Semiconductor chip package manufacturing method

Abstract

To provide a method for manufacturing semiconductor chip packages using a prepreg that can produce a cured product with low dielectric loss tangent, a small number of needle voids, and suppressed plating penetration. [Solution] A method for manufacturing a semiconductor chip package, comprising the steps of (I) laminating a prepreg containing a sheet-like fibrous substrate and a resin composition impregnated into the sheet-like fibrous substrate onto a substrate, (II) curing the prepreg to form an insulating layer, and (V) forming a conductive layer, wherein the resin composition comprises (a) an epoxy resin and (b) an active ester-based curing agent, the ratio of component (a) to component (b) is 0.7 or more and 1.4 or less, the sheet-like fibrous substrate is surface-treated with a surface treatment agent, and the content of the surface treatment agent per unit weight of the sheet-like fibrous substrate, as measured by the heat weight loss method, is 0.25% by mass or more and 0.4% by mass or less.

Description

[Technical Field]

[0001] This invention relates to a method for manufacturing a semiconductor chip package and a cured product. [Background technology]

[0002] Insulating materials that can be used as insulating layers for semiconductor chip packages include, for example, prepregs obtained by impregnating a resin composition into a sheet-like fibrous substrate such as glass cloth (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2014-185221 [Overview of the project] [Problems that the invention aims to solve]

[0004] In recent years, with the increasing sophistication of semiconductor chip packages, there has been a growing demand for narrower via hole openings (narrower pitch). Furthermore, with the advancement of semiconductor chip packages, there is a growing demand for lower dielectric loss tangents in the cured prepreg.

[0005] When forming narrow-pitch via holes with a laser after forming an insulating layer with a prepreg, stress is easily generated due to the energy during laser processing. Therefore, if the adhesion strength between the sheet-like fibrous base material of the prepreg and the cured resin composition is low, the interface between the sheet-like fibrous base material and the cured resin composition may delaminate. When the interface delaminates, when forming a conductive layer on the insulating layer after forming the insulating layer with the prepreg, plating solutions or the like may seep between the fibers (filaments) of the sheet-like fibrous base material and the cured resin composition, which can reduce the insulation reliability. This phenomenon of plating solutions or the like seeping in is sometimes called plating penetration.

[0006] Therefore, in order to increase the adhesion strength between the sheet-like fiber substrate and the cured resin composition, it is necessary to use a sheet-like fiber substrate that has been surface-treated with a larger amount of surface treatment agent.

[0007] Furthermore, to lower the dielectric loss tangent of the cured prepreg, it is conceivable to include a large amount of active ester-based curing agent in the resin composition.

[0008] When a resin composition contains a large amount of active ester-based curing agent, the polarity of the resin composition decreases. On the other hand, the polarity of a sheet-like fibrous substrate that has been surface-treated with a surface treatment agent is high. Therefore, a polarity difference occurs between the sheet-like fibrous substrate and the resin composition. As a result, the resin composition has difficulty impregnating between the fibers of the sheet-like fibrous substrate, and needle-shaped voids may occur along the fibers of the sheet-like fibrous substrate. In particular, when the resin composition contains a large amount of active ester-based curing agent, the polarity difference becomes larger, and the occurrence of needle-shaped voids becomes more frequent. These needle-shaped voids are sometimes called needle voids. When needle voids occur, adhesion problems between via holes are more likely to occur when manufacturing semiconductor chip packages.

[0009] The present invention was devised in view of the above-mentioned problems, and aims to provide a method for manufacturing a semiconductor chip package using a prepreg that can produce a cured product with low dielectric loss tangent, a small number of needle voids, and suppressed plating penetration; and a cured body containing the prepreg. [Means for solving the problem]

[0010] As a result of diligent research to solve the above-mentioned problems, the inventors have completed the present invention by using a sheet-like fiber substrate surface-treated with a predetermined amount of surface treatment agent, and by incorporating a combination of epoxy resin and active ester-based curing agent in the resin composition so that the ratio of these components is within a predetermined range.

[0011] In other words, the present invention includes the following: [1] A step of laminating a prepreg containing a sheet-like fiber substrate and a resin composition impregnated in the sheet-like fiber substrate on a substrate, (II) A step of curing the prepreg to form an insulating layer, and (V) A method for manufacturing a semiconductor chip package, including a step of forming a conductor layer, The resin composition contains (a) an epoxy resin and (b) an active ester-based curing agent, The quantitative ratio of component (a) to component (b) ([(total number of active groups of component (b)) / (total number of epoxy groups of component (a))]) is 0.7 or more and 1.4 or less, The sheet-like fiber substrate is surface-treated with a surface treatment agent, and the content of the surface treatment agent per unit weight of the sheet-like fiber substrate, measured by the thermogravimetric reduction method, is 0.25% by mass or more and 0.4% by mass or less. A method for manufacturing a semiconductor chip package. [2] Further, the resin composition contains (c) an inorganic filler. The method for manufacturing a semiconductor chip package according to [1]. [3] The surface treatment agent contains any one of an aminosilane-based coupling agent, an epoxysilane-based coupling agent, and a (meth)acrylicsilane-based coupling agent. The method for manufacturing a semiconductor chip package according to [1] or [2]. [4] The thickness of the sheet-like fiber substrate is 26 μm or less. The method for manufacturing a semiconductor chip package according to any one of [1] to [3]. [5] Further, the resin composition contains (k) a solvent, and the content of the aromatic hydrocarbon-based solvent in the (k) solvent contained in the dried resin composition is 0% by mass or more and 40% by mass or less when the total solvent contained in the resin composition is 100% by mass. The method for manufacturing a semiconductor chip package according to any one of [1] to [4]. [6] Further, after the completion of step (II), it includes a step of (III) drilling holes in the insulating layer to form via holes in the insulating layer. The method for manufacturing a semiconductor chip package according to any one of [1] to [5]. [7] The distance between the openings of the via holes is 200 μm or less. The method for manufacturing a semiconductor chip package according to [6]. The method for manufacturing a semiconductor chip package according to any one of [1] to [7], wherein the substrate is peeled off after the completion of the step (V). [9] When the quantitative ratio between the component (a) and the component (b) is α, and the content of the surface treatment agent per unit weight of the sheet-like fiber base material is β, β 2 The method for manufacturing a semiconductor chip package according to any one of [1] to [8], wherein β / α is 0.01 or more and 0.5 or less.

[10] A cured body obtained by curing a prepreg containing a sheet-like fiber base material and a resin composition impregnated in the sheet-like fiber base material, which has via holes penetrating in the thickness direction of the cured body, wherein the resin composition contains (a) an epoxy resin and (b) an active ester-based curing agent, the quantitative ratio between the component (a) and the component (b) ([the total number of active groups of the component (b)] / [the total number of epoxy groups of the component (a)]) is 0.7 or more and 1.4 or less, the sheet-like fiber base material is surface-treated with a surface treatment agent, and the content of the surface treatment agent per unit weight of the sheet-like fiber base material measured by the thermogravimetric method is 0.25% by mass or more and 0.4% by mass or less, and the distance between the openings of the via holes is 200 μm or less. [Advantages of the Invention]

[0012] According to the present invention, there are provided a method for manufacturing a semiconductor chip package using a prepreg capable of obtaining a cured product having a low dielectric tangent, a small number of needle voids, and suppressed plating penetration; and a cured body containing the prepreg. [Embodiments for Carrying Out the Invention]

[0013] Hereinafter, the present invention will be described with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and its equivalent scope.

[0014] Before describing in detail the method for manufacturing the semiconductor chip package of the present invention, we will first describe the prepregs that can be used in the method for manufacturing the semiconductor chip package of the present invention.

[0015] [Prepreg] The prepreg comprises a sheet-like fibrous substrate and a resin composition impregnated into the sheet-like fibrous substrate, wherein the resin composition comprises (a) an epoxy resin and (b) an active ester-based curing agent, the ratio of component (a) to component (b) (total number of epoxy groups in component (a) / total number of active groups in component (b)) is 0.7 or more and 1.4 or less, the sheet-like fibrous substrate is surface-treated with a surface treatment agent, and the content of the surface treatment agent per unit weight of the sheet-like fibrous substrate, as measured by the heat weight loss method, is 0.25% by mass or more and 0.4% by mass or less. By using the prepreg of the present invention, a cured product with low dielectric loss tangent, a small number of needle voids, and suppressed plating penetration can be obtained.

[0016] <Sheet-like fiber base material> The sheet-like fibrous substrate used in the prepreg has a low number of needle voids and is surface-treated with a surface treatment agent to suppress plating penetration. The content of the surface treatment agent per unit weight of the sheet-like fibrous substrate, as measured by the heat weight loss method, is 0.25% by mass or more and 0.4% by mass or less.

[0017] As described above, if the surface treatment agent content is too high, a polarity difference will occur between the surface treatment agent and the resin composition containing an active ester-based curing agent to lower the dielectric loss tangent, resulting in the formation of needle voids. In the present invention, by adjusting the content of the surface treatment agent used to surface-treat the sheet-like fiber substrate, and further adjusting the ratio of epoxy resin and active ester-based curing agent contained in the resin composition described later, it becomes possible to obtain a cured product with a low dielectric loss tangent, a small number of needle voids, and suppressed plating penetration.

[0018] The content of the surface treatment agent per unit weight of the sheet-like fibrous substrate is 0.25% by mass or more, preferably 0.28% by mass or more, and more preferably 0.3% by mass or more, from the viewpoint of reducing the number of needle voids and suppressing plating penetration. The upper limit is 0.4% by mass or less, preferably 0.38% by mass or less, and more preferably 0.36% by mass or less. The content of the surface treatment agent is measured by the heating weight loss method, specifically by measuring the weight of the sheet-like fibrous substrate before and after heating it in an electric furnace at a high temperature of 625°C or higher for 10 minutes.

[0019] Examples of surface treatment agents include silane coupling agents such as aminosilane-based coupling agents, epoxysilane-based coupling agents, (meth)acrylicsilane-based coupling agents, imidazolesilane-based coupling agents, fluorine-containing silane coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, and titanate-based coupling agents; and silane compounds such as alkoxysilanes and organosilazane compounds. From the viewpoint of significantly obtaining the effects of the present invention, silane coupling agents are preferred as surface treatment agents, and it is more preferable that the surface treatment agent contains any of aminosilane-based coupling agents, epoxysilane-based coupling agents, and (meth)acrylicsilane-based coupling agents, with aminosilane-based coupling agents being even more preferred. The surface treatment agent may be used alone or in any combination of two or more types. (Meth)acrylic is a concept that includes acrylic and methacrylic.

[0020] Commercial surface treatment agents may be used. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) from Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) from Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) from Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) from Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) from Shin-Etsu Chemical Co., Ltd., and "KBM103" (phenyl Examples include trimethoxysilane, Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy type silane coupling agent), Shin-Etsu Chemical Co., Ltd.'s "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM5783" (N-phenyl-8-aminooctyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM4803" (8-glycidoxyoctyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM503" (3-methacryloxypropyltrimethoxysilane), etc.

[0021] The degree of surface treatment by a surface treatment agent can be evaluated by the carbon content per unit weight of the surface-treated sheet-like fiber substrate. From the viewpoint of reducing the number of needle voids and suppressing plating penetration, the carbon content per unit weight of the surface-treated sheet-like fiber substrate is preferably 0.1% by mass or more, more preferably 0.13% by mass or more, even more preferably 0.15% by mass or more, or 0.18% by mass or more, preferably 0.3% by mass or less, more preferably 0.28% by mass or less, even more preferably 0.25% by mass or less, or 0.23% by mass or less.

[0022] The carbon content per unit surface area of ​​a surface-treated sheet-like fiber substrate can be measured using a carbon analyzer. A carbon analyzer such as the Horiba EMA-321V2 can be used. Since the sheet-like fiber substrate does not burn during measurement with a carbon analyzer, the amount of carbon originating from the surface treatment agent can be calculated using the carbon analyzer.

[0023] The sheet-like fibrous substrate can be surface-treated with a surface treatment agent, for example, by the method described in paragraph 0057 of Japanese Patent No. 7183344.

[0024] In this specification, unless otherwise specified, sheet-like fibrous substrates are assumed to be surface-treated with a surface treatment agent.

[0025] The material of the sheet-like fiber base material used in the prepreg is not particularly limited, and commonly used prepreg base materials such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used.

[0026] From the viewpoint of suppressing needle voids and facilitating impregnation with the resin composition, the number of filaments in the sheet-like fiber substrate is preferably 120 or less, more preferably 110 or less, and even more preferably 100 or less. There is no particular lower limit, but it is preferably 20 or more, more preferably 30 or more, and even more preferably 40 or more.

[0027] From the viewpoint of facilitating impregnation of the resin composition, the warp density and weft density of the sheet-like fiber base material are preferably 50 threads / 25 mm or more, more preferably 55 threads / 25 mm or more, even more preferably 60 threads / 25 mm or more, particularly preferably 70 threads / 25 mm or more, preferably 150 threads / 25 mm or less, more preferably 130 threads / 25 mm or less, and even more preferably 120 threads / 25 mm or less.

