JP2022184518A - resin sheet - Google Patents

Abstract

To provide a resin sheet or the like, which can obtain a cured product that is excellent on a thickness uniformity of an insulating layer, an embedding property and an insulating reliability.SOLUTION: There is provided a resin sheet for forming an insulating layer by using vacuum press processing, which comprises: a support body; and a resin composition layer provided on the support body, and the resin sheet is configured in that: the support body has a metal foil with an arithmetic mean roughness (Ra) of more than 300 nm on a surface of a side bonded to the resin composition layer; the resin composition layer contains an inorganic filler having a specific surface area (A) of 10 m2/g or more; and in dynamic viscoelasticity measurement of the resin composition layer at 60°C to 200°C, a maximum value of tan δ at 100°C or higher is 1.0 or more and 2.0 or less.SELECTED DRAWING: None

Description

The present invention relates to resin sheets. Furthermore, the present invention relates to a printed wiring board, a semiconductor device, and a method for manufacturing a printed wiring board obtained using the resin sheet.

In manufacturing a printed wiring board, an insulating layer is formed by laminating and curing a prepreg on a circuit board using a vacuum press process, as described in Patent Document 1, for example.

JP 2017-57352 A

With recent miniaturization of printed wiring boards and the like, use of a resin composition layer of a resin sheet instead of prepreg is required from the viewpoint of thinning an insulating layer. In forming an insulating layer with a resin composition layer of a resin sheet, a method of laminating and curing a resin composition layer on a circuit board by a vacuum lamination method, and a method of laminating a resin composition layer on a circuit board by a vacuum press process.・There is a way to harden it.

In forming an insulating layer using a resin composition layer of a resin sheet by a vacuum press process, the pressure applied to the resin composition layer of the resin sheet during lamination is higher in the vacuum press process than in the vacuum lamination method. In some cases, the uniformity of the thickness of the insulating layer deteriorates due to the resin flow (resin exudation) in the resin composition layer, and as a result, the insulation reliability deteriorates. On the other hand, if the viscosity of the resin is increased in order to suppress the resin flow, the insulating layer cannot embed the wiring of the circuit board, and the embedding property is lowered, resulting in poor insulation in some cases. In addition, when the support of the resin sheet has a metal foil with a large roughness, the thickness of the insulating layer tends to be thin at a portion with a large roughness, and as a result, the insulation reliability may deteriorate remarkably.

An object of the present invention is to provide a resin sheet capable of obtaining a cured product having excellent insulating layer thickness uniformity, embedding properties, and insulation reliability; a printed wiring board and a semiconductor device formed using the resin sheet; An object of the present invention is to provide a method for manufacturing a wiring board.

As a result of intensive studies on the above problems, the present inventors have found a support comprising a metal foil having a surface surface bonded to the resin composition layer with an arithmetic mean roughness (Ra) exceeding 300 nm, and a support on the support. (A) a resin composition layer containing an inorganic filler having a specific surface area of 10 m ² /g or more, and the dynamic viscoelasticity measurement of the resin composition layer at 60 ° C. to 200 ° C. is 100 The maximum value of tan δ at ° C. or higher is 1.0 or more and 2.0 or less, and the resin sheet is used to form an insulating layer by vacuum press treatment. Completed.

That is, the present invention includes the following contents.
[1] A resin sheet for forming an insulating layer using a vacuum press,
comprising a support and a resin composition layer provided on the support;
The support has a metal foil with an arithmetic mean roughness (Ra) of more than 300 nm on the side bonded to the resin composition layer,
The resin composition layer contains (A) an inorganic filler having a specific surface area of 10 m ² /g or more,
The resin sheet, wherein the maximum value of tan δ at 100°C or higher is 1.0 or more and 2.0 or less in the dynamic viscoelasticity measurement of the resin composition layer at 60°C to 200°C.
[2] The resin sheet according to [1], wherein the resin composition layer has a thickness of 30 µm or less.
[3] The resin sheet according to [1] or [2], wherein the resin composition layer contains any one of active ester resin, maleimide resin and vinyl resin.
[4] The resin sheet according to any one of [1] to [3], wherein the content of component (A) is 73% by mass or less when the non-volatile component in the resin composition layer is taken as 100% by mass. .
[5] The resin sheet according to any one of [1] to [4], wherein the metal foil includes copper foil.
[6] The resin sheet according to any one of [1] to [5], wherein the support has a thickness of 9 μm or more.
[7] A printed wiring board comprising an insulating layer made of a cured product of the resin composition layer of the resin sheet according to any one of [1] to [6].
[8] A semiconductor device including the printed wiring board according to [7].
[9] (I) A step of laminating the resin sheet according to any one of [1] to [6] on the inner layer substrate by vacuum pressing, and (II) thermosetting the resin composition layer. forming an insulating layer;
A method of manufacturing a printed wiring board, comprising:

INDUSTRIAL APPLICABILITY According to the present invention, a resin sheet from which a cured product having excellent insulating layer thickness uniformity, embedding properties, and insulation reliability can be obtained; a printed wiring board and a semiconductor device formed using the resin sheet; and a print. A wiring board manufacturing method can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents.

[Resin sheet]
The resin sheet of the present invention is a resin sheet for forming an insulating layer using vacuum press processing. The resin sheet comprises a support comprising a metal foil having a surface surface that is bonded to the resin composition layer and having an arithmetic mean roughness (Ra) of more than 300 nm, and a (A) ratio provided on the support A resin composition layer containing an inorganic filler having a surface area of 10 m ² /g or more, and a dynamic viscoelasticity measurement of the resin composition layer at 60 ° C. to 200 ° C. The maximum value of tan δ , from 1.0 to 2.0.

As mentioned above, in forming an insulating layer using a resin sheet (a resin composition layer thereof), in comparison with the conventionally used vacuum lamination method, the vacuum press process allows the resin sheet (a resin composition layer of the resin sheet) to have a higher degree of In some cases, the applied pressure is high and the thickness of the insulating layer cannot be made uniform due to resin flow. On the other hand, when the viscosity of the resin composition layer is increased in order to suppress resin exudation, the embedding property is lowered and the insulation may be poor. The inventors of the present invention regard the uniformity of the thickness of the insulating layer, the embedding property, and the insulating reliability, and the maximum value of tan δ (tan δ is the storage elastic modulus E' (GPa) and loss modulus E'' (Pa), which is the ratio E''/E'). In addition, the present inventors have found that the maximum value of tan δ can be adjusted by adjusting the amount of residual solvent in the resin composition layer in addition to the specific surface area of the inorganic filler in the resin composition layer. It has been found that it is possible to obtain a cured product excellent in uniformity of thickness, embeddability and insulation reliability.

Each layer constituting the resin sheet will be described in detail below.

<Support>
In the resin sheet of the present invention, the support has a metal foil having an arithmetic mean roughness (Ra) of more than 300 nm on the surface of the support on which the resin composition layer is provided. Usually, the support surface having the arithmetic mean roughness (Ra) is the surface of a metal foil, and the surface of the metal foil is in contact with the resin composition layer. Thereby, a conductor layer, which will be described later, can be formed from the support.

The arithmetic mean roughness (Ra) of the surface of the support on which the resin composition layer is provided is greater than 300 nm, preferably 350 nm or more, more preferably 400 nm or more, from the viewpoint of improving adhesion to the resin composition layer. More preferably, it is 500 nm or more. Although the upper limit is not particularly limited, it is preferably 1000 nm or less, more preferably 900 nm or less, and still more preferably 800 nm or less. Arithmetic mean roughness (Ra) is a value measured according to ISO 25178, and can be measured using a non-contact surface roughness meter.

The ten-point average roughness (Rz) of the surface of the support on which the resin composition layer is provided is preferably greater than 7000 nm, more preferably 8000 nm or more, still more preferably 8000 nm or more, from the viewpoint of improving adhesion to the resin composition layer. is greater than or equal to 9000 nm. Although the upper limit is not particularly limited, it is preferably 30000 nm or less, more preferably 20000 nm or less, and still more preferably 10000 nm or less. Ten-point average roughness (Rz) is a value measured according to ISO 25178, and can be measured using a non-contact surface roughness meter.

The arithmetic mean roughness (Ra) and ten-point mean roughness (Rz) of the support surface can be adjusted within the above ranges by, for example, etching and polishing the support surface.

The support comprises a metal foil, preferably a metal foil. The thickness of the support is preferably 9 μm or more, more preferably 10 μm or more, and even more preferably 11 μm or more, from the viewpoint of significantly obtaining the effects of the present invention. Although the upper limit is not particularly limited, it is preferably 30 μm or less, more preferably 20 μm or less, and still more preferably 15 μm or less. The metal foil may have a single layer structure or a multilayer structure. When the metal foil has a multilayer structure, the thickness of the entire metal foil is preferably within such a range, and the thickness of the ultra-thin metal foil may be, for example, in the range of 0.1 μm or more and 10 μm or less.

Examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.

The metal foil may have a single layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated. Examples of metal foils having a multilayer structure include metal foils containing a carrier metal foil and an ultra-thin metal foil bonded to the carrier metal foil. The metal foil having such a multilayer structure may include a release layer between the carrier metal foil and the ultra-thin metal foil, which enables the ultra-thin metal foil to be peeled off from the carrier metal foil. The release layer is not particularly limited as long as it can release the ultra-thin metal foil from the carrier metal foil. A film etc. are mentioned. In addition, when a metal foil having a multilayer structure is used as the support, the resin composition layer is provided on the ultrathin metal foil.

Although the method for producing the metal foil is not particularly limited, it can be produced by, for example, a known method such as an electrolysis method or a rolling method.

The support may comprise any layer other than the metal foil in combination with the metal foil. In this case, from the viewpoint of allowing the metal foil and the resin composition layer to come into direct contact with each other, the optional layer is preferably provided on the opposite side of the metal foil to the resin composition layer. Here, "direct contact" between the metal foil and the resin composition layer means that there is no other layer between the metal foil and the resin composition layer. Above all, it is preferred that there are no optional layers, so the support preferably comprises only a metal foil.

A commercially available product may be used as the support. Examples of commercially available products include "HLP foil" and "JXUT-III foil" manufactured by JX Nippon Mining & Metals Co., Ltd., "Microshin MT-Ex copper foil" and "TP-III foil" manufactured by Mitsui Kinzoku Mining Co., Ltd., "MW-G" manufactured by Mitsui Mining & Smelting Co., Ltd. and the like can be mentioned.

<Resin composition layer>
In the resin sheet of the present invention, the resin composition layer provided on the support contains (A) an inorganic filler having a specific surface area of 10 m ² /g or more.

The resin composition layer may further contain optional components in combination with the component (A). Optional components include, for example, (B) an epoxy resin, (C) a curing agent, (D) a radically polymerizable compound, (E) a thermoplastic resin, (F) a curing accelerator, (G) a polymerization initiator, and (H) other additives and the like. Each component contained in the resin composition layer will be described in detail below.

-(A) Inorganic filler having a specific surface area of 10 m ² /g or more-
The resin composition layer contains (A) an inorganic filler having a specific surface area of 10 m ² /g or more as the component (A). By using the resin composition layer containing the component (A), it is possible to improve the embedding property and the uniformity of the thickness of the insulating layer.

The specific surface area of the component (A) is 10 m ² /g or more from the viewpoint of improving the embedding property and from the viewpoint of improving the uniformity of the thickness of the insulating layer by suppressing the thickness variation caused by the oozing of the resin. , preferably 15 m ² /g or more, more preferably 20 m ² /g or more, still more preferably 25 m ² /g or more. Although there is no particular upper limit, it is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area is calculated according to the BET method by allowing nitrogen gas to be adsorbed on the sample surface using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) and calculating the specific surface area using the BET multipoint method. is obtained by

The average particle diameter of the component (A) is preferably 0.01 μm or more from the viewpoint of improving embeddability and improving the uniformity of the thickness of the insulating layer by suppressing variations in thickness caused by resin flow. It is more preferably 0.05 µm or more, still more preferably 0.1 µm or more, preferably 5 µm or less, more preferably 4 µm or less, still more preferably 3 µm or less.

The average particle size of component (A) can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement. A measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them with ultrasonic waves for 10 minutes. The volume-based particle size distribution of the component (A) was measured by a flow cell method using a laser diffraction particle size distribution analyzer, using blue and red wavelengths as the light source, and the resulting particle size distribution was obtained. The average particle diameter can be calculated as the median diameter from Examples of the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.

An inorganic compound is used as the material for the component (A). Examples of materials for component (A) include silica, alumina, aluminosilicate, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, oxide Examples include titanium, 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. Moreover, as silica, spherical silica is preferable. (A) component may be used individually by 1 type, and may be used in combination of 2 or more types.

Commercially available products of component (A) include, for example, “UFP-30” and “ASFP-20” manufactured by Denka; “SP60-05”, “SP507-05” and “SPH516” manufactured by Nippon Steel Chemical & Materials -05”; “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C” manufactured by Admatechs; "; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Admatechs;

Component (A) is preferably treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility. Examples of surface treatment agents include vinylsilane coupling agents, (meth)acrylic coupling agents, fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, Examples include silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, and the like. Among them, an aminosilane-based coupling agent is preferable from the viewpoint of significantly obtaining the effects of the present invention. Moreover, one type of surface treatment agent may be used alone, or two or more types may be used in combination.

Commercially available surface treatment agents include, for example, Shin-Etsu Chemical Co., Ltd. "KBM1003" (vinyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM503" (3-methacryloxypropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) , Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyl trimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane coupling agent), Shin-Etsu Chemical Co., Ltd. "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) etc.

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

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and more preferably 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of suppressing the melt viscosity of the resin varnish and the melt viscosity in the sheet form, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and further preferably 0.5 mg/m ² or less. preferable.

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (eg, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.

From the viewpoint of adjusting the maximum value of tan δ to an appropriate range, the content of component (A) is preferably 73% by mass or less, more preferably 72% by mass, when the non-volatile component in the resin composition layer is 100% by mass. % by mass or less, more 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, further preferably 50% by mass or less % by mass or more. In the present invention, the content of each component in the resin composition layer is a value when the non-volatile component in the resin composition layer is 100% by mass, unless otherwise specified.

-(B) epoxy resin-
The resin composition layer may contain (B) an epoxy resin as the (B) component. (B) Epoxy resins may be used singly or in combination of two or more.

