TW201840437A - Resin composition capable of reducing dielectric constant and improving adhesion with conductor layer - Google Patents

Abstract

The subject of the present invention is to provide a resin composition which may obtain an insulation layer capable of reducing dielectric constant and improving adhesion with conductor layer. The solution of the present invention provides a resin composition, which contains component (A) epoxy resin, component (B) active ester compound, component (C) inorganic filler, and component (D) fluoro-filler. While nonvolatile components of the resin composition is set as 100 weight %, a content of component (D) is 10 to 40 weight %. a total content of component (C) and component (D) is set as 100 weight %, the content of component (D) is 20 to 70 weight %.

Description

Resin composition

The present invention relates to a resin composition, a bonding film, a circuit substrate, and a semiconductor device.

As a manufacturing technique of a circuit board, a manufacturing method of a build-up method in which an insulating layer and a conductor layer are alternately overlapped on an inner layer circuit board is known. The insulating layer is generally formed by curing a resin composition layer which is a coating film of a resin varnish containing a resin composition. For example, Patent Document 1 describes a resin composition comprising an epoxy resin, a curing agent, and a resin composition of a fluororesin filler, characterized in that the content of the fluororesin filler is relative to the resin composition. The solid shape is divided into 50% by mass to 85% by mass. [Prior Technical Literature] [Patent Literature]

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

[Problems to be solved by the invention]

However, the resin composition disclosed in the above-mentioned Patent Document 1 has a large amount of the fluororesin filler containing 50% by mass to 85% by mass, so that the adhesion to the inner layer circuit substrate is impaired, and it is difficult to apply to the high-frequency circuit substrate. And a multilayer wiring board.

Therefore, an object of the present invention is to provide a resin composition which is excellent in dielectric properties and excellent in adhesion to an inner layer circuit board. [Means for solving the problem]

As a result of intensive studies on the above-mentioned problems, the present inventors have found that the above problems can be solved by adjusting the content of the inorganic filler and the fluorine-based filler in the resin composition to a predetermined ratio, and thus the present invention has been completed.

That is, the present invention provides the following [1] to [10]. [1] A resin composition comprising a resin composition of the component (A) epoxy resin, the component (B) active ester compound, the component (C) inorganic filler, and the component (D) fluorine-based filler, When the nonvolatile content in the resin composition is 100% by mass, the content of the component (D) is 10% by mass to 40% by mass; and the total content of the component (C) and the component (D) is 100. In the case of % by mass, the component (D) is 20% by mass to 70% by mass. [2] The resin composition according to [1], wherein the component (D) is a fluorine-based polymer particle. [3] The resin composition according to [2], wherein the fluorine-based polymer particles are polytetrafluoroethylene (PTFE) particles. [4] The resin composition according to any one of [1], wherein the component (E) further contains a compound having an unsaturated hydrocarbon group. [5] The resin composition according to [4], wherein the component (E) has a group consisting of an acrylic group, a methacryl group, a styryl group, an allyl group, a vinyl group, and a propylene group. One or more compounds of an unsaturated hydrocarbon group are selected. [6] The resin composition according to the above [5], wherein the component (E) is a compound having a vinyl group and a cyclic ether structure of a 5-membered or higher ring. [7] The resin composition according to any one of [1] to [6] which is used for forming an insulating layer of a high-frequency circuit substrate. [8] A film comprising a support material and a resin composition layer comprising the resin composition according to any one of [1] to [6], which is provided on the support. [9] A high-frequency circuit board comprising the insulating layer of the cured product of the resin composition according to any one of [1] to [6]. [10] A semiconductor device comprising the high-frequency circuit substrate according to [9]. [Effects of the Invention]

According to the present invention, it is possible to provide a resin composition which is low in dielectric properties (particularly, dielectric constant and dielectric tangent) and excellent in adhesion to an inner layer circuit substrate (particularly, a conductor layer). Insulation.

[Best Mode for Carrying Out the Invention]

Hereinafter, the resin composition, the adhesive film, the high-frequency circuit substrate, and the semiconductor device will be described in detail.