[0028] Specific examples of glass cloth that can be used as a sheet-like fiber substrate include "Style WEA1027" manufactured by Nitto Boseki Co., Ltd. (warp density 74 threads / 25 mm, weft density 74 threads / 25 mm, fabric weight 19 g / m 2 , thickness 20 μm), "Style WEA1017" manufactured by Nitto Boseki Co., Ltd. (warp density 95 threads / 25 mm, weft density 95 threads / 25 mm, fabric weight 13 g / m 2 , thickness 17 μm), "Style WEA1010" manufactured by Nitto Boseki Co., Ltd. (warp density 95 threads / 25 mm, weft density 95 threads / 25 mm, fabric weight 10 g / m 2 , thickness 13 μm), "Style WEA1006" manufactured by Nitto Boseki Co., Ltd. (warp density 105 threads / 25 mm, weft density 110 threads / 25 mm, fabric weight 8.5 g / m 2 , thickness 12 μm), "Style 1027MS" manufactured by Asahi Schaefer Co., Ltd. (warp density 75 threads / 25 mm, weft density 75 threads / 25 mm, fabric weight 20 g / m 2 , thickness 19 μm), "Style 1037MS" manufactured by Asahi Schaefer Co., Ltd. (warp density 70 threads / 25 mm, weft density 73 threads / 25 mm, fabric weight 24 g / m 2 , thickness 28 μm), "1078" manufactured by Arisawa Manufacturing Co., Ltd. (warp density 54 threads / 25 mm, weft density 54 threads / 25 mm, fabric weight 48 g / m 2 , thickness 43 μm), "1037NS" manufactured by Arisawa Manufacturing Co., Ltd. (warp density 72 threads / 25 mm, weft density 69 threads / 25 mm, fabric weight 23 g / m 2 , thickness 21 μm), "1027NS" manufactured by Arisawa Manufacturing Co., Ltd. (warp density 75 threads / 25 mm, weft density 75 threads / 25 mm, fabric weight 19.5 g / m 2 , thickness 16 μm), "1015NS" manufactured by Arisawa Manufacturing Co., Ltd. (warp density 95 threads / 25 mm, weft density 95 threads / 25 mm, fabric weight 17.5 g / m 2 , thickness 15 μm), "1000NS" manufactured by Arisawa Manufacturing Co., Ltd. (warp density 85 threads / 25 mm, weft density 85 threads / 25 mm, fabric weight 11 g / m 2 , thickness 10 μm), etc. Specific examples of liquid crystal polymer non-woven fabric include "Vecrus" (basis weight 6 g / m 2 ~15 g / m 2 ) and "Vectran" etc. manufactured by Kuraray Co., Ltd. by the melt blowing method of aromatic polyester non-woven fabric.

[0029] The thickness of the sheet-like fiber substrate is preferably 26 μm or less, more preferably 25 μm or less, even more preferably 20 μm or less, preferably 8 μm or more, more preferably 10 μm or more, and even more preferably 12 μm or more, from the viewpoint of thinning, fine wiring, and high density of the insulating layer included in the circuit board of the semiconductor chip package. In the circuit board of a semiconductor chip package where thinning to 26 μm or less is required, the wiring pitch becomes narrower, and the problems of the present invention become more apparent, so the effects of the present invention can be demonstrated more significantly.

[0030] <Resin composition> The resin composition impregnated into the sheet-like fibrous substrate comprises (a) an epoxy resin and (b) an active ester-based curing agent, wherein the ratio of component (a) to component (b) (total number of epoxy groups in component (a) / total number of active groups in component (b)) is 0.7 or more and 1.4 or less.

[0031] To lower the dielectric loss tangent of the cured prepreg, it is conceivable to include an active ester-based curing agent in the resin composition. However, including an active ester-based curing agent lowers the polarity of the resin composition, creating a polarity difference between it and the polarity of the sheet-like fibrous substrate. In this invention, by adjusting the ratio of epoxy resin to active ester-based curing agent, as well as the content of the surface treatment agent used to surface-treat the sheet-like fibrous substrate, it becomes possible to obtain a cured product with a low dielectric loss tangent, a small number of needle voids, and suppressed plating penetration.

[0032] The resin composition may optionally further contain (c) inorganic fillers, (d) curing accelerators, (e) curing agents other than active ester-based curing agents, (f) thermoplastic resins, (g) radical polymerizable compounds, (h) organic fillers, (i) flame retardants, (j) other additives, and (k) solvents. Each component contained in the resin composition will be described in detail below.

[0033] -(a) Epoxy resin- The resin composition contains (a) epoxy resin as component (a). By including (a) epoxy resin, a cured product exhibiting good mechanical strength and insulation reliability can be obtained. (a) epoxy resin may be used alone or in combination of two or more types.

[0034] (a) Examples of epoxy resins include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, and glycidyl ester type epoxy resin. Examples include epoxy resins, glycidylcyclohexane type epoxy resins, alkyl diglycidyl ether 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, spiroring-containing epoxy resins, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, tetraphenylethane type epoxy resins, phenolphthaleimidine type epoxy resins, and the like. Epoxy resins may be used individually or in combination of two or more types.

[0035] The resin composition preferably contains, as component (a), an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of significantly obtaining the desired effects of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the epoxy resin (a) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0036] Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition may contain only liquid epoxy resin as component (a), only solid epoxy resin, or a combination of liquid epoxy resin and solid epoxy resin.

[0037] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0038] Preferred liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having a butadiene structure, glycidylcyclohexane type epoxy resin, phenolphthaleimidine type epoxy resin, and alkyl diglycidyl ether type epoxy resin, with bisphenol A type epoxy resin, bisphenol F type epoxy resin, and naphthalene type epoxy resin being more preferred.

[0039] Specific examples of liquid epoxy resins include DIC's "HP4032," "HP4032D," and "HP4032SS" (naphthalene-type epoxy resin); Mitsubishi Chemical's "828US," "jER828EL," "825," and "Epicote 828EL" (bisphenol A-type epoxy resin); Mitsubishi Chemical's "jER807" and "1750" (bisphenol F-type epoxy resin); Mitsubishi Chemical's "jER152" (phenol novolac-type epoxy resin); Mitsubishi Chemical's "630" and "630LSD" (glycidylamine-type epoxy resin); and Nippon Steel Chemical & Material's "ZX1 Examples include "059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) from Nagase ChemteX Corporation; "Celoxide 2021P" (alicyclic epoxy resin with an ester skeleton) from Daicel Corporation; "PB-3600" (epoxy resin with a butadiene structure) from Daicel Corporation; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) from Nippon Steel Chemical & Material Corporation; and "YED216D" (alkyl diglycidyl ether type epoxy resin) from Mitsubishi Chemical Corporation. These may be used individually or in combination of two or more types.

[0040] As for the solid epoxy resin, a solid epoxy resin having two or more epoxy groups per molecule is preferred, a solid epoxy resin having three or more epoxy groups per molecule is more preferred, and an aromatic solid epoxy resin having three or more epoxy groups per molecule is even more preferred.

[0041] Preferred solid epoxy resins include bixylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, and tetraphenylethane-type epoxy resin, with biphenyl-type epoxy resin being more preferred.

[0042] Specific examples of solid epoxy resins include DIC's "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin), "N-690" (cresol novolac-type epoxy resin), "N-695" (cresol novolac-type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene-type epoxy resin), and "EXA-731" 1", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd.'s "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); Nippon Steel Chemical & Material's "ESN475V", "ESN4100V" (naphthalene-type epoxy resin), "ESN485" (naphthol novolac-type epoxy resin), "ESN4100-VEK75" (naphthol aralkyl-type epoxy resin); Mitsubishi Chemical's "YX4000H", "YL6121" (biphenyl-type epoxy resin), "YX4000HK" (bixylenol-type epoxy resin), "YX8800" (anthracene-type epoxy resin) Examples of xylyl resins include "PG-100" and "CG-500" from Osaka Gas Chemical Co., Ltd., and "YL7760" (bisphenol AF type epoxy resin), "YL7800" (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin), and "jER1031S" (tetraphenylethane type epoxy resin) from Mitsubishi Chemical Corporation; as well as "WHR-991S" (phenolphthalein type epoxy resin) from Nippon Kayaku Co., Ltd. These may be used individually or in combination of two or more types.

[0043] (a) When liquid epoxy resin and solid epoxy resin are used in combination as components, their mass ratio (liquid epoxy resin:solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.15 to 1:10, and particularly preferably 1:0.2 to 1:5.

[0044] (a) The epoxy equivalent of component is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., even more preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. This range ensures that the crosslinking density of the cured resin composition is sufficient to produce a cured product. The epoxy equivalent is the mass of epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0045] (a) The weight-average molecular weight (Mw) of component is preferably 100 to 5000, more preferably 150 to 3000, and even more preferably 200 to 1500, from the viewpoint of significantly obtaining the desired effects of the present invention. The weight-average molecular weight of the epoxy resin is the weight-average molecular weight on a polystyrene basis, measured by gel permeation chromatography (GPC).

[0046] (a) The content of component (a) is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, when the nonvolatile components in the resin composition are considered to be 100% by mass, from the viewpoint of obtaining a cured product that exhibits good mechanical strength and insulation reliability. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.

[0047] (a) The content of component (a) is preferably 20% by mass or more, more preferably 25% by mass or more, and even more preferably 30% by mass or more, when the total resin component in the resin composition is considered to be 100% by mass, from the viewpoint of obtaining a cured product that exhibits good mechanical strength and insulation reliability. The upper limit is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less.

[0048] In this invention, unless otherwise specified, the content of each component in the resin composition is the value when the non-volatile components in the resin composition are taken as 100% by mass, and non-volatile components refer to the components of the resin composition other than the solvent described later. Furthermore, in this invention, the resin components of the resin composition refer to the components of the resin composition excluding (c) inorganic fillers from the non-volatile components in the resin composition.

[0049] -(b) Active ester-based curing agent- The resin composition contains a (b) active ester curing agent as component (b). This (b) active ester curing agent does not include any of the components described above as component (a). The (b) active ester curing agent can lower the polarity of the cured product of the resin composition, thereby effectively lowering the dielectric loss tangent of the insulating layer. Component (b) may be used alone or in combination of two or more types.

[0050] The ratio (equivalent ratio) of (a) epoxy resin to (b) active ester curing agent is the ratio of [total number of active groups of component (b)] / [total number of epoxy groups of component (a)], which is 0.7 or more, preferably 0.71 or more, more preferably 0.73 or more, and even more preferably 0.75 or more. The upper limit is 1.4 or less, preferably 1.35 or less, more preferably 1.3 or less, even more preferably 1.25 or less, 1.2 or less, 1.15 or less, 1.1 or less, 1.05 or less, 1 or less, 0.95 or less, or 0.9 or less. Here, "number of epoxy groups of component (a)" is the sum of all values ​​obtained by dividing the mass of nonvolatile components of the epoxy resin (a) present in the resin composition by the epoxy equivalent. Also, "number of active groups of component (b)" is the sum of all values ​​obtained by dividing the mass of nonvolatile components of the active ester curing agent (b) present in the resin composition by the active ester group equivalent. By keeping the ratio of (a) epoxy resin to (b) active ester-based curing agent within this range, the polarity difference between the surface treatment agent and the resin composition in the sheet-like fibrous substrate can be reduced. As a result, it becomes possible to obtain a cured product with a low dielectric loss tangent, a small number of needle voids, and suppressed plating penetration.

[0051] (a) When the ratio of epoxy resin to (b) active ester-based curing agent is α, and the content (mass%) of the surface treatment agent per unit weight of the sheet-like fiber substrate is β, 2 / α is preferably 0.01 or higher, more preferably 0.03 or higher, even more preferably 0.05 or higher, 0.06 or higher, 0.07 or higher, 0.08 or higher, or 0.09 or higher, and preferably 0.5 or lower, more preferably 0.4 or lower, even more preferably 0.3 or lower, 0.2 or lower, or 0.18 or lower. β 2 By adjusting the ratio of components (a) and (b), and the content of the surface treatment agent, so that / α falls within the specified range, it becomes possible to obtain a cured product with a low dielectric loss tangent, a small number of needle voids, and suppressed plating penetration.

[0052] (b) As the active ester curing agent, a compound having one or more active ester groups in one molecule may be used. Among these, (b) as the active ester curing agent, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferred.

[0053] (b) The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by the condensation of two phenol molecules with one dicyclopentadiene molecule.

[0054] Specifically, (b) as the active ester curing agent, dicyclopentadiene-type active ester curing agents, naphthalene-type active ester curing agents containing a naphthalene structure, active ester curing agents containing an acetylated phenol novolac, and active ester curing agents containing a benzoylated phenol novolac are preferred, with naphthalene-type active ester curing agents being more preferred. As the dicyclopentadiene-type active ester curing agent, an active ester curing agent containing a dicyclopentadiene-type diphenol structure is preferred.

[0055] (b) Examples of commercially available active ester curing agents include, for example, as active ester curing agents containing a dicyclopentadiene-type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC Corporation); as active ester curing agents containing a naphthalene structure, "HP-B-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", Examples include "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", "HPC-8151-62T", and "EXB-8" (manufactured by DIC Corporation) as phosphorus-containing active ester curing agents, "EXB9401" (manufactured by DIC Corporation) as an active ester curing agent that is an acetylated phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation) as an acetylated phenol novolac, "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester curing agents that are benzoylated phenol novolacs, and "PC1300-02-65MA" (manufactured by Air Water Corporation) as an active ester curing agent containing a styryl group and a naphthalene structure.

[0056] (b) The active ester group equivalent of the active ester curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., even more preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The active ester group equivalent represents the mass of resin per equivalent of one active ester group.

[0057] In one example, the range of the weight-average molecular weight (Mw) of the active ester curing agent (b) may be the same as the range of the weight-average molecular weight (Mw) of the epoxy resin (a).

[0058] (b) The content of component (b) is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, when the nonvolatile components in the resin composition are considered to be 100% by mass, from the viewpoint of obtaining a cured product with a low dielectric loss tangent. The upper limit is preferably 35% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less.

[0059] (b) The content of component (b) is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more, when the resin component in the resin composition is considered to be 100% by mass, from the viewpoint of obtaining a cured product with a low dielectric loss tangent. The upper limit is preferably 50% by mass or less, more preferably 45% by mass or less, and particularly preferably 40% by mass or less.