(B) Epoxy resins include, for example, bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, and trisphenol type epoxy resins. Epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin , glycidylcyclohexane type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, Cyclohexane-type epoxy resin, cyclohexanedimethanol-type epoxy resin, naphthylene ether-type epoxy resin, trimethylol-type epoxy resin, tetraphenylethane-type epoxy resin, phenolphthalimidine-type epoxy resin, and the like. Epoxy resins may be used singly or in combination of two or more.

The resin composition layer preferably contains, as component (B), an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of obtaining the desired effects of the present invention remarkably, the ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the non-volatile components of the thermosetting resin is preferably 50% by mass. Above, more preferably 60% by mass or more, particularly preferably 70% by mass or more.

Epoxy resins include liquid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “liquid epoxy resins”) and solid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “solid epoxy resins”). ). The resin composition layer may contain only a liquid epoxy resin as a thermosetting resin, or may contain only a solid epoxy resin, but may contain a combination of a liquid epoxy resin and a solid epoxy resin. is preferred.

A liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin.

Examples of liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolak type epoxy resin, ester skeleton. Alicyclic epoxy resins, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, glycidylamine-type epoxy resins, and epoxy resins having a butadiene structure, glycidylcyclohexane-type epoxy resins, and phenolphthalimidine-type epoxy resins are preferable, and glycidyl A cyclohexane type epoxy resin is more preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC; 828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical Corporation "jER807", "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical Corporation "jER152" (phenol novolac type epoxy resin); Mitsubishi Chemical Corporation "630", "630LSD" (glycidylamine type epoxy resin); Nippon Steel Chemical & Materials "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase ChemteX Co., Ltd. "EX-721" (glycidyl ester type epoxy resin); "Celoxide 2021P" manufactured by Daicel (alicyclic epoxy resin having an ester skeleton); "PB-3600" manufactured by Daicel (epoxy resin having a butadiene structure) "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd.; These may be used individually by 1 type, and may be used in combination of 2 or more types.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferred, and bixylenol type epoxy resin and naphthalene type epoxy resin are more preferred. .

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 novolak type epoxy resin), "N-695" (cresol novolak 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", "HP6000L" (naphthylene ether type epoxy resin); "EPPN" manufactured by Nippon Kayaku Co., Ltd. -502H” (trisphenol type epoxy resin), “NC7000L” (naphthol novolac type epoxy resin), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin); Nippon Steel Chemical & Materials Co., Ltd. "ESN475V" (naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; resin), "YX8800" (anthracene type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals Co., Ltd., "YL7760" (bisphenol AF type epoxy resin) and "YL7800" manufactured by Mitsubishi Chemical Co., Ltd. (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin); Nippon Kayaku "WHR-991S" (phenolphthalimidine type epoxy resin) and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

When a combination of a liquid epoxy resin and a solid epoxy resin is used as component (B), the ratio by mass (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:0. 20, more preferably 1:0.3 to 1:10, particularly preferably 1:0.5 to 1:5. The desired effect of the present invention can be remarkably obtained by setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range.

The epoxy equivalent of component (B) is preferably 50 g/eq. ~5000g/eq. , more preferably 50 g/eq. ~3000g/eq. , more preferably 80 g/eq. ~2000 g/eq. , even more preferably 110 g/eq. ~1000g/eq. is. By setting it within this range, it is possible to provide a cured product having a sufficient crosslink density of the cured product of the resin composition layer. Epoxy equivalent weight is the weight of an epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of component (B) is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500 from the viewpoint of significantly obtaining the desired effects of the present invention. The weight average molecular weight of the epoxy resin is the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of component (B) is preferably 5% by mass or more, or more when the non-volatile component in the resin composition layer is 100% by mass. It is preferably 10% by mass or more, more preferably 15% by mass or more. 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, from the viewpoint of significantly obtaining the desired effects of the present invention.

-(C) curing agent-
The resin composition layer may contain (C) a curing agent as the (C) component. (C) Curing agent usually has the function of reacting with component (B) to cure the resin composition. (C) A hardening agent may be used individually by 1 type, and may use 2 or more types together.

As the curing agent (C), a low-polarity curing agent is preferable. (C) Curing agents include, for example, active ester-based resins, phenol-based resins, naphthol-based resins, benzoxazine-based resins, cyanate ester-based resins, carbodiimide-based resins, amine-based resins, and acid anhydride-based resins. Among them, it is preferable to contain an active ester resin from the viewpoint of obtaining the effect of the present invention remarkably.

As the active ester-based resin, a resin having one or more active ester groups in one molecule can be used. Among them, active ester resins have two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, heterocyclic hydroxy compound esters, etc. Resins are preferred. The active ester resin is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based resin obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester-based resin obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred.

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

Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Preferred specific examples of the active ester resin include an active ester resin containing a dicyclopentadiene type diphenol structure, an active ester resin containing a naphthalene structure, an active ester resin containing an acetylated product of phenol novolak, and benzoyl of phenol novolak. active ester-based resins containing compounds. Among them, an active ester resin containing a naphthalene structure and an active ester resin containing a dicyclopentadiene type diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Commercially available active ester resins include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H-" as active ester resins containing a dicyclopentadiene type diphenol structure. 65TM", "EXB-8000L-65TM" (manufactured by DIC); active ester resins containing a naphthalene structure: "EXB9416-70BK", "EXB-8150-65T", "HP-B-8151-62T" (DIC "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester resin containing an acetylated phenol novolac (manufactured by Mitsubishi Chemical); "YLH1026" (manufactured by Mitsubishi Chemical) as an active ester resin containing a benzoylated phenol novolak; "DC808" (Mitsubishi Chemical Co., Ltd.) as an active ester resin that is an acetylated product of phenol novolac; ), “YLH1048” (manufactured by Mitsubishi Chemical Corporation);

From the viewpoint of heat resistance and water resistance, the phenolic resin and naphtholic resin preferably have a novolak structure. From the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based resin is more preferable.

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

Specific examples of benzoxazine-based resins include "JBZ-OD100" (benzoxazine ring equivalent: 218), "JBZ-OP100D" (benzoxazine ring equivalent: 218), "ODA-BOZ" (benzoxazine ring equivalent) manufactured by JFE Chemical Co., Ltd. Equivalent 218); "Pd" (benzoxazine ring equivalent 217), "Fa" (benzoxazine ring equivalent 217) manufactured by Shikoku Kasei Kogyo Co., Ltd.; "HFB2006M" (benzoxazine ring equivalent 432) and the like.

Examples of cyanate ester resins include bisphenol A dicyanate, polyphenolcyanate, oligo(3-methylene-1,5-phenylenecyanate), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4,4' -ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5-dimethylphenyl ) bifunctional cyanate resins such as methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether; phenol Polyfunctional cyanate resins derived from novolacs, cresol novolacs, etc.; prepolymers obtained by partially triazinizing these cyanate resins; and the like. Specific examples of cyanate ester resins include "PT30", "PT30S" and "PT60" (phenol novolac type polyfunctional cyanate ester resins) manufactured by Lonza Japan, "ULL-950S" (polyfunctional cyanate ester resins), "BA230", "BA230S75" (prepolymer in which part or all of bisphenol A dicyanate is triazined to form a trimer), "BADCy" (bisphenol A dicyanate), and the like.

Specific examples of carbodiimide resins include Carbodiimide (registered trademark) V-03 (carbodiimide group equivalent: 216, V-05 (carbodiimide group equivalent: 216), V-07 (carbodiimide group equivalent: 200) manufactured by Nisshinbo Chemical Co., Ltd. V-09 (carbodiimide group equivalent: 200); Stabaxol (registered trademark) P (carbodiimide group equivalent: 302) manufactured by Rhein Chemie.

Amine-based resins include resins having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. Among them, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine-based resin is preferably a primary amine or a secondary amine, more preferably a primary amine. Specific examples of amine-based curing agents include 4,4′-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 3,3′. -diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, 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-diphenylmethane Diamine, 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, and the like. Commercially available amine-based resins may be used. AS", Mitsubishi Chemical's "Epicure W", and the like.

Acid anhydride resins include resins having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride resins include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic anhydride. trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyl Sulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1, Polymer type acid anhydrides such as 3-dione, ethylene glycol bis(anhydrotrimellitate), styrene/maleic acid resin obtained by copolymerizing styrene and maleic acid, and the like can be mentioned.

When the resin composition layer contains an epoxy resin and a curing agent, the amount ratio of the epoxy resin to all the curing agents is [total number of epoxy groups in the epoxy resin]:[total number of reactive groups in the curing agent]. The ratio is preferably in the range of 1:0.01 to 1:5, more preferably 1:0.05 to 1:3, even more preferably 1:0.1 to 1:2. Here, the "epoxy group number of the epoxy resin" is a value obtained by dividing the mass of the non-volatile component of the epoxy resin present in the first resin composition by the epoxy equivalent and totaling all the values. In addition, "the number of active groups of the curing agent" is a value obtained by dividing the mass of the non-volatile component of the curing agent present in the first resin composition by the active group equivalent and totaling all the values. As the thermosetting resin, by setting the ratio of the epoxy resin to the curing agent within the above range, a cured body having excellent flexibility can be obtained.

(C) The content of the curing agent is preferably 1% by mass or more, more preferably 3% by mass or more, relative to 100% by mass of the nonvolatile components in the resin composition layer, from the viewpoint of significantly obtaining the effects of the present invention. , more preferably 5% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less.

-(D) radically polymerizable compound-
The resin composition layer may contain a radically polymerizable compound as the (D) component. (D) Component may be used individually by 1 type, and may use 2 or more types together.

(D) The radically polymerizable compound is, in one embodiment, a radically polymerizable compound having an ethylenically unsaturated bond. (D) The radically polymerizable compound is not particularly limited, but for example, allyl group, 3-cyclohexenyl group, 3-cyclopentenyl group, p-vinylphenyl group, m-vinylphenyl group, o-vinyl Unsaturated hydrocarbon groups such as phenyl group; α,β-unsaturated carbonyl groups such as acryloyl group, methacryloyl group, maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group) can have a radically polymerizable group such as (D) The radically polymerizable compound preferably has two or more radically polymerizable groups.

(D) The radically polymerizable compound may be, for example, a maleimide-based resin, a vinyl-based resin, a (meth)acrylic-based resin, an allyl-based resin, or the like. Above all, the component (D) preferably contains either a maleimide resin or a vinyl resin, and more preferably contains both a maleimide resin and a vinyl resin.

The maleimide-based resin (maleimide-based radical polymerizable compound) is, for example, a compound having one or more, preferably two or more maleimide groups. The maleimide resin may be an aliphatic maleimide compound containing an aliphatic amine skeleton or an aromatic maleimide compound containing an aromatic amine skeleton. Commercially available products include, for example, " SLK-2600", "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", "BMI-2500" manufactured by Designer Molecules (a maleimide compound containing a dimer diamine structure), Designer Molecules "BMI-6100" (aromatic maleimide compound), Nippon Kayaku "MIR-5000-60T", "MIR-3000-70MT" (biphenylaralkyl type maleimide compound), Kei Examples include “BMI-70” and “BMI-80” manufactured by Ai Kasei Co., Ltd., and “BMI-2300” and “BMI-TMH” manufactured by Daiwa Kasei Kogyo Co., Ltd. As the maleimide-based resin, a maleimide-based resin (a maleimide compound containing an indane ring skeleton) disclosed in Technical Report No. 2020-500211 of Japan Institute of Invention and Innovation may be used.

A vinyl resin (vinyl radically polymerizable compound (also referred to as a styrene radically polymerizable compound)) is, for example, a compound having one or more, preferably two or more vinyl groups directly bonded to an aromatic carbon atom. . Examples of vinyl resins include divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4′-divinylbiphenyl, 1,2-bis(4-vinylphenyl ) Low molecular weight (molecular weight less than 1000) styrene compounds such as ethane, 2,2-bis(4-vinylphenyl)propane, bis(4-vinylphenyl)ether; vinylbenzyl-modified polyphenylene ether resin, styrene-divinylbenzene High-molecular-weight (molecular weight of 1000 or more) styrene-based compounds such as polymers can be used. Examples of commercially available styrene-based radical polymerizable compounds include "ODV-XET (X03)", "ODV-XET (X04)", and "ODV-XET (X05)" (styrene -divinylbenzene copolymer), Mitsubishi Gas Chemical Company's "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resin).

The (meth)acrylic resin ((meth)acrylic radically polymerizable compound) is, for example, a compound having one or more, preferably two or more acryloyl groups and/or methacryloyl groups. Examples of (meth)acrylic resins include cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, (meth)acrylates, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate ) acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc. Aliphatic (meth)acrylic acid ester compound with molecular weight (molecular weight less than 1000); dioxane glycol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, 3,6,9-trio xanedecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylation Low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylic acid ester compounds such as bisphenol A di(meth)acrylate and propoxylated bisphenol A di(meth)acrylate; tris(3-hydroxypropyl)isocyanurate tri(meth) Low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylic acid ester compounds such as acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate; (meth) High molecular weight (molecular weight of 1000 or more) acrylic acid ester compounds such as acrylic-modified polyphenylene ether resins and the like can be mentioned. Examples of commercially available (meth)acrylic resins include "A-DOG" (dioxane glycol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" (tricyclodecanedimethanol diacrylate) manufactured by Kyoeisha Chemical Co., Ltd. acrylate), “DCP” (tricyclodecanedimethanol dimethacrylate), Nippon Kayaku Co., Ltd. “KAYARAD R-684” (tricyclodecanedimethanol diacrylate), “KAYARAD R-604” (dioxane glycol diacrylate) , "SA9000" and "SA9000-111" (methacrylic-modified polyphenylene ether) manufactured by SABIC Innovative Plastics.

An allyl-based resin (allyl-based radically polymerizable compound) is, for example, a compound having one or more, preferably two or more allyl groups. Examples of allyl-based resins include aromatics such as diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, and diallyl 2,3-naphthalenecarboxylate. Carboxylic acid allyl ester compounds; isocyanuric acid allyl ester compounds such as 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; 2,2-bis[3-allyl-4-(glycidyl Epoxy-containing aromatic allyl compounds such as oxy)phenyl]propane; benzoxazine-containing compounds such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane aromatic allyl compounds; ether-containing aromatic allyl compounds such as 1,3,5-triallyletherbenzene; and allylsilane compounds such as diallyldiphenylsilane. Commercially available allyl-based resins include "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Co., Ltd., "DAD" (diallyl diphenate) manufactured by Nissho Techno Fine Chemical Co., Ltd., and Wako Pure Chemical Industries. "TRIAM-705" (triallyl trimellitate) manufactured by Nippon Distillery Co., Ltd., trade name "DAND" (diallyl 2,3-naphthalenecarboxylate) manufactured by Shikoku Kasei Kogyo Co., Ltd. "ALP-d" (bis [ 3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane), "RE-810NM" (2,2-bis[3 -allyl-4-(glycidyloxy)phenyl]propane), "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Kasei Co., Ltd., and the like.

