TW201925332A - Resin composition - Google Patents

Abstract

Provided is a resin composition capable of obtaining an insulating layer having a low dielectric constant and excellent temperature stability of a dielectric tangent. The resin composition comprises: (A) an epoxy resin; (B) a maleimide compound; (C) an inorganic filler; and (D) a fluorine-based filler, wherein the amount of the component (B) is 10-70 mass% relative to 100 mass% of the component (A).

Description

Resin composition

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

A manufacturing method of a circuit board is known, for example, by a manufacturing method of an overlay method in which an insulating layer and a conductor layer are alternately laminated on an inner substrate. The insulating layer generally has a resin composition layer obtained by applying a coating film of a resin varnish containing the resin composition, and is formed by curing the resin composition layer. For example, Patent Document 1 describes a resin composition that is a resin composition containing an epoxy resin, a hardener, and a fluororesin filler. The content of the fluororesin filler is 50% by mass relative to the solid content of the resin composition. ~ 85% by mass.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2016-166347

[Problems to be Solved by the Invention]

A resin composition for forming an insulating layer generally contains many thermosetting resins from the viewpoint of achieving high insulation performance. This thermosetting resin is usually epoxy resin. On the other hand, in order to develop an insulating layer having a low dielectric constant, the inventors have reviewed using a fluorine-based filler in a resin composition containing an epoxy resin.

The inventors further tried to use a resin composition containing an epoxy resin and a fluorine-based filler as the insulation layer of an antenna circuit board of a radar, as described above. However, a radar equipped with the antenna circuit board is known, and a detectable range thereof varies depending on temperature. For example, even a wide radar that can detect a range of 20m at a certain temperature may narrow the detectable range to 5m at another temperature.

The present invention has been made in view of the aforementioned problems, and an object of the present invention is to provide an antenna circuit board installed on a radar, which can suppress a change in the detectable range of the radar due to temperature, and can obtain an insulating layer with a low dielectric constant. A resin composition; a laminar laminated material including the resin composition; a circuit board and a semiconductor device including an insulating layer formed of a cured product of the resin composition;

[Means to solve the problem]

The present inventors have carefully reviewed in order to solve the aforementioned problems. As a result, the present inventors have obtained the knowledge that the temperature-induced change in the range detectable by the radar is due to the temperature stability of the dielectric tangent of the insulating layer. Specifically, when the dielectric tangent of the insulating layer of the antenna circuit board of a radar changes due to temperature, the magnitude of the loss of the antenna circuit board changes due to temperature, so the sensitivity of the antenna circuit board changes due to temperature, and the result can be detected. The range varies with temperature. Therefore, the present inventors have found that a resin composition capable of obtaining an insulating layer having excellent temperature stability of a dielectric tangent can solve the aforementioned problems and complete the present invention.
That is, the present invention includes the following.

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

[Inventive effect]

According to the present invention, when an antenna circuit board provided in a radar is provided, a resin composition capable of suppressing a change in a detectable range of the radar due to temperature and obtaining an insulating layer having a low dielectric constant can be obtained; A sheet-shaped laminated material; a circuit board and a semiconductor device including an insulating layer formed of a hardened body of the resin composition.

[Form of Implementing Invention]

Hereinafter, embodiments and exemplified objects will be described, and the present invention will be described in detail. However, the present invention is not limited to the embodiments and examples shown below, and can be arbitrarily changed and implemented as long as it does not depart from the scope of the patent application of the present invention and its equivalent range.

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

In the following description, the term "dielectric constant" means a specific inductive capacity unless otherwise specified.

[1. Resin composition of the first embodiment]
[1.1. Overview of resin composition]
The resin composition system 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 a fluorine atom. The term "fluorine-based filler" refers to a filler containing a compound containing a fluorine atom as a material. In this resin composition, the amount of the (B) maleimide compound is within a specific range.

The hardened material of this resin composition has a low dielectric constant. The hardened material of such a resin composition is excellent in temperature stability of the dielectric tangent. Therefore, by using the aforementioned resin composition, since the temperature tangent of the dielectric tangent is excellent, when the antenna circuit board of the radar is installed, the change in the detectable range of the radar due to temperature can be suppressed, and a dielectric constant can be obtained. A resin composition having a low insulating layer can obtain the desired effect of the present invention.

[1.2. (A) Epoxy resin]
Examples of the epoxy resin of the component (A) include bisxylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AF type. Epoxy resin, dicyclopentadiene epoxy resin, triphenol epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin , Naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, epoxypropylamine epoxy resin, epoxypropyl ester epoxy resin, cresol novolac epoxy resin, biphenyl Epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro epoxy resin, cyclohexane epoxy resin Resin, cyclohexanedimethanol type epoxy resin, dnaphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin. One type of epoxy resin can be used alone, or two or more types can be used in combination.

(A) Epoxy resins have small changes in properties due to temperature, so epoxy resins having cyclic structures such as alicyclic structures and aromatic ring structures are preferred in addition to epoxy groups. Among these, an aromatic epoxy resin is preferable from the viewpoint of reducing the average linear thermal expansion coefficient of the insulating layer. Here, the aromatic epoxy resin refers to an epoxy resin whose molecule contains an aromatic skeleton. The aromatic skeleton refers to a chemical structure generally defined as aromatic, and includes not only a monocyclic structure such as a benzene ring but also a polycyclic aromatic structure and an aromatic heterocyclic structure such as a naphthalene ring. Among them, from the viewpoint that the desired effect of the present invention is clearly obtained, (A) the epoxy resin is selected from the group consisting of bisphenol A type epoxy resin, bisxylenol type epoxy resin, and biphenylaralkyl type. Epoxy resin, naphthyl ether type epoxy resin, naphthalene type 4-functional epoxy resin, and naphthol type epoxy resin are more than one type of epoxy resin, and particularly preferred is bisxylenol type epoxy resin. .

The resin composition is preferably an epoxy resin containing (A) an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint that the desired effect of the present invention is clearly obtained, the ratio of the epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of the non-volatile content of the epoxy resin (A) is relatively large. It is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

Epoxy resins include liquid epoxy resins (hereinafter sometimes referred to as "liquid epoxy resins") at a temperature of 20 ° C and solid epoxy resins (sometimes referred to as a "solid ring" at a temperature of 20 ° C). Oxygen resin "). The resin composition may include only a liquid epoxy resin as the (A) epoxy resin, may include only a solid epoxy resin, or may contain a liquid epoxy resin and a solid epoxy resin in combination. By using a combination of a liquid epoxy resin and a solid epoxy resin as the (A) epoxy resin, the flexibility of the resin composition layer can be improved, or the fracture strength of the hardened product of the resin composition can be improved.

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

The liquid epoxy resin is preferably a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol AF epoxy resin, a naphthalene epoxy resin, a glycidyl ester epoxy resin, or glycidol. Amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type ring Oxygen resins and epoxy resins with butadiene structure, more preferably glycidylamine epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AF epoxy resin and The naphthalene type epoxy resin is particularly preferably a bisphenol A type epoxy resin.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC; "828US", "jER828US", and "jER828EL" manufactured by Mitsubishi Chemical. "825", "Epikote828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) made by Mitsubishi Chemical; "jER152" (phenol made by Mitsubishi Chemical) Novolac type epoxy resin); "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical; "ZX1059" (bisphenol A type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. Mixture with bisphenol F-type epoxy resin); "EX-721" (glycidyl ester epoxy resin) manufactured by Nagase Chemtex; "CELLOXID2021P" (alicyclic ring with ester skeleton) manufactured by DAICEL Oxygen resin); "PB-3600" (epoxy resin with butadiene structure) manufactured by DAICEL; "ZX1658", "ZX1658GS" (liquid 1,4-epoxy propylene) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. Cyclohexane type epoxy resin); etc. These can be used alone or in combination of two or more.

