Resin sheet

Abstract

The present invention provides a resin sheet and the like, which can provide a cured product having excellent uniformity of the thickness of an insulating layer, embeddability, and insulating reliability. The present invention provides a resin sheet for forming an insulating layer by vacuum press treatment, which comprises a support and a resin composition layer provided on the support, wherein the support has a metal foil having an arithmetic mean roughness (Ra) of the surface on the side to be bonded to the resin composition layer of more than 300 nm, and the resin composition layer contains (A) an inorganic filler having a specific surface area of 10 m 2 / g or more, and a maximum value of tan δ at a temperature of 100°C or higher in dynamic viscoelasticity measurement of the resin composition layer from 60°C to 200°C is 1.0 or more and 2.0 or less.

Description

Technical Field

[0001] This invention relates to resin sheets. Furthermore, it relates to printed wiring boards, semiconductor devices, and methods for manufacturing printed wiring boards using the resin sheets. Background Technology

[0002] In the manufacture of printed wiring boards, the insulating layer is formed, for example, as described in Patent Document 1, by laminating prepreg on a circuit board using a vacuum pressing process and then curing it.

[0003] Existing technical documents Patent documents Patent document 1: Japanese Patent Application Publication No. 2017-57352. Summary of the Invention

[0004] The technical problem that the invention aims to solve With the recent miniaturization of printed wiring boards and the like, from the perspective of making the insulating layer thin film, there is a demand for resin composition layers made of resin sheets instead of prepregs. Methods for forming insulating layers using resin composition layers made of resin sheets include: methods for laminating resin composition layers on a circuit board by vacuum lamination and curing them, and methods for laminating resin composition layers on a circuit board by vacuum pressing and curing them.

[0005] When forming an insulating layer from a resin composition layer using a resin sheet through vacuum pressing, the pressure applied to the resin composition layer during lamination is higher than that of vacuum lamination. This can lead to resin flow (resin exudation) within the resin composition layer, sometimes resulting in poor uniformity of the insulating layer thickness and consequently, reduced insulation reliability. Furthermore, if the resin viscosity is increased to suppress resin flow, it may be impossible to embed circuit board wiring within the insulating layer, leading to reduced embedding quality and poor insulation. Additionally, when the resin sheet support has a metal foil with high roughness, the insulating layer thickness tends to be thinner in the rougher areas, sometimes resulting in significant degradation of insulation reliability.

[0006] The subject matter of this invention (the technical problem to be solved) is to provide: a resin sheet of cured material that can produce excellent uniformity of insulation layer thickness, embeddability and insulation reliability; a printed wiring board and a semiconductor device formed using the resin sheet; and a method for manufacturing the printed wiring board.

[0007] Technical solutions for solving technical problems The inventors conducted in-depth research on the above-mentioned problems and found that the above-mentioned problems can be solved by using a resin sheet and forming an insulating layer by vacuum pressing. The resin sheet includes a support body and a resin composition layer disposed on the support body. The support body includes a metal foil with an arithmetic mean roughness (Ra) of more than 300 nm on the surface of the side bonded to the resin composition layer. The resin composition layer contains (A) a specific surface area of ​​10 m². 2 The present invention is completed by measuring the dynamic viscoelasticity of the resin composition layer at temperatures above 100°C in the range of 60°C to 200°C using inorganic filler material of g or more.

[0008] That is, the present invention includes the following: [1] A resin sheet for forming an insulating layer using vacuum pressing, the resin sheet comprising a support and a resin composition layer disposed on the support, the support having a metal foil having an arithmetic mean roughness (Ra) of more than 300 nm on the side of the surface that is bonded to the resin composition layer, and the resin composition layer containing (A) a specific surface area of ​​10 m². 2 For inorganic fillers of / g or more, in the dynamic viscoelasticity test of the resin composition layer from 60°C to 200°C, the maximum value of tanδ at a temperature of 100°C or higher is 1.0 or higher and 2.0 or lower. [2] The resin sheet according to [1], wherein the thickness of the resin composition layer is less than 30 μm; [3] The resin sheet according to [1] or [2], wherein the resin composition layer contains any one selected from active ester resin, maleimide resin and vinyl resin; [4] The resin sheet according to any one of [1] to [3], wherein when the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (A) is 73% by mass or less; [5] The resin sheet according to any one of [1] to [4], wherein the metal foil comprises copper foil; [6] The resin sheet according to any one of [1] to [5], wherein the thickness of the support is 9 μm or more; [7] A printed wiring board, comprising an insulating layer formed by a cured resin composition layer of a resin sheet as described in any one of [1] to [6]; [8] A semiconductor device comprising the printed wiring board of [7]; [9] A method for manufacturing a printed wiring board, the method comprising: (I) The process of laminating the resin sheet described in any one of [1] to [6] onto the inner substrate by vacuum pressing, and (II) The process of heat curing the resin composition layer to form an insulating layer.

[0009] The effects of the invention According to the present invention, a resin sheet with excellent uniformity of insulation layer thickness, embedment properties and insulation reliability can be provided; a printed wiring board and a semiconductor device formed using the resin sheet; and a method for manufacturing the printed wiring board. Detailed Implementation

[0010] The present invention will now be described in detail according to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be implemented with any modifications without departing from the scope of the claims and their equivalents.

[0011] [Resin Sheets] The resin sheet of the present invention is a resin sheet for forming an insulating layer using vacuum pressing. The resin sheet is characterized in that it comprises a support body and a resin composition layer disposed on the support body, the support body comprising a metal foil with an arithmetic mean roughness (Ra) of more than 300 nm on the surface of the side bonded to the resin composition layer, and the resin composition layer containing (A) a specific surface area of ​​10 m². 2 For inorganic fillers of / g or more, in the dynamic viscoelasticity test of the resin composition layer from 60°C to 200°C, the maximum value of tanδ at 100°C or above is 1.0 or more and 2.0 or less.

[0012] As described above, when forming an insulating layer using resin sheets (resin composition layers), compared to conventional vacuum lamination methods, the pressure applied to the resin sheets (resin composition layers) during lamination in vacuum pressing is higher, sometimes resulting in uneven insulation layer thickness due to resin flow. On the other hand, if the viscosity of the resin composition layer is increased to suppress resin exudation, the embedding properties and insulation performance sometimes decrease. The inventors have discovered that the uniformity of insulation layer thickness, embedding properties, and insulation reliability are related to the maximum value of tanδ (tanδ is the ratio of loss modulus E (Pa) to storage modulus E' (GPa) E” / E') at a specific temperature range in the dynamic viscoelasticity of the resin composition layer. Furthermore, the inventors have discovered that by adjusting the specific surface area of ​​the inorganic filler material in the resin composition layer and adjusting the amount of residual solvent in the resin composition layer, the maximum value of tanδ can be adjusted, resulting in a cured product with excellent uniformity of insulation layer thickness, embedding properties, and insulation reliability.

[0013] The following is a detailed description of each layer that makes up the resin sheet.

[0014] <Support Body> In the resin sheet of the present invention, the support body includes a metal foil having an arithmetic mean roughness (Ra) of more than 300 nm on the surface of the support body to which the resin composition layer is disposed. Typically, the support body surface having the aforementioned arithmetic mean roughness (Ra) is the surface of the metal foil, which is in contact with the resin composition layer. Thus, the conductor layer described later can be formed from the support body.

[0015] The arithmetic mean roughness (Ra) of the support surface on which the resin composition layer is disposed is, from the viewpoint of improving adhesion to the resin composition layer, greater than 300 nm, preferably 350 nm or more, more preferably 400 nm or more, and even more preferably 500 nm or more. There is no particular upper limit, but it is preferably 1000 nm or less, more preferably 900 nm or less, and even more preferably 800 nm or less. The arithmetic mean roughness (Ra) is a value measured according to ISO 25178 and can be measured using a non-contact surface roughness meter.

[0016] The ten-point average roughness (Rz) of the support surface on which the resin composition layer is disposed is preferably greater than 7000 nm, more preferably 8000 nm or more, and even more preferably 9000 nm or more, from the viewpoint of improving adhesion to the resin composition layer. There is no particular upper limit, but it is preferably 30000 nm or less, more preferably 20000 nm or less, and even more preferably 10000 nm or less. The ten-point average roughness (Rz) is a value measured according to ISO 25178 and can be measured using a non-contact surface roughness meter.

[0017] For the surface of the support, for example, by etching or grinding the surface of the support, the arithmetic mean roughness (Ra) and the ten-point mean roughness (Rz) can be adjusted to the aforementioned range.

[0018] The support body has a metal foil, preferably a metal foil. From the viewpoint of achieving significant effects of the present invention, the thickness of the support body is preferably 9 μm or more, more preferably 10 μm or more, and even more preferably 11 μm or more. There is no particular limitation on the upper limit, but it is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less. It should be noted that the metal foil can be a single-layer structure or a multi-layer structure. When the metal foil is a multi-layer structure, the overall thickness of the metal foil is preferably within the range mentioned above, wherein the thickness of an extremely thin metal foil can, for example, be in the range of 0.1 μm or more and 10 μm or less.

[0019] Examples of metal foils include copper foil and aluminum foil, with copper foil being preferred. Copper foil can be used as the copper foil, either as a single metal of copper or as an alloy of copper with other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0020] Metal foil can be a single-layer structure or a multi-layer structure obtained by stacking two or more single metal layers or alloy layers formed of different kinds of metals or alloys. Examples of multi-layer metal foils include, for instance, a metal foil comprising a carrier metal foil and an extremely thin metal foil bonded to the carrier metal foil. The multi-layer metal foil may further include a release layer between the carrier metal foil and the extremely thin metal foil, making it possible to peel the extremely thin metal foil from the carrier metal foil. The release layer is not particularly limited as long as it allows the extremely thin metal foil to be peeled from the carrier metal foil; examples include, for instance, an alloy layer selected from elements selected from Cr, Ni, Co, Fe, Mo, Ti, W, and P; and an organic coating. It should be noted that when using a multi-layer metal foil as a support, a resin composition layer may be disposed on the extremely thin metal foil.

[0021] There are no particular limitations on the manufacturing method of metal foil; it can be manufactured using known methods such as electrolysis and rolling.

[0022] The support may also include any layer other than the metal foil in combination with the metal foil. From the viewpoint that the metal foil and the resin composition layer can be directly contacted, the arbitrary layer is preferably located on the side of the metal foil opposite to the resin composition layer. Here, "directly" contacting the metal foil and the resin composition layer means that there are no other layers between the metal foil and the resin composition layer. Preferably, there are no arbitrary layers, therefore the support preferably consists only of the metal foil.

[0023] Commercially available products can be used as supports. Examples of commercially available products include "HLP foil" and "JXUT-III foil" manufactured by JX Minerals & Metals Corporation, "MicroThin MT-Ex copper foil" and "TP-III foil" manufactured by Mitsui Metals & Mining Corporation, and "MW-G" manufactured by Mitsui Metals & Mining Corporation.

[0024] <Resin Composition Layer> In the resin sheet of the present invention, the resin composition layer disposed on the support contains: (A) a specific surface area of ​​10 m² 2 Inorganic filler materials of / g or higher.

[0025] In addition to component (A), the resin composition layer may further contain any other components. Examples of such components include: (B) epoxy resin, (C) curing agent, (D) free radical polymerizable compound, (E) thermoplastic resin, (F) curing accelerator, (G) polymerization initiator, and (H) other additives. The components contained in the resin composition layer will be described in detail below.

[0026] -(A) Specific surface area is 10m² 2 / g or more of inorganic filler materials- In the resin composition layer, as component (A), it contains (A) with a specific surface area of ​​10m². 2 / g or more of inorganic filler material. By using a resin composition layer containing component (A), the embeddability and uniformity of the insulation layer thickness can be improved.

[0027] From the perspective of improving embeddability and enhancing the uniformity of insulation layer thickness by suppressing thickness unevenness caused by resin exudation, the specific surface area of ​​component (A) is 10m². 2 / g or more, preferably 15m 2 / g or more, more preferably 20m 2 / g or more, further preferably 25m 2 / g or more. There is no particular limit to the upper limit, but 60m is preferred. 2 / g or less, more preferably 50m 2 / g or less, more preferably 40m 2 / g or less. For specific surface area, it can be obtained by using the BET method, using a fully automated BET specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) to adsorb nitrogen gas onto the sample surface, and then calculating the specific surface area using the BET multi-point method.

[0028] Regarding the average particle size of component (A), from the viewpoint of improving embeddability and suppressing thickness unevenness caused by resin flow to improve the uniformity of the insulation layer thickness, it is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, preferably 5 μm or less, more preferably 4 μm or less, and further preferably 3 μm or less.

[0029] The average particle size of component (A) can be determined using laser diffraction-scattering based on the Mie scattering theory. Specifically, a laser diffraction-scattering particle size distribution measuring device can be used to prepare the particle size distribution of the inorganic filler material on a volume basis, and the median particle size can be used as the average particle size for measurement. The sample for testing can be obtained by weighing 100 mg of inorganic filler material and 10 g of methyl ethyl ketone into a vial and dispersing it ultrasonically for 10 minutes. For the sample for testing, a laser diffraction-scattering particle size distribution measuring device is used, with blue and red light source wavelengths, to measure the volume-based particle size distribution of component (A) in a flow cell manner. The average particle size can be calculated from the obtained particle size distribution as the median particle size. Examples of laser diffraction-scattering particle size distribution measuring devices include the "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

[0030] Inorganic compounds are used as the material for component (A). Examples of materials for component (A) include silica, alumina, aluminosilicates, 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. Furthermore, spherical silica is preferred as silica. Component (A) may be used alone or in combination of two or more.

[0031] Commercially available products that are components (A) include, for example: Denka's "UFP-30" and "ASFP-20"; Nippon Steel Chemical Materials' "SP60-05", "SP507-05", and "SPH516-05"; Admatechs' "YC100C", "YA050C", "YA050C-MJE", and "YA010C"; Tokuyama's "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N"; Admatechs' "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1"; etc.

[0032] From the viewpoint of improving moisture resistance and dispersibility, component (A) is preferably treated with a surface treatment agent. Examples of surface treatment agents include vinyl silane coupling agents, (meth)acrylic acid coupling agents, fluorinated silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. Among these, aminosilane coupling agents are preferred from the viewpoint of significantly achieving the effects of the present invention. Furthermore, a single surface treatment agent may be used, or two or more may be used in any combination.

[0033] Commercially available surface treatment agents include, for example: Shin-Etsu Chemical Industry Co., Ltd.'s "KBM1003" (vinyltriethoxysilane), Shin-Etsu Chemical Industry Co., Ltd.'s "KBM503" (3-methacryloyloxypropyltriethoxysilane), Shin-Etsu Chemical Industry Co., Ltd.'s "KBM403" (3-epoxypropoxypropyltrimethoxysilane), Shin-Etsu Chemical Industry Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), and Shin-Etsu Chemical Industry Co., Ltd.'s "KBE903" (3-amino... Examples of silanes include N-phenyl-3-aminopropyltrimethoxysilane, KBM573 (N-phenyl-3-aminopropyltrimethoxysilane), SZ-31 (hexamethyldisilazane), KBM103 (phenyltrimethoxysilane), KBM-4803 (long-chain epoxy silane coupling agent), and KBM-7103 (3,3,3-trifluoropropyltrimethoxysilane).

[0034] From the viewpoint of improving the dispersibility of inorganic filler materials, the degree of surface treatment by surface treatment agent is preferably within a specified range. Specifically, 100 parts by mass of inorganic filler material is preferably surface treated with 0.2 parts by mass to 5 parts by mass of surface treatment agent, preferably with 0.2 parts by mass to 3 parts by mass of surface treatment agent, and preferably with 0.3 parts by mass to 2 parts by mass of surface treatment agent.

[0035] The degree of surface treatment by the surface treatment agent can be evaluated by the carbon content per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content per unit surface area of ​​the inorganic filler is preferably 0.02 mg / m². 2 The above, more preferably 0.1 mg / m 2 The above is further preferred to be 0.2 mg / m³. 2 That's all. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish and the melt viscosity in sheet form, 1 mg / m³ is preferable. 2The following is more preferably 0.8 mg / m³ 2 The following is a further preferred value: 0.5 mg / m³ 2 the following.