The ethylenically unsaturated bond equivalent of component (D) is preferably 20 g/eq. ~3000g/eq. , more preferably 50 g/eq. ~2500 g/eq. , more preferably 70 g/eq. ~2000 g/eq. , particularly preferably 90 g/eq. ~1500 g/eq. is. The ethylenically unsaturated bond equivalent is the mass of the radically polymerizable compound per equivalent of ethylenically unsaturated bond.

The weight average molecular weight (Mw) of component (D) 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, but may be, for example, 150 or more.

From the viewpoint of significantly obtaining the effect of the present invention, the content of component (D) is preferably 10% by mass or more, more preferably 20% by mass or more, when the non-volatile component in the resin composition layer is 100% by mass. , more preferably 25% by mass or more. 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, from the viewpoint of significantly obtaining the desired effects of the present invention.

From the viewpoint of improving resin flow and insulation reliability, it is preferable to use a material with low polarity as the component to be contained in the resin composition layer. Active ester-based resins, maleimide-based resins, vinyl-based resins, and the like are examples of such low-polarity materials. Therefore, as a preferred embodiment of the resin sheet, it is preferable that at least one of (B) an epoxy resin, (C) a curing agent and (D) a radically polymerizable compound is included in combination with the (A) component. It is more preferable to contain any one of active ester resin, maleimide resin and vinyl resin in combination with component A).

-(E) thermoplastic resin-
The resin composition layer may contain (E) a thermoplastic resin as the (E) component. By including the component (E) in the resin composition layer, it is possible to obtain a cured product exhibiting good mechanical strength. (E) component may be used individually by 1 type, and may use 2 or more types together.

The weight-average molecular weight (Mn) of component (E) is preferably 5,000 or more, more preferably 8,000 or more, particularly preferably 10,000 or more, and more preferably 100,000 or less, more preferably, from the viewpoint of significantly obtaining the effects of the present invention. is 80,000 or less, particularly preferably 50,000 or less. The weight average molecular weight of the component (E) is the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

As the component (E), those having a high molecular weight with a weight average molecular weight within the above range can be used. Examples of such components include thermoplastic resins such as polyimide resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, and polyester resins. Resin; Elastomers can be mentioned. Among them, the (E) component is preferably at least one selected from polyimide resins, elastomers and phenoxy resins from the viewpoint of obtaining the effects of the present invention remarkably.

Polyimide resins include those containing a structural unit represented by the following formula (e1) (hereinafter also referred to as “structural unit (e1)”) (hereinafter sometimes referred to as “first polyimide resin”. ). In the first polyimide resin, the number of structural units (e1) is 1 or more and is not particularly limited, but may be 100 or less, 50 or less, or 30 or less. When there are a plurality of structural units (e1), the structural units (e1) may be linked to each other as repeating units, or may not be linked to each other. When the structural units (e1) are not connected to each other, other structural units (for example, structural units represented by formula (e2) described below) are preferably interposed between them.

［式（ｅ１）中、
Ｒ_１は、下記式（ｅ１－１）で表される４価の基であり、
Ｒ_２は、下記式（ｅ１－２）で表される２価の基である。 The structural unit (e1) is represented by the following formula (e1).

[In formula (e1),
R ₁ is a tetravalent group represented by the following formula (e1-1),
R ₂ is a divalent group represented by formula (e1-2) below.

（式（ｅ１－１）中、
Ａｒ_１１、Ａｒ_１２、Ａｒ_１３及びＡｒ_１４は、それぞれ独立に、置換基を有していてもよい芳香族環を表し、
Ｌ_１１、Ｌ_１２及びＬ_１３は、それぞれ独立に、２価の連結基を表し、
ｎｃ１は、０以上の整数を表す。）

(In formula (e1-1),
Ar ₁₁ , Ar ₁₂ , Ar ₁₃ and Ar ₁₄ each independently represent an aromatic ring optionally having a substituent,
L ₁₁ , L ₁₂ and L ₁₃ each independently represent a divalent linking group,
nc1 represents an integer of 0 or more. )

（式（ｅ１－２）中、
Ａｒ_２１、Ａｒ_２２、Ａｒ_２３及びＡｒ_２４は、それぞれ独立に、置換基を有していてもよい芳香族環を表し、
Ｌ_２１、Ｌ_２２及びＬ_２３は、それぞれ独立に、２価の連結基を表し、
ｎｃ２は、１以上の整数を表す。）］

(In formula (e1-2),
Ar ₂₁ , Ar ₂₂ , Ar ₂₃ and Ar ₂₄ each independently represent an aromatic ring optionally having a substituent,
L ₂₁ , L ₂₂ and L ₂₃ each independently represent a divalent linking group,
nc2 represents an integer of 1 or more. )]

In formula (e1-1), the aromatic ring represented by Ar ₁₁ , Ar ₁₂ , Ar ₁₃ and Ar ₁₄ (hereinafter also referred to as “aromatic ring C”) preferably has 6 to 100 carbon atoms, more preferably It is an aromatic ring having 6 to 50 carbon atoms, more preferably an aromatic carbocyclic ring having 6 to 100 carbon atoms, still more preferably 6 to 50 carbon atoms. Therefore, in a preferred embodiment, in formula (e1-1), Ar ₁₁ , Ar ₁₂ , Ar ₁₃ and Ar ₁₄ are each independently It is an aromatic carbocycle. Here, the term "aromatic ring" as used herein means a ring according to Hückel's rule in which the number of electrons contained in the π-electron system on the ring is 4n+2 (n is a natural number). It includes aromatic rings and condensed aromatic rings in which two or more monocyclic aromatic rings are condensed. Aromatic rings may be carbocyclic or heterocyclic. Examples of aromatic rings include single rings such as benzene ring, furan ring, thiophene ring, pyrrole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, imidazole ring, pyridine ring, pyridazine ring, pyrimidine ring and pyrazine ring. Cyclic aromatic ring; naphthalene ring, anthracene ring, benzofuran ring, isobenzofuran ring, indole ring, isoindole ring, benzothiophene ring, benzimidazole ring, indazole ring, benzoxazole ring, benzoisoxazole ring, benzothiazole ring , quinoline ring, isoquinoline ring, quinoxaline ring, acridine ring, quinazoline ring, cinnoline ring, phthalazine ring, and the like condensed ring of two or more monocyclic aromatic rings; indane ring, fluorene ring, tetralin ring, etc. Examples include condensed rings in which one or more monocyclic aromatic rings are condensed with one or more monocyclic non-aromatic rings. Among these, an aromatic carbocyclic ring having 6 to 14 carbon atoms is preferred, and a benzene ring is more preferred.

In formula (e1-1), when Ar ₁₁ , Ar ₁₂ , Ar ₁₃ and Ar ₁₄ represent an aromatic ring having a substituent, the number of substituents is not limited. Such substituents (hereinafter also referred to as “substituent S”) independently of each other include halogen atoms, alkyl groups, cycloalkyl groups, alkoxy groups, cycloalkyloxy groups, aryl groups, aryloxy groups, aryl an alkyl group, an arylalkoxy group, a monovalent heterocyclic group, an alkylidene group, an amino group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group and an oxo group; mentioned.

In formula (e1-1), the divalent linking group represented by L ₁₁ , L ₁₂ and L ₁₃ is preferably one or more selected from carbon atom, oxygen atom, nitrogen atom, sulfur atom and silicon atom (e.g. 1 to 3000, 1 to 1000, 1 to 100, 1 to 50) skeletal atoms. Examples of divalent linking groups include -SO ₂ -, -CO-, -COO-, -O-, -S-, -O-C ₆ H ₄ -O- (where -C ₆ H ₄ — represents a phenylene group.), —OC ₆ H ₄ —C(CH ₃ ) ₂ —C ₆ H ₄ —O—, —COO—(CH ₂ ) _q —OCO— (where q is , represents an integer of 1 to 20.), -COO-H ₂ C-HC(-OC(=O)-CH ₃ )-CH ₂ -OCO-, an alkylene group, an alkenylene group, an alkynylene group, an arylene group , heteroarylene group, -C(=O)-, -C(=O)-O-, -NR ⁰ - (here, R ⁰ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ) and -C(=O)-NR ⁰ -. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 4 carbon atoms. is more preferred. The alkylene group includes, for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, dimethylmethylene group and the like, and dimethylmethylene group is preferred. The alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 6 carbon atoms, and even more preferably an alkenylene group having 2 to 5 carbon atoms. As the arylene group and heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferable, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferable. The alkyl group, alkylene group, alkenylene group, alkynylene group, arylene group, and heteroarylene group described above may further have a substituent. Examples of the substituent are the same as those of the substituent S. The divalent linking groups represented by L ₁₁ , L ₁₂ and L ₁₃ preferably do not contain an aromatic ring. In one embodiment, the divalent linking group represented by L ₁₁ and the divalent linking group represented by L ₁₃ are the same, and the divalent linking group represented by L ₁₁ and the divalent linking group represented by L ₁₂ are the same. are different from each other. In a preferred embodiment, in formula (e1-1), L ₁₁ and L ₁₃ are —O—, and L ₁₂ is an optionally substituted alkylene group, a more preferred embodiment in formula (e1-1), Ar ₁₁ , Ar ₁₂ , Ar ₁₃ and Ar ₁₄ are each independently an optionally substituted aromatic carbocyclic ring having 6 to 14 carbon atoms, Further, in formula (e1-1), L ₁₁ and L ₁₃ are —O—, and L ₁₂ is an optionally substituted alkylene group. In a further preferred embodiment, in formula (e1-1), L ₁₁ and L ₁₃ are —O— and L ₁₂ is a dimethylmethylene group.

In formula (e1-2), examples of the aromatic ring represented by Ar ₂₁ , Ar ₂₂ , Ar ₂₃ and Ar ₂₄ and the substituents that the aromatic ring may have are, respectively, the aromatic ring C and the substituent It is the same as the example of the group S. Therefore, in a preferred embodiment, in formula (e1-2), Ar ₂₁ , Ar ₂₂ , Ar ₂₃ and Ar ₂₄ are each independently It is an aromatic carbocycle. Further, in a preferred embodiment, in formula (e1-2), L ₂₁ and L ₂₃ are —O—, and L ₂₂ is an optionally substituted alkylene group; In an embodiment, in formula (e1-2), Ar ₂₁ , Ar ₂₂ , Ar ₂₃ and Ar ₂₄ are each independently an optionally substituted aromatic carbocyclic ring having 6 to 14 carbon atoms. and in formula (e1-2), L ₂₁ and L ₂₃ are —O—, and L ₂₂ is an optionally substituted alkylene group. In a further preferred embodiment, in formula (e1-2), L ₂₁ and L ₂₃ are —O— and L ₂₂ is a dimethylmethylene group. In a particularly preferred embodiment, in formula (e1-1), Ar ₁₁ , Ar ₁₂ , Ar ₁₃ and Ar ₁₄ are each independently an optionally substituted aromatic having 6 to 14 carbon atoms. is a group carbocyclic ring, and in formula (e1-2), Ar ₂₁ , Ar ₂₂ , Ar ₂₃ and Ar ₂₄ are each independently an optionally substituted aromatic having 6 to 14 carbon atoms; is a group carbocycle. In another particularly preferred embodiment, in formula (e1-1), L ₁₁ and L ₁₃ are —O—, L ₁₂ is an optionally substituted alkylene group, and , in formula (e1-2), L ₂₁ and L ₂₃ are —O—, and L ₂₂ is an optionally substituted alkylene group. In a more particularly preferred embodiment, in formula (e1-1), Ar ₁₁ , Ar ₁₂ , Ar ₁₃ and Ar ₁₄ each independently represent optionally substituted C 6-14 is an aromatic carbocyclic ring, and in formula (e1-2), Ar ₂₁ , Ar ₂₂ , Ar ₂₃ and Ar ₂₄ are each independently an optionally substituted aromatic having 6 to 14 carbon atoms; a carbocyclic ring, in formula (e1-1), L ₁₁ and L ₁₃ are —O—, L ₁₂ is an optionally substituted alkylene group, and formula (e1-2) Among them, L ₂₁ and L ₂₃ are —O—, and L ₂₂ is an optionally substituted alkylene group.

In formula (e1-1), nc1 preferably represents an integer of 1 or more. The upper limit of the integer represented by nc1 is not particularly limited, but may be 50, 40, 30 or 20, for example.

In formula (e1-2), nc2 preferably represents an integer of 2 or more. The upper limit of the integer represented by nc2 is not particularly limited, but may be 60, 50, 40 or 30, for example. In one embodiment, in formula (e1-1), the integer represented by nc2 is greater than the integer represented by nc1 and less than nc1+5. In certain embodiments, nc1 is 1 and nc2 is 2 in formula (e1-1).

The above-described structural unit (e1) is produced by, for example, a known method for producing a polyimide resin, typically a method of imidizing by polymerizing a monomer composition containing a tetracarboxylic dianhydride and a diamine compound, or a method of imidizing a tetracarboxylic acid It can be obtained according to a method of polymerizing and imidizing a monomer composition containing a dianhydride and a diisocyanate compound. It should be noted that the first polyimide resin is allowed to partially contain a polyamic acid structure that may be generated during the process of imidization.

Structural unit (e1) in the above specific embodiment is, for example, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (a compound represented by the following formula (eI); hereinafter also referred to as “BPADA”) and 4,4′-[1,4-phenylenebis[(1-methylethylidene)-4,1-phenyleneoxy]]bisbenzenamine (represented by the following formula (eII) (hereinafter also referred to as “BPPAN”). That is, _R1 in such structural unit (e1) is a skeleton derived from BPADA, and _R2 is a skeleton derived from BPPAN.

Further, the first polyimide resin may be a resin further containing a structural unit represented by the following formula (e2) (hereinafter also referred to as "structural unit (e2)"). Therefore, in one embodiment, the first polyimide resin is a resin further containing a structural unit represented by the following formula (e2). In the first polyimide resin, the number of structural units (e2) is 0 or more and is not particularly limited, but may be 100 or less, 50 or less, or 30 or less. Structural unit (e2) may be linked to group _R2 of structural unit (e1) via the nitrogen atom of its imide group, or may not be linked to structural unit (e1). When there are a plurality of structural units (e2), the structural units (e2) may be linked to each other as repeating units, or may not be linked to each other. When not connected to each other, it is preferable that the plurality of structural units (e2) have another structural unit (for example, structural unit (e1)) interposed therebetween.