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

The solid epoxy resin is preferably a bisxylenol type epoxy resin, a biphenylaralkyl type epoxy resin, a naphthalene type epoxy resin, a naphthalene type 4-functional epoxy resin, a cresol novolac type epoxy resin. , Dicyclopentadiene epoxy resin, triphenol epoxy resin, naphthol epoxy resin, biphenyl epoxy resin, naphthyl ether epoxy resin, anthracene epoxy resin, bisphenol A Type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin, more preferably bisxylenol type epoxy resin, biphenylaralkyl type epoxy resin, and naphthyl ether Type epoxy resin, naphthalene type 4-functional epoxy resin, and naphthol type epoxy resin, and particularly preferred is bisxylenol type epoxy resin.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene-type 4-functional epoxy resin) manufactured by DIC ; "N-690" (cresol novolac type epoxy resin) made by DIC; "N-695" (cresol novolac type epoxy resin) made by DIC; "HP-7200" (two Cyclopentadiene epoxy resin); "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA" -7311-G4S "," HP6000 "(Darylene Ether Type Epoxy Resin);" EPPN-502H "(triphenol epoxy resin) made by Nippon Kayaku Co .;" NC7000L "(made by Nippon Kayaku Co., Ltd.) Naphthol novolac epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenylaralkyl-based epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; Nippon Steel & Sumitomo Chemical Co., Ltd. "ESN475V" (naphthol type epoxy resin) made by Nippon Steel; "ESN485" (naphthol novolac type epoxy resin) made by Nippon Steel & Sumitomo Chemical Corporation; "YX4000H", "YX40" made by Mitsubishi Chemical "00", "YL6121" (biphenyl epoxy resin); "YX4000HK" (bis xylenol epoxy resin) manufactured by Mitsubishi Chemical; "YX8800" (anthracene epoxy resin) manufactured by Mitsubishi Chemical; "PG-100" and "CG-500" (bisphenol AF-type epoxy resin) manufactured by Osaka Gas Chemical Co., Ltd .; "YL7760" (bisphenol AF-type epoxy resin) manufactured by Mitsubishi Chemical Co .; manufactured by Mitsubishi Chemical Co., Ltd. "YL7800" (茀 -type epoxy resin); "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical . These can be used alone or in combination of two or more.

When the liquid epoxy resin and the solid epoxy resin are used as the (A) epoxy resin, the mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1: 0.1 to 1: 15, more preferably 1: 0.5 to 1:10, and particularly preferably 1: 1 to 1: 8. Since the mass ratio of the liquid epoxy resin to the solid epoxy resin is in the aforementioned range, when used in the form of a film, better adhesion can be obtained. Moreover, when it is used in the form of an adhesive film, sufficient flexibility can be obtained, and workability can be improved. In addition, it is possible to effectively increase the breaking strength of the hardened material of the resin composition.

(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 1,000. Since the epoxy equivalent of (A) epoxy resin is in the said range, the crosslinking density of the hardened | cured material of a resin composition becomes sufficient, and an insulating layer with small surface roughness can be obtained. The epoxy equivalent is the mass of a resin containing one equivalent of an epoxy group, and can be measured in accordance with JIS K7236.

(A) The weight-average molecular weight of the epoxy resin is preferably from 100 to 5,000, more preferably from 250 to 3,000, and still more preferably from 400 to 1500 from the viewpoint that the desired effect of the present invention is clearly obtained. 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 from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability, and is preferably 3% by mass relative to 100% by mass of the nonvolatile matter in the resin composition. Above, more preferably, it is 5 mass% or more, particularly preferably 9 mass% or more, more preferably 70 mass% or less, more preferably 50 mass% or less, and particularly preferably 30 mass% or less.

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

(B) The number of maleimide imide groups in one molecule of the maleimide compound can be one, but it is preferably two or more, preferably ten or less, and more preferably six or less. Especially good is 3 or less. By using the (B) maleimide compound having two or more maleimide groups in one molecule, the desired effect of the present invention can be obviously obtained, and the dielectric tangent of the cured product can be effectively improved. Temperature stability.

(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 clearly obtained, and particularly, the temperature stability of the dielectric tangent of the cured product can be effectively improved. In particular, the (B) maleimide compound preferably contains a benzene ring as an aromatic skeleton.

(B) Maleimide compounds include, for example, 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, phenylene bismaleimide, bis Phenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl -1,3-phenylene bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bis Maleimide, 4,4'-diphenylpyrenebismaleimide, 1,3-bis (3-maleimidephenoxy) benzene, 1,3-bis (4-maleimide Lyme imine phenoxy) benzene and the like.

From the viewpoint that the desired effect of the present invention is clearly obtained, as the (B) maleimide imine compound, polyphenylmethane maleimide represented by the formula (B2) is particularly preferred, and (B3) ) Represents phenyl bismaleimide. In formula (B2), n represents an integer of 0 or more.

(B) Specific examples of maleimide compounds include "BMI-1000" manufactured by Daiwa Chemical Industry Co., Ltd. and "BMI" (4,4'-diphenylmethane bismaleimide) manufactured by Ki-chemica Corporation. ); "BMI-2000" (polyphenylmethane maleimide) manufactured by Daiwa Chemical Industry Company; "BMI-3000" (m-phenylene bismaleimide) manufactured by Yamato Chemical Industry Company; Yamato Chemical "BMI4000" manufactured by Industrial Corporation, "BMI-80" manufactured by Ki-chemica Corporation (bisphenol A diphenyl ether bismaleimide); "BMI5100" manufactured by Daiwa Chemical Industry Corporation, and "BMI-70" manufactured by Ki-chemica Corporation "(3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide);" BMI-7000 "(4- Methyl-1,3-phenylenebismaleimide); "BMI-TMH" (1,6'-bismaleimide- (2,2,4-trimethyl) manufactured by Daiwa Chemical Industry Co., Ltd. Hexane); "BMI-6000" (4,4'-diphenyl ether bismaleimide) manufactured by Daiwa Chemical Industry Co., Ltd .; "BMI-8000" (4,4'-Di) manufactured by Daiwa Chemical Industry Co., Ltd. Phenylpyrenebismaleimideimine); 1,3-bis (3-maleimideiminophenoxy) benzene manufactured by Daiwa Chemical Industry Co., Ltd. 1,3-bis Daiwa Kasei Industry Co., Ltd. of (4-maleic (PEI) phenoxy) benzene; MITSUI FINE CHEMICALS Co., Ltd. "ANILIX-MI"; and the like. Moreover, (B) maleimide imine compound may be used individually by 1 type, and may be used in combination of 2 or more type.

(B) The maleimidine imine compound can be produced by, for example, reacting maleic anhydride with an appropriate amine compound.

The amount of the (B) maleimide compound in the resin composition is 100% by mass relative to the (A) epoxy resin, preferably 10% by mass or more, more preferably 11% by mass or more, and even more preferably 12% by mass. % Or more, preferably 70% by mass or less, more preferably 69% by mass or less, and particularly preferably 68% by mass or less. When the amount of the (B) maleimide imine compound is within the aforementioned range, the temperature stability of the dielectric tangent of the hardened product of the resin composition can be made good.

The amount of the (B) maleimide compound in the resin composition is 100% by mass based on the non-volatile content in the resin composition, preferably 0.5% by mass or more, more preferably 0.8% by mass or more, particularly preferably 1.0% by mass or more, preferably 7.0% by mass or less, more preferably 6.7% by mass or less, and particularly preferably 6.2% by mass or less. When the amount of the (B) maleimidine imine compound is within the aforementioned range, the desired effect of the present invention can be clearly obtained, and particularly, the temperature stability of the dielectric tangent of the hardened material can be effectively improved.

[1.4. (C) Inorganic filler]
Examples of the material of the inorganic filler of the component (C) include silicon dioxide, aluminum oxide, glass, sapphire, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, and hydrotalcite. , Gibbsite, alumina, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, titanic acid Magnesium, bismuth titanate, titanium oxide, zirconia, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silicon dioxide is particularly preferable from the viewpoint that the desired effect of the present invention is clearly obtained. Examples of the silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. Among them, spherical silica is preferred. (C) The inorganic filler may be used alone or in combination of two or more kinds.

Generally, (C) an inorganic filler is contained in a resin composition in the state of a particle. (C) The average particle diameter of the inorganic filler, from the viewpoint of clearly obtaining the desired effect of the present invention, 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 less, more preferably 2.0 μm or less, and still more preferably 1.0 μm or less. In addition, when the average particle diameter of the (C) inorganic filler is within the aforementioned range, the circuit embedability of the resin composition layer can generally be improved, or the surface roughness of the insulating layer can be reduced.

(C) Commercial products of inorganic fillers include, for example, "SP60-05" and "SP507-05" manufactured by NIPPON STEEL & SUMIKIN MATERIALS; "YC100C", "YA050C", "YA050C-MJE" manufactured by admatechs "," YA010C ";" UFP-30 "by Denka;" SilFileNSS-3N "," SilFileNSS-4N "," SilFileNSS-5N "by Tokuyama;" SC2500SQ "," SO- "by admatechs C4 "," SO-C2 "," SO-C1 "; etc.

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

(C) The specific surface area of the inorganic filler, from the viewpoint of clearly obtaining the desired effect of the present invention, 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. . 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 was obtained by using a specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH) to adsorb nitrogen on the surface of the sample according to the BET method, and using the BET multipoint method to calculate the specific surface area.

(C) An inorganic filler can be surface-treated with any surface-treating agent. Examples of the surface treating agent include coupling agents such as aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, titanate-based coupling agents, and the like; alkoxysilane compounds; organic silazane compounds ;Wait. These surface treatment agents can improve the moisture resistance and dispersibility of the (C) inorganic filler by surface treatment.

