JP2019035051A - Resin composition - Google Patents

Abstract

To provide a resin composition that makes it possible to obtain an insulating layer having a low dielectric constant and being excellent in temperature stability of dielectric loss tangent.SOLUTION: A resin composition contains (A) an epoxy resin, (B) a maleimide compound, (C) an inorganic filler, and (D) a fluorine-based filler, with the content of (B) component being 10 mass%-70 mass% to (A) component 100 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a sheet-like laminated material, a circuit board, and a semiconductor device.

  As a circuit board manufacturing technique, a build-up manufacturing method in which an insulating layer and a conductor layer are alternately stacked on an inner layer substrate is known. The insulating layer is generally formed by obtaining a resin composition layer as a coating film of a resin varnish containing the resin composition and curing the resin composition layer. For example, Patent Document 1 discloses a resin composition containing an epoxy resin, a curing agent, and a fluororesin filler, and the content of the fluororesin filler is 50 with respect to the solid content of the resin composition. A resin composition characterized in that it is from mass% to 85 mass% is described.

Japanese Patent Laid-Open No. 2006-166347

  In order to form an insulating layer, the resin composition generally contains a large amount of thermosetting resin from the viewpoint of achieving high insulating performance. As this thermosetting resin, it is usual to use an epoxy resin. On the other hand, the present inventor examined applying a fluorine-based filler to a resin composition containing an epoxy resin in order to develop an insulating layer having a low dielectric constant.

  The inventor further tried to apply the resin composition containing the epoxy resin and the fluorine-based filler as described above to the insulating layer of the radar antenna circuit board. However, it has been found that the detectable range of a radar equipped with this antenna circuit board changes depending on the temperature. For example, even if the radar has a wide detection range of 20 m at a certain temperature, the detection range at another temperature may be as narrow as 5 m.

  The present invention was devised in view of the above problems, and when provided on an antenna circuit board of a radar, an insulating layer having a low dielectric constant capable of suppressing changes in the radar detectable range due to temperature can be obtained. An object of the present invention is to provide a resin composition that can be obtained; a sheet-like laminated material containing the resin composition; a circuit board and a semiconductor device including an insulating layer made of a cured product of the resin composition.

The inventor has intensively studied to solve the above problems. As a result, the present inventor has obtained knowledge that the cause of the change in the detectable range of the radar due to the temperature is the temperature stability of the dielectric loss tangent of the insulating layer. Specifically, when the dielectric loss tangent of the insulating layer of the radar antenna circuit board changes with temperature, the magnitude of the loss of the antenna circuit board changes with temperature, so the sensitivity of the antenna circuit board changes with temperature, As a result, a change in the detectable range due to temperature occurred. Therefore, the present inventor has found that the above problem can be solved by a resin composition capable of obtaining an insulating layer excellent in temperature stability of dielectric loss tangent, and has completed the present invention.
That is, the present invention includes the following.

[1] A resin composition comprising (A) an epoxy resin, (B) a maleimide compound, (C) an inorganic filler, and (D) a fluorine-based filler,
(B) The resin composition whose quantity of a component is 10 mass%-70 mass% with respect to 100 mass% of (A) component.
[2] A resin composition comprising (A) an epoxy resin and (D) a fluorine-based filler,
The dielectric loss tangents at −10 ° C., 25 ° C. and 100 ° C. of the cured product obtained by heat-treating the resin composition at 200 ° C. for 90 minutes are respectively expressed as Df (−10 ° C.), Df (25 ° C.) and Df (100 ° C. )
The ratio Df (−10 ° C.) / Df (25 ° C.) of Df (−10 ° C.) to Df (25 ° C.) is 85% to 115%,
The resin composition whose ratio Df (100 degreeC) / Df (25 degreeC) of Df (100 degreeC) with respect to Df (25 degreeC) is 85%-115%.
[3] The resin composition according to [1], which contains (B) a maleimide compound.
[4] The resin composition according to any one of [1] to [3], wherein the component (D) is a fluorine-based polymer particle.
[5] The resin composition according to any one of [1] to [4], wherein the component (D) is polytetrafluoroethylene particles.
[6] The resin composition according to any one of [1] to [5], comprising (E) a resin having an unsaturated hydrocarbon group.
[7] The component (E) has one or more unsaturated hydrocarbon groups selected from the group consisting of an acryl group, a methacryl group, a styryl group, an allyl group, a vinyl group, and a propenyl group. Resin composition.
[8] The resin composition according to [6] or [7], wherein the component (E) has a vinyl group and a cyclic ether structure having a 5-membered ring or more.
[9] The resin composition according to any one of [1] to [8], which is used for forming an insulating layer of a circuit board.
[10] A sheet-like laminate material comprising the resin composition according to any one of [1] to [9].
[11] A circuit board including an insulating layer made of a cured product of the resin composition according to any one of [1] to [9].
[12] A semiconductor device comprising the circuit board according to [11].

  According to the present invention, when provided on an antenna circuit board of a radar, the resin composition capable of suppressing the change in the detectable range of the radar due to temperature and obtaining an insulating layer having a low dielectric constant; A circuit board and a semiconductor device including an insulating layer made of a cured product of the resin composition.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and exemplifications, and can be implemented with any modifications without departing from the scope of the claims of the present invention and the equivalents thereof.

  In the following description, the amount of each component in the resin composition is a value relative to 100% by mass of the nonvolatile component in the resin composition unless otherwise specified.

  In the following description, the term “dielectric constant” indicates a relative dielectric constant unless otherwise specified.

[1. Resin composition according to first embodiment]
[1.1. Outline of Resin Composition]
The resin composition according to the first embodiment of the present invention includes (A) an epoxy resin, (B) a maleimide compound, (C) an inorganic filler, and (D) a fluorine-based filler. Here, the term “fluorine-based” means containing a fluorine atom. The term “fluorine-based filler” refers to a filler that contains a compound containing a fluorine atom as a material. In this resin composition, the amount of (B) maleimide compound is in a predetermined range.

  A cured product of such a resin composition has a low dielectric constant. In addition, a cured product of such a resin composition is excellent in temperature stability of dielectric loss tangent. Therefore, by using the above resin composition, it is possible to suppress a change in the detectable range of the radar due to the temperature when it is provided on the antenna circuit board of the radar by being excellent in the temperature stability of the dielectric loss tangent, and the dielectric The desired effect of the present invention can be obtained that a resin composition capable of obtaining an insulating layer having a low rate can be realized.

[1.2. (A) Epoxy resin]
Examples of the epoxy resin as the component (A) include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, Trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak 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, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic Epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

  (A) As an epoxy resin, since the change of the characteristic by temperature is small, the epoxy resin which has cyclic structures, such as an alicyclic structure and an aromatic ring structure other than an epoxy group, is preferable. Among these, an aromatic epoxy resin is preferable from the viewpoint of reducing the average linear thermal expansion coefficient of the insulating layer. Here, the aromatic epoxy resin refers to an epoxy resin whose molecule contains an aromatic skeleton. The aromatic skeleton is a chemical structure generally defined as aromatic, and includes not only a monocyclic structure such as a benzene ring but also a polycyclic aromatic structure such as a naphthalene ring and an aromatic heterocyclic structure. Among these, from the viewpoint of remarkably obtaining the desired effect of the present invention, the (A) epoxy resin is bisphenol A type epoxy resin, bixylenol type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, naphthalene type 4 One or more epoxy resins selected from the group consisting of a functional epoxy resin and a naphthol type epoxy resin are preferable, and a xylenol type epoxy resin is particularly preferable.

  It is preferable that a resin composition contains the epoxy resin which has a 2 or more epoxy group in 1 molecule as (A) epoxy resin. From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule with respect to 100% by mass of the nonvolatile component (A) of the epoxy resin is preferably 50 masses. % Or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

  As the epoxy resin, an epoxy resin that is liquid at a temperature of 20 ° C. (hereinafter sometimes referred to as “liquid epoxy resin”) and an epoxy resin that is a solid at a temperature of 20 ° C. (sometimes referred to as “solid epoxy resin”). There is. The resin composition may contain only the liquid epoxy resin as the (A) epoxy resin, may contain only the solid epoxy resin, or contain a combination of the liquid epoxy resin and the solid epoxy resin. Also good. (A) By using a combination of a liquid epoxy resin and a solid epoxy resin as an epoxy resin, the flexibility of the resin composition layer can be improved, and the breaking strength of the cured product of the resin composition can be improved. .

  The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule, and more preferably an aromatic liquid epoxy resin having two or more epoxy groups in one molecule.

  Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, and ester skeletons. Preferred are cycloaliphatic epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having butadiene structure, glycidylamine type epoxy resin, bisphenol A type epoxy resin, bisphenol F type Epoxy resins, bisphenol AF type epoxy resins and naphthalene type epoxy resins are more preferred, and bisphenol A type epoxy resins are particularly preferred.

  Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC; “828US”, “jER828US”, “jER828EL”, “825” manufactured by Mitsubishi Chemical Corporation. "Epicoat 828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical; “630”, “630LSD” (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “ZX1059” (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; Nagase ChemteX Corporation "EX" made “721” (glycidyl ester type epoxy resin); “Celoxide 2021P” (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel; “PB-3600” (epoxy resin having a butadiene structure) manufactured by Daicel; “ZX1658”, “ZX1658GS” (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Kagaku Co., Ltd .; These may be used alone or in combination of two or more.

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

  Solid epoxy resins include bixylenol type epoxy resins, biphenyl aralkyl type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, Naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, bixylenol type epoxy resin, biphenyl More preferred are aralkyl type epoxy resins, naphthylene ether type epoxy resins, naphthalene type tetrafunctional epoxy resins and naphthol type epoxy resins. Le epoxy resins are particularly preferred.

  Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin) manufactured by DIC; “HP-4700” and “HP-4710” (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200" (dicyclopentadiene type epoxy resin) manufactured by DIC; “HP-7200HH”, “HP-7200H”, “EXA-7311”, “EXA-7311-G3”, “EXA-7311-G4”, “EXA-7311-G4S”, “HP6000” (manufactured by DIC) Naphthylene ether type epoxy resin) “EPPN-502H” (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Resin); “NC7000L” (naphthol novolak type epoxy resin) manufactured by Nippon Kayaku; “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenylaralkyl type epoxy resin) manufactured by Nippon Kayaku; Nippon Steel “ESN475V” (naphthol type epoxy resin) manufactured by Sumikin Chemical Co., Ltd .; “ESN485” (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; “YX4000H”, “YX4000”, “YL6121” (biphenyl) manufactured by Mitsubishi Chemical Corporation Type epoxy resin); “YX4000HK” (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical; “YX8800” (anthracene type epoxy resin) manufactured by Mitsubishi Chemical; “PG-100” and “CG” manufactured by Osaka Gas Chemical -500 "(bisphenol F type epoxy resin); “YL7760” (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical; “YL7800” (fluorene type epoxy resin) manufactured by Mitsubishi Chemical; “jER1010” (solid bisphenol A) manufactured by Mitsubishi Chemical Type epoxy resin); “jER1031S” (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used alone or in combination of two or more.

  (A) When using a combination of a liquid epoxy resin and a solid epoxy resin as the epoxy resin, their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1: 0.1 to 1:15, More preferably, it is 1: 0.5 to 1:10, and particularly preferably 1: 1 to 1: 8. When the mass ratio between the liquid epoxy resin and the solid epoxy resin is in the above range, preferable adhesiveness can be obtained when the adhesive is used in the form of an adhesive film. Moreover, when using it with the form of an adhesive film, sufficient flexibility is acquired and a handleability can be improved. Furthermore, the breaking strength of the cured product of the resin composition can be effectively increased.

  (A) The epoxy equivalent of an epoxy resin becomes like this. Preferably it is 50-5000, More preferably, it is 50-3000, More preferably, it is 80-2000, Most preferably, it is 110-1000. (A) When the epoxy equivalent of an epoxy resin exists in the said range, the crosslinked density of the hardened | cured material of a resin composition becomes sufficient, and an insulating layer with small surface roughness can be obtained. The epoxy equivalent is the mass of a resin containing 1 equivalent of an epoxy group, and can be measured according to JIS K7236.

  (A) The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and further preferably 400 to 1500 from the viewpoint of remarkably obtaining the desired effect of the present invention. The weight average molecular weight of a resin such as an epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

  The amount of the (A) epoxy resin in the resin composition is preferably 3% by mass or more with respect to 100% by mass of the nonvolatile component in the resin composition from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. More preferably, it is 5% by mass or more, particularly preferably 9% by mass or more, preferably 70% by mass or less, more preferably 50% by mass or less, and particularly preferably 30% by mass or less.

[1.3. (B) Maleimide compound]
The maleimide compound as the component (B) is a compound containing a maleimide group represented by the following formula (B1) in the molecule.

  (B) The number of maleimide groups per molecule of the maleimide compound may be 1, but is preferably 2 or more, preferably 10 or less, more preferably 6 or less, and particularly preferably 3 or less. . By using the (B) maleimide compound having two or more maleimide groups per molecule, the desired effect of the present invention can be remarkably obtained, and in particular, the temperature stability of the dielectric loss tangent of the cured product can be effectively improved. Can improve.

  (B) The maleimide compound preferably contains an aromatic skeleton in combination with a maleimide group. By using the (B) maleimide compound containing an aromatic skeleton, the desired effect of the present invention can be remarkably obtained, and in particular, the temperature stability of the dielectric loss tangent of the cured product can be effectively improved. In particular, the (B) maleimide compound preferably contains a benzene ring as an aromatic skeleton.

  (B) Examples of the maleimide compound include 4,4′-diphenylmethane bismaleimide, polyphenylmethane maleimide, phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4, 4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6′-bismaleimide- (2,2,4-trimethyl) hexane, 4,4′-diphenyl ether bismaleimide, 4,4 Examples include '-diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene and the like.

  From the viewpoint of remarkably obtaining the desired effect of the present invention, the (B) maleimide compound is particularly preferably a polyphenylmethane maleimide represented by the formula (B2) and a phenylene bismaleimide represented by the formula (B3). . In the formula (B2), n represents an integer of 0 or more.

  (B) Specific examples of the maleimide compound include “BMI-1000” manufactured by Daiwa Kasei Kogyo Co., Ltd., “BMI” (4,4′-diphenylmethane bismaleimide) manufactured by Kay Kasei Co., Ltd .; 2000 "(polyphenylmethane maleimide);" BMI-3000 "(m-phenylene bismaleimide) manufactured by Daiwa Kasei Kogyo Co., Ltd .;" BMI 4000 "manufactured by Daiwa Kasei Kogyo Co., Ltd. Diphenyl ether bismaleimide); “BMI5100” manufactured by Daiwa Kasei Kogyo Co., Ltd., “BMI-70” manufactured by Kay Chemical Co., Ltd. (3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide); “BMI-7000” (4-methyl-1,3-phenylenebismaleimide) manufactured by Daiwa Kasei Kogyo Co., Ltd .; “BMI-TMH” (1,6′-bismaleimide- (2,2,4-trimethyl) hexane) manufactured by Seiko Industry Co., Ltd .; “BMI-6000” (4,4′-diphenyl ether bismaleimide) manufactured by Daiwa Kasei Kogyo Co., Ltd. "BMI-8000" (4,4'-diphenylsulfone bismaleimide) manufactured by Daiwa Kasei Kogyo Co., Ltd .; 1,3-bis (3-maleimidophenoxy) benzene manufactured by Daiwa Kasei Kogyo Co .; 3-bis (4-maleimidophenoxy) benzene; “ANILIX-MI” manufactured by Mitsui Chemical Fine Co., Ltd. Moreover, (B) maleimide compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  (B) The maleimide compound can be produced, for example, by reacting maleic anhydride with a suitable amine compound.

  The amount of the (B) maleimide compound in the resin composition is preferably 10% by mass or more, more preferably 11% by mass or more, and particularly preferably 12% by mass or more, with respect to 100% by mass of the (A) epoxy resin. Preferably it is 70 mass% or less, More preferably, it is 69 mass% or less, Most preferably, it is 68 mass% or less. (B) When the amount of the maleimide compound is within the above range, the temperature stability of the dielectric loss tangent of the cured product of the resin composition can be improved.

  The amount of the (B) maleimide compound in the resin composition is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and particularly preferably 1% with respect to 100% by mass of the nonvolatile component in the resin composition. It is 0.0 mass% or more, preferably 7.0 mass% or less, more preferably 6.7 mass% or less, and particularly preferably 6.2 mass% or less. (B) When the amount of the maleimide compound is in the above range, the desired effect of the present invention can be remarkably obtained, and in particular, the temperature stability of the dielectric loss tangent of the cured product can be effectively improved.

[1.4. (C) Inorganic filler]
Examples of the material of the inorganic filler as the component (C) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate , Titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferable from the viewpoint of remarkably obtaining the desired effect of the present invention. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Among these, spherical silica is preferable. (C) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types.

  Usually, the (C) inorganic filler is contained in the resin composition in the form of particles. (C) The average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. Preferably it is 5.0 micrometers or less, More preferably, it is 2.0 micrometers or less, More preferably, it is 1.0 micrometers or less. Moreover, (C) The average particle diameter of an inorganic filler exists in the said range, Usually, the circuit embedding property of a resin composition layer can be improved, or the surface roughness of an insulating layer can be made small.

  (C) Examples of commercially available inorganic fillers include “SP60-05” and “SP507-05” manufactured by Nippon Steel & Sumikin Materials; “YC100C”, “YA050C”, and “YA050C-MJE” manufactured by Admatechs. "YA010C"; Denka's "UFP-30"; Tokuyama's "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N"; Admatechs' "SC2500SQ" “SO-C4”, “SO-C2”, “SO-C1”; and the like.

  (C) The average particle diameter of particles such as inorganic fillers can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the particles is measured on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the average particle size can be obtained as the median diameter from the particle size distribution. As the measurement sample, particles in which particles are dispersed in a solvent such as water by ultrasonic waves can be preferably used. As the laser diffraction / scattering particle size distribution measuring apparatus, “LA-500” manufactured by Horiba, Ltd. or the like can be used.

  (C) The inorganic filler may be surface-treated with an arbitrary surface treatment agent. Examples of the surface treatment agent include coupling agents such as aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, titanate coupling agents; alkoxysilane compounds; organosilazane compounds; It is done. By performing the surface treatment with these surface treatment agents, the moisture resistance and dispersibility of the inorganic filler (C) can be improved.

  Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu. “KBE903” (3-aminopropyltriethoxysilane) manufactured by Chemical Industry Co., Ltd. “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “SZ-31” manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), “KBM-103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-4803” (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and the like. Moreover, a surface treating agent may be used individually by 1 type, and may be used in combination of 2 or more types.

The degree of the surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the (C) inorganic filler. Carbon content per unit surface area of the inorganic filler (C), (C) from the viewpoint of the dispersibility of the inorganic filler improved, preferably 0.02 mg / ^{m 2} or more, more preferably 0.1 mg / ^{m 2} or more, Particularly preferably, it is 0.2 mg / m ² or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the sheet form, the carbon amount is preferably 1 mg / m ² or less, more preferably 0.8 mg / m ² or less, particularly preferably. 0.5 mg / m ² or less.