[0060] -(c) Inorganic filler- The resin composition may contain, as an optional component, (c) an inorganic filler. By including (c) an inorganic filler in the resin composition, the dielectric loss tangent of the cured product of the resin composition can be further reduced. (c) The inorganic filler may be used alone or in combination of two or more types.

[0061] Inorganic compounds are used as materials for inorganic fillers. Examples of inorganic filler materials include silica, alumina, aluminosilicate, 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 titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, calcium carbonate and silica are preferred, and silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Spherical silica is also preferred.

[0062] (c) Examples of commercially available products of component (c) include "SP60-05" and "SP507-05" from Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" from Admatex Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" from Denka Co., Ltd.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" from Tokuyama Corporation; and "Cellspheres" and "MGH-005" from Taiheiyo Cement Corporation.

[0063] (c) The specific surface area of ​​component is preferably 1 m². 2 / g or more, more preferably 2m 2 / g or more, particularly preferably 3m 2 It must be 1 / g or more. There is no particular upper limit, but preferably 60m 2 / g or less, 50m 2 / g or less or 40m 2The value is less than or equal to / g. The specific surface area is obtained by adsorbing nitrogen gas onto the sample surface using a specific surface area measuring device (Macsorb HM-1210, manufactured by Mountec Co., Ltd.) according to the BET method, and then calculating the specific surface area using the BET multipoint method.

[0064] (c) The average particle size of component is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, preferably 5 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less, from the viewpoint of significantly obtaining the desired effects of the present invention.

[0065] The average particle size of component (c) can be measured by a laser diffraction-scattering method based on Mie scattering theory. Specifically, a volume-based particle size distribution of the inorganic filler can be created using a laser diffraction-scattering particle size distribution analyzer, and the median diameter can be used as the average particle size. A sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them using ultrasound for 10 minutes. The sample can be measured using a laser diffraction-type particle size distribution analyzer with blue and red light source wavelengths, and the volume-based particle size distribution of component (c) can be measured using a flow cell method. The average particle size can then be calculated as the median diameter from the obtained particle size distribution. An example of a laser diffraction-type particle size distribution analyzer is the "LA-960" manufactured by Horiba, Ltd.

[0066] (c) Component is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include vinylsilane coupling agents, (meth)acrylic coupling agents, fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. Among these, vinylsilane coupling agents, (meth)acrylic coupling agents, and aminosilane coupling agents are preferred from the viewpoint of obtaining the effects of the present invention, and aminosilane coupling agents are more preferred. Furthermore, the surface treatment agent may be used alone or two or more types may be used in any combination.

[0067] Examples of commercially available surface treatment agents include Shin-Etsu Chemical Co., Ltd.'s "KBM1003" (vinyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM503" (3-methacryloxypropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), and Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxy Examples include sisilane, Shin-Etsu Chemical Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd.'s "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy-type silane coupling agent), Shin-Etsu Chemical Co., Ltd.'s "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), etc.

[0068] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably within a predetermined range. Specifically, it is preferable that the inorganic filler is surface-treated with 0.2% to 5% by mass of the surface treatment agent, preferably 0.2% to 3% by mass, and preferably 0.3% to 2% by mass, per 100% by mass of the inorganic filler.

[0069] The degree of surface treatment by a surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler should be 0.02 mg / m². 2 The above is preferred, and 0.1 mg / m² 2 The above is more preferable, 0.2 mg / m² 2 The above is even more preferable. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin varnish and the melt viscosity in sheet form, 1 mg / m 2 The following is preferred: 0.8 mg / m² 2 The following is more preferable: 0.5 mg / m² 2 The following is even more preferable.

[0070] The amount of carbon per unit surface area of ​​an inorganic filler can be measured after surface treatment of the inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solids, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. A carbon analyzer such as the "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0071] (c) The content of component (c) is preferably 45% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less, when the nonvolatile components in the resin composition are taken as 100% by mass.

[0072] -(d) Curing accelerator- The resin composition may further contain, as an optional component, a curing accelerator (d) as component (d). This curing accelerator (d) as component (d) does not include any of the components (a) to (c) described above. By including component (d), it is possible to further accelerate the curing of component (a). Component (d) may be used alone or in combination of two or more types.

[0073] (d) Examples of components include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators, with amine-based curing accelerators and imidazole-based curing accelerators being preferred, and imidazole-based curing accelerators being more preferred.

[0074] Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

[0075] Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.

[0076] Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-Cyanoethyl-2-methylimidazole, 1-Cyanoethyl-2-undecylimidazole, 1-Cyanoethyl-2-ethyl-4-methylimidazole, 1-Cyanoethyl-2-phenylimidazole, 1-Cyanoethyl-2-undecylimidazolium trimellitate, 1-Cyanoethyl-2-phenylimidazolium trimellitate, 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2, 4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-F Examples include imidazole compounds such as phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds with epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

[0077] Commercial imidazole-based curing accelerators may be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0078] Examples of guanidine-based curing accelerators 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]deca-5-ene, and 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene. Examples include ro[4.4.0]deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, and the like, with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]deca-5-ene being preferred.

[0079] Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0080] (d) The content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, particularly preferably 0.1% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, or 0.3% by mass or less, when the nonvolatile components in the resin composition are taken as 100% by mass.

[0081] (d) The content of component (d) is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more, when the resin component in the resin composition is considered to be 100% by mass, from the viewpoint of obtaining a cured product with a low dielectric loss tangent. The upper limit is preferably 50% by mass or less, more preferably 45% by mass or less, or 40% by mass or less.

[0082] -(e) Curing agents other than active ester-based curing agents- The resin composition may further contain, as an optional component, a curing agent other than the active ester curing agent (hereinafter sometimes simply referred to as "(e) curing agent") as component (e). By including the (e) curing agent, a bond can be formed through a reaction with the (a) epoxy resin, thereby curing the resin composition. This (e) curing agent as component (e) does not include those corresponding to components (a) to (d) described above. The (e) curing agent may be used alone or in combination of two or more types.

[0083] (e) Examples of curing agents include phenolic curing agents, naphthol-based curing agents, carbodiimide-based curing agents, benzoxazine-based curing agents, and cyanate ester-based curing agents. Among these, (e) the curing agent is preferably a phenolic curing agent, from the viewpoint of obtaining the effects of the present invention in particular.

[0084] From the viewpoint of heat resistance and water resistance, phenolic curing agents having a novolac structure or naphthol curing agents having a novolac structure are preferred. Furthermore, from the viewpoint of adhesion to the conductive layer, nitrogen-containing phenolic curing agents are preferred, and triazine skeleton-containing phenolic curing agents are more preferred.

[0085] Specific examples of phenol-based and naphthol-based curing agents include, for example, "MEH-7700," "MEH-7810," and "MEH-7851" from Meiwa Chemical Co., Ltd., "NHN," "CBN," and "GPH" from Nippon Kayaku Co., Ltd., "SN170," "SN180," "SN190," "SN475," "SN485," "SN495," "SN-495V," "SN375," and "SN395" from Nippon Steel & Sumitomo Metal Chemical Co., Ltd., and "TD-2090," "LA-7052," "LA-7054," "LA-1356," "LA3018-50P," "EXB-9500," and "KA-1163" from DIC Corporation.

[0086] Carbodiimide-based curing agents are compounds having one or more carbodiimide groups (-N=C=N-) in one molecule, and it is preferable that carbodiimide-based curing agents are compounds having two or more carbodiimide groups in one molecule.

[0087] Specific examples of carbodiimide-based curing agents include commercially available carbodiimide-based curing agents such as Carbodilite V-03 (carbodiimide group equivalent: 216 g / eq.), V-05 (carbodiimide group equivalent: 262 g / eq.), V-07 (carbodiimide group equivalent: 200 g / eq.), V-09 (carbodiimide group equivalent: 200 g / eq.) manufactured by Nisshinbo Chemical Co., Ltd., and Stavaxol P (carbodiimide group equivalent: 302 g / eq.) manufactured by Arxada Co., Ltd.

[0088] Specific examples of benzoxazine-based curing agents include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemicals Co., Ltd.

[0089] Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl) thioether, and bis(4-cyanatephenyl) ether; polyfunctional cyanate resins derived from phenol novolacs and cresol novolacs; and prepolymers in which these cyanate resins are partially triazined. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resins) manufactured by Lonza Corporation, "ULL-950S" (polyfunctional cyanate ester resin), "BA230", and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate is triazined and trimerized).

[0090] The ratio (equivalent ratio) of (a) epoxy resin to (e) curing agent is the ratio of [total number of active groups of (e) curing agent] / [total number of epoxy groups of (a) epoxy resin], preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0.5 or more. The upper limit is preferably 2 or less, more preferably 1.5 or less, and even more preferably 1.4 or less. "(e) number of active groups of curing agent" is the sum of all values ​​obtained by dividing the mass of the nonvolatile components of (e) curing agent present in the resin composition by the equivalent amount of active groups. By setting the ratio of (a) epoxy resin to (e) curing agent within this range, the effects of the present invention can be significantly obtained.

[0091] The ratio (equivalent ratio) of (a) epoxy resin to (b) active ester curing agent and (e) curing agent is the ratio of [total number of active groups of (b) active ester curing agent and (e) curing agent] / [total number of epoxy groups of (a) epoxy resin], preferably 0.5 or more, more preferably 0.6 or more, and even more preferably 0.7 or more. The upper limit is preferably 2 or less, more preferably 1.5 or less, and even more preferably 1.4 or less. Here, "total number of active groups of (b) active ester curing agent and (e) curing agent" is the sum of all values ​​obtained by dividing the mass of the nonvolatile components of the active groups of (b) active ester curing agent and (e) curing agent present in the resin composition by the equivalent amount of active groups. By setting the ratio of (a) epoxy resin to (b) active ester curing agent and (e) curing agent within this range, the effects of the present invention can be significantly obtained.

[0092] (e) The content of component is preferably 0.5% by mass or more, more preferably 1% by mass or more, and more preferably 1.5% by mass or more, when the nonvolatile components in the resin composition are considered to be 100% by mass. The upper limit is preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 10% by mass or less.

[0093] (e) The content of component (e) is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, when the total resin component in the resin composition is considered to be 100% by mass. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0094] -(f)Thermoplastic resin- The resin composition may optionally contain a thermoplastic resin as component (f). This thermoplastic resin as component (f) does not include any of the components (a) to (e) described above. Component (f) may be used alone or in combination of two or more types.

[0095] (f) Examples of thermoplastic resins include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polyetheretherketone resin, polyester resin, and the like.

[0096] (f) The weight-average molecular weight of the thermoplastic resin in terms of polystyrene is preferably 10,000 or more, more preferably 15,000 or more, and even more preferably 18,000 or more. The upper limit is preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 60,000 or less. (f) The weight-average molecular weight of the thermoplastic resin in terms of polystyrene is measured by gel permeation chromatography (GPC). Specifically, (f) the weight-average molecular weight of the thermoplastic resin in terms of polystyrene can be calculated using a Shimadzu LC-9A / RID-6A measuring device, a Showa Denko Shodex K-800P / K-804L / K-804L column, and chloroform or the like as the mobile phase, with the column temperature measured at 40°C, and using a calibration curve for standard polystyrene.

[0097] Examples of phenoxy resins include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The ends of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Phenoxy resins may be used alone or in combination of two or more types. Specific examples of phenoxy resins include "1256" and "4250" (both phenoxy resins containing a bisphenol A skeleton), "YX8100" (phenoxy resin containing a bisphenol S skeleton), "YX7800BH40" (phenoxy resin containing a fluorene skeleton), and "YX6954" (phenoxy resin containing a bisphenol acetophenone skeleton), all manufactured by Mitsubishi Chemical Corporation. Other examples include "FX280" and "FX293" from Nippon Steel Chemical & Material Corporation, and "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", and "YL7482" from Mitsubishi Chemical Corporation.

[0098] Examples of polyvinyl acetal resins include polyvinyl formal resin and polyvinyl butyral resin, with polyvinyl butyral resin being preferred. Specific examples of polyvinyl acetal resins include, for example, the S-Rec BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.

[0099] Specific examples of polyimide resins include "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shin Nippon Rika Co., Ltd. Other specific examples of polyimide resins include linear polyimides obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (polyimides described in Japanese Patent Publication No. 2006-37083), and modified polyimides containing a polysiloxane skeleton (polyimides described in Japanese Patent Publication No. 2002-12667 and Japanese Patent Publication No. 2000-319386, etc.).

[0100] Specific examples of polyamide-imide resins include "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo Co., Ltd. Other specific examples of polyamide-imide resins include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imide) manufactured by Resonaq Corporation.

[0101] Specific examples of polyethersulfone resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. Specific examples of polyphenylene ether resins include "OPE-2St 1200," an oligophenylene ether-styrene resin manufactured by Mitsubishi Gas Chemical Company. Specific examples of polyetheretherketone resins include "Sumiproi K" manufactured by Sumitomo Chemical Co., Ltd. Specific examples of polyetherimide resins include "Ultem" manufactured by GE.

[0102] Specific examples of polysulfone resins include Solvay Advanced Polymers' polysulfones "P1700" and "P3500".

[0103] Examples of polyolefin resins include ethylene-based copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; and polyolefin-based elastomers such as polypropylene and ethylene-propylene block copolymer.

[0104] Examples of polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexanedimethyl terephthalate resin.

[0105] Among these, (f) phenoxy resin is preferred as the thermoplastic resin, and phenoxy resin with a weight-average molecular weight of 40,000 or more is more preferred.

[0106] (f) The content of thermoplastic resin is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 0.8% by mass or more, when the nonvolatile components in the resin composition are taken as 100% by mass. The upper limit is preferably 7% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0107] (f) The content of thermoplastic resin is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, when the total resin components in the resin composition are considered to be 100% by mass. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less.