[0036] The carbon content per unit surface area of ​​inorganic filler materials can be determined after cleaning the surface-treated inorganic filler material with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, sufficient MEK as a solvent is added to the surface-treated inorganic filler material, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid components, the carbon content per unit surface area of ​​the inorganic filler material can be determined using a carbon analyzer. A carbon analyzer such as the "EMIA-320V" manufactured by Horiba Corporation can be used.

[0037] From the viewpoint of adjusting the maximum value of tanδ to a suitable range, when the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (A) is preferably 73% by mass or less, more preferably 72% by mass or less, further preferably 71% by mass or less, 70% by mass or less, 69% by mass or less, 68% by mass or less, preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more. It should be noted that, unless otherwise explicitly stated, the content of each component in the resin composition layer in this invention refers to the value when the non-volatile component in the resin composition layer is set to 100% by mass.

[0038] -(B) Epoxy Resin- The resin composition layer may contain epoxy resin (B) as component (B). Epoxy resin (B) may be used alone or in combination with two or more.

[0039] Examples of epoxy resins (B) include: bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolac type epoxy resin, phenolnovolac 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, glycidyl ester type epoxy resin, glycidyl cyclohexane type epoxy resin, and cresol novolac. Novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins with butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spirocyclic epoxy resins, cyclohexane type epoxy resins, cyclohexane-diethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylolpropionic acid type epoxy resins, tetraphenylethane type epoxy resins, phenolphthalimidine type epoxy resins, etc. Epoxy resins can be used alone or in combination of two or more.

[0040] In the resin composition layer, as component (B), it is preferable to include an epoxy resin having two or more epoxy groups per molecule. From the viewpoint of significantly obtaining the desired effect of the present invention, the proportion of epoxy resin having two or more epoxy groups per molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, relative to 100% by mass of the non-volatile component of the thermosetting resin.

[0041] The epoxy resin includes an epoxy resin that is liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at 20°C (hereinafter sometimes referred to as "solid epoxy resin"). The resin composition layer, as a thermosetting resin, may contain only liquid epoxy resin or only solid epoxy resin, but preferably a combination of both.

[0042] As a liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0043] As liquid epoxy resins, preferred types 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, phenolic varnish type epoxy resin, alicyclic epoxy resin with an ester skeleton, cyclohexane type epoxy resin, cyclohexanediol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin with a butadiene structure, glycidyl cyclohexane type epoxy resin, phenol benzopyrrolidone type epoxy resin, and more preferably glycidyl cyclohexane type epoxy resin.

[0044] Specific examples of liquid epoxy resins include: DIC's "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin); Mitsubishi Chemical's "828US", "jER828EL", "825", and "EPIKOTE828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical's "jER807" and "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical's "jER152" (phenolic varnish type epoxy resin); Mitsubishi Chemical's "630" and "630LSD" (glycidylamine type epoxy resin); Nippon Steel Chemical Materials Co., Ltd.'s "ZX1059" (a mixture of bisphenol A and bisphenol F type epoxy resins); Nagase ChemteX's "EX-721" (glycidyl ester type epoxy resin); and Daicel's "CELLOXIDE". 2021P (an alicyclic epoxy resin with an ester backbone); PB-3600 (an epoxy resin with a butadiene structure) manufactured by Daicel Corporation; ZX1658 and ZX1658GS (liquid 1,4-glycidylcyclohexane type epoxy resins) manufactured by Nippon Steel Chemical Materials Co., Ltd. These can be used individually or in combination.

[0045] As a solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred.

[0046] As a solid epoxy resin, the preferred types are xylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol-phenolic varnish-type epoxy resin, dicyclopentadiene-type epoxy resin, triphenol-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 xylenol-type epoxy resin and naphthalene-type epoxy resin being more preferred.

[0047] 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 phenolic varnish type epoxy resin), "N-695" (cresol phenolic varnish type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", and "HP6000L" (naphthyl ether type epoxy resin); and Nippon Kayaku Co., Ltd.'s "EPPN-502H" (triphenol type epoxy resin), "NC7000L" (naphthalene phenolic varnish type epoxy resin), "NC3000H", and "NC3" (naphthalene phenolic varnish type epoxy resin). 000, NC3000L, NC3100 (biphenyl type epoxy resin); Nippon Steel Chemical Materials Co., Ltd.'s "ESN475V" (naphthalene type epoxy resin) and "ESN485" (naphthalene phenolic varnish type epoxy resin); Mitsubishi Chemical Co., Ltd.'s "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), and "YX8800" (anthracite type epoxy resin) Epoxy resins include: "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin), "YL7800" (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin), and "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; and "WHR-991S" (phenol benzopyrrolidone type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These can be used individually or in combination.

[0048] When liquid epoxy resin and solid epoxy resin are used as components (B), their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.3 to 1:10, and particularly preferably 1:0.5 to 1:5. By keeping the mass ratio of liquid epoxy resin to solid epoxy resin within the aforementioned range, the desired effects of the present invention can be significantly obtained.

[0049] (B) The epoxy equivalent of component B is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., further preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. Within this range, a cured body with sufficient crosslinking density of the resin composition layer can be obtained. The epoxy equivalent is the mass of epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be determined according to JIS K7236.

[0050] From the viewpoint of significantly achieving the desired effects of the present invention, the weight-average molecular weight (Mw) of component (B) is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. The weight-average molecular weight of the epoxy resin is the weight-average molecular weight converted from polystyrene by gel permeation chromatography (GPC).

[0051] From the viewpoint of obtaining a cured body exhibiting good mechanical strength and insulation reliability, when the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (B) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. From the viewpoint of significantly obtaining the desired effects of the present invention, the upper limit of the epoxy resin content is preferably 35% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less.

[0052] -(C) Curing Agent - The resin composition layer may contain a curing agent (C) as component (C). The curing agent (C) typically has the function of reacting with component (B) to cure the resin composition. The curing agent (C) may be used alone or in combination with two or more.

[0053] As the curing agent (C), a low-polarity curing agent is preferred. Examples of curing agents (C) include: active ester resins, phenol resins, naphthol resins, benzoxazine resins, cyanate ester resins, carbodiimide resins, amine resins, and acid anhydride resins, etc., among which, from the viewpoint of significantly obtaining the effects of the present invention, it is preferable to include an active ester resin.

[0054] As an active ester resin, a resin having one or more active ester groups per molecule can be used. Among these, resins having two or more highly reactive ester groups per molecule, such as phenolic esters, thiophenolic esters, N-hydroxyamine esters, and heterocyclic hydroxyl compounds, are preferred. This active ester resin is preferably a resin obtained through a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxyl compound and / or a thiol compound. Particularly from the viewpoint of improved heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxyl compound is preferred, and an active ester resin obtained from a carboxylic acid compound and a phenolic compound and / or a naphthol compound is more preferred.

[0055] Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0056] Examples of phenolic 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-dihydroxynaphthol, 1,6-dihydroxynaphthol, 2,6-dihydroxynaphthol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyroglucinol, dicyclopentadiene-type diphenol compounds, and linear phenolic resins. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0057] Preferred examples of active ester resins include: active ester resins containing a dicyclopentadiene-type diphenol structure, active ester resins containing a naphthalene structure, active ester resins containing acetylated linear phenolic resins, and active ester resins containing benzoylated linear phenolic resins. More preferably, active ester resins contain a naphthalene structure or an active ester resin containing a dicyclopentadiene-type diphenol structure are preferred. "Dicyclopentadiene-type diphenol structure" refers to a divalent structural unit formed from a phenylene-dicyclopentylene-phenylene group.

[0058] Commercially available reactive ester resins include, for example, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", and "EXB-8000L-65TM" (manufactured by DIC); for example, "EXB9416-70BK", "EXB-8150-65T", and "HP-B-8151-62T" (manufactured by DIC); and for example, "EXB9416-70BK", "EXB-8150-65T", and "HP-B-8151-62T" (manufactured by DIC); and for example, linear phenolic resins... Examples of active ester resins containing acetylated esters include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of active ester resins containing benzoyl derivatives of linear phenolic resins include "YLH1026" (manufactured by Mitsubishi Chemical Corporation); examples of active ester resins containing acetylated linear phenolic resins include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of active ester resins containing benzoyl derivatives of linear phenolic resins include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); etc.

[0059] From the viewpoint of heat resistance and water resistance, resins with a phenolic (novolac) structure are preferred as phenolic and naphthol-based resins. Furthermore, from the viewpoint of adhesion to the conductor layer, nitrogen-containing phenolic curing agents are preferred, and phenolic resins containing a triazine backbone are more preferred.

[0060] Specific examples of phenolic and naphthol resins include: "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Corporation; "NHN", "CBN", "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN395" manufactured by Nippon Steel Chemical Materials Co., Ltd.; and "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" manufactured by DIC Corporation.

[0061] Specific examples of benzoxazine resins include: JFE Chemical Co., Ltd.'s "JBZ-OD100" (benzoxazine ring equivalent 218 g / eq.), "JBZ-OP100D" (benzoxazine ring equivalent 218 g / eq.), and "ODA-BOZ" (benzoxazine ring equivalent 218 g / eq.); Shikoku Chemical Industry Co., Ltd.'s "Pd" (benzoxazine ring equivalent 217 g / eq.) and "Fa" (benzoxazine ring equivalent 217 g / eq.); and Showa Polymer Co., Ltd.'s "HFB2006M" (benzoxazine ring equivalent 432 g / eq.).

[0062] Examples of difunctional cyanate resins include: bisphenol A dicyanate, polyphenol cyanate, oligomeric (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate-phenylpropane), 1,1-bis(4-cyanate-phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate-phenyl-1-(methylethylene))benzene, bis(4-cyanate-phenyl) sulfide, and bis(4-cyanate-phenyl) ether; polyfunctional cyanate resins derived from phenolic varnish resins and cresol varnish resins; prepolymers obtained by partially triazinizing these cyanate resins; and so on. Specific examples of cyanate ester resins include "PT30", "PT30S" and "PT60" (phenolic varnish type multifunctional cyanate ester resin), "ULL-950S" (multifunctional cyanate ester resin), "BA230", "BA230S75" (prepolymer obtained by triazinizing part or all of bisphenol A dicyanate to form a trimer), and "BADCy" (bisphenol A dicyanate), etc., manufactured by Lonza Japan.

[0063] Specific examples of carbodiimide resins include: CARBODILITE (registered trademark) V-03 (carbodiimide equivalent: 216 g / eq.), V-05 (carbodiimide equivalent: 216 g / eq.), V-07 (carbodiimide equivalent: 200 g / eq.), and V-09 (carbodiimide equivalent: 200 g / eq.) manufactured by Nisshinbo Chemical Co., Ltd.; and Stabaxol (registered trademark) P (carbodiimide equivalent: 302 g / eq.) manufactured by Rhein Chemie Co., Ltd.

[0064] As amine resins, examples include resins having one or more amino groups per molecule, such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. From the viewpoint of achieving the desired effect of the present invention, aromatic amines are preferred. The amine resin is preferably a primary or secondary amine, more preferably a primary amine. Specific examples of amine curing agents include: 4,4'-methylenebis(2,6-dimethylaniline), diphenyl diamino sulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino- 4-Hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. Amine resins can be commercially available products, such as "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., and "Epicure (エピキュア)W" manufactured by Mitsubishi Chemical Co., Ltd.

[0065] As anhydride-based resins, examples include resins having one or more anhydride groups within one molecule. Specific examples of anhydride-based resins include: phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and diphenylene oxide. Polymer-type anhydrides such as methyl ketone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyl sulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(triphenyl phthalic anhydride), and styrene-maleic acid resin obtained by copolymerizing styrene with maleic acid.

[0066] When the resin composition layer contains epoxy resin and a curing agent, the ratio of epoxy resin to all curing agent, expressed as the ratio of [total number of epoxy groups in the epoxy resin] to [total number of reactive groups in the curing agent], is preferably in the range of 1:0.01 to 1:5, more preferably 1:0.05 to 1:3, and even more preferably 1:0.1 to 1:2. Here, "number of epoxy groups in the epoxy resin" refers to the sum of all values ​​obtained by dividing the mass of the non-volatile component of the epoxy resin present in the resin composition by the epoxy equivalent. Similarly, "number of reactive groups in the curing agent" refers to the sum of all values ​​obtained by dividing the mass of the non-volatile component of the curing agent present in the resin composition by the reactive group equivalent. As a thermosetting resin, by maintaining the ratio of epoxy resin to curing agent within the aforementioned range, a cured body with excellent flexibility can be obtained.

[0067] From the viewpoint that the effects of the present invention are significantly obtained, the content of (C) curing agent relative to 100% by mass of the non-volatile component in the resin composition layer is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 8% by mass or less.

[0068] -(D) Free radical polymerizable compounds- The resin composition layer may contain a free radical polymerizable compound as component (D). Component (D) may be used alone or in combination with two or more.

[0069] In one embodiment, (D) the free radical polymerizable compound is a free radical polymerizable compound having an olefinically unsaturated bond. (D) The free radical polymerizable compound is not particularly limited and may have, for example, unsaturated hydrocarbon groups such as allyl, 3-cyclohexenyl, 3-cyclopentenyl, p-vinylphenyl, m-vinylphenyl, o-vinylphenyl; and α,β-unsaturated carbonyl groups such as acryloyl, methacryloyl, and maleimide (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl). (D) The free radical polymerizable compound preferably has two or more free radical polymerizable groups.

[0070] The (D) radical polymerizable compound can be, for example, a maleimide resin, a vinyl resin, a (meth)acrylic resin, an allyl resin, etc. Among them, as the (D) component, it is preferable to include any one of a maleimide resin and a vinyl resin, and more preferably, it includes both a maleimide resin and a vinyl resin.

[0071] Maleimide-based resins (maleimide-based free radical polymerizable compounds) are, for example, compounds having one or more, preferably two or more, maleimide groups. Maleimide resins can be aliphatic maleimide compounds containing an aliphatic amine skeleton or aromatic maleimide compounds containing an aromatic amine skeleton. Examples of commercially available products include: Shin-Etsu Chemical Co., Ltd.'s "SLK-2600"; Designer Molecules' "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", "BMI-2500" (maleimide compounds containing a dimer diamine structure); Designer Molecules' "BMI-6100" (aromatic maleimide compound); Nippon Kayaku Co., Ltd.'s "MIR-5000-60T" and "MIR-3000-70MT" (biphenyl aryl maleimide compounds); KI Chemical Co., Ltd.'s "BMI-70" and "BMI-80"; and Daiwa Chemical Industry Co., Ltd.'s "BMI-2300" and "BMI-TMH". In addition, maleimide-based resins (maleimide compounds containing an indenyl ring skeleton) disclosed in Japanese Invention Association Publication No. 2020-500211 can also be used as maleimide-based resins.