[Resin Composition] The resin composition includes the component (A) epoxy resin, the component (B) active ester compound, the component (C) inorganic filler, and the component (D) fluorine-based filler, and the resin composition When the nonvolatile content is 100% by mass, the content of the component (D) is 10% by mass to 40% by mass, and when the total content of the component (C) and the component (D) is 100% by mass, the component (D) It is 20% by mass to 70% by mass. Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

<Component (A) Epoxy Resin> The resin composition contains the component (A) epoxy resin. Examples of the epoxy resin include a bixylenol type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, and a bisphenol AF type epoxy resin. Resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type Epoxy resin, naphthol type epoxy resin, bismuth type oxygen resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear Aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane dimethanol type epoxy resin, naphthene Ethylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin. The epoxy resin may be used alone or in combination of two or more.

From the viewpoint of lowering the average linear thermal expansion coefficient, the component (A) is preferably an epoxy resin containing an aromatic skeleton, and is composed of a bisphenol A epoxy resin, a bisphenol F epoxy resin, and a naphthalene type. One or more selected epoxy resins, biphenyl type epoxy resins, and dicyclopentadiene type epoxy resins are preferable, and a biphenyl type epoxy resin is more preferable. Further, the term "aromatic skeleton" refers to a chemical structure generally defined as aromatic, and therefore includes polycyclic aromatic and aromatic heterocyclic rings.

The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100% by mass, an epoxy resin having at least 50% by mass or more of two or more epoxy groups in one molecule is preferable. Among them, an epoxy resin (referred to as "solid epoxy resin") having three or more epoxy groups in one molecule and being solid at a temperature of 20 ° C is preferable. The epoxy resin may be an epoxy resin containing only a solid epoxy resin, or may be an epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C ("called a liquid ring" Oxygen resin"), and solid epoxy resin. As the epoxy resin, a liquid epoxy resin and a solid epoxy resin are used in combination to obtain a resin composition having excellent flexibility. Further, the breaking strength of the cured product of the resin composition is also improved.

As the liquid epoxy resin, it is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine. Type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane dimethanol type epoxy resin, glycidylamine type epoxy resin, and ring having a butadiene structure An oxygen resin is preferable, and a glycidylamine type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, and a naphthalene type epoxy resin are preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Co., Ltd., "828US" and "jER828EL" manufactured by Mitsubishi Chemical Corporation. , "825", "Epikote 828EL" (bisphenol A epoxy resin), "jER807", "1750" (bisphenol F epoxy resin), "jER152" (phenol novolak epoxy resin), " 630", "630LSD" (glycidylamine type epoxy resin), "ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), Nagasechemtex "EX-721" (glycidyl ester type epoxy resin), "shares" "CELOXIDE 2021P" made by Daicel (alicyclic epoxy resin having an ester skeleton), "PB-3600" (with Ding Er) "Epoxy resin of olefin structure", "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel Chemical Co., Ltd. These may be used alone or in combination of two or more.

The solid epoxy resin is a naphthalene type tetrafunctional epoxy resin, a cresol novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol type epoxy resin, and a combination. Benzene type epoxy resin, stilbene ether type epoxy resin, hydrazine type oxygen resin, bisphenol A type epoxy resin, tetraphenylethane type epoxy resin are preferred, naphthalene type 4 functional epoxy resin, naphthalene Phenolic epoxy resins and biphenyl type epoxy resins are also preferred.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene epoxy resin), "HP-4700", and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Co., Ltd. "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "HP -7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (stretching naphthyl ether ring) "Oxygen resin", "EPPN-502H" (trisphenol type epoxy resin) made by Nippon Kayaku Co., Ltd., "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L" "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., "ESN485" (naphthol novolac type epoxy resin), Mitsubishi Chemical ( "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (dixylenol type epoxy resin), "YX8800" (蒽 type oxygen resin), Osaka Gas Chemicals (share) system "PG-100", "CG-500", three "YL7760" (bisphenol AF type epoxy resin), "YL7800" (芴 type epoxy resin), and "jER1010" (solid bisphenol A type epoxy resin) made by Mitsubishi Chemical Co., Ltd. "jER1031S" (tetraphenylethane type epoxy resin). These may be used alone or in combination of two or more.

When the liquid epoxy resin and the solid epoxy resin are used in combination as the epoxy resin, the mass ratio (liquid epoxy resin: solid epoxy resin) is 1:0.1 to 1 in mass ratio. The range of :15 is preferred. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin to the above range, the following effects can be obtained: i) when used in the form of a film, appropriate adhesion can be obtained, ii) followed by When the form of the film is used, sufficient flexibility can be obtained, workability can be improved, and iii) a cured product having sufficient fracture strength can be obtained. From the viewpoint of the effects of the above i) to iii), the ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is preferably 1:0.5. The range of ~1:10 is better in the range of 1:1~1:8.