[0108] -(g) Radical polymerizable compounds- The resin composition may optionally contain a radical polymerizable compound as component (g). This radical polymerizable compound as component (g) does not include those corresponding to components (a) to (f) described above. Component (g) may be used alone or in combination of two or more types.

[0109] (g) A radical polymerizable compound may be, for example, a compound having a radical polymerizable unsaturated group. The radical polymerizable unsaturated group is not particularly limited as long as it is radical polymerizable, but an ethylenically unsaturated group having a carbon-carbon double bond at the terminal or in the interior is preferred, and specifically may be an unsaturated aliphatic group such as an allyl group or a 3-cyclohexenyl group; an unsaturated aliphatic group-containing aromatic group such as a p-vinylphenyl group, an m-vinylphenyl group or a styryl group; or an α,β-unsaturated carbonyl group such as an acryloyl group, a methacryloyl group or a maleoyl group (maleimide group if imidized), or a fumaroyl group. (g) A radical polymerizable compound preferably has one or more radical polymerizable unsaturated groups, and more preferably has two or more.

[0110] Other radical polymerizable compounds can be broadly selected from known radical polymerizable compounds and are not particularly limited. Examples include maleimide-based radical polymerizable compounds having two or more maleimide groups, vinylphenyl-based radical polymerizable compounds having two or more vinylphenyl groups, and (meth)acrylic-based radical polymerizable compounds having two or more acryloyl groups and / or methacryloyl groups.

[0111] Maleimide-based radical polymerizable compounds are not particularly limited and may be aliphatic maleimide compounds containing an aliphatic amine skeleton or aromatic maleimide compounds containing an aromatic amine skeleton. Examples of commercially available products include "BMI-1500," "BMI-1700," "BMI-3000J," "BMI-689," and "BMI-2500" (maleimide compounds containing a dimer amine structure) from Designer Molecules, "BMI-6100" (aromatic maleimide compound) from Designer Molecules, "MIR-5000-60T" and "MIR-3000-70MT" (biphenyl aralkyl type maleimide compounds) from Nippon Kayaku Co., Ltd., "BMI-70" and "BMI-80" from K.I. Chemicals, Inc., "BMI-2300" and "BMI-TMH" from Yamato Chemical Industries, Ltd., and "SLK-2600" from Shin-Etsu Chemical Co., Ltd. Furthermore, as a maleimide-based radical polymerizable compound, a maleimide resin (indane ring skeleton-containing maleimide compound) disclosed in the Japan Institute of Invention and Innovation Publication No. 2020-500211 may be used.

[0112] The vinylphenyl-based radical polymerizable compound is not particularly limited, but in one embodiment, it is preferably a thermoplastic resin having vinylphenyl groups, and more preferably a resin selected from modified polyphenylene ether resins having vinylphenyl groups and modified polystyrene resins having vinylphenyl groups. Examples of commercially available products include "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resins) from Mitsubishi Gas Chemical Co., Ltd.; "ODV-XET-X03," "ODV-XET-X04," and "ODV-XET-X05" (divinylbenzene / styrene copolymer) from Nippon Steel Chemical & Material Co., Ltd.; "A-DOG" from Shin Nakamura Chemical Industry Co., Ltd.; and "DCP-A" from Kyoeisha Chemical Co., Ltd.

[0113] The (meth)acrylic radical polymerizable compound is not particularly limited, but in one embodiment, it is preferably a thermoplastic resin having acryloyl groups and / or methacryloyl groups, and more preferably a resin selected from modified polyphenylene ether resins having acryloyl groups and / or methacryloyl groups, and modified polystyrene resins having acryloyl groups and / or methacryloyl groups. Examples of commercially available products include "SA9000" and "SA9000-111" (methacrylic modified polyphenylene ether resin) manufactured by SABIC Innovative Plastics.

[0114] The functional group equivalent of component (g) is preferably 100 g / eq. to 20,000 g / eq., more preferably 200 g / eq. to 15,000 g / eq., and even more preferably 300 g / eq. to 10,000 g / eq. The functional group equivalent of component (g) is the mass of (g) other radical polymerizable compounds per equivalent of radical polymerizable unsaturated groups (i.e., maleimide groups, vinylphenyl groups, acryloyl groups, methacryloyl groups, etc.).

[0115] (g) The weight-average molecular weight (Mw) of component (g) is preferably 500 to 50,000, more preferably 700 to 20,000. (g) The number-average molecular weight (Mn) of the other radical polymerizable compounds is preferably 500 to 50,000, more preferably 700 to 20,000. The weight-average molecular weight is the weight-average molecular weight on a polystyrene basis, measured using gel permeation chromatography (GPC).

[0116] The content of component (g) is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less, when the nonvolatile components in the resin composition are taken as 100% by mass.

[0117] (g) The content of thermoplastic resin is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, when the total resin components in the resin composition are considered as 100% by mass. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0118] -(h)Organic filler- The resin composition may contain, as an optional component, (h) component, an organic filler (h). This organic filler (h) component does not include those corresponding to components (a) to (g) described above. The organic filler (h) is usually immiscible with resin components other than the organic filler (h) and is included in the resin composition in granular form, and is included in the cured product while maintaining that granular form. Furthermore, one type of organic filler (h) may be used alone, or two or more types may be used in combination.

[0119] (h) As the organic filler, particles of organic material may be used. (h) As the organic material contained in the organic filler, rubber components are preferred. Examples of rubber components include silicone elastomers such as polydimethylsiloxane; olefin-based thermoplastic elastomers such as polybutadiene, polyisoprene, polychlorobutadiene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutylene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutylene copolymer, isobutylene-butadiene copolymer, ethylene-propylene-diene terpolymer, ethylene-propylene-butene terpolymer; and thermoplastic elastomers such as acrylic-based thermoplastic elastomers such as propyl poly(meth)acrylate, butyl poly(meth)acrylate, cyclohexyl poly(meth)acrylate, and octyl poly(meth)acrylate. Furthermore, silicone-based rubbers such as polyorganosiloxane rubber may be mixed with the rubber component. The rubber component contained in the rubber particles has a glass transition temperature of, for example, 0°C or lower, preferably -10°C or lower, more preferably -20°C or lower, and even more preferably -30°C or lower.

[0120] (h) The organic filler may be a core-shell type rubber particle consisting of a core particle containing the rubber component mentioned above and a shell portion formed by graft copolymerization of a monomer component copolymerizable with the rubber component contained in the core particle. Here, "core-shell type" does not necessarily refer only to those in which the core particle and the shell portion can be clearly distinguished, but also includes those in which the boundary between the core particle and the shell portion is unclear, and the core particle does not have to be completely covered by the shell portion.

[0121] (h)Specific examples of organic fillers include, for example, "CHT" from Samsung SDI; "B602" from Techno UMG; "Paraloid EXL-2602", "Paraloid EXL-2603", "Paraloid EXL-2655", "Paraloid EXL-2311", "Paraloid-EXL2313", "Paraloid EXL-2315", "Paraloid KM-330", "Paraloid KM-336P", "Paraloid KCZ-201" from Dow Corporation; and "Metablen C-223A", "Metablen E- Examples include "901", "Metablen S-2001", "Metablen W-450A", "Metablen SRK-200", Kaneka Corporation's "Kaneace M-511", "Kaneace M-600", "Kaneace M-400", "Kaneace M-580", "Kaneace MR-01", and Aica Kogyo Co., Ltd.'s "Stafiloid AC3355", "Stafiloid AC3816", "Stafiloid AC3816N", "Stafiloid AC3832", "Stafiloid AC4030", and "Stafiloid AC3364".

[0122] (h) The content of the organic filler is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1.5% by mass or less, when the nonvolatile components in the resin composition are taken as 100% by mass.

[0123] (h) The content of the organic filler is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, when the resin component in the resin composition is considered to be 100% by mass. The upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.

[0124] -(i) Flame retardant- The resin composition may optionally contain, as component (i), a flame retardant. This flame retardant as component (i) does not include those corresponding to components (a) to (h) described above. Component (i) may be used alone or in combination of two or more types.

[0125] (i) Examples of flame retardants include phosphazene compounds, organophosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, metal hydroxides, etc., with phosphazene compounds being preferred.

[0126] The phosphazene compound is not particularly limited as long as it is a cyclic compound with nitrogen and phosphorus as constituent elements, but it is preferable that the phosphazene compound is a phosphazene compound having a phenolic hydroxyl group.

[0127] Specific examples of phosphazene compounds include, for example, "SPH-100," "SPS-100," "SPB-100," and "SPE-100" manufactured by Otsuka Chemical Co., Ltd., and "FP-100," "FP-110," "FP-300," and "FP-400" manufactured by Fushimi Pharmaceutical Co., Ltd., with "SPH-100" manufactured by Otsuka Chemical Co., Ltd. being preferred.

[0128] As a flame retardant other than a phosphazene compound, commercially available products may be used, such as "HCA-HQ" manufactured by Sanko Co., Ltd. and "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd. As a flame retardant, one that is not easily hydrolyzed is preferred, such as 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide.

[0129] (i) The flame retardant content is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 0.8% by mass or more, preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less, when the nonvolatile components in the resin composition are taken as 100% by mass.

[0130] (i) The flame retardant content is preferably 1% by mass or more, more preferably 1.5% by mass or more, even more preferably 2% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less, when the resin components in the resin composition are considered as 100% by mass.

[0131] -(j) Other additives- In addition to the components described above, the resin composition may further contain (j) other additives as non-volatile components. Examples of such additives include: radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; organometallic compounds such as organocopper compounds, organozinc compounds, and organocalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentonite and montmorillonite; defoaming agents such as silicone-based defoaming agents, acrylic-based defoaming agents, fluorine-based defoaming agents, and vinyl resin-based defoaming agents; and benzotriazole Examples of additives include ultraviolet absorbers such as fluorine-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion improvers such as triazole-based adhesion improvers, tetrazole-based adhesion improvers, and triazine-based adhesion improvers; antioxidants such as hindered phenol-based antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; and stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers. (j) Other additives may be used individually or in combination of two or more in any ratio. (j) The content of other additives can be appropriately determined by a person skilled in the art.

[0132] -(k) solvent- In addition to the non-volatile components described above, the resin composition may also contain (k) a solvent as a volatile component. By including (k) a solvent in the resin composition, the generation of needle voids can be suppressed. (k) a solvent may be used alone, or two or more may be used in any ratio.

[0133] (k) Any known solvent can be used as appropriate, and the type is not particularly limited, but an organic solvent is preferred. Furthermore, (k) the solvent is preferably one whose polarity is close to that of the sheet-like fibrous substrate.

[0134] (k) Examples of solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; and 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate. Examples of solvents include ether ester solvents; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, and solvent naphtha. It is preferable that (k) the solvent does not contain aromatic hydrocarbon solvents from the viewpoint of significantly obtaining the effects of the present invention.

[0135] From the viewpoint of suppressing the generation of needle voids, the (k) solvent in the dried resin composition is preferably 3% by mass or less, more preferably 2.5% by mass or less, even more preferably 2% by mass or less, or 1% by mass or less, based on 100% by mass of all components of the resin composition. There is no particular lower limit, but it is preferably 0% by mass or more, more preferably 0.5% by mass or more, even more preferably 0.8% by mass or more, or 1% by mass or more. The dried resin composition refers to the resin composition after drying in a vertical drying oven at 110°C for 5 minutes.

[0136] It is preferable that the content of aromatic hydrocarbon solvents in the (k) solvent contained in the dried resin composition is small. When the total solvent contained in the resin composition is taken as 100% by mass, it is preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, 26% by mass or less, preferably 0% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. As for the (k) solvent, from the viewpoint of obtaining the effects of the present invention in particular, it is preferable that it does not contain aromatic hydrocarbon solvents, i.e., 0% by mass.

[0137] Of the (k) solvent contained in the dried resin composition, the amount of aromatic hydrocarbon solvent is preferably 0.9 or less, more preferably 0.8 or less, even more preferably 0.7 or less, 0.6 or less, or 0.5 or less, when the total amount of (k) solvent is set to 1, from the viewpoint of suppressing the generation of needle voids. There is no particular lower limit, but for example it can be 0.01 or more, or 0.03 or more, and it is particularly preferable that it be 0.

[0138] The resin composition can be manufactured, for example, by mixing the above-mentioned components in any order. Furthermore, heating and / or cooling may be performed during the mixing process by appropriately adjusting the temperature. Additionally, stirring may be performed using a stirring device such as a mixer during or after mixing to ensure uniform dispersion of each component. Furthermore, if necessary, the resin composition may be subjected to a degassing treatment.

[0139] The method for preparing the resin composition is not particularly limited, and examples include mixing and dispersing the constituent components together with a solvent, if necessary, using a rotary mixer or the like.

[0140] <Other layers> The prepreg may have a protective film laminated on the surface of a sheet-like fibrous base material, if necessary.

[0141] Examples of protective films include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyether sulfide (PES), polyether ketones, and polyimides. Alternatively, a support with a release layer may be used as the protective film. Examples of release agents used in the release layer of a support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available supports with a release layer may be used, for example, PET films having a release layer mainly composed of an alkyd resin-based release agent, such as "SK-1", "AL-5", and "AL-7" from Lintec Corporation, and "Lumirror T6AM" from Toray Industries, Inc.

[0142] The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film prevents dust and other debris from adhering to the surface of the prepreg, as well as scratches.

[0143] <Prepreg manufacturing method> Prepregs can be manufactured by known methods such as the hot melt method and the solvent method.

