A型环氧树脂(三菱化学公司制“jER828EL”)3份、联苯型环氧树脂(日本化药公司制“NC3000L”)1份和缩水甘油基胺型环氧树脂(三菱化学公司制“630”)2份、双酚A型环氧树脂(三菱化学公司制“jER828EL”、环氧当量：184~194g/eq.)2份、萘型环氧树脂(DIC公司制“HP4032”、环氧当量：135~165g/eq.)2份和联苯型环氧树脂(三菱化学公司制“YX4000”、环氧当量：约185g/eq.)2份。In Example 1, the components (A) were changed to 3 parts of a bisphenol A type epoxy resin ("jER828EL" manufactured by Mitsubishi Chemical Corporation), 1 part of a biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd.), 2 parts of a glycidylamine type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation), 2 parts of a bisphenol A type epoxy resin ("jER828EL" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 184 to 194 g/eq.), 2 parts of a naphthalene type epoxy resin ("HP4032" manufactured by DIC Corporation, epoxy equivalent: 135 to 165 g/eq.), and 2 parts of a biphenyl type epoxy resin ("YX4000" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 185 g/eq.).

进一步，实施例1中，变更为作为(B-2)成分的甲酚酚醛清漆树脂(DIC公司制“KA-1160”)2份、作为(B-2)成分的活性酯树脂(DIC公司制、“HPC-8000-65T”)1.54份和作为(B-1)成分的马来酰亚胺化合物(デザイナーモレキュールズ制“BMI-689”)4份、作为(B-2)成分的甲酚酚醛清漆树脂(DIC公司制“KA-1160”)1份和作为(B-1)成分的马来酰亚胺化合物(デザイナーモレキュールズ制“BMI-689”)4份。Furthermore, in Example 1, the components (B-2) were changed to 2 parts of a cresol novolac resin (“KA-1160” manufactured by DIC Corporation), 1.54 parts of an active ester resin (“HPC-8000-65T” manufactured by DIC Corporation) as the component (B-2), and 4 parts of a maleimide compound (“BMI-689” manufactured by Desiana Morcell) as the component (B-1), 1 part of a cresol novolac resin (“KA-1160” manufactured by DIC Corporation) as the component (B-2), and 4 parts of a maleimide compound (“BMI-689” manufactured by Desiana Morcell) as the component (B-1).

进一步，实施例1中，变更为作为(D)成分的热塑性树脂溶液A(不挥发成分：50%)20份、作为(D)成分的热塑性树脂溶液A(不挥发成分：50%)12份和作为(D)成分的热塑性树脂溶液B(不挥发成分：50%)12份。此外，实施例1中，变更为作为(E)成分的固化促进剂(四国化成工业公司制、“1B2PZ”)0.05份、作为(E)成分的固化促进剂(4-二甲基氨基吡啶(DMAP))0.05份。Furthermore, in Example 1, the components (D) were changed to 20 parts of thermoplastic resin solution A (non-volatile content: 50%), 12 parts of thermoplastic resin solution A (non-volatile content: 50%), and 12 parts of thermoplastic resin solution B (non-volatile content: 50%). In addition, in Example 1, the components (E) were changed to 0.05 parts of a curing accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ"), and 0.05 parts of a curing accelerator (4-dimethylaminopyridine (DMAP)) as the component (E).

除了以上的事项之外，以与实施例1相同的方式，制备包含树脂组合物的树脂清漆A。并且，使用树脂清漆A，以与实施例1相同的方式，得到树脂片材B和评价用固化物C，使用树脂片材B的树脂组合物层和评价用固化物C，以与实施例1相同的方式，供于对树脂组合物的固化物进行评价。Except for the above matters, a resin varnish A containing a resin composition was prepared in the same manner as in Example 1. Furthermore, a resin sheet B and a cured product C for evaluation were obtained using the resin varnish A in the same manner as in Example 1, and the resin composition layer of the resin sheet B and the cured product C for evaluation were used in the same manner as in Example 1 to evaluate the cured product of the resin composition.

[比较例1][Comparative Example 1]

实施例1中，变更为作为(A)成分的双酚A型环氧树脂(三菱化学公司制“jER828EL”)3份、联苯型环氧树脂(日本化药公司制“NC3000L”)1份和缩水甘油基胺型环氧树脂(三菱化学公司制“630”)2份、双酚A型环氧树脂(三菱化学公司制“jER828EL”、环氧当量：184~194g/eq.)1份、萘型环氧树脂(DIC公司制“HP4032”、环氧当量：135~165g/eq.)6份和联苯型环氧树脂(日本化药公司制“NC3000L”、环氧当量：276g/eq.)1份。In Example 1, the components (A) were changed to 3 parts of a bisphenol A type epoxy resin ("jER828EL" manufactured by Mitsubishi Chemical Corporation), 1 part of a biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd.), 2 parts of a glycidylamine type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation), 1 part of a bisphenol A type epoxy resin ("jER828EL" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 184 to 194 g/eq.), 6 parts of a naphthalene type epoxy resin ("HP4032" manufactured by DIC Corporation, epoxy equivalent: 135 to 165 g/eq.), and 1 part of a biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 276 g/eq.).

进一步，实施例1中，变更为作为(B-2)成分的甲酚酚醛清漆树脂(DIC公司制“KA-1160”)2份、作为(B-2)成分的活性酯树脂(DIC公司制、“HPC-8000-65T”)1.54份和作为(B-1)成分的马来酰亚胺化合物(デザイナーモレキュールズ制“BMI-689”)4份、作为(B-2)成分的活性酯树脂(DIC公司制、“HPC-8000-65T”)4.62份。不使用(B-1)成分。Furthermore, in Example 1, the components (B-2) were changed to 2 parts of a cresol novolac resin ("KA-1160" manufactured by DIC Corporation), 1.54 parts of an active ester resin ("HPC-8000-65T" manufactured by DIC Corporation), and 4 parts of a maleimide compound ("BMI-689" manufactured by Desinair Molecule Co., Ltd.), and 4.62 parts of an active ester resin ("HPC-8000-65T" manufactured by DIC Corporation) as the component (B-1). The component (B-2) was not used.