The content of the epoxy resin in the resin composition is preferably 5% by mass or more when the non-volatile content is 100% by mass, from the viewpoint of obtaining a good mechanical strength and an insulating layer exhibiting insulation reliability. It is preferably 8% by mass or more, and more preferably 10% by mass or more. The content of the epoxy resin is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less, as a condition that the effect of the present invention can be obtained.

The epoxy equivalent of the epoxy resin is preferably from 50 to 5,000, more preferably from 50 to 3,000, still more preferably from 80 to 2,000, still more preferably from 110 to 1,000. By setting it as this range, the crosslinking density of a hardened material will become sufficient, and the insulating layer of the surface roughness is small. Further, the epoxy equivalent is a mass of a resin containing one equivalent of an epoxy group, and can be measured in accordance with JIS K7236.

The weight average molecular weight of the epoxy resin is preferably from 100 to 5,000, more preferably from 250 to 3,000, still more preferably from 400 to 1,500. Here, the weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

<Component (B) Active Ester Compound> Component (B) The active ester compound is a compound having one or more active ester groups in one molecule. In general, the active ester compound can function as a curing agent that reacts with the epoxy resin of the component (A) described above to cure the resin composition. By using the component (B) active ester compound, the dielectric tangent of the cured product of the resin composition can be lowered, and generally, an insulating layer having a small surface roughness can be obtained.

The component (B) active ester compound is preferably one or more active ester groups in one molecule. As such an active ester compound, for example, a phenol ester, a thiophenol ester, an N-hydroxylamine, or an ester of a heterocyclic hydroxy compound has two or more reactive activities in one molecule. Ester-based compound. Further, the component (B) active ester compound may be used alone or in combination of two or more types in any ratio.

From the viewpoint of improving heat resistance, the active ester compound (B) is preferably obtained by subjecting a carboxylic acid compound and/or a thiocarboxylic acid compound to a condensation reaction with a hydroxy compound and/or a thiol compound. Active ester compound. In particular, an active ester compound obtained by reacting one or more selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound is more preferable. Further, an aromatic compound having two or more active ester groups in one molecule obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group is further preferred. Among them, an aromatic compound having two or more active ester groups in one molecule is particularly preferable, and a carboxylic acid compound having at least two or more carboxyl groups in one molecule and an aromatic compound having a phenolic hydroxyl group are used. The aromatic compound obtained after the reaction. Further, the component (B) active ester compound may be linear or branched. Further, when the carboxylic acid compound having two or more carboxyl groups in one molecule is a compound containing an aliphatic chain, compatibility with a resin composition can be improved, and when it is a compound having an aromatic ring, heat resistance can be improved. .

The carboxylic acid compound may, for example, be an aliphatic carboxylic acid having 1 to 20 carbon atoms (preferably 2 to 10, preferably 2 to 8), and have 7 to 20 carbon atoms (preferably 7 to 10). Aromatic carboxylic acid. Examples of the aliphatic carboxylic acid include acetic acid, malonic acid, succinic acid, maleic acid, and itaconic acid. Examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyrogal acid. Among them, from the viewpoint of heat resistance, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred, and isophthalic acid and terephthalic acid are used. It is better. Further, the carboxylic acid compound may be used alone or in combination of two or more types in any ratio.

The thiocarboxylic acid compound may, for example, be thioacetic acid or thiobenzoic acid. Further, the thiocarboxylic acid compound may be used alone or in combination of two or more kinds in any ratio.

The phenol compound may, for example, be a phenol compound having 6 to 40 carbon atoms (preferably 6 to 30, preferably 6 to 23, more preferably 6 to 22). Specific examples of suitable phenol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, reduced phenolphthalein, methylated bisphenol A, methylated bisphenol F, and A. Bisphenol bisphenol, phenol, o-cresol, m-cresol, p-cresol, catechol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, Pyrogallol, dicyclopentadiene type diphenol. Here, the "dicyclopentadiene type diphenol" means a phenol compound obtained by condensing two molecules of phenol in one molecule of dicyclopentadiene. As the phenol compound, a phenol novolak or a phosphorus atom-containing oligomer having a phenolic hydroxyl group described in JP-A-2013-40270 can be used. Further, the phenol compound may be used alone or in combination of two or more types in any ratio.