[0144] In the hot melt method, the resin composition is not dissolved in an organic solvent. Instead, the resin composition is first coated onto a release paper with good release properties, and then laminated onto a sheet-like fibrous substrate. Alternatively, the prepreg is manufactured by directly coating the sheet-like fibrous substrate with a die coater.

[0145] In the solvent method, a prepreg is produced by immersing a sheet-like fibrous substrate in a resin varnish, which is a resin composition dissolved in a solvent such as an organic solvent, thereby impregnating the sheet-like fibrous substrate with the resin composition, and then drying it. Furthermore, a prepreg can also be produced by sandwiching a sheet-like fibrous substrate between two resin sheets made of the resin composition and continuously heat-laminating it under heated and pressurized conditions. The solvent is as described above.

[0146] Drying may be carried out by known methods such as heating or blowing hot air. The drying conditions are not particularly limited, but the drying should be carried out so that the solvent content in the resin composition falls within the above range. For example, the drying conditions are preferably 50°C or higher, more preferably 90°C or higher, even more preferably 105°C or higher, preferably 150°C or lower, more preferably 145°C or lower, and even more preferably 140°C or lower. The drying time is preferably 1 minute or more, more preferably 2 minutes or more, even more preferably 3 minutes or more, preferably 10 minutes or less, more preferably 9 minutes or less, and even more preferably 8 minutes or less.

[0147] The prepreg can be manufactured using a roll-to-roll method with a long sheet-like fiber base material, or it can be manufactured using a batch method.

[0148] From the viewpoint of thinning the semiconductor chip package, the thickness of the prepreg is preferably 100 μm or less, more preferably 80 μm or less, even more preferably 70 μm or less, even more preferably 60 μm or less, preferably 15 μm or more, more preferably 17 μm or more, and even more preferably 20 μm or more.

[0149] <Properties of the prepreg> The prepreg exhibits the characteristic of suppressing the generation of needle voids because, as measured by the heat weight loss method, the content of the surface treatment agent per unit weight of the sheet-like fibrous substrate is 0.25% by mass or more and 0.4% by mass or less, and the ratio of component (a) to component (b) in the resin composition is 0.7 or more and 1.4 or less. Needle voids can be observed, for example, in the cured prepreg under a microscope (magnification 100x, vertical length of one field of view 2.3 mm, area of ​​one field of view 60 mm²). 2 Using the ) tool, any five fields of view are examined, and the number of needle voids in each is measured. This is repeated 10 times, and the average value is calculated. At that time, the number of needle voids is 6 or less, preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. There is no particular lower limit, but it can be 0 or more, etc. Needle voids can be measured by the method described in the examples below.

[0150] The prepreg exhibits the characteristic of producing a cured product with suppressed plating penetration, as measured by the heat weight loss method, where the content of the surface treatment agent per unit weight of the sheet-like fibrous substrate is 0.25% by mass or more and 0.4% by mass or less, and the ratio of component (a) to component (b) in the resin composition is 0.7 or more and 1.4 or less. For example, a conductor layer is formed on the cured prepreg by wet plating to obtain a sample. The sample is cut to a size of 1 cm, the surface of the conductor layer is ground until the sheet-like fibrous substrate is exposed, and the length of the deepest penetration point is measured using five blind vias with a microscope. This measurement is repeated five times, and the average value is calculated. At that time, the maximum length of copper plating penetration is 23 μm or less, preferably 22 μm or less, and more preferably 21 μm or less. There is no particular limit to the lower limit, but it can be 0 μm or more, 0.1 μm or more, etc. The plating penetration can be measured by the method described in the examples below.

[0151] The prepreg exhibits the characteristic of yielding a cured product with excellent dielectric loss tangent, as measured by the heat weight loss method, the content of the surface treatment agent per unit weight of the sheet-like fibrous substrate is 0.25% by mass or more and 0.4% by mass or less, and the ratio of component (a) to component (b) contained in the resin composition is 0.7 or more and 1.4 or less. The dielectric loss tangent of the cured prepreg is preferably 0.01 or less, more preferably 0.008 or less, and even more preferably 0.006 or less. There is no particular limit to the lower limit, but it can be 0.0001 or more. The dielectric loss tangent can be measured by the method described in the examples below.

[0152] The prepreg of the present invention can be suitably used to form an insulating layer of a semiconductor chip package (for the insulating layer of a semiconductor chip package), suitably used to form an insulating layer of a printed wiring board (for the insulating layer of a printed wiring board), and more suitably used to form an interlayer insulating layer of a printed wiring board (for the interlayer insulating layer of a printed wiring board). Furthermore, the prepreg of the present invention can be suitably used to form an insulating layer of a redistribution substrate for a semiconductor chip package (for the insulating layer of a redistribution substrate). In other words, the prepreg of the present invention can be suitably used as an insulating layer for a circuit board. In this invention, semiconductor chip packages, printed wiring boards, and redistribution substrates are collectively referred to as "circuit boards," and therefore the prepreg of the present invention can be suitably used as an insulating layer for a circuit board.

[0153] [Semiconductor chip package and method for manufacturing the same] The semiconductor chip package of the present invention includes a circuit board and a semiconductor chip mounted on the circuit board, wherein the circuit board includes an insulating layer formed from a cured prepreg of the present invention. Because the insulating layer of the semiconductor chip package of the present invention is formed using the prepreg of the present invention, it is possible to achieve a low dielectric loss tangent, a small number of needle voids, and low plating penetration. This semiconductor chip package can be manufactured by bonding a semiconductor chip to a circuit board.

[0154] As long as the terminal electrodes of the semiconductor chip are conductively connected to the circuit wiring of the circuit board, the bonding conditions are not particularly limited, and known conditions used in flip-chip mounting of semiconductor chips may be used. Alternatively, the semiconductor chip and the circuit board may be bonded via an insulating adhesive.

[0155] A preferred embodiment involves crimping a semiconductor chip onto a circuit board. For example, the crimping conditions can be a crimping temperature 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 a crimping time in the range of 1 second to 60 seconds (preferably in the range of 5 seconds to 30 seconds).

[0156] Another preferred embodiment involves reflow bonding the semiconductor chip to the circuit board. The reflow conditions can be, for example, in the range of 120°C to 300°C.

[0157] After bonding the semiconductor chip to the circuit board, it is also possible to obtain a semiconductor chip package by, for example, filling the semiconductor chip with mold underfill material. The method of filling with mold underfill material can be carried out by known methods.

[0158] The method for manufacturing a semiconductor chip package of the present invention is as follows: (I) A process of laminating prepregs onto a substrate, (II) A step of curing the prepreg and forming an insulating layer, (V) A step of forming a conductor layer, including

[0159] The method for manufacturing a semiconductor chip package of the present invention involves, after the completion of step (II), (III) The process of drilling holes in the insulating layer, (IV) The process may include a step of desmearing the insulating layer.

[0160] Furthermore, the method for manufacturing a semiconductor chip package of the present invention, after the completion of step (V), (VI) The process may include a step of bonding a semiconductor chip to a circuit board. Step (VI) is as described above.

[0161] The semiconductor chip package manufacturing method of the present invention uses the above-described prepreg to form an insulating layer, making it possible to obtain a semiconductor chip package with low dielectric loss tangent, a small number of needle voids, and low plating penetration.

[0162] The method for manufacturing the semiconductor chip package of the present invention is preferably carried out in the order of step (I) to step (VI).

[0163] <Process (I)> In step (I), a substrate is prepared. The substrate may be an inner layer substrate used for printed circuit boards, etc. Examples of substrates include glass epoxy substrates, metal substrates (such as stainless steel or cold-rolled steel sheet (SPCC)), polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. The substrate may also have a metal layer, such as copper foil, on its surface as 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 that can function as a wiring layer is usually formed on the side of the second metal layer opposite to the first metal layer. Examples of materials for the metal layer include copper foil, copper foil with carriers, and the material for the conductor layer described later, with copper foil being preferred. Commercially available products can be used as substrates having such metal layers, for example, the ultra-thin copper foil with carrier copper foil "Micro Thin" manufactured by Mitsui Mining & Smelting Co., Ltd.

[0164] Furthermore, a conductive layer may be formed on one or both surfaces of the substrate. In the following description, a component including the substrate and the conductive layer formed on the surface of the substrate may be appropriately referred to as a "substrate with wiring layer". Examples of conductive materials included in the conductive layer include materials containing one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. As the conductive material, a single metal may be used, or an alloy may be used. Examples of alloys include alloys of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among these, from the viewpoint of versatility in conductive layer formation, cost, and ease of patterning, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as single metals; and nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy alloys as alloys; are preferred. Among these, single metals such as chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper; and nickel-chromium alloys are more preferred, with single metal copper being particularly preferred.

[0165] The conductor layer may be patterned, for example, to function as a wiring layer. In this case, the line (circuit width) / space (width between circuits) ratio (line and space (L / S)) of the conductor layer is not particularly limited, but is preferably 20 / 20 μm or less (i.e., pitch of 40 μm or less), more preferably 10 / 10 μm or less, even more preferably 5 / 5 μm or less, even more preferably 1 / 1 μm or less, and particularly preferably 0.5 / 0.5 μm or less. The pitch does not need to be the same throughout the entire conductor layer. The minimum pitch of the conductor layer may be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.

[0166] The thickness of the conductor layer depends on the design of the circuit board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, even more preferably 10 μm to 20 μm, and particularly preferably 15 μm to 20 μm.

[0167] The conductive layer can be formed by a method that includes, for example, the steps of laminating a dry film (photosensitive resist film) on a substrate, forming a pattern on the dry film by exposing and developing it under predetermined conditions using a photomask to form a pattern dry film, forming a conductive layer by a plating method such as electroplating using the developed pattern dry film as a plating mask, and peeling off the pattern dry film. As the dry film, a photosensitive dry film made of a photoresist composition can be used, for example, a dry film made of a resin such as novolac resin or acrylic resin can be used. The lamination conditions between the substrate and the dry film may be the same as the lamination conditions between the substrate and the prepreg described later. The dry film can be peeled off by using an alkaline peeling solution such as a sodium hydroxide solution.

[0168] Lamination of the substrate and prepreg can be carried out, for example, by heat-pressing the prepreg onto the substrate. The prepreg used in the present invention is as described above.

[0169] Examples of components used to heat-press the prepreg onto the substrate (hereinafter also referred to as "heat-pressing components") include heated metal plates (such as SUS end plates) or metal rolls (SUS rolls). It is preferable to press the heat-pressing components onto the prepreg via an elastic material such as heat-resistant rubber, rather than pressing the prepreg directly onto the substrate, so that the prepreg can adequately conform to the surface irregularities of the substrate.

[0170] Lamination of the substrate and prepreg is preferably carried out by laminating the prepreg onto the substrate. In one embodiment, lamination of the substrate and prepreg is preferably carried out by a vacuum lamination method. In the vacuum lamination method, the heat-pressure temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heat-pressure pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the heat-pressure time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

[0171] Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressure laminators manufactured by Meiki Seisakusho Co., Ltd., vacuum applicators manufactured by Nikko Materials Co., Ltd., and batch-type vacuum pressure laminators.

[0172] After lamination, the laminated prepregs may be smoothed by pressing a heat-sealing member from the prepreg side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing process can be the same as the heat-sealing conditions for lamination. The smoothing process can be performed using a commercially available laminator. Lamination and smoothing may be performed continuously using a commercially available vacuum laminator.

[0173] <Process (II)> In step (II), the prepreg is heat-cured to form an insulating layer. The heat-curing conditions for the prepreg are not particularly limited, and conditions commonly used when forming the insulating layer of a printed circuit board may be used. The prepreg may be cured by irradiation with active energy rays such as ultraviolet light, but it is usually heat-cured by heating.

[0174] For example, the thermal curing conditions for prepregs vary depending on the type of resin composition, but the curing temperature can be in the range of 120°C to 240°C (preferably 150°C to 220°C, more preferably 170°C to 200°C), and the curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

[0175] Prior to heat-curing the prepreg, it may be preheated at a temperature lower than the curing temperature. For example, prior to heat-curing the prepreg, it may be preheated at a temperature of 50°C or higher but less than 120°C (preferably 60°C or higher but 110°C or lower, more preferably 70°C or higher but 100°C or lower) for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

[0176] <Process (III)> Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. It is preferable to perform step (III) after the completion of step (II). Step (III) may be carried out using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed circuit board.

[0177] The shape of the via holes formed by step (III) is not particularly limited, but is generally circular (approximately circular). The top diameter (opening diameter) of the via holes that can be formed by step (III) is preferably 5 μm or more, more preferably 10 μm or more, more preferably 30 μm or more, preferably 100 μm or less, more preferably 90 μm or less, and even more preferably 80 μm or less, or 70 μm or less. Here, the top diameter (opening diameter) of the via hole refers to the diameter of the opening of the via hole on the surface of the insulating layer. Normally, the diameter of the opening of the via hole on the surface of the insulating layer can be the top diameter.

[0178] The holes, such as via holes, formed by step (III) usually consist of multiple holes. The distance between the openings of the via holes is preferably 200 μm or less, more preferably 160 μm or less, even more preferably 140 μm or less, even more preferably 120 μm or less, or 100 μm or less. There is no particular lower limit, but it can be 0.1 μm or more. As described above, conventionally, if the distance between the openings of the via holes is short, stress due to the energy during laser processing is likely to occur, and delamination of the sheet-like fiber material and the resin composition is likely to occur. However, in the semiconductor chip package manufacturing method of the present invention, since the above-mentioned prepreg is used, the distance (pitch) between the openings of the via holes can be made even narrower. Therefore, the present invention is ideal for semiconductor chip package applications with a short distance between the openings of the via holes and a narrow pitch.