Commercially available products of the surface treatment agent include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd. and "KBM803" (3-mercaptopropyltrimethyl) manufactured by Shin-Etsu Chemical Industry Oxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxy) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Silane), Shin-Etsu Chemical Industry Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Industry Co., Ltd. "KBM-103" (phenyltrimethoxysilane), Shin-Etsu Chemical Industry Co., Ltd. "KBM- 4803 "(long-chain epoxy-type silane coupling agent) and the like. The surface treatment agent may be used alone or in combination of two or more kinds.

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

(C) The amount of carbon per unit surface area of the inorganic filler, the (C) inorganic filler after surface treatment can be washed with a solvent (for example, methyl ethyl ketone (hereinafter sometimes referred to as "MEK")) Measure after processing. Specifically, a sufficient amount of MEK was mixed with the (C) inorganic filler surface-treated with the surface-treating agent, and ultrasonic cleaning was performed at 25 ° C. for 5 minutes. Next, after removing the upper liquid and drying the non-volatile components, the carbon content per unit surface area of the inorganic filler (C) can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

The amount of the (C) inorganic filler in the resin composition is 100% by mass based on the non-volatile content in the resin composition, preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass. % Or more, particularly 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. Since the amount of the (C) inorganic filler is greater than or equal to the lower limit of the aforementioned range, the thermal expansion rate of the hardened material of the resin composition can be reduced, so that warpage of the insulating layer can be suppressed. In addition, since the amount of the (C) inorganic filler is equal to or less than the upper limit of the aforementioned range, the mechanical strength of the hardened material of the resin composition can be improved, and in particular, the resistance to elongation can be improved.

[1.5. (D) Fluorine-based filler]
The fluorine-based filler as the component (D) is a filler containing a compound containing a fluorine atom as a material. The fluorine-based filler is generally particles. Therefore, (D) a fluorine-based filler generally uses a compound containing a fluorine atom as particles contained in the material.

(D) The material of the fluorine-based filler includes, for example, a fluorine-based polymer and a fluorine-based rubber. Among these, from the viewpoint of reducing the dielectric constant of the insulating layer, a fluorine-based polymer is preferred. Therefore, the (D) fluorine-based filler is preferably fluorine-based polymer particles.

Examples of the fluorine-based polymer include polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene propylene copolymer (FEP), ethylene / tetrafluoroethylene copolymer (ETFE), and tetrafluoroethylene- Perfluorodioxolene copolymer (TFE / PDD), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyfluoroethylene ( PVF). These can be used alone or in combination of two or more.

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

The weight-average molecular weight of the fluorine-based polymer is preferably not more than 5,000,000, more preferably not more than 4,000,000, and particularly preferably not more than 3,000,000 from the viewpoint that the desired effect of the present invention is clearly obtained.

(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, more preferably 10 μm or less, even more preferably 5 μm or less, and particularly preferably 4 μm or less. . Since the average particle diameter of the (D) fluorine-based filler is in the aforementioned range, the desired effect of the present invention is clearly obtained, and the dispersibility of the (D) fluorine-based filler in the resin composition is generally better. The average particle diameter of the (D) fluorine-based filler is the same as that of the (C) inorganic filler, and can be measured by the laser diffraction chirped scattering method based on the Mie scattering theory.

(D) Commercial products of fluorine-based fillers include, for example, "ruburonL-2", "ruburonL-5", "ruburonL-5F" manufactured by DAIKIN INDUSTRIES, and "FluonPTFE L-170JE" and "FruonPTFE L" "FluonPTFEL-172JE", "FluonPTFE L-173JE"; "KTL-500F", "KTL-2N", "KTL-1N" manufactured by Kitamura; "TLP10F-1" manufactured by Mitsui & Dupont Fluorochemicals; etc.

(D) The fluorine-based filler may be surface-treated. For example, (D) a fluorine-based filler may be surface-treated with any surface-treating agent. Examples of the surface treatment agent include, for example, nonionic surfactants, amphoteric surfactants, cationic surfactants, anionic surfactants, and the like; inorganic fine particles; and the like. From the viewpoint of affinity, it is preferable to use a fluorine-based surfactant as the surface treatment agent. Specific examples of the fluorine-based surfactant include "SurflonS-243" (perfluoroalkyl ethylene oxide adduct) manufactured by AGC Kiyomi Chemical Co., and "MegafacF-251" and "MegafacF-" manufactured by DIC Corporation. 477 "," MegafacF-553 "," MegafacR-40 "," MegafacR-43 "," MegafacR-94 ";" FTX-218 "and" Ftergent610FM "manufactured by NEOS Corporation.

The amount of the (D) fluorine-based filler in the resin composition is preferably 100% by mass or more, more preferably 15% by mass or more, and more preferably 20% by mass relative to 100% by mass of the nonvolatile component in the resin composition. % Or more, preferably 80% by mass or less, more preferably 60% by mass or less, and particularly preferably 40% by mass or less. Since the amount of the (D) fluorine-based filler is in the aforementioned range, the desired effect of the present invention can be significantly obtained, and particularly the dielectric constant of the hardened material of the resin composition can be effectively reduced.

The amount of the (D) fluorine-based filler in the resin composition is 100% by mass relative to the total of the (C) inorganic filler and (D) fluorine-based filler, preferably 20% by mass or more, more preferably 30% by mass % Or more, particularly preferably 35% by mass or more, preferably 90% by mass or less, more preferably 70% by mass or less, and particularly preferably 50% by mass or less. Since the amount of the (D) fluorine-based filler is in the aforementioned range, the desired effect of the present invention can be significantly obtained, and particularly the dielectric constant of the hardened material of the resin composition can be effectively reduced.

[1.6. (E) Resin having unsaturated hydrocarbon group]
The resin composition may contain, in addition to the above-mentioned components, a resin having an unsaturated hydrocarbon group as an optional component (E). In the following description, the "resin having an unsaturated hydrocarbon group" as the component (E) may be referred to as an "unsaturated resin". The carbon-carbon unsaturated bond may include only one or a plurality of carbon atoms in one molecule of the (E) unsaturated resin. The hardened body of a resin composition containing (E) an unsaturated resin usually includes a molecular structure site formed by the reaction of an unsaturated bond site of the (E) unsaturated resin. This reduces the polarity of the hardened material and reduces the value of the dielectric tangent. In addition, the dispersibility of the (D) fluorine-based filler can be generally improved by the (E) unsaturated resin. Therefore, since the uniformity of the composition of the resin composition is improved, the adhesiveness to the conductor layer of the cured product can be further improved.

(E) Unsaturated resin: The (E) unsaturated resin contains unsaturated hydrocarbon groups in the molecule. The unsaturated hydrocarbon group is preferably one or more groups selected from the group consisting of an acrylfluorenyl group, a methacrylfluorenyl group, a styryl group, and an olefin group. Here, the "olefin group" means an aliphatic hydrocarbon group having a carbon-carbon double bond in the molecule. Preferable examples of the olefin group include an allyl group, a vinyl group, and a propenyl group. Therefore, the (E) unsaturated resin is preferably one having at least one unsaturated hydrocarbon group selected from the group consisting of acrylfluorenyl, methacrylfluorenyl, styryl, allyl, vinyl, and acryl. .

(E) The unsaturated resin is preferably a compound having a cyclic ether structure of 5 or more members. In the following description, the aforementioned "compound having a cyclic ether structure of 5 or more members" may be referred to as an "unsaturated cyclic ether compound". Unsaturated cyclic ether compounds usually have restricted molecular behavior, so they can effectively reduce the dielectric tangent.

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

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

The number of oxygen atoms contained in one cyclic ether structure is obviously from the viewpoint that the desired effect of the present invention is obtained, preferably 1 or more, more preferably 2 or more, more preferably 5 or less, and even more preferably 4 or less , And more preferably 3 or less.

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

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

Among the unsaturated cyclic ether compounds, those having a vinyl group are preferred. The present invention can be remarkably obtained by using an unsaturated cyclic ether compound having a vinyl group (that is, a compound having a vinyl group and a cyclic ether structure of 5 or more members) as the (E) unsaturated resin. The desired effect. In addition, the dielectric tangent of the resin composition is usually effectively reduced.

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

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

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

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

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

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

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

In formula (E5), R ¹ to R ⁶ are synonymous with R ¹ to R ⁶ in the aforementioned formula (E1), B is synonymous with B in the aforementioned formula (E2), and a and b are identical to the aforementioned formula (E4) A and b are synonymous.

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

Examples of the divalent group having a cyclic ether structure of five or more members include furan-2,5-diyl, tetrahydrofuran-2,5-diyl, dioxolane-2,5-diyl, Pyran-2,5-diyl, dihydropyran-2,5-diyl, tetrahydropyran-2,5-diyl, 1,2-dioxane-3,6-diyl, 1 , 3-dioxane-2,5-diyl, 1,4-dioxane-2,5-diyl, 5-ethyl-1,3-dioxane-2,5-diyl. Among these, 5-ethyl-1,3-dioxane-2,5-diyl is preferred.