The naphthol compound may, for example, be a naphthol compound having 10 to 40 carbon atoms (preferably 10 to 30, preferably 10 to 20). Specific examples of suitable naphthol compounds include α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene. A naphthol novolak can also be used as a naphthol compound. Further, the naphthol compound may be used alone or in combination of two or more types in any ratio.

Among them, in terms of heat resistance improvement and solubility improvement, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, and children Tea phenol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, four Hydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene-type diphenol, phenol novolac, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are preferred. Further, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, and Further, benzenetriol, benzenetriol, dicyclopentadiene-type diphenol, phenol novolac, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferable. Among them, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene type Diphenol, a phenol novolak, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are further preferred. Further, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenol, phenol novolac, and phosphorus atom-containing oligomer having a phenolic hydroxyl group Things are better. Among them, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenol, and phosphorus atom-containing oligomer having a phenolic hydroxyl group are particularly good. Further, it is particularly preferable to use dicyclopentadiene type diphenol.

Examples of the thiol compound include benzenedithiol and triazinedithiol. In addition, the thiol compound can be used in combination of two or more types in a single type or in any ratio.

Specific examples of suitable active ester compounds include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, and an active ester compound containing an acetylated phenol novolak. An active ester compound of a benzamidine compound of a phenol novolak, and an active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group. Among them, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, and an activity obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group Ester compounds are also preferred. Here, the "dicyclopentadiene type diphenol structure" means a divalent structural unit formed of a phenyl-dicyclopentylene-phenylene group.

A particularly suitable specific example of the active ester compound containing a dicyclopentadiene type diphenol structure is a compound represented by the following formula.

In the above formula, R is independently represented by a phenyl group or a naphthyl group. Among them, from the viewpoint of lowering the dielectric tangent and improving the heat resistance, R is preferably a naphthyl group.

In the above formula, k represents 0 or 1. Among them, from the viewpoint of lowering the dielectric tangent and improving the heat resistance, k is preferably 0. In the above formula, the average number of n-type repeating units is 0.05 to 2.5. Among them, from the viewpoint of lowering the dielectric tangent and improving the heat resistance, n is preferably 0.25 to 1.5.

As the component (B), the active ester compound may be an active ester compound disclosed in JP-A-2004-277460 or JP-A-2013-40270. Further, as the component (B) active ester compound, a commercially available active ester compound can also be used. As a commercial item of the active ester compound, for example, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000L-65M" (including dicyclopentadiene type II) manufactured by DIC Corporation are mentioned. "EXB9416-70BK" (active ester compound containing naphthalene structure) manufactured by DIC Corporation; "DC808" (active ester compound of acetylated phenol containing phenol novolac) by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "YLH1026" (active ester compound of benzamidine compound containing phenol novolac); "EXB9050L-62M" (active ester compound containing a phosphorus atom) manufactured by DIC Corporation.

The active group equivalent of the active ester compound of the component (B) is preferably from 120 to 500, more preferably from 150 to 400, particularly preferably from 180 to 300. By setting the active group equivalent of the active ester compound of the component (B) to the above range, the crosslinking density of the cured product of the resin composition is sufficient, and an insulating layer having a small surface roughness can be obtained. Here, the active group equivalent means a resin mass containing 1 equivalent of an active group.

Further, the active ester compound may be used alone or in combination of two or more kinds in any ratio.

The content of the component (B) in the resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, and more preferably 10% by mass based on 100% by mass of the nonvolatile component in the resin composition. The mass% or more is more preferably 15% by mass or more, more preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less. When the content of the component (B) active ester compound is at least the lower limit of the above range, the adhesion between the conductor layer and the insulating layer can be particularly improved, and when the content is at most the upper limit of the above range, the heat resistance can be improved. Or can inhibit the generation of stains.