[0179] Examples of laser light sources that can be used to form via holes include CO2 lasers (carbon dioxide lasers), UV-YAG lasers, UV lasers, YAG lasers, and excimer lasers. Among these, CO2 lasers or UV-YAG lasers are preferred from the viewpoint of processing speed and cost, and CO2 lasers are more preferred.

[0180] When irradiating with a CO2 laser, the number of shots is preferably 2 or less, more preferably 1, from the viewpoint of improving via processing performance. In order to keep the number of shots within the above range, it is preferable to set the energy and pulse width of the CO2 laser to a certain value or higher. The energy of the CO2 laser is preferably 0.3 W or more, more preferably 0.5 W or more, even more preferably 1.0 W or more, preferably 30 W or less, more preferably 20 W or less, and even more preferably 15 W or less. The pulse width of the CO2 laser is preferably 3 μsec or more, more preferably 5 μsec or more, even more preferably 8 μsec or more, preferably 40 μsec or less, more preferably 30 μsec or less, and even more preferably 20 μsec or less.

[0181] When irradiating with a UV-YAG laser, the number of shots is preferably 20 or less, more preferably 15, from the viewpoint of improving via processing performance. In order to keep the number of shots within the above range, it is preferable to set the energy and pulse width of the UV-YAG laser to a certain value or higher. The energy of the UV-YAG laser is preferably 0.05 W or more, more preferably 0.10 W or more, even more preferably 0.15 W or more, preferably 20 W or less, more preferably 10 W or less, and even more preferably 5 W or less.

[0182] Via holes can be formed using commercially available laser devices. Examples of commercially available carbon dioxide laser devices include the "LC-2K212" from Via Mechanics, the "LC-2E21B / 1C" from Hitachi Via Mechanics, the "ML605GTWII" and "605GTWIII(-P)" from Mitsubishi Electric, and the laser drilling machine for circuit boards from Matsushita Welding Systems. Examples of UV-YAG laser devices include the "LU-2L212 / M50L" from Via Mechanics.

[0183] <Process (IV)> Step (IV) is a process of desmearing the insulating layer. Typically, in this step (IV), the surface of the insulating layer is roughened along with the removal of smear. The procedure and conditions for desmearing are not particularly limited. For example, the insulating layer can be desmeared by performing swelling treatment with a swelling solution, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing solution in this order.

[0184] Examples of swelling solutions used in desmear treatment include alkaline solutions and surfactant solutions, with alkaline solutions being preferred. Sodium hydroxide solution and potassium hydroxide solution are more preferred as alkaline solutions. Examples of commercially available swelling solutions include "Swelling Dip Security P" and "Swelling Dip Security SBU" manufactured by Atotec Japan. The swelling treatment with the swelling solution is not particularly limited, but can be carried out, for example, by immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 to 15 minutes.

[0185] Examples of oxidizing agents used in the roughening treatment include alkaline permanganate solutions obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. Furthermore, the concentration of permanganate in the alkaline permanganate solution is preferably 5% to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Atotec Japan.

[0186] As the neutralizing solution used for roughening treatment, an acidic aqueous solution is preferred, and a commercially available example is "Reduction Solution Securigant P" manufactured by Attec Japan. Treatment with the neutralizing solution can be carried out by immersing the treated surface, which has been roughened with an oxidizing agent, in a neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From the viewpoint of workability, it is preferable to immerse the object that has been roughened with an oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

[0187] In one embodiment, the arithmetic mean roughness Ra of the insulating layer surface after desmearing is preferably 500 nm or less, more preferably 200 nm or less, even more preferably 100 nm or less, and even more preferably less than 100 nm. The lower limit is not particularly limited and can be, for example, 1 nm or more, 2 nm or more, etc. Also, the root mean square roughness (Rq) of the insulating layer surface after desmearing is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited and can be, for example, 1 nm or more, 2 nm or more, etc. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

[0188] <Process (V)> Step (V) is a step of forming a conductive layer, in which a conductive layer is formed on an insulating layer to manufacture a circuit board. The conductive material used for the conductive layer is not particularly limited. In a preferred embodiment, the conductive layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductive layer may be a single-metal layer or an alloy layer, and examples of alloy layers include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). In particular, from the viewpoint of versatility in conductor layer formation, cost, and ease of patterning, single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or alloy layers of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy are preferred, single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or alloy layers of nickel-chromium alloy are more preferred, and single metal layers of copper are even more preferred.

[0189] The conductive layer may be a single-layer structure, or it may be a multi-layer structure in which two or more single-metal layers or alloy layers made of different types of metals or alloys are stacked. When the conductive layer is a multi-layer structure, the layer in contact with the insulating layer is preferably a single-metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0190] The thickness of the conductor layer depends on the desired printed circuit board design, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0191] In the present invention, since the insulating layer is formed using the prepreg described above, it exhibits the characteristic of excellent plating penetration. Therefore, in step (V), it is preferable to form the conductor layer by wet plating. In step (V), for example, the surface of the insulating layer can be plated by a method such as a semi-additive method or a fully additive method to form a conductor layer having a desired wiring pattern. From the viewpoint of ease of manufacture, it is preferable to form it by a semi-additive method. An example of forming the conductor layer by a semi-additive method is shown below.

[0192] A plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer, exposing a portion of the plating seed layer corresponding to the desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electroplating, the mask pattern is removed. Subsequently, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having the desired wiring pattern.

[0193] In the method for manufacturing a semiconductor chip package, each of the above-described steps may be performed only once or repeated two or more times. For example, steps (I) to (V) may be repeatedly performed to form a semiconductor chip package having a multilayer structure comprising multiple insulating layers and conductive layers.

[0194] Furthermore, after the completion of step (V), the substrate may be peeled off if necessary. The method for peeling off the substrate can be appropriately selected depending on the material of the substrate, and examples include a method of peeling off the substrate by heating it, or a method of removing it by etching. In addition, if the substrate is a substrate having a peelable first metal layer and a second metal layer on both surfaces, the substrate may be peeled off and separated by inserting a blade such as a cutter into the interface between the first metal layer and the second metal layer.

[0195] [Semiconductor device] A semiconductor device according to one embodiment of the present invention includes the semiconductor chip package described above. This semiconductor device can be manufactured using the semiconductor chip package described above.

[0196] Examples of semiconductor devices include various types of semiconductor devices used in electrical products (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft).

[0197] [Cured body] The cured body of the present invention is a cured body obtained by curing a prepreg comprising a sheet-like fibrous substrate and a resin composition impregnated into the sheet-like fibrous substrate, and has via holes penetrating in the thickness direction of the cured body. The prepreg in the cured body is as described above.

[0198] The conditions for thermal curing the prepreg to obtain a cured body are the same as the conditions for curing the prepreg to form an insulating layer in step (II) above.

[0199] The cured body has multiple via holes formed that penetrate in the thickness direction of the cured body, and the distance between the openings of the via holes is 200 μm or less. The preferred range for the distance between the openings of the via holes and the diameter of the openings of the via holes are as described above. [Examples]

[0200] The present invention will be described in detail below with reference to examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" refer to "parts by mass" and "mass%" respectively, unless otherwise specified. Furthermore, the operations described below were carried out in an environment of normal temperature and pressure unless otherwise specified.

[0201] <Measurement of surface treatment amount per unit weight of sheet-like fibrous substrate> The amount of surface treatment agent adhering to the sheet-like fibrous substrate after surface treatment was measured using the heating weight loss method with an electric furnace. Specifically, 2 g of the surface-treated sheet-like fibrous substrate was heated at 625°C for 10 minutes using an electric furnace (Yamato Scientific Co., Ltd., F0300). The amount of surface treatment per unit weight of the sheet-like fibrous substrate was calculated by similarly measuring and correcting the carbon content of untreated glass cloth to determine the carbon content based on the surface treatment.

[0202] <Preparation of Resin Composition 1> 15 parts of naphthalene-type epoxy resin (DIC Corporation "HP4032SS", epoxy equivalent approximately 144 g / eq.), 10 parts of biphenyl-type epoxy resin (Mitsubishi Chemical Corporation "YX4000", epoxy equivalent 194 g / eq.), 20 parts of naphthol aralkyl-type epoxy resin (Nippon Steel Chemical Corporation "ESN-4100VEK75", epoxy equivalent 332 g / eq., methyl ethyl ketone solution with 75% solids), triazine skeleton and 7 parts of a phenolic curing agent having a novolac structure (DIC Corporation's "LA-3018-50P", active group equivalent approximately 151 g / eq., 2-methoxypropanol solution with 60% solids), 65 parts of an active ester curing agent (DIC Corporation's "HPC-8151-62T", active group equivalent approximately 238 g / eq., toluene solution with 62% solids by mass), and a phenolic hydroxyl group-containing phosphaphenanthrene flame retardant (Sanko Co., Ltd.'s "HCA-HQ-H") 5 parts of "ST", phenol equivalent 162 g / eq., phosphorus content 9.5% by mass; 10 parts of phenoxy resin (Mitsubishi Chemical's "YX7553BH30", a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass); inorganic filler surface-treated with amino silane coupling agent (Shin-Etsu Chemical's "KBM573", N-phenyl-3-aminopropyltrimethoxysilane) (surface treatment amount: inorganic filler 100% by mass) Resin composition 1 was prepared by uniformly dispersing 150 parts of 0.6% by mass of an amino-based silane coupling agent, 2 parts of organic filler (EXL2655, manufactured by Dow Chemical), 3 parts of imidazole reaction accelerator (1B2PZ-10M, manufactured by Shikoku Chemicals, a MEK solution with 10% by mass of solids), 15 parts of methyl ethyl ketone (MEK), 15 parts of toluene, and 10 parts of solvent naphtha (#150:IP150) using a mixer.

[0203] <Preparation of Resin Composition 2> 15 parts naphthalene-type epoxy resin (DIC Corporation "HP4032SS", epoxy equivalent approximately 144 g / eq.), 10 parts biphenyl-type epoxy resin (Mitsubishi Chemical Corporation "YX4000", epoxy equivalent 194 g / eq.), 20 parts naphthol aralkyl-type epoxy resin (Nippon Steel Chemical Corporation "ESN-4100VEK75", epoxy equivalent 332 g / eq., methyl ethyl ketone solution with 75% solids), triazine skeleton and 7 parts of a phenolic curing agent having a novolac structure (DIC Corporation's "LA-3018-50P", active group equivalent approximately 151 g / eq., 2-methoxypropanol solution with 60% solids), 55 parts of an active ester curing agent (DIC Corporation's "HPC-8151-62T", active group equivalent approximately 238 g / eq., toluene solution with 62% solids by mass), and a phenolic hydroxyl group-containing phosphaphenanthrene flame retardant (Sanko Co., Ltd.'s "HCA-H 5 parts of "Q-HST", phenol equivalent 162 g / eq., phosphorus content 9.5% by mass; 10 parts of phenoxy resin (Mitsubishi Chemical's "YX7553BH30", a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass); inorganic filler surface-treated with an amino silane coupling agent (Shin-Etsu Chemical's "KBM573", N-phenyl-3-aminopropyltrimethoxysilane) (surface treatment amount: inorganic filler 1 Resin composition 2 was prepared by uniformly dispersing 140 parts of 0.6% by mass of an amino-based silane coupling agent per 00% by mass, 2 parts of organic filler (EXL2655 manufactured by Dow Chemical), 3 parts of imidazole reaction accelerator (1B2PZ-10M manufactured by Shikoku Chemicals, MEK solution with 10% by mass of solids), 15 parts of methyl ethyl ketone (MEK), 15 parts of toluene, and 10 parts of solvent naphtha (#150) using a mixer.

[0204] <Preparation of resin composition 3> 15 parts naphthalene-type epoxy resin (DIC Corporation "HP4032SS", epoxy equivalent approximately 144 g / eq.), 10 parts biphenyl-type epoxy resin (Mitsubishi Chemical Corporation "YX4000", epoxy equivalent 194 g / eq.), 20 parts naphthol aralkyl-type epoxy resin (Nippon Steel Chemical Corporation "ESN-4100VEK75", epoxy equivalent 332 g / eq., methyl ethyl ketone solution with 75% solids), triazine skeleton and 7 parts of a phenolic curing agent having a novolac structure (DIC Corporation's "LA-3018-50P", active group equivalent approximately 151 g / eq., 2-methoxypropanol solution with 60% solids), 100 parts of an active ester curing agent (DIC Corporation's "HPC-8151-62T", active group equivalent approximately 238 g / eq., toluene solution with 62% solids by mass), and a phenolic hydroxyl group-containing phosphaphenanthrene flame retardant (Sanko Co., Ltd.'s "HCA- 5 parts of "HQ-HST", phenol equivalent 162 g / eq., phosphorus content 9.5% by mass; 10 parts of phenoxy resin (Mitsubishi Chemical's "YX7553BH30", a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass); inorganic filler surface-treated with an amino silane coupling agent (Shin-Etsu Chemical's "KBM573", N-phenyl-3-aminopropyltrimethoxysilane) (surface treatment amount: inorganic filler 1 Resin composition 3 was prepared by uniformly dispersing 180 parts of 0.6% by mass of an amino-based silane coupling agent per 00% by mass, 2 parts of organic filler (EXL2655 manufactured by Dow Chemical), 3 parts of imidazole reaction accelerator (1B2PZ-10M manufactured by Shikoku Chemicals, MEK solution with 10% by mass of solids), 15 parts of methyl ethyl ketone (MEK), 15 parts of toluene, and 10 parts of solvent naphtha (#150) using a mixer.