  (C) The amount of carbon per unit surface area of the inorganic filler is determined by washing the surface-treated (C) inorganic filler with a solvent (for example, methyl ethyl ketone (hereinafter sometimes referred to as “MEK”)). Can be measured. Specifically, a sufficient amount of MEK and (C) the inorganic filler surface-treated with the surface treatment agent are mixed and ultrasonically cleaned at 25 ° C. for 5 minutes. Next, after removing the supernatant and drying the non-volatile components, the amount of carbon per unit surface area of the (C) inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. can be used.

  The amount of the (C) inorganic filler in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more with respect to 100% by mass of the nonvolatile component in the resin composition. Particularly preferably, it is 20% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, and particularly preferably 50% by mass or less. (C) Since the thermal expansion coefficient of the hardened | cured material of a resin composition can be made low because the quantity of an inorganic filler is more than the lower limit of the said range, the curvature of an insulating layer can be suppressed. Moreover, when the amount of (C) the inorganic filler is not more than the upper limit of the above range, the mechanical strength of the cured product of the resin composition can be improved, and in particular, the resistance to elongation can be increased.

[1.5. (D) Fluorine-based filler]
(D) The fluorine-type filler as a component is a filler which contains the compound containing a fluorine atom as a material. The fluorine-based filler is generally particles. Therefore, as the (D) fluorine-based filler, particles containing a compound containing a fluorine atom are usually used.

  (D) As a material of a fluorine-type filler, a fluorine-type polymer, fluorine-type rubber, etc. are mentioned, for example. Among these, a fluoropolymer is preferable from the viewpoint of reducing the dielectric constant of the insulating layer. Therefore, as the (D) fluorine-based filler, fluorine-based polymer particles are preferable.

  Examples of the fluoropolymer include polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene propene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-perfluorodiode. Xol copolymer (TFE / PDD), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride (PVF). These may be used alone or in combination of two or more.

  Among these, from the viewpoint of particularly reducing the dielectric constant of the insulating layer, polytetrafluoroethylene is preferable as the fluoropolymer. Therefore, as the (D) fluorine-based filler, polytetrafluoroethylene particles as particles containing polytetrafluoroethylene are preferable.

  The weight average molecular weight of the fluoropolymer is preferably 5000000 or less, more preferably 4000000 or less, and particularly preferably 3000000 or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.

  (D) The average particle diameter of the fluorine-based filler is preferably 0.05 μm or more, more preferably 0.08 μm or more, particularly preferably 0.10 μm or more, preferably 10 μm or less, more preferably 5 μm or less, particularly Preferably it is 4 micrometers or less. When the average particle diameter of the (D) fluorine-based filler is in the above range, the desired effect of the present invention can be remarkably obtained, and usually (D) the fluorine-based filler in the resin composition. The dispersibility can be improved. (D) The average particle diameter of the fluorine-based filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory, as in the case of (C) the inorganic filler.

  (D) Examples of commercially available fluorine-based fillers include “Lublon L-2”, “Lublon L-5” and “Lublon L-5F” manufactured by Daikin Industries, Ltd .; “Fluon PTFE L-170JE” manufactured by Asahi Glass Co., Ltd. ”,“ FluonPTFEEL-172JE ”,“ FluonPTFE L-173JE ”;“ KTL-500F ”,“ KTL-2N ”,“ KTL-1N ”manufactured by Kitamura Co., Ltd .;“ TLP10F-1 ”manufactured by Mitsui DuPont Fluorochemical Co., Ltd. And the like.

  (D) The fluorine-based filler may be surface-treated. For example, (D) the fluorine-based filler may be surface-treated with an arbitrary surface treatment agent. Examples of the surface treatment agent include surfactants such as nonionic surfactants, amphoteric surfactants, cationic surfactants and anionic surfactants; inorganic fine particles. From the viewpoint of affinity, it is preferable to use a fluorosurfactant as the surface treatment agent. Specific examples of the fluorosurfactant include “Surflon S-243” (perfluoroalkyl ethylene oxide adduct) manufactured by AGC Seimi Chemical Co .; “Megafac F-251” and “Megafac F-” manufactured by DIC "477", "Megafuck F-553", "Megafuck R-40", "Megafuck R-43", "Megafuck R-94"; "FTX-218", "Futgent 610FM" manufactured by Neos ;

  The amount of (D) fluorine-based filler in the resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, and particularly preferably 20% by mass with respect to 100% by mass of the nonvolatile component in the resin composition. It is above, Preferably it is 80 mass% or less, More preferably, it is 60 mass% or less, Most preferably, it is 40 mass% or less. (D) When the amount of the fluorine-based filler is in the above range, the desired effect of the present invention can be remarkably obtained, and in particular, the dielectric constant of the cured product of the resin composition can be effectively reduced. it can.

  The amount of (D) fluorine-based filler in the resin composition is preferably 20% by mass or more, more preferably 30% by mass with respect to 100% by mass in total of (C) inorganic filler and (D) fluorine-based filler. % Or more, particularly preferably 35% by mass or more, preferably 90% by mass or less, more preferably 70% by mass or less, and particularly preferably 50% by mass or less. (D) When the amount of the fluorine-based filler is in the above range, the desired effect of the present invention can be remarkably obtained, and in particular, the dielectric constant of the cured product of the resin composition can be effectively reduced. it can.

[1.6. (E) Resin having an unsaturated hydrocarbon group]
The resin composition may include (E) a resin having an unsaturated hydrocarbon group as an optional component in addition to the components described above. In the following description, “resin having an unsaturated hydrocarbon group” as the component (E) may be referred to as “unsaturated resin”. Only one carbon-carbon unsaturated bond may be included in one molecule of (E) unsaturated resin, or a plurality of carbon-carbon unsaturated bonds may be included. (E) The hardened | cured material of the resin composition containing unsaturated resin normally contains the molecular structure site | part formed when the unsaturated bond site | part of (E) unsaturated resin reacts. Thereby, the polarity of the said hardened | cured material becomes small and the value of a dielectric loss tangent can be made small. Further, (E) the unsaturated resin can usually improve the dispersibility of the (D) fluorine-based filler. Therefore, since the uniformity of the composition of the resin composition is improved, the adhesion of the cured product to the conductor layer can be further improved.

  The (E) unsaturated resin contains an unsaturated hydrocarbon group in the molecule of the (E) unsaturated resin. The unsaturated hydrocarbon group is preferably one or more groups selected from the group consisting of an acryl group, a methacryl group, a styryl group, and an olefin group. Here, the “olefin group” refers to an aliphatic hydrocarbon group having a carbon-carbon double bond in the molecule. Preferable examples of the olefin group include an allyl group, a vinyl group, and a propenyl group. Therefore, (E) the unsaturated resin preferably has one or more unsaturated hydrocarbon groups selected from the group consisting of an acryl group, a methacryl group, a styryl group, an allyl group, a vinyl group, and a propenyl group.

  (E) The unsaturated resin is preferably a compound having a cyclic ether structure having 5 or more members. In the following description, the above-mentioned “compound having a cyclic ether structure having 5 or more members” may be referred to as “unsaturated cyclic ether compound”. Unsaturated cyclic ether compounds usually have a limited molecular movement, so that the dielectric loss tangent can be effectively lowered.

The unsaturated cyclic ether compound may contain a carbon-carbon unsaturated bond in the cyclic ether structure or outside the cyclic ether structure.
The unsaturated cyclic ether compound may contain only one cyclic ether structure or a plurality of cyclic ether structures.

  The cyclic ether structure may have a monocyclic structure including only one ring, may have a polycyclic structure including two or more rings, and has a condensed ring structure including a condensed ring. May be.

  The number of oxygen atoms contained in one cyclic ether structure is preferably 1 or more, more preferably 2 or more, preferably 5 or less, more preferably 4 or less, from the viewpoint of remarkably obtaining the desired effect of the present invention. More preferably, it is 3 or less.

  The cyclic ether structure is preferably a 5- to 10-membered ring, more preferably a 5- to 8-membered ring, and further preferably a 5- to 6-membered ring. Specific examples of the cyclic ether structure having five or more members include a furan structure, a tetrahydrofuran structure, a dioxolane structure, a pyran structure, a dihydropyran structure, a tetrahydropyran structure, and a dioxane structure. Among these, a dioxane structure is preferable from the viewpoint of improving compatibility. The dioxane structure includes a 1,2-dioxane structure, a 1,3-dioxane structure, and a 1,4-dioxane structure, and a 1,3-dioxane structure is preferable.

  A substituent such as an alkyl group or an alkoxy group may be bonded to the cyclic ether structure. The number of carbon atoms of the substituent is usually 1 to 6, preferably 1 to 3.

  Among the unsaturated cyclic ether compounds described above, those having a vinyl group are preferred. By using an unsaturated cyclic ether compound having a vinyl group (that is, a compound having a vinyl group and a cyclic ether structure having a 5-membered ring or more) as the unsaturated resin (E), the desired effect of the present invention can be obtained. Remarkably can be obtained. Further, usually, the dielectric loss tangent of the resin composition can be effectively reduced.

  Preferable examples of the unsaturated resin (E) include a compound represented by the following formula (E1), a compound represented by the following formula (E6), and a compound represented by the following formula (E7). . Among these, the compound represented by the formula (E7) is an unsaturated cyclic ether compound, and is particularly preferable.

In formula (E1), R ^{1 to} R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. In the formula (E1), A represents a divalent group represented by the following formula (E2) or the following formula (E3).

  In formula (E2), B represents a divalent group represented by the following formula (E2-1), (E2-2) or (E2-3).