In formula (E7), B ¹ and B ² each independently represent a single bond or a divalent linking group. B ¹ and B ² preferably based in the divalent linking group. Examples of the divalent linking group include an alkylene group which may have a substituent, an alkynyl group which may have a substituent, an arylene group which may have a substituent, a heteroarylene group which may have a substituent, and -COO- Base represented by -CO-, base represented by -CONH-, base represented by -NHCONH-, base represented by -NHCOO-, base represented by -C (= O)-, base represented by -S-, The bases represented by SO-, the bases represented by -NH-, and bases of plural combinations of these bases.

Examples of the substituent include a halogen atom, -OH, -OC _1-6 alkyl, -N (C _1-6 alkyl) ₂ , C _1-6 alkyl, C _6-10 aryl, -NH ₂ , -CN, -C (O) OC _1-6 alkyl, -COOH, -C (O) H, -NO ₂ and the like. Here, the term "C _pq " (p and q are positive integers and satisfy p <q) means that the number of carbon atoms of the organic group described later in this term is p to q. For example, the expression "C _1-6 alkyl" means an alkyl group having 1 to 6 carbon atoms.

The substituent may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). Examples of the secondary substituent include the same ones as those described above.

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

In formula (E7), C ¹ and C ² each independently represent a functional group. Examples of the functional group include a vinyl group, a methacryl group, an acryl group, an allyl group, a styryl group, a propenyl group, and an epoxy group. The functional group is preferably a vinyl group.

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

(E) Unsaturated resin includes, for example, "OPE-2St 1200" (a styrene-modified polyphenylene ether resin, a number average molecular weight of 1200, equivalent to the aforementioned formula (E5)) manufactured by Mitsubishi Gas Chemical Corporation, and "Mitsubishi Chemical Corporation" "YL7776" (bisxylenol diallyl ether resin, number average molecular weight 331, equivalent to the aforementioned formula (E6)), "A-DOG" (dioxane acrylic monomer ethylene glycol diacrylic acid) manufactured by Shin Nakamura Chemical Industry An ester, a number average molecular weight of 326, corresponds to the aforementioned formula (E8)), and "KAYARAD R-604" manufactured by Nippon Kayaku Co., Ltd. corresponds to the aforementioned formula (E8). Moreover, (E) unsaturated resin may be used individually by 1 type, and may be used in combination of 2 or more type.

(E) The number average molecular weight of the unsaturated resin is preferably 100 or more, more preferably 200 or more, more preferably 10,000 or less, and even more preferably 3,000 or less. When the number average molecular weight of the unsaturated resin (E) is in the aforementioned range, volatilization of the resin varnish during drying can be suppressed, or the melt viscosity of the resin composition can be suppressed from becoming too large. The number average molecular weight is measured by a gel permeation chromatography (GPC) method in terms of polystyrene conversion. For the measurement of the number average molecular weight by the GPC method, for example, a measuring device "LC-9A / RID-6A" manufactured by Shimadzu Corporation can be used, and the column is "Shodex K-800P / K-804L / K-" manufactured by Showa Denko Corporation. 804L ", the mobile phase uses chloroform, and the column temperature can be measured at 40 ° C.

The amount of (E) unsaturated resin in the resin composition is 100% by mass, preferably 1% by mass or more, more preferably 3% by mass or more, and more preferably 15% by mass based on the nonvolatile content in the resin composition. Hereinafter, it is more preferably 10% by mass or less. When the amount of (E) unsaturated resin is above the lower limit of the aforementioned range, the dielectric tangent of the hardened material of the resin composition can be effectively reduced. By being below the upper limit of the aforementioned range, the resin varnish can be improved. Compatibility.

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

[1.7. (F) Hardener]
The resin composition may contain (F) a curing agent as an optional component in addition to the above-mentioned components. The curing agent as the component (F) generally has a function of reacting with the epoxy resin (A) to harden the resin composition. Examples of such (F) curing agents include active ester curing agents, phenol curing agents, naphthol curing agents, benzoxazine curing agents, cyanate curing agents, and carbodiimide curing agents. Agent. Moreover, 1 type of hardener can be used individually, or 2 or more types can be used together.

As the active ester-based hardener, a compound having one or more active ester groups in one molecule can be used. Among them, active ester-based hardeners are phenolic esters, thiophenol esters, N-hydroxyamine esters, heterocyclic hydroxy compound esters, etc., which have two or more molecules with high reactivity. Ester-based compounds are preferred. The active ester hardener is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. Especially from the viewpoint of improving heat resistance, an active ester-based hardener obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based hardener obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. .

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

Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, and methyl alcohol. Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-di Hydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, resorcinol, benzenetriol, dicyclopentadiene type diphenol compound , Phenol novolac, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Preferred specific examples of the active ester-based hardener include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetic acid compound of phenol novolac, and An active ester compound of benzamidine of phenol novolac. Among these, 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" means a divalent structural unit formed of phenylene-dicyclopentyl-phenylene.

Commercial products of active ester-based hardeners, such as active ester compounds containing a dicyclopentadiene-type diphenol structure, include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC -8000H-65TM "," EXB-8000L-65TM "," EXB-8150-65T "(manufactured by DIC Corporation); active ester compounds containing a naphthalene structure include" EXB9416-70BK "(manufactured by DIC Corporation); includes phenol Examples of the active ester compound of the acetic acid compound of novolac include "DC808" (manufactured by Mitsubishi Chemical); and the example of the active ester compound containing the benzoic acid compound of phenol novolak includes "YLH1026" (manufactured by Mitsubishi Chemical); Examples of active ester-based hardeners for the acetic acid compounds of phenol novolac include "DC808" (manufactured by Mitsubishi Chemical); examples of active ester-based hardeners for the benzoic acid compounds of phenol novolak include "YLH1026" (Mitsubishi Chemical (Manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (Mitsubishi Chemical Co., Ltd.); etc.

The phenol-based hardener and naphthol-based hardener are preferably those having a novolac structure from the viewpoints of heat resistance and water resistance. From the viewpoint of the adhesion between the insulating layer and the conductor layer, a nitrogen-containing phenol-based hardener is preferred, and a phenol-based hardener containing a triazine skeleton is more preferred.

Specific examples of the phenol-based hardener and naphthol-based hardener include, for example, "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Corporation; "CBN", "GPH"; "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375" manufactured by Nippon Steel & Sumitomo Chemical Corporation; DIC Company-made "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500"; etc.

Specific examples of the benzoxazine-based hardener include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industry Co., Ltd.

Examples of the cyanate-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), and 4,4'-subline. Methylbis (2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis ( 4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3- 2 of bis (4-cyanatephenyl-1- (methylethylene)) benzene, bis (4-cyanatephenyl) sulfide, and bis (4-cyanatephenyl) ether Functional cyanate resins; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; etc .; these cyanate resins are partially triazinated prepolymers; etc. Specific examples of the cyanate-based curing agent include "PT30" and "PT60" (phenol novolac-type polyfunctional cyanate resin) and "ULL-950S" (polyfunctional cyanate resin) manufactured by Lonza Japan. , "BA230", "BA230S75" (a prepolymer of a trimer in which a part or all of the bisphenol A dicyanate is triazinated).

Specific examples of the carbodiimide-based hardener include "V-03" and "V-07" manufactured by Nishinbo Chemical.

Among the above, from the viewpoint that the desired effect of the present invention is clearly obtained, the (F) curing agent is preferably an active ester curing agent. When using an active ester-based hardener, the amount of the active ester-based hardener is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more relative to 100% by mass of the (F) hardener. It is preferably 100% by mass or less. Since the amount of the active ester-based hardener is in the aforementioned range, the desired effect of the present invention can be clearly obtained, and particularly the dielectric constant of the hardened product of the resin composition can be effectively reduced.

The amount of the (F) hardener in the resin composition is from the viewpoint that the desired effect of the present invention is clearly obtained, and is preferably 0.1% by mass or more with respect to 100% by mass of the non-volatile content in the resin composition. It is preferably 0.5% by mass or more, more preferably 1% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less.

When the number of epoxy groups of (A) epoxy resin is 1, the number of active groups of (F) hardener is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, more preferably 1.5 or less, more It is preferably 1.2 or less, and more preferably 1 or less. Here, "the epoxy group number of (A) epoxy resin" means the sum total of the mass of the non-volatile component of (A) epoxy resin which exists in a resin composition, divided by the epoxy equivalent. The "number of active groups of (F) hardener" refers to a value obtained by dividing the total mass of the nonvolatile components of the (F) hardener present in the resin composition by the value of the equivalent of the active group. Since the active group number of the (F) hardener when the epoxy group number of the (A) epoxy resin is 1 is in the aforementioned range, the desired effect of the present invention can be obviously obtained, and in addition, the hardening of the resin composition is generally further improved. The heat resistance of the material.