When the number of epoxy groups of the epoxy resin of the component (A) is 1, the active base of the component (B) active ester compound is preferably 0.1 or more from the viewpoint of obtaining an insulating layer having a good mechanical strength. It is preferably 0.2 or more, more preferably 0.3 or more, particularly preferably 0.4 or more, preferably 2 or less, more preferably 1.5 or less, still more preferably 1 or less. Here, the term "the number of epoxy groups of the epoxy resin" means a value obtained by dividing the amount of the nonvolatile component of the epoxy resin present in the resin composition by the epoxy equivalent, and is performed for all the epoxy resins. The total value. In addition, the "active group" means a functional group reactive with an epoxy group, and the "active number of active ester compound" means the amount of the nonvolatile component of the active ester compound present in the resin composition divided by The active base equivalent and the obtained value are combined with the total value obtained.

<Component (C) Inorganic filler> The resin composition contains the component (C) inorganic filler. The material of the inorganic filler is not particularly limited. Examples of the material of the inorganic filler include cerium oxide, aluminum oxide, glass, cordierite, cerium oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, gibbsite, hydrogen. Alumina, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, barium carbonate, barium titanate, calcium titanate, magnesium titanate, barium titanate, Titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium phosphotungstate. Among these, cerium oxide is particularly suitable. Further, as the cerium oxide, spherical cerium oxide is preferred. The inorganic filler may be used alone or in combination of two or more.

The average particle diameter of the inorganic filler is preferably 5 μm or less, more preferably 2.5 μm or less, from the viewpoint of improving the embedding property of the conductor layer and obtaining an insulating layer having a low surface roughness. 2 μm or less, and more preferably 1.5 μm or less. The average particle diameter is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, 0.5 μm or more, or 1 μm or more. Commercial products of the inorganic filler having such an average particle diameter include, for example, "SP60-05" manufactured by Nippon Steel-Sumikin Materials Co., Ltd., "SP507-05", and "YC100C" manufactured by Admatechs. "YA050C", "YA050C-MJE", "YA010C", Denca ("share") "UFP-30", "share" Tokuyama "Shirufiru NSS-3N", "Shirufiru NSS-4N", "Shirufiru NSS-5N" , (shares) Admatechs "SC2500SQ", "SO-C4", "SO-C2", "SO-C1".

The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared by a laser diffraction scattering type particle size distribution measuring apparatus on a volume basis, and the median diameter of the inorganic filler can be measured as an average particle diameter. As the measurement sample, a sample in which an inorganic filler is dispersed into water by ultrasonic waves is preferably used. As the laser diffraction scattering type particle size distribution measuring apparatus, "LA-500" manufactured by Horiba, Ltd., etc. can be used.

From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler is an amine decane coupling agent, an epoxy decane coupling agent, a mercapto decane coupling agent, an alkoxy decane compound, or an organic decazane compound. It is preferred to treat one or more kinds of surface treatment agents such as a titanate coupling agent. As a commercially available product of the surface treatment agent, "KBM403" (3-glycidoxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" manufactured by Shin-Etsu Chemical Co., Ltd. (3- "Methyl propyl trimethoxy decane", "KBE903" (3-aminopropyltriethoxy decane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3) manufactured by Shin-Etsu Chemical Co., Ltd. -Aminopropyltrimethoxydecane), "SZ-31" (hexamethyldiazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-103" manufactured by Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type decane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd.).

The degree of surface treatment by the surface treatment agent can be evaluated in accordance with the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and 0.2 mg from the viewpoint of improving the dispersibility of the inorganic filler. /m ² or more is better. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or preventing an increase in the melt viscosity when the resin varnish is formed into a sheet form, the amount of carbon per unit surface area of the inorganic filler is 1 mg/m ² or less. Preferably, it is preferably 0.8 mg/m ² or less, more preferably 0.5 mg/m ² or less.

The amount of carbon per unit surface area of the inorganic filler can be measured by washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, first, a sufficient amount of MEK as a solvent was added to an inorganic filler which was surface-treated with a surface treatment agent, and ultrasonically washed at 25 ° C for 5 minutes. Next, after removing the supernatant and drying the nonvolatile matter, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.

In the case where the content of the inorganic filler in the resin composition is such that the insulating layer having a low thermal expansion coefficient is obtained, when the nonvolatile content in the resin composition is 100% by mass, it is preferably 10% by mass or more. It is preferably 15% by mass or more, and more preferably 20% by mass or more. The content of the inorganic filler in the resin composition is preferably 70% by mass or less, more preferably 60% by mass or less, more preferably from the viewpoint of improving the mechanical strength (especially elongation) of the insulating layer. 50% by mass or less.