[0072] Vinyl-based resins (vinyl-based free radical polymerizable compounds (also known as styrene-based free radical polymerizable compounds)) are, for example, compounds having one or more, preferably two or more, vinyl groups directly bonded to aromatic carbon atoms. Examples of vinyl-based resins include, for example, low molecular weight (molecular weight less than 1000) styrene-based compounds such as divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl) ether; and high molecular weight (molecular weight 1000 or more) styrene-based compounds such as vinylbenzyl-modified polyphenylene ether resin and styrene-divinylbenzene copolymer. Commercially available styrene-based free radical polymerizable compounds include, for example: "ODV-XET(X03)", "ODV-XET(X04)", and "ODV-XET(X05)" (styrene-divinylbenzene copolymer) manufactured by Nippon Steel Chemical Materials Co., Ltd., and "OPE-2St 1200" and "OPE-2St 2200" (vinyl benzyl modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0073] (Meth)acrylic resins ((meth)acrylic free radical polymerizable compounds) are, for example, compounds having one or more, preferably two or more, acryloyl groups and / or methacryloyl groups. Examples of (meth)acrylate resins include, for example, low molecular weight (molecular weight less than 1000) aliphatic (meth)acrylate compounds such as cyclohexane-1,4-diethanol di(meth)acrylate, cyclohexane-1,3-diethanol di(meth)acrylate, tricyclodecane-diethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; dioxanediol di(meth)acrylate, 3,6-dioxane-1,8-octanediol di(meth)acrylate, etc. Low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylate compounds such as (meth)acrylates, 3,6,9-trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, etc.; low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylate compounds such as tri(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, etc.; high molecular weight (molecular weight greater than 1000) acrylate compounds such as (meth)acrylate-modified polyphenylene ether resin, etc. Commercially available (meth)acrylic resins include, for example: "A-DOG" (dioxanediol diacrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd.; "DCP-A" (tricyclodecanediethanol diacrylate) and "DCP" (tricyclodecanediethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd.; "KAYARAD R-684" (tricyclodecanediethanol diacrylate) and "KAYARAD R-604" (dioxanediol diacrylate) manufactured by Nippon Kayaku Co., Ltd.; and "SA9000" and "SA9000-111" (methacrylic acid modified polyphenylene ether) manufactured by SABIC Innovative Plastics Co., Ltd.

[0074] Allyl resins (allyl-based free radical polymerizable compounds) are, for example, compounds having one or more, preferably two or more, allyl groups. Examples of allyl resins include: diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, diallyl 2,3-naphthalenedicarboxylate, and other aromatic carboxylic acid allyl ester compounds; 1,3,5-triallyl isocyanurate, 1,3-diallyl-5-glycidyl isocyanuric acid. Allyl isocyanurate compounds such as esters; epoxy aromatic allyl compounds such as 2,2-bis[3-allyl-4-(glycidoxy)phenyl]propane; benzoxazine-containing aromatic allyl compounds such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazine-3-yl)phenyl]methane; ether-containing aromatic allyl compounds such as 1,3,5-triallyl ether benzene; allyl silane compounds such as diallyl diphenylsilane, etc. Commercially available allyl resins include: TAIC (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Corporation; DAD (dallyl biphenyl dicarboxylate) manufactured by Nippon Techno Fine Corporation; TRIAM-705 (triallyl trimellitate) manufactured by Wako Pure Chemical Industries Co., Ltd.; DAND (dallyl 2,3-naphthylcarboxylate) manufactured by Nippon Distillation Industries Co., Ltd.; ALP-d (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane) manufactured by Shikoku Kasei Corporation; RE-810NM (2,2-bis[3-allyl-4-(glycidoxy)phenyl]propane) manufactured by Nippon Kayaku Co., Ltd.; and DA-MGIC (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Kasei Corporation.

[0075] The olefinic unsaturated bond equivalent of component (D) is preferably 20 g / eq. to 3000 g / eq., more preferably 50 g / eq. to 2500 g / eq., further preferably 70 g / eq. to 2000 g / eq., and particularly preferably 90 g / eq. to 1500 g / eq. The olefinic unsaturated bond equivalent is the mass of the free radical polymerizable compound per 1 olefinic unsaturated bond.

[0076] (D) The weight-average molecular weight (Mw) of component (Mw) is preferably 40,000 or less, more preferably 10,000 or less, even more preferably 5,000 or less, and particularly preferably 3,000 or less. The lower limit is not particularly limited, and for example, it can be 150 or more.

[0077] From the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (D) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more. From the viewpoint of significantly obtaining the desired effects of the present invention, the upper limit of the content of component (D) is preferably 40% by mass or less, more preferably 35% by mass or less, and particularly preferably 30% by mass or less.

[0078] From the viewpoint of improving resin flow and insulation reliability, materials with low polarity are preferred as components contained in the resin composition layer. Examples of such low-polarity materials include reactive ester resins, maleimide resins, and vinyl resins. Therefore, as a preferred embodiment of the resin sheet, it is preferable to include at least one of (B) epoxy resin, (C) curing agent, and (D) free radical polymerizable compound in combination with component (A), and more preferably, any component of reactive ester resin, maleimide resin, and vinyl resin in combination with component (A).

[0079] -(E) Thermoplastic resin- The resin composition layer may contain thermoplastic resin (E) as component (E). By containing component (E) in the resin composition layer, a cured product exhibiting good mechanical strength can be obtained. Component (E) may be used alone or in combination with two or more.

[0080] From the viewpoint of achieving significant effects of the present invention, the weight-average molecular weight (Mn) of component (E) is preferably 5000 or more, more preferably 8000 or more, particularly preferably 10000 or more, preferably 100000 or less, more preferably 80000 or less, and particularly preferably 50000 or less. The weight-average molecular weight of component (E) is the weight-average molecular weight converted to polystyrene by gel permeation chromatography (GPC).

[0081] As component (E), a high molecular weight component with a weight-average molecular weight within the above-mentioned range can be used. Examples of such components include thermoplastic resins such as polyimide resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polyamide-imide resins, polyether-imide resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, and polyester resins; and elastomers. From the viewpoint of significantly obtaining the effects of the present invention, component (E) is preferably selected from at least one of polyimide resins, elastomers, and phenoxy resins.

[0082] Examples of polyimide resins include polyimide resins comprising structural units (hereinafter also referred to as "structural units (e1)") shown in the following formula (e1). In the first polyimide resin, the number of structural units (e1) is 1 or more, without particular limitation, and can be 100 or less, 50 or less, or 30 or less. When there are multiple structural units (e1), the structural units (e1) may be connected to each other as repeating units or may not be connected to each other. When they are not connected to each other, for multiple structural units (e1), it is preferable that other structural units (e.g., structural units shown in formula (e2) described later) exist between them.

[0083] The structural unit (e1) is represented by the following equation (e1); [Chemical Formula 1] In formula (e1), R1 is a tetravalent group as shown in the following formula (e1-1). R2 is a divalent group as shown in the following formula (e1-2).

[0084] [Chemical Formula 2] (in equation (e1-1), Ar 11 Ar 12 Ar 13 and Ar 14 Each can be independently represented as an aromatic ring with optional substituents. L 11 L 12 and L 13 Each independently represents a divalent linker. nc1 represents an integer greater than or equal to 0.

[0085] [Chemical Formula 3] (in equation (e1-2), Ar 21 Ar 22 Ar 23 and Ar 24 Each can be independently represented as an aromatic ring with optional substituents. L 21 L 22 and L 23 Each independently represents a divalent linker. nc2 represents an integer greater than or equal to 1).

[0086] In equation (e1-1), Ar 11 Ar12 Ar 13 and Ar 14 The aromatic ring shown (hereinafter also referred to as "aromatic ring C") is preferably an aromatic ring with 6 to 100 carbon atoms, more preferably an aromatic ring with 6 to 50 carbon atoms, even more preferably an aromatic carbon ring with 6 to 100 carbon atoms, and even more preferably an aromatic carbon ring with 6 to 50 carbon atoms. Therefore, in a preferred embodiment, in formula (e1-1), Ar 11 Ar 12 Ar 13 and Ar 14 Each is an aromatic carbon ring, optionally containing 6 to 14 carbon atoms with substituents. Here, the term "aromatic ring" in this specification refers to a ring whose π-electron system contains 4n+2 electrons (n ​​being a natural number), following Hückel's rule, including monocyclic aromatic rings and fused aromatic rings formed by the fusion of two or more monocyclic aromatic rings. Aromatic rings can be carbon rings or heterocyclic rings. Examples of aromatic rings include: monocyclic aromatic rings such as benzene rings, furan rings, thiophene rings, pyrrole rings, pyrazole rings, oxazole rings, isoxazole rings, thiazole rings, imidazole rings, pyridine rings, pyridazine rings, pyrimidine rings, and pyrazine rings; fused rings formed by the fusion of two or more monocyclic aromatic rings such as naphthyl rings, anthracene rings, benzofuran rings, isobenzofuran rings, indole rings, isoindole rings, benzothiophene rings, benzimidazole rings, indazole rings, benzoxazole rings, benzoisoxazole rings, benzothiazole rings, quinoline rings, isoquinoline rings, quinoxaline rings, acridine rings, quinazoline rings, borazine rings, and phthalazine rings; and fused rings formed by the fusion of one or more monocyclic non-aromatic rings onto one or more monocyclic aromatic rings such as indanium rings, fluorene rings, and tetrahydronaphthalene rings. Among these, aromatic carbon rings with 6 to 14 carbon atoms are preferred, and benzene rings are more preferred.

[0087] In equation (e1-1), when Ar 11 Ar 12 Ar 13 and Ar 14 When representing an aromatic ring with substituents, the number of substituents is not limited. Such substituents (hereinafter also referred to as "substituent S") can be listed independently of each other: halogen atom, alkyl, cycloalkyl, alkoxy, cycloalkyloxy, aryl, aryloxy, arylalkyl, arylalkoxy, monovalent heterocyclic group, alkylidene group, amino, silyl, acyl, acyloxy, carboxyl, sulfonyl, cyano, nitro, hydroxyl, mercapto, and oxo.

[0088] In equation (e1-1), L 11 L 12 and L 13The divalent linking group shown is preferably a divalent group formed from one or more skeletal atoms selected from carbon, oxygen, nitrogen, sulfur, and silicon atoms (e.g., 1 to 3000, 1 to 1000, 1 to 100, or 1 to 50 atoms, respectively). Examples of divalent linking groups include: -SO2-, -CO-, -COO-, -O-, -S-, -O-C6H4-O- (where -C6H4- represents phenylene), -O-C6H4-C(CH3)2-C6H4-O-, and -COO-(CH2). q -OCO- (where q represents an integer from 1 to 20), -COO-H2C-HC(-OC(=O)-CH3)-CH2-OCO-, alkylene, alkenylene, ynylene, arylene, heteroarylene, -C(=O)-, -C(=O)-O-, -NR 0 -(Here, R) 0 (representing hydrogen atoms, alkyl groups with 1 to 3 carbon atoms) and -C(=O)-NR 0 - As an alkylene group, it is preferably an alkylene group with 1 to 10 carbon atoms, more preferably an alkylene group with 1 to 6 carbon atoms, even more preferably an alkylene group with 1 to 5 carbon atoms, or an alkylene group with 1 to 4 carbon atoms. As an alkylene group, it is preferably, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, dimethylmethylene, etc., preferably dimethylmethylene. As an alkenyl group, it is preferably an alkenyl group with 2 to 10 carbon atoms, more preferably an alkenyl group with 2 to 6 carbon atoms, even more preferably an alkenyl group with 2 to 5 carbon atoms. As an aryl group or heteroaryl group, it is preferably an aryl group or heteroaryl group with 6 to 20 carbon atoms, more preferably an aryl group or heteroaryl group with 6 to 10 carbon atoms. The above-mentioned alkyl, alkylene, alkenyl, ynylene, aryl, and heteroaryl groups may optionally further have substituents. Examples of these substituents are the same as those of substituent S. L 11 L 12 and L 13 The divalent linker indicated preferably does not contain an aromatic ring. In one embodiment, L 11 The divalent linker represented by L 13 The divalent linking groups represented are identical to each other, L 11 The divalent linker represented by L 12 The divalent linking groups represented are different from each other. In a preferred embodiment, in formula (e1-1), L 11 and L 13 It's -O-, L 12 It is optionally an alkylene group having substituents; in a more preferred embodiment, in formula (e1-1), Ar 11 Ar 12 Ar 13and Ar 14 Each is independently an aromatic carbon ring with 6 to 14 carbon atoms, optionally having substituents, and in formula (e1-1), L 11 and L 13 It's -O-, L 12 It is optionally an alkylene group having substituents. In a further preferred embodiment, in formula (e1-1), L 11 and L 13 It's -O-, L 12 It is dimethylmethylene.

[0089] In equation (e1-2), Ar 21 Ar 22 Ar 23 and Ar 24 The examples of the aromatic ring and the substituents optionally present on the aromatic ring are the same as those of the aromatic ring C and the substituent S. Therefore, in a preferred embodiment, in formula (e1-2), Ar 21 Ar 22 Ar 23 and Ar 24 Each is independently an aromatic carbon ring with 6 to 14 carbon atoms, optionally having substituents. Furthermore, in a preferred embodiment, in formula (e1-2), L... 21 and L 23 -O-, L 22 The alkylene group can be optionally substituted; in a more preferred embodiment, Ar is a substituent in formula (e1-2). 21 Ar 22 Ar 23 and Ar 24 Each is an aromatic carbon ring with 6 to 14 carbon atoms, optionally with substituents, and in formula (e1-2), L 21 and L 23 -O-, L 22 It can be an alkylene group with substituents, optionally. In a further preferred embodiment, in formula (e1-2), L 21 and L 23 -O-, L 22 It is a dimethylmethylene. In a particularly preferred embodiment, in formula (e1-1), Ar 11 Ar 12 Ar 13 and Ar 14 Each is an aromatic carbon ring with 6 to 14 carbon atoms, optionally with substituents, and in formula (e1-2), Ar 21 Ar 22 Ar 23 and Ar 24Each is independently an aromatic carbon ring with 6 to 14 carbon atoms, optionally having substituents. Furthermore, in another particularly preferred embodiment, in formula (e1-1), L... 11 and L 13 -O-, L 12 For optional alkylene groups having substituents, and in formula (e1-2), L 21 and L 23 -O-, L 22 It is optionally an alkylene group having substituents. In a particularly preferred embodiment, in formula (e1-1), Ar 11 Ar 12 Ar 13 and Ar 14 Each is an aromatic carbon ring with 6 to 14 carbon atoms, each optionally having substituents, in formula (e1-2), Ar 21 Ar 22 Ar 23 and Ar 24 Each is an aromatic carbon ring with 6 to 14 carbon atoms, each optionally having substituents, in formula (e1-1), L 11 and L 13 -O-, L 12 The alkylene group is optionally substituted, and in formula (e1-2), L 21 and L 23 -O-, L 22 It can be an alkylene group with optional substituents.

[0090] In equation (e1-1), nc1 preferably represents an integer greater than or equal to 1. There is no particular upper limit to the integer represented by nc1; for example, it can be 50, 40, 30, or 20.

[0091] In equation (e1-2), nc2 preferably represents an integer greater than 2. There is no particular upper limit to the integer represented by nc2; for example, it can be 60, 50, 40, or 30. In one embodiment, in equation (e1-1), the integer represented by nc2 is greater than the integer represented by nc1 and less than nc1+5. In a specific embodiment, in equation (e1-1), nc1 is 1 and nc2 is 2.

[0092] The aforementioned structural unit (e1) can be obtained, for example, by a known method for manufacturing polyimide resins, typically by polymerizing a monomer composition containing a tetracarboxylic dianhydride and a diamine compound to perform imidization, or by polymerizing a monomer composition containing a tetracarboxylic dianhydride and a diisocyanate compound to perform imidization. It should be noted that the first polyimide resin may contain a portion of a polyamic acid structure that can be generated during the imidization process.

[0093] The structural unit (e1) in the specific embodiments described above can be obtained, for example, by reacting 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (the compound shown in formula (eI) below; also referred to as "BPADA") with 4,4'-[1,4-phenylenebis[(1-methylethylene)-4,1-phenyleneoxy]]bisaniline (the compound shown in formula (eII) below; also referred to as "BPPAN"). That is, R1 in the structural unit (e1) is derived from the BPADA skeleton, and R2 is derived from the BPPAN skeleton.

[0094] [Chemical Formula 4]

[0095] [Chemical Formula 5]

[0096] Furthermore, the first polyimide resin may be a resin that further comprises a structural unit (hereinafter also referred to as "structural unit (e2)") shown in the following formula (e2). Therefore, in some embodiments, the first polyimide resin is a resin that further comprises a structural unit shown in the following formula (e2). In the first polyimide resin, the number of structural units (e2) is 0 or more, without particular limitation, and may be 100 or less, 50 or less, or 30 or less. The structural unit (e2) may be connected to the group R2 of the structural unit (e1) via the nitrogen atom of its imide group, or it may not be connected to the structural unit (e1). When there are multiple structural units (e2), the structural units (e2) may be connected to each other as repeating units, or they may not be connected to each other. When they are not connected to each other, for multiple structural units (e2), it is preferable that other structural units (e.g., structural units (e1)) exist between them.