[1.8. (G) Hardening accelerator]
The resin composition may contain (G) a hardening accelerator as an arbitrary component in addition to the above-mentioned components. By using a (G) hardening accelerator, when hardening a resin composition, hardening can be accelerated | stimulated.

(G) The hardening accelerator includes, for example, a phosphorus-based hardening accelerator, an amine-based hardening accelerator, an imidazole-based hardening accelerator, a guanidine-based hardening accelerator, a metal-based hardening accelerator, and a peroxide-based hardening accelerator. Among them, particularly preferred are amine-based hardening accelerators and peroxide-based hardening accelerators. (G) A hardening accelerator may be used alone or in combination of two or more kinds.

Examples of the phosphorus-based hardening accelerator include triphenylphosphine, osmium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4- (Methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate. Among them, triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine, tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and Methylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) -undecene. Among them, 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferred.

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole. , 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl- 4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-benzene Imidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino- 6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazole -(1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isotriazine Polycyanic acid adduct, 2-phenylimidazole isotricyanic acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl Imidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] Imidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and the like; and imidazole compounds and epoxy resins Adduct. Among these, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

A commercially available product can be used as the imidazole-based hardening accelerator, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Company.

Examples of guanidine-based hardening accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, and dimethyl. Guanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5,7-triazabicyclo [4.4.0] dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1- (o-tolyl) biguanide. Among them, dicyandiamide and 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

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) acetoacetone, cobalt (III) acetoacetone, and copper complexes of copper (II) acetonate, etc. Organic zinc complexes such as osmium zinc acetone (II), organic iron complexes such as ethyl acetone iron (III), organic nickel complexes such as ethyl acetonide nickel (II), and manganese (II) ) And other organomanganese complexes. Examples of the organic metal salt include zinc octoate, tin octoate, zinc decalinate, cobalt decalinate, tin stearate, and zinc stearate.

Examples of the peroxide-based hardening accelerator include cyclohexanone peroxide, third butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, and third butyl cumyl peroxide. Oxides, di-third butyl peroxide, diisopropylbenzene hydrogen peroxide, cumene hydrogen peroxide, third butyl hydrogen peroxide.

As the peroxide-based hardening accelerator, a commercially available product can be used, and examples thereof include "percumyl D" manufactured by Nippon Oil Corporation.

When the (G) hardening accelerator is used, the amount of the (G) hardening accelerator in the resin composition is obviously from the viewpoint that the desired effect of the present invention is obtained, with respect to 100% by mass of the nonvolatile component in the resin composition. It is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, particularly preferably 0.03% by mass or more, more preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less.

[1.9. (H) Additives]
The resin composition may further contain an additive as an optional component in addition to the above-mentioned components. Examples of such additives include organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; thickeners; antifoaming agents; flattening agents; adhesion imparting agents; colorants; flame retardants; thermoplastic resins ;Wait. Moreover, one type of additive may be used alone, or two or more types may be used in combination.

[1.10. Manufacturing method of resin composition]
The resin composition can be produced, for example, by a method of mixing the ingredients, mixing with a solvent if necessary, and using a stirring device such as a rotary mixer.

[1.11. Characteristics of resin composition]
The hardened product of the resin composition can reduce its dielectric constant. Therefore, the hardened | cured material of this resin composition can obtain the insulating layer with a low dielectric constant. For example, the resin composition is hardened by the method described in the examples, and when a hardened material is obtained, the dielectric constant of the hardened material may be preferably 3.0 or less, and more preferably 2.9 or less. Here, the dielectric constant of the hardened material can be measured by the method described in the examples.

The hardened | cured material of the said resin composition is excellent in the temperature stability of dielectric tangent. Specifically, the hardened product of this resin composition can reduce the difference between the value of the dielectric tangent at normal temperature and the value of the dielectric tangent at high temperature, and can reduce the value of the dielectric tangent at normal temperature and the dielectric tangent at low temperature. The difference in values.

Therefore, the hardened | cured material of this resin composition can obtain the insulation layer excellent in the temperature stability of a dielectric tangent. Specifically, the dielectric tangents at -10 ° C, 25 ° C, and 100 ° C of the hardened product obtained by heat-treating the resin composition at 200 ° C for 90 minutes are set to Df (-10 ° C), Df (25 ° C), and At Df (100 ° C), the ratio Df (-10 ° C) to Df (25 ° C) Df (-10 ° C) / Df (25 ° C), and the ratio Df (100 ° C) to Df (25 ° C) Df ( 100 ° C) / Df (25 ° C) is in the following range.
That is, the ratio of the dielectric tangent Df (-10 ° C) / Df (25 ° C) is usually 85% or more, preferably 87% or more, particularly preferably 90% or more, usually 115% or less, and preferably 114% or less, and particularly preferred 113% or less.
The ratio of the dielectric tangent Df (100 ° C) / Df (25 ° C) is usually 85% or more, preferably 90% or more, more preferably 95% or more, usually 115% or less, and preferably 114%. Below, particularly preferred is 113% or less.
The dielectric tangents Df (-10 ° C), Df (25 ° C), and Df (100 ° C) can be measured by the method described in the examples.

As described above, the present inventors speculated that the structure having excellent temperature stability of the dielectric tangent is as follows. However, the technical scope of the present invention is not limited by the structure described below.
According to the inventor's review, it was found that the dielectric tangent of the hardened product of the resin composition containing (A) epoxy resin and (D) fluorine-based filler is in a practical temperature range up to -10 ° C to 100 ° C. In the medium, the lower the temperature, the smaller, and the higher the temperature, the larger the tendency. On the contrary, the dielectric tangent of the polymer of the maleimide imine compound (B). In the aforementioned practical temperature range, due to the action of the maleimide group, the lower the temperature, the higher, and the higher the temperature, the lower the tendency. . Thus, the temperature dependence of the dielectric tangent of the hardened product of the resin composition containing (A) the epoxy resin and (D) the fluorine-based filler is the same as that of (B) the dielectric tangent of the polymer of the maleimide compound Temperature dependence is opposite. Therefore, when (A) epoxy resin and (D) fluorine-based filling material are combined with (B) maleimide imine compound, the temperature dependence of the dielectric tangent of the two is canceled, and the temperature dependence of either Temperature can obtain the same degree of dielectric tangent Df. Therefore, the dielectric tangent of the hardened | cured material of the resin composition containing (A) an epoxy resin, (B) a maleimide compound, and (D) a fluorine-based filler has good temperature stability.

The hardened product of the resin composition generally has a small dielectric tangent at 25 ° C. For example, the dielectric tangent Df (25 ° C) at 25 ° C of a hardened 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, and still more preferably 0.009 or less. It is preferably 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 of the second embodiment]
The resin composition according to the second embodiment of the present invention includes (A) an epoxy resin and (D) a fluorine-based filler. In addition, the dielectric tangents at -10 ° C, 25 ° C, and 100 ° C of the hardened product obtained by heat-treating the resin composition of the second embodiment for 90 minutes at 200 ° C 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 (100 ° C) vs. Df (25 ° C) The ratio Df (100 ° C) / Df (25 ° C) is 85% to 115%.

The hardened material of this resin composition has a low dielectric constant due to the action of the (D) fluorine-based filler. In addition, since the ratios of the dielectric tangent Df (-10 ° C) / Df (25 ° C) and Df (100 ° C) / Df (25 ° C) are within a specific range of 85% to 115%, the cured product of the resin composition , Its dielectric tangent has excellent temperature stability. Therefore, according to the resin composition of the second embodiment, since the temperature tangent of the dielectric tangent is excellent, when it is installed on the antenna circuit board of the radar, it is possible to suppress changes due to the temperature of the detectable range of the radar. In addition, a resin composition of an insulating layer having a low dielectric constant can be obtained, and the desired effect of the present invention can be obtained. Moreover, according to the resin composition of the second embodiment, the same advantages as those of the resin composition of the first embodiment can be obtained.

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

The resin composition of the second embodiment includes (B) from the viewpoint that the dielectric tangent ratios Df (-10 ° C) / Df (25 ° C) and Df (100 ° C) / Df (25 ° C) are within a specific range. Maleimide compounds are preferred. Usually, by adjusting the amount of the maleimide imine compound (B), the ratios Df (-10 ° C) / Df (25 ° C) and Df (100 ° C) / Df (25 ° C) can be collected in a specific range. Regarding the (B) maleimide compound of the resin composition of the second embodiment, the matters described in the first embodiment can be used in the same manner as in the first embodiment.

The resin composition of the second embodiment may include, in addition to the above-mentioned components, (C) an inorganic filler, (E) an unsaturated resin, (F) a hardener, (G) a hardening accelerator, and ( H) One or more of the additives. The (C) inorganic filler, (E) unsaturated resin, (F) hardener, (G) hardening accelerator, and (H) additive of the resin composition of the second embodiment may be the same as those of the first embodiment. The matters described in the first embodiment will be used.