进一步，实施例1中，变更为作为(C)成分的无机填充材料A70份、无机填充材料A60份。进一步，实施例1中，变更为作为(D)成分的热塑性树脂溶液A(不挥发成分：50%)20份、作为(D)成分的热塑性树脂溶液B(不挥发成分：50%)16份。此外，实施例1中，变更为作为(E)成分的固化促进剂(四国化成工业公司制、“1B2PZ”)0.05份、固化促进剂(四国化成工业公司制、“1B2PZ”)0.10份。Furthermore, in Example 1, the inorganic filler A as component (C) was changed to 70 parts and the inorganic filler A was changed to 60 parts. Furthermore, in Example 1, the thermoplastic resin solution A (non-volatile component: 50%) as component (D) was changed to 20 parts and the thermoplastic resin solution B (non-volatile component: 50%) as component (D) was changed to 16 parts. In addition, in Example 1, the curing accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ") as component (E) was changed to 0.05 parts and the curing accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ") was changed to 0.10 parts.

除了以上的事项之外，以与实施例1相同的方式，制备包含树脂组合物的树脂清漆A。并且，使用树脂清漆A，以与实施例1相同的方式，得到树脂片材B和评价用固化物C，使用树脂片材B的树脂组合物层和评价用固化物C，以与实施例1相同的方式，供于对树脂组合物的固化物进行评价。Except for the above matters, a resin varnish A containing a resin composition was prepared in the same manner as in Example 1. Furthermore, a resin sheet B and a cured product C for evaluation were obtained using the resin varnish A in the same manner as in Example 1, and the resin composition layer of the resin sheet B and the cured product C for evaluation were used in the same manner as in Example 1 to evaluate the cured product of the resin composition.

[比较例2][Comparative Example 2]

实施例1中，变更为作为(A)成分的双酚A型环氧树脂(三菱化学公司制“jER828EL”)3份、联苯型环氧树脂(日本化药公司制“NC3000L”)1份和缩水甘油基胺型环氧树脂(三菱化学公司制“630”)2份、双酚A型环氧树脂(三菱化学公司制“jER828EL”、环氧当量：184~194g/eq.)1份、联苯型环氧树脂(日本化药公司制“NC3000L”、环氧当量：276g/eq.)4份、联苯型环氧树脂(三菱化学公司制“YX4000”、环氧当量：约185g/eq.)2份。In Example 1, the components (A) were changed to 3 parts of a bisphenol A type epoxy resin ("jER828EL" manufactured by Mitsubishi Chemical Corporation), 1 part of a biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd.), and 2 parts of a glycidylamine type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation), 1 part of a bisphenol A type epoxy resin ("jER828EL" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 184 to 194 g/eq.), 4 parts of a biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 276 g/eq.), and 2 parts of a biphenyl type epoxy resin ("YX4000" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 185 g/eq.).

进一步，实施例1中，变更为作为(B-2)成分的甲酚酚醛清漆树脂(DIC公司制“KA-1160”、酚性羟基当量：117g/eq.)2份、作为(B-2)成分的活性酯树脂(DIC公司制、“HPC-8000-65T”)1.54份和作为(B-1)成分的马来酰亚胺化合物(デザイナーモレキュールズ制“BMI-689”)4份、作为(B-2)成分的甲酚酚醛清漆树脂(DIC公司制“KA-1160”、酚性羟基当量：117g/eq.)2份和作为(B-2)成分的活性酯树脂(DIC公司制、“HPC-8000-65T”)6.16份。不使用(B-1)成分。Furthermore, in Example 1, the components (B-2) were changed to 2 parts of a cresol novolac resin (“KA-1160” manufactured by DIC Corporation, phenolic hydroxyl equivalent: 117 g/eq.), 1.54 parts of an active ester resin (“HPC-8000-65T” manufactured by DIC Corporation) as the component (B-2), and 4 parts of a maleimide compound (“BMI-689” manufactured by Desinair Molecule Co., Ltd.), 2 parts of a cresol novolac resin (“KA-1160” manufactured by DIC Corporation, phenolic hydroxyl equivalent: 117 g/eq.) as the component (B-2), and 6.16 parts of an active ester resin (“HPC-8000-65T” manufactured by DIC Corporation) as the component (B-2). The component (B-1) was not used.

进一步，实施例1中，变更为作为(C)成分的无机填充材料A70份、无机填充材料A50份。进一步，实施例1中，替代作为(D)成分的热塑性树脂溶液A(不挥发成分：50%)20份，使用含环氧基的苯氧基树脂(三菱化学公司制“YX7200B35”、环氧当量：3000~16000g/eq.、不挥发成分：35%)5.71份。实施例1中，变更为作为(E)成分的固化促进剂(四国化成工业公司制、“1B2PZ”)0.05份、固化促进剂(四国化成工业公司制、“1B2PZ”)0.10份。Furthermore, in Example 1, the inorganic filler A as component (C) was changed to 70 parts and the inorganic filler A was changed to 50 parts. Furthermore, in Example 1, 5.71 parts of epoxy-containing phenoxy resin ("YX7200B35" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 3000-16000 g/eq., non-volatile component: 35%) were used instead of 20 parts of thermoplastic resin solution A (non-volatile component: 50%) as component (D). In Example 1, 0.05 parts of curing accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ") and 0.10 parts of curing accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ") were changed as component (E).