In Formula (E2-1), R ^{15 to} R ¹⁸ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, preferably a hydrogen atom or a methyl group.
In Formula (E2-2), R ^{19 to} R ²⁶ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and preferably a hydrogen atom or a methyl group.
In the formula (E2-3), R ^{27 to} R ³⁴ each independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, preferably a hydrogen atom or a methyl group. In the formula (E2-3), E represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

  In the formula (E3), D represents a divalent group represented by the following formula (E4).

In the formula (E4), R ^{7 to} R ¹⁴ each independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, preferably a hydrogen atom or a methyl group. In particular, R ⁷ , R ⁸ , R ¹³ and R ¹⁴ more preferably represent a methyl group. In the formula (E4), a and b are integers of 0 or more and 100 or less, at least one of which is not 0. In the formula (E4), B represents a divalent group represented by the formula (E2-1), (E2-2) or (E2-3).

  The compound represented by the formula (E1) is preferably a compound represented by the following formula (E5).

In the formula ^(E5), R 1 ~R ⁶ has the same meaning as ^R 1 to R ⁶ in the formula (E1), B has the same meaning as B in the formula (E2), a and b are And have the same meanings as a and b in the formula (E4).

  In formula (E7), ring F represents a divalent group having a cyclic ether structure of 5 or more members. The range of the cyclic ether structure is as described above. Further, as described above, a substituent may be bonded to the cyclic ether structure.

  Examples of the divalent group having a cyclic ether structure having a 5-membered ring or more include, for example, a furan-2,5-diyl group, a tetrahydrofuran-2,5-diyl group, a dioxolane-2,5-diyl group, a pyran-2, 5-diyl group, dihydropyran-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,2-dioxane-3,6-diyl group, 1,3-dioxane-2,5-diyl group 1,4-dioxane-2,5-diyl group, 5-ethyl-1,3-dioxane-2,5-diyl group. Of these, a 5-ethyl-1,3-dioxane-2,5-diyl group is preferable.

In Formula (E7), B ¹ and B ² each independently represent a single bond or a divalent linking group. B ¹ and B ² are preferably a divalent linking group. Examples of the divalent linking group include an alkylene group that may have a substituent, an alkynylene group that may have a substituent, an arylene group that may have a substituent, and a substituent. A heteroarylene group, a group represented by —COO—, a group represented by —CO—, a group represented by —CONH—, a group represented by —NHCONH—, and a group represented by —NHCOO—. A group represented by -C (= O)-, a group represented by -S-, a group represented by -SO-, a group represented by -NH-, and these groups. Examples include a combination of a plurality of groups.

Examples of the substituent include a halogen atom, —OH, —O—C _1-6 alkyl group, —N (C _1-6 alkyl group) ₂ , C _1-6 alkyl group, C _6-10 aryl group, — NH ₂ , —CN, —C (O) O—C _1-6 alkyl group, —COOH, —C (O) H, —NO _{2 and the} like can be mentioned. Here, the term “C _pq ” (p and q are positive integers, satisfying p <q) means that the number of carbon atoms of the organic group described immediately after this term is p to q. Represents something. For example, the expression “C _1-6 alkyl group” refers to an alkyl group having 1 to 6 carbon atoms.

  The substituent may further have a substituent (hereinafter sometimes referred to as “secondary substituent”). Examples of the secondary substituent include the same groups as those already described.

Among these, B ¹ and B ² are represented by an alkylene group which may have a substituent, an alkynylene group which may have a substituent, a group represented by —COO—, and —O—. A group obtained by selecting and combining two or more groups from the group consisting of the above groups is preferred. In particular, B ¹ and B ² are more preferably a group obtained by selecting and combining two or more groups from the group consisting of an alkylene group which may have a substituent and a group represented by —COO—. .

In Formula (E7), C ¹ and C ² each independently represent a functional group. Examples of the functional group include a vinyl group, a methacryl group, an acrylic group, an allyl group, a styryl group, a propenyl group, and an epoxy group. As the functional group, a vinyl group is preferable.

  Specific examples of the compound represented by the formula (E7) include a compound represented by the following formula (E8).

  (E) As unsaturated resin, for example, “OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Co., Inc. (styrene-modified polyphenylene ether resin, number average molecular weight 1200, equivalent to the above formula (E5)), “YL7776” manufactured by Mitsubishi Chemical Corporation ( Bixylenol diallyl ether resin, number average molecular weight 331, equivalent to the formula (E6)), Shin-Nakamura Chemical Co., Ltd. “A-DOG” (dioxane acrylic monomer glycol diacrylate, number average molecular weight 326, equivalent to the formula (E8)) And “KAYARAD R-604” (corresponding to the formula (E8)) manufactured by Nippon Kayaku Co., Ltd. Moreover, (E) unsaturated resin may be used individually by 1 type, and may be used in combination of 2 or more types.

  (E) The number average molecular weight of unsaturated resin becomes like this. Preferably it is 100 or more, More preferably, it is 200 or more, Preferably it is 10,000 or less, More preferably, it is 3000 or less. (E) When the number average molecular weight of unsaturated resin exists in the said range, the volatilization at the time of drying of a resin varnish can be suppressed, or it can suppress that the melt viscosity of a resin composition becomes excessive. The number average molecular weight can be measured in terms of polystyrene by gel permeation chromatography (GPC). The number average molecular weight is measured by the GPC method using, for example, “LC-9A / RID-6A” manufactured by Shimadzu Corporation as a measuring device and “Shodex K-800P / K-804L / K-804L” manufactured by Showa Denko KK as a column. Can be measured at a column temperature of 40 ° C. using chloroform as the mobile phase.

  The amount of the unsaturated resin (E) in the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, and preferably 15% by mass with respect to 100% by mass of the nonvolatile component in the resin composition. Hereinafter, it is more preferably 10% by mass or less. (E) When the amount of the unsaturated resin is not less than the lower limit of the above range, the dielectric loss tangent of the cured product of the resin composition can be effectively lowered, and when it is not more than the upper limit of the above range, the resin varnish It is possible to improve the compatibility.

  The mass ratio of (A) epoxy resin to (E) unsaturated resin ((A) mass of epoxy resin: mass of (E) unsaturated resin) is in the range of 1: 0.01 to 1: 100. Is preferable, the range of 1: 0.1 to 1:90 is more preferable, and the range of 1: 0.2 to 1:80 is more preferable. When the mass ratio of (A) epoxy resin to (E) unsaturated resin is in the above range, the compatibility of the resin composition can be improved.

[1.7. (F) Curing agent]
In addition to the components described above, the resin composition may contain (F) a curing agent as an optional component. The curing agent as the component (F) usually has a function of reacting with the epoxy resin (A) to cure the resin composition. Examples of the (F) curing agent include an active ester curing agent, a phenol curing agent, a naphthol curing agent, a benzoxazine curing agent, a cyanate ester curing agent, and a carbodiimide curing agent. . Moreover, a hardening | curing agent may be used individually by 1 type, or may use 2 or more types together.

  As the active ester curing agent, a compound having one or more active ester groups in one molecule can be used. Among them, as the active ester curing agent, two or more ester groups having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compound esters in one molecule are used. The compound which has is preferable. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. .

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

  Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac and the like can be mentioned. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  Preferable specific examples of the active ester curing agent include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoylated product of phenol novolac. The active ester compound containing is mentioned. Of these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure are more preferred. The “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

  As a commercial product of an active ester type curing agent, for example, as an active ester compound containing a dicyclopentadiene type diphenol structure, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T”, “HPC-” 8000H-65TM "," EXB-8000L-65TM "," EXB-8150-65T "(manufactured by DIC);" EXB9416-70BK "(manufactured by DIC) as an active ester compound containing a naphthalene structure; Phenol novolac acetylated product "DC808" (manufactured by Mitsubishi Chemical Corp.) as an active ester compound containing: YLH1026 (manufactured by Mitsubishi Chemical Corp.) as an active ester compound containing a benzoylated phenol novolac; an active ester which is an acetylated phenol novolac “DC808” (manufactured by Mitsubishi Chemical Corporation) as a curing agent; “YLH1026” (manufactured by Mitsubishi Chemical Corporation), “YLH1030” (manufactured by Mitsubishi Chemical Corporation), “YLH1048” (manufactured by Mitsubishi Chemical Corporation) as benzoylated phenol novolac Mitsubishi Chemical Co., Ltd.);

  As a phenol type hardening | curing agent and a naphthol type | system | group hardening | curing agent, what has a novolak structure from a heat resistant and water-resistant viewpoint is preferable. Further, from the viewpoint of adhesion between the insulating layer and the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd .; “NHN” manufactured by Nippon Kayaku Co., Ltd. "CBN", "GPH": "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375" manufactured by Nippon Steel & Sumikin Chemical; “TD-2090”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018-50P”, “EXB-9500”, and the like.

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd. and “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether; Phenol novolac and Polyfunctional cyanate resin derived from resol novolac; prepolymer these cyanate resin is partially triazine of; and the like. Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (phenol novolac type polyfunctional cyanate ester resin), “ULL-950S” (polyfunctional cyanate ester resin), and “BA230” manufactured by Lonza Japan. , “BA230S75” (a prepolymer in which part or all of bisphenol A dicyanate is triazine-modified into a trimer), and the like.

  Specific examples of the carbodiimide curing agent include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.

  Among the above-mentioned, from the viewpoint of obtaining the desired effect of the present invention remarkably, as the (F) curing agent, an active ester curing agent is preferable. When using an active ester type curing agent, the amount of the active ester type curing agent with respect to 100% by mass of the (F) curing agent is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more. Yes, preferably 100% by mass or less. When the amount of the active ester curing agent is within the above range, the desired effect of the present invention can be remarkably obtained, and in particular, the dielectric constant of the cured product of the resin composition can be effectively reduced.