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

The resin composition of the second embodiment generally has the same characteristics as the resin composition of the first embodiment. Therefore, the hardened product of the resin composition of the second embodiment has a low dielectric constant and excellent temperature stability of the dielectric tangent. In addition, the dielectric tangent at 25 ° C. is usually small.

[3. Use of resin composition]
The resin composition 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 can also 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 an insulating layer for forming an insulating layer in the manufacture of a circuit board in a build-up manner.

In particular, due to the advantage of an insulating layer having a low dielectric constant, this resin composition is suitable for use as a resin composition for forming an insulating layer of a high-frequency circuit board (a resin composition for forming an insulating layer of a high-frequency circuit board). . Among them, this resin composition is more suitable for use as a resin composition for forming an interlayer insulating layer of a high-frequency circuit board (a resin composition for forming an interlayer insulating layer of a high-frequency circuit board). Here, the "high-frequency circuit board" refers to a circuit board that can operate even with electrical signals in a high frequency band. In addition, the "high frequency band region" generally refers to a band region of 1 GHz or more, and the above-mentioned resin composition is particularly applicable to a band region of 28 GHz to 150 GHz.

In addition, due to the advantage of good temperature stability of the dielectric tangent, this resin composition is preferably used as a resin composition for an insulating layer of an antenna circuit board for radar. Examples of the insulating layer of the antenna circuit board include a wiring formation layer. As described above, by using a hardened product with good temperature stability of the dielectric tangent as the material of the insulating layer, the size of the loss in the antenna circuit board can be reduced, and changes due to temperature can be achieved without relying on the use temperature. High-sensitivity radar.

In addition, an insulating layer having a low dielectric constant contributes to a low back surface of a circuit board, and thus is suitable for applications requiring a thin circuit board. In addition, the insulating layer with low dielectric constant makes the impedance control of the circuit board easy, so it is suitable for improving the design freedom of the circuit board. From this viewpoint, when a preferable use of the resin composition is mentioned, for example, a circuit board such as a main board, an IC package substrate, a camera module substrate, and a fingerprint identification sensor substrate that can be used in a portable device. To take a specific example, the fingerprint recognition sensor has an insulating layer and a plurality of electrodes and an insulating film formed on the insulating layer in this order in order. In this fingerprint recognition sensor, by using the capacitance value of a capacitor formed by a finger and an electrode placed on the insulating film and the insulating film, the difference between the concave portion and the convex portion of the fingerprint is used to identify the fingerprint. In such a fingerprint recognition sensor, when the insulating layer is made thin, the sensor itself can be miniaturized.

In addition, the resin composition can be used as a laminar laminated material for bonding films, prepregs, solder resists, underfill materials, die bonding materials, semiconductor packaging materials, buried resins, and parts-embedded resins. A wide range of applications using resin compositions.

[4. Lamellar laminated material]
The resin composition is applied in a varnished state and can be used for forming an insulating layer. However, industrially, it is preferable to use it in the form of a laminar laminated material containing this resin composition. Preferable examples of the laminar laminated material include an adhesive film and a prepreg.

In one embodiment, the subsequent film includes a support and a resin composition layer provided on the support. The resin composition layer is a layer formed of the resin composition, and is sometimes referred to as a "adhesion layer".

From the viewpoint of thinning, the thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, and still more preferably 60 μm or less. Among these, 50 μm or less is preferable. 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, 10 μm or more.

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

When a film made of a plastic material is used as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate (hereinafter sometimes referred to as "PET") Polyesters such as "PEN"); polycarbonates (hereinafter sometimes referred to as "PC"); acrylic polymers such as polymethyl methacrylate (hereinafter sometimes referred to as "PMMA"); cyclic polyolefins ; Triethyl cellulose (hereinafter sometimes referred to as "TAC"); polyether sulfide (hereinafter sometimes referred to as "PES"); polyether ketone; polyfluorene. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and polyethylene terephthalate is particularly preferred because of its low cost and excellent availability.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil. Among them, copper foil is preferred. The copper foil may be a foil made of a single metal of copper, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

The support may be subjected to a treatment such as a matt finish, a corona treatment, an antistatic treatment, or the like on the surface bonded to the resin composition layer.

As the support, a support with a release layer having a release layer on a surface bonded to the resin composition layer may be used. The mold release agent which can be used for the mold release layer of the support body with a mold release layer includes, for example, one or more types selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. Release agent. Commercially available products of the release agent include, for example, "SK-1", "AL-5", "AL-7" made by Lintec Corporation of alkyd resin-based release agents. Examples of the support with a release layer include "lumirrorT60" manufactured by Toray; "Purex" manufactured by Teijin; "unipeel" manufactured by unitika; and the like.

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. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

Next, the film can be produced, for example, by 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 drying the resin varnish to form a resin composition layer. .

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbidine Acetate solvents such as alcohol acetate; carbitol solvents such as lysin and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide and dimethylacetamidine Amine solvents such as amines (DMAc) and N-methylpyrrolidone. The organic solvents may be used singly or in combination of two or more kinds.

Drying can be performed by a known method such as heating or blowing hot air. The drying conditions are set such that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, and preferably 5% by mass or less. It varies depending on the boiling point of the organic solvent in the resin varnish, but when using a resin varnish containing an organic solvent of 30% to 60% by mass, a resin composition can be formed by drying at 50 ° C to 150 ° C for 3 minutes to 10 minutes. Physical layer. Generally, the resin composition layer is obtained by forming a coating film of a resin varnish into a semi-hardened film.

The film may include any layer other than the support and the resin composition layer, if necessary. For example, a protective film depending on the support may be provided on the surface of the adhesive film that is not bonded to the support of the resin composition layer (that is, the surface opposite to the support). The thickness of the protective film is, for example, 1 μm to 40 μm. By the protective film, adhesion or scratches on dirt, etc. on the surface of the resin composition layer can be suppressed. When the next film has a protective film, the protective film is usually used after peeling the protective film. In addition, the film can then be wound into a roll and stored.

In one embodiment, the prepreg system is formed by impregnating a sheet-like fiber substrate with a resin composition.

The sheet-like fibrous substrate used for the prepreg is not particularly limited. As the sheet-like fibrous substrate, any fibrous substrate that can be used as a substrate for a prepreg, such as glass cloth, aromatic polyamide nonwoven fabric, and liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of thinning, the thickness of the sheet-like fiber substrate 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 that the penetration depth of the plating applied to the conductor layer formation can be suppressed to be shallow, the thickness of the sheet-like fiber substrate 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 fibrous substrate is usually 1 μm or more, and may be 1.5 μm or more or 2 μm or more.

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

[5.Circuit board]
The circuit board of the present invention includes an insulating layer formed of a hardened body of the resin composition. In one embodiment, the circuit board includes an inner layer substrate and an insulating layer provided on the inner layer substrate.

"Inner substrate" refers to a member that becomes the 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, the inner layer substrate generally includes a conductor layer formed directly or indirectly on one or both sides of the core substrate. This conductor layer may be patterned in order to function as an electrical circuit, for example. An inner-layer substrate in which a conductor layer of a circuit is formed on one or both sides of a core substrate is sometimes referred to as an "inner-layer circuit board". In addition, in order to manufacture a circuit board, an intermediate manufactured product that further forms at least one of an insulating layer and a conductor layer is also included in the term "inner substrate". When the circuit board has built-in parts, the inner substrate of the built-in parts can also be used.

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

In order to electrically connect the conductor layers on both sides of the inner substrate, one or more through holes may be provided from one side to the other. In addition, the inner substrate may include components such as a passive element.

The insulating layer is a hardened layer of a resin composition. The insulating layer formed of a hardened material is particularly suitable for a circuit board, a high-frequency circuit board, a radar antenna circuit board, and a host board, an IC package substrate used in a portable device, and the like. Insulating layers for circuit boards such as camera module substrates and fingerprint sensor substrates.

The circuit board may have only one insulating layer or two or more insulating layers. When the circuit board has two or more insulating layers, the conductor layer and the insulating layer may be laminated in an overlapping manner.

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

The insulating layer may be provided with one or more via holes in order to electrically connect the conductor layers of the circuit board to each other.

Since the said insulating layer is a layer formed from the hardened | cured material of the said resin composition, the outstanding characteristics of the hardened | cured material of the said resin composition can be exhibited. Therefore, the insulation layer of the circuit board is preferably a ratio of the dielectric constant and the dielectric tangent of the insulation layer, Df (-10 ° C) / Df (25 ° C), and the ratio of the dielectric tangent Df (100 ° C) / Df. (25 ° C), and dielectric tangent Df (25 ° C) at 25 ° C are adjusted to the same ranges as those described in the aforementioned resin composition item. These characteristics can be measured using the method described in the examples.