除了以上的事项之外，以与实施例1相同的方式，制备包含树脂组合物的树脂清漆A。并且，使用树脂清漆A，以与实施例1相同的方式，得到树脂片材B和评价用固化物C，使用树脂片材B的树脂组合物层和评价用固化物C，以与实施例1相同的方式，供于对树脂组合物的固化物进行评价。Except for the above matters, a resin varnish A containing a resin composition was prepared in the same manner as in Example 1. Furthermore, a resin sheet B and a cured product C for evaluation were obtained using the resin varnish A in the same manner as in Example 1, and the resin composition layer of the resin sheet B and the cured product C for evaluation were used in the same manner as in Example 1 to evaluate the cured product of the resin composition.

[比较例3][Comparative Example 3]

实施例1中，变更为作为(A)成分的双酚A型环氧树脂(三菱化学公司制“jER828EL”)3份、联苯型环氧树脂(日本化药公司制“NC3000L”)1份和缩水甘油基胺型环氧树脂(三菱化学公司制“jER630”)2份、双酚A型环氧树脂(三菱化学公司制“jER828EL”、环氧当量：184~194g/eq.)2份、联苯型环氧树脂(日本化药公司制“NC3000L”、环氧当量：276g/eq.)1份和缩水甘油基胺型环氧树脂(三菱化学公司制“630”、环氧当量：95g/eq.)1份。In Example 1, the components (A) were changed to 3 parts of a bisphenol A type epoxy resin ("jER828EL" manufactured by Mitsubishi Chemical Corporation), 1 part of a biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd.), and 2 parts of a glycidylamine type epoxy resin ("jER630" manufactured by Mitsubishi Chemical Corporation), 2 parts of a bisphenol A type epoxy resin ("jER828EL" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 184 to 194 g/eq.), 1 part of a biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 276 g/eq.), and 1 part of a glycidylamine type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95 g/eq.).

进一步，实施例1中，变更为作为(B-2)成分的甲酚酚醛清漆树脂(DIC公司制“KA-1160”)2份、作为(B-2)成分的活性酯树脂(DIC公司制、“HPC-8000-65T”)1.54份和作为(B-1)成分的马来酰亚胺化合物(デザイナーモレキュールズ制“BMI-689”)4份、作为(B-2)成分的甲酚酚醛清漆树脂(DIC公司制“KA-1160”、酚性羟基当量：117g/eq.)2份和作为(B-2)成分的活性酯树脂(DIC公司制、“HPC-8000-65T”)1.54份。不使用(B-1)成分。Furthermore, in Example 1, the components (B-2) were changed to 2 parts of a cresol novolac resin ("KA-1160" manufactured by DIC Corporation), 1.54 parts of an active ester resin ("HPC-8000-65T" manufactured by DIC Corporation) as the component (B-2), and 4 parts of a maleimide compound ("BMI-689" manufactured by Desinair Molecule) as the component (B-1), 2 parts of a cresol novolac resin ("KA-1160" manufactured by DIC Corporation, phenolic hydroxyl equivalent: 117 g/eq.) as the component (B-2), and 1.54 parts of an active ester resin ("HPC-8000-65T" manufactured by DIC Corporation) as the component (B-2). The component (B-1) was not used.

进一步，实施例1中，变更为作为(C)成分的无机填充材料A70份、无机填充材料A40份。进一步，实施例1中，变更为作为(D)成分的热塑性树脂溶液A(不挥发成分：50%)20份、热塑性树脂溶液A(不挥发成分：50%)32份。Furthermore, in Example 1, the inorganic filler A as the (C) component was changed to 70 parts and the inorganic filler A was changed to 40 parts. Furthermore, in Example 1, the thermoplastic resin solution A (non-volatile component: 50%) as the (D) component was changed to 20 parts and the thermoplastic resin solution A (non-volatile component: 50%) was changed to 32 parts.

除了以上的事项之外，以与实施例1相同的方式，制备包含树脂组合物的树脂清漆A。并且，使用树脂清漆A，以与实施例1相同的方式，得到树脂片材B和评价用固化物C，使用树脂片材B的树脂组合物层和评价用固化物C，以与实施例1相同的方式，供于对树脂组合物的固化物进行评价。Except for the above matters, a resin varnish A containing a resin composition was prepared in the same manner as in Example 1. Furthermore, a resin sheet B and a cured product C for evaluation were obtained using the resin varnish A in the same manner as in Example 1, and the resin composition layer of the resin sheet B and the cured product C for evaluation were used in the same manner as in Example 1 to evaluate the cured product of the resin composition.

[评价方法][Evaluation method]

使用上述实施例和比较例中得到的树脂片材B的树脂组合物层或评价用固化物C，针对树脂组合物的固化物，在获取各种参数的同时，从耐热性、翘曲和长期可靠性的观点出发，通过下述方法而评价。进一步，使用评价用固化物C，从耐药品性的观点出发，通过下述方法而评价。应予说明，表1中，所获取的参数之中，记载了评价中使用的参数。此外，评价结果为表1所示。The resin composition layer of the resin sheet B obtained in the above-mentioned embodiment and comparative example or the evaluation cured product C was used, and the cured product of the resin composition was evaluated by the following method from the viewpoints of heat resistance, warping and long-term reliability while obtaining various parameters. Furthermore, the evaluation cured product C was used and evaluated from the viewpoint of chemical resistance by the following method. It should be noted that in Table 1, the parameters used in the evaluation are recorded among the parameters obtained. In addition, the evaluation results are shown in Table 1.