  The amount of the (F) curing agent in the resin composition is preferably 0.1% by mass or more with respect to 100% by mass of the nonvolatile component in the resin composition, from the viewpoint of remarkably obtaining the desired effect of the present invention. Preferably it is 0.5 mass% or more, More preferably, it is 1 mass% or more, Preferably it is 40 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less.

  (A) When the number of epoxy groups of the epoxy resin is 1, (F) the number of active groups of the curing agent is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, preferably Is 1.5 or less, more preferably 1.2 or less, and still more preferably 1 or less. Here, “(A) the number of epoxy groups of the epoxy resin” is a value obtained by adding up all the values obtained by dividing the mass of the nonvolatile component of the (A) epoxy resin present in the resin composition by the epoxy equivalent. Further, “(F) the number of active groups of the curing agent” is a value obtained by adding up all the values obtained by dividing the mass of the non-volatile component of the (F) curing agent present in the resin composition by the active group equivalent. (A) When the number of epoxy groups in the epoxy resin is 1, the active group number of the (F) curing agent is in the above range, so that the desired effect of the present invention can be remarkably obtained. The heat resistance of the cured product is further improved.

[1.8. (G) Curing accelerator]
In addition to the components described above, the resin composition may contain (G) a curing accelerator as an optional component. (G) By using a curing accelerator, curing can be accelerated when the resin composition is cured.

  (G) As a hardening accelerator, a phosphorus hardening accelerator, an amine hardening accelerator, an imidazole hardening accelerator, a guanidine hardening accelerator, a metal hardening accelerator, a peroxide hardening accelerator is mentioned, for example. It is done. Of these, amine-based curing accelerators and peroxide-based curing accelerators are particularly preferable. (G) A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

  Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. Of these, triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

  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. Of these, 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2 Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-me Le benzyl-imidazolium chloride, 2-methyl-imidazoline, 2-phenyl imidazole compounds of imidazoline and the like; and, adducts of imidazole compounds and epoxy resin; and the like. Of these, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

  A commercial item may be used as an imidazole series hardening accelerator, for example, "P200-H50" by Mitsubishi Chemical Corporation is mentioned.

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl), and the biguanide. Of these, dicyandiamide and 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned, for example. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper 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, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

  Examples of the peroxide curing accelerator include cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydro Examples thereof include peroxide, cumene hydroperoxide, and tert-butyl hydroperoxide.

  A commercially available product can be used as the peroxide curing accelerator, and examples thereof include “Park Mill D” manufactured by NOF Corporation.

  When the (G) curing accelerator is used, the amount of the (G) curing accelerator in the resin composition is based on 100% by mass of the non-volatile component in the resin composition from the viewpoint of remarkably obtaining the desired effect of the present invention. , Preferably 0.01% by weight or more, more preferably 0.02% by weight or more, particularly preferably 0.03% by weight or more, preferably 3% by weight or less, more preferably 2% by weight or less, particularly preferably 1% by mass or less.

[1.9. (H) Additive]
The resin composition may further contain an additive as an optional component in addition to the components described above. Examples of such additives include organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; thickeners; antifoaming agents; leveling agents; adhesion promoters; coloring agents; flame retardants; Plastic resin; and the like. Moreover, an additive may be used individually by 1 type and may be used in combination of 2 or more types.

[1.10. Method for producing resin composition]
The resin composition can be produced, for example, by a method in which the compounding components are mixed with a solvent as necessary and stirred using a stirring device such as a rotary mixer.

[1.11. Characteristics of resin composition]
The hardened | cured material of the resin composition mentioned above can make the dielectric constant low. Therefore, an insulating layer having a low dielectric constant can be obtained from the cured product of the resin composition. For example, when the resin composition is cured by the method described in Examples to obtain a cured product, the dielectric constant of the cured product can be preferably 3.0 or less, more preferably 2.9 or less. Here, the dielectric constant of the cured product can be measured by the method described in Examples.

  The cured product of the resin composition described above is excellent in temperature stability of its dielectric loss tangent. Specifically, the cured product of this resin composition can reduce the difference between the dielectric tangent value at room temperature and the dielectric tangent value at high temperature, and further, the dielectric tangent value at room temperature and the dielectric tangent value at low temperature. The difference with can be reduced.

Therefore, an insulating layer excellent in temperature stability of dielectric loss tangent can be obtained from the cured product of the resin composition. Specifically, the dielectric loss tangent at −10 ° C., 25 ° C., and 100 ° C. of the cured product obtained by heat-treating the resin composition at 200 ° C. for 90 minutes is Df (−10 ° C.) and Df (25 ° C.), respectively. And Df (100 ° C.), the ratio of Df (−10 ° C.) to Df (25 ° C.) Df (−10 ° C.) / Df (25 ° C.), and Df (100 ° C.) to Df (25 ° C.) The ratio Df (100 ° C.) / Df (25 ° C.) is in the following range.
That is, the dielectric loss tangent ratio Df (−10 ° C.) / Df (25 ° C.) is usually 85% or more, preferably 87% or more, particularly preferably 90% or more, and usually 115% or less, preferably 114% or less. Particularly preferably, it is 113% or less.
Further, the dielectric loss tangent ratio Df (100 ° C.) / Df (25 ° C.) is usually 85% or more, preferably 90% or more, more preferably 95% or more, and usually 115% or less, preferably 114% or less. Particularly preferably, it is 113% or less.
Said dielectric loss tangent Df (-10 degreeC), Df (25 degreeC), and Df (100 degreeC) can be measured by the method as described in an Example.

As described above, the present inventor presumes the mechanism excellent in the temperature stability of the dielectric loss tangent as follows. However, the technical scope of the present invention is not limited by the mechanism described below.
According to the study of the present inventors, the dielectric loss tangent of the cured product of the resin composition containing (A) an epoxy resin and (D) a fluorine-based filler is in a practical temperature range from −10 ° C. to 100 ° C. It has been found that temperatures tend to be smaller at lower temperatures and larger at higher temperatures. Conversely, the dielectric loss tangent of the polymer of (B) maleimide compound tends to be larger at lower temperatures and smaller at higher temperatures due to the action of the maleimide group in the above practical temperature range. Thus, (A) the temperature dependence of the dielectric loss tangent of the cured product of the resin composition containing the epoxy resin and (D) the fluorine-based filler, and (B) the temperature dependence of the dielectric loss tangent of the polymer of the maleimide compound Is the opposite. Therefore, when (A) an epoxy resin and (D) a fluorine-based filler and (B) a maleimide compound are combined, the temperature dependence of the dielectric tangent of both cancels each other, and is the same at both low and high temperatures. Is obtained. Accordingly, the dielectric loss tangent of the cured product of the resin composition containing (A) an epoxy resin, (B) a maleimide compound, and (D) a fluorine-based filler has good temperature stability.

  The cured product of the resin composition described above usually has a small dielectric loss tangent at 25 ° C. For example, the dielectric loss tangent Df (25 ° C.) at 25 ° C. of a cured product obtained by heat-treating the resin composition at 200 ° C. for 90 minutes is preferably 0.020 or less, more preferably 0.010 or less, still more preferably It is 0.009 or less, particularly preferably 0.008 or less, 0.007 or less, or 0.006 or less. Although there is no restriction | limiting in particular in a minimum, Usually, it is 0.001 or more.

[2. Resin composition according to second embodiment]
The resin composition according to the second embodiment of the present invention includes (A) an epoxy resin and (D) a fluorine-based filler. Furthermore, the dielectric loss tangents at −10 ° C., 25 ° C., and 100 ° C. of the cured product obtained by heat-treating the resin composition according to the second embodiment at 200 ° C. for 90 minutes are respectively expressed as Df (−10 ° C.) and Df ( 25 ° C.) and Df (100 ° C.), the ratio Df (−10 ° C.) / Df (25 ° C.) of Df (−10 ° C.) to Df (25 ° C.) is 85% to 115%, and The ratio Df (100 ° C.) / Df (25 ° C.) of Df (100 ° C.) to Df (25 ° C.) is 85% to 115%.

  A cured product of such a resin composition has a low dielectric constant due to the action of (D) the fluorine-based filler. Further, since the dielectric loss tangent ratios Df (−10 ° C.) / Df (25 ° C.) and Df (100 ° C.) / Df (25 ° C.) are within a predetermined range of 85% to 115%, this resin composition The cured product is excellent in the temperature stability of dielectric loss tangent. Therefore, according to the resin composition according to the second embodiment, when it is provided on the antenna circuit board of the radar by being excellent in temperature stability of the dielectric loss tangent, it is possible to suppress a change due to the temperature of the radar detectable range, And the desired effect of this invention that the resin composition which can obtain an insulating layer with a low dielectric constant is realizable can be acquired. Moreover, according to the resin composition which concerns on 2nd embodiment, the same advantage as the resin composition which concerns on 1st embodiment can be acquired.

  About (A) epoxy resin and (D) fluorine-type filler of the resin composition which concerns on 2nd embodiment, the matter demonstrated by 1st embodiment is applicable similarly to 1st embodiment.

  From the viewpoint of keeping the dielectric loss tangent ratios Df (−10 ° C.) / Df (25 ° C.) and Df (100 ° C.) / Df (25 ° C.) within a predetermined range, the resin composition according to the second embodiment (B ) It preferably contains a maleimide compound. Usually, the ratios Df (−10 ° C.) / Df (25 ° C.) and Df (100 ° C.) / Df (25 ° C.) can be kept within a predetermined range by adjusting the amount of (B) maleimide compound. . About the maleimide compound (B) of the resin composition which concerns on 2nd embodiment, the matter demonstrated by 1st embodiment is applicable similarly to 1st embodiment.