The circuit board can be manufactured by a manufacturing method including the following steps (I) and (II) using an adhesive film, for example.
(I) a step of bonding the resin composition layer of the adhesive film to the internal substrate on the internal substrate to laminate the adhesive film,
(II) A step of thermally curing the resin composition layer to form an insulating layer.

The lamination of the inner substrate and the adhesive film can be performed, for example, by a heating and compression bonding step of pressing the adhesive film onto the inner substrate from the support side. Examples of the members in the heat-pressing step (hereinafter also referred to as "heat-pressing members") include heated metal plates (SUS mirror plates, etc.), metal rollers (SUS rollers), and the like. In addition, instead of pressing and pressing the heating and pressure-bonding member directly on the support of the film, it is better to press the film through the elastic material such as heat-resistant rubber to fully follow the unevenness of the surface of the inner substrate and press. .

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

Lamination can be performed by a commercially available vacuum laminator. Commercially available vacuum lamination machines include, for example, vacuum pressure lamination machines manufactured by Nagaku Seisakusho, vacuum coating machines manufactured by nikko-materials, and batch vacuum pressure lamination machines.

After lamination, the resin composition layer after lamination can also be smoothed by pressing under pressure (atmospheric pressure), for example, by heating and pressing the member from the support side, and laminating the resin composition layer. The pressing conditions for the smoothing treatment may be the same conditions as those of the heat-pressing conditions for the above-mentioned laminated layer. The smoothing process can be performed by a commercially available laminator. The lamination and smoothing treatment can also be performed continuously using the above-mentioned commercially available vacuum laminator.

The support can be removed between step (I) and step (II), and can also be removed after step (II).

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

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

Before the resin composition layer is thermally hardened, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before thermosetting the resin composition layer, the resin composition layer is usually at a temperature of 50 ° C or higher and less than 120 ° C (preferably 60 ° C or higher and 110 ° C or lower, more preferably 70 ° C or higher and 100 ° C or lower). The preliminary heating is usually 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

The method for manufacturing a circuit board may further include (III) a step of opening a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductive layer. These steps (III) to (V) can be performed in accordance with a suitable method used for manufacturing a circuit board. In addition, when 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 step (IV). It should be implemented in a timely manner with step (V).

Step (III) is a step of making holes in the insulating layer. Through openings, holes such as via holes and through holes can be formed in the insulating layer. Step (III) can be performed according to the composition of the resin composition used for forming the insulating layer, for example, using a drill, a laser, a plasma, or the like. The size or 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 a known order and conditions used when forming the insulating layer of the circuit board can be adopted. For example, a swelling treatment using a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing solution may be sequentially performed, and the insulating layer may be subjected to a roughening treatment.

Examples of the swelling liquid include an alkali solution and a surfactant solution, and an alkali solution is preferred. The alkali solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. The swelling liquid may be used singly or in combination of two or more kinds. The swelling treatment by the swelling liquid is not particularly limited. For example, the swelling treatment can be performed by 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 the swelling of the resin of the insulating layer to a moderate level, it is preferred that the insulating layer is immersed in a swelling solution at 40 ° C to 80 ° C for 5 to 15 minutes.

Examples of the oxidant include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The oxidant may be used singly or in combination of two or more kinds. The roughening treatment of an oxidant such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidant solution heated to 60 ° C to 80 ° C for 10 minutes to 30 minutes. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by mass. Examples of commercially available oxidants include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan.

The neutralizing solution is preferably an acidic aqueous solution. Examples of the commercially available products of the neutralizing solution include "Reduction solution Securiganth P" manufactured by Atotech Japan. The neutralizing solution may be used singly or in combination of two or more kinds. The treatment with the neutralizing solution can be performed by immersing the treated surface of the insulating layer roughened with an oxidizing agent in a neutralizing solution at 30 ° C to 80 ° C for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing the insulating layer roughened with an oxidizing agent at a neutralizing solution at 40 ° C to 70 ° C for 5 to 20 minutes is preferred.

Step (V) is a step of forming a conductor layer. The material used for the conductor layer is not particularly limited. In a more suitable embodiment, the conductor layer includes 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. The alloy layer includes, for example, a layer formed of an alloy of two or more metals selected from the group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among these, from the viewpoints of versatility, cost, and ease of patterning of the conductor layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper is preferred; or nickel Alloy layer of chromium alloy, copper-nickel alloy, copper-titanium alloy. More preferably, it is a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper or an alloy layer of a nickel-chromium alloy, and even more preferably a single metal layer of copper.

The conductor layer may have a single-layer structure or a single-metal layer made of different kinds of metals or alloys or a multilayer structure including two or more alloy layers. 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 conductive layer is usually 3 μm to 200 μm, and preferably 10 μm to 100 μm.

The conductor layer can be formed by directly patterning this using a metal foil used as a support for a thin film, for example. The conductive layer can be formed by, for example, plating. By the method of forming the plating, for example, the surface of the insulating layer can be plated by a method such as a semi-additive method or a full-additive method to form a conductive layer having a desired wiring pattern. Among them, from the standpoint of simplicity of production, it is preferably formed by a semi-additive method.

Hereinafter, an example in which a conductive layer is formed by a semi-additive method will be described. First, a shield layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating protection layer, a mask pattern corresponding to a desired wiring pattern and exposing a part of the plating protection layer is formed. On the exposed plating protection layer, after forming a metal layer by electroplating, the mask pattern is removed. Then, an unnecessary plating protection layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

The conductive layer can be formed using, for example, a metal foil. When the conductive layer is formed using a metal foil, step (V) is preferably performed between step (I) and step (II). For example, after step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil can be performed by a vacuum lamination method. The conditions for lamination can be the same as those for the inner substrate and the adhesive film in step (I). Next, step (II) is performed to form an insulating layer. Then, using a metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by a method such as a subtractive process method, a modified semi-additive method, or the like. The metal foil can be produced by, for example, an electrolytic method or a rolling method. Examples of commercially available metal foils include HLP foils manufactured by JX Nippon Nissei Metal Co., Ltd., JXUT-III foils, 3EC-III foils manufactured by Mitsui Metal Mining Corporation, and TP-III foils.

When the circuit board includes two or more insulating layers and conductor layers (Build-up Layers), by repeating the formation steps of the insulating layers and the conductor layer formation steps more than once, it is possible to manufacture multilayers having circuit functions. Circuit board with wiring structure.

In other embodiments, the circuit board may be manufactured using a prepreg instead of an adhesive film. The manufacturing method using a prepreg is basically the same as the case where an adhesive film is used.

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

Examples of the semiconductor device include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trams, ships, and airplanes).

A semiconductor device can be manufactured by, for example, mounting a component (semiconductor wafer) at a conductive portion of a circuit board. "Continuity" means "the place where the electrical signal is transmitted on the circuit board". This place can be the surface of the circuit board or it can be buried in the circuit board. In addition, as the semiconductor wafer, an electric circuit element using a semiconductor as a material can be arbitrarily used.

As a method for mounting a semiconductor wafer when manufacturing a semiconductor device, any method capable of effectively functioning the semiconductor wafer can be adopted. Examples of the method for mounting the semiconductor wafer include a wire bonding method, a flip chip method, a BBUL-free method, an anisotropic conductive film (ACF) method, Non-conductive film (NCF) mounting method. Here, the "mounting method by bumpless layer (BBUL)" refers to the "mounting method of directly burying a semiconductor wafer into a circuit board and connecting the semiconductor wafer to the wiring of the circuit board".

[Example]

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these embodiments. In addition, in the following description, "part" and "%" show "mass part" and "mass%" respectively unless otherwise stated.

[Example 1]
20 parts of bisxylenol-type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., epoxy equivalent of about 185) and phenylmethane maleimide resin ("BMI-2000" manufactured by Yamato Chemical Industry Co., Ltd.) 2.5 After dissolving in 20 parts of solvent petroleum naphtha while stirring and heating, it was cooled to room temperature to obtain a resin solution.

In this resin solution, 100 parts of an inorganic filler ("SO-C2" manufactured by admatechs, an average particle diameter of 0.5 μm, a specific surface area of 5.9 m ² / g, and a carbon content per unit surface area of 0.38 mg / m ² ) were mixed, and 55 parts of polytetrafluoroethylene particles ("ruburon L-2" manufactured by Daikin Industries Co., Ltd., average particle diameter: 3 μm) were kneaded and dispersed using 3 rolls.

In addition, to this resin solution, 31 parts of an active ester-based hardener ("HPC-8000-65T" manufactured by DIC, a 65% non-volatile toluene solution with an active group equivalent of about 223), and an acrylic resin (Sinakamura Chemical Industries) were mixed. 10 parts of `` A-DOG '' made by the company, 2 parts of hardening accelerator (5% methyl ethyl ketone solution of 4-dimethylaminopyridine (DMAP)), and 2 parts of hardening accelerator (Nippon Oil Co., Ltd. 0.13 parts of cumyl peroxide "percumyl D") was uniformly dispersed using a rotary mixer to prepare a resin varnish 1.