[0097] The structural unit (e2) is represented by the following equation (e2), [Chemical Formula 6] (in equation (e2),) R3 represents either a tetravalent aliphatic group with optional substituents or a tetravalent aromatic group with optional substituents. R4 represents a divalent aliphatic group or a divalent aromatic group that may optionally have substituents. However, when R3 is the same as R1, R4 is different from R2; when R4 is the same as R2, R3 is different from R1.

[0098] In formula (e2), R3 represents a tetravalent aliphatic group that contains at least a carbon atom, preferably a tetravalent group formed from one or more skeletal atoms selected from carbon, oxygen, nitrogen, sulfur, and silicon atoms (e.g., 1 to 3000, 1 to 1000, 1 to 100, or 1 to 50 atoms). In formula (e2), R3 represents a tetravalent aliphatic group that more preferably has 1 to 100 carbon atoms, and even more preferably has 1 to 50 carbon atoms. When R3 represents a tetravalent aliphatic group with a substituent in formula (e2), the examples of the substituent are the same as those of the substituent S.

[0099] In formula (e2), the tetravalent aromatic group represented by R3 is preferably a tetravalent aromatic group with 6 to 100 carbon atoms, more preferably a tetravalent aromatic group with 6 to 50 carbon atoms, even more preferably a tetravalent aromatic hydrocarbon group with 6 to 100 carbon atoms, and even more preferably a tetravalent aromatic hydrocarbon group with 6 to 50 carbon atoms. The aromatic group contains at least an aromatic ring. Examples of aromatic rings contained in the aromatic group are related to Ar in formula (e1-1). 11 Ar 12 Ar 13 and Ar 14 The examples of aromatic rings represented are the same. In formula (e2), when R3 represents a tetravalent aromatic group with a substituent, the examples of the substituent are the same as those of the substituent S.

[0100] As R3 represents a tetravalent aromatic group, examples include groups obtained by removing two anhydride groups from a tetracarboxylic dianhydride having optionally substituent aromatic groups. The aromatic group contains at least an aromatic ring. Examples of aromatic rings contained in the aromatic group are the same as those for aromatic ring C. When the aromatic group has substituents, examples of substituents are the same as those for substituent S. Specific examples of tetracarboxylic dianhydrides having optionally substituent aromatic groups include BPADA, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, and 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride.

[0101] In formula (e2), R4 represents a divalent aliphatic group that contains at least a carbon atom, preferably a divalent group formed from one or more skeletal atoms selected from carbon, oxygen, nitrogen, sulfur, and silicon atoms (e.g., 1 to 3000, 1 to 1000, 1 to 100, or 1 to 50 atoms). In formula (e2), R4 is more preferably a divalent aliphatic group with 1 to 100 carbon atoms, and even more preferably a divalent aliphatic group with 1 to 50 carbon atoms. When R4 represents a divalent aliphatic group with a substituent in formula (e2), the examples of the substituent are the same as those of the substituent S, for example, an alkyl group with 1 to 6 carbon atoms. Therefore, in some embodiments, R4 is optionally a divalent aliphatic group with a substituent, one of which is an alkyl group with 1 to 6 carbon atoms. Furthermore, in a particular embodiment, R4 is optionally a divalent aliphatic group having substituents, and is a divalent group obtained by removing two amino groups from isophorone diamine.

[0102] When R4 represents a divalent aliphatic group with optional substituents, it can be a group obtained by removing two amino groups from a diamine compound selected from 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine. These diamine compounds are characterized in that their aliphatic groups are linear.

[0103] When R4 represents a divalent aliphatic group with optional substituents, it can be a group obtained by removing two amino groups from a diamine compound selected from 1,2-diaminopropane, 1,2-diamino-2-methylpropane, 1,3-diamino-2-methylpropane, 1,3-diamino-2,2-dimethylpropane, 1,3-diaminopentane, and 1,5-diamino-2-methylpentane with optional substituents. These diamine compounds are characterized in that their aliphatic groups are branched.

[0104] When R4 represents an optional divalent aliphatic group with substituents, it can be selected from 5-amino-1,3,3-trimethylcyclohexanemethylamine (isophorone diamine), 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-cyclohexane bis(methylamine), 1,3-cyclohexane bis(methylamine), 4,4'-diaminodicyclohexylmethane, bis(4-amino-3-methylcyclohexyl)methane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0] 2,6The diamine compound obtained by removing two amino groups from a diamine compound having an optionally substituent aliphatic group, such as decane, 2,5(6)-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,3-diaminoadamantane, 3,3'-diamino-1,1'-bisadamantane, and 1,6-diaminoadamantane. These diamine compounds are characterized in that their aliphatic group comprises an alicyclic carbocyclic ring.

[0105] In formula (e2), the divalent aromatic group represented by R4 is preferably a divalent aromatic group with 6 to 100 carbon atoms, more preferably a divalent aromatic group with 6 to 50 carbon atoms, even more preferably a divalent aromatic hydrocarbon group with 6 to 100 carbon atoms, and even more preferably a divalent aromatic hydrocarbon group with 6 to 50 carbon atoms. The aromatic group contains at least an aromatic ring. Examples of aromatic rings contained in the aromatic group are the same as examples of aromatic ring C. When R4 represents a divalent aromatic group having a substituent in formula (e2), examples of such substituents are the same as examples of substituent S.

[0106] When R4 represents a divalent aromatic group with optional substituents, it can be a group obtained by removing two amino groups from a diamine compound with an optional aromatic group selected from 4,4'-diaminodiphenyl ether, 1,4-phenylenediamine, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane.

[0107] However, when R3 and R1 are the same, R4 and R2 are different; when R4 and R2 are the same, R3 and R1 are different. In some embodiments, R3 and R1 are the same. That is, structural unit (e2) is different from structural unit (e1).

[0108] The aforementioned structural unit (e2) can be obtained, for example, according to a known method for manufacturing polyimide resins. In the specific embodiment described above, the structural unit (e2) can be obtained, for example, by reacting BPADA with isophorone diamine. That is, R3 in the structural unit (e2) is a backbone derived from BPADA, and R4 is a backbone derived from isophorone diamine. When R3 and R1 are the same, both R3 and R1 are backbones derived from BPADA. It should be noted that the first polyimide resin may contain a portion of a polyamic acid structure that can be generated during the imidization process.

[0109] The end structure of the first polyimide resin is not particularly limited as long as it has a structural unit (e1). For example, the end structure of the polyimide resin can be an anhydride group, carboxyl group, or amino group derived from the raw material compound of the polyimide resin (e.g., an acid such as BPADA, an amine such as BPPAN). When the raw material compound further contains maleic anhydride, the end structure of the polyimide resin can be a maleimide group.

[0110] Glass transition temperature Tg of polyimide resin(c) The glass transition temperature (Tg) is preferably 140°C or higher, more preferably 145°C or higher, even more preferably 150°C or higher, and even more preferably 160°C or higher, and particularly preferably 170°C or higher. There is no particular upper limit, and it can be 300°C or lower, etc. Regarding the glass transition temperature Tg... (c) The temperature (°C) can be measured using a Rigaku TMA apparatus at a heating rate of 5°C / min from 25°C to 250°C.

[0111] From the viewpoint of achieving significant effects of the present invention, the content (percentage) of the structural unit (e1) in the polyimide resin is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 40% by mass or more. The content (percentage) of the structural unit (e1) in the polyimide resin can, for example, be 98% by mass or less, 95% by mass or less, 90% by mass or less, or 85% by mass or less. Here, the content (percentage) of the structural unit (e1) can be calculated from the proportion of the charge (parts by mass) of each material used to synthesize the polyimide resin. Alternatively, the molecular weight of the polyimide resin and the formula weight of the structural unit (e1) can be determined and calculated as the ratio of the formula weight of the structural unit (e1) to the molecular weight. When the polyimide resin is a polymer, the content (percentage) of the structural unit (e1) estimated from the degree of polymerization is preferably within the aforementioned range.

[0112] When the polyimide resin further comprises the structural unit (e2), the percentage of the structural unit (e2) is allowed to be 0% by mass (i.e., without the structural unit (e2)), and there is no upper limit as long as it does not impair the effects of the present invention. Therefore, the percentage of the structural unit (e2) in the polyimide resin can be, for example, 1% or more by mass, 5% or more by mass, 10% or more by mass, 20% or more by mass, or 30% or more by mass, and less than 95% by mass, less than 90% by mass, less than 80% by mass, less than 70% by mass, or less than 60% by mass. Here, the percentage of the structural unit (e2) can be calculated in the same way as the percentage of the structural unit (e1). When the polyimide resin is a polymer, the percentage of the structural unit (e2) estimated from the degree of polymerization is preferably within the aforementioned range.

[0113] The weight-average molecular weight (Mw) of the polyimide resin is typically 1,000 or more, preferably 1,000 to 10,000, more preferably 1,000 to 5,000, and even more preferably 1,000 to 3,000. The weight-average molecular weight of the resin can be determined by gel permeation chromatography (GPC) as a value converted from polystyrene.

[0114] Other embodiments of the polyimide resin include: a resin comprising a first backbone derived from BPADA and a second backbone derived from BPPAN (hereinafter sometimes referred to as "second polyimide resin"). If the first backbone is the same as the backbone derived from BPADA, its material is not limited to BPADA. If the second backbone is the same as the backbone derived from BPPAN, its material is not limited to BPPAN. In the second polyimide resin, the number of first backbones is 1 or more, without particular limitation, and may be 100 or less, 50 or less, or 30 or less. In the second polyimide resin, the number of second backbones is 1 or more, without particular limitation, and may be 100 or less, 50 or less, or 30 or less.

[0115] The aforementioned first and second skeletons can, for example, be derived from known methods of manufacturing polyimide resins, typically by polymerizing and imidizing a monomer composition comprising a tetracarboxylic dianhydride and a diamine compound. It should be noted that the first and second skeletons can also be derived from a method of polymerizing and imidizing a monomer composition comprising a tetracarboxylic dianhydride and a diisocyanate compound. Therefore, the second polyimide resin may contain the structural units (e1) contained in the first polyimide resin. It should be noted that the second polyimide resin is permitted to contain a portion of polyamic acid structures that may be generated during the imidization process.

[0116] Furthermore, the second polyimide resin may also be a resin comprising a third backbone different from the second backbone. This third backbone is derived from the backbone of one or more diamine compounds selected from aliphatic compounds having optional substituents and aromatic compounds having optional substituents. Therefore, in some embodiments, the second polyimide resin is a resin comprising a third backbone different from the second backbone, which is derived from the backbone of one or more diamine compounds selected from aliphatic compounds having optional substituents and aromatic compounds having optional substituents. In the second specific polyimide resin, the number of third backbones is 0 or more, not particularly limited, but may be 100 or less, 50 or less, or 30 or less.

[0117] When the diamine compound is a diamine compound having an aliphatic group, the aliphatic group is a group comprising at least a carbon atom, preferably formed from one or more skeletal atoms selected from carbon, oxygen, nitrogen, sulfur, and silicon atoms (e.g., 1 to 3000, 1 to 1000, 1 to 100, 1 to 50), more preferably an aliphatic group having 1 to 100 carbon atoms, and even more preferably an aliphatic group having 1 to 50 carbon atoms. When the aliphatic group has a substituent, the examples of the substituent are the same as the examples of substituent S.

[0118] When the diamine compound is a diamine compound having an aromatic group, the aromatic group is preferably a tetravalent aromatic group having 6 to 100 carbon atoms, more preferably a tetravalent aromatic group having 6 to 50 carbon atoms, even more preferably a tetravalent aromatic hydrocarbon group having 6 to 100 carbon atoms, and even more preferably a tetravalent aromatic hydrocarbon group having 6 to 50 carbon atoms. The aromatic group contains at least an aromatic ring. Examples of aromatic rings contained in the aromatic group are the same as examples of aromatic ring C. When the aromatic group has a substituent, examples of the substituent are the same as examples of substituent S.

[0119] The third skeleton can be derived from a diamine compound having an aliphatic group, wherein the aliphatic group has an alkyl group having 1 to 6 carbon atoms as a substituent. Alternatively, the third skeleton can be derived from isophorone diamine. Therefore, in some embodiments, the second polyimide resin is a resin further comprising a skeleton derived from a diamine compound having an aliphatic group having an alkyl group having 1 to 6 carbon atoms as a substituent. Specifically, the third skeleton is derived from isophorone diamine. The skeleton derived from isophorone diamine (5-amino-1,3,3-trimethylcyclohexanemethylamine) can be derived from 5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane.

[0120] The third skeleton can be derived from the skeleton of one or more diamine compounds selected from 4,4'-diaminodiphenyl ether, 1,4-phenylenediamine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, etc., having an aromatic group optionally having a substituent. Such a third skeleton is characterized by having an aromatic group.

[0121] The third skeleton can be derived from one or more diamine compounds selected from 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, etc., having an aliphatic group optionally having substituents. Such a third skeleton is characterized by the aliphatic group being linear.

[0122] The third skeleton can be derived from one or more diamine compounds selected from 1,2-diaminopropane, 1,2-diamino-2-methylpropane, 1,3-diamino-2-methylpropane, 1,3-diamino-2,2-dimethylpropane, 1,3-diaminopentane, 1,5-diamino-2-methylpentane, etc., having an aliphatic group optionally with substituents. Such a third skeleton is characterized by the aliphatic group being branched.

[0123] The third skeleton can be derived from a selection of 5-amino-1,3,3-trimethylcyclohexanemethylamine (isophorone diamine), 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-cyclohexane bis(methylamine), 1,3-cyclohexane bis(methylamine), 4,4'-diaminodicyclohexylmethane, bis(4-amino-3-methylcyclohexyl)methane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0] 2,6 The skeleton of one or more compounds of diamine compounds having optionally substituted aliphatic groups, such as decane, 2,5(6)-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,3-diaminoadamantane, 3,3'-diamino-1,1'-bisadamantane, and 1,6-diaminoadamantane. Such a third skeleton is characterized in that the aliphatic group comprises an alicyclic carbocyclic ring.

[0124] Regarding the aforementioned third backbone, for example, in a method of polymerizing and imidizing a monomer composition containing a tetracarboxylic dianhydride that can serve as a first backbone and a diamine compound that can serve as a second backbone, the diamine compound or diisocyanate compound that can serve as a third backbone is included in the monomer composition or is sequentially mixed during polymerization, thereby generating the aforementioned third backbone in the second polyimide resin. Therefore, the second polyimide resin may contain the structural units (e2) that the first polyimide resin may contain. It should be noted that the second polyimide resin is permitted to contain a portion of the polyamic acid structure that may be generated during the imidization process.

[0125] Furthermore, the second polyimide resin may be a resin that further includes a fourth backbone different from the first backbone. This fourth backbone is derived from one or more acids selected from acids other than BPADA. In the second polyimide resin, the number of fourth backbones is 0 or more, without particular limitation, and may be 100 or less, 50 or less, or 30 or less.

[0126] As an acid other than BPADA, tetracarboxylic dianhydrides having optional substituent aromatic groups can be cited. The aromatic group is preferably an aromatic group with 6 to 100 carbon atoms, more preferably an aromatic group with 6 to 50 carbon atoms, even more preferably an aromatic hydrocarbon group with 6 to 100 carbon atoms, and even more preferably an aromatic hydrocarbon group with 6 to 50 carbon atoms. The aromatic group contains at least an aromatic ring. Examples of aromatic rings contained in the aromatic group are the same as examples of aromatic ring C. When the aromatic group has substituents, examples of substituents are the same as examples of substituent S. Specific examples of tetracarboxylic dianhydrides having optional substituent aromatic groups include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, and 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride.

[0127] The glass transition temperature (Tg) of the second polyimide resin (c ' ) The temperature (°C) is preferably 140°C or higher, more preferably 145°C or higher, further preferably 150°C or higher, even more preferably 160°C or higher, and particularly preferably 170°C or higher. There is no particular upper limit, and it can be 300°C or lower, etc. Regarding the glass transition temperature Tg... (c ' ) The temperature (°C) can be determined using the same method as for the first polyimide resin.