[0205] <Preparation of resin composition 4> 15 parts of naphthalene-type epoxy resin (DIC Corporation "HP4032SS", epoxy equivalent approximately 144 g / eq.), 10 parts of biphenyl-type epoxy resin (Mitsubishi Chemical Corporation "YX4000", epoxy equivalent 194 g / eq.), 20 parts of naphthol aralkyl-type epoxy resin (Nippon Steel Chemical Corporation "ESN-4100VEK75", epoxy equivalent 332 g / eq., methyl ethyl ketone solution with 75% solids), triazine skeleton and novolac structure 7 parts of a phenolic curing agent (DIC Corporation's "LA-3018-50P", active group equivalent approximately 151 g / eq., 2-methoxypropanol solution with 60% solids), 100 parts of an active ester curing agent (DIC Corporation's "HPC-8151-62T", active group equivalent approximately 238 g / eq., toluene solution with 62% solids by mass), and a phenolic hydroxyl group-containing phosphaphenanthrene flame retardant (Sanko Co., Ltd.'s "HCA-HQ-HST", phenol equivalent 1 5 parts of 62 g / eq., phosphorus content 9.5% by mass), 10 parts of phenoxy resin (Mitsubishi Chemical's "YX7553BH30", a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass), and an inorganic filler surface-treated with an amino-based silane coupling agent (Shin-Etsu Chemical's "KBM573", N-phenyl-3-aminopropyltrimethoxysilane) (surface treatment amount: 0% amino-based silane coupling agent per 100% by mass of inorganic filler). Resin composition 4 was prepared by uniformly dispersing 170 parts of 0.6% by mass, 2 parts of organic filler (EXL2655, manufactured by Dow Chemical), 15 parts of maleimide resin (BMI-2300, manufactured by Yamato Chemical Industries), 3 parts of imidazole reaction accelerator (1B2PZ-10M, manufactured by Shikoku Chemicals, a MEK solution with 10% by mass of solids), 15 parts of methyl ethyl ketone (MEK), 15 parts of toluene, and 10 parts of solvent naphtha (#150) using a mixer.

[0206] <Preparation of resin composition 5> 15 parts of naphthalene-type epoxy resin (DIC Corporation "HP4032SS", epoxy equivalent approximately 144 g / eq.), 10 parts of biphenyl-type epoxy resin (Mitsubishi Chemical Corporation "YX4000", epoxy equivalent 194 g / eq.), 20 parts of naphthylene ether-type epoxy resin (DIC Corporation "HP6000H", epoxy equivalent 277 g / eq.), and a phenolic curing agent having a triazine skeleton and novolac structure. (DIC Corporation's "LA-3018-50P", active group equivalent approximately 151 g / eq., 2-methoxypropanol solution with 60% solids) 7 parts, active ester curing agent (DIC Corporation's "HPC-8151-62T", active group equivalent approximately 238 g / eq., toluene solution with 62% solids by mass) 100 parts, phenolic hydroxyl group-containing phosphaphenanthrene flame retardant (Sanko Co., Ltd.'s "HCA-HQ-HST", phenol equivalent 5 parts of 162 g / eq., phosphorus content 9.5% by mass), 10 parts of phenoxy resin (Mitsubishi Chemical's "YX7553BH30", a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass), and an inorganic filler surface-treated with an amino silane coupling agent (Shin-Etsu Chemical's "KBM573", N-phenyl-3-aminopropyltrimethoxysilane) (surface treatment amount: relative to 100% by mass of inorganic filler). Resin composition 5 was prepared by uniformly dispersing 155 parts of 0.6% by mass of an amino-based silane coupling agent, 2 parts of organic filler (EXL2655 manufactured by Dow Chemical), 3 parts of imidazole reaction accelerator (1B2PZ-10M manufactured by Shikoku Chemicals, MEK solution with 10% by mass of solids), 15 parts of methyl ethyl ketone (MEK), 15 parts of toluene, and 10 parts of solvent naphtha (#150) using a mixer.

[0207] <Preparation of resin composition 6> 15 parts of naphthalene-type epoxy resin (DIC Corporation "HP4032SS", epoxy equivalent approximately 144 g / eq.), 10 parts of biphenyl-type epoxy resin (Mitsubishi Chemical Corporation "YX4000", epoxy equivalent 194 g / eq.), 20 parts of naphthol aralkyl-type epoxy resin (Nippon Steel Chemical Corporation "ESN-4100VEK75", epoxy equivalent 332 g / eq., methyl ethyl ketone solution with 75% solids), Tria 7 parts of a phenolic curing agent having a din skeleton and novolac structure (DIC Corporation's "LA-3018-50P", active group equivalent approximately 151 g / eq., 2-methoxypropanol solution with 60% solids), 50 parts of an active ester curing agent (DIC Corporation's "HPC-8151-62T", active group equivalent approximately 238 g / eq., toluene solution with 62% solids by mass), and a phenolic hydroxyl group-containing phosphaphenanthrene flame retardant (three 5 parts of Hikari Co., Ltd.'s "HCA-HQ-HST" (phenol equivalent 162 g / eq., phosphorus content 9.5% by mass), 10 parts of phenoxy resin (Mitsubishi Chemical Corporation's "YX7553BH30", a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass), and an inorganic filler surface-treated with an amino silane coupling agent (Shin-Etsu Chemical Co., Ltd.'s "KBM573", N-phenyl-3-aminopropyltrimethoxysilane). Resin composition 6 was prepared by uniformly dispersing 150 parts of (surface treatment amount: 0.6 mass of amino-based silane coupling agent per 100 mass of inorganic filler), 2 parts of organic filler (Dow Chemical's "EXL2655"), 3 parts of imidazole-based reaction accelerator (Shikoku Chemicals' "1B2PZ-10M", MEK solution with 10 mass of solids), 30 parts of toluene, and 10 parts of solvent naphtha (#150) using a mixer.

[0208] <Preparation of resin composition 7> 15 parts naphthalene-type epoxy resin (DIC Corporation "HP4032SS", epoxy equivalent approximately 144 g / eq.), 10 parts biphenyl-type epoxy resin (Mitsubishi Chemical Corporation "YX4000", epoxy equivalent 194 g / eq.), 20 parts naphthol aralkyl-type epoxy resin (Nippon Steel Chemical Corporation "ESN-4100VEK75", epoxy equivalent 332 g / eq., methyl ethyl ketone solution with 75% solids), triazine skeleton and 7 parts of a phenolic curing agent having a novolac structure (DIC Corporation's "LA-3018-50P", active group equivalent approximately 151 g / eq., 2-methoxypropanol solution with 60% solids), 50 parts of an active ester curing agent (DIC Corporation's "HPC-8151-62T", active group equivalent approximately 238 g / eq., toluene solution with 62% solids by mass), and a phenolic hydroxyl group-containing phosphaphenanthrene flame retardant (Sanko Co., Ltd.'s "HCA-H 5 parts of "Q-HST", phenol equivalent 162 g / eq., phosphorus content 9.5% by mass; 10 parts of phenoxy resin (Mitsubishi Chemical's "YX7553BH30", a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass); inorganic filler surface-treated with an amino silane coupling agent (Shin-Etsu Chemical's "KBM573", N-phenyl-3-aminopropyltrimethoxysilane) (surface treatment amount: inorganic filler 1 Resin composition 7 was prepared by uniformly dispersing 135 parts of 0.6% by mass of an amino-based silane coupling agent per 00% by mass, 2 parts of organic filler (EXL2655 manufactured by Dow Chemical), 3 parts of imidazole reaction accelerator (1B2PZ-10M manufactured by Shikoku Chemicals, MEK solution with 10% by mass of solids), 15 parts of methyl ethyl ketone (MEK), 15 parts of toluene, and 10 parts of solvent naphtha (#150) using a mixer.

[0209] <Preparation of resin composition 8> 15 parts naphthalene-type epoxy resin (DIC Corporation "HP4032SS", epoxy equivalent approximately 144 g / eq.), 10 parts biphenyl-type epoxy resin (Mitsubishi Chemical Corporation "YX4000", epoxy equivalent 194 g / eq.), 20 parts naphthol aralkyl-type epoxy resin (Nippon Steel Chemical Corporation "ESN-4100VEK75", epoxy equivalent 332 g / eq., methyl ethyl ketone solution with 75% solids), triazine skeleton and 3 parts of a phenolic curing agent having a novolac structure (DIC Corporation's "LA-3018-50P", active group equivalent approximately 151 g / eq., 2-methoxypropanol solution with 60% solids), 115 parts of an active ester curing agent (DIC Corporation's "HPC-8151-62T", active group equivalent approximately 238 g / eq., toluene solution with 62% solids by mass), and a phenolic hydroxyl group-containing phosphaphenanthrene flame retardant (Sanko Co., Ltd.'s "HCA- 5 parts of "HQ-HST", phenol equivalent 162 g / eq., phosphorus content 9.5% by mass; 10 parts of phenoxy resin (Mitsubishi Chemical's "YX7553BH30", a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass); inorganic filler surface-treated with an amino silane coupling agent (Shin-Etsu Chemical's "KBM573", N-phenyl-3-aminopropyltrimethoxysilane) (surface treatment amount: inorganic filler 1 Resin composition 8 was prepared by uniformly dispersing 195 parts of 0.6% by mass of an amino-based silane coupling agent per 00% by mass, 2 parts of organic filler (EXL2655 manufactured by Dow Chemical), 3 parts of imidazole reaction accelerator (1B2PZ-10M manufactured by Shikoku Chemicals, MEK solution with 10% by mass of solids), 15 parts of methyl ethyl ketone (MEK), 15 parts of toluene, and 10 parts of solvent naphtha (#150) using a mixer.

[0210] <Preparation of resin composition 9> 15 parts of naphthalene-type epoxy resin (DIC Corporation "HP4032SS", epoxy equivalent approximately 144 g / eq.), 10 parts of biphenyl-type epoxy resin (Mitsubishi Chemical Corporation "YX4000", epoxy equivalent 194 g / eq.), 20 parts of naphthol aralkyl-type epoxy resin (Nippon Steel Chemical Corporation "ESN-4100VEK75", epoxy equivalent 332 g / eq., methyl ethyl ketone solution with 75% solids), Tria 15 parts of a phenolic curing agent having a din skeleton and novolac structure (DIC Corporation's "LA-3018-50P", active group equivalent approximately 151 g / eq., 2-methoxypropanol solution with 60% solids), 15 parts of a phenolic curing agent (Nippon Steel Chemical Co., Ltd.'s "SN485", phenol group equivalent approximately 215 g / eq.), and a phenolic hydroxyl group-containing phosphaphenanthrene flame retardant (Sanko Co., Ltd.'s "HCA-HQ-HST", ph 5 parts of phenol equivalent 162 g / eq., phosphorus content 9.5% by mass), 10 parts of phenoxy resin (Mitsubishi Chemical's "YX7553BH30", a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass), and an inorganic filler surface-treated with an amino silane coupling agent (Shin-Etsu Chemical's "KBM573", N-phenyl-3-aminopropyltrimethoxysilane) (surface treatment amount: inorganic filler 100% by mass) Resin composition 9 was prepared by uniformly dispersing 130 parts of 0.6% by mass of an amino-based silane coupling agent, 2 parts of organic filler (EXL2655 manufactured by Dow Chemical), 3 parts of imidazole reaction accelerator (1B2PZ-10M manufactured by Shikoku Chemicals, a MEK solution with a solid content of 10% by mass), 15 parts of methyl ethyl ketone (MEK), 15 parts of toluene, and 10 parts of solvent naphtha (#150) using a mixer.

[0211] [Table 1]

[0212] [Example 1] <Prepreg fabrication> Resin composition 1 is surface-treated with an amino-based silane coupling agent (KBM573, N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) to create glass cloth manufactured by Nitto Boseki Co., Ltd. (Style WEA1027: IPC-EG-140 standard 1027, 100 filament bundles, warp density 74 threads / 25mm, weft density 74 threads / 25mm, fabric weight 19g / m²). 2 A prepreg was prepared by impregnating a material to a thickness of 20 μm (surface treatment amount 0.32 mass%) and drying it in a vertical drying oven at 110°C for 5 minutes. The resin composition content in the prepreg was 75 mass%, and the thickness of the prepreg was 50 μm. The length of the prepreg in the vertical direction was 30 cm, and the length in the horizontal direction was 20 cm.

[0213] <Analysis of solvents in resin compositions> A 5 mg sample of the resin composition was taken from the dried prepreg and measured using a GCMS-QP2020-NX (Shimadzu Corporation) under oven conditions of 250°C for 10 minutes. The sample was then processed and measured under conditions of a sample line temperature of 260°C, a transfer line temperature of 260°C, and a cycle time of 55 minutes. The type of solvent was identified from each detected peak, and the type and content of solvent contained in the dried resin composition were analyzed by comparing it with a pre-prepared calibration curve.

[0214] <Sample Preparation> (Preparation of the circuit board (core board)) A glass cloth substrate epoxy resin double-sided copper-clad laminate with copper layers on both surfaces was prepared as the substrate (layer composition: Mitsui Mining & Smelting Co., Ltd.'s Microthin MT-Ex copper foil (3 μm thick copper foil / 18 μm thick carrier foil) / Panasonic Corporation's "R1515A" substrate (0.2 mm thick) / Mitsui Mining & Smelting Co., Ltd.'s Microthin MT-Ex copper foil (18 μm thick carrier foil / 3 μm thick copper foil)). The copper layer surface was roughened by immersing both sides of the substrate in MEC Corporation's "CZ8100".

[0215] (Lamination of prepregs) The fabricated prepreg was laminated onto both sides of the substrate prepared above, so that the prepreg bonded to the substrate. Lamination was performed using a vacuum pressure laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.), by vacuum suction at 130°C for 30 seconds, followed by pressing from above the support via heat-resistant rubber for 60 seconds at 130°C and a pressure of 0.7 MPa. Next, under atmospheric pressure, a SUS end plate was used to perform a hot press for 90 seconds at 130°C and a pressure of 0.54 MPa.