＜各种参数的获取＞＜Acquisition of various parameters＞

(平均线热膨胀系数(CTE)α的测定)(Determination of average linear thermal expansion coefficient (CTE) α)

评价用固化物C裁切为宽度约5mm、长度约15mm，得到试验片D。针对试验片D，使用热机械分析装置(リガク公司制“Thermo Plus TMA8310”)，通过拉伸加重法进行热机械分析。详细而言，将试验片D装配上前述热机械分析装置上后，在载重1g、升温速度5℃/分钟的测定条件下连续测定2次热膨胀率。并且基于第2次的测定结果，算出从25℃(298K)至150℃(423K)的范围中的平均线热膨胀系数α(ppm/K)。The evaluation cured product C was cut into a width of about 5 mm and a length of about 15 mm to obtain a test piece D. For the test piece D, a thermomechanical analysis was performed by a tensile weighting method using a thermomechanical analysis device ("Thermo Plus TMA8310" manufactured by Rigaku Corporation). In detail, after the test piece D was assembled on the aforementioned thermomechanical analysis device, the thermal expansion coefficient was continuously measured twice under the measurement conditions of a load of 1 g and a heating rate of 5°C/min. And based on the second measurement result, the average linear thermal expansion coefficient α (ppm/K) in the range from 25°C (298K) to 150°C (423K) was calculated.

(动态弹性模量的测定；玻璃化转变温度Tg、储能模量E'和交联密度n的获取)(Determination of dynamic elastic modulus; acquisition of glass transition temperature Tg, storage modulus E' and crosslinking density n)

将评价用固化物C裁切为宽度5mm、长度15mm，得到试验片E。针对该试验片E，使用粘弹性测定装置(日立ハイテクサイエンス公司制“DMA7100”)，通过该拉伸加重法，进行热机械分析。具体而言，将试验片E装配上前述热机械分析装置后，在载重200mN、升温速度5℃/分钟的测定条件下，测定储能模量和损耗模量。The cured product C for evaluation was cut into pieces with a width of 5 mm and a length of 15 mm to obtain a test piece E. The test piece E was subjected to thermomechanical analysis by the tensile weighting method using a viscoelasticity measuring device ("DMA7100" manufactured by Hitachi High-Tech Science & Technology Co., Ltd.). Specifically, the test piece E was mounted on the aforementioned thermomechanical analysis device, and the storage modulus and loss modulus were measured under the measurement conditions of a load of 200 mN and a heating rate of 5°C/min.

首先，根据作为测定结果而得到的tanδ(储能模量和损耗模量的比的温度依赖曲线)的峰位，获取玻璃化转变温度Tg(℃)。First, the glass transition temperature Tg (° C.) is obtained from the peak position of tan δ (temperature dependency curve of the ratio of storage modulus to loss modulus) obtained as a measurement result.

接着，确定规定的温度T(K)。具体而言，将规定的温度T(K)为了将已获取的玻璃化转变温度Tg(℃)换算为单位K而加算273K，且加算80K的温度，由此确定。应予说明，规定的温度T(K)附近的温度区域中，储能模量的值存在不会大幅变动的倾向，因此关于确定的规定的温度T(K)，允许在-5℃~+5℃的范围内中可以生成误差。并且，获取确定的规定的温度T(K)下的储能模量的测定值E'(单位：GPa、即109Pa)。Next, a predetermined temperature T(K) is determined. Specifically, the predetermined temperature T(K) is determined by adding 273K to convert the obtained glass transition temperature Tg(°C) into the unit K, and adding a temperature of 80K. It should be noted that in the temperature range near the predetermined temperature T(K), the value of the storage modulus tends not to change significantly, so an error is allowed within the range of -5°C to +5°C for the determined predetermined temperature T(K). In addition, the measured value E' (unit: GPa, i.e., 10 9 Pa) of the storage modulus at the determined predetermined temperature T(K) is obtained.

接着，将所获取的储能模量的E'(Pa)代入以下的式中，由此算出交联密度n(mol/cm3)。在此，交联密度n可以考虑作为表示单位体积存在的交联分子的数量的指标。Next, the storage modulus E' (Pa) thus obtained is substituted into the following formula to calculate the crosslinking density n (mol/cm 3 ). Here, the crosslinking density n can be considered as an index representing the number of crosslinking molecules present per unit volume.

n=E'/3RTn=E'/3RT

(上述式中，T是规定的温度T(K)，E'是规定的温度T(K)下的储能模量的测定值(Pa)，R是作为气体常数的8310000(Pa・cm3/mol・K)。应予说明，作为E'/3，可以使用规定的温度T(K)下的剪切弹性模量G'的测定值(109Pa))。(In the above formula, T is a predetermined temperature T (K), E' is a measured value (Pa) of the storage modulus at the predetermined temperature T (K), and R is 8310000 (Pa·cm 3 /mol·K) which is a gas constant. It should be noted that as E'/3, a measured value (10 9 Pa) of the shear modulus G' at the predetermined temperature T (K) can be used).

(值Zf的获取)(Obtaining the value Z f )

值Zf被定义为固化物的平均线热膨胀系数α(ppm/K)除以该固化物的交联密度n(mol/cm3)而得到的值，获取该值Zf(ppm・cm3/mol・K)作为树脂组合物的固化物的参数。所获取的值Zf与后述各评价的评价结果对照，由此研究了能够解决本发明的课题的范围。The value Zf is defined as the value obtained by dividing the average linear thermal expansion coefficient α (ppm/K) of the cured product by the crosslinking density n (mol/ cm3 ) of the cured product, and the value Zf (ppm・cm3 /mol・K) is obtained as a parameter of the cured product of the resin composition. The obtained value Zf is compared with the evaluation results of each evaluation described below, thereby examining the range of the problems that can be solved by the present invention.