  In addition to the components described above, the resin composition according to the second embodiment includes (C) an inorganic filler, (E) an unsaturated resin, (F) a curing agent, (G) a curing accelerator, and (H) One or more of the additives may be included. For the (C) inorganic filler, (E) unsaturated resin, (F) curing agent, (G) curing accelerator, and (H) additive of the resin composition according to the second embodiment, the first embodiment The matters described in (1) can be applied as in the first embodiment.

  The resin composition according to the second embodiment can be usually produced by the same production method as the resin composition according to the first embodiment.

  The resin composition according to the second embodiment usually has the same characteristics as the resin composition according to the first embodiment. Therefore, the cured product of the resin composition according to the second embodiment has a low dielectric constant, excellent temperature stability of dielectric loss tangent, and usually has a low dielectric loss tangent at 25 ° C.

[3. Application of resin composition]
The resin composition described above can be used as a resin composition for forming an insulating layer of a circuit board such as a printed circuit board, and in particular, build-up insulation for forming an insulating layer in manufacturing a circuit board by a build-up method. It is preferably used as a resin composition for layer formation.

  In particular, taking advantage of the fact that an insulating layer having a low dielectric constant can be obtained, this resin composition is a resin composition for forming an insulating layer of a high-frequency circuit board (for forming an insulating layer of a high-frequency circuit board). Resin composition) can be suitably used. Especially, this resin composition can be more suitably used as a resin composition (resin composition for forming an interlayer insulating layer of a high frequency circuit board) for forming an interlayer insulating layer of a high frequency circuit board. Here, the “high frequency circuit board” means a circuit board that can be operated even with an electric signal in a high frequency band. The “high frequency band” usually means a band of 1 GHz or more, and the above resin composition is particularly effective in a band of 28 GHz to 150 GHz.

  Furthermore, taking advantage of the good temperature stability of dielectric loss tangent, this resin composition can be used as a resin composition for an insulating layer (for example, a wiring forming layer) of an antenna circuit board for radar. preferable. As described above, by using a cured product having a good temperature stability of dielectric loss tangent as the material of the insulating layer, a change in the magnitude of the loss in the antenna circuit board due to the temperature can be reduced. Radar can be realized.

  In addition, since the insulating layer having a low dielectric constant can contribute to a reduction in the height of the circuit board, it is suitable for applications requiring a thin circuit board. Furthermore, an insulating layer having a low dielectric constant facilitates impedance control of the circuit board, and thus is suitable for increasing the degree of design freedom of the circuit board. From this point of view, examples of suitable applications of the resin composition include circuit boards such as a mother board, an IC package board, a camera module board, and a fingerprint authentication sensor board used for portable devices. As a specific example, the fingerprint authentication sensor may include an insulating layer included in a circuit board, a plurality of electrodes formed on the insulating layer, and an insulating film in this order. In this fingerprint authentication sensor, fingerprint authentication is performed by utilizing the fact that the capacitance value of the capacitor formed by the finger, electrode and insulating film placed on the insulating film differs between the concave and convex parts of the fingerprint. Is called. In such a fingerprint authentication sensor, if the insulating layer can be made thin, the sensor itself can be miniaturized.

  In addition, the resin composition described above is a resin composition such as an adhesive film, a sheet-like laminated material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a hole-filling resin, and a component-filling resin. Can be used for a wide range of applications.

[4. Sheet-like laminated material]
The resin composition described above can be applied in a varnish state and used for forming an insulating layer. However, industrially, it is preferably used in the form of a sheet-like laminated material containing this resin composition. Preferable examples of the sheet-like laminated material include an adhesive film and a prepreg.

  In one embodiment, the adhesive film includes a support and a resin composition layer provided on the support. The resin composition layer is a layer formed of the above-described resin composition and may be referred to as an “adhesion layer”.

  The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, and particularly preferably 50 μm or less from the viewpoint of thinning. The minimum of the thickness of a resin composition layer is not specifically limited, For example, it may be 1 micrometer or more, 5 micrometers or more, 10 micrometers or more.

  Examples of the support include a film made of a plastic material, a metal foil, and a release paper. The support is preferably a film made of a plastic material or a metal foil.

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as “PET”) and polyethylene naphthalate (hereinafter sometimes referred to as “PEN”). Polyester; Polycarbonate (hereinafter sometimes referred to as “PC”); Acrylic polymer such as polymethyl methacrylate (hereinafter sometimes referred to as “PMMA”); Cyclic polyolefin; Triacetylcellulose (hereinafter sometimes referred to as “TAC”). ); Polyether sulfide (hereinafter sometimes referred to as “PES”); polyether ketone; polyimide; Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and polyethylene terephthalate is particularly preferable because it is inexpensive and excellent in availability.

  When metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil. Among these, copper foil is preferable. 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 another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.). It may be used.

  The support may be subjected to a treatment such as a mat treatment, a corona treatment, or an antistatic treatment on the surface to be joined to the resin composition layer.

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. Examples of the release agent that can be used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . Examples of commercially available release agents include “SK-1”, “AL-5”, and “AL-7” manufactured by Lintec Corporation, which are alkyd resin release agents. In addition, examples of the support with a release layer include “Lumirror T60” manufactured by Toray Industries, Inc., “Purex” manufactured by Teijin Limited, “Unipeel” manufactured by Unitika, and the like.

  The thickness of the support is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. In addition, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  For the adhesive film, for example, a resin varnish containing an organic solvent and a resin composition is prepared, and this resin varnish is applied to a support using a coating device such as a die coater and further dried to form a resin composition layer. By making it, it can manufacture.

  Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; cellosolve and butyl carbitol Carbitol solvents of the following: aromatic hydrocarbon solvents such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone; One organic solvent may be used alone, or two or more organic solvents may be used in combination.

  Drying can be carried out by a known method such as heating or hot air blowing. The drying conditions are set so that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. 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, the resin composition is dried at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes. A physical layer can be formed. Usually, the resin composition layer is obtained as a film obtained by semi-curing a coating film of a resin varnish.

  The adhesive film may contain arbitrary layers other than a support body and a resin composition layer as needed. For example, a protective film according to the support may be provided on the surface of the adhesive film that is not joined to the support of the resin composition layer (that is, the surface opposite to the support). The thickness of the protective film is, for example, 1 μm to 40 μm. By the protective film, it is possible to suppress the adhesion and scratches of dust and the like to the surface of the resin composition layer. When the adhesive film has a protective film, the adhesive film can usually be used by peeling off the protective film. The adhesive film can be stored in a roll.

  In one embodiment, the prepreg can be formed by impregnating a sheet-like fiber base material with a resin composition.

  The sheet-like fiber base material used for the prepreg is not particularly limited. As a sheet-like fiber base material, arbitrary fiber base materials used as a base material for prepregs, such as a glass cloth, an aramid nonwoven fabric, and a liquid crystal polymer nonwoven fabric, can be used, for example. From the viewpoint of thinning, the thickness of the sheet-like fiber base material is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, and particularly preferably 600 μm or less. From the viewpoint of reducing the depth of plating for forming the conductor layer, the thickness of the sheet-like fiber base material is preferably 30 μm or less, more preferably 20 μm or less, and particularly preferably 10 μm or less. The lower limit of the thickness of the sheet fiber substrate is usually 1 μm or more, and may be 1.5 μm or more, or 2 μm or more.

The prepreg can be produced by a method such as a hot melt method or a solvent method.
The thickness of the prepreg may be in the same range as the resin composition layer in the adhesive film described above.

[5. Circuit board]
The circuit board of this invention contains the insulating layer formed with the hardened | cured material of the resin composition mentioned above. In one embodiment, the circuit board includes an inner layer substrate and an insulating layer provided on the inner layer substrate.

  The “inner layer substrate” is a member that becomes a base material of the circuit board. Examples of the inner layer substrate include those including a core substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. In general, the inner layer substrate includes a conductor layer formed directly or indirectly on one side or both sides of the core base material. This conductor layer may be patterned so as to function as an electrical circuit, for example. An inner layer substrate in which a conductor layer is formed as a circuit on one side or both sides of the core substrate may be referred to as an “inner layer circuit board”. Further, an intermediate product in which at least one of an insulating layer and a conductor layer is to be formed for manufacturing a circuit board is also included in the term “inner layer board”. When the circuit board incorporates components, an inner layer substrate incorporating the components may be used.

  The thickness of the inner layer substrate is usually from 50 μm to 4000 μm, and preferably from 200 μm to 3200 μm from the viewpoint of improving the mechanical strength and reducing the height (reducing thickness) of the circuit board.

  The inner layer substrate may be provided with one or more through holes extending from one surface to the other surface in order to electrically connect the conductor layers on both sides thereof. Further, the inner layer substrate may be provided with further components such as passive elements.

  The insulating layer is a layer of a cured product of the resin composition. Insulating layers formed of this cured product are particularly for build-up circuit boards, high-frequency circuit boards, radar antenna circuit boards, and mother boards, IC package boards, camera module boards, and fingerprints used in portable devices. It can be suitably applied to an insulating layer for a circuit board such as an authentication sensor board.

  The circuit board may have only one insulating layer or may have two or more layers. When the circuit board has two or more insulating layers, it can be provided as a build-up layer in which conductor layers and insulating layers are alternately laminated.

  The thickness of the insulating layer is usually 20 μm to 200 μm, and preferably 50 μm to 150 μm from the viewpoint of improving electrical characteristics and reducing the height of the circuit board.

  The insulating layer may be provided with one or more via holes for electrically connecting the conductor layers included in the circuit board.