<Component (D) Fluorine Filler> The resin composition contains the component (D) fluorine-based filler. Here, the term "fluorine-based" means a fluorine atom. Moreover, the "fluorine-based filler" means that the material contained in the filler is a compound containing a fluorine atom. The component (D) is in the form of particles, and the particle diameter is not particularly limited. Since the dispersibility in the resin composition is excellent, the average particle diameter of the component (D) is preferably 5 μm or less, more preferably 4 μm or less, and still more preferably 3 μm or less. The average particle diameter of the component (D) is preferably 0.05 μm or more, more preferably 0.08 μm or more, and still more preferably 0.10 μm or more. Therefore, the component (D) is preferably an average particle diameter of 0.05 μm to 5 μm, more preferably 0.08 μm to 4 μm, still more preferably 0.10 μm to 3 μm.

As the component (D), particles containing a material selected from, for example, a fluororesin or a fluororubber may be mentioned.

As the component (D), a fluorine-based polymer particle containing a fluororesin is preferable from the viewpoint of reducing the dielectric constant of the insulating layer.

Examples of the fluororesin include polytetrafluoroethylene (PTFE), perfluoroalkoxy alkane (PFA), perfluoroethylene propylene copolymer (FEP), ethylene/tetrafluoroethylene copolymer (ETFE), and tetrafluoroethylene. Perfluoro-dioxole copolymer (TFE/PDD), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride (PVF). These resins may be used alone or in combination of two or more.

From the viewpoint of further reducing the dielectric constant of the insulating layer, it is preferred to use PTFE as the fluorine-based resin. In other words, as the component (D), PTFE particles using fluorine-based polymer particles containing PTFE as a fluorine-based resin are preferable.

The weight average molecular weight of PTFE is preferably 5,000,000 or less, more preferably 4,000,000 or less, and still more preferably 3,000,000 or less.

A commercially available product can also be used for the fluorine-based polymer particle system. Specific examples of the PTFE particles of the commercially available fluorine-based polymer particles include "LUBRON L-2" manufactured by Daikin Industries Co., Ltd., "LUBRON L-5" manufactured by Daikin Industries Co., Ltd., and Daikin Industries. "Fluon PTFE L-170JE" manufactured by Asahi Glass Co., Ltd., "Fluon PTFE L-172JE" manufactured by Asahi Glass Co., Ltd., "Fluon PTFE L-173JE" manufactured by Asahi Glass Co., Ltd., and "Fluon PTFE L-173JE" "KTL-500F", "KTL-2N", "KTL-2N", "KTL-1N", and "TLP10F-1" manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd.

Component (D) may, for example, also comprise surface treated particles. As the surface treatment, for example, a surface treatment using a surface treatment agent can be mentioned. The surface treatment agent is not particularly limited. The surface treatment agent contains inorganic fine particles and the like in addition to a surfactant such as a nonionic surfactant, an amphoteric surfactant, a cationic surfactant, or an anionic surfactant. From the viewpoint of affinity, it is preferred to use a fluorine-based surfactant as the surface treatment agent. Specific examples of the fluorine-based surfactant include "Surflon S-243" (perfluoroalkyl oxirane adduct) manufactured by AGC Seimi Chemical Co., Ltd., and "Megaface F-made by DIC Co., Ltd." 251", "Megaface F-477" by DIC (share), "Megaface F-553" by DIC (share), "Megaface R-40" by DIC (share), "Megaface R-43" by DIC (share) DIC (share) system "Megaface R-94", Neos (share) system "FTX-218", Neos (share) system "Ftergent 610FM", Neos (share) system "Ftergent 730LM".

In addition, when the content of the component (D) is effectively reduced in the dielectric constant of the insulating layer or the adhesion strength is maintained, when the nonvolatile content in the resin composition is 100% by mass, the component (D) The content will be 10% by mass to 40% by mass. From the viewpoint of effectively reducing the dielectric constant of the insulating layer, it is preferably 15% by mass or more, and more preferably 20% by mass or more. From the viewpoint of maintaining the adhesion strength, it is preferably 35 mass% or less, more preferably 30 mass% or less, and still more preferably 25% by mass or less.

In this case, when the total content of the component (C) and the component (D) is 100% by mass, the component (D) becomes 20 from the viewpoint of effectively reducing the dielectric constant of the insulating layer or maintaining the adhesion strength. Mass%~70% by mass. From the viewpoint of effectively reducing the dielectric constant of the insulating layer, it is preferably 25% by mass or more, and more preferably 30% by mass or more. From the viewpoint of maintaining the adhesion strength, it is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less.