＜长期可靠性的评价＞＜Evaluation of long-term reliability＞

长期可靠性的评价对树脂组合物的固化物实施HTS试验，在HTS试验的前后测定断裂点强度，算出断裂点强度的变化度(%)，由此进行。The long-term reliability was evaluated by subjecting the cured product of the resin composition to an HTS test, measuring the breaking strength before and after the HTS test, and calculating the degree of change (%) in the breaking strength.

(HTS试验)(HTS test)

评价用固化物C供于HTS试验(High Thermal Storage test)。HTS试验中，将150℃下1000小时的条件下保持评价用固化物C。由此，得到HTS试验后的评价用固化物C'。The evaluation cured product C was subjected to a HTS test (High Thermal Storage test). In the HTS test, the evaluation cured product C was kept at 150° C. for 1000 hours. Thus, an evaluation cured product C′ after the HTS test was obtained.

(HTS试验前后的断裂点强度的测定)(Determination of breaking point strength before and after HTS test)

通过将评价用固化物C切出为顶视图哑铃形状的1号形状，由此得到5个的试验片F。同样地，将评价用固化物C'切出为顶视图哑铃形状的1号形状，由此得到5个的试验片F'。针对各个试验片F、F'，使用オリエンテック公司制拉伸试验机“RTC-1250A”，在23℃、试验速度5mm/min的测定条件下进行拉伸试验，根据应力-应变曲线，求出拉伸断裂点强度(以下也简称为“断裂点强度”)。测定按照JIS K7127：1999实施。5个试验片F的断裂点强度的平均值除以HTS试验前的拉伸断裂点强度σ0。5个试验片F'的断裂点强度的平均值除以HTS试验后的拉伸断裂点强度σ1。The evaluation cured product C was cut into a top view dumbbell shape No. 1, thereby obtaining five test pieces F. Similarly, the evaluation cured product C' was cut into a top view dumbbell shape No. 1, thereby obtaining five test pieces F'. For each test piece F, F', a tensile test was performed using a tensile testing machine "RTC-1250A" manufactured by Orientec Co., Ltd. under the measuring conditions of 23°C and a test speed of 5 mm/min, and the tensile breaking point strength (hereinafter also referred to as "breaking point strength") was calculated based on the stress-strain curve. The measurement was carried out in accordance with JIS K7127:1999. The average value of the breaking point strengths of the five test pieces F was divided by the tensile breaking point strength σ 0 before the HTS test. The average value of the breaking point strengths of the five test pieces F' was divided by the tensile breaking point strength σ 1 after the HTS test.

(变化度(%)的算出)(Calculation of the degree of change (%))

接着，HTS试验前后的拉伸断裂点强度的变化度(%)基于下述式算出。Next, the change (%) of the tensile breaking strength before and after the HTS test was calculated based on the following formula.

变化度(%)={(σ1-σ0)/σ0}×100Degree of change (%)={(σ 1 -σ 0 )/σ 0 }×100

(评价)(evaluate)

如上述那样得到的变化度(%)按照以下的基准，进行评价。The degree of change (%) obtained as described above was evaluated according to the following criteria.

“○”：变化度(%)处于-10%~+10%的范围内的情况下，变化度小，长期可靠性优异"○": When the variation (%) is within the range of -10% to +10%, the variation is small and the long-term reliability is excellent

“×”：变化度(%)不在-10%~+10%的范围内，变化度大，长期可靠性差“×”: The variation (%) is not within the range of -10% to +10%, the variation is large, and the long-term reliability is poor

此外，如果观察评价为长期可靠性差的比较例3的试验片F'，则确认利用氧化的劣化。Furthermore, when the test piece F' of Comparative Example 3 evaluated as having poor long-term reliability was observed, degradation due to oxidation was confirmed.

＜翘曲的评价＞＜Warping Evaluation＞

(翘曲测定用的带绝缘层的硅晶片的制作)(Preparation of Silicon Wafer with Insulating Layer for Warpage Measurement)

树脂片材B以在12英寸圆盘状的硅晶片(厚度775μm)的单面全体上接合树脂组合物层的方式，使用间歇式真空加压层压机(ニッコー・マテリアルズ公司制2台积层层压机“CVP700”)来层压，其后，剥离支撑体。在硅晶片上层压的树脂组合物层上，可以进一步反复进行2次利用相同的流程的树脂片材的层压和支撑体的剥离。由此，在硅晶片上，形成包含总计3层的树脂组合物层的厚度300μm的树脂组合物层的层叠体。将带所得树脂组合物层的层叠体的硅晶片在烘箱内在180℃和90分钟的条件下进行热处理。由此，得到带进行了固化的树脂组合物层的硅晶片(即带绝缘层的硅晶片)。Resin sheet B is laminated using an intermittent vacuum pressure laminating machine (2 stacking laminating machines "CVP700" manufactured by Niccolo Materials Co., Ltd.) in a manner of bonding a resin composition layer on the entire single side of a 12-inch disc-shaped silicon wafer (thickness 775 μm), and then peeling off the support. On the resin composition layer laminated on the silicon wafer, the lamination of the resin sheet and the peeling of the support using the same process can be further repeated twice. Thus, on the silicon wafer, a laminate of a resin composition layer having a thickness of 300 μm including a total of 3 layers of resin composition layers is formed. The silicon wafer with the laminate of the obtained resin composition layer is heat-treated in an oven at 180 ° C and 90 minutes. Thus, a silicon wafer with a cured resin composition layer (i.e., a silicon wafer with an insulating layer) is obtained.