[0216] (Thermosetting and laser processing of prepreg) Subsequently, the substrate with the laminated prepregs was heated at 130°C for 30 minutes, then at 180°C for 30 minutes to heat-cur the prepregs and form an insulating layer. Vias with a diameter of 60 μm were then formed at a pitch of 90 μm using a CO2 laser processing machine LC-2K212 manufactured by Via Mechanics Co., Ltd. to obtain a cured substrate A.

[0217] (Insulation layer roughening treatment) A desmear treatment was performed on the cured substrate A as a roughening treatment. The following wet desmear treatment was carried out.

[0218] The cured substrate A was immersed in a swelling solution (Atotec Japan's "Swelling Dip Securigant P," an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 10 minutes, then immersed in an oxidizing agent solution (Atotec Japan's "Concentrate Compact CP," an aqueous solution with approximately 6% potassium permanganate and approximately 4% sodium hydroxide) at 80°C for 20 minutes, then immersed in a neutralizing solution (Atotec Japan's "Reduction Solution Securigant P," an aqueous sulfuric acid solution) at 40°C for 5 minutes, and finally dried at 80°C for 15 minutes. The resulting substrate is referred to as a "roughened substrate."

[0219] (Formation of the conductive layer) 1. Electroless plating process To form a conductive layer on the surface of the roughened substrate, an electroless plating process (copper plating process using chemicals manufactured by Attec Japan Co., Ltd.) including the following treatments (1) to (6) was performed to form a conductive layer (plating seed layer). A substrate on which a conductive layer has been formed on the surface of the roughened substrate is called a "conductive layer substrate". (1) Alkaline cleaning (cleaning of the insulating layer surface and adjustment of charge) The surface of the roughened substrate was cleaned at 60°C for 5 minutes using Cleaning Cleaner Securiganth 902 (product name). (2) Soft etching The surface of the roughened substrate was treated with a sulfuric acid-acidified sodium peroxodisulfate aqueous solution at 30°C for 1 minute. (3) Pre-dip (adjustment of the charge on the insulating layer surface for Pd deposition) The surface of the roughened substrate was treated with Pre. Dip Neoganth B (trade name) at room temperature for 1 minute. (4) Activator application (application of Pd to the surface of the insulating layer) The surface of the roughened substrate was treated with Activator Neoganth 834 (trade name) at 35°C for 5 minutes. (5) Reduction (reduction of Pd deposited on the insulating layer) The surface of the roughened substrate was treated with a mixture of Reducer Neoganth WA (product name) and Reducer Acceralator 810 mod. (product name) at 30°C for 5 minutes. (6) Electroless copper plating process (deposition of Cu on the surface of the insulating layer (Pd surface)) A mixture of Basic Solution Printganth MSK-DK (product name), Copper Solution Printganth MSK (product name), Stabilizer Printganth MSK-DK (product name), and Reducer Cu (product name) was used to treat the surface of a roughened substrate at 35°C for 15 minutes to form an electroless copper plating layer. The thickness of the formed electroless copper plating layer was 1.0 μm.

[0220] 2. Electrolytic Plating Process After the electroless plating process, an electrolytic copper plating process was performed using a chemical solution manufactured by Attec Japan, under conditions that copper was filled into the via holes. Subsequently, a land pattern with a diameter of 150 μm corresponding to the via holes was formed as a resist pattern for etching (a land pattern was also formed on the entire surface at a 600 μm pitch, even in areas without via connections). Using this land pattern, a conductive layer with a conductive pattern and a thickness of 15 μm was formed on the surface of the insulating layer. Next, an annealing treatment was performed at 190°C for 90 minutes.

[0221] (Process of removing the substrate) For a substrate with a conductive layer, a cutter blade was inserted at the interface between the 3 μm thick copper foil and the 18 μm thick carrier foil of a glass cloth substrate epoxy resin double-sided copper-clad laminate. The substrate was peeled off and separated to obtain a sample.

[0222] <Preparation of hardened material> The prepreg was laminated onto a polyimide film (Toray DuPont's "Kapton H", 50 μm thick) using a vacuum pressure laminator (Meiki Seisakusho's "MVLP-500") by vacuum suction at 100°C for 30 seconds, then pressing it onto the support via heat-resistant rubber for 30 seconds at 100°C and a pressure of 0.7 MPa, followed by heat curing at 200°C for 30 minutes. After peeling off the support, the prepreg was further heat-cured at 200°C for 60 minutes to obtain a cured prepreg product.

[0223] <Evaluation of Needle Void> For the cured prepreg, a KEYENCE VHX-7000 microscope was used to examine the material at 100x magnification (2.3 mm length, 60 mm field of view). 2 This was performed by checking any five fields of view. Then, the presence or absence of needle voids was evaluated based on the following evaluation criteria (average of 10 evaluations, rounded to the nearest whole number). ○: 5 or fewer needle voids in the field of view. △: The number of needle voids in the field of view is greater than 5 but less than or equal to 6. ×: The number of needle voids in the field of view exceeds 6, but is 7 or more.

[0224] <Measurement and evaluation of copper plating penetration> The prepared sample was cut to a size of 1 cm, the surface of the conductive layer was ground until the glass cloth was exposed, and five blind vias were identified using a KEYENCE microscope (VHX-7000). The length of the point where the conductive layer penetrated the material most deeply was measured, and this was repeated five times. The average value was determined as the penetration length of the copper plating. Furthermore, the copper plating penetration was evaluated based on the evaluation criteria described below. ○: The maximum length of copper plating penetration is 23 μm or less. ×: The maximum length of copper plating penetration is greater than 23 μm.

[0225] <Measurement and evaluation of dielectric loss tangent> The cured prepregs prepared in the examples and comparative examples were heated at 200°C for 90 minutes to heat-cur the resin composition layer, and then the support was peeled off. The obtained cured material is referred to as the "evaluation cured material." The evaluation cured material was cut into test pieces 2 mm wide and 80 mm long. The dielectric loss tangent of each test piece was measured using the cavity resonance perturbation method with an Agilent Technologies HP8362B at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Measurements were performed on two test pieces, and the average value was calculated. The dielectric properties were then evaluated based on the following evaluation criteria.

[0226] [Example 2] In Example 1, the surface treatment amount of the glass cloth was changed from 0.32% by mass to 0.27% by mass. Aside from the above, evaluation and other procedures were carried out in the same manner as in Example 1.

[0227] [Example 3] In Example 1, the surface treatment amount of the glass cloth was changed from 0.32% by mass to 0.38% by mass. Aside from the above, evaluation and other procedures were carried out in the same manner as in Example 1.

[0228] [Example 4] In Example 1, the following glass cloth was used instead. Aside from the above, evaluations were performed in the same manner as in Example 1. Glass cloth manufactured by Nitto Boseki Co., Ltd., surface-treated with an epoxy silane coupling agent (KBM403, 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), style WEA1027: IPC-EG-140 standard 1027, 100 filament bundles, warp density 74 threads / 25mm, weft density 74 threads / 25mm, fabric weight 19g / m². 2 20 μm thick (surface treatment amount 0.3 mass%).

[0229] [Example 5] In Example 1, the following glass cloth was used instead. Aside from the above, evaluations were performed in the same manner as in Example 1. Glass cloth manufactured by Nitto Boseki Co., Ltd., surface-treated with an amine-based silane coupling agent (KBM5783, N-phenyl-8-aminooctyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), style WEA1027: IPC-EG-140 standard 1027, 100 filament bundles, warp density 74 threads / 25mm, weft density 74 threads / 25mm, fabric weight 19g / m². 2 20 μm thick (surface treatment amount 0.3 mass%).

[0230] [Example 6] In Example 1, the following glass cloth was used instead. Aside from the above, evaluations were performed in the same manner as in Example 1. Glass cloth manufactured by Nitto Boseki Co., Ltd., surface-treated with an epoxy silane coupling agent (KBM4803, 8-glycidoxyoctyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), style WEA1027: IPC-EG-140 standard 1027, 100 filament bundles, warp density 74 threads / 25mm, weft density 74 threads / 25mm, fabric weight 19g / m². 2 20 μm thick (surface treatment amount 0.3 mass%).

[0231] [Example 7] In Example 1, resin composition 1 was replaced with resin composition 2. Aside from the above, evaluation and other procedures were carried out in the same manner as in Example 1.

[0232] [Example 8] In Example 1, resin composition 1 was replaced with resin composition 3. Aside from the above, evaluation and other procedures were carried out in the same manner as in Example 1.

[0233] [Example 9] In Example 1, resin composition 1 was replaced with resin composition 4, and the following glass cloth was used instead. Evaluation and other procedures were carried out in the same manner as in Example 1, except for the above. Glass cloth manufactured by Nitto Boseki Co., Ltd., surface-treated with an amino-based silane coupling agent (KBM573, N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) and a methacrylic-based silane coupling agent (KBM503, 3-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), is of the style WEA1027 (IPC-EG-140 standard 1027, 100 filament bundles, warp density 74 threads / 25mm, weft density 74 threads / 25mm, fabric weight 19g / m²). 2 20 μm thick (surface treatment amount 0.35 mass%).

[0234] [Example 10] In Example 1, resin composition 1 was replaced with resin composition 5. Aside from the above, evaluation and other procedures were carried out in the same manner as in Example 1.

[0235] [Example 11] In Example 1, resin composition 1 was replaced with resin composition 6. Aside from the above, evaluation and other procedures were carried out in the same manner as in Example 1.

[0236] [Comparative Example 1] In Example 1, the amount of surface treatment with an amino-based silane coupling agent (KBM573, N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 0.32% by mass to 0.23% by mass. Evaluations and other procedures were carried out in the same manner as in Example 1, except for the above.

[0237] [Comparative Example 2] In Example 1, the surface treatment amount of the amino-based silane coupling agent (Shin-Etsu Chemical Co., Ltd.'s "KBM573", N-phenyl-3-aminopropyltrimethoxysilane) was changed from 0.32% by mass to 0.42% by mass. Evaluation and the like were carried out in the same manner as in Example 1 except for the above matters.

[0238] [Comparative Example 3] In Example 1, Resin Composition 1 was changed to Resin Composition 7. Evaluation and the like were carried out in the same manner as in Example 1 except for the above matters.

[0239] [Comparative Example 4] In Example 1, Resin Composition 1 was changed to Resin Composition 8. Evaluation and the like were carried out in the same manner as in Example 1 except for the above matters.

[0240] [Comparative Example 5] In Example 1, Resin Composition 1 was changed to Resin Composition 9. Evaluation and the like were carried out in the same manner as in Example 1 except for the above matters.

[0241]

Table 2

Table 3

Claims

1. (I) A step of laminating a sheet-like fibrous substrate and a prepreg containing a resin composition impregnated into the sheet-like fibrous substrate onto a substrate. (II) A step of curing the prepreg to form an insulating layer, and (V) A method for manufacturing a semiconductor chip package, which includes a step of forming a conductive layer, The resin composition comprises (a) epoxy resin and (b) an active ester-based curing agent. The ratio of component (a) to component (b) ([total number of active groups in component (b)] / [total number of epoxy groups in component (a)]) is 0.7 or more and 1.4 or less. A method for manufacturing a semiconductor chip package, wherein a sheet-like fibrous substrate is surface-treated with a surface treatment agent, and the content of the surface treatment agent per unit weight of the sheet-like fibrous substrate, as measured by the heat weight loss method, is 0.25% by mass or more and 0.4% by mass or less.

2. Furthermore, the resin composition comprises (c) an inorganic filler, the method for manufacturing a semiconductor chip package according to claim 1.

3. A method for manufacturing a semiconductor chip package according to claim 1, wherein the surface treatment agent comprises any one of an aminosilane coupling agent, an epoxysilane coupling agent, and a (meth)acrylsilane coupling agent.

4. A method for manufacturing a semiconductor chip package according to claim 1, wherein the thickness of the sheet-like fiber substrate is 26 μm or less.

5. Furthermore, the resin composition contains a (k) solvent, and the content of aromatic hydrocarbon solvents in the (k) solvent contained in the dried resin composition is 0% by mass or more and 40% by mass or less, when the total solvent contained in the resin composition is taken as 100% by mass, the method for manufacturing a semiconductor chip package according to claim 1.

6. Furthermore, the method for manufacturing a semiconductor chip package according to claim 1, further comprising the step of drilling holes in the insulating layer after the completion of step (II), thereby forming via holes in the insulating layer.

7. A method for manufacturing a semiconductor chip package according to claim 1, wherein the distance between the openings of the via holes is 200 μm or less.

8. A method for manufacturing a semiconductor chip package according to claim 1, wherein the substrate is peeled off after the completion of step (V).

9. Let α be the ratio of the amounts of component (a) and component (b). When β is the content of the surface treatment agent per unit weight of the sheet-like fiber substrate, β ２ A method for manufacturing a semiconductor chip package according to claim 1, wherein / α is 0.01 or more and 0.5 or less.

10. A cured body obtained by curing a prepreg containing a sheet-like fibrous substrate and a resin composition impregnated into the sheet-like fibrous substrate, It has via holes that penetrate in the thickness direction of the hardened body, The resin composition comprises (a) epoxy resin and (b) an active ester-based curing agent. The ratio of component (a) to component (b) ([total number of active groups in component (b)] / [total number of epoxy groups in component (a)]) is 0.7 or more and 1.4 or less. The sheet-like fibrous substrate is surface-treated with a surface treatment agent, and the content of the surface treatment agent per unit weight of the sheet-like fibrous substrate, as measured by the heat weight loss method, is 0.25% by mass or more and 0.4% by mass or less. A hardened body in which the distance between the openings of the beer holes is 200 μm or less.

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