When the dielectric constant of the cured product of the resin composition is particularly focused, in the present embodiment, the component (D) used for reducing the dielectric constant of the cured product is preferably a fluorine-based polymerization containing PTFE. PTFE particles of particles.

Here, the dielectric ratio of PTFE is 2.1. Therefore, when PTFE particles are used as a component of the resin composition, for example, even if the dielectric constant of the cured product is reduced to about 0.1, it is extremely difficult to reduce the dielectric constant and the physical properties of the resin composition, and further The physical properties and electrical properties of the cured product are good. The reason is that, in order to reduce the dielectric constant, when a large amount of PTFE particles are blended into the resin composition as described in Patent Document 1, the dielectric constant of the hardened body can be reduced, but the PTFE particles are in the resin composition. The substance becomes easily aggregated, and the PTFE particles cannot be uniformly distributed in the resin composition and the cured body. As a result, not only the adhesion to the conductor layer is remarkably lowered, but also the physical properties and electric properties of the cured product are impaired. The essence of the feature.

However, according to the resin composition according to the present embodiment, it is found that the content of the component (C) and the component (D) in the resin composition is adjusted to a solution such as the above numerical range, and further consideration is given to other components. Since it is blended, even if the content of the component (D) is further reduced, the dielectric constant of the cured product can be reduced, so that not only the dielectric constant can be reduced, but also the adhesion to the conductor layer can be improved, and the cured product can be obtained. Dielectric tangent is also a reduction effect.

<Component (E) Compound Having Unsaturated Hydrocarbyl Group> The resin composition system may further contain the component (E). Since the cured product has a molecular structure portion formed by the reaction of the unsaturated bond portion of the component (E), the polarity of the cured product becomes small, and the value of the dielectric tangent can be reduced.

The component (E) is not particularly limited as long as it has an unsaturated hydrocarbon group. By using an unsaturated hydrocarbon group, the dielectric tangent of the cured product can be lowered. The unsaturated hydrocarbon group is preferably an acrylic group, a methacryl group, a styryl group or an olefin group. Here, the "olefin group" means an aliphatic hydrocarbon group having a carbon-carbon double bond in a molecule. For example, an allyl group, a vinyl group, or a propylene group can be mentioned. In other words, the component (E) is preferably a compound having one or more unsaturated hydrocarbon groups selected from the group consisting of an acrylic group, a methacryl group, a styryl group, an allyl group, a vinyl group, and a propylene group. .

The component (E) is preferably a compound represented by the following formula (2), the following formula (7), and the following formula (8).

In the formula (2), R ¹ to R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. The line A represents a structure (a divalent group) represented by the following formula (3) or the following formula (4).

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

In the formula (4), D represents a structure represented by the following formula (5).

In the formula (5), R ⁷ to R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, and preferably a hydrogen atom or a methyl group. Particularly, R ⁷ , R ⁸ , R ¹³ and R ¹⁴ are preferably a methyl group. At least one of a and b is not an integer but 0 to 100. The B system represents a structure (a divalent group) represented by the following formula (B-1), (B-2) or (B-3).

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

The compound represented by the above formula (2) is preferably a compound represented by the following formula (6).

In the formula (6), R ¹ to R ⁶ are synonymous with R ¹ to R ⁶ in the above formula (2), and B is synonymous with B in the above formula (3), and a and b are the same as the above formula ( 5) A and b are synonymous. The compound represented by the formula (7) is as follows.

The component (E) is more preferably a "compound having a cyclic ether structure of a 5-membered or more ring" represented by the following formula (8).

In the formula (8), the ring F represents a divalent group having a cyclic ether structure of a 5-membered or higher ring. The B ¹ and B ² systems are each independently represented as a single bond or a divalent linking group. The C ¹ and C ² groups represent functional groups which may be the same or different from each other.

The cyclic ether of the 5-membered ring or higher has a property of lowering the dielectric tangent because the activity of the molecule is restricted. The carbon-carbon unsaturated bond may be included in the cyclic ether structure or may be included in the cyclic ether structure. There may also be a plurality of carbon-carbon unsaturated bonds.