(翘曲的测定)(Measurement of Warpage)

将所得带绝缘层的硅晶片的一端按压在平坦的台上的状态下，将带绝缘层的硅晶片的端部的下面与台的上面之间的铅直方向上的距离测定为翘曲量，确定示出最大翘曲量(μm)的端部。While one end of the obtained silicon wafer with an insulating layer is pressed against a flat table, the vertical distance between the bottom surface of the end of the silicon wafer with an insulating layer and the top surface of the table is measured as the warpage amount, and the end showing the maximum warpage amount (μm) is determined.

(评价)(evaluate)

如上述那样，按照以下的基准，评价特定的最大翘曲量(μm)。As described above, the specific maximum warpage amount (μm) was evaluated according to the following criteria.

“○”：最大翘曲量处于0μm以上且2000μm以下的范围内的情况下，翘曲小，翘曲被充分抑制。“◯”: When the maximum warpage amount is within the range of 0 μm or more and 2000 μm or less, the warpage is small and the warpage is sufficiently suppressed.

“×”：最大翘曲量大于2000μm的情况下，翘曲大，难以充分翘曲。"×": When the maximum warpage amount is larger than 2000 μm, the warpage is large and sufficient warping is difficult.

＜耐药品性的评价＞＜Evaluation of chemical resistance＞

(药品浸渍试验)(Drug immersion test)

将评价用固化物C切断为1边5cm的正方形，由此得到多个试验片G。将试验片G在70℃的强碱水溶液中浸渍1小时。作为强碱水溶液，使用1质量%的氢氧化钾水溶液。其后，取出试验片G，用蒸馏水洗涤，在130℃的烘箱内进行1小时干燥。由此，得到药品浸渍试验后的试验片G'。The evaluation solidified product C was cut into squares with a side of 5 cm to obtain a plurality of test pieces G. The test piece G was immersed in a strong alkaline aqueous solution at 70°C for 1 hour. As the strong alkaline aqueous solution, a 1% by mass potassium hydroxide aqueous solution was used. Thereafter, the test piece G was taken out, washed with distilled water, and dried in an oven at 130°C for 1 hour. Thus, a test piece G' after the drug immersion test was obtained.

(药品浸渍试验前后的质量的测定和质量减少率的算出)(Measurement of mass before and after chemical immersion test and calculation of mass reduction rate)

测定试验片G的质量，将其记作药品浸渍试验前的质量M0。此外，测定试验片G'的质量，将其记作药品浸渍试验前的质量M1。The mass of the test piece G was measured and recorded as the mass M 0 before the chemical immersion test. In addition, the mass of the test piece G′ was measured and recorded as the mass M 1 before the chemical immersion test.

接着，药品浸渍试验前后的质量减少率(%)基于下述式而算出。Next, the mass reduction rate (%) before and after the chemical immersion test was calculated based on the following formula.

质量减少率(%)={(M0-M1)/M0}×100Mass reduction rate (%) = {(M 0 -M 1 )/M 0 } × 100

(评价)(evaluate)

如上述那样得到的质量减少率(%)按照以下的基准进行评价。The mass reduction rate (%) obtained as described above was evaluated according to the following criteria.

“○”：质量减少率(%)低于1质量%的情况下，相对于药品而言溶解的部分充分少，耐药品性优异"○": When the mass reduction rate (%) is less than 1 mass %, the dissolved portion relative to the chemical is sufficiently small, and the chemical resistance is excellent

“×”：质量减少率(%)为1质量%以上的情况下，相对于药品而言溶解的部分多，耐药品性差。“×”: When the mass reduction rate (%) is 1 mass % or more, the dissolved portion is large relative to the chemical, and the chemical resistance is poor.

[结果][result]

上述实施例和比较例的结果示于下述表1。下述表1中，各成分的量表示不挥发成分换算量。此外，表1所示的“无机填充材料含有比例”表示将树脂组合物中的树脂成分设为100质量%的情况下的(C)成分的含量。此外，α表示平均线热膨胀系数，T表示规定的温度，E'表示规定的温度T下的储能模量，n表示交联密度，Zf表示平均线热膨胀系数α除以在规定的温度T下的储能模量E'而得到的值，Tg表示玻璃化转变温度。The results of the above-mentioned embodiments and comparative examples are shown in Table 1 below. In Table 1 below, the amount of each component represents the amount of non-volatile components. In addition, the "inorganic filler content ratio" shown in Table 1 represents the content of the (C) component when the resin component in the resin composition is set to 100% by mass. In addition, α represents the average linear thermal expansion coefficient, T represents the specified temperature, E' represents the storage modulus at the specified temperature T, n represents the crosslinking density, Zf represents the average linear thermal expansion coefficient α divided by the storage modulus E' at the specified temperature T, and Tg represents the glass transition temperature.

【表1】【Table 1】

。 .

＜研究＞＜Research＞

由表1可知，根据实施例与比较例的对比，实施例中，在包含(A)成分和(B)成分的树脂组合物中，固化物的平均线热膨胀系数α(ppm/K)除以该固化物的交联密度n(mol/cm3)而得到的值Zf(ppm・cm3/mol・K)满足下述式：As can be seen from Table 1, according to the comparison between the Examples and the Comparative Examples, in the Examples, in the resin composition comprising the components (A) and (B), the value Z f (ppm・cm 3 /mol・K) obtained by dividing the average linear thermal expansion coefficient α (ppm/K) of the cured product by the crosslinking density n (mol/cm 3 ) of the cured product satisfies the following formula:

145＜Zf＜1300145＜Z f ＜1300

从而存在可以提供能够翘曲被抑制、且长期可靠性优异的固化物的树脂组合物的倾向。Therefore, there is a tendency to provide a resin composition that can suppress warping and has a cured product that is excellent in long-term reliability.