[Example 2]
The amount of phenylmethane maleimide resin ("BMI-2000" manufactured by Yamato Chemical Industry Co., Ltd.) was changed to 10 parts.
In addition, acrylic resin ("A-DOG" manufactured by Shin Nakamura Chemical Industry Co., Ltd.) and dicumyl peroxide ("percumyl D" manufactured by Nippon Oil Co., Ltd.) were not used.
Except for the above matters, the same operation as in Example 1 was performed to prepare a resin varnish 2.

[Example 3]
The amount of phenylmethane maleimide resin ("BMI-2000" manufactured by Yamato Chemical Industry Co., Ltd.) was changed to 13.5 parts.
Except for the above matters, the same operation as in Example 1 was performed to prepare a resin varnish 3.

[Example 4]
2.5 parts of phenylmethane maleimide resin ("BMI-2000" by Daiwa Chemical Industry Co., Ltd.) was changed to m-phenylene bismaleimide resin ("BMI-3000" by Yamato Chemical Industry Co., Ltd.) 2.5 servings.
Except for the above matters, the same operation as in Example 1 was performed to produce a resin varnish 4.

[Example 5]
2.5 parts of phenylmethane maleimide resin ("BMI-2000" by Daiwa Chemical Industry Co., Ltd.) was changed to m-phenylene bismaleimide resin ("BMI-3000" by Yamato Chemical Industry Co., Ltd.) 10 servings.
In addition, acrylic resin ("A-DOG" manufactured by Shin Nakamura Chemical Industry Co., Ltd.) and dicumyl peroxide ("percumyl D" manufactured by Nippon Oil Co., Ltd.) were not used.
Except for the above matters, the same operation as in Example 1 was performed to prepare a resin varnish 5.

[Example 6]
2.5 parts of phenylmethane maleimide resin ("BMI-2000" by Daiwa Chemical Industry Co., Ltd.) was changed to m-phenylene bismaleimide resin ("BMI-3000" by Yamato Chemical Industry Co., Ltd.) 13.5 servings.
Except for the above matters, the same operation as in Example 1 was performed to prepare a resin varnish 6.

[Comparative Example 1]
The amount of phenylmethane maleimide resin ("BMI-2000" manufactured by Yamato Chemical Industry Co., Ltd.) was changed to 1 part.
Except for the above matters, the same operation as in Example 1 was performed to prepare a resin varnish 7.

[Comparative Example 2]
The amount of phenylmethane maleimide resin ("BMI-2000" manufactured by Yamato Chemical Industries, Ltd.) was changed to 16 parts.
Except for the above matters, the same operation as in Example 1 was performed to prepare a resin varnish 8.

[Comparative Example 3]
2.5 parts of phenylmethane maleimide resin ("BMI-2000" by Daiwa Chemical Industry Co., Ltd.) was changed to m-phenylene bismaleimide resin ("BMI-3000" by Yamato Chemical Industry Co., Ltd.) 1 serving.
Except for the above matters, the same operation as in Example 1 was performed to produce a resin varnish 9.

[Comparative Example 4]
2.5 parts of phenylmethane maleimide resin ("BMI-2000" by Daiwa Chemical Industry Co., Ltd.) was changed to m-phenylene bismaleimide resin ("BMI-3000" by Yamato Chemical Industry Co., Ltd.) 16 servings.
Except for the above matters, the same operation as in Example 1 was performed to produce a resin varnish 10.

[Evaluation method]
(Preparation of evaluation samples of hardened products)
A polyethylene terephthalate film ("PET501010", manufactured by Lintec) was prepared as a support, and the surface was subjected to a release treatment. The resin varnishes obtained in the examples and comparative examples were uniformly coated on this support with a die coater so that the thickness of the dried resin composition layer became 40 μm. The coated resin varnish was dried at 80 ° C to 110 ° C (average 95 ° C) for 6 minutes to obtain a resin composition layer. Then, this 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 of a cured product of the resin composition. This cured product film was cut to a length of 80 mm and a width of 2 mm to obtain an evaluation sample.

(Measurement of dielectric constant Dk and dielectric tangent Df)
For this evaluation sample, the dielectric tangent and the dielectric constant were measured at a measurement frequency of 10 GHz by a resonant cavity perturbation method using a measuring device ("HP8362B" manufactured by Agilent Technologies). The measurement of the dielectric tangent is performed at -10 ° C, 25 ° C and 100 ° C. The measurement of the dielectric constant was performed at 25 ° C.

(Evaluation of dielectric constant Dk)
When the dielectric constant Dk was 3.0 or less, it was evaluated as "good". When the dielectric constant Dk exceeds 3.0, it is evaluated as "defective".

(Evaluation of Temperature Stability of Dielectric Tangent)
Calculate the ratio Df (-10 ° C) / Df (25 ° C) of the dielectric tangent Df (-10 ° C) to the dielectric tangent Df (25 ° C) at 25 ° C. When the ratio Df (-10 ° C) / Df (25 ° C) is in the range of 85% to 115%, the temperature stability at a low temperature is judged to be "good". When the ratio Df (-10 ° C) / Df (25 ° C) is not in the range of 85% to 115%, the temperature stability at a low temperature is judged to be "bad".

The ratio Df (100 ° C) / Df (25 ° C) of the dielectric tangent Df (100 ° C) at 25 ° C to the dielectric tangent Df (25 ° C) at 25 ° C was calculated. When the ratio Df (100 ° C) / Df (25 ° C) is in the range of 85% to 115%, the temperature stability at high temperature is judged to be "good". When the ratio Df (100 ° C) / Df (25 ° C) is not in the range of 85% to 115%, the temperature stability at a high temperature is judged to be "bad".

[result]
The results of the above examples and comparative examples are shown in the following table. In the following table, the amount of each component represents the mass part of the non-volatile component. In the following tables, the meanings of the abbreviations are as follows.
(B) / (A): The mass ratio of (B) component to 100% by mass of (A) component.

[Review]
As can be seen from Table 1, the embodiment can obtain a low dielectric constant. In the embodiment, the ratio of the dielectric tangent Df (100 ° C) / Df (25 ° C) is close to a specific range (100% ± 15%) close to 100%, and the temperature tangent of the dielectric tangent is good . In addition, in the embodiment, the ratio of the dielectric tangent Df (-10 ° C) / Df (25 ° C) is close to a specific range (100% ± 15%) close to 100%, and the temperature dependence of the dielectric tangent at low temperature good. Therefore, from this result, it was confirmed that the resin composition which can obtain the insulating layer which has a low dielectric constant and excellent temperature stability of a dielectric tangent is realizable by this invention. In addition, when using an insulation layer with excellent temperature stability of the dielectric tangent in the antenna circuit board of a radar, those skilled in the art can clearly understand that the change in the detectable range of the radar due to temperature can be suppressed.

In the foregoing embodiment, even when the components (E) to (G) are not used, there is a certain degree of difference, but the conclusion is the same as that of the foregoing embodiment.

Claims (12)

A resin composition comprising a resin composition including (A) an epoxy resin, (B) a maleimide compound, (C) an inorganic filler, and (D) a fluorine-based filler, Among them, when the content of (B) component is 100% by mass with respect to (A) component, it is 10% to 70% by mass. A resin composition comprising a resin composition including (A) an epoxy resin and (D) a fluorine-based filler, The dielectric tangents at -10 ° C, 25 ° C, and 100 ° C of the hardened product obtained by heat-treating the resin composition at 200 ° C for 90 minutes are Df (-10 ° C), Df (25 ° C), and Df (100 ° C), respectively. Time, The ratio of Df (-10 ℃) to Df (25 ℃) Df (-10 ℃) / Df (25 ℃) is 85% ～ 115%, The ratio of Df (100 ° C) to Df (25 ° C) Df (100 ° C) / Df (25 ° C) is 85% to 115%. The resin composition according to claim 2, which comprises (B) a maleimide compound. The resin composition according to claim 1 or 2, wherein the component (D) is a fluorine-based polymer particle. The resin composition according to claim 1 or 2, wherein the component (D) is polytetrafluoroethylene particles. The resin composition as claimed in claim 1 or 2, which comprises (E) a resin having an unsaturated hydrocarbon group. The resin composition according to claim 6, wherein the component (E) is one or more compounds selected from the group consisting of acrylfluorenyl, methacrylfluorenyl, styryl, allyl, vinyl, and acryl. Saturated hydrocarbyl. The resin composition according to claim 6, wherein the component (E) has a vinyl group and a cyclic ether structure having a 5-membered ring or more. The resin composition of claim 1 or 2 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 9. A circuit board comprising an insulating layer made of a hardened body of a resin composition according to any one of claims 1 to 9. A semiconductor device includes a circuit board as claimed in claim 11.