The number of oxygen atoms contained in the cyclic ether structure related to the "compound having a cyclic ether structure of 5 or more rings" is preferably 1 or more, and is preferably 1 or more. It is preferably 2 or more, preferably 5 or less, more preferably 4 or less, still more preferably 3 or less.

The cyclic ether structure having a 5-membered ring or more is not particularly limited as long as the cyclic ether is a multi-membered ring structure having a 5-membered ring or more. The cyclic ether structure above the 5-membered ring may be a monocyclic, polycyclic or condensed ring. Moreover, the "compound having a cyclic ether structure having a 5-membered ring or more" may have a plurality of cyclic ether structures. The cyclic ether structure is preferably a 5-10 member ring, a 5-8 member ring is preferred, and a 5-6 member ring is preferred. Specific examples of the cyclic ether structure of the 5-membered or higher ring 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, from the viewpoint of enhancing compatibility, a compound having a cyclic ether structure of a 5-membered or higher ring is preferably a structure including a dioxane. The dioxane structure includes a 1,2-dioxane structure, a 1,3-dioxane structure, and a 1,4-dioxane structure, and is preferably a 1,3-dioxane structure.

Further, in the cyclic ether structure of a 5-membered or higher ring, a substituent such as an alkyl group or an alkoxy group may be bonded. The number of carbon atoms of the above substituent is usually from 1 to 6, preferably from 1 to 3.

Specific examples of the divalent group having a cyclic ether structure of a 5-membered or higher ring 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-di Base, 1,3-dioxane-2,5-diyl, 1,4-dioxane-2,5-diyl, 5-ethyl-1,3-dioxane-2,5-di base. The divalent base having a cyclic ether structure of a 5-membered or higher ring is preferably 5-ethyl-1,3-dioxane-2,5-diyl.

The B ¹ and B ² systems are each independently represented as a single bond or a divalent linking group. B ¹ and B ² are preferably a divalent linking group. The divalent linking group may, for example, be an alkylene group which may have a substituent, an alkynyl group which may have a substituent, an extended aryl group which may have a substituent, a heteroaryl group which may have a substituent, or -COO a group represented by a group, a group represented by -CO-, a group represented by -CONH-, a group represented by -NHCONH-, a group represented by -NHCOO-, a group represented by -C(=O)-, a group represented by -S-, a group represented by -SO-, a group represented by -NH-, and a group of a plurality of such groups.

The substituent is not particularly limited. The substituent may, for example, be a halogen atom or a group represented by -OH, -OC _1-6 alkyl group, -N(C _1-6 alkyl) ₂ , C _1-6 alkyl group or C _6-10 aryl group. , a group represented by -NH ₂ , a group represented by -CN, a -C(O)OC _1-6 alkyl group, a group represented by -COOH, a group represented by -C(O)H, -NO ₂ The base of expression. These terms are generally referred to as "C _pq " to describe the meanings of "C _1-6 " and "C _6-10 " in relation to the above substituents. "C _pq " (wherein p and q are positive integers and satisfies p < q) means that the number of carbon atoms of the organic group described after the term is p - q. Specifically, for example, "C _1-6 alkyl group" means "alkyl group having 1 to 6 carbon atoms".

The substituent system may further have a substituent (hereinafter sometimes referred to as a "second substituent"). The secondary substituent may, for example, be the same group as the substituent described above.

In the above, 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-. Any of the groups to be combined is preferable, and a group selected from two or more selected from the group consisting of an alkyl group having a substituent and a group represented by -COO- is used as a group. good.

The C ¹ and C ² systems represent mutually identical or mutually different functional groups. The functional group may, for example, be a vinyl group, a methacryl group, an acryl group, an allyl group, a styryl group, a propenyl group or an epoxy group. A vinyl group is preferred as the functional group.

Specific examples of the "compound having a cyclic ether structure having a 5-membered or higher ring" include compounds represented by the following formulas.

The component (E) may, for example, be a styrene-modified polyphenylene ether resin ("OPE-2 St 1200 (number average molecular weight: 1200)" manufactured by Mitsubishi Gas Chemical Co., Ltd.), which corresponds to the above formula (6)), and bisphenol 2 Allyl ether resin ("YL7776 (number average molecular weight 331)" manufactured by Mitsubishi Chemical Corporation, which corresponds to the above formula (7)) and dioxane acrylic acid monomer ethylene glycol diacrylate ("Naka Nakamura Chemical