进一步，值Zf满足上述式，由此还可知可以提供能够得到耐药品性优异的固化物的树脂组合物。此外，可知还能够提供实施例所涉及的树脂组合物的固化物、该树脂组合物的固化物、树脂片材、印刷配线板、半导体芯片封装和半导体装置。Furthermore, the value Z f satisfies the above formula, and thus it can be known that a resin composition capable of obtaining a cured product having excellent chemical resistance can be provided. In addition, it can be known that a cured product of the resin composition according to the embodiment, a cured product of the resin composition, a resin sheet, a printed wiring board, a semiconductor chip package, and a semiconductor device can also be provided.

应予说明，实施例1~3中，即使在不含(C)成分~(E)成分的情况下，虽然程度存在差异，但确认到归属于与上述实施例相同的结果。此外，实施例1~3中，将耐药品性的评价中使用的强碱水溶液替代氢氧化钾水溶液，使用氢氧化四甲基铵溶液、氢氧化钠水溶液和碳酸钠水溶液中任一者，也确认到归属于与上述实施例相同的结果。It should be noted that in Examples 1 to 3, even when the components (C) to (E) were not included, the same results as those in the above examples were confirmed, although the degree was different. In addition, in Examples 1 to 3, the strong alkali aqueous solution used in the evaluation of chemical resistance was replaced with the potassium hydroxide aqueous solution, and any one of tetramethylammonium hydroxide solution, sodium hydroxide aqueous solution and sodium carbonate aqueous solution was used, and the same results as those in the above examples were confirmed.

Claims (73)