  Since the said insulating layer is a layer formed with the hardened | cured material of the resin composition mentioned above, the outstanding characteristic of the hardened | cured material of the resin composition mentioned above can be exhibited. Therefore, the insulating layer of the circuit board is preferably a dielectric constant, a dielectric loss tangent ratio Df (−10 ° C.) / Df (25 ° C.), and a dielectric loss tangent ratio Df (100 ° C.) / Df (25 ° C.). And characteristics such as dielectric loss tangent Df (25 ° C.) at 25 ° C. can be adjusted to the same range as described in the section of the resin composition. These characteristics can be measured by the methods described in the examples.

A circuit board can be manufactured by the manufacturing method including the following process (I) and process (II), for example using an adhesive film.
(I) The process of laminating | stacking an adhesive film on an inner layer board | substrate so that the resin composition layer of this adhesive film may join an inner layer board | substrate.
(II) A step of thermosetting the resin composition layer to form an insulating layer.

  Lamination | stacking with an inner layer board | substrate and an adhesive film can be performed by the thermocompression bonding process heated, for example, pressing an adhesive film to an inner layer board | substrate from the support body side. Examples of the member for the thermocompression bonding process (also referred to as “thermocompression bonding member”) include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). In addition, the thermocompression bonding member is not directly pressed against the support of the adhesive film and pressed, but through an elastic material such as heat-resistant rubber so that the adhesive film sufficiently follows the unevenness of the surface of the inner layer substrate. It is preferable to press.

  Lamination | stacking with an inner layer board | substrate and an adhesive film can be implemented by the vacuum laminating method, for example. In the vacuum laminating method, the temperature for thermocompression bonding is preferably 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C. The pressure for thermocompression bonding is preferably 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa. The time for thermocompression bonding is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

  Lamination can be performed with a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressurizing laminator.

  After the lamination, the laminated resin composition layer may be smoothed by pressing from the support side under normal pressure (under atmospheric pressure), for example, with a thermocompression bonding member. The pressing conditions for the smoothing treatment can be the same as the conditions for the thermocompression bonding of the laminate. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform a lamination | stacking and smoothing process continuously using said commercially available vacuum laminator.

  The support may be removed between step (I) and step (II), or may be removed after step (II).

  In step (II), the resin composition layer is thermally cured to form an insulating layer. The conditions for thermosetting the resin composition layer are not particularly limited, and the conditions employed when forming the insulating layer of the circuit board can be arbitrarily employed.

  The thermosetting conditions of the resin composition layer vary depending on, for example, the type of resin composition. The curing temperature of the resin composition layer is usually in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 220 ° C, more preferably in the range of 170 ° C to 200 ° C). The curing time is usually in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

  Before the resin composition layer is thermally cured, 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 usually at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). May be preheated for usually 5 minutes or longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

  The method for manufacturing a circuit board may further include (III) a step of drilling the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer. These steps (III) to (V) can be performed according to an appropriate method used for manufacturing a circuit board. When the support is removed after step (II), the support is removed between step (II) and step (III), between step (III) and step (IV), or step You may implement at any time between (IV) and process (V).

  Step (III) is a step of making a hole in the insulating layer. By drilling, holes such as via holes and through holes can be formed in the insulating layer. Step (III) can be performed, for example, by a method such as drilling, lasering, or plasma depending on the composition of the resin composition used for forming the insulating layer. The size and shape of the hole can be appropriately determined according to the design of the circuit board.

  Step (IV) is a step of subjecting the insulating layer to a roughening treatment. The procedure and conditions of the roughening treatment are not particularly limited, and any procedure and conditions used when forming the insulating layer of the circuit board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

  Examples of the swelling liquid include an alkaline solution and a surfactant solution, and preferably an alkaline solution. As an alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan. Moreover, a swelling liquid may be used individually by 1 type, and may be used in combination of 2 or more types. The swelling treatment with the swelling liquid is not particularly limited. The swelling treatment can be performed, for example, by immersing the insulating layer in a swelling liquid at 30 ° C. to 90 ° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes.

  Examples of the oxidizing agent include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. Moreover, an oxidizing agent may be used individually by 1 type, and may be used in combination of 2 or more types. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizers include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan.

  As the neutralizing solution, an acidic aqueous solution is preferable. As a commercial item of the neutralization liquid, for example, “Reduction Solution Securigans P” manufactured by Atotech Japan Co., Ltd. may be mentioned. Moreover, a neutralization liquid may be used individually by 1 type, and may be used in combination of 2 or more types. The treatment with the neutralizing solution can be performed by immersing the treated surface of the insulating layer subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing the insulating layer subjected to the roughening treatment with the oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

  Step (V) is a step of forming a conductor layer. The material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include a layer formed of an alloy of two or more kinds of metals selected from the above group (for example, a nickel / chromium alloy, a copper / nickel alloy, and a copper / titanium alloy). Among them, from the viewpoint of versatility of forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; or nickel / chromium alloy, copper -An alloy layer of nickel alloy or copper / titanium alloy is preferable. Further, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; or an alloy layer of nickel / chromium alloy is more preferable, and a single metal layer of copper is still more preferable.

  The conductor layer may have a single layer structure, or may have a multilayer structure including two or more single metal layers or alloy layers made of different types of metals or alloys. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel / chromium alloy.

  The thickness of the conductor layer is usually 3 μm to 200 μm, preferably 10 μm to 100 μm.

  The conductor layer can be formed by, for example, directly patterning a metal foil used as a support for the adhesive film. The conductor layer can be formed by plating, for example. As a formation method by plating, for example, the surface of the insulating layer can be plated by a method such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern. Especially, it is preferable to form by a semi-additive method from a viewpoint of the simplicity of manufacture.

  Hereinafter, an example in which the conductor layer is formed by the semi-additive method will be described. First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern for exposing a part of the plating seed layer is formed on the formed plating seed layer so as to correspond to a desired wiring pattern. A metal layer is formed by electrolytic plating on the exposed plating seed layer, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

  The conductor layer may be formed using a metal foil, for example. When forming a conductor layer using metal foil, it is preferable to implement process (V) between process (I) and process (II). For example, after the step (I), the support is removed, and a metal foil is laminated on the exposed surface of the resin composition layer. Lamination of the resin composition layer and the metal foil can be performed by a vacuum laminating method. The lamination conditions may be the same as the lamination conditions of the inner layer substrate and the adhesive film in step (I). Next, step (II) is performed to form an insulating layer. Thereafter, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by a method such as a subtractive method or a modified semi-additive method. A metal foil can be manufactured by methods, such as an electrolytic method and a rolling method, for example. Examples of commercially available metal foil include HLP foil manufactured by JX Nippon Mining & Metals, JXUT-III foil, 3EC-III foil, TP-III foil manufactured by Mitsui Metal Mining.

  When the circuit board includes two or more insulating layers and a conductor layer (build-up layer), the above-described insulating layer forming step and conductor layer forming step are repeated one or more times to obtain a circuit. A circuit board having a functioning multilayer wiring structure can be manufactured.

  In another embodiment, the circuit board can be manufactured using prepreg instead of the adhesive film. The manufacturing method using a prepreg is basically the same as the case of using an adhesive film.

[6. Semiconductor device]
A semiconductor device includes the circuit board. This semiconductor device can be manufactured using a circuit board.

  Examples of the semiconductor device include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

  The semiconductor device can be manufactured, for example, by mounting a component (semiconductor chip) on a conductive portion of a circuit board. The “conducting part” is “a part where an electric signal can be transmitted on the circuit board”, and the part may be a surface of the circuit board or a part embedded in the circuit board. Absent. In addition, an electric circuit element made of a semiconductor can be arbitrarily used for the semiconductor chip.

  As a method for mounting a semiconductor chip when manufacturing a semiconductor device, any method in which the semiconductor chip functions effectively can be adopted. As a semiconductor chip mounting method, for example, a wire bonding mounting method, a flip chip mounting method, a mounting method using a bumpless buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a non-conductive film (NCF) ) Mounting method. Here, the “mounting method using a build-up layer without bumps (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a circuit board and the semiconductor chip and wiring of the circuit board are connected”.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples. In the following description, “parts” and “%” mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.

[Example 1]
20 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 185) and 2.5 parts of phenylmethanemaleimide resin (“BMI-2000” manufactured by Daiwa Kasei Kogyo Co., Ltd.) 20 parts of solvent naphtha The solution was heated and dissolved with stirring, and then cooled to room temperature to obtain a resin solution.

To this resin solution, 100 parts of an inorganic filler (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm, carbon amount 0.38 mg / m ² per unit surface area), and polytetrafluoroethylene particles ( Daikin Industries, Ltd. “Lublon L-2” (average particle size 3 μm) 55 parts was mixed, and kneaded with three rolls and dispersed.

  Further, to this resin solution, 31 parts of an active ester curing agent (“HPC-8000-65T” manufactured by DIC, toluene solution with a non-volatile content of 65% having an active group equivalent of about 223), an acrylic resin (manufactured by Shin-Nakamura Chemical Co., Ltd.) "A-DOG") 10 parts, curing accelerator (4-dimethylaminopyridine (DMAP) in 5% methyl ethyl ketone solution) 2 part, and curing accelerator (Nippon Corporation Dicumyl peroxide "Park Mill D") The resin varnish 1 was prepared by mixing 0.13 parts and uniformly dispersing with a rotary mixer.

[Example 2]
The amount of phenylmethane maleimide resin (“BMI-2000” manufactured by Daiwa Kasei Kogyo Co., Ltd.) was changed to 10 parts.
Moreover, acrylic resin (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.) and dicumyl peroxide (“Park Mill D” manufactured by NOF Corporation) were not used.
Except for the above, the same operation as in Example 1 was performed to produce a resin varnish 2.