[0128] From the viewpoint of improving the desired effect of the present invention, the total content (percentage) of the first backbone and the second backbone in the second polyimide resin is preferably 4% by mass or more, more preferably 9% by mass or more, further preferably 19% by mass or more, even more preferably 29% by mass or more, and particularly preferably 39% by mass or more. The total content (percentage) of the first backbone and the second backbone can, for example, be 97% by mass or less, 94% by mass or less, 89% by mass or less, or 84% by mass or less. Here, the total content (percentage) of the first backbone and the second backbone can be calculated from the proportion of the charge amount (parts by mass) that contributes to the reaction of each material used in the synthesis of the second polyimide resin. Alternatively, the molecular weight of the second polyimide resin and the formula weight of the first backbone and the second backbone incorporated in the resin can be determined and calculated as the ratio of the total formula weight of the first backbone and the second backbone to the molecular weight. When the second polyimide resin is a polymer, the total content (percentage) of the first backbone and the second backbone, estimated by the degree of polymerization, is preferably within the aforementioned range.

[0129] When the second polyimide resin further comprises a third backbone, the percentage of the third backbone is allowed to be 0% by mass (i.e., without the third backbone), and there is no upper limit as long as it does not impair the effects of the present invention. Therefore, the percentage of the third backbone in the second polyimide resin can be, for example, greater than 0% by mass, 4% or more by mass, 9% or more by mass, 19% or more by mass, or 29% or more by mass, and less than 94% by mass, less than 89% by mass, less than 79% by mass, less than 69% by mass, or less than 59% by mass. Here, the percentage of the third backbone can be calculated in the same way as the percentage of the first backbone and the second backbone. When the second polyimide resin is a polymer, the percentage of the third backbone estimated from the degree of polymerization is preferably within the aforementioned range. When the second polyimide resin further comprises a fourth backbone, the percentage of the fourth backbone is the same as the percentage of the third backbone.

[0130] The end structure of the second polyimide resin is not particularly limited as long as it contains a first backbone derived from BPADA and a second backbone derived from BPPAN. For example, the end structure of the second polyimide resin can be an anhydride group, carboxyl group, or amino group derived from the raw material compound of the second polyimide resin (e.g., an acid such as BPADA, an amine such as BPPAN). When the raw material compound further contains maleic anhydride, the end structure of the second polyimide resin can be a maleimide group.

[0131] The weight-average molecular weight (Mw) of the second polyimide resin is typically 1,000 or more, preferably 1,000 to 10,000, more preferably 1,000 to 5,000, and even more preferably 1,000 to 3,000. The weight-average molecular weight of the resin can be determined by gel permeation chromatography (GPC) as a value converted from polystyrene.

[0132] Other embodiments of the polyimide resin include: a resin obtained by polymerizing and imidizing a monomer composition containing at least BPADA and BPPAN (hereinafter sometimes referred to as "third polyimide resin"). Polymerization and imidization are not particularly limited and are generally carried out in a solvent. During polymerization, the ratio of BPADA to BPPAN is preferably determined based on the total number of functional groups of each component. In one embodiment, the ratio of the total number of amino groups in BPPAN to the total number of anhydride groups in BPADA in the monomer composition is in the range of 0.1:1 to 10:1, preferably in the range of 0.5:1 to 10:1, more preferably in the range of 0.8:1 to 10:1, and even more preferably in the range of 0.9:1 to 10:1. Imidization is not particularly limited and is generally carried out in a solvent, by heating in the absence of a catalyst, by heating in the presence of a catalyst, or by heating at room temperature in the presence of a catalyst. From the viewpoint of improving the desired effect of the present invention, imidization is preferably carried out by heating in the absence of a catalyst. The third polyimide resin can be any of a random copolymer, an alternating copolymer, or a block copolymer. The third polyimide resin is not limited to the aforementioned polymerization and imidization methods. The third polyimide resin may contain a portion of the polyamic acid structure that may be generated during the imidization process. The third polyimide resin thus obtained contains the aforementioned structural unit (e1) contained in the first polyimide resin. Furthermore, the third polyimide resin thus obtained contains the aforementioned first and second backbones contained in the second polyimide resin.

[0133] In the above monomer composition, other monomers may include acids other than BPADA and / or diamine compounds other than BPPAN, or other monomers may be added during the reaction.

[0134] As an acid other than BPADA, tetracarboxylic dianhydrides having optional substituent aromatic groups can be cited. This aromatic group is preferably a tetravalent aromatic group having 6 to 100 carbon atoms, more preferably a tetravalent aromatic group having 6 to 50 carbon atoms, even more preferably a tetravalent aromatic hydrocarbon group having 6 to 100 carbon atoms, and even more preferably a tetravalent aromatic hydrocarbon group having 6 to 50 carbon atoms. The aromatic group contains at least an aromatic ring. Examples of aromatic rings contained in the aromatic group are the same as examples of aromatic ring C. When the aromatic group has substituents, examples of substituents are the same as examples of substituent S. Specific examples of tetracarboxylic dianhydrides having optional substituent aromatic groups include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, and 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride. The molar ratio of the content of acids other than BPADA in the monomer composition to the content of BPADA is not particularly limited, but may be set to less than 0.5, less than 0.4, or less than 0.3.

[0135] In some embodiments, the aforementioned monomer composition further contains one or more diamine compounds selected from diamine compounds having optional aliphatic groups with substituents and diamine compounds having optional aromatic groups with substituents. The molar ratio of the content of diamine compounds other than BPPAN in the monomer composition relative to the content of BPPAN is not particularly limited, and may be, for example, 0.5 or less, 0.4 or less, or 0.3 or less.

[0136] When the diamine compound is a diamine compound having an aliphatic group, the aliphatic group is a group containing at least a carbon atom, preferably formed by one or more skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, and silicon atoms (e.g., 1 to 3000, 1 to 1000, 1 to 100, 1 to 50), more preferably an aliphatic group with 1 to 100 carbon atoms, and even more preferably an aliphatic group with 1 to 50 carbon atoms. When the aliphatic group has a substituent, the examples of the substituent are the same as the examples of substituent S.

[0137] When the diamine compound is a diamine compound having an aromatic group, the aromatic group is preferably a tetravalent aromatic group having 6 to 100 carbon atoms, more preferably a tetravalent aromatic group having 6 to 50 carbon atoms, even more preferably a tetravalent aromatic hydrocarbon group having 6 to 100 carbon atoms, and even more preferably a tetravalent aromatic hydrocarbon group having 6 to 50 carbon atoms. The aromatic group at least contains an aromatic ring. Examples of aromatic rings contained in the aromatic group are the same as examples of aromatic ring C. When the aromatic group has a substituent, examples of the substituent are the same as examples of substituent S. When the diamine compound is a diamine compound having an aromatic group that optionally has a substituent, examples include one or more diamine compounds having an aromatic group selected from 4,4'-diaminodiphenyl ether, 1,4-phenylenediamine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, etc.

[0138] When the diamine compound is a diamine compound having an aliphatic group optionally having a substituent, as a first example, it can be derived from the skeleton of one or more compounds selected from diamine compounds having an aliphatic group optionally having a substituent, such as 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine. The diamine compound involved in this first example is characterized in that the aliphatic group is linear.

[0139] When the diamine compound is a diamine compound having an optional aliphatic group with substituents, as a second example, it can be derived from the skeleton of one or more diamine compounds having an optional aliphatic group selected from 1,2-diaminopropane, 1,2-diamino-2-methylpropane, 1,3-diamino-2-methylpropane, 1,3-diamino-2,2-dimethylpropane, 1,3-diaminopentane, 1,5-diamino-2-methylpentane, etc. The diamine compound involved in this second example is characterized in that the aliphatic group is branched.

[0140] When the diamine compound is a diamine compound having an aliphatic group optionally having a substituent, as a third example, it may be derived from 5-amino-1,3,3-trimethylcyclohexanemethylamine (isophorone diamine), 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-cyclohexane bis(methylamine), 1,3-cyclohexane bis(methylamine), 4,4'-diaminodicyclohexylmethane, bis(4-amino-3-methylcyclohexyl)methane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0] 2,6The skeleton of a compound having one or more of the following diamine compounds having optionally substituted aliphatic groups: decane, 2,5(6)-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,3-diaminoadamantane, 3,3'-diamino-1,1'-bisadamantane, and 1,6-diaminoadamantane. The diamine compound involved in this third example is characterized in that the aliphatic group comprises an alicyclic carbocyclic ring.

[0141] Based on the above, in some embodiments, the aforementioned monomer composition further contains a diamine compound having an aliphatic group, wherein the aliphatic group has an alkyl group having 1 to 6 carbon atoms as a substituent. Furthermore, in specific embodiments, the aforementioned monomer composition further contains isophorone diamine.

[0142] The terminal structure of the third polyimide resin is not particularly limited as long as it is obtained by polymerizing and imidizing the aforementioned monomer composition. For example, the terminal structure of the third polyimide resin may be an anhydride group, carboxyl group, or amino group derived from the raw material compound (e.g., an acid such as BPADA, an amine compound such as BPPAN) contained in the monomer composition of the third polyimide resin. When the raw material compound further contains maleic anhydride, the terminal structure of the third polyimide resin may be a maleimide group.

[0143] The weight-average molecular weight (Mw) of the third polyimide resin is 1,000 or more, preferably 1,000 to 10,000, more preferably 1,000 to 5,000, and even more preferably 1,000 to 3,000. The weight-average molecular weight of the resin can be determined by gel permeation chromatography (GPC) as a value converted from polystyrene.

[0144] Examples of phenoxy resins include those having one or more skeletons selected from the following: bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, phenolic skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal end of the phenoxy resin may have any functional group such as a phenolic hydroxyl group or an epoxy group. Phenoxy resins with a weight-average molecular weight of 30,000 or more are preferred.

[0145] Specific examples of phenoxy resins include: Mitsubishi Chemical's "1256" and "4250" (both phenoxy resins containing a bisphenol A backbone); Mitsubishi Chemical's "YX8100" (phenoxy resin containing a bisphenol S backbone); Mitsubishi Chemical's "YX6954" (phenoxy resin containing a bisphenol acetophenone backbone); Nippon Steel Chemical Materials' "FX280" and "FX293"; Mitsubishi Chemical's "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", and "YL7482"; etc.

[0146] Polyamide-imide resin is a resin having an amide-imide structure. From the viewpoint of compatibility with other components in the resin composition layer, polyamide-imide resins having an alicyclic structure in their molecular structure, polyamide-imide resins having a siloxane structure as described in Japanese Patent Application Publication No. 05-112760, polyamide-imide resins having a sterically hindered branched structure, polyamide-imide resins using asymmetric monomers as raw materials, and polyamide-imide resins having a multi-branched structure are preferred.

[0147] Among these, from the viewpoint that the compatibility and dispersibility of the resin varnish are improved by having an isocyanuric acid ring structure, the following are more preferred for polyamide-imide resins: (i) polyamide-imide resins having an isocyanuric acid ring structure in their molecular structure (i.e., polyamide-imide resins having an "isocyanuric acid ring structure" and an "imide skeleton or amide skeleton"), (ii) polyamide-imide resins having an isocyanuric acid ring structure and an alicyclic structure in their molecular structure (i.e., polyamide-imide resins having an "isocyanuric acid ring structure", an "alicyclic structure" and an "imide skeleton or amide skeleton"), and (iii) polyamide-imide resins having repeating units containing an isocyanuric acid ring structure and an alicyclic structure (i.e., polyamide-imide resins having repeating units containing an "isocyanuric acid ring structure", an "alicyclic structure" and an "imide skeleton or amide skeleton").

[0148] As a preferred embodiment of the polyamide-imide resin described in (i) to (iii) above, examples include: (1) a compound obtained by reacting a polyisocyanate compound containing an isocyanuric acid ring derived from an alicyclic diisocyanate with an anhydride of a polycarboxylic acid having three or more carboxyl groups, i.e., a branched polyamide-imide containing a carboxylic acid group (hereinafter sometimes referred to as "(compound E-e1)"), (2) a compound obtained by reacting a compound having one epoxy group and one or more free radical polymerizable unsaturated groups with compound (E-e1), i.e., a branched polymerizable polyamide-imide containing a carboxylic acid group (hereinafter sometimes referred to as "compound (E-e2)"), or (3) a compound obtained by reacting a compound having one hydroxyl group and one or more free radical polymerizable unsaturated groups with the isocyanate group remaining during the synthesis of compound (E-e1), i.e., a branched polymerizable polyamide-imide containing a carboxylic acid group (hereinafter sometimes referred to as "compound (E-e3)"), etc.

[0149] As compounds (E-e1), specifically, compounds represented by the following general formula (I) can be cited. It should be noted that the repeating unit in the compound represented by general formula (I) is designated as repeating unit (I-1); [Chemical Formula 7] (In the formula, w represents 0 to 15).

[0150] As a compound (E-e2), a compound (II) can be cited as having a structure (I-2) obtained by adding GMA (glycidyl methacrylate) to any part of the repeating unit (I-1) in general formula (I). [Chemical Formula 8] (where R is in the formula) 40 Residues in expression (I).

[0151] Regarding the proportion of GMA modification of the carboxyl group, the range of added GMA relative to the molar number of carboxyl groups in the compound (E-e1) is preferably 0.3 mol% or more, more preferably 0.5 mol% or more, even more preferably 0.7 mol% or more, or 0.9 mol% or more. The upper limit is preferably 50 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, or 20 mol% or less.

[0152] As a compound (E-e3), a compound (III) having the structure (I-3) can be cited, which is formed by adding a hydroxyl group of pentaerythritol triacrylate to any part of the repeating unit (I-1) in the above formula (I) and / or the terminal imide group is an isocyanate residue. [Chemical Formula 9] (In the formula, R' represents the residue in formula (I)).

[0153] The addition amount of pentaerythritol triacrylate is preferably 40 mol% or less, more preferably 38 mol% or less, and even more preferably 35 mol% or less, relative to the number of moles of isocyanate groups in the polyisocyanate at the time of addition. On the other hand, from the viewpoint of fully obtaining the effect brought about by the addition, the addition amount of pentaerythritol triacrylate is preferably 0.3 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, relative to the number of moles of isocyanate groups in the polyisocyanate at the time of addition.

[0154] Polyamide-imide resins can be synthesized using various known methods. For example, reference can be made to paragraphs 0020 to 0030 of International Publication No. 2010 / 074197, the contents of which are incorporated herein by reference.

[0155] Commercially available polyamide-imide resins can be used. Examples of commercially available products include "UNIDIC V-8000" manufactured by DIC Corporation, "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Corporation, and modified polyamide-imides such as "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane backbone) manufactured by Hitachi Chemical Corporation.

[0156] From the viewpoint of compatibility with other components in the resin composition layer, it is preferable for the polyester resin to have a fluorene structure in its molecular structure, and it is even more preferable for it to have structural units derived from diols and structural units derived from dicarboxylic acids in addition to having a fluorene structure.

[0157] Specific examples of polyester resins include "OKP4HT" manufactured by Osaka Gas Chemical Co., Ltd.

[0158] Specific examples of polysulfone resins include polysulfones such as "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0159] Examples of polyvinyl acetal resins include polyvinyl formal resin and polyvinyl butyral resin, with polyvinyl butyral resin being the most preferred. Specific examples of polyvinyl acetal resins include the S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemicals Co., Ltd.

[0160] Specific examples of polyethersulfone resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0161] (E) The elastomer in component (E) is a flexible resin, preferably a resin with rubber elasticity or a resin that exhibits rubber elasticity by polymerization with other components. Examples of rubber elasticity include resins that exhibit an elastic modulus of 1 GPa or less after a tensile test at 25°C and 40% RH, according to Japanese Industrial Standard (JIS K7161). The elastomer is typically an amorphous resin component soluble in organic solvents. This elastomer can be used alone or in combination of two or more in any ratio.

[0162] In one embodiment, the elastomer is preferably a resin having one or more structures selected from polybutadiene, polysiloxane, poly(meth)acrylate, polyalkylene, polyalkyleneoxy, polyisoprene, polyisobutylene, polycarbonate, and polystyrene within its molecule. "(Meth)acrylate" refers to methacrylates and acrylates.

[0163] In another embodiment, the elastomer is preferably selected from one or more of "resins with a glass transition temperature (Tg) of 25°C or less" and "resins that are liquid at 25°C or less". The glass transition temperature of the resin with a glass transition temperature (Tg) of 25°C or less is preferably 20°C or less, more preferably 15°C or less. The lower limit of the glass transition temperature is not particularly limited and is generally -15°C or more. Furthermore, as a resin that is liquid at 25°C, a resin that is liquid at 20°C or less is preferred, more preferably a resin that is liquid at 15°C or less. The glass transition temperature can be determined by DSC (differential scanning calorimetry).

[0164] Examples of elastomers include resins containing a polybutadiene structure. The polybutadiene structure can be contained in the main chain or in the side chains. Furthermore, the polybutadiene structure can be partially or completely hydrogenated. Resins containing a polybutadiene structure are sometimes referred to as "polybutadiene resins." Specific examples of polybutadiene resins include: "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", and "Ricon 184MA6" (polybutadiene containing anhydride groups) manufactured by Cray Valley; "GQ-1000" (polybutadiene with introduced hydroxyl and carboxyl groups), "G-1000", "G-2000", and "G-3000" (polybutadiene with two-terminated hydroxyl groups), "GI-1000", "GI-2000", and "GI-3000" (hydrogenated polybutadiene with two-terminated hydroxyl groups) manufactured by Nippon Soda; and "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin) manufactured by Nagase ChemteX. Furthermore, specific examples of polybutadiene resins include linear polyimides (as described in Japanese Patent Application Publication No. 2006-37083 and International Publication No. 2008 / 153208) made from hydroxyl-terminated polybutadiene, diisocyanate compounds, and tetrabasic anhydrides, and butadiene containing phenolic hydroxyl groups. The butadiene content of this polyimide resin is preferably 60% to 95% by mass, more preferably 75% to 85% by mass. Detailed information about this polyimide resin can be found in Japanese Patent Application Publication No. 2006-37083 and International Publication No. 2008 / 153208, the contents of which are incorporated herein by reference.

[0165] Examples of elastomers include resins containing a poly(meth)acrylate structure. Sometimes, resins containing a poly(meth)acrylate structure are referred to as "poly(meth)acrylate resins." Specific examples of poly(meth)acrylate resins include: TEISANRESIN manufactured by Nagase ChemteX, and "ME-2000," "W-116.3," "W-197C," "KG-25," and "KG-3000" manufactured by Negami Kogyo Co., Ltd.

[0166] Examples of elastomers include resins containing a polycarbonate structure. Resins containing a polycarbonate structure are sometimes referred to as "polycarbonate resins." Examples of such resins include: carbonate resins without reactive groups, carbonate resins containing hydroxyl groups, carbonate resins containing phenolic hydroxyl groups, carbonate resins containing carboxyl groups, carbonate resins containing acid anhydride groups, carbonate resins containing isocyanate groups, carbonate resins containing urethane groups, and carbonate resins containing epoxy groups. Here, a reactive group refers to a functional group that can react with other components such as hydroxyl, phenolic hydroxyl, carboxyl, acid anhydride, isocyanate, urethane, and epoxy groups. Specific examples of polycarbonate resins include "FPC0220" and "FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemical Co., Ltd., and "C-1090", "C-2090", and "C-3090" (polycarbonate diol) manufactured by Kuraray Co., Ltd. Linear polyimides made from hydroxyl-terminated polycarbonate, diisocyanate compounds, and tetrabasic anhydrides can also be used. The carbonate structure content of this polyimide resin is preferably 60% to 95% by mass, more preferably 75% to 85% by mass. Detailed information about this polyimide resin can be found in International Publication No. 2016 / 129541, the contents of which are incorporated herein by reference.

[0167] Examples of elastomers include resins containing polysiloxane structures. Resins containing polysiloxane structures are sometimes referred to as "siloxane resins." Specific examples of siloxane resins include: Shin-Etsu Silicones' "SMP-2006," "SMP-2003PGMEA," and "SMP-5005PGMEA," and linear polyimides made from amine-terminated polysiloxanes and tetrabasic anhydrides (International Publication No. 2010 / 053185, Japanese Patent Application Publication No. 2002-12667, and Japanese Patent Application Publication No. 2000-319386, etc.).

[0168] Examples of elastomers include resins containing polyalkylene structures or polyalkylene oxide structures. Resins containing polyalkylene structures are sometimes referred to as "alkylene resins." Furthermore, resins containing polyalkylene oxide structures are sometimes referred to as "alkylene oxide resins." The polyalkylene oxide structure is preferably a polyalkylene oxide structure with 2 to 15 carbon atoms, more preferably a polyalkylene oxide structure with 3 to 10 carbon atoms, and particularly preferably a polyalkylene oxide structure with 5 to 6 carbon atoms. Specific examples of alkylene resins and alkylene oxide resins include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Corporation.

[0169] Examples of elastomers include resins containing a polyisoprene structure. Resins containing a polyisoprene structure are sometimes referred to as "isoprene resins." Specific examples of isoprene resins include "KL-610" and "KL613" manufactured by Kuraray Co., Ltd.

[0170] Examples of elastomers include resins containing a polyisobutylene structure. Resins containing a polyisobutylene structure are sometimes referred to as "isobutylene resins." Specific examples of isobutylene resins include Kaneka's "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer).

[0171] Examples of elastomers include resins containing a polystyrene structure. Resins containing a polystyrene structure are sometimes referred to as "styrene resins." Styrene resins and polystyrene resins can be copolymers containing, in addition to styrene units, any repeating units different from the aforementioned styrene units, or they can be hydrogenated polystyrene resins.

[0172] Examples of possible repeating units include repeating units having a structure obtained by polymerizing a conjugated diene (conjugated diene unit) and repeating units having a structure obtained by hydrogenating a conjugated diene (hydrogenated conjugated diene unit). Examples of conjugated dienes include aliphatic conjugated dienes such as butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, and 1,3-hexadiene; and halogenated aliphatic conjugated dienes such as chloroprene. From the viewpoint of significantly obtaining the effects of the present invention, aliphatic conjugated dienes are preferred, and butadiene is more preferred. A single conjugated diene may be used, or two or more may be used in combination. Furthermore, the polystyrene resin may be a random copolymer or a block copolymer.

[0173] Examples of styrene resins include: styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-butene-styrene block copolymer (SBBS), styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, hydrogenated styrene-butadiene random copolymer, and styrene-maleic anhydride copolymer. Specific examples of styrene resins include: hydrogenated styrene-based thermoplastic elastomers "H1041", "Tuftec H1043", "Tuftec P2000", and "Tuftec MP10" (manufactured by Asahi Kasei Corporation); epoxidized styrene-butadiene thermoplastic elastomers "Epofriend AT501" and "CT310" (manufactured by Daicel Corporation); hydroxyl-modified styrene-based elastomer "SEPTON HG252" (manufactured by Kuraray Corporation); carboxyl-modified styrene-based elastomers "Tuftec N503M", amino-modified styrene-based elastomers "Tuftec N501", and anhydride-modified styrene-based elastomers "Tuftec N503M". M1913 (manufactured by Asahi Kasei Chemicals); unmodified styrene-based elastomer "SEPTONS8104" (manufactured by Kuraray); styrene-ethylene / butene-styrene block copolymer "FG1924" (manufactured by Kraton) and "EF-40" (manufactured by Crayvalley).

[0174] The number-average molecular weight (Mn) of the elastomer is preferably 1,000 or more, more preferably 1,500 or more, further preferably 3,000 or more, particularly preferably 5,000 or more, preferably 1,000,000 or less, and more preferably 900,000 or less. The number-average molecular weight (Mn) can be determined using GPC (gel permeation chromatography) in polystyrene form.

[0175] From the viewpoint of achieving significant effects of the present invention, when the content of the non-volatile component in the resin composition layer is set to 100% by mass, it is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0176] -(F) Curing Accelerator - The resin composition may contain a (F) curing accelerator as component (F). Examples of (F) curing accelerators 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 more preferred. A single curing accelerator may be used, or two or more may be used in combination.

[0177] Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

[0178] Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyl dimethylamine, 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.

[0179] Examples of imidazole-based curing accelerators include: 2-methylimidazolium, 2-undecylimidazolium, 2-heptadecylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine, 2,4-di... Amino-6-[2'-undecylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine isocyanuric acid adduct, 2-phenylimidazolyl isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds with epoxy resins, preferably 2-ethyl-4-methylimidazolium or 1-benzyl-2-phenylimidazolium.

[0180] As an imidazole-based curing accelerator, commercially available products can be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0181] 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]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, 1-(o-tolyl)biguanidine, etc., with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being preferred.

[0182] Examples of organometallic curing 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: cobalt(II) acetylacetonate, cobalt(III) acetylacetonate, cobalt(II) acetylacetonate, copper(II) acetylacetonate, zinc(II) acetylacetonate, iron(III) acetylacetonate, nickel(II) acetylacetonate, and manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0183] From the viewpoint of achieving significant effects of the present invention, when the non-volatile component in the resin composition layer is set to 100% by mass, the content of the curing accelerator (F) is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, particularly preferably 0.03% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less.

[0184] -(G) Polymerization initiator- The resin composition layer may contain a polymerization initiator (G) as component (G). The presence of a polymerization initiator (G) particularly facilitates the curing of component (D).

[0185] There are no particular limitations on the types of polymerization initiators, but examples include: cyclohexanone peroxide, tert-butyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, dicumyl hydroperoxide, cumyl hydroperoxide, tert-butyl hydroperoxide, and free radical generators such as 2,3-dimethyl-2,3-diphenylbutane. One or more of these can be used in combination.

[0186] (G) Commercially available polymerization initiators can be used. Examples of commercially available initiators include "PERHEXYNE25B" manufactured by Nippon Oil Company.

[0187] From the viewpoint of significantly obtaining the effects of the present invention, when the content of the (G) polymerization initiator is set to 100% by mass, it is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, more preferably 0.05% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.

[0188] -(H) Other additives- In addition to the components described above, the resin composition layer may further include other additives as optional components. Examples of such additives include resin additives such as thickeners, defoamers, leveling agents, and adhesion promoters. These additives may be used individually or in combination of two or more. Those skilled in the art can appropriately determine their respective contents.

[0189] The resin composition layer may further contain any solvent as a volatile component. By containing a solvent in the resin composition used to form the resin composition layer, the viscosity of the varnish can be adjusted. Examples of solvents include organic solvents. Preferably, toluene is not present, and when the total amount of the resin composition layer is set to 100% by mass, the toluene content is preferably 0.1% by mass or less, 0.01% by mass or less, 0.001% by mass or less, or 0.0001% by mass or less.

[0190] Examples of organic solvents include: ketones such as methyl ethyl ketone (MEK) and cyclohexanone; aromatics such as xylene and tetramethylbenzene; glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, and diethylene glycol monoethyl ether acetate; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha. These can be used individually or in combination of two or more.

[0191] From the viewpoint of improving embeddability and the uniformity of the insulation layer thickness, the melt viscosity can be adjusted by regulating the specific surface area of ​​the inorganic filler and the amount of solvent in the resin composition layer, resulting in a maximum tanδ value of 1.0 or more and 2.0 or less. The amount of solvent in the resin composition layer (residual solvent content) is preferably 3% by mass or less, more preferably 2.5% by mass or less, further preferably 2% by mass or less, even more preferably 1.5% by mass or less, and particularly preferably 1% by mass or less. The lower limit is not particularly limited and can be 0.0001% by mass or more, etc.

[0192] In the dynamic viscoelasticity measurement of the resin composition layer from 60°C to 200°C, from the viewpoint of improving embeddability, the maximum value of tanδ at 100°C or above is 1.0 or above, preferably 1.1 or above, and more preferably 1.3 or above. Furthermore, from the viewpoint of improving the uniformity of the insulation layer thickness, the maximum value of tanδ is 2.0 or below, preferably 1.9 or below, and more preferably 1.8 or below. The maximum value of tanδ can be measured according to the method described in the examples below.

[0193] Regarding the thickness of the resin composition layer, from the viewpoint of achieving thinner printed wiring boards and providing a cured product of the resin composition that exhibits excellent insulation even as a thin film, it is preferable to have a thickness of 30 μm or less, more preferably 25 μm or less, and even more preferably 20 μm or less. From the viewpoint of improving insulation reliability, the lower limit of the resin composition layer thickness is typically 5 μm or more, 10 μm or more, etc.

[0194] <Other Layers> In one embodiment, the resin sheet may further contain other layers as needed. Examples of such other layers include, for instance, a protective film disposed on the side of the resin composition layer that is not bonded to the support (i.e., the side opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion of debris or other contaminants to the surface of the resin composition layer, or to prevent damage from forming.

[0195] <Method for manufacturing resin sheets> Resin sheets can be manufactured, for example, by preparing a resin varnish by dissolving a resin composition in an organic solvent, applying the resin varnish onto a support using a die coater or similar device, and then drying it to form a resin composition layer. The organic solvents described above can be used.

[0196] Drying can be carried out using known methods such as heating or blowing hot air. There are no particular limitations on drying conditions; drying is carried out when the content of organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although the drying time varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% to 60% by mass of organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0197] Resin sheets can be stored in rolls. When resin sheets have a protective film, they can be used by peeling off the protective film.

[0198] <Properties and Applications of Resin Sheets> The resin sheet of the present invention is a resin sheet for forming an insulating layer using vacuum pressing processing. It comprises a support body and a resin composition layer disposed on the support body. The support body has a metal foil with an arithmetic mean roughness (Ra) of more than 300 nm on the surface of the side bonded to the resin composition layer. The resin composition layer contains (A) a specific surface area of ​​10 m². 2 For inorganic fillers of / g or more, in the dynamic viscoelasticity test of the resin composition layer from 60°C to 200°C, the maximum tanδ value at 100°C or above is 1.0 or more and 2.0 or less. By using such resin sheets and employing vacuum pressing to form an insulating layer, an insulating layer with excellent embeddability and uniformity of thickness, as well as excellent insulation properties, can be achieved.

[0199] The cured resin composition layer, obtained by laminating a resin sheet with a circuit board using vacuum pressing, heat curing the resin composition layer at 100°C for 30 minutes, and then heat curing at 200°C for 120 minutes, exhibits excellent embedding properties. Therefore, the aforementioned cured product provides an insulating layer with excellent embedding properties. Specifically, a resin composition layer of a resin sheet is laminated onto a glass cloth substrate epoxy resin double-sided copper-clad laminate (hereinafter referred to as "copper-clad laminate") with circuit conductors (copper) formed on both sides by a wiring pattern with a 1 mm square grid (59% residual copper content). After laminating the resin composition layer onto the copper-clad laminate, the resin composition layer is heat-cured under the aforementioned heat curing conditions using vacuum pressing to obtain an insulating layer. After etching the support, the embedding properties of the resin composition layer in the 1 mm square grid wiring pattern are observed using a FIB-SEM composite apparatus; the grid pattern is embedded in the resin composition layer. The embedding properties can be evaluated according to the methods described in the examples below.

[0200] A cured resin composition layer, obtained by laminating a resin sheet with a circuit board using vacuum pressing, then heat-curing the resin composition layer at 100°C for 30 minutes and then at 200°C for 120 minutes, exhibits excellent insulation reliability. Therefore, the aforementioned cured product provides an insulating layer with excellent insulation reliability. Specifically, a resin composition layer of a resin sheet is laminated onto a glass cloth substrate epoxy resin double-sided copper-clad laminate (hereinafter referred to as "copper-clad laminate") with circuit conductors (copper) formed on both sides by a wiring pattern with a 1mm square grid (59% residual copper content). After laminating the resin composition layer onto the copper-clad laminate, the resin composition layer is heat-cured under the aforementioned heat-curing conditions using vacuum pressing to obtain an insulating layer. After peeling off the support, an electrolytic plating process is performed to obtain a conductor layer on the insulating layer. Using the conductor layer side as the positive electrode and the copper-clad laminate side as the negative electrode, the insulation resistance value was measured six times after 100 hours at 110°C, 85% relative humidity, and 20V DC voltage using an electrochemical migration analyzer, employing a high-accelerated life testing apparatus. At this point, the insulation resistance value of at least one test piece is preferably 1.00 × 10⁻⁶. 8 Ω or higher, more preferably 1.00 × 10 9 Ω or higher. Furthermore, the average insulation resistance value of the six test pieces is preferably 1.00 × 10⁻⁶. 8 Ω or higher, more preferably 1.00 × 10 9 Ω or higher. The insulation reliability can be evaluated according to the methods described in the examples below.

[0201] By using the resin sheet of the present invention and employing vacuum pressing to form an insulating layer, an insulating layer exhibiting good embedding properties and insulation resistance can be obtained. Therefore, the resin sheet of the present invention can be suitably used as a resin sheet for forming an insulating layer using vacuum pressing (for forming an insulating layer using vacuum pressing). The resin sheet of the present invention includes a support comprising a metal foil, which can be used to form a conductor layer. Therefore, the resin sheet of the present invention can be suitably used as a resin sheet for forming both an insulating layer and a conductor layer using vacuum pressing in the manufacture of printed wiring boards (for forming an insulating layer and a conductor layer using vacuum pressing). The resin sheet of the present invention can be suitably used to form the insulating layer (and conductor layer) of a printed wiring board, preferably to form the interlayer insulating layer (and conductor layer) of a printed wiring board. In this invention, the term "printed wiring board" also includes a rewiring substrate for semiconductor packaging.

[0202] [Printed wiring board, manufacturing method of printed wiring board] The printed wiring board of the present invention comprises an insulating layer formed by a cured resin composition layer of the resin sheet of the present invention.

[0203] For printed wiring boards, for example, the resin sheet described above can be used to manufacture them by a method comprising the steps (I) and (II) below: (I) The process of laminating resin sheets onto the inner substrate using vacuum pressing. (II) The process of heat curing the resin composition layer to form an insulating layer.

[0204] The "inner layer substrate" used in process (I) refers to the component that becomes the substrate of the printed wiring board, such as glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermosetting polyphenylene ether substrate, etc. Furthermore, this substrate may have a conductor layer on one or both sides, and this conductor layer may be patterned. Sometimes, an inner layer substrate with conductor layers (circuit) formed on one or both sides of the substrate is called an "inner layer circuit substrate". Additionally, intermediate products for which insulating layers and / or conductor layers are to be further formed during the manufacture of the printed wiring board are also included in the "inner layer substrate" as described in this invention. When the printed wiring board is a component-integrated circuit board, an inner layer substrate with built-in components can be used.

[0205] Regarding the lamination of the inner layer substrate and the resin sheet, a vacuum pressing process is used to bond the resin composition layer of the resin sheet to the inner layer substrate. By using vacuum pressing to laminate the inner layer substrate and the resin composition layer, the dielectric properties, mechanical strength, and electrical properties can be improved.

[0206] First, the inner layer substrate and the resin sheet are placed in a vacuum pressing apparatus to bond the resin composition layer of the resin sheet to the inner layer substrate. Next, a vacuum pressing process is performed under reduced pressure to heat and press the inner layer substrate and the resin composition layer together. The vacuum pressing process is preferably a heated vacuum hot pressing process (vacuum heating pressing process).

[0207] The inner substrate and resin sheet are preferably disposed in a vacuum pressing device through a metal plate such as cushion paper or stainless steel plate (SUS plate) or a release film.

[0208] Vacuum pressing can be performed using existing vacuum pressing apparatuses that press the inner layer substrate and resin sheet from both sides of a heated metal plate, such as a SUS plate. Examples of commercially available vacuum pressing apparatuses include, for instance, the "VH1-1603" manufactured by Kitagawa Seiki Co., Ltd.

[0209] Vacuum pressing can be performed once or repeated two or more times. When repeated two or more times, the pressing pressure, heating temperature, pressing time, etc., can be the same or different.

[0210] In the vacuum pressing process, the pressing pressure is preferably 0.49 MPa or more, more preferably 0.98 MPa or more, preferably 7.9 MPa or less, and more preferably 5.9 MPa or less.

[0211] In vacuum pressing, the atmospheric pressure, i.e., the pressure (decompression degree) during decompression within the chamber containing the stacked structure of the object being processed, is preferably 3 × 10⁻⁶. -2 Below MPa, preferably 1×10 -2 Below MPa. There is no specific restriction on the lower limit; it can be set to 1×10. -10 MPa and above, etc.

[0212] In vacuum pressing, the heating temperature varies depending on the composition of the resin composition layer, and is typically 150°C or higher, preferably 160°C or higher, more preferably 170°C or higher, or 180°C or higher. There is no particular upper limit to the heating temperature, and it can typically be set to 240°C or lower. It should be noted that, from the viewpoint of achieving significant effects of the present invention, vacuum pressing can be performed by progressively or continuously increasing the temperature and / or progressively or continuously decreasing the temperature. Furthermore, as described later, the resin composition layer can be thermo-cured by heating during vacuum pressing to form an insulating layer.

[0213] In the vacuum pressing process, the pressing time is preferably 5 minutes or more, more preferably 10 minutes or more, and even more preferably 15 minutes or more. There is no particular upper limit, but it is preferably 300 minutes or less, more preferably 200 minutes or less, and even more preferably 150 minutes or less.

[0214] After the resin sheet is laminated onto the inner substrate using a vacuum pressing process, the resin composition layer is thermally cured in step (II) to form an insulating layer. As a method for thermally curing the resin composition layer, for example, in the case of a vacuum hot pressing process, the resin composition layer is thermally cured using the heat generated during pressing to form an insulating layer.

[0215] There are no particular limitations on the thermosetting conditions of the resin composition layer; the conditions typically used when forming the insulating layer of a printed wiring board can be used.

[0216] For example, the thermosetting conditions of the resin composition layer vary depending on the type of resin composition, etc. The curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0217] Before heat curing the resin composition layer, the resin composition layer can be preheated at a temperature lower than the curing temperature. For example, before heat curing the resin composition layer, the resin composition layer can be preheated for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes) at a temperature of 50°C or higher and less than 120°C (preferably 60°C or higher and less than 115°C, more preferably 70°C or higher and less than 110°C).

[0218] Compared to vacuum lamination, the inventors have confirmed that in vacuum pressing, the uniformity of the insulation layer thickness sometimes deteriorates due to resin flow during the lamination of resin sheets. Regarding this, the uniformity of the insulation layer thickness after vacuum pressing can be improved by adjusting the specific surface area of ​​the inorganic filler material in the resin composition layer, adjusting the amount of residual solvent, and setting the maximum value of tanδ to 1.0 or more and 2.0 or less. Specifically, the deviation of the insulation layer thickness after hot pressing is preferably less than ±20%, more preferably less than ±15%, and even more preferably less than ±10%, relative to a reference thickness. That is, the insulation layer preferably has a thickness reference where the thickness deviation is within the aforementioned range. The thickness reference can typically be the designed thickness of the insulation layer. The lower limit can be 0%, ±0.1% or more, etc. The thickness of the insulation layer after vacuum pressing can be measured according to the method described in the examples below.

[0219] For the resin sheet used in this invention, since the support body contains metal foil, it may also include a process of forming a circuit by subtractive or modified semi-additive methods as process (III).

[0220] In process (III), a circuit can be formed using a support (metal foil) by a subtractive or modified semi-additive method.

[0221] In subtractive processing, unwanted portions (non-circuit forming portions) of a metal foil are selectively removed by etching or the like to form a circuit. Circuit formation using subtractive processing can be performed according to known steps. For example, circuit formation using subtractive processing can be performed by a method including the following steps: i) applying an etching resist to the surface of the metal foil (i.e., the side opposite to the side bonded to the resin composition layer); ii) exposing and developing the etching resist to form a wiring pattern; iii) etching away the exposed metal foil portions; and iv) removing the etching resist.

[0222] In the modified semi-additive process, a plating resist is used to protect the non-circuit forming portion of the metal foil. After electroplating a thickened metal such as copper onto the circuit forming portion, the plating resist is removed, and the metal foil outside the circuit forming portion is removed by etching to form a circuit. Circuit formation using the modified semi-additive process can be performed according to known steps. For example, circuit formation using the modified semi-additive process can be performed by a method including the following steps: i) applying a plating resist to the surface of the metal foil (i.e., the side opposite to the side bonded to the resin composition layer); ii) exposing and developing the plating resist to form a wiring pattern; iii) electroplating via the plating resist; iv) removing the plating resist; v) etching away the metal foil outside the circuit forming portion. It should be noted that if the metal foil is thick, before step i), the entire metal foil can be thinned by etching or the like to achieve the desired thickness (typically 5 μm or less, 4 μm or less, or 3 μm or less).

[0223] In the manufacturing of printed wiring boards, steps (IV) of opening holes and (V) of roughening the insulating layer can be further performed. These steps (IV) to (V) can be performed according to various methods known to those skilled in the art in the manufacture of printed wiring boards. In addition, the formation of insulating and conductor layers in steps (I) to (V) can be repeated as needed to form a multilayer wiring board.

[0224] [Semiconductor Devices] The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

[0225] Examples of semiconductor devices include various semiconductor devices used in electrical products (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., motorcycles, automobiles, trams, ships, and airplanes).

[0226] The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. A "conductive portion" refers to a portion that transmits electrical signals in the printed wiring board, and its location can be either on the surface or embedded. Furthermore, the semiconductor chip is not particularly limited to any electrical circuit element made of semiconductor material.

[0227] The method of mounting semiconductor chips during the manufacture of semiconductor devices is not particularly limited as long as it enables the semiconductor chip to function effectively. Specific examples include wire bonding mounting, flip chip mounting, mounting using a bumpless build-up layer (BBUL), mounting using anisotropic conductive film (ACF), and mounting using non-conductive film (NCF). Here, "mounting using a bumpless build-up layer (BBUL)" refers to "a mounting method in which the semiconductor chip is directly embedded into a recess in a printed circuit board, connecting the semiconductor chip to the wiring on the printed circuit board." Example

[0228] The present invention will now be described in more detail with reference to the embodiments, but the present invention is not limited to these embodiments. It should be noted that, unless otherwise expressly stated, "parts" and "%" refer to "parts by mass" and "% by mass," respectively.

[0229] <Inorganic filler material used> Inorganic filler material 1: Spherical silica (UFP-30 manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 0.30 μm, specific surface area 30.7 m²). 2 100 parts (g) of a material that has been surface-treated with 2 parts of N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd., KBM573); Inorganic filler material 2: Spherical silica (Yarduma Corporation's "SO-Cl", average particle size 0.25 μm, specific surface area 11.2 m²) 2 100 parts (g) of a material that has been surface-treated with 1 part of N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd., KBM573); Inorganic filler material 3: Spherical silica (Yarduma Corporation's "SO-C2"), average particle size 0.50 μm, specific surface area 5.8 m². 2 100 parts (g) of a material that has been surface-treated with 1 part of N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd., KBM573).

[0230] <Synthesis Example 1: Synthesis of Polyimide Resin 1> 49.6 g of BPADA, 50.4 g of BPPAN, and 40 g of toluene were mixed in 400 g of N,N-dimethylacetamide (hereinafter also referred to as "DMAc") as solvent. The resulting monomer composition was stirred at room temperature and atmospheric pressure for 3 hours to allow it to react. A solution of polyamic acid was thus obtained.

[0231] Next, the polyamic acid solution was heated to approximately 160°C, and the condensed water was removed by azeotropic extraction with toluene under a nitrogen stream. It was confirmed that "a specified amount of water accumulated in the moisture metering receiver" and "no more water outflow was observed." After confirmation, the reaction solution was further heated to 200°C and stirred for 1 hour. Then it was cooled. This yielded a varnish containing 20% ​​by mass of polyimide resin 1 as a non-volatile component.

[0232] Based on the above reaction pathway, it is presumed that polyimide resin 1 comprises the structural unit shown in the following formula (e1a). Furthermore, based on the above reaction pathway, it is presumed that polyimide resin 1 comprises a first backbone derived from BPADA and a second backbone derived from BPPAN.

[0233] [Chemical Formula 10]

[0234] <Synthesis Example 2: Synthesis of Elastomer 1> In a reaction vessel, 50 g of G-3000 (difunctional hydroxyl-terminated polybutadiene, number-average molecular weight = 5047 (GPC method), hydroxyl equivalent = 1798 g / eq., solid content 100% by mass: manufactured by Nippon Soda Co., Ltd.), 23.5 g of Ipzole 150 (aromatic mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.), and 0.005 g of dibutyltin laurate were mixed and dissolved uniformly. After homogenization, the temperature was raised to 50°C, and then 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g / eq.) was added while stirring, and the reaction was carried out for about 3 hours. Next, after cooling the reactants to room temperature, 8.96 g of benzophenone tetracarboxylic dianhydride (anhydride equivalent = 161.1 g / eq.), 0.07 g of triethylenediamine, and 40.4 g of diethylene glycol monoethyl ether acetate (Daicel) were added. The mixture was stirred and heated to 130 °C for approximately 4 hours. The reaction was then carried out by FTIR at 2250 cm⁻¹. -1 The disappearance of the NCO peak was confirmed. Based on the confirmation of the disappearance of the NCO peak, it was regarded as the endpoint of the reaction. After cooling the reactants to room temperature, they were filtered through a 100-mesh filter cloth to obtain elastomer 1 with an imide backbone, a urethane backbone, and a butadiene backbone. Viscosity: 7.5 Pa·s (25℃, E-type viscometer) Acid value: 16.9 mg KOH / g Solid content: 50% by mass Number average molecular weight: 13723 Glass transition temperature: -10℃ The content of the polybutadiene structural portion is: 50 / (50+4.8+8.96)×100=78.4% by mass.

[0235] <Example 1: Preparation of Resin Composition 1> While stirring, heat and dissolve 5 parts of xylenol-type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000HK", epoxy equivalent approximately 185 g / eq.), 5 parts of naphthalene-type epoxy resin (Nippon Steel & Sumitomo Chemical Co., Ltd. "ESN475V", epoxy equivalent approximately 332 g / eq.), 2 parts of cyclohexane-type epoxy resin (Mitsubishi Chemical Co., Ltd. "ZX1658GS", epoxy equivalent approximately 135 g / eq.), 10 parts of phenoxy resin (Mitsubishi Chemical Co., Ltd. "YX7553BH30", a 1:1 solution of cyclohexanone and methyl ethyl ketone (MEK) with a solid content of 30% by weight, Mw = 35000) in a mixed solvent of 20 parts naphtha and 10 parts cyclohexanone. After cooling to room temperature, 4.5 parts of an active ester-based curing agent (DIC Corporation's "HPC-8000L-65TM", with an active group equivalent of approximately 220 g / eq. and a 1:1 solution of toluene and MEK with 65% by mass of non-volatile components), 35 parts of inorganic filler 1, and 0.1 parts of an amine-based curing accelerator (4-dimethylaminopyridine (DMAP)) were uniformly dispersed using a high-speed rotary mixer and then filtered through a cartridge filter (ROKITECHNO Corporation's "SHP020") to prepare resin composition 1.

[0236] <Example 2: Preparation of Resin Composition 2> In Example 1, 4.5 parts of an active ester curing agent (DIC's "EXB-8000L-65TM", an active group equivalent of approximately 220 g / eq., and a 1:1 solution of toluene and MEK with 65% by mass of non-volatile components) were replaced with 4.7 parts of an active ester curing agent (DIC's "HP-B-8151-62T", an active group equivalent of 238 g / eq., and a toluene solution with 62% solids). Except for the above, resin composition 2 was prepared in the same manner as in Example 1.

[0237] <Example 3: Preparation of Resin Composition 3> In Example 1, 35 parts of inorganic filler 1 were replaced with 50 parts of inorganic filler 2. Except for the above, resin composition 3 was prepared in the same manner as in Example 1.

[0238] <Example 4: Preparation of Resin Composition 4> In Example 1, 4.5 parts of the reactive ester curing agent (DIC Corporation's "EXB-8000L-65TM", with an active group equivalent of approximately 220 g / eq. and a 1:1 solution of toluene and MEK containing 65% by mass of non-volatile components) were replaced with 10 parts of a maleimide compound (Designer Molecules' "BMI-689"). The amount of the amine curing accelerator (4-dimethylaminopyridine (DMAP)) was changed from 0.1 parts to 0.05 parts, and 0.1 parts of a polymerization initiator (Nippon Oil Corporation's "PERHEXYNE25B") were used. Except for the above, resin composition 4 was prepared in the same manner as in Example 1.

[0239] <Example 5: Preparation of Resin Composition 5> In Example 4, 10 parts of the maleimide compound (Designer Molecules, "BMI-689") were replaced with 10 parts of a styrene-modified polyphenylene ether resin (Mitsubishi Gas Chemical, "OPE-2St 1200", Mn=1200, a toluene solution with a solid content of 65% by mass). Except as described above, resin composition 5 was prepared in the same manner as in Example 4.

[0240] <Example 6: Preparation of Resin Composition 6> In Example 4, 4.5 parts of an active ester-based curing agent (DIC's "EXB-8000L-65TM", with an active group equivalent of approximately 220 g / eq. and a 1:1 solution of toluene and MEK containing 65% by mass of non-volatile components) were used. Except as described above, resin composition 6 was prepared in the same manner as in Example 4.

[0241] <Example 7: Preparation of Resin Composition 7> In Example 6, instead of 10 parts of phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", a 1:1 solution of cyclohexanone and methyl ethyl ketone (MEK) with a solid content of 30% by weight, Mw = 35000), 15 parts of polyimide resin 1 (20% by weight of non-volatile components) obtained in Synthesis Example 1 were used. Except as described above, resin composition 7 was prepared in the same manner as in Example 6.

[0242] <Example 8: Preparation of Resin Composition 8> In Example 6, instead of 10 parts of phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", a 1:1 solution of cyclohexanone and methyl ethyl ketone (MEK) with a solid content of 30% by weight, Mw = 35000), 6 parts of the elastomer (50% by weight of non-volatile components) obtained in Synthesis Example 2 were used. Except as described above, resin composition 8 was prepared in the same manner as in Example 6.

[0243] <Example 9: Preparation of Resin Composition 9> While stirring, 10 parts of maleimide compound (Designer Molecules "BMI-689"), 10 parts of maleimide resin containing biphenyl skeleton (Nippon Kayaku Co., Ltd. "MIR-3000", a 1:1 solution of toluene:MEK with 70% by mass of non-volatile components), 10 parts of styrene-modified polyphenylene ether resin (Mitsubishi Gas Chemical Co., Ltd. "OPE-2St 1200", Mn=1200, a toluene solution with 65% by mass of solid components), and 6 parts of hydrogenated styrene-based thermoplastic elastomer (Asahi Kasei Corporation "H1043", styrene / ethylene·butene·butadiene ratio = 67 / 33) were heated and dissolved in a mixed solvent of 20 parts naphtha and 10 parts cyclohexanone. After cooling to room temperature, 50 parts of inorganic filler material 1 and 0.1 parts of polymerization initiator (PERHEXYNE 25B manufactured by Nippon Oil Co., Ltd.) were mixed in, and the mixture was evenly dispersed using a high-speed rotary mixer and then filtered through a cartridge filter (SHP020 manufactured by ROKITECHNO Co., Ltd.) to prepare resin composition 9.

[0244] <Example 10: Preparation of Resin Composition 10> In Example 9, 50 parts of inorganic filler 1 were replaced with 65 parts of inorganic filler 2. Except as described above, resin composition 10 was prepared in the same manner as in Example 9.

[0245] <Example 11: Preparation of Resin Composition 11> In the preparation of Example 9, 10 parts of styrene-modified polyphenylene ether resin ("OPE-2St1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., Mn=1200, 65% by mass toluene solution) were replaced with 10 parts of a vinyl-containing resin ("ODV-XET-X04" manufactured by Nippon Steel Chemical Materials Co., Ltd., weight average molecular weight 3110, 65% by mass solution). Except for the above, resin composition 11 was prepared in the same manner as in Example 9.

[0246] <Example 12: Preparation of Resin Composition 12> In Example 1, 4.5 parts of an active ester-based curing agent (DIC's "EXB-8000L-65TM", an active group equivalent of approximately 220 g / eq., and a 1:1 solution of toluene and MEK with 65% by mass of non-volatile components) were replaced with 5 parts of a phenolic resin containing a triazine backbone (DIC's "LA7054", a MEK solution with approximately 125 g / eq. of hydroxyl equivalent and 60% solid components). Except for the above, resin composition 12 was prepared in the same manner as in Example 1.

[0247] <Comparative Example 1: Preparation of Resin Composition 13> In Example 1, 35 parts of inorganic filler 1 were replaced with 35 parts of inorganic filler 3. Except as described above, resin composition 13 was prepared in the same manner as in Example 1.

[0248] <Comparative Example 2: Preparation of Resin Composition 14> In Example 1, the amount of inorganic filler 1 was changed from 35 parts to 50 parts. Except as described above, resin composition 14 was prepared in the same manner as in Example 1.

[0249] <Comparative Example 3: Preparation of Resin Composition 15> In Example 9, 50 parts of inorganic filler 1 were replaced with 50 parts of inorganic filler 3. Except as described above, resin composition 15 was prepared in the same manner as in Example 9.

[0250] <Determination of the thickness of resin composition layers, etc.> The thickness of the resin composition layer, etc., was measured using a contact film thickness gauge (Mitutoyo Corporation, MCD-25MJ).

[0251] <Preparation of Resin Sheet A> As a support, an extremely thin copper foil (MW-G manufactured by Mitsui Metals & Mining Co., Ltd., a single-layer copper foil with a thickness of 12 μm, an arithmetic mean roughness (Ra) of 900 nm, and a ten-point mean roughness (Rz) of 8000 nm) was prepared. Resin compositions 1 to 15 were uniformly coated onto the extremely thin copper foil of the support using a die coater, so that the thickness of the dried resin composition layer was 15 μm. The resin composition layer was obtained on the support by drying at 70°C to 120°C for 7 minutes. Next, on the surface of the resin composition layer that was not bonded to the support, a polypropylene film (ALPHAN MA-411 manufactured by Oji F-Tex Co., Ltd., with a thickness of 15 μm) was laminated with the resin composition layer, its rough surface bonded to the resin composition layer. Thus, a resin sheet A was obtained, sequentially composed of an extremely thin copper foil (support), a resin composition layer, and a protective film. It should be noted that the arithmetic mean roughness (Ra) and ten-point mean roughness (Rz) of the ultrathin copper foil were measured using a non-contact surface roughness meter.

[0252] <Determination of tanδ in dynamic viscoelasticity> For the resin composition layer of resin sheet A, dynamic viscoelasticity was measured using a dynamic viscoelasticity measuring device (UBM Rheosol-G3000). For a 1g sample of resin composition collected from the resin composition layer, using a parallel plate with a diameter of 18mm, the temperature was increased from an initial temperature of 60℃ to 200℃ at a rate of 5℃ / min. The dynamic viscoelastic modulus was measured under the following conditions: a temperature interval of 2.5℃, a vibration frequency of 1Hz, and a deformation of 1deg. Using the obtained values ​​of E' and E”, tanδ was calculated using the following formula. Then, the maximum value of tanδ above 100℃ was determined. tanδ=E” / E'.

[0253] <Evaluation of the thickness (resin flow), insulation reliability, and embeddability of the insulation layer after vacuum pressing> 1) Vacuum-pressed, laminated sheets were used for lamination on copper-clad laminates. As a copper-clad laminate, a glass cloth substrate epoxy resin double-sided copper-clad laminate (copper foil thickness 12μm, substrate thickness 0.15mm, Mitsubishi Gas Chemical Co., Ltd. "HL832NSF LCA", 255×340mm size) with circuit conductors (copper) formed on both sides by wiring patterns with a square grid of 1mm on both sides is prepared. The copper surface of the inner circuit board is roughened on both sides using MEC Co., Ltd. "CZ8201" (copper etching depth 0.5μm). The protective film is peeled off from resin sheet A, exposing the resin composition layer. Then, using a vacuum hot press (Kitagawa Seiki Co., Ltd., VH1-1603), the exposed resin composition layer is laminated to both sides of the copper-clad laminate in contact with the copper-clad laminate. The pressing conditions are set to a pressure reduction of 1×10⁻⁶. -3 Under pressure reduction below MPa, at a pressure condition of 20 kgf / cm 2 Under the specified heating conditions, the first stage of pressing was carried out at a temperature of 100°C for 30 minutes, and the second stage of pressing was carried out at a temperature of 190°C for 120 minutes. After the resin composition layer was cured by heating based on pressing, the support was peeled off to obtain the cured substrate A.

[0254] 2) Electroplating Electrolytic copper plating was performed using a solution manufactured by Amtech Japan, with copper filling the through-holes. Then, as a resist pattern for etching-based patterning, a conductor layer with pads and conductor patterns was formed on the surface of the insulating layer to a thickness of 10 μm using a 1 mm diameter pad pattern connected to the underlying conductor and a 10 mm diameter circular conductor pattern not connected to the underlying conductor. Next, an annealing treatment was performed at 200°C for 90 minutes. This substrate was designated as "Insulation Evaluation Substrate A".

[0255] 3) Evaluation of the insulation reliability of the insulation layer The 10mm diameter circular conductor side of the insulation evaluation substrate A was used as the positive electrode, and the grid circuit conductor (copper) side of the inner layer circuit substrate connected to the 1mm diameter pads was used as the negative electrode. The insulation resistance value was measured after 100 hours at 110°C, 85% relative humidity, and an applied 20V DC voltage using an electrochemical migration analyzer (J-RAS "ECM-100") with an ETAC PM422 high-accelerated life testing apparatus. Six measurements were performed, and the evaluation criteria and insulation resistance values ​​are shown in the table below. It should be noted that the insulation resistance values ​​listed in the table below are the average insulation resistance values ​​of the six test pieces. The average insulation resistance of the test piece after 6 tests was 1.00 × 10⁶. 9 Ω or above; △: The average insulation resistance value of the test piece after 6 tests is 1.00×10. 8 Ω or higher and lower than 1.00×10 9 Ω; ×: The average insulation resistance value of the test piece after 6 tests is less than 1.00×10. 8 Ω.

[0256] 4) Evaluation of the thickness (resin flow) of the insulating layer after vacuum pressing. After etching the ultrathin copper foil of the solidified substrate A, cross-sectional observation was performed using a FIB-SEM composite instrument (SII Nanotechnology Corporation "SMI3050SE"). The thickness of the insulating layer after vacuum pressing was evaluated according to the following criteria. 〇: When the baseline thickness of the insulating layer is set to 10μm, the thickness of the insulating layer is less than 10μm ± 20%; ×: When the baseline thickness of the insulation layer is set to 10μm, the thickness of the insulation layer is 10μm ± 20% or more.

[0257] 5) Evaluation of the embeddability of the insulation layer after vacuum pressing After etching the ultrathin copper foil of the cured substrate A, the embedding of the wiring pattern with a 1 mm square grid in the resin composition layer was observed using a FIB-SEM composite instrument (SII Nanotechnology Co., Ltd. "SMI3050SE") and evaluated according to the following criteria. 〇: The wiring pattern is embedded in the insulation layer; ×: Gaps are caused by poor embedding.

[0258] [Table 1] *(A) The content of component A indicates the content when the non-volatile component in the resin composition is set to 100% by mass.

Claims

1. A resin sheet, which is a resin sheet used for forming an insulating layer by vacuum pressing. The resin sheet includes a support and a resin composition layer disposed on the support. The support has a metal foil with an arithmetic mean roughness (Ra) of more than 300 nm on the side of the surface that bonds to the resin composition layer. The resin composition layer contains (A) with a specific surface area of ​​10m². 2 Inorganic filler materials of / g or above In the dynamic viscoelasticity test, the resin composition layer was heated from 60°C to 200°C at a heating rate of 5°C / min, and the test conditions were 2.5°C temperature intervals, 1Hz vibration frequency, and 1°C deformation. The maximum value of tanδ at a temperature above 100°C was 1.1 or more and 2.0 or less.

2. The resin sheet according to claim 1, wherein, The thickness of the resin composition layer is less than 30 μm.

3. The resin sheet according to claim 1, wherein, The resin composition layer contains any one of an active ester resin, a maleimide resin, and a vinyl resin.

4. The resin sheet according to claim 1, wherein, When the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (A) is 73% by mass or less.

5. The resin sheet according to claim 1, wherein, Metal foil includes copper foil.

6. The resin sheet according to claim 1, wherein, The thickness of the support body is 9μm or more.

7. The resin sheet according to claim 1, wherein, The arithmetic mean roughness (Ra) of the support surface on the side bonded to the resin composition layer is 500 nm or more, and the support surface is the surface of the metal foil.

8. The resin sheet according to claim 1, wherein, The arithmetic mean roughness (Ra) of the support surface on the side bonded to the resin composition layer is less than 1000 nm, and the support surface is the surface of the metal foil.

9. The resin sheet according to claim 1, wherein, The arithmetic mean roughness (Ra) of the support surface on the side bonded to the resin composition layer is less than 800 nm, and the support surface is the surface of the metal foil.

10. The resin sheet according to claim 1, wherein, (A) The specific surface area of ​​component A is 25m². 2 / g or more.

11. The resin sheet according to claim 1, wherein, (A) The specific surface area of ​​component A is 60 m². 2 / g or less.

12. The resin sheet according to claim 1, wherein, (A) The specific surface area of ​​component A is 40 m². 2 / g or less.

13. The resin sheet according to claim 1, wherein, In the dynamic viscoelasticity test, the resin composition layer was heated from 60°C to 200°C at a heating rate of 5°C / min, and the test conditions were 2.5°C temperature intervals, 1Hz vibration frequency, and 1°C deformation. The maximum value of tanδ at a temperature above 100°C was 1.3 or higher.

14. The resin sheet according to claim 1, wherein, In the dynamic viscoelasticity test, the resin composition layer was heated from 60°C to 200°C at a heating rate of 5°C / min, and the test conditions were 2.5°C temperature intervals, 1Hz vibration frequency, and 1°C deformation. The maximum value of tanδ at a temperature above 100°C was less than 1.

8.

15. The resin sheet according to claim 1, wherein, The thickness of the resin composition layer is less than 20 μm.

16. The resin sheet according to claim 1, wherein, The thickness of the resin composition layer is 5 μm or more.

17. The resin sheet according to claim 1, wherein, The thickness of the resin composition layer is 10 μm or more.

18. The resin sheet according to claim 1, wherein, When the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (A) is 68% by mass or less.

19. The resin sheet according to claim 1, wherein, When the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (A) is 30% by mass or more.

20. The resin sheet according to claim 1, wherein, When the non-volatile component in the resin composition layer is set to 100% by mass, the content of component (A) is 50% by mass or more.

21. The resin sheet according to claim 1, wherein, The thickness of the support body is 11 μm or more.

22. The resin sheet according to claim 1, wherein, The thickness of the support is less than 30 μm.

23. The resin sheet according to claim 1, wherein, The thickness of the support is less than 15 μm.

24. A printed wiring board, wherein, An insulating layer comprising a cured product of a resin composition layer of a resin sheet according to any one of claims 1 to 23.

25. A semiconductor device, wherein, It includes the printed wiring board of claim 24.

26. A method for manufacturing a printed wiring board, the method comprising: (I) The process of laminating the resin sheet of any one of claims 1 to 23 onto the inner substrate by vacuum pressing, and (II) The process of heat curing the resin composition layer to form an insulating layer.

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