1. A resin composition comprising (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler and (D) a thermoplastic resin,
(B) The component (C) is a maleimide compound having at least one hydrocarbon chain selected from an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms and optionally having a substituent in the molecule,
(C) The content of the component (A) is 60% by mass or more based on 100% by mass of the nonvolatile component in the resin composition,
The value Z f(ppm·cm3/mol.K obtained by dividing the average linear thermal expansion coefficient alpha (ppm/K) of a cured product obtained by curing the resin composition at 180 ℃ for 90 minutes by the crosslink density n (mol/cm 3) of the cured product satisfies the following formula:
145＜Zf＜1300。
2. The resin composition according to claim 1, wherein the content of the component (C) is 70% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.
3. The resin composition according to claim 1, wherein the content of the component (C) is 71% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.
4. The resin composition according to claim 1, wherein the content of the component (C) is 95% by mass or less based on 100% by mass of the nonvolatile component in the resin composition.
5. The resin composition according to claim 1, wherein the content of the component (C) is 93 mass% or less based on 100 mass% of the nonvolatile component in the resin composition.
6. The resin composition according to claim 1, wherein the average particle diameter of the component (C) is 20 μm or less.
7. The resin composition according to claim 1, wherein the average particle diameter of the component (C) is 10 μm or less.
8. The resin composition according to claim 1, wherein the average particle diameter of the component (C) is 2.0 μm or less.
9. The resin composition according to claim 1, wherein the average particle diameter of the component (C) is 1nm or more.
10. The resin composition according to claim 1, wherein the average particle diameter of the component (C) is 10nm or more.
11. The resin composition according to claim 1, wherein the component (B) is a maleimide compound represented by the following general formula (B1) or a maleimide compound represented by the following general formula (B2),
In the general formula (B1), M represents an optionally substituted aliphatic hydrocarbon group having 2 valences including an alkylene group having 5 or more carbon atoms, L represents a single bond or a 2-valent linking group,
In the general formula (B2), M 1 each independently represents a 2-valent aliphatic hydrocarbon group containing an alkylene group having 5 or more carbon atoms, which may have a substituent, a each independently represents a 2-valent group having an alkylene group having 5 or more carbon atoms, which may have a substituent, or an aromatic ring, which may have a substituent, and t represents an integer of 1 to 10.
12. The resin composition according to claim 1, wherein the component (B) is a compound represented by the following formula (B1), (B2), (B3), (B4), (B5) or (B6),
Wherein n9, n10, n11, n12 and n13 represent integers of 1 to 10.
13. The resin composition according to claim 1, wherein the content of the component (B) is 0.5% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.
14. The resin composition according to claim 1, wherein the content of the component (B) is 3% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.
15. The resin composition according to claim 1, wherein the content of the component (B) is 50% by mass or less based on 100% by mass of the nonvolatile component in the resin composition.
16. The resin composition according to claim 1, wherein the content of the component (B) is 25% by mass or less based on 100% by mass of the nonvolatile component in the resin composition.
17. The resin composition according to claim 1, wherein component (A) comprises (A-1) a liquid epoxy resin.
18. The resin composition according to claim 17, wherein the content of the component (A-1) is 0.1% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.
19. The resin composition according to claim 17, wherein the content of the component (A-1) is 2% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.
20. The resin composition according to claim 17, wherein the content of the component (A-1) is 40% by mass or less based on 100% by mass of the nonvolatile component in the resin composition.
21. The resin composition according to claim 17, wherein the content of the component (A-1) is 25% by mass or less based on 100% by mass of the nonvolatile component in the resin composition.
22. The resin composition according to claim 1, wherein component (A) comprises (A-2) a solid epoxy resin.
23. The resin composition according to claim 22, wherein the content of the component (A-2) is 0.01% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.
24. The resin composition according to claim 22, wherein the content of the component (A-2) is 0.2% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.
25. The resin composition according to claim 22, wherein the content of the component (A-2) is 10% by mass or less based on 100% by mass of the nonvolatile component in the resin composition.
26. The resin composition according to claim 22, wherein the content of the component (A-2) is 3% by mass or less based on 100% by mass of the nonvolatile component in the resin composition.
27. The resin composition according to claim 1, wherein the content of the component (A) is 0.5% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.
28. The resin composition according to claim 1, wherein the content of the component (A) is 3% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.
29. The resin composition according to claim 1, wherein the content of the component (A) is 70% by mass or less based on 100% by mass of the nonvolatile component in the resin composition.
30. The resin composition according to claim 1, wherein the content of the component (A) is 35% by mass or less based on 100% by mass of the nonvolatile component in the resin composition.
31. The resin composition according to claim 1, wherein the content of the component (D) is 25% by mass or less based on 100% by mass of the nonvolatile component in the resin composition.
32. The resin composition according to claim 1, wherein the content of the component (D) is 15% by mass or less based on 100% by mass of the nonvolatile component in the resin composition.
33. The resin composition according to claim 1, wherein the content of the component (D) is 0.1% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.
34. The resin composition according to claim 1, wherein the content of the component (D) is 5% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.
35. The resin composition according to claim 1, wherein the content of the component (D) is 65% by mass or less based on 100% by mass of the resin component in the resin composition.
36. The resin composition according to claim 1, wherein the content of the component (D) is 55 mass% or less based on 100 mass% of the resin component in the resin composition.
37. The resin composition according to claim 1, wherein the content of the component (D) is 0.1% by mass or more based on 100% by mass of the resin component in the resin composition.
38. The resin composition according to claim 1, wherein the content of the component (D) is 30% by mass or more based on 100% by mass of the resin component in the resin composition.
39. The resin composition according to claim 1, wherein the component (D) comprises a resin having a structure of 1 or more selected from the group consisting of a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene oxide structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in a molecule.
40. The resin composition according to claim 1, wherein the component (D) has a functional group selected from the group consisting of hydroxyl group, carboxyl group, amino group, vinyl group, acryl group, and methacryl group.
41. The resin composition according to claim 1, wherein the content of the component (D) is 0.5 mass% or more and 25 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition.
42. The resin composition of claim 1, further comprising (E) a cure accelerator.
43. The resin composition according to claim 42, wherein,
(E) The content of the component (A) is 0.001% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.
44. The resin composition according to claim 42, wherein,
(E) The content of the component (A) is 0.02% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.
45. The resin composition according to claim 42, wherein,
(E) The content of the component (A) is 3% by mass or less based on 100% by mass of the nonvolatile component in the resin composition.
46. The resin composition according to claim 42, wherein,
(E) The content of the component (A) is 1% by mass or less based on 100% by mass of the nonvolatile component in the resin composition.
47. The resin composition according to claim 1, wherein the glass transition temperature Tg (. Degree. C.) of the cured product is in the range of 150 to 240 ℃.
48. The resin composition according to claim 1, wherein the cured product has a glass transition temperature Tg (. Degree. C.) of 176℃or higher.
49. The resin composition according to claim 1, wherein the cured product has a glass transition temperature Tg (. Degree. C.) of 205℃or lower.
50. The resin composition according to claim 1, wherein the cured product has an average linear thermal expansion coefficient α of less than 30ppm/K.
51. The resin composition according to claim 1, wherein the cured product has an average linear thermal expansion coefficient α of 25ppm/K or less.
52. The resin composition according to claim 1, wherein the cured product has an average linear thermal expansion coefficient α of 20ppm/K or less.
53. The resin composition according to claim 1, wherein the cured product has an average linear thermal expansion coefficient α of 1ppm/K or more.
54. The resin composition according to claim 1, wherein the cured product has an average linear thermal expansion coefficient α of 7ppm/K or more.
55. The resin composition according to claim 1, wherein the storage modulus E' of the cured product is less than 1.50X10- 9 Pa at a predetermined temperature T (K), wherein the predetermined temperature T (K) is a temperature representing a sum of glass transition temperature Tg (. Degree. C.) and 353 (K) of the cured product.
56. The resin composition according to claim 55, wherein the cured product has a storage modulus E' of 1.20X10 9 Pa or less at a predetermined temperature T (K).
57. The resin composition according to claim 55, wherein the cured product has a storage modulus E' at a predetermined temperature T (K) of greater than 0.30X10 9 Pa.
58. The resin composition according to claim 55, wherein the cured product has a storage modulus E' of 0.40X10 9 Pa or more at a predetermined temperature T (K).
59. The resin composition according to claim 1, wherein the cured product has a crosslinking density n of not more than 0.15mol/cm 3.
60. The resin composition according to claim 1, wherein the cured product has a crosslinking density n of not more than 0.07mol/cm 3.
61. The resin composition according to claim 1, wherein the cured product has a crosslinking density n of 0.01mol/cm 3 or more.
62. The resin composition according to claim 1, wherein the cured product has a crosslinking density n of 0.03mol/cm 3 or more.
63. The resin composition according to claim 1, wherein the aforementioned value Z f satisfies the following formula:
150≤Zf≤1000。
64. the resin composition according to claim 1, wherein the value Z f is 160 or more.
65. The resin composition according to claim 1, wherein the value Z f is 500 or less.
66. The resin composition according to claim 1, which is used for forming an insulating layer.
67. The resin composition according to claim 1, which is used for forming a solder resist layer.
68. The cured product of a resin composition according to any one of claims 1 to 67.
69. A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of claims 1 to 67 provided on the support.
70. A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 67 or a cured product according to claim 68.
71. A semiconductor chip package comprising the printed wiring board of claim 70, and a semiconductor chip mounted on the printed wiring board.
72. A semiconductor chip package comprising a semiconductor chip and a cured product of the resin composition according to any one of claims 1 to 67 or a cured product according to claim 68, wherein the semiconductor chip is sealed.
73. A semiconductor device comprising the printed wiring board of claim 70, or the semiconductor chip package of claim 71 or 72.
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