（式（ｅ２）中、
Ｒ_３は、置換基を有していてもよい４価の脂肪族基又は置換基を有していてもよい４価の芳香族基を表し、
Ｒ_４は、置換基を有していてもよい２価の脂肪族基又は置換基を有していてもよい２価の芳香族基を表す。但し、Ｒ_３がＲ_１と同じ場合、Ｒ_４はＲ_２とは異なり、Ｒ_４がＲ_２と同じ場合、Ｒ_３はＲ_１とは異なる。） The structural unit (e2) is represented by the following formula (e2).

(In formula (e2),
R ₃ represents an optionally substituted tetravalent aliphatic group or an optionally substituted tetravalent aromatic group,
R ₄ represents an optionally substituted divalent aliphatic group or an optionally substituted divalent aromatic group. However, if _R3 is the same as _R1 , then _R4 is different from _R2 , and if _R4 is the same as _R2 , then _R3 is different from _R1 . )

In formula (e2), the tetravalent aliphatic group represented by R ₃ contains at least carbon atoms, preferably one or more selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms and silicon atoms (e.g., 1 It is a tetravalent group consisting of skeletal atoms of up to 3000, 1 to 1000, 1 to 100, 1 to 50). In formula (e2), the tetravalent aliphatic group represented by R ₃ is more preferably a tetravalent aliphatic group having 1 to 100 carbon atoms, still more preferably 1 to 50 carbon atoms. In formula (e2), when R ₃ represents a tetravalent aliphatic group having a substituent, examples of the substituent are the same as those of the substituent S.

In formula (e2), the tetravalent aromatic group represented by R ₃ is preferably a tetravalent aromatic group having 6 to 100 carbon atoms, more preferably 6 to 50 carbon atoms, still more preferably 6 carbon atoms. to 100, more preferably 6 to 50 tetravalent aromatic hydrocarbon groups. An aromatic group contains at least an aromatic ring. Examples of the aromatic ring contained in the aromatic group are the same as the aromatic rings represented by Ar ₁₁ , Ar ₁₂ , Ar ₁₃ and Ar ₁₄ in formula (e1-1). In formula (e2), when R ₃ represents a tetravalent aromatic group having a substituent, examples of the substituent are the same as those of the substituent S.

Examples of the tetravalent aromatic group represented by R ₃ include a group obtained by removing two acid anhydride groups from a tetracarboxylic dianhydride having an optionally substituted aromatic group. An aromatic group contains at least an aromatic ring. Examples of the aromatic ring contained in the aromatic group are the same as the examples of the aromatic ring C. When the aromatic group has a substituent, examples of the substituent are the same as those of the substituent S. Specific examples of tetracarboxylic dianhydrides having an optionally substituted aromatic group include BPADA, pyromellitic dianhydride, and 3,3′,4,4′-biphenyltetracarboxylic acid. dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride is mentioned.

In formula (e2), the divalent aliphatic group represented by R ₄ contains at least carbon atoms, preferably one or more selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms and silicon atoms (e.g., 1 3000, 1 to 1000, 1 to 100, 1 to 50) skeletal atoms. In formula (e2), the divalent aliphatic group represented by R ₄ is more preferably a divalent aliphatic group having 1 to 100 carbon atoms, more preferably 1 to 50 carbon atoms. In formula (e2), when R ₄ represents a divalent aliphatic group having a substituent, examples of the substituent are the same as examples of the substituent S, for example, an alkyl group having 1 to 6 carbon atoms is. Therefore, in certain embodiments, R ₄ is an optionally substituted divalent aliphatic group, one of which is an alkyl group having 1 to 6 carbon atoms. In a specific embodiment, R ₄ is an optionally substituted divalent aliphatic group and is a divalent group obtained by removing two amino groups from isophoronediamine.

When R ₄ represents an optionally substituted divalent aliphatic group, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, selected from 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine or a group obtained by removing two amino groups from a diamine compound having an optionally substituted aliphatic group. These diamine compounds are characterized by their straight-chain aliphatic groups.

When R ₄ represents an optionally substituted divalent aliphatic group, 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, having an optionally substituted aliphatic group It may be a group obtained by removing two amino groups from a diamine compound. These diamine compounds are characterized by their branched aliphatic groups.

When R ₄ represents an optionally substituted divalent aliphatic group, 5-amino-1,3,3-trimethylcyclohexanemethylamine (isophoronediamine), 1,4-diaminocyclohexane, 1, 3-diaminocyclohexane, 1,4-cyclohexanebis(methylamine), 1,3-cyclohexanebis(methylamine), 4,4'-diaminodicyclohexylmethane, bis(4-amino-3-methylcyclohexyl)methane, 3 (4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0 ^2,6 ]decane, 2,5(6)-bis(aminomethyl)bicyclo[2.2.1]heptane , 1,3-diaminoadamantane, 3,3′-diamino-1,1′-biadamantyl and 1,6-diaminoadamantane, a diamine compound having an optionally substituted aliphatic group It may be a group obtained by removing two amino groups from . These diamine compounds are characterized in that the aliphatic group contains an alicyclic carbocyclic ring.

In formula (e2), the divalent aromatic group represented by R ₄ is preferably a divalent aromatic group having 6 to 100 carbon atoms, more preferably 6 to 50 carbon atoms, still more preferably 6 carbon atoms. to 100, more preferably 6 to 50 divalent aromatic hydrocarbon groups. An aromatic group contains at least an aromatic ring. Examples of the aromatic ring contained in the aromatic group are the same as the examples of the aromatic ring C. In formula (e2), when R ₄ represents a divalent aromatic group having a substituent, examples of the substituent are the same as those of the substituent S.

When R ₄ represents an optionally substituted divalent aromatic group, 4,4'-diaminodiphenyl ether, 1,4-phenylenediamine, 2,2-bis[4-(4-amino It may be a group obtained by removing two amino groups from a diamine compound having an optionally substituted aromatic group selected from phenoxy)phenyl]propane.

However, if _R3 is the same as _R1 , then _R4 is different from _R2 , and if _R4 is the same as _R2 , then _R3 is different from _R1 . In some embodiments, _R3 is the same as _R1 . That is, structural unit (e2) is different from structural unit (e1).

The structural unit (e2) described above can be obtained, for example, according to a known method for producing a polyimide resin. Structural unit (e2) in the specific embodiment above can be obtained, for example, by reacting BPADA with isophorone diamine. That is, _R3 in the structural unit (e2) is a skeleton derived from BPADA, and _R4 is a skeleton derived from isophoronediamine. When R ₃ is the same as R ₁ , R ₃ and R ₁ are skeletons derived from BPADA. It should be noted that the first polyimide resin is allowed to partially contain a polyamic acid structure that may be generated during the process of imidization.

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

The glass transition temperature Tg ^(c) (° C.) of the polyimide resin is preferably 140° C. or higher, more preferably 145° C. or higher, still more preferably 150° C. or higher, still more preferably 160° C. or higher, and particularly preferably 170° C. or higher. be. Although the upper limit is not particularly limited, it may be 300° C. or less. The glass transition temperature Tg ^(c) (°C) can be measured from 25°C to 250°C at a heating rate of 5°C/min using a TMA apparatus manufactured by Rigaku.

The content ratio (percentage) of the structural unit (e1) in the polyimide resin is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more, from the viewpoint of significantly obtaining the effects of the present invention. Still more preferably 30% by mass or more, particularly preferably 40% by mass or more. The content ratio (percentage) of the structural unit (e1) of the polyimide resin can be, for example, 98% by mass or less, 95% by mass or less, 90% by mass or less, or 85% by mass or less. Here, the content ratio (percentage) of the structural unit (e1) can be calculated from the ratio of the charged amount (parts by mass) of each material used to synthesize the polyimide resin. and the formula weight of the structural unit (e1) are specified, and the ratio of the formula weight of the structural unit (e1) to the molecular weight may be calculated. 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 above range.

When the polyimide resin is a resin further containing a structural unit (e2), the content ratio (percentage) of the structural unit (e2) is allowed to be 0% by mass (that is, the structural unit (e2) is not included), and the present invention There is no upper limit as long as the effect is not excessively impaired. Therefore, the content ratio (percentage) of the structural unit (e2) in the polyimide resin is, for example, 1% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, or 30% by mass or more, 95% by mass or less, It can be 90% by mass or less, 80% by mass or less, 70% by mass or less, or 60% by mass or less. Here, the content ratio (percentage) of the structural unit (e2) is calculated in the same manner as the content ratio (percentage) of the structural unit (e1). When the polyimide resin is a polymer, the content (percentage) of the structural unit (e2) estimated from the degree of polymerization is preferably within the above range.

The weight average molecular weight (Mw) of the polyimide resin is usually 1,000 or more, preferably 1,00 to 10,000, more preferably 1,000 to 5,000, still more preferably 1,000 to 3,000. is. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

Another embodiment of the polyimide resin is a resin containing a first skeleton derived from BPADA and a second skeleton derived from BPPAN (hereinafter sometimes referred to as "second polyimide resin"). The material of the first skeleton is not limited to BPADA as long as it is the same as the skeleton derived from BPADA. The material of the second skeleton is not limited to BPPAN as long as it is the same as the skeleton derived from BPPAN. In the second polyimide resin, the number of first skeletons is 1 or more, and is not particularly limited, but can be 100 or less, 50 or less, or 30 or less. In the second polyimide resin, the number of second skeletons is 1 or more, and is not particularly limited, but can be 100 or less, 50 or less, or 30 or less.

The first skeleton and the second skeleton described above are produced by, for example, a known method for producing a polyimide resin, typically a method of imidizing by polymerizing a monomer composition containing a tetracarboxylic dianhydride and a diamine compound. can arise from In addition, the first skeleton and the second skeleton can also be generated by a method of imidating by polymerizing a monomer composition containing a tetracarboxylic dianhydride and a diisocyanate compound. Therefore, the second polyimide resin may contain the structural unit (e1) contained in the first polyimide resin. It should be noted that the second polyimide resin is allowed to partially contain a polyamic acid structure that may be generated during the process of imidization.

Also, the second polyimide resin may be a resin further including a third skeleton different from the second skeleton. The third skeleton is one or more selected from the group consisting of a diamine compound having an optionally substituted aliphatic group and a diamine compound having an optionally substituted aromatic group. is a skeleton derived from the diamine compound of Therefore, in one embodiment, the second polyimide resin is a resin further comprising a third skeleton different from the second skeleton, and the third skeleton is an aliphatic polyimide resin which may have a substituent. A skeleton derived from one or more diamine compounds selected from the group consisting of a diamine compound having a group and a diamine compound having an aromatic group which may have a substituent. In the second specific polyimide resin, the number of third skeletons is 0 or more, and is not particularly limited, but can be 100 or less, 50 or less, or 30 or less.

When the diamine compound is a diamine compound having an aliphatic group, the aliphatic group contains at least carbon atoms, preferably one or more selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms and silicon atoms. (for example, 1 to 3000, 1 to 1000, 1 to 100, 1 to 50) skeleton atoms, more preferably 1 to 100 carbon atoms, more preferably 1 to 50 aliphatic is the base. When the aliphatic group has a substituent, examples of the substituent are the same as those of the substituent S.

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 6 to 50 carbon atoms, more preferably carbon It is a tetravalent aromatic hydrocarbon group having 6 to 100 atoms, more preferably 6 to 50 atoms. An aromatic group contains at least an aromatic ring. Examples of the aromatic ring contained in the aromatic group are the same as the examples of the aromatic ring C. When the aromatic group has a substituent, examples of the substituent are the same as those of the substituent S.

The third skeleton may be a skeleton derived from a diamine compound having an aliphatic group having an alkyl group having 1 to 6 carbon atoms as a substituent. Also, the third skeleton may be a skeleton derived from isophoronediamine. Therefore, in one embodiment, 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. To give a specific example thereof, the third skeleton is a skeleton derived from isophoronediamine. The skeleton derived from isophoronediamine (5-amino-1,3,3-trimethylcyclohexanemethylamine) is a skeleton derived from 5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane. may

The third skeleton is an aromatic optionally having substituents such as 4,4′-diaminodiphenyl ether, 1,4-phenylenediamine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane It may be a skeleton derived from one or more selected from diamine compounds having a group group. Such a third skeleton is characterized by having an aromatic group.

The third backbone is 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-hexanediamine, 1,7-heptanediamine, 1, Diamine compounds having an optionally substituted aliphatic group such as 8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine It may be a skeleton derived from one or more selected species. Such a third skeleton is characterized in that the aliphatic groups are linear.

The third backbone is 1,2-diaminopropane, 1,2-diamino-2-methylpropane, 1,3-diamino-2-methylpropane, 1,3-diamino-2,2-dimethylpropane, 1, The skeleton may be derived from one or more selected from diamine compounds having an optionally substituted aliphatic group such as 3-diaminopentane and 1,5-diamino-2-methylpentane. Such a third skeleton is characterized by a branched aliphatic group.

The third backbone is 5-amino-1,3,3-trimethylcyclohexanemethylamine (isophoronediamine), 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-cyclohexanebis(methylamine), 1,3-cyclohexanebis(methylamine), 4,4′-diaminodicyclohexylmethane, bis(4-amino-3-methylcyclohexyl)methane, 3(4),8(9)-bis(aminomethyl)tricyclo[ 5.2.1.0 ^2,6 ]decane, 2,5(6)-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,3-diaminoadamantane, 3,3′-diamino-1 , 1′-biadamantyl, 1,6-diaminoadamantane, and the like, and may be a skeleton derived from one or more selected from diamine compounds having an optionally substituted aliphatic group. Such third skeletons are characterized in that the aliphatic groups contain alicyclic carbocycles.

The above-mentioned third skeleton is produced by, for example, imidizing by polymerizing a monomer composition containing a tetracarboxylic dianhydride that can be a material for the first skeleton and a diamine compound that can be a material for the second skeleton. In the second polyimide resin, the diamine compound or diisocyanate compound, which can be the material of the third skeleton, is included in the monomer composition or is sequentially mixed during polymerization. Therefore, the second polyimide resin can contain structural units (e2) that the first polyimide resin can contain. It should be noted that the second polyimide resin is allowed to partially contain a polyamic acid structure that may be generated during the process of imidization.

Also, the second polyimide resin may be a resin further including a fourth skeleton different from the first skeleton. This fourth skeleton is a skeleton derived from one or more acids selected from the group consisting of acids other than BPADA. In the second polyimide resin, the number of fourth skeletons is 0 or more, and is not particularly limited, but can be 100 or less, 50 or less, or 30 or less.

Acids other than BPADA include tetracarboxylic dianhydrides having an optionally substituted aromatic group. The aromatic group is preferably an aromatic group having 6 to 100 carbon atoms, more preferably 6 to 50 carbon atoms, more preferably an aromatic hydrocarbon having 6 to 100 carbon atoms, still more preferably 6 to 50 carbon atoms. is the base. An aromatic group contains at least an aromatic ring. Examples of the aromatic ring contained in the aromatic group are the same as the examples of the aromatic ring C. When the aromatic group has a substituent, examples of the substituent are the same as those of the substituent S. Specific examples of the tetracarboxylic dianhydride having an optionally substituted aromatic group include pyromellitic dianhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride. 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride. be done.

The glass transition temperature Tg ^(c′) (° C.) of the second polyimide resin is preferably 140° C. or higher, more preferably 145° C. or higher, still more preferably 150° C. or higher, still more preferably 160° C. or higher, particularly preferably 170° C. or higher. Although the upper limit is not particularly limited, it may be 300° C. or less. The glass transition temperature Tg ^(c') (°C) can be measured according to the same method as for the first polyimide resin.

The total content ratio (percentage) of the first skeleton and the second skeleton in the second polyimide resin is preferably 4% by mass or more, more preferably 9% by mass, from the viewpoint of enhancing the intended effects of the present invention. Above, more preferably 19% by mass or more, still more preferably 29% by mass or more, particularly preferably 39% by mass or more. The total content ratio (percentage) of the first skeleton and the second skeleton can be, for example, 97% by mass or less, 94% by mass or less, 89% by mass or less, or 84% by mass or less. Here, the sum of the content ratio (percentage) of the first skeleton and the second skeleton is the amount (parts by mass) charged that contributes to the reaction of each material used to synthesize the second polyimide resin. Alternatively, by identifying the molecular weight of the second polyimide resin and the formula weights of the first and second backbones incorporated into the resin, It may be calculated as a ratio of the formula weight of the skeleton to the total molecular weight. When the second polyimide resin is a polymer, the total content (percentage) of the first skeleton and the second skeleton estimated from the degree of polymerization is preferably within the above range.

When the second polyimide resin is a resin further containing a third skeleton, the content ratio (percentage) of the third skeleton is allowed to be 0% by mass (that is, the third skeleton is not included), and the present invention There is no upper limit as long as the effect is not excessively impaired. Therefore, the content ratio (percentage) of the third skeleton in the second polyimide resin is, for example, more than 0% by mass, 4% by mass or more, 9% by mass or more, 19% by mass or more, or 29% by mass or more, 94% by mass 89% by mass or less, 79% by mass or less, 69% by mass or less, or 59% by mass or less. Here, the content ratio (percentage) of the third skeleton is calculated in the same manner as the content ratio (percentage) of the first skeleton and the content ratio (percentage) of the second skeleton. When the second polyimide resin is a polymer, the content (percentage) of the third skeleton estimated from the degree of polymerization is preferably within the above range. When the second polyimide resin further contains a fourth skeleton, the content ratio (percentage) of the fourth skeleton is the same as the content ratio (percentage) of the third skeleton.

The terminal structure of the second polyimide resin is not particularly limited as long as it is a resin containing the first skeleton derived from BPADA and the second skeleton derived from BPPAN. For example, the terminal structure of the second polyimide resin may be an acid anhydride group or a carboxyl group or an amino group derived from the raw material compound of the second polyimide resin (for example, an acid such as BPADA, an amine compound such as BPPAN). . When the raw material compound further contains maleic anhydride, the terminal structure of the second polyimide resin may be a maleimide group.

The weight average molecular weight (Mw) of the second polyimide resin is usually 1,000 or more, preferably 1,00 to 10,000, more preferably 1,000 to 5,000, more preferably 1,000 to 3,000. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

Another embodiment of the polyimide resin is a resin obtained by imidizing by polymerizing a monomer composition containing at least BPADA and BPPAN (hereinafter sometimes referred to as "third polyimide resin". ). Polymerization and imidization are not particularly limited, but are usually carried out in a solvent. In the polymerization, the blending ratio of BPADA and BPPAN is preferably determined according to the total number of functional groups possessed by each component. In one embodiment, the total number of amino groups possessed by BPPAN in the monomer composition: The total ratio of the number of acid anhydride groups possessed by BPADA is within the range of 0.1:1 to 10:1, preferably within the range of 0.5:1 to 10:1, more preferably 0.8: It is in the range of 1 to 10:1, more preferably in the range of 0.9:1 to 10:1. Imidation is not particularly limited, but is usually carried out in a solvent by heating in the absence of a catalyst, by heating in the presence of a catalyst, or in the presence of a catalyst at room temperature. . From the viewpoint of enhancing the intended effects of the present invention, imidization is preferably carried out by heating in the absence of a catalyst. The third polyimide resin may be a random copolymer, an alternating copolymer, or a block copolymer. The third polyimide resin is not limited to such polymerization and imidization methods. It is permissible for the third polyimide resin to partially contain a polyamic acid structure that may be generated during the course of imidization. The third polyimide resin thus obtained contains the aforementioned structural unit (e1) contained in the first polyimide resin. Moreover, the third polyimide resin obtained in this way contains the aforementioned first skeleton and second skeleton contained in the second polyimide resin.

The monomer composition may contain, as other monomers, an acid other than BPADA and/or a diamine compound other than BPPAN, or other monomers may be added during the reaction.

Acids other than BPADA include tetracarboxylic dianhydrides having an optionally substituted aromatic group. The aromatic group is preferably a tetravalent aromatic group having 6 to 100 carbon atoms, more preferably 6 to 50 carbon atoms, more preferably 6 to 100 carbon atoms, still more preferably 6 to 50 carbon atoms. is a valent aromatic hydrocarbon group. An aromatic group contains at least an aromatic ring. Examples of the aromatic ring contained in the aromatic group are the same as the examples of the aromatic ring C. When the aromatic group has a substituent, examples of the substituent are the same as those of the substituent S. Specific examples of the tetracarboxylic dianhydride having an optionally substituted aromatic group include pyromellitic dianhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride. 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride. be done. The molar ratio of the content of the acid other than BPADA to the content of BPADA in the monomer composition is not particularly limited, but can be, for example, 0.5 or less, 0.4 or less, or 0.3 or less.

In one embodiment, the monomer composition is selected from the group consisting of a diamine compound having an optionally substituted aliphatic group and a diamine compound having an optionally substituted aromatic group. It further contains one or more diamine compounds. The molar ratio of the content of diamine compounds other than BPPAN to the content of BPPAN in the monomer composition is not particularly limited, but can be, for example, 0.5 or less, 0.4 or less, or 0.3 or less. .

When the diamine compound is a diamine compound having an aliphatic group, the aliphatic group contains at least carbon atoms, preferably one or more selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms and silicon atoms. (for example, 1 to 3000, 1 to 1000, 1 to 100, 1 to 50) skeleton atoms, more preferably 1 to 100 carbon atoms, more preferably 1 to 50 aliphatic is the base. When the aliphatic group has a substituent, examples of the substituent are the same as those of the substituent S.

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 6 to 50 carbon atoms, more preferably carbon It is a tetravalent aromatic hydrocarbon group having 6 to 100 atoms, more preferably 6 to 50 atoms. An aromatic group contains at least an aromatic ring. Examples of the aromatic ring contained in the aromatic group are the same as the examples of the aromatic ring C. When the aromatic group has a substituent, examples of the substituent are the same as those of the substituent S. When the diamine compound is a diamine compound having an optionally substituted aromatic group, examples thereof include 4,4′-diaminodiphenyl ether, 1,4-phenylenediamine, 2,2-bis[ One or more selected from diamine compounds having an aromatic group such as 4-(4-aminophenoxy)phenyl]propane can be used.

When the diamine compound is a diamine compound having an optionally substituted aliphatic group, the first examples thereof include 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., may be a skeleton derived from one or more selected from diamine compounds having an aliphatic group which may have a substituent such as 1,12-dodecanediamine. The diamine compound according to the first example is characterized in that the aliphatic group is linear.

When the diamine compound is a diamine compound having an optionally substituted aliphatic group, examples thereof include 1,2-diaminopropane, 1,2-diamino-2-methylpropane, Having a substituent such as 1,3-diamino-2-methylpropane, 1,3-diamino-2,2-dimethylpropane, 1,3-diaminopentane, 1,5-diamino-2-methylpentane It may be a skeleton derived from one or more selected from diamine compounds having a good aliphatic group. The diamine compound according to the second example is characterized in that the aliphatic group is branched.

When the diamine compound is a diamine compound having an optionally substituted aliphatic group, a third example thereof is 5-amino-1,3,3-trimethylcyclohexanemethylamine (isophorone diamine) , 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-cyclohexanebis(methylamine), 1,3-cyclohexanebis(methylamine), 4,4′-diaminodicyclohexylmethane, bis(4- amino-3-methylcyclohexyl)methane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0 ^2,6 ]decane, 2,5(6)-bis(aminomethyl) ) may have substituents such as bicyclo[2.2.1]heptane, 1,3-diaminoadamantane, 3,3′-diamino-1,1′-biadamantyl and 1,6-diaminoadamantane The skeleton may be derived from one or more selected from diamine compounds having an aliphatic group. The diamine compound according to this third example is characterized in that the aliphatic group contains an alicyclic carbocyclic ring.

According to the above, in one embodiment, the monomer composition further contains a diamine compound having an aliphatic group having an alkyl group having 1 to 6 carbon atoms as a substituent. Also, in certain embodiments, the monomer composition further comprises isophorone diamine.

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

The weight average molecular weight (Mw) of the third polyimide resin is 1,000 or more, preferably 1,00 to 10,000, more preferably 1,000 to 5,000, still more preferably 1,000 to 3 , 000. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

Examples of phenoxy resins include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, and terpene. Examples include phenoxy resins having one or more skeletons selected from the group consisting of skeletons and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin is preferably a phenoxy resin having a weight average molecular weight of 30,000 or more.

Specific examples of the phenoxy resin include Mitsubishi Chemical's "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resins); Mitsubishi Chemical's "YX8100" (bisphenol S skeleton-containing phenoxy resin); Mitsubishi Chemical "YX6954" (bisphenolacetophenone skeleton-containing phenoxy resin) manufactured by Nippon Steel Chemical &Materials; "FX280" and "FX293" manufactured by Nippon Steel Chemical &Materials; ", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482";

A polyamideimide resin is a resin having an amideimide structure. Polyamideimide resin, from the viewpoint of compatibility with other components in the resin composition layer, polyamideimide resin having an alicyclic structure in the molecular structure, has a siloxane structure described in JP-A-05-112760. It is preferable to use a polyamideimide resin, a polyamideimide resin having a bulky branched chain structure, a polyamideimide resin using an asymmetric monomer as a raw material, a polyamideimide resin having a multi-branched structure, or the like.

Among them, the polyamideimide resin has an isocyanuric ring structure, and from the viewpoint of improving the compatibility and dispersibility of the resin varnish, (i) a polyamideimide resin having an isocyanuric ring structure in the molecular structure (i.e., isocyanuric ring structure and an imide skeleton or an amide skeleton) (ii) a polyamideimide resin having an isocyanuric ring structure and an alicyclic structure in the molecular structure (that is, an isocyanuric ring structure, an alicyclic structure and an imide skeleton or (iii) a polyamideimide resin having a repeating unit containing an isocyanuric ring structure and an alicyclic structure (that is, an isocyanuric ring structure, an alicyclic structure, an imide skeleton or an amide skeleton, and Polyamide-imide resins having repeating units containing polyimide) are more preferable.

As a preferred embodiment of the polyamideimide resins (i) to (iii), (1) an isocyanuric ring-containing polyisocyanate compound derived from an alicyclic structure diisocyanate and a polycarboxylic acid having 3 or more carboxyl groups Carboxylic acid group-containing branched polyamideimide, which is a compound obtained by reacting an acid anhydride (hereinafter, the compound may be referred to as "(compound E-e1)".), (2) compound (E -e1) is a compound obtained by reacting a compound having one epoxy group and one or more radically polymerizable unsaturated groups with a carboxylic acid group-containing branched polymerizable polyamideimide (hereinafter referred to as "compound (E- e2)”), or (3) in the process of synthesizing the compound (E-e1), the residual isocyanate group is reacted with a compound having one hydroxyl group and one or more radically polymerizable unsaturated groups. carboxylic acid group-containing branched polymerizable polyamideimide (hereinafter sometimes referred to as "compound (E-e3)"), which is a compound obtained by the above.

（式中、ｗは０～１５を表す。） Specific examples of the compound (E-e1) include compounds represented by the following general formula (I). The repeating unit in the compound represented by formula (I) is referred to as repeating unit (I-1).

(In the formula, w represents 0 to 15.)

（式中、Ｒ^４０は式（Ｉ）中の残基を表す。） As the compound (E-e2), a structure (I- 2) is exemplified by compound (II).

(Wherein R ⁴⁰ represents the residue in formula (I).)

The ratio of GMA-modified carboxyl groups is preferably 0.3 mol% or more, more preferably 0.5 mol% or more, still more preferably 0.5 mol% or more, with respect to the number of moles of carboxyl groups in the compound (E-e1), in which GMA is added. It is 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, still more preferably 30 mol% or less, or 20 mol% or less.

（式中、Ｒ’は式（Ｉ）中の残基を表す。） As the compound (E-e3), any part of the repeating unit (I-1) in the above formula (I) and/or the terminal imide group is an isocyanate residue, to which the hydroxyl group of pentaerythritol triacrylate is added. Compound (III) having the structure (I-3) represented by

(Wherein, R' represents a residue in formula (I).)

The amount of pentaerythritol triacrylate added is preferably 40 mol % or less, more preferably 38 mol % or less, still more preferably 35 mol % or less, relative to the number of moles of isocyanate groups in the polyisocyanate at the time of preparation. On the other hand, the amount of pentaerythritol triacrylate added is preferably 0.3 mol% or more, more preferably 0.3 mol% or more, based on the number of moles of isocyanate groups in the polyisocyanate at the time of preparation, from the viewpoint of sufficiently obtaining the effect of addition. It is 3 mol % or more, more preferably 5 mol % or more.

Polyamideimide resins can be synthesized by various known methods. As a method for synthesizing a polyamideimide resin, for example, paragraphs 0020 to 0030 of International Publication No. WO 2010/074197 can be referred to, the contents of which are incorporated herein.

A commercially available product can be used as the polyamide-imide resin. Commercially available products include, for example, "Unidic V-8000" manufactured by DIC, "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo, "KS9100" and "KS9300" manufactured by Hitachi Chemical Co., Ltd. (polysiloxane skeleton-containing polyamideimide) and other modified polyamideimides.

From the viewpoint of compatibility with other components in the resin composition layer, the polyester resin preferably has a fluorene structure in its molecular structure. It is preferable to have a structural unit.

Specific examples of the polyester resin include "OKP4HT" manufactured by Osaka Gas Chemicals Co., Ltd., and the like.

Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of polyvinyl acetal resins include S-lec BH series, BX series (eg BX-5Z), KS series (eg KS-1), BL series and BM series manufactured by Sekisui Chemical Co., Ltd.

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

The elastomer in component (E) is a resin having flexibility, preferably a resin having rubber elasticity or a resin exhibiting rubber elasticity when polymerized with other components. Examples of rubber elasticity include resins exhibiting an elastic modulus of 1 GPa or less when subjected to a tensile test at a temperature of 25° C. and a humidity of 40% RH according to Japanese Industrial Standards (JIS K7161). Elastomers are usually amorphous resin components that are soluble in organic solvents. One type of this elastomer may be used alone, or two or more types may be used in combination at an arbitrary ratio.

In one embodiment, the elastomer is intramolecularly selected from a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, a polycarbonate structure, a polystyrene structure. It is preferably a resin having one or more structures that are "(Meth)acrylate" refers to methacrylate and acrylate.

In another embodiment, the elastomer is preferably one or more selected from resins having a glass transition temperature (Tg) of 25° C. or lower and resins that are liquid at 25° C. or lower. The glass transition temperature of the resin having a glass transition temperature (Tg) of 25° C. or lower is preferably 20° C. or lower, more preferably 15° C. or lower. Although the lower limit of the glass transition temperature is not particularly limited, it is usually −15° C. or higher. The resin that is liquid at 25°C is preferably a resin that is liquid at 20°C or lower, more preferably a resin that is liquid at 15°C or lower. The glass transition temperature can be measured by DSC (differential scanning calorimetry).

Examples of elastomers include resins containing a polybutadiene structure. The polybutadiene structure may be contained in the main chain or may be contained in the side chain. Moreover, a part or all of the polybutadiene structure may be hydrogenated. A resin containing a polybutadiene structure is sometimes called a "polybutadiene resin". Specific examples of the polybutadiene resin include “Ricon 130MA8”, “Ricon 130MA13”, “Ricon 130MA20”, “Ricon 131MA5”, “Ricon 131MA10”, “Ricon 131MA17”, “Ricon 131MA20” and “Ricon 184MA6" (acid anhydride group-containing polybutadiene), Nippon Soda's "GQ-1000" (hydroxyl group- and carboxyl group-introduced polybutadiene), "G-1000", "G-2000", "G-3000" (both ends hydroxyl group polybutadiene), "GI-1000", "GI-2000", "GI-3000" (hydrogenated polybutadiene with both hydroxyl groups), "FCA-061L" manufactured by Nagase ChemteX Corporation (hydrogenated polybutadiene skeleton epoxy resin), etc. Further, specific examples of polybutadiene resins include linear polyimides made from hydroxyl group-terminated polybutadiene, diisocyanate compounds and tetrabasic acid anhydride (the polyimides described in JP-A-2006-37083 and WO 2008/153208). ), phenolic hydroxyl group-containing butadiene, and the like. The butadiene structure content of the polyimide resin is preferably 60% to 95% by mass, more preferably 75% to 85% by mass. Details of the polyimide resin can be referred to in JP-A-2006-37083 and WO 2008/153208, the contents of which are incorporated herein.

Examples of elastomers include resins containing poly(meth)acrylate structures. A resin containing a poly(meth)acrylate structure is sometimes called a "poly(meth)acrylic resin". Specific examples of poly(meth)acrylic resins include Teisan resin manufactured by Nagase ChemteX Corporation, and "ME-2000", "W-116.3", "W-197C" and "KG-25" manufactured by Negami Kogyo Co., Ltd. ”, “KG-3000” and the like.

Examples of elastomers include resins containing a polycarbonate structure. A resin containing a polycarbonate structure is sometimes called a "polycarbonate resin". Examples of such resins include carbonate resins having no reactive groups, hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxy group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, urethane group-containing carbonate resins, containing carbonate resins, epoxy group-containing carbonate resins, and the like. Here, the reactive group means a functional group capable of reacting with other components such as a hydroxyl group, a phenolic hydroxyl group, a carboxyl group, an acid anhydride group, an isocyanate group, a urethane group and an epoxy group.
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 Chemicals, "C-1090" manufactured by Kuraray Co., Ltd., "C-2090","C-3090" (polycarbonate diol) and the like. Linear polyimides made from hydroxyl-terminated polycarbonates, diisocyanate compounds and tetrabasic acid anhydrides can also be used. The carbonate structure content of the polyimide resin is preferably 60% to 95% by mass, more preferably 75% to 85% by mass. Details of the polyimide resin can be referred to in International Publication No. 2016/129541, the content of which is incorporated herein.

Examples of elastomers include resins containing a polysiloxane structure. A resin containing a polysiloxane structure is sometimes called a "siloxane resin". Specific examples of siloxane resins include "SMP-2006", "SMP-2003PGMEA", and "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone Co., Ltd., linear polyimides made from amine group-terminated polysiloxane and tetrabasic acid anhydride ( International Publication No. WO 2010/053185, JP-A-2002-12667 and JP-A-2000-319386) and the like.

Examples of elastomers include resins containing polyalkylene structures or polyalkyleneoxy structures. A resin containing a polyalkylene structure is sometimes called an "alkylene resin". Also, a resin containing a polyalkyleneoxy structure is sometimes referred to as an "alkyleneoxy resin". The polyalkyleneoxy structure is preferably a polyalkyleneoxy structure having 2 to 15 carbon atoms, more preferably a polyalkyleneoxy structure having 3 to 10 carbon atoms, and particularly preferably a polyalkyleneoxy structure having 5 to 6 carbon atoms. Specific examples of alkylene resins and alkyleneoxy resins include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers.

Examples of elastomers include resins containing a polyisoprene structure. A resin containing a polyisoprene structure is sometimes called an "isoprene resin". Specific examples of the isoprene resin include “KL-610” and “KL613” manufactured by Kuraray Co., Ltd.

Examples of elastomers include resins containing a polyisobutylene structure. A resin containing a polyisobutylene structure is sometimes called an "isobutylene resin". Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation.

Examples of elastomers include resins containing polystyrene structures. A resin containing a polystyrene structure is sometimes called a "styrene resin". The styrene resin may be a copolymer containing any repeating unit different from the styrene unit in combination with the styrene unit, or may be a hydrogenated polystyrene resin.

Examples of the optional repeating unit include a repeating unit having a structure obtained by polymerizing a conjugated diene (conjugated diene unit), a repeating unit having a structure obtained by hydrogenating it (hydrogenated conjugated diene unit), and the like. be done. 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. As the conjugated diene, an aliphatic conjugated diene is preferable, and butadiene is more preferable, from the viewpoint of significantly obtaining the effects of the present invention. Conjugated dienes may be used singly or in combination of two or more. Moreover, the polystyrene resin may be a random copolymer or a block copolymer.

Styrene resins include, for example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene- Ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-butylene-styrene block copolymer (SBBS), styrene-butadiene diblock copolymers, hydrogenated styrene-butadiene block copolymers, hydrogenated styrene-isoprene block copolymers, hydrogenated styrene-butadiene random copolymers, styrene-maleic anhydride copolymers, and the like. Specific examples of styrene resins include hydrogenated styrene thermoplastic elastomers "H1041", "Tuftec H1043", "Tuftec P2000" and "Tuftec MP10" (manufactured by Asahi Kasei Corporation); epoxidized styrene-butadiene thermoplastic elastomer "Epofriend AT501", "CT310" (manufactured by Daicel); modified styrene elastomer having hydroxyl group "Septon HG252" (manufactured by Kuraray); modified styrenic elastomer having carboxyl group "Tuftec N503M", modified styrene having amino group Elastomer "Tuftec N501", modified styrene elastomer "Tuftec M1913" (manufactured by Asahi Kasei Chemicals Corporation) having an acid anhydride group; unmodified styrene elastomer "Septon S8104" (manufactured by Kuraray Co., Ltd.); styrene-ethylene/butylene-styrene block Examples thereof include copolymers “FG1924” (manufactured by Kraton) and “EF-40” (manufactured by Cray Valley).

The number average molecular weight (Mn) of the elastomer is preferably 1,000 or more, more preferably 1,500 or more, still more preferably 3,000 or more, particularly preferably 5,000 or more, and preferably 1,000,000 or less, more preferably 900. ,000 or less. The number average molecular weight (Mn) can be measured in terms of polystyrene using GPC (gel permeation chromatography).

The content of the component (E) is preferably 1% by mass or more, more preferably 2% by mass, when the non-volatile component in the resin composition layer is 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention. Above, 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.

-(F) Curing accelerator-
The resin composition may contain (F) a curing accelerator as the (F) component. Examples of (F) curing accelerators include phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, guanidine curing accelerators, metal curing accelerators, and the like. , an imidazole-based curing accelerator is preferred, and an amine-based curing accelerator is more preferred. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

Phosphorus curing accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

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

Examples of imidazole curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and the like, and adducts of imidazole compounds and epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

As the imidazole-based curing accelerator, a commercially available product may be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Guanidine curing accelerators include, for example, 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-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like, with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being preferred.

Metal-based curing accelerators include, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. organic zinc complexes such as iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; organic manganese complexes such as manganese (II) acetylacetonate; Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

(F) The content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.01% by mass or more, and more preferably It is 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.

-(G) polymerization initiator-
The resin composition layer may contain (G) a polymerization initiator as the (G) component. By containing the polymerization initiator (G), it is possible to cure the component (D) in particular.

Although the type of polymerization initiator is not particularly limited, cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydro Examples include radical generators such as peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, and 2,3-dimethyl-2,3-diphenylbutane. These may be used singly or in combination of two or more.

(G) A polymerization initiator may be a commercially available product. Commercially available products include "Perhexin 25B" manufactured by NOF Corporation.

(G) The content of the polymerization initiator is preferably 0.01% by mass or more, more preferably 0.01% by mass or more, when the non-volatile component in the resin composition layer is 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention. is 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.

-(H) Other additives-
The resin composition layer may further contain other additives as optional components in addition to the components described above. Examples of such additives include resin additives such as thickeners, antifoaming agents, leveling agents, and adhesiveness imparting agents. These additives may be used singly or in combination of two or more. Each content can be appropriately set by those skilled in the art.

The resin composition layer may further contain any solvent as a volatile component. The viscosity of the varnish can be adjusted by adding a solvent to the resin composition used for forming the resin composition layer. Examples of solvents include organic solvents. However, it is preferable that toluene is not contained, and the content of toluene is 0.1% by mass or less and 0.01% by mass or less, 0.001% by mass or less, or 0.01% by mass or less when the entire resin composition layer is 100% by mass. It is preferably 0001% by mass or less.

Examples of organic solvents include ketones such as methyl ethyl ketone (MEK) and cyclohexanone, aromatic hydrocarbons such as xylene and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, di Glycol ethers such as propylene 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 ethyl diglycol acetate, octane, decane, etc. and petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. These are used individually by 1 type or in combination of 2 or more types.

From the viewpoint of improving the embedding property and the uniformity of the thickness of the insulating layer, the resin composition layer is adjusted to increase the melt viscosity by adjusting the amount of the solvent in the resin composition layer in addition to adjusting the specific surface area of the inorganic filler. adjusted so that the maximum value of tan δ is 1.0 or more and 2.0 or less. The amount of solvent (residual solvent amount) in the resin composition layer is preferably 3% by mass or less, more preferably 2.5% by mass or less, still more preferably 2% by mass or less, and even more preferably 1.5% by mass. Below, particularly preferably, it is 1% by mass or less. Although the lower limit is not particularly limited, it may be 0.0001% by mass or more.

In the dynamic viscoelasticity measurement of the resin composition layer at 60° C. to 200° C., the maximum value of tan δ at 100° C. or higher is 1.0 or more, preferably 1.1 or more, from the viewpoint of improving embeddability. , more preferably 1.3 or more. The maximum value of tan δ is 2.0 or less, preferably 1.9 or less, more preferably 1.8 or less, from the viewpoint of improving the uniformity of the thickness of the insulating layer. The maximum value of tan δ can be measured according to the method described in Examples below.

The thickness of the resin composition layer is preferably 30 μm or less, more It is preferably 25 μm or less, more preferably 20 μm or less. The lower limit of the thickness of the resin composition layer can be usually 5 μm or more, 10 μm or more, or the like, from the viewpoint of enhancing insulation reliability.

<Other layers>
In one embodiment, the resin sheet may further contain other layers as necessary. Such other layers include, for example, a protective film provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, the surface of the resin composition layer can be prevented from being dusted or scratched.

<Method for manufacturing resin sheet>
For the resin sheet, for example, a resin varnish is prepared by dissolving a resin composition in an organic solvent, the resin varnish is applied onto a support using a die coater or the like, and dried to form a resin composition layer. It can be manufactured by As for the organic solvent, those mentioned above can be used.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, drying at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes The resin composition layer can be formed.

The resin sheet can be wound into a roll and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

<Physical properties and applications of the resin sheet>
The resin sheet of the present invention is a resin sheet for forming an insulating layer using vacuum press treatment, and includes a support and a resin composition layer provided on the support, wherein the support comprises a resin composition. The resin composition layer has (A) an inorganic filler with a specific surface area of 10 m ² /g or more. In the dynamic viscoelasticity measurement of the resin composition layer at 60°C to 200°C, the maximum value of tan δ at 100°C or higher is 1.0 or more and 2.0 or less. By forming an insulating layer by vacuum pressing using such a resin sheet, it is possible to realize an insulating layer that is excellent in embedding properties and thickness uniformity, and is also excellent in insulating properties.

The resin composition layer of the resin sheet and the circuit board are laminated by vacuum pressing, and the resin composition layer is heat-cured at 100° C. for 30 minutes and then at 200° C. for 120 minutes. It exhibits excellent embeddability. Therefore, the cured product provides an insulating layer with excellent embedding properties. Specifically, the resin composition layer of the resin sheet is a glass cloth base epoxy resin double-sided copper having circuit conductors (copper) formed on both sides with a wiring pattern of 1 mm square grid (remaining copper rate is 59%) It is laminated on a clad laminate (hereinafter referred to as "copper-clad laminate"). After laminating the resin composition layer on the copper-clad laminate, the resin composition layer is thermally cured by vacuum pressing under the above thermal curing conditions to obtain an insulating layer. After etching the support, the embedding property of the resin composition layer in the wiring pattern of 1 mm square grid was observed using an FIB-SEM composite apparatus, and the grid pattern was embedded with the resin composition layer. The evaluation of embeddability can be measured according to the method described in Examples below.

The resin composition layer of the resin sheet and the circuit board are laminated by vacuum pressing, and the resin composition layer is heat-cured at 100° C. for 30 minutes and then at 200° C. for 120 minutes. It exhibits excellent insulation reliability. Therefore, the cured product provides an insulating layer with excellent insulating reliability. Specifically, the resin composition layer of the resin sheet is a glass cloth base epoxy resin double-sided copper having circuit conductors (copper) formed on both sides with a wiring pattern of 1 mm square grid (remaining copper rate is 59%) It is laminated on a clad laminate (hereinafter referred to as "copper-clad laminate"). After laminating the resin composition layer on the copper-clad laminate, the resin composition layer is thermally cured by vacuum pressing under the above thermal curing conditions to obtain an insulating layer. After peeling off the support, electrolytic plating is performed to obtain a conductor layer on the insulating layer. Insulation after 100 hours under the conditions of 110°C, 85% relative humidity, and 20V DC voltage applied using a highly accelerated life test equipment with the conductor layer side as the + electrode and the copper-clad laminate side as the - electrode. The resistance value is measured 6 times with an electrochemical migration tester. At this time, the insulation resistance value of at least one test piece is preferably 1.00×10 ⁸ Ω or more, more preferably 1.00×10 ⁹ Ω or more. Also, the average value of the insulation resistance values of the six test pieces is preferably 1.00×10 ⁸ Ω or more, more preferably 1.00×10 ⁹ Ω or more. Evaluation of insulation reliability can be measured according to the method described in the examples below.

By using the resin sheet of the present invention to form an insulating layer by vacuum pressing, an insulating layer exhibiting good embeddability 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 a vacuum press process (for forming an insulating layer using a vacuum press process). The resin sheet of the present invention includes a support containing metal foil, and the metal foil can be used to form a conductor layer. Therefore, the resin sheet of the present invention is a resin sheet for forming both an insulating layer and a conductor layer using a vacuum press process in the manufacture of a printed wiring board (a resin sheet for forming an insulating layer and a conductor layer using a vacuum press process). for) can be suitably used. The resin sheet of the present invention can be suitably used to form an insulating layer (and conductor layer) of a printed wiring board, preferably an interlayer insulation layer (and conductor layer) of a printed wiring board. In the present invention, the term "printed wiring board" also includes rewiring boards for semiconductor packages.

[Printed wiring board, method for manufacturing printed wiring board]
The printed wiring board of the present invention includes an insulating layer comprising a cured product of the resin composition layer of the resin sheet of the present invention.

A printed wiring board can be manufactured, for example, using the resin sheet described above by a method including the following steps (I) and (II).
(I) Step of laminating a resin sheet on the inner layer substrate by vacuum pressing (II) Step of thermosetting the resin composition layer to form an insulating layer

The "inner layer substrate" used in step (I) is a member that serves as a printed wiring board substrate, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc. The substrate may also have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate having conductor layers (circuits) formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board." Further, an intermediate product on which an insulating layer and/or a conductor layer are to be further formed when manufacturing a printed wiring board is also included in the "inner layer substrate" as used in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components can be used.

The lamination of the inner layer substrate and the resin sheet is carried out by vacuum pressing so that the resin composition layer of the resin sheet is bonded to the inner layer substrate. By laminating the inner layer substrate and the resin composition layer by vacuum pressing, it is possible to improve dielectric properties, mechanical strength, and electrical properties.

First, the inner layer substrate and the resin sheet are set in a vacuum press so that the resin composition layer of the resin sheet and the inner layer substrate are bonded. Next, a vacuum press process is performed to heat and pressure-bond the inner layer substrate and the resin composition layer under reduced pressure conditions. The vacuum press treatment is preferably vacuum heat press treatment (vacuum hot press treatment) in which heat is applied.

The inner layer substrate and the resin sheet are preferably set in a vacuum press device via cushion paper, a metal plate such as a stainless steel plate (SUS plate), a release film, or the like.

The vacuum press treatment can be performed using a conventionally known vacuum press apparatus that presses the inner layer substrate and the resin sheet from both sides with heated metal plates such as SUS plates. Examples of commercially available vacuum press machines include "VH1-1603" manufactured by Kitagawa Seiki Co., Ltd., and the like.

The vacuum press treatment may be performed only once, or may be performed repeatedly two or more times. When repeated two or more times, the compression pressure, heating temperature, pressing time, etc. may be the same or different.

In the vacuum press treatment, the compression pressure (pressing force) is preferably 0.49 MPa or more, more preferably 0.98 MPa or more, and preferably 7.9 MPa or less, more preferably 5.9 MPa or less.

In vacuum press processing, the pressure of the atmosphere, that is, the pressure (degree of pressure reduction) in the chamber in which the laminated structure to be processed is stored is preferably 3×10 ⁻² MPa or less, more preferably 1×10 ^{− 2} MPa or less. Although the lower limit is not particularly limited, it may be 1×10 ⁻¹⁰ MPa or more.

In the vacuum press treatment, the heating temperature varies depending on the composition of the resin composition layer, but is usually 150° C. or higher, preferably 160° C. or higher, more preferably 170° C. or higher, or 180° C. or higher. Although the upper limit of the heating temperature is not particularly limited, it can usually be 240° C. or lower. In addition, from the viewpoint of obtaining the effect of the present invention remarkably, the vacuum press treatment is performed while increasing the temperature stepwise or continuously and/or while decreasing the temperature stepwise or continuously. good too. Moreover, as will be described later, the insulating layer may be formed by thermally curing the resin composition layer by heating in the vacuum press treatment.

In the vacuum press treatment, the press time is preferably 5 minutes or longer, more preferably 10 minutes or longer, and even more preferably 15 minutes or longer. Although the upper limit is not particularly limited, it is preferably 300 minutes or less, more preferably 200 minutes or less, and still more preferably 150 minutes or less.

After laminating a resin sheet on the inner layer substrate by vacuum pressing, in step (II), the resin composition layer is thermally cured to form an insulating layer. As a method for thermosetting the resin composition layer, for example, in the case of performing a press treatment by a vacuum heat press treatment, a method of thermosetting the resin composition layer using the heat during pressing to form an insulating layer can be mentioned. be done.

The thermosetting conditions for the resin composition layer are not particularly limited, and conditions that are commonly used for forming insulating layers of printed wiring boards may be used.

For example, although the thermosetting conditions for 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 still more preferably 170°C to 210°C. °C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, even more preferably 15 minutes to 100 minutes.

Before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is cured at a temperature of 50° C. or higher and less than 120° C. (preferably 60° C. or higher and 115° C. or lower, more preferably 70° C. or higher and 110° C. or lower). Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes).

The inventors of the present invention have confirmed that the vacuum press treatment sometimes deteriorates the uniformity of the thickness of the insulating layer due to resin flow during lamination of the resin sheets, as compared with the vacuum lamination method. In this regard, by adjusting the residual solvent amount in addition to the specific surface area of the inorganic filler in the resin composition layer and setting the maximum value of tan δ to 1.0 or more and 2.0 or less, the insulation after the vacuum press treatment Improved uniformity of layer thickness can be achieved. Specifically, the variation in the thickness of the insulating layer after the hot press treatment is preferably less than ±20%, more preferably less than ±15%, and still more preferably ±10% or less with respect to the reference thickness of the insulating layer. is. In other words, it is preferable that the insulating layer have a thickness standard such that the variation in thickness is within the above range. The thickness criterion can usually be the design thickness of the insulating layer. The lower limit can be 0%, ±0.1% or more, and the like. Evaluation of the thickness of the insulating layer after the vacuum press treatment can be measured according to the method described in Examples below.

Since the support of the resin sheet used in the present invention includes a metal foil, the step (III) may include a step of forming a circuit by a subtractive method or a modified semi-additive method.

In step (III), a substrate (metal foil) can be used to form a circuit by a subtractive method or a modified semi-additive method.

In the subtractive method, unnecessary portions (non-circuit forming portions) of the metal foil are selectively removed by etching or the like to form circuits. Circuit formation by the subtractive method may be performed according to known procedures. For example, circuit formation by a subtractive method includes i) providing an etching resist on the surface of the metal foil (that is, the surface opposite to the surface bonded to the resin composition layer), ii) exposing the etching resist, It can be implemented by a method including developing to form a wiring pattern, iii) etching and removing the exposed metal foil portion, and iv) removing the etching resist.

In the modified semi-additive method, the non-circuit-forming part of the metal foil is protected with a plating resist, and a metal such as copper is thickly applied to the circuit-forming part by electroplating. The foil is etched away to form the circuit. Circuit formation by the modified semi-additive method may be carried out according to known procedures. For example, circuit formation by a modified semi-additive method includes i) providing a plating resist on the surface of the metal foil (that is, the surface opposite to the surface bonded to the resin composition layer), and ii) exposing the plating resist. , developing to form a wiring pattern, iii) electrolytic plating through the plating resist, iv) removing the plating resist, and v) etching and removing the metal foil other than the circuit forming portion. can be carried out by a method comprising: If the metal foil is thick, before step i) above, the entire surface of the metal foil is thinned by etching or the like so that the metal foil has a desired thickness (usually 5 μm or less, 4 μm or less, or 3 μm or less). good too.

When manufacturing a printed wiring board, (IV) a step of making a hole, and (V) a step of roughening the insulating layer may be further carried out. These steps (IV) to (V) may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards. If necessary, the steps (I) to (V) of forming the insulating layer and the conductor layer may be repeated to form a multilayer wiring board.

[Semiconductor device]
A 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.

Examples of semiconductor devices include various semiconductor devices used in electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

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 "conducting part" is a "part where an electric signal is transmitted on a printed wiring board", and the place may be a surface or an embedded part. Also, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. (BBUL) mounting method, anisotropic conductive film (ACF) mounting method, non-conductive film (NCF) mounting method, and the like. Here, "a mounting method using a build-up layer without bumps (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected." is.

EXAMPLES The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. In the description below, unless otherwise specified, "parts" and "%" mean "mass parts" and "mass%", respectively.

<Inorganic filler used>
Inorganic filler 1: N-phenyl- ³ -aminopropyltri The surface was treated with 2 parts of methoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573).
Inorganic filler 2: N-phenyl-3-aminopropyltrimethoxy is added to 100 parts of spherical silica (“SO-C1” manufactured by Admatechs, average particle diameter 0.25 μm, specific surface area 11.2 m ² /g) Surface-treated with 1 part of silane (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.).
Inorganic filler 3: N-phenyl-3-aminopropyltrimethoxy is added to 100 parts of spherical silica (“SO-C2” manufactured by Admatechs, average particle diameter 0.50 μm, specific surface area 5.8 m ² /g) Surface-treated with 1 part of silane (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.).

<Synthesis Example 1: Synthesis of polyimide resin 1>
A monomer composition obtained by mixing 49.6 g of BPADA, 50.4 g of BPPAN, and 40 g of toluene as a solvent in 400 g of N,N-dimethylacetamide (hereinafter also referred to as "DMAc") as a solvent, The mixture was stirred and reacted at normal temperature and atmospheric pressure for 3 hours. This gave a polyamic acid solution.

Subsequently, after raising the temperature of the polyamic acid solution, the condensed water was azeotropically removed together with toluene under a nitrogen stream while maintaining the temperature at about 160°C. It was confirmed that a predetermined amount of water was accumulated in the water content receiver, and that water was no longer seen to flow out. After confirmation, the reaction solution was further heated and stirred at 200° C. for 1 hour. It was then cooled. As a result, a varnish containing 20% by mass of polyimide resin 1 as a non-volatile component was obtained.

Polyimide resin 1 was presumed to contain a structural unit represented by the following formula (e1a) from the above reaction pathway. Also, from the above reaction pathway, it was presumed that the polyimide resin 1 contained a first skeleton derived from BPADA and a second skeleton derived from BPPAN.

<Synthesis Example 2: Synthesis of Elastomer 1>
G-3000 (bifunctional hydroxyl group-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl group equivalent = 1798 g / eq., solid content 100% by mass: manufactured by Nippon Soda Co., Ltd.) 50 g and Ipsol 150 in a reaction vessel (Aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) 23.5 g and dibutyltin laurate 0.005 g were mixed and uniformly dissolved. When the mixture became uniform, the temperature was raised to 50° C., and 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent=87.08 g/eq.) was added with further stirring, and the reaction was carried out for about 3 hours. The reaction was then allowed to cool to room temperature before adding 8.96 g of benzophenonetetracarboxylic dianhydride (anhydride equivalent = 161.1 g/eq.), 0.07 g of triethylenediamine, and ethyl diglycol. 40.4 g of acetate (manufactured by Daicel) was added, the temperature was raised to 130° C. with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ⁻¹ was confirmed by FTIR. Confirmation of the disappearance of the NCO peak was regarded as the end point of the reaction, and the reactant was cooled to room temperature and filtered through a 100-mesh filter cloth to obtain elastomer 1 having an imide skeleton, a urethane skeleton, and a butadiene skeleton.
Viscosity: 7.5 Pa s (25°C, E-type viscometer)
Acid value: 16.9mgKOH/g
Solid content: 50% by mass
Number average molecular weight: 13723
Glass transition temperature: -10°C
Content of polybutadiene structural portion: 50/(50+4.8+8.96)×100=78.4% by mass

<Example 1: Preparation of resin composition 1>
Bixylenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent of about 185) 5 parts, naphthalene type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V", epoxy equivalent of about 332) 5 parts, cyclohexane type epoxy resin (Mitsubishi Kagaku Co., Ltd. "ZX1658GS", epoxy equivalent about 135) 2 parts, phenoxy resin (Mitsubishi Chemical Co., Ltd. "YX7553BH30", 1:1 solution of cyclohexanone:methyl ethyl ketone (MEK) with a solid content of 30% by mass, Mw = 35000) 10 parts , and 10 parts of cyclohexanone in a mixed solvent while stirring. After cooling to room temperature, 4.5 parts of an active ester curing agent ("HPC-8000L-65TM" manufactured by DIC, active group equivalent of about 220, nonvolatile component of 65% by mass toluene:MEK 1:1 solution), 35 parts of the inorganic filler 1 and 0.1 part of an amine-based curing accelerator (4-dimethylaminopyridine (DMAP)) were mixed, and after uniformly dispersing with a high-speed rotating mixer, a cartridge filter ("SHP020" manufactured by ROKITECHNO) was added. ) to prepare a resin composition 1.

<Example 2: Preparation of resin composition 2>
In Example 1, 4.5 parts of an active ester curing agent ("EXB-8000L-65TM" manufactured by DIC Corporation, an active group equivalent of about 220, a 1:1 solution of toluene:MEK with a nonvolatile content of 65% by mass) was added to an active The ester curing agent ("HP-B-8151-62T" manufactured by DIC, active group equivalent weight 238, solid content 62% toluene solution) was changed to 4.7 parts. A resin composition 2 was prepared in the same manner as in Example 1 except for the above matters.

<Example 3: Preparation of resin composition 3>
In Example 3, the inorganic filler 1 35 parts was changed to the inorganic filler 2 50 parts. A resin composition 3 was prepared in the same manner as in Example 1 except for the above matters.

<Example 4: Preparation of resin composition 4>
In Example 1, 4.5 parts of an active ester curing agent ("EXB-8000L-65TM" manufactured by DIC Corporation, an active group equivalent of about 220, a 1:1 solution of toluene:MEK with a nonvolatile content of 65% by mass) was added to maleimide. Change to 10 parts of the compound ("BMI-689" manufactured by Designer Molecules),
The amount of amine-based curing accelerator (4-dimethylaminopyridine (DMAP)) was changed from 0.1 part to 0.05 part,
Furthermore, 0.1 part of a polymerization initiator (“Perhexyne 25B” manufactured by NOF Corporation) was used.
A resin composition 4 was prepared in the same manner as in Example 1 except for the above matters.

<Example 5: Preparation of resin composition 5>
In Example 4, 10 parts of a maleimide compound (“BMI-689” manufactured by Designer Molecules) was added to a styrene-modified polyphenylene ether resin (“OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Co., Ltd., Mn = 1200, solid content 65 mass % toluene solution) to 10 parts. Resin composition 5 was prepared in the same manner as in Example 4 except for the above matters.

<Example 6: Preparation of resin composition 6>
In Example 4, 4.5 parts of an active ester curing agent ("EXB-8000L-65TM" manufactured by DIC Corporation, an active group equivalent of about 220, a 1:1 solution of toluene:MEK with a nonvolatile content of 65% by mass) was used. board. A resin composition 6 was prepared in the same manner as in Example 4 except for the above matters.

<Example 7: Preparation of resin composition 7>
In Example 6, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, cyclohexanone with a solid content of 30% by mass: methyl ethyl ketone (MEK) 1:1 solution, Mw = 35000) was added to 10 parts of the polyimide resin obtained in Synthesis Example 1. 1 (20% by mass of non-volatile components) was used. Resin composition 7 was prepared in the same manner as in Example 6 except for the above matters.

<Example 8: Preparation of resin composition 8>
In Example 6, 10 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of cyclohexanone:methyl ethyl ketone (MEK) with a solid content of 30% by mass, Mw = 35000) was added to the elastomer obtained in Synthesis Example 2 ( 6 parts of non-volatile components (50% by mass) were used. A resin composition 8 was prepared in the same manner as in Example 6 except for the above matters.

<Example 9: Preparation of resin composition 9>
10 parts of a maleimide compound ("BMI-689" manufactured by Designer Molecules), a biphenyl skeleton-containing maleimide resin ("MIR-3000" manufactured by Nippon Kayaku Co., Ltd., a 1:1 solution of toluene:MEK with a nonvolatile content of 70% by mass) 10 parts, styrene-modified polyphenylene ether resin (manufactured by Mitsubishi Gas Chemical Co., Ltd. "OPE-2St 1200", Mn = 1200, solid content 65% by mass toluene solution) 10 parts, hydrogenated styrene thermoplastic elastomer (manufactured by Asahi Kasei Corporation "H1043 6 parts of styrene/ethylene-butylene-butadiene ratio=67/33) were heated and dissolved in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone with stirring. After cooling to room temperature, 50 parts of the inorganic filler 1 and 0.1 part of a polymerization initiator ("Perhexin 25B" manufactured by NOF Corporation) were mixed therein, and after uniformly dispersing with a high-speed rotating mixer, the cartridge was prepared. A resin composition 9 was prepared by filtering with a filter (“SHP020” manufactured by ROKITECHNO).

<Example 10: Preparation of resin composition 10>
In Example 9, the inorganic filler 1 50 parts was changed to the inorganic filler 2 65 parts. A resin composition 10 was prepared in the same manner as in Example 9 except for the above matters.

<Example 11: Preparation of resin composition 11>
In the preparation of Example 9, 10 parts of a styrene-modified polyphenylene ether resin (“OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Co., Ltd., Mn = 1200, a toluene solution with a solid content of 65% by mass) was added to a vinyl group-containing resin (Nippon Steel Chemical &Materials "ODV-XET-X04", weight average molecular weight 3110, 65% by mass solution)) was changed to 10 parts. A resin composition 11 was prepared in the same manner as in Example 9 except for the above matters.

<Example 12: Preparation of resin composition 12>
In Example 1, 4.5 parts of an active ester curing agent ("EXB-8000L-65TM" manufactured by DIC Corporation, an active group equivalent of about 220, a 1:1 solution of toluene:MEK with a nonvolatile content of 65% by mass) was added to triazine. It was changed to 5 parts of a skeleton-containing phenolic resin ("LA7054" manufactured by DIC, a MEK solution having a hydroxyl equivalent of about 125 and a solid content of 60%). A resin composition 12 was prepared in the same manner as in Example 1 except for the above matters.

<Comparative Example 1: Preparation of Resin Composition 13>
In Example 1, 35 parts of inorganic filler 1 was changed to 35 parts of inorganic filler. A resin composition 13 was prepared in the same manner as in Example 1 except for the above matters.

<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. A resin composition 14 was prepared in the same manner as in Example 1 except for the above matters.

<Comparative Example 3: Preparation of Resin Composition 15>
In Example 9, the inorganic filler 1 50 parts was changed to the inorganic filler 3 50 parts. A resin composition 15 was prepared in the same manner as in Example 9 except for the above matters.

<Measurement of thickness of resin composition layer, etc.>
The thickness of the resin composition layer and the like was measured using a contact film thickness gauge (MCD-25MJ, manufactured by Mitutoyo Corporation).

<Preparation of resin sheet A>
As a support, an ultra-thin copper foil (MW-G manufactured by Mitsui Kinzoku Mining Co., Ltd. (single-layer copper foil with a thickness of 12 μm, an arithmetic average roughness (Ra) of 900 nm and a ten-point average roughness (Rz) of 8000 nm)). prepared. Resin compositions 1 to 15 are uniformly coated on an ultrathin copper foil of a support with a die coater so that the thickness of the resin composition layer after drying is 15 μm, and dried at 70° C. to 120° C. for 7 minutes. By doing so, a resin composition layer was obtained on the support. Next, on the surface of the resin composition layer that is not bonded to the support, a rough surface of a polypropylene film (manufactured by Oji F-Tex Co., Ltd. "Alphan MA-411", thickness 15 μm) as a protective film is bonded to the resin composition layer. It was laminated so as to As a result, a resin sheet A consisting of an ultrathin copper foil (support), a resin composition layer, and a protective film was obtained. The arithmetic mean roughness (Ra) and ten-point mean roughness (Rz) of the ultra-thin copper foil were measured using a non-contact surface roughness meter.

<Measurement of tan δ in dynamic viscoelasticity>
The dynamic viscoelasticity of the resin composition layer of the resin sheet A was measured using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM). Using a parallel plate with a diameter of 18 mm, 1 g of a sample resin composition sampled from the resin composition layer was heated from a starting temperature of 60° C. to 200° C. at a heating rate of 5° C./min. The dynamic viscoelastic modulus was measured under the measurement conditions of 5° C., frequency of 1 Hz, and strain of 1 deg, and the obtained values of E′ and E″ were used to calculate tan δ using the following formula. Then, the maximum value of tan δ at 100°C or higher was determined.
tan δ=E''/E'

<Evaluation of insulation layer thickness (resin flow), insulation reliability, and embeddability after vacuum press treatment>
1) Lamination of laminate sheets on copper-clad laminates using vacuum press As copper-clad laminates, circuit conductors (copper) formed with a 1 mm square grid wiring pattern (remaining copper rate is 59%) are placed on both sides. A glass cloth-based epoxy resin double-sided copper clad laminate (copper foil thickness 12 μm, substrate thickness 0.15 mm, “HL832NSF LCA” manufactured by Mitsubishi Gas Chemical Co., Ltd., size 255×340 mm) was prepared. Both surfaces of the inner layer circuit board were subjected to a copper surface roughening treatment (copper etching amount: 0.5 μm) using “CZ8201” manufactured by MEC. The protective film was peeled off from the resin sheet A to expose the resin composition layer. Then, using a vacuum hot press machine (manufactured by Kitagawa Seiki Co., Ltd., VH1-1603), both surfaces of the copper-clad laminate were laminated so that the exposed resin composition layer was in contact with the copper-clad laminate. Pressing conditions are under reduced pressure of 1×10 ⁻³ MPa or less, under pressure conditions of 20 kgf/cm ² , and as heating conditions, the first stage pressing is performed at a temperature of 100° C. for 30 minutes and 2 The first step of pressing was performed at a temperature of 190° C. for 120 minutes. After the resin composition layer was cured by heating with a press, a cured substrate A was obtained by peeling off the support.

2) Electroplating A chemical solution manufactured by Atotech Japan Co., Ltd. was used to carry out an electrolytic copper plating process under the condition that the via holes were filled with copper. After that, as a resist pattern for patterning by etching, a land pattern with a diameter of 1 mm connected to the lower layer conductor and a circular conductor pattern with a diameter of 10 mm not connected to the lower layer conductor were used on the surface of the insulating layer with a thickness of 10 μm. A conductor layer having a thickness of land and a conductor pattern was formed. Annealing was then performed at 200° C. for 90 minutes. This substrate was designated as "insulation evaluation substrate A".

3) Evaluation of insulation reliability of the insulating layer The circular conductor side with a diameter of 10 mm on the insulation evaluation board A was used as a + electrode, and the lattice circuit conductor (copper) side of the inner layer circuit board connected to the land with a diameter of 1 mm was used as a - electrode. , Using a highly accelerated life test device ("PM422" manufactured by ETAC), the insulation resistance value when 100 hours have passed under the conditions of 110 ° C., 85% relative humidity, and 20 V DC voltage application was measured by an electrochemical migration tester ( Measured with "ECM-100" manufactured by J-RAS. This measurement was performed 6 times, and the following evaluation criteria and insulation resistance values are shown in the table below. The insulation resistance values listed in the table below are the average values of the insulation resistance values of six test pieces.
◯: The average value of the insulation resistance values of the 6 test pieces is 1.00×10 ⁹ Ω or more.
Δ: The average insulation resistance value of the 6 test pieces is 1.00×10 ⁸ Ω or more and less than 1.00×10 ⁹ Ω.
×: The average insulation resistance value of the 6 test pieces is less than 1.00×10 ⁸ Ω.

4) Evaluation of the thickness of the insulating layer (resin flow) after vacuum press processing After etching the ultra-thin copper foil of the cured substrate A, the cross section was observed using a FIB-SEM composite device ("SMI3050SE" manufactured by SII Nanotechnology). was performed, and the thickness of the insulating layer after the vacuum press treatment was evaluated according to the following criteria.
◯: The thickness of the insulating layer is less than 10 μm±20% when the reference thickness of the insulating layer is 10 μm.
x: The thickness of the insulating layer is 10 μm±20% or more when the standard of the thickness of the insulating layer is 10 μm.

5) Evaluation of embeddability of insulating layer after vacuum press treatment After etching the ultra-thin copper foil of the cured substrate A, using a FIB-SEM composite device ("SMI3050SE" manufactured by SII Nano Technology Co., Ltd.), a 1 mm square grid. The embeddability of the resin composition layer in the wiring pattern was observed and evaluated according to the following criteria.
◯: The wiring pattern is embedded with an insulating layer.
x: Voids are generated due to poor embedding.

＊（Ａ）成分の含有量は、樹脂組成物中の不揮発成分を１００質量％とした場合の含有量を表す。

* The content of component (A) represents the content when the non-volatile component in the resin composition is 100% by mass.

Claims (9)

A resin sheet for forming an insulating layer using a vacuum press process,
comprising a support and a resin composition layer provided on the support;
The support has a metal foil with an arithmetic mean roughness (Ra) of more than 300 nm on the side bonded to the resin composition layer,
The resin composition layer contains (A) an inorganic filler having a specific surface area of 10 m ² /g or more,
The resin sheet, wherein the maximum value of tan δ at 100°C or higher is 1.0 or more and 2.0 or less in the dynamic viscoelasticity measurement of the resin composition layer at 60°C to 200°C. 2. The resin sheet according to claim 1, wherein the resin composition layer has a thickness of 30 [mu]m or less. 3. The resin sheet according to claim 1, wherein the resin composition layer contains any one of active ester resin, maleimide resin and vinyl resin. The resin sheet according to any one of claims 1 to 3, wherein the content of component (A) is 73% by mass or less when the non-volatile components in the resin composition layer are taken as 100% by mass. The resin sheet according to any one of claims 1 to 4, wherein the metal foil comprises copper foil. The resin sheet according to any one of claims 1 to 5, wherein the support has a thickness of 9 µm or more. A printed wiring board comprising an insulating layer comprising a cured product of the resin composition layer of the resin sheet according to any one of claims 1 to 6. A semiconductor device comprising the printed wiring board according to claim 7 . (I) a step of laminating the resin sheet according to any one of claims 1 to 6 on an inner layer substrate by vacuum pressing; and (II) thermosetting the resin composition layer to form an insulating layer. forming,
A method of manufacturing a printed wiring board, comprising: