KR102514145B1 - Resin composition - Google Patents

Abstract

[PROBLEMS] To provide a resin composition capable of obtaining an insulating layer having a low dielectric constant and excellent temperature stability of dielectric loss tangent.
[Solution] A resin composition comprising (A) an epoxy resin, (B) a maleimide compound, (C) an inorganic filler, and (D) a fluorine-based filler, wherein the amount of component (B) is 100% by mass of component (A) 10% by mass to 70% by mass relative to the resin composition.
[Selectivity] None

Description

Resin composition {RESIN COMPOSITION}

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

As a manufacturing technology of a circuit board, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are laminated alternately 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 is a resin composition containing an epoxy resin, a curing agent, and a fluororesin filler, wherein the content of the fluororesin filler is 50 to 85 mass% with respect to the solid content of the resin composition. A resin composition is described.

Japanese Unexamined Patent Publication No. 2016-166347

The resin composition for forming the insulating layer generally contains a large amount of thermosetting resin from the viewpoint of achieving high insulating performance. As this thermosetting resin, it was common to use an epoxy resin. In contrast, the present inventors studied 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 present inventors also attempted to apply a resin composition containing an epoxy resin and a fluorine-based filler as described above to an insulating layer of a radar antenna circuit board. However, it has been found that the detectable range of the radar equipped with this antenna circuit board changes depending on the temperature. For example, even if the detection range at a certain temperature is wide at 20 m, there may be cases where the detection range at another temperature is narrowed to 5 m.

The present invention has been devised in view of the above problems, and when installed on a radar antenna circuit board, a resin composition capable of suppressing temperature-induced changes in a radar detectable range and obtaining an insulating layer having a low dielectric constant; a sheet-like laminated material containing the above resin composition; It is an object of the present invention to provide a circuit board and a semiconductor device including an insulating layer made of a cured product of the resin composition.

The present inventors intensively studied to solve the above problems. As a result, the inventors have found that the temperature stability of the dielectric loss tangent of the insulating layer is the cause of the temperature-dependent change in the detectable range of the radar. 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 occurred due to the temperature within the detectable range. Then, this inventor discovered that the said subject could be solved by the resin composition which can obtain the insulating layer excellent in temperature stability of dielectric loss tangent, and completed this invention.

That is, the present invention includes the following.

[1] A resin composition containing (A) an epoxy resin, (B) a maleimide compound, (C) an inorganic filler, and (D) a fluorine-based filler, wherein the amount of component (B) is based on 100% by mass of component (A) 10% by mass to 70% by mass relative to the resin composition.

[2] (A) a resin composition containing an epoxy resin and (D) a fluorine-based filler, wherein the dielectric loss tangent at -10 ° C, 25 ° C and 100 ° C of a cured product obtained by heat-treating the resin composition at 200 ° C for 90 minutes, In the case of Df(-10℃), Df(25℃) and Df(100℃), the ratio of Df(-10℃) to Df(25℃) Df(-10℃)/Df(25℃) is 85% to 115%, and the ratio of Df (100 ° C) to Df (25 ° C) Df (100 ° C) / Df (25 ° C) is 85% to 115%, the resin composition.

[3] (B) The resin composition according to [2], containing a maleimide compound.

[4] The resin composition according to any one of [1] to [3], wherein the component (D) is fluorine-based polymer particles.

[5] The resin composition according to any one of [1] to [4], wherein component (D) is polytetrafluoroethylene particles.

[6] (E) The resin composition according to any one of [1] to [5], containing a resin having an unsaturated hydrocarbon group.

[7] The resin composition according to [6], wherein component (E) has at least one unsaturated hydrocarbon group selected from the group consisting of an acrylic group, a methacrylic group, a styryl group, an allyl group, a vinyl group, and a propenyl group.

[8] The resin composition according to [6] or [7], wherein the component (E) has a vinyl group and has a 5- or more-membered ring cyclic ether structure.

[9] The resin composition according to any one of [1] to [8], for forming an insulating layer of a circuit board.

[10] A sheet-like laminated material comprising the resin composition according to any one of [1] to [9].

[11] A circuit board comprising 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 installed on a radar antenna circuit board, a resin composition capable of suppressing temperature-induced changes in a radar detectable range and obtaining an insulating layer having a low permittivity; a sheet-like laminated material containing the above resin composition; A circuit board and a semiconductor device including an insulating layer made of a cured product of the resin composition may be provided.

Hereinafter, the present invention will be described in detail by disclosing embodiments and examples. However, the present invention is not limited to the embodiments and examples disclosed below, and can be implemented with arbitrary changes without departing from the scope of the claims of the present invention and their equivalents.

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

In the following description, the term “permittivity” indicates relative permittivity unless otherwise specified.

[One. Resin composition according to the first embodiment]

[1.1. Overview 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" refers to one containing a fluorine atom. In addition, the term "fluorine-based filler" refers to a filler containing a compound containing a fluorine atom as a material. In addition, in this resin composition, the amount of the (B) maleimide compound is within a predetermined range.

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

[1.2. (A) Epoxy Resin]

(A) As an epoxy resin as a component, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin , trisphenol type epoxy resin, naphthol 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 resins, glycidyl ester type epoxy resins, cresol novolak type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spirocyclic epoxy resins resins, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, and tetraphenylethane type epoxy resins. An epoxy resin may be used individually by 1 type, or may be used in combination of 2 or more types.

(A) As the epoxy resin, since the change in properties due to temperature is small, an epoxy resin having a cyclic structure such as an alicyclic structure and an aromatic ring structure in addition to an epoxy group is preferable. Among them, an aromatic epoxy resin is preferable from the viewpoint of reducing the average coefficient of linear thermal expansion of the insulating layer. Here, an aromatic epoxy resin refers to an epoxy resin whose molecule contains an aromatic skeleton. In addition, an aromatic skeleton is a chemical structure generally defined as aromatic, and includes not only monocyclic structures such as benzene rings, but also polycyclic aromatic structures such as naphthalene rings and aromatic heterocyclic structures. Among them, from the viewpoint of remarkably obtaining the desired effects of the present invention, (A) epoxy resins include bisphenol A type epoxy resins, bixylenol type epoxy resins, biphenylaralkyl type epoxy resins, naphthylene ether type epoxy resins, and naphthalene type 4 It is preferably at least one type of epoxy resin selected from the group consisting of functional epoxy resins and naphthol type epoxy resins, and bixylenol type epoxy resins are particularly preferable.

It is preferable that a resin composition contains the epoxy resin which has 2 or more epoxy groups in 1 molecule as (A) epoxy resin. From the viewpoint of remarkably obtaining the desired effect of the present invention, (A) the ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the non-volatile component of the epoxy resin is preferably 50% by mass or more, More preferably, it is 60 mass % or more, Especially preferably, it is 70 mass % or more.

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

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable, and an aromatic liquid epoxy resin having two or more epoxy groups in one molecule is more preferable.

Examples of 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, glycidylamine type epoxy resins, and phenol novolac type epoxy resins. , An alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a glycidylamine type epoxy resin , bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins and naphthalene type epoxy resins are more preferable, and bisphenol A type epoxy resins are particularly preferable.

As a specific example of a liquid epoxy resin, "HP4032" by DIC Corporation, "HP4032D", "HP4032SS" (naphthalene type epoxy resin); "828US", "jER828US", "jER828EL", "825", "Epicoat 828EL" (bisphenol A type epoxy resin) by Mitsubishi Chemical Corporation; "jER807" by Mitsubishi Chemical Corporation, "1750" (bisphenol F-type epoxy resin); "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" by Mitsubishi Chemical Corporation, "630LSD" (glycidylamine type|mold epoxy resin); "ZX1059" manufactured by Nippon Steel & Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" by Nagase ChemteX Co., Ltd. (glycidyl ester type epoxy resin); "Celoxide 2021P" by Daicel Co., Ltd. (alicyclic epoxy resin having an ester skeleton); "PB-3600" by the Daicel company (epoxy resin which has a butadiene structure); “ZX1658” and “ZX1658GS” (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel & Chemical Co., Ltd., and the like are exemplified. These may be used individually by 1 type, or may be used in combination of 2 or more types.

As a solid-state epoxy resin, the solid-state epoxy resin which has 3 or more epoxy groups in 1 molecule is preferable, and the aromatic solid-state epoxy resin which has 3 or more epoxy groups in 1 molecule is more preferable.

Examples of solid epoxy resins include bixylenol-type epoxy resins, biphenylaralkyl-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, and trisphenol-type epoxy resins. Preferable are naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, and tetraphenylethane type epoxy resins, and bixylenol type epoxy resins. Resins, biphenylaralkyl type epoxy resins, naphthylene ether type epoxy resins, naphthalene type tetrafunctional epoxy resins and naphthol type epoxy resins are more preferable, and bixylenol type epoxy resins are particularly preferable.

As a specific example of a solid-state epoxy resin, "HP4032H" by DIC Corporation (naphthalene-type epoxy resin); "HP-4700" by DIC Corporation, "HP-4710" (naphthalene type tetrafunctional epoxy resin); "N-690" by DIC Corporation (cresol novolak-type epoxy resin); "N-695" by DIC Corporation (cresol novolak-type epoxy resin); "HP-7200" by DIC Corporation (dicyclopentadiene type epoxy resin); "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" manufactured by DIC ( naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol-type epoxy resin); Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolak-type epoxy resin); Nihon Kayaku Co., Ltd. "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl aralkyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Chemical Co., Ltd.; "ESN485" (naphthol novolak-type epoxy resin) manufactured by Nippon Steel & Chemical Co., Ltd.; Mitsubishi Chemical Corporation "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin); Mitsubishi Chemical Corporation "YX4000HK" (bixylenol type epoxy resin); Mitsubishi Chemical Corporation "YX8800" (anthracene type epoxy resin); "PG-100" by Osaka Gas Chemical Co., Ltd., "CG-500" (bisphenol AF type epoxy resin); Mitsubishi Chemical Corporation "YL7760" (bisphenol AF type epoxy resin); Mitsubishi Chemical Corporation "YL7800" (fluorene type epoxy resin); "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) by the Mitsubishi Chemical Corporation is mentioned. These may be used individually by 1 type, or may be used in combination of 2 or more types.

(A) As the epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used in combination, their mass ratio (liquid epoxy resin:solid epoxy resin) is preferably 1:0.1 to 1:15, more preferably 1 :0.5 to 1:10, particularly preferably 1:1 to 1:8. When the mass ratio of the liquid epoxy resin and the solid epoxy resin is within the above range, when used in the form of an adhesive film, desirable adhesiveness can be obtained. Further, when used in the form of an adhesive film, sufficient flexibility can be obtained and handling properties can be improved. Moreover, the breaking strength of the cured product of the resin composition can be effectively increased.

(A) The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and particularly preferably 110 to 1000. (A) When the epoxy equivalent of the epoxy resin is within the above range, the crosslinking density of the cured product of the resin composition becomes sufficient, and an insulating layer with small surface roughness can be obtained. In addition, epoxy equivalent is the mass of resin containing an epoxy group of 1 equivalent, and can be measured according to JISK7236D.

(A) The weight average molecular weight of the epoxy resin is preferably from 100 to 5000, more preferably from 250 to 3000, still more preferably from 400 to 1500, from the viewpoint of significantly 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, more preferably 3% by mass or more, based on 100% by mass of the non-volatile component in the resin composition, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. 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 component (B) is a compound containing a maleimide group represented by the following formula (B1) in its molecule.

Formula (B1)

(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. am. 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.

(B) It is preferable that the maleimide compound 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, it is preferable that the maleimide compound (B) 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 diphenylether bismaleimide, and 3,3'- Dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2, 4-trimethyl)hexane, 4,4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonebismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis (4-maleimide phenoxy) benzene etc. are mentioned.

From the viewpoint of remarkably obtaining the desired effects of the present invention, as the maleimide compound (B), polyphenylmethane maleimide represented by the general formula (B2) and phenylene bismaleimide represented by the general formula (B3) are particularly preferred. . In formula (B2), n represents an integer greater than or equal to 0.

Formula (B2)

Formula (B3)

(B) As a specific example of a maleimide compound, "BMI-1000" by Daiwa Kasei Co., Ltd. and "BMI" (4,4'-diphenylmethane bismaleimide) by Kei-Ikasei Co., Ltd.; "BMI-2000" (polyphenylmethane maleimide) manufactured by Daiwa Chemical Industry Co., Ltd.; "BMI-3000" by Daiwa Chemical Industry Co., Ltd. (m-phenylene bismaleimide); "BMI-4000" by Daiwa Chemical Industry Co., Ltd., "BMI-80" (bisphenol A diphenylether bismaleimide) by Kei-Ikasei Co., Ltd.; "BMI-5100" manufactured by Daiwa Kasei Co., Ltd., "BMI-70" manufactured by Kei-Ikasei Co., Ltd. (3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide) ; Daiwa Chemical Industry Co., Ltd. "BMI-7000" (4-methyl-1, 3-phenylene bismaleimide); "BMI-TMH" (1,6'-bismaleimide (2,2,4-trimethyl)hexane) manufactured by Daiwa Chemical Industry Co., Ltd.; "BMI-6000" (4,4'-diphenyl ether bismaleimide) manufactured by Daiwa Chemical Industry Co., Ltd.; "BMI-8000" (4,4'-diphenylsulfone bismaleimide) manufactured by Daiwa Chemical Industry Co., Ltd.; 1,3-bis(3-maleimidephenoxy)benzene manufactured by Daiwa Chemical Industry Co., Ltd.; 1,3-bis(4-maleimidephenoxy)benzene manufactured by Daiwa Chemical Industry Co., Ltd.; "ANILIX-MI" by Mitsui Chemicals Fine Inc., etc. are mentioned. In addition, (B) maleimide compound may be used individually by 1 type, and may be used in combination of 2 or more types.

(B) A maleimide compound can be manufactured by making maleic anhydride and an appropriate amine compound react, for example.

The amount of the maleimide compound (B) in the resin composition is preferably 10% by mass or more, more preferably 11% by mass or more, particularly preferably 12% by mass or more with respect to 100% by mass of the (A) epoxy resin, It is preferably 70% by mass or less, more preferably 69% by mass or less, and particularly preferably 68% by 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 1.0% by mass or more based on 100% by mass of the non-volatile component in the resin composition. , Preferably it is 7.0 mass % or less, More preferably, it is 6.7 mass % or less, Especially preferably, it is 6.2 mass % or less. (B) When the amount of the maleimide compound is within 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 inorganic filler material as component (C) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, and 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, titanic acid and barium titanate-zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and phosphate-zirconium tungstate. Among these, silica is particularly suitable from the viewpoint of remarkably obtaining the desired effects of the present invention. As silica, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica etc. are mentioned, for example. Among them, spherical silica is preferable. (C) An inorganic filler may be used individually by 1 type, or may be used in combination of 2 or more types.

Usually, (C) an inorganic filler is contained in a 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, and preferably 5.0 µm or more, from the viewpoint of significantly obtaining the desired effect of the present invention. μm or less, more preferably 2.0 μm or less, still more preferably 1.0 μm or less. Further, (C) when the average particle diameter of the inorganic filler is within the above range, the circuit embeddability of the resin composition layer can be improved or the surface roughness of the insulating layer can be reduced.

(C) Examples of commercially available inorganic fillers include "SP60-05" and "SP507-05" manufactured by Nippon Steel Sumikin Materials; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Adomatex; "UFP-30" by Denka Corporation; "Silent NSS-3N", "Seal NSS-4N", and "Seal NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" etc. by the Adomatex company are mentioned.

(C) The average particle diameter of particles such as an inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of particles is measured on a volume basis with a laser diffraction scattering type particle size distribution analyzer, and the average particle size can be obtained as the median size from the particle size distribution. As the measurement sample, a particle obtained by dispersing particles in a solvent such as water by ultrasonic waves can be preferably used. As the laser diffraction scattering type particle size distribution measuring device, "LA-500" manufactured by Horiba Seisakusho Co., Ltd. or the like can be used.

(C) The specific surface area of the inorganic filler is preferably 1 m 2 /g or more, more preferably 2 m 2 /g or more, and particularly preferably 3 m 2 /g or more, from the viewpoint of significantly obtaining the desired effect of the present invention. . The upper limit is not particularly limited, but is preferably 60 m 2 /g or less, 50 m 2 /g or less, or 40 m 2 /g or less. The specific surface area can be obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multi-point method.

(C) The inorganic filler may be surface treated with an optional surface treatment agent. Examples of the surface treatment agent include coupling agents such as aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, and titanate coupling agents; alkoxysilane compounds; An organosilazane compound etc. are mentioned. By surface treatment with these surface treatment agents, the moisture resistance and dispersibility of (C) inorganic filler can be improved.

As a commercial item of a surface treatment agent, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyl trimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane), for example Silane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane) manufactured by Kogyo Co., Ltd. "KBM-103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long chain epoxy type) manufactured by Shin-Etsu Chemical Co., Ltd. A silane coupling agent) etc. are mentioned. In addition, a surface treatment agent may be used individually by 1 type, and may be used in combination of 2 or more types.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of (C) inorganic filler. (C) The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 from the viewpoint of improving the dispersibility of the (C) inorganic filler. or more, particularly preferably 0.2 mg/m 2 or more. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, the carbon amount is preferably 1 mg/m 2 or less, more preferably 0.8 mg/m 2 or less, particularly preferably It is less than 0.5mg/m2.

(C) The amount of carbon per unit surface area of the inorganic filler is measured after washing the (C) inorganic filler after surface treatment with a solvent (for example, methyl ethyl ketone (hereinafter sometimes abbreviated as “MEK”)). can do. Specifically, a sufficient amount of MEK and (C) inorganic filler surface-treated with a surface treatment agent are mixed, and ultrasonic cleaning is performed at 25°C for 5 minutes. Then, after removing the supernatant and drying the non-volatile components, the amount of carbon per unit surface area of (C) the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Seisakusho Co., 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, still more preferably 15% by mass or more, especially with respect to 100% by mass of the non-volatile component in the resin composition. It is preferably 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 when 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. Further, (C) When the amount of the inorganic filler is equal to or less than the upper limit of the above range, the mechanical strength of the cured product of the resin composition can be improved, and especially resistance to elongation can be enhanced.

[1.5. (D) fluorine-based filler]

The fluorine-based filler as component (D) is a filler containing a compound containing a fluorine atom as a material. Fluorine-based fillers are generally in the form of particles. Therefore, as the (D) fluorine-based filler, particles containing a compound containing a fluorine atom as a material are usually used.

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

Examples of the fluorine-based polymer include polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene propene copolymer (FEP), ethylene/tetrafluoroethylene copolymer (ETFE), Tetrafluoroethylene-perfluorodioxole copolymer (TFE/PDD), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyfluorinated Vinyl (PVF) is exemplified. These may be used individually by 1 type, or may be used in combination of 2 or more types.

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

The weight average molecular weight of the fluorine-based polymer is preferably 5000000 or less, more preferably 4000000 or less, 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, Especially preferably, it is 4 micrometers or less. When the average particle diameter of the (D) fluorine-based filler is within the above range, the desired effect of the present invention can be remarkably obtained, and the dispersibility of the (D) fluorine-based filler in the ordinary resin composition 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, similarly to the inorganic filler (C).

(D) Examples of commercially available fluorine-based fillers include "Lubron L-2", "Lubron L-5" and "Lubron L-5F" manufactured by Daikin Kogyo Co., Ltd.; "FluonPTFE L-170JE" by Asahi Glass Co., Ltd., "FluonPTFEL-172JE", "FluonPTFE L-173JE"; "KTL-500F", "KTL-2N", "KTL-1N" by the Kitamura company; "TLP10F-1" by Mitsui-DuPont Fluorochemical Co., Ltd., etc. are mentioned.

(D) The fluorine-based filler may be surface treated. For example (D), the fluorine-based filler may be surface-treated with an optional 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 etc. are mentioned. From the viewpoint of affinity, it is preferable to use a fluorine-based surfactant as the surface treatment agent. As a specific example of a fluorine-type surfactant, "Suffron S-243" by the AGC Semichemical company (perfluoroalkyl ethylene oxide adduct); "Megapack F-251", "Megapack F-477", "Megapack F-553", "Megapack R-40", "Megapack R-43", "Megapack R-94" manufactured by DIC 」; "FTX-218" and "Futagent 610FM" manufactured by Neos Co., Ltd. are exemplified.

The amount of the (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 or more, based on 100% by mass of the non-volatile component in the resin composition, It is preferably 80% by mass or less, more preferably 60% by mass or less, and particularly preferably 40% by mass or less. (D) When the amount of the fluorine-based filler 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 (D) fluorine-based filler in the resin composition is preferably 20% by mass or more, more preferably 30% by mass or more, particularly preferably, based on 100% by mass of the total of the inorganic filler (C) and the fluorine-based filler (D). It is 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 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.

[1.6. (E) resin having an unsaturated hydrocarbon group]

The resin composition may contain (E) resin having an unsaturated hydrocarbon group as an optional component other than the components described above. In the following description, "resin having an unsaturated hydrocarbon group" as component (E) may be referred to as "unsaturated resin". As for the carbon-carbon unsaturated bond, only one may be contained in one molecule of (E) unsaturated resin, or a plurality may be contained. (E) A cured product of a resin composition containing an unsaturated resin usually contains a molecular structure site formed by reaction of an unsaturated bond site of the (E) unsaturated resin. As a result, the polarity of the cured product is reduced, and the value of the dielectric loss tangent can be reduced. In addition, the dispersibility of the fluorine-based filler (D) can be improved by the unsaturated resin (E). 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.

(E) The unsaturated resin contains an unsaturated hydrocarbon group in the molecule of the (E) unsaturated resin. The unsaturated hydrocarbon group is preferably at least one group selected from the group consisting of an acryl group, a methacryl group, a styryl group, and an olefin group. Here, "olefin group" refers to an aliphatic hydrocarbon group having a carbon-carbon double bond in the molecule. Preferred examples of the olefin group include an allyl group, a vinyl group, and a propenyl group. Accordingly, the (E) unsaturated resin preferably has at least one unsaturated hydrocarbon group 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) It is preferable that unsaturated resin is a compound which has a cyclic ether structure of 5 or more membered rings. In the following description, the "compound having a 5-membered ring or more cyclic ether structure" may be referred to as an "unsaturated cyclic ether compound". Unsaturated cyclic ether compounds usually have limited molecular motion, so the dielectric loss tangent can be effectively lowered.

The unsaturated cyclic ether compound may contain a carbon-carbon unsaturated bond within the cyclic ether structure or outside the cyclic ether structure.

The unsaturated cyclic ether compound may contain only one cyclic ether structure, or may contain a plurality of cyclic ether structures.

The cyclic ether structure may have a monocyclic structure containing only one ring, may have a polycyclic structure containing two or more rings, or may have a condensed ring structure containing condensed rings.

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 3 or less.

The cyclic ether structure is preferably a 5- to 10-membered ring, more preferably a 5- to 8-membered ring, still more preferably a 5- to 6-membered ring. Specific examples of the 5-membered ring or higher cyclic ether structure include a furan structure, a tetrahydrofuran structure, a dioxolan structure, a pyran structure, a dihydropyran structure, a tetrahydropyran structure, and a dioxane structure. Especially, a dioxane structure is preferable from a 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 in this substituent is usually 1 to 6, preferably 1 to 3.

Among the unsaturated cyclic ether compounds described above, those having a vinyl group are preferable. By using an unsaturated cyclic ether compound having a vinyl group (i.e., a compound having a vinyl group and a 5- or more-membered cyclic ether structure) as the (E) unsaturated resin, the desired effects of the present invention can be remarkably obtained. In addition, the dielectric loss tangent of the ordinary resin composition can be effectively lowered.

(E) Preferred examples of the unsaturated resin include compounds represented by the following formula (E1), compounds represented by the following formula (E6), and compounds represented by the following formula (E7). Among them, the compound represented by the formula (E7) is an unsaturated cyclic ether compound and is particularly preferred.

Formula (E1)

In formula (E1), R ¹ to R ⁶ each independently represent 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).

Formula (E2)

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

Formula (E2-1)

Formula (E2-2)

Formula (E2-3)

In the 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 the 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, preferably a hydrogen atom or a methyl group.

In the formula (E2-3), R ²⁷ to R ³⁴ 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 the formula (E2-3), E represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

Formula (E3)

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

Formula (E4)

In formula (E4), R ⁷ to R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and preferably represent 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 above formulas (E2-1), (E2-2) or (E2-3).

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

Formula (E5)

In formula (E5), R ¹ to R ⁶ have the same meaning as R ¹ to R ⁶ in formula (E1), B has the same meaning as B in formula (E2), and a and b have the same meaning as in formula (E4 ) has the same meaning as a and b of

Formula (E6)

Formula (E7)

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

Examples of the divalent group having a 5-membered ring or more cyclic ether structure include a furan-2,5-diyl group, a tetrahydrofuran-2,5-diyl group, a dioxolan-2,5-diyl group, and a pyran-2,5-diyl group. 2,5-diyl group, dihydropyran-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,2-dioxane-3,6-diyl group, 1,3-dioxane- A 2,5-diyl group, a 1,4-dioxane-2,5-diyl group, and a 5-ethyl-1,3-dioxane-2,5-diyl group are mentioned. Especially, 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 divalent linking groups. As a divalent linking group, for example, an alkylene group which may have a substituent, an alkynylene group which may have a substituent, an arylene group which may have a substituent, a heteroarylene group which may have a substituent, a group represented by -COO- , a group represented by -CO-, a group represented by -CONH-, a group represented by -NHCONH-, a group represented by -NHCOO-, a group represented by -C(=O)-, a group represented by -S- groups represented by -SO-, groups represented by -NH-, and groups combining a plurality of these groups.

As a substituent, for example, a halogen atom, -OH, -OC _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)OC _1-6 alkyl group, -COOH, -C(O)H, -NO ₂ and the like. Here, the term "C _pq " (p and q are positive integers and satisfies p<q) indicates that the number of carbon atoms in the organic group described immediately after the term is p to q. For example, the expression "C _1-6 alkyl group" represents 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 groups similar to the substituents already described.

Among these, B ¹ and B ² are two or more groups selected from the group consisting of an alkylene group which may have a substituent, an alkynylene group which may have a substituent, a group represented by -COO-, and a group represented by -O- Groups in combination are 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 represents a functional group. As a functional group, a vinyl group, a methacryl group, an acryl group, an allyl group, a styryl group, a propenyl group, and an epoxy group are mentioned, for example. As a functional group, a vinyl group is preferable.

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

Formula (E8)

(E) As the unsaturated resin, for example, "OPE-2St 1200" (styrene-modified polyphenylene ether resin, number average molecular weight 1200, equivalent to the above formula (E5)) manufactured by Mitsubishi Gas Chemical Co., Ltd. " YL7776" (bixylenoldiallyl ether resin, number average molecular weight 331, equivalent to the above formula (E6)), Shin Nakamura Kagaku Kogyo Co., Ltd. "A-DOG" (dioxane acrylic monomer glycol diacrylate, number average molecular weight 326, Corresponding to the said chemical formula (E8)), "KAYARAD R-604" by Nippon Kayaku Co., Ltd. (corresponding to the said chemical formula (E8)) is mentioned. 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 the unsaturated resin is preferably 100 or more, more preferably 200 or more, and is preferably 10000 or less, more preferably 3000 or less. (E) When the number average molecular weight of the unsaturated resin is within the above range, volatilization during drying of the resin varnish can be suppressed or excessive melt viscosity of the resin composition can be suppressed. The number average molecular weight can be measured as a value in terms of polystyrene by a gel permeation chromatography (GPC) method. The measurement of the number average molecular weight by the GPC method uses, for example, "LC-9A/RID-6A" manufactured by Shimadzu Corporation as a measuring device, and "Shodex K-800P/K manufactured by Showa Denko Corporation" as a column. -804L/K-804L”, using chloroform as a mobile phase, and measuring at a column temperature of 40°C.

The amount of the (E) unsaturated resin in the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, and preferably 15% by mass or less based on 100% by mass of the non-volatile component in the resin composition. Preferably it is 10 mass % or less. (E) When the amount of the unsaturated resin is equal to or more than the lower limit of the range, the dielectric loss tangent of the cured product of the resin composition can be effectively lowered, and when the amount is equal to or less than the upper limit of the range, the compatibility of the resin varnish can be improved.

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

[1.7. (F) curing agent]

The resin composition may contain (F) a hardening|curing agent as an arbitrary component other than the above-mentioned component. The curing agent as 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 phenolic curing agent, a naphthol curing agent, a benzoxazine curing agent, a cyanate ester curing agent, and a carbodiimide curing agent. In addition, 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, compounds having two or more ester groups with high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. this is preferable The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound, 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 phenolic compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxy benzophenone, tetrahydroxy benzophenone, phloroglucine, benzene triol, dicyclopentadiene type diphenol compound, phenol novolak, etc. are mentioned. Here, "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensation of 2 molecules of phenol to 1 molecule of dicyclopentadiene.

Preferred specific examples of the active ester curing agent include active ester compounds containing a dicyclopentadiene type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated product of phenol novolac, and phenol novolak. and active ester compounds containing benzoylides. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

Examples of commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" and "HPC" as active ester compounds containing a dicyclopentadiene type diphenol structure. -8000H-65TM", "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC Corporation); "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoyl compound of phenol novolak; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent that is an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc. are mentioned as an active ester type curing agent which is a benzoyl compound of phenol novolac.

As the phenol-based curing agent and the naphthol-based curing agent, those having a novolak structure are preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion between the insulating layer and the conductor layer, a nitrogen-containing phenolic curing agent is preferable, and a triazine skeleton-containing phenolic curing agent is more preferable.

As a specific example of a phenol type hardening|curing agent and a naphthol type hardening|curing agent, it is "MEH-7700" by a Meiwa Kasei company, "MEH-7810", "MEH-7851", for example; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V" and "SN375" manufactured by Nippon Steel & Chemical Co., Ltd.; "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" etc. made by DIC Corporation are mentioned.

As a specific example of a benzoxazine type hardening|curing agent, "HFB2006M" by the Showa Kobunshi company, "P-d" by the Shikoku Kasei Kogyo Co., Ltd., and "F-a" are mentioned.

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylencyanate), 4,4'-methylenebis(2,6- dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4- cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanate) Bifunctional cyanate resins, such as nate phenyl) thioether and bis (4-cyanate phenyl) ether; polyfunctional cyanate resins derived from phenol novolaks, cresol novolacs, and the like; and prepolymers in which these cyanate resins are partially triazinated. As specific examples of the cyanate ester curing agent, "PT30" and "PT60" (phenol novolak type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), and "BA230" manufactured by Lonza Japan Co., Ltd. ”, “BA230S75” (a prepolymer obtained by triazation of part or all of bisphenol A dicyanate to form a trimer), and the like.

As a specific example of a carbodiimide type hardening|curing agent, "V-03" by Nissinbo Chemical Co., Ltd., "V-07", etc. are mentioned.

Among the above, an active ester type curing agent is preferable as the curing agent (F) from the viewpoint of remarkably obtaining the desired effect of the present invention. When an active ester-based curing agent is used, (F) the amount of the active ester-based curing agent relative to 100% by mass of the curing agent is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more and is preferably 100% by mass or less. When the amount of the active ester-based 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 lowered.

The amount of the curing agent (F) in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on 100% by mass of the non-volatile component in the resin composition, from the viewpoint of significantly obtaining the desired effect of the present invention. , More preferably 1% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by 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, and preferably 1.5 or less, More preferably, it is 1.2 or less, and still more preferably 1 or less. Here, "the number of epoxy groups of the (A) epoxy resin" is a value obtained by summing all the values obtained by dividing the mass of the non-volatile component of the (A) epoxy resin present in the resin composition by the epoxy equivalent. In addition, "the number of active groups of the (F) curing agent" is a value 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 of the epoxy resin is 1, when the number of active groups of the curing agent (F) is within the above range, the desired effect of the present invention can be remarkably obtained, and the heat resistance of the cured product of the normal resin composition is further improved. do.

[1.8. (G) curing accelerator]

The resin composition may contain (G) a hardening accelerator as an optional component other than the above components. (G) When hardening a resin composition, hardening can be accelerated|stimulated by using a hardening accelerator.

(G) Examples of the curing accelerator include phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, guanidine curing accelerators, metal curing accelerators, and peroxide curing accelerators. Among them, amine-based hardening accelerators and peroxide-based hardening accelerators are particularly preferred. (G) A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

Examples of the phosphorus curing accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl)triphenyl. Phosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyl triphenylphosphonium thiocyanate are mentioned. Among them, triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1, and 8-diazabicyclo(5,4,0)-undecene. Among them, 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl Imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s- Triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine 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 ] Imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzimidazolium chloride, 2-methyl imidazoline, and 2-phenyl imidazoline; And an adduct of an imidazole compound and an epoxy resin is mentioned. Among them, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As an imidazole type hardening accelerator, you may use a commercial item, for example, "P200-H50" by the 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, and diphenylguanidine. , trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide. Among them, dicyandiamide and 1,5,7-triazabicyclo[4.4.0]deca-5-ene are preferable.

Examples of the metal-based hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. 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 iron complexes such as organic zinc complexes and iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate and zinc stearate.

As the peroxide-based curing accelerator, for example, cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, diiso Propylbenzene hydroperoxide, cumene hydroperoxide, and tert-butyl hydroperoxide are exemplified.

As a peroxide type hardening accelerator, a commercial item can be used, for example, "Percumyl D" by Nichiyu Co., Ltd. is mentioned.

(G) In the case of using a curing accelerator, the amount of the (G) curing accelerator in the resin composition is preferably 0.01 mass% relative to 100 mass% of the non-volatile component in the resin composition from the viewpoint of significantly obtaining the desired effect of the present invention. % or more, more preferably 0.02 mass% or more, particularly preferably 0.03 mass% or more, preferably 3 mass% or less, more preferably 2 mass% or less, and particularly preferably 1 mass% or less.

[1.9. (H) Additives]

The resin composition may further contain an additive as an optional component other than the components described above. Examples of such additives include organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds; thickening agent; antifoam; leveling agent; adhesion imparting agent; coloring agent; flame retardants; A thermoplastic resin etc. are mentioned. In addition, an additive may be used individually by 1 type, and may be used in combination of 2 or more types.

[1.10. Manufacturing method of resin composition]

The resin composition can be prepared, for example, by a method of mixing the ingredients with a solvent as needed and stirring them using a stirring device such as a rotary mixer.

[1.11. Characteristics of Resin Composition]

The cured product of the resin composition described above can have a low dielectric constant. Therefore, with the cured product of this resin composition, an insulating layer with a low dielectric constant can be obtained. For example, when a cured product is obtained by curing a resin composition by the method described in Examples, the cured product can have a dielectric constant of 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.

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

Therefore, with the cured product of this resin composition, an insulating layer excellent in temperature stability of dielectric loss tangent can be obtained. Specifically, the dielectric loss tangents at -10 ° C, 25 ° C and 100 ° C of a cured product obtained by heat-treating a resin composition at 200 ° C for 90 minutes are Df (-10 ° C), Df (25 ° C) and Df (100 ° C), respectively. ℃), the ratio of Df (-10 ° C) to Df (25 ° C) Df (-10 ° C) / Df (25 ° C), and the ratio of Df (100 ° C) to Df (25 ° C) Df (100 ° C.) / Df (25 ° C.) becomes the following range.

That is, the ratio of dielectric loss tangent 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 113% or less.

Further, the ratio of dielectric loss tangent 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 113% or less.

The dielectric loss tangents Df (-10°C), Df (25°C), and Df (100°C) can be measured by the method described in Examples.

As described above, the present inventors estimate a structure excellent in temperature stability of the dielectric loss tangent as follows. However, the technical scope of the present invention is not limited by the structure described below.

According to the study of the present inventors, the dielectric loss tangent of a cured product of a resin composition containing (A) an epoxy resin and (D) a fluorine-based filler is smaller at a lower temperature and smaller at a higher temperature in a practical temperature range from -10°C to 100°C. It has been found that there is a large tendency Conversely, the dielectric loss tangent of the polymer of the maleimide compound (B) tends to be larger at lower temperatures and smaller at higher temperatures due to the action of maleimide groups in the practical temperature range of the singe group. Thus, the temperature dependence of the dielectric loss tangent of the cured product of the resin composition containing (A) the epoxy resin and the fluorine-based filler (D) and the temperature dependence of the dielectric loss tangent of the polymer of the maleimide compound (B) are 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 loss tangent of both cancels each other, and the same dielectric loss tangent Df is obtained at both low and high temperatures. You can get it. Accordingly, the dielectric loss tangent of a cured product of a 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 a resin composition at 200°C for 90 minutes is preferably 0.020 or less, more preferably 0.010 or less, still more preferably 0.009 or less, Especially preferably, it is 0.008 or less, 0.007 or less, or 0.006 or less. The lower limit is not particularly limited, but is usually 0.001 or more.

[2. Resin composition according to the second embodiment]

A resin composition according to a second embodiment of the present invention includes (A) an epoxy resin and (D) a fluorine-based filler. In addition, 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 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) is 85% to 115%, and Df (25 ° C) The ratio of Df (100 ° C) to ° C) Df (100 ° C) / 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 ratios of the dielectric loss tangent Df(-10°C)/Df(25°C) and Df(100°C)/Df(25°C) fall within a predetermined range of 85% to 115%, the hardness of this resin composition Cargo has excellent temperature stability of dielectric loss tangent. Therefore, according to the resin composition according to the second embodiment, since the temperature stability of the dielectric loss tangent is excellent, it is possible to suppress the change due to the temperature of the radar detectable range when installed on the radar antenna circuit board, and the dielectric constant is low. The present invention can obtain the desired effect that a resin composition capable of obtaining an insulating layer can be realized. Further, according to the resin composition according to the second embodiment, the same advantages as the resin composition according to the first embodiment can be obtained.

Regarding the (A) epoxy resin and (D) fluorine-based filler of the resin composition according to the second embodiment, the matters described in the first embodiment can be applied in the same manner as in the first embodiment.

The resin composition according to the second embodiment, from the viewpoint of bringing the dielectric loss tangent ratios Df (-10 ° C) / Df (25 ° C) and Df (100 ° C) / Df (25 ° C) within a predetermined range, (B ) It is preferable that a maleimide compound is included. Usually, by adjusting the amount of (B) maleimide compound, the ratio Df (-10 ° C) / Df (25 ° C) and Df (100 ° C) / Df (25 ° C) can be made to fall within a predetermined range. Regarding the (B) maleimide compound of the resin composition according to the second embodiment, the matters described in the first embodiment can be applied in the same manner as in the first embodiment.

The resin composition according to the second embodiment includes one or more of (C) an inorganic filler, (E) an unsaturated resin, (F) a curing agent, (G) a curing accelerator, and (H) additives as optional components in addition to the above components. You may include two or more. (C) inorganic filler, (E) unsaturated resin, (F) curing agent, (G) curing accelerator, and (H) additive of the resin composition according to the second embodiment are the same as those described in the first embodiment. It can be applied like the embodiment.

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

The resin composition according to the second embodiment usually has the same properties 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 the dielectric loss tangent, and usually has a small dielectric loss tangent at 25°C.

[3. Use 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. The insulating layer includes an insulating layer for forming a conductor layer (including a redistribution layer) on the insulating layer. Therefore, the resin composition may be used as a resin composition for forming an insulating layer for forming a conductor layer. Among them, the resin composition is preferably used as a resin composition for forming a build-up insulating layer for forming an insulating layer in manufacture of a circuit board by a build-up method.

In particular, taking advantage of the advantage of being able to obtain an insulating layer having a low dielectric constant, this resin composition can be suitably used as a resin composition for forming an insulating layer of a high-frequency circuit board (resin composition for forming an insulating layer of a high-frequency circuit board). can Especially, this resin composition can be used more suitably as a resin composition for forming the interlayer insulating layer of a high-frequency circuit board (resin composition for forming the interlayer insulating layer of a high-frequency circuit board). Here, "high-frequency circuit board" means a circuit board capable of operating even electric signals in a high-frequency band. In addition, "high frequency band" usually means a band of 1 GHz or higher, and the resin composition is particularly effective in a band of 28 GHz to 150 GHz.

In addition, it is preferable to use this resin composition as a resin composition for an insulating layer of an antenna circuit board for a radar, taking advantage of the good temperature stability of the dielectric loss tangent. As an insulating layer of this antenna circuit board, a wiring formation layer etc. are mentioned, for example. As described above, by using a cured material having good temperature stability of the dielectric loss tangent as the material of the insulating layer, it is possible to reduce the temperature-dependent change in the loss in the antenna circuit board, so that a highly sensitive radar that does not depend on the operating temperature can be obtained. It can be realized.

In addition, since an insulating layer with a low dielectric constant can contribute to a low profile of a circuit board, it is suitable for applications requiring a thin circuit board. In addition, since the insulating layer having a low permittivity facilitates impedance control of the circuit board, it is suitable for increasing the degree of freedom in designing the circuit board. From this point of view, suitable uses of the resin composition include, for example, circuit boards such as motherboards used for mobile devices, IC package boards, camera module boards, and fingerprint authentication sensor boards. For example, a 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 using the fact that the concave and convex portions of the fingerprint have different capacitance values of the capacitance formed by the finger, the electrode, and the insulating coating placed on the insulating film. 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 can be used for a wide range of applications in which the resin composition is used, such as adhesive films, sheet-like laminate materials such as prepreg, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, and parts embedding resins. can

[4. Sheet-like laminated material]

The above resin composition may be applied in a varnish state and used for forming an insulating layer. However, industrially, it is preferable to use it in the form of a sheet-like laminated material containing this resin composition. Preferred examples of the sheet-like laminated material include adhesive films and prepregs.

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 resin composition, and is sometimes referred to as an “adhesive layer”.

The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, even more preferably 60 μm or less, and particularly preferably 50 μm or less, from the viewpoint of thinning. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be, for example, 1 μm or more, 5 μm or more, or 10 μm or more.

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

When using a film made of a plastic material as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter sometimes referred to as "PEN"), and the like. of polyester; polycarbonate (hereinafter sometimes referred to as "PC"); acrylic polymers such as polymethyl methacrylate (hereinafter sometimes referred to as "PMMA"); cyclic polyolefin; triacetyl cellulose (hereinafter sometimes referred to as "TAC"); polyether sulfide (hereinafter sometimes referred to as "PES"); polyether ketone; Polyimide is mentioned. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and polyethylene terephthalate is particularly preferable because it is inexpensive and has excellent availability.

When using metal foil as a support body, as a metal foil, copper foil, aluminum foil, etc. are mentioned, for example. Especially, copper foil is preferable. As the copper foil, foil made of a single metal of copper may be used, or foil made of an alloy of copper and another metal (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used .

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

Moreover, as a support body, you may use the support body with a release layer which has a release layer on the surface to which it joins with a resin composition layer. As a release agent which can be used for the release layer of the support body with a release layer, one or more types of release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins are exemplified. As a commercial item of a release agent, "SK-1" by a Lintec company which is an alkyd resin type release agent, "AL-5", "AL-7" etc. are mentioned, for example. In addition, as a support body with a mold release layer, it is "Lumiror T60" by a Toray company, for example; "Purex" by the Teijin company; "Uni-Peel" manufactured by Unitica Co., Ltd., and the like are exemplified.

The thickness of the support is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. Moreover, 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.

The adhesive film is obtained by, for example, preparing a resin varnish containing an organic solvent and a resin composition, applying the resin varnish to a support using a coating device such as a die coater, and further drying to form a resin composition layer. can be manufactured

Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; Acetate ester solvents, such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitol solvents such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; Amide type solvents, such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone, are mentioned. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

Drying can be performed by a known method such as heating or hot air spraying. 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. Although it depends 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, by drying at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes, the resin A composition layer may be formed. Usually, the resin composition layer is obtained as a film obtained by semi-curing a coating film of resin varnish.

The adhesive film may contain arbitrary layers other than a support body and a resin composition layer as needed. For example, in the adhesive film, a protective film conforming to the support may be provided on the surface of the resin composition layer not bonded to the support (ie, the surface on the opposite side to the support). The thickness of the protective film is, for example, 1 μm to 40 μm. With the protective film, adhesion of dust or the like to the surface of the resin composition layer and scratches can be suppressed. When the adhesive film has a protective film, usually the adhesive film becomes usable by peeling off the protective film. In addition, the adhesive film can be rolled into a roll shape and stored.

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

The sheet-like fiber substrate used for the prepreg is not particularly limited. As the sheet-like fiber substrate, any fiber substrate used as a prepreg substrate such as glass cloth, aramid nonwoven fabric, and 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 suppressing the depth of plating involved in forming the conductor layer to a small level, 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-like fiber substrate is usually 1 µm or more, and may be 1.5 µm or more or 2 µm or more.

Prepreg can be manufactured by methods such as a hot melt method and a solvent method. The thickness of the prepreg may be in the same range as that of the resin composition layer in the adhesive film.

[5. circuit board]

The circuit board of the present invention includes an insulating layer formed of a cured product of the above resin composition. In one embodiment, the circuit board includes an inner layer substrate and an insulating layer provided on the inner layer substrate.

An "inner layer board" is a member used as a base material of a circuit board. Examples of the inner layer substrate include 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 addition, usually, the inner layer substrate has a conductor layer formed directly or indirectly on one side or both sides of the core substrate. This conductor layer may be subjected to pattern processing in order to function as an electrical circuit, for example. An inner layer board in which a conductor layer as a circuit is formed on one side or both sides of the core board is sometimes called an "inner layer circuit board". In addition, an intermediate product in which at least one of an insulating layer and a conductor layer is to be further formed in order to manufacture a circuit board is also included in the term "inner layer board". When the circuit board has built-in components, an inner-layer board with built-in components may be used.

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

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 to each other. Further, the inner layer substrate may include additional components such as passive elements.

The insulating layer is a layer of a cured product of a resin composition. The insulating layer formed of this cured material is particularly used for build-up circuit boards, high-frequency circuit boards, radar antenna circuit boards, and motherboards, IC package boards, camera module boards, and fingerprint authentication used in mobile devices. It is suitably applicable to the insulating layer for circuit boards, such as a board|substrate for sensors.

The circuit board may have only one insulating layer, or may have two or more layers. When a circuit board has two or more insulating layers, it can provide as a buildup layer in which a conductor layer and an insulating layer were alternately laminated.

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

In the insulating layer, one or more via holes for electrically connecting the conductor layers of the circuit board may be provided.

Since the insulating layer is a layer formed of a cured product of the above-described resin composition, the cured product of the above-described resin composition can exhibit excellent properties. Therefore, the insulating layer of the circuit board preferably has the dielectric constant of the insulating layer, the ratio of the dielectric loss tangent Df (-10 ° C) / Df (25 ° C), the ratio of the dielectric loss tangent Df (100 ° C) / Df (25 ° C), and dielectric loss tangent Df (25°C) at 25°C can be adjusted within the same range as described in the section on the resin composition. In addition, these properties can be measured by the method described in the Examples.

A circuit board can be manufactured by the manufacturing method including the following process (I) and process (II) using an adhesive film, for example.

(I) A step of laminating an adhesive film on an inner layer substrate so that the resin composition layer of the adhesive film is bonded to the inner layer substrate.

(II) A step of forming an insulating layer by thermally curing the resin composition layer.

Lamination of the inner layer substrate and the adhesive film can be performed by, for example, a heat press step of heating while pressing the adhesive film against the inner layer substrate from the support side. As a member (also referred to as a "heat-compression member") for the heat-pressing step, a heated metal plate (SUS head plate or the like) or a metal roll (SUS roll) is exemplified. In addition, it is preferable to press the heat-compressed member through an elastic material such as heat-resistant rubber so that the adhesive film sufficiently follows the irregularities on the surface of the inner layer substrate, rather than pressing the hot-press member directly onto the support of the adhesive film.

Lamination of the inner layer substrate and the adhesive film can be performed by, for example, a vacuum lamination method. The temperature of hot pressing in the vacuum lamination method is preferably 60°C to 160°C, more preferably 80°C to 140°C. The pressure of heat compression is preferably 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa. The heat compression time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

Lamination can be performed with a commercially available vacuum laminator. As a commercially available vacuum laminator, a vacuum pressure type laminator by Meiki Seisakusho, a vacuum applicator by Nikko Materials, a batch type vacuum pressure laminator, etc. are mentioned, for example.

After lamination, the laminated resin composition layer may be smoothed by pressing from the support body side under normal pressure (under atmospheric pressure), for example, with a hot pressing member. The press conditions for the smoothing treatment can be the same as the conditions for the thermal compression of the laminate. The smoothing process can be performed with a commercially available laminator. In addition, the lamination and smoothing treatment may be performed continuously using the commercially available vacuum laminator described above.

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

In step (II), the resin composition layer is thermally cured to form an insulating layer. Conditions for thermal curing of the resin composition layer are not particularly limited, and conditions employed in forming an insulating layer of a circuit board can be arbitrarily adopted.

Conditions for thermal curing of the resin composition layer also differ depending on the type of the resin composition, for example. 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). In addition, 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 thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer is usually at a temperature of 50°C or more and less than 120°C (preferably 60°C or more and 110°C or less, more preferably 70°C or more and 100°C or less). You may preheat normally for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

The manufacturing method of the circuit board may further include (III) a step of perforating 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 carried out according to an appropriate method used for manufacturing a circuit board. In the case where the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). You may carry out at any point in between.

Step (III) is a step of perforating the insulating layer. Holes such as via holes and through holes can be formed in the insulating layer by perforation. Step (III) can be carried out by, for example, a method such as a drill, laser, 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 roughening the insulating layer. The order and conditions of the roughening treatment are not particularly limited, and any order and conditions used in forming the insulating layer of the circuit board can be employed. For example, the insulation layer can be roughened by sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralization liquid.

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

As an oxidizing agent, the alkaline permanganic acid solution which melt|dissolved potassium permanganate or sodium permanganate in the aqueous solution of sodium hydroxide is mentioned, for example. In addition, 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°C to 80°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan.

As the neutralization liquid, an acidic aqueous solution is preferable. As a commercial item of a neutralization liquid, "Reduction Solution Securiganth P" by the Atotech Japan company is mentioned, for example. In addition, 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 neutralization solution can be performed by immersing the treated surface of the insulating layer subjected to the roughening treatment with the oxidizing agent in the neutralization solution at 30°C to 80°C for 5 minutes to 30 minutes. From the standpoint of workability and the like, a method in which the insulating layer subjected to the roughening treatment with an oxidizing agent is immersed in a neutralization 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 suitable embodiments, the conductor layer comprises one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. . The 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 types of metals selected from the above groups (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, from the viewpoints of versatility of formation of a conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; Alternatively, an alloy layer of a nickel/chromium alloy, a copper/nickel alloy, or a copper/titanium alloy is preferable. Further, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; Alternatively, an alloy layer of a 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 multi-layer 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 a 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 direct patterning using, for example, a metal foil used as a support for an adhesive film. In addition, the conductor layer can be formed by plating, for example. As a formation method by plating, for example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a method such as a semi-additive method or a full additive method. Especially, it is preferable to form by the semi-additive method from a viewpoint of the simplicity of manufacture.

Hereinafter, an example in which the conductor layer is formed by a semi-additive method will be described. First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Subsequently, a mask pattern exposing a portion of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. After forming a metal layer by electroplating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

You may form a conductor layer using 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 step (I), the support is removed and 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 lamination 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. After that, 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 using the metal foil on the insulating layer. Metal foil can be manufactured by methods, such as an electrolysis method and a rolling method, for example. As a commercial item of metal foil, HLP foil by the JX Nikko Nisseki Ginzoku company, JXUT-III foil, 3EC-III foil by the Mitsui Ginzoku Kozan company, TP-III foil, etc. are mentioned, for example.

When the circuit board has two or more insulating layers and a conductor layer (build-up layer), the above insulating layer formation step and the conductor layer formation step are further repeated one or more times to function as a circuit. A circuit board having a multilayer wiring structure can be manufactured.

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

[6. semiconductor device]

A semiconductor device includes the circuit board. This semiconductor device can be manufactured using a circuit board.

Examples of semiconductor devices include various semiconductor devices provided for electric appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, electric cars, ships, aircraft, etc.). there is.

A semiconductor device can be manufactured, for example, by mounting a component (semiconductor chip) on a conduction location of a circuit board. A "conductive location" is "a location through which an electric signal is transmitted on a circuit board", and the location may be the surface of the circuit board or a location embedded in the circuit board. Also, as the semiconductor chip, an electric circuit element made of a semiconductor can be arbitrarily used.

As a method of mounting a semiconductor chip when manufacturing a semiconductor device, any method that effectively functions the semiconductor chip can be employed. Examples of the semiconductor chip mounting method include a wire bonding mounting method, a flip chip mounting method, a mounting method using a bumpless build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a non-conductive film (NCF). The mounting method by can be mentioned. Here, the "mounting method using a bumpless build-up layer (BBUL)" means a "mounting method in which a semiconductor chip is directly embedded in a circuit board to connect wiring between the semiconductor chip and the circuit board."

Example

Hereinafter, the present invention will be described in detail by disclosing examples. However, the present invention is not limited to these examples. In addition, in the description below, "part" and "%" mean "part by mass" and "% by mass", respectively, unless otherwise specified.

[Example 1]

While stirring 20 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) and 2.5 parts of phenylmethane maleimide resin (“BMI-2000” manufactured by Daiwa Kasei Co., Ltd.) with 20 parts of solvent naphtha It melt|dissolved by heating, and then cooled to room temperature, and the resin solution was obtained.

To this resin solution, 100 parts of an inorganic filler ("SO-C2" manufactured by Adomatex, average particle diameter: 0.5 µm, specific surface area: 5.9 m/g, carbon content per unit surface area: 0.38 mg/m), and polytetrafluorocarbon 55 parts of ethylene particles ("Lubron L-2" manufactured by Daikin Kogyo Co., Ltd., average particle size: 3 µm) were mixed, and kneaded and dispersed with three rolls.

In addition, to this resin solution, 31 parts of an active ester curing agent ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution of 65% of a non-volatile matter having an active group equivalent of about 223), an acrylic resin (manufactured by Shin Nakamura Chemical Co., Ltd. " A-DOG”) 10 parts, a curing accelerator (5% methylethyl ketone solution of 4-dimethylaminopyridine (DMAP)) 2 parts, and a curing accelerator (dicumyl peroxide “Percumyl D” manufactured by Nichiyu Co., Ltd.) 0.13 part mixed And, it was uniformly dispersed with a rotary mixer to prepare a resin varnish 1.

[Example 2]

The amount of phenylmethane maleimide resin (“BMI-2000” manufactured by Daiwa Chemical Industry Co., Ltd.) was changed to 10 parts. In addition, an acrylic resin (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.) and dicumyl peroxide (“Percumyl D” manufactured by Nichiyu Co., Ltd.) were not used. Resin varnish 2 was produced by performing the same operation as in Example 1 except for the above matters.

[Example 3]

The amount of phenylmethane maleimide resin (“BMI-2000” manufactured by Daiwa Chemical Industry Co., Ltd.) was changed to 13.5 parts. Resin varnish 3 was produced by performing the same operation as in Example 1 except for the above matters.

[Example 4]

2.5 parts of phenylmethane maleimide resin (“BMI-2000” manufactured by Daiwa Chemical Industry Co., Ltd.) was changed to 2.5 parts of m-phenylene bismaleimide resin (“BMI-3000” manufactured by Daiwa Chemical Industry Co., Ltd.) 2.5 parts. Resin varnish 4 was produced by performing the same operation as in Example 1 except for the above matters.

[Example 5]

2.5 parts of phenylmethane maleimide resin (“BMI-2000” manufactured by Daiwa Chemical Industry Co., Ltd.) was changed to 10 parts of m-phenylene bismaleimide resin (“BMI-3000” manufactured by Daiwa Chemical Industry Co., Ltd.). In addition, an acrylic resin (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.) and dicumyl peroxide (“Percumyl D” manufactured by Nichiyu Co., Ltd.) were not used. Resin varnish 5 was produced by performing the same operation as in Example 1 except for the above matters.

[Example 6]

2.5 parts of phenylmethane maleimide resin (“BMI-2000” manufactured by Daiwa Chemical Industry Co., Ltd.) was changed to 13.5 parts of m-phenylene bismaleimide resin (“BMI-3000” manufactured by Daiwa Chemical Industry Co., Ltd.). Resin varnish 6 was produced by performing the same operation as in Example 1 except for the above matters.

[Comparative Example 1]

The amount of phenylmethane maleimide resin (“BMI-2000” manufactured by Daiwa Chemical Industry Co., Ltd.) was changed to 1 part. Resin varnish 7 was produced by performing the same operation as in Example 1 except for the above matters.

[Comparative Example 2]

The amount of phenylmethane maleimide resin (“BMI-2000” manufactured by Daiwa Chemical Industry Co., Ltd.) was changed to 16 parts. Resin varnish 8 was produced by performing the same operation as in Example 1 except for the above matters.

[Comparative Example 3]

2.5 parts of phenylmethane maleimide resin (“BMI-2000” manufactured by Daiwa Chemical Industry Co., Ltd.) was changed to 1 part of m-phenylene bismaleimide resin (“BMI-3000” manufactured by Daiwa Chemical Industry Co., Ltd.). Resin varnish 9 was produced by performing the same operation as in Example 1 except for the above matters.

[Comparative Example 4]

2.5 parts of phenylmethane maleimide resin (“BMI-2000” manufactured by Daiwa Chemical Industry Co., Ltd.) was changed to 16 parts of m-phenylene bismaleimide resin (“BMI-3000” manufactured by Daiwa Chemical Industry Co., Ltd.). Resin varnish 10 was produced by performing the same operation as in Example 1 except for the above matters.

[Assessment Methods]

(Preparation of evaluation sample of cured product)

A polyethylene terephthalate film ("PET501010" manufactured by Lintec Corporation) to which a release treatment was performed on the surface was prepared as a support. On this support, the resin varnish obtained in Examples and Comparative Examples was uniformly applied using a die coater so that the thickness of the resin composition layer after drying was 40 µm. 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 product film formed from a cured product of the resin composition. This cured product film was cut into a length of 80 mm and a width of 2 mm to obtain evaluation samples.

(Measurement of permittivity (Dk) and dielectric loss tangent (Df))

About this evaluation sample, the dielectric loss tangent and dielectric constant were measured with the measurement frequency of 10 GHz by the cavity resonance perturbation method using the measuring apparatus ("HP8362B" by Agilent Technologies). The dielectric loss tangent was measured at -10°C, 25°C and 100°C. In addition, the dielectric constant was measured at 25 degreeC.

(Evaluation of permittivity (Dk))

A case where the dielectric constant (Dk) was 3.0 or less was evaluated as "good". In addition, the case where the permittivity (Dk) exceeded 3.0 was evaluated as "defective".

(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) was in the range of 85% to 115%, the temperature stability at low temperature was judged to be "good". In addition, 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 judged to be "defective".

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) was in the range of 85% to 115%, the temperature stability at high temperature was judged to be "positive". In addition, 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 judged to be "poor".

[result]

The results of the above examples and comparative examples are shown in the table below. In the table below, the amount of each component represents the mass part of the non-volatile component. In addition, in the table below, the meaning of the abbreviation is as follows.

(B)/(A): Mass ratio of component (B) to 100% by mass of component (A).

[examine]

As can be seen from Table 1, a low permittivity was obtained in the examples. Further, in the examples, 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 temperatures is good. do. Further, in the examples, the ratio of dielectric loss tangent Df(-10°C)/Df(25°C) falls within a predetermined range (100%±15%) close to 100%, and the temperature dependence of the dielectric loss tangent at low temperatures is good Therefore, as a result, it was confirmed that a resin composition capable of obtaining an insulating layer having a low dielectric constant and excellent temperature stability of the dielectric loss tangent can be realized by the present invention. In addition, 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 radar antenna circuit board, the change due to the temperature of the radar detectable range can be suppressed.

In the above examples, even when components (E) to (G) were not used, it was confirmed that the same results as those of the above examples were obtained, although there were differences in degree.

Claims (14)

A resin composition comprising (A) an epoxy resin, (B) a maleimide compound, (C) an inorganic filler, (D) a fluorine-based filler, and an active ester-based curing agent, wherein the amount of component (B) is 100 masses of component (A) 10% by mass to 70% by mass relative to %, the resin composition. A resin composition comprising (A) an epoxy resin, (D) a fluorine-based filler, and an active ester-based curing agent; When the tangents are Df(-10℃), Df(25℃) and Df(100℃), the ratio of Df(-10℃) to Df(25℃) Df(-10℃)/Df( 25 ° C.) is 85% to 115%, and the ratio Df (100 ° C.) to Df (25 ° C.) Df (100 ° C.) / Df (25 ° C.) is 85% to 115%, the resin composition. A resin composition comprising (A) an epoxy resin, (B) a maleimide compound, (C) an inorganic filler, and (D) a fluorine-based filler, wherein the amount of component (B) is 10 mass% with respect to 100 mass% of component (A). % to 70% by mass, and the amount of component (D) relative to 100% by mass of the non-volatile component in the resin composition is 15% by mass or more and 80% by mass or less, and the total of component (C) and component (D) is 100% by mass A resin composition in which the amount of component (D) is 20% by mass or more and 70% by mass or less. A resin composition comprising (A) an epoxy resin, (C) an inorganic filler, and (D) a fluorine-based filler, wherein the amount of the component (D) is 15% by mass or more and 80% by mass relative to 100% by mass of the non-volatile component in the resin composition. Below, the amount of component (D) relative to 100 mass% of the total of component (C) and component (D) is 20% by mass or more and 70% by mass or less, and a cured product obtained by heat-treating a resin composition at 200 ° C. for 90 minutes. When the dielectric loss tangents at -10°C, 25°C, and 100°C are Df(-10°C), Df(25°C), and Df(100°C), respectively, Df(-10°C) for Df(25°C) ) The ratio Df(-10℃)/Df(25℃) is 85% to 115%, and the ratio Df(100℃) to Df(25℃) Df(100℃)/Df(25℃) is 85 % to 115%, the resin composition. (B) The resin composition of Claim 2 or 4 containing a maleimide compound. The resin composition according to any one of claims 1 to 4, wherein component (D) is fluorine-based polymer particles. The resin composition according to any one of claims 1 to 4, wherein component (D) is polytetrafluoroethylene particles. (E) The resin composition of any one of Claims 1-4 containing resin which has an unsaturated hydrocarbon group. The resin composition according to claim 8, wherein component (E) has at least one unsaturated hydrocarbon group 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 8, wherein the component (E) has a vinyl group and a 5-membered or higher cyclic ether structure. The resin composition according to any one of claims 1 to 4, which is for forming an insulating layer of a circuit board. A sheet-like laminated material comprising the resin composition according to any one of claims 1 to 4. A circuit board comprising an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 4. A semiconductor device comprising the circuit board according to claim 13.