[Example 3]
The amount of phenylmethane maleimide resin (“BMI-2000” manufactured by Daiwa Kasei Kogyo Co., Ltd.) was changed to 13.5 parts.
Except for the above, the same operation as in Example 1 was performed to prepare a resin varnish 3.

[Example 4]
2.5 parts of phenylmethane maleimide resin (“BMI-2000” manufactured by Daiwa Kasei Kogyo Co., Ltd.) was changed to 2.5 parts of m-phenylene bismaleimide resin (“BMI-3000” manufactured by Daiwa Kasei Kogyo Co., Ltd.).
Except for the above, the same operation as in Example 1 was performed to prepare a resin varnish 4.

[Example 5]
2.5 parts of phenylmethane maleimide resin (“BMI-2000” manufactured by Daiwa Kasei Kogyo Co., Ltd.) was changed to 10 parts of m-phenylene bismaleimide resin (“BMI-3000” manufactured by Daiwa Kasei Kogyo Co., Ltd.).
Moreover, acrylic resin (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.) and dicumyl peroxide (“Park Mill D” manufactured by NOF Corporation) were not used.
Except for the above, the same operation as in Example 1 was performed to prepare a resin varnish 5.

[Example 6]
2.5 parts of phenylmethanemaleimide resin (“BMI-2000” manufactured by Daiwa Kasei Kogyo Co., Ltd.) was changed to 13.5 parts of m-phenylene bismaleimide resin (“BMI-3000” manufactured by Daiwa Kasei Kogyo Co., Ltd.).
Except for the above, the same operation as in Example 1 was performed to prepare a resin varnish 6.

[Comparative Example 1]
The amount of phenylmethane maleimide resin (“BMI-2000” manufactured by Daiwa Kasei Kogyo Co., Ltd.) was changed to 1 part.
Except for the above, the same operation as in Example 1 was performed to prepare a resin varnish 7.

[Comparative Example 2]
The amount of phenylmethane maleimide resin (“BMI-2000” manufactured by Daiwa Kasei Kogyo Co., Ltd.) was changed to 16 parts.
Except for the above, the same operation as in Example 1 was performed to prepare a resin varnish 8.

[Comparative Example 3]
2.5 parts of phenylmethanemaleimide resin (“BMI-2000” manufactured by Daiwa Kasei Kogyo Co., Ltd.) was changed to 1 part of m-phenylene bismaleimide resin (“BMI-3000” manufactured by Daiwa Kasei Kogyo Co., Ltd.).
Except for the above, the same operation as in Example 1 was performed to prepare a resin varnish 9.

[Comparative Example 4]
2.5 parts of phenylmethanemaleimide resin (“BMI-2000” manufactured by Daiwa Kasei Kogyo Co., Ltd.) was changed to 16 parts of m-phenylene bismaleimide resin (“BMI-3000” manufactured by Daiwa Kasei Kogyo Co., Ltd.).
Except for the above, the same operation as in Example 1 was performed to prepare a resin varnish 10.

[Evaluation method]
(Preparation of evaluation sample of cured product)
A polyethylene terephthalate film ("PET501010" manufactured by Lintec Corporation) having a release treatment on the surface was prepared as a support. On this support body, the resin varnish obtained by the Example and the comparative example was apply | coated uniformly using the die-coater so that the thickness of the resin composition layer after drying might be set to 40 micrometers. The applied resin varnish was dried at 80 ° C. to 110 ° C. (average 95 ° C.) for 6 minutes to obtain a resin composition layer. Thereafter, the resin composition layer was cured by heat treatment at 200 ° C. for 90 minutes, and the support was peeled off to obtain a cured film formed of a cured product of the resin composition. This cured film was cut into a length of 80 mm and a width of 2 mm to obtain an evaluation sample.

(Measurement of dielectric constant Dk and dielectric loss tangent Df)
With respect to this evaluation sample, a dielectric loss tangent and a dielectric constant were measured at a measurement frequency of 10 GHz by a cavity resonance perturbation method using a measuring apparatus (“HP 8362B” manufactured by Agilent Technologies). The dielectric loss tangent was measured at −10 ° C., 25 ° C. and 100 ° C. The dielectric constant was measured at 25 ° C.

(Evaluation of dielectric constant Dk)
The case where the dielectric constant Dk was 3.0 or less was evaluated as “good”. Further, the case where the dielectric constant Dk exceeded 3.0 was evaluated as “bad”.

(Evaluation of temperature stability of dielectric loss tangent)
The ratio Df (−10 ° C.) / Df (25 ° C.) of the dielectric loss tangent Df (−10 ° C.) at −10 ° C. to the dielectric loss tangent Df (25 ° C.) at 25 ° C. was calculated. When this ratio Df (−10 ° C.) / Df (25 ° C.) is in the range of 85% to 115%, the temperature stability at low temperature was determined as “good”. Further, when the ratio Df (−10 ° C.) / Df (25 ° C.) was not in the range of 85% to 115%, the temperature stability at low temperature was determined as “bad”.

  The ratio Df (100 ° C.) / Df (25 ° C.) of the dielectric loss tangent Df (100 ° C.) at 100 ° C. to the dielectric loss tangent Df (25 ° C.) at 25 ° C. was calculated. When this ratio Df (100 ° C.) / Df (25 ° C.) is in the range of 85% to 115%, the temperature stability at high temperature was determined as “good”. Further, when the ratio Df (100 ° C.) / Df (25 ° C.) was not in the range of 85% to 115%, the temperature stability at high temperature was determined as “bad”.

[result]
The results of the above-described examples and comparative examples are shown in the following table. In the following table, the amount of each component represents parts by mass of the non-volatile component. In the table below, the meanings of the abbreviations are as follows.
YX4000HK: Bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185).
BMI-2000: Phenylmethane maleimide resin (“BMI-2000” manufactured by Daiwa Kasei Kogyo Co., Ltd.).
BMI-3000: m-phenylene bismaleimide resin (“BMI-3000” manufactured by Daiwa Kasei Kogyo Co., Ltd.).
SO-C2: inorganic filler (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, carbon amount per unit surface area 0.38 mg / m ² ).
Lubron L-2: polytetrafluoroethylene particles (“Lublon L-2” manufactured by Daikin Industries, Ltd., average particle diameter: 3 μm).
A-DOG: Acrylic resin (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.).
HPC-8000-65T: active ester type curing agent (“HPC-8000-65T” manufactured by DIC, toluene solution with a non-volatile content of 65% having an active group equivalent of about 223).
DMAP: curing accelerator (5% methyl ethyl ketone solution of 4-dimethylaminopyridine (DMAP)).
Park Mill D: Curing accelerator (Dicumyl peroxide “Park Mill D” manufactured by NOF Corporation).
(B) / (A): The mass ratio of the component (B) to 100% by mass of the component (A).

[Consideration]
As can be seen from Table 1, in the examples, a low dielectric constant is obtained. Further, in the example, the dielectric loss tangent ratio Df (100 ° C.) / Df (25 ° C.) is within a predetermined range (100% ± 15%) close to 100%, and the temperature stability of the dielectric loss tangent at high temperature is high. It is good. Further, in the example, the dielectric loss tangent ratio Df (−10 ° C.) / Df (25 ° C.) is within a predetermined range (100% ± 15%) close to 100%, and the temperature dependence of the dielectric loss tangent at a low temperature. Is good. Therefore, from this result, it was confirmed that the present invention can realize a resin composition capable of obtaining an insulating layer having a low dielectric constant and excellent temperature stability of dielectric loss tangent. It can be clearly understood by those skilled in the art that when the insulating layer having excellent temperature stability of the dielectric loss tangent is applied to the antenna circuit board of the radar, the change in the detectable range of the radar due to the temperature can be suppressed.

  In the above examples, even when the components (E) to (G) are not used, it has been confirmed that the results are the same as those in the above examples although there is a difference in degree.

Claims (12)

A resin composition comprising (A) an epoxy resin, (B) a maleimide compound, (C) an inorganic filler, and (D) a fluorine-based filler,
(B) The resin composition whose quantity of a component is 10 mass%-70 mass% with respect to 100 mass% of (A) component. A resin composition comprising (A) an epoxy resin and (D) a fluorine-based filler,
The dielectric loss tangents at −10 ° C., 25 ° C. and 100 ° C. of the cured product obtained by heat-treating the resin composition at 200 ° C. for 90 minutes are respectively expressed as Df (−10 ° C.), Df (25 ° C.) and Df (100 ° C. )
The ratio Df (−10 ° C.) / Df (25 ° C.) of Df (−10 ° C.) to Df (25 ° C.) is 85% to 115%,
The resin composition whose ratio Df (100 degreeC) / Df (25 degreeC) of Df (100 degreeC) with respect to Df (25 degreeC) is 85%-115%.   (B) The resin composition of Claim 2 containing a maleimide compound.   (D) The resin composition of any one of Claims 1-3 whose component is a fluorine-type polymer particle.   (D) The resin composition of any one of Claims 1-4 whose component is a polytetrafluoroethylene particle.   (E) The resin composition of any one of Claims 1-5 containing resin which has an unsaturated hydrocarbon group.   The resin composition according to claim 6, wherein the component (E) has one or more unsaturated hydrocarbon groups selected from the group consisting of an acryl group, a methacryl group, a styryl group, an allyl group, a vinyl group, and a propenyl group. .   The resin composition according to claim 6 or 7, wherein the component (E) has a vinyl group and a cyclic ether structure having a 5-membered ring or more.   The resin composition according to claim 1, which is used for forming an insulating layer on a circuit board.   A sheet-like laminate material comprising the resin composition according to claim 1.   The circuit board containing the insulating layer which consists of a hardened | cured material of the resin composition of any one of Claims 1-9.   A semiconductor device comprising the circuit board according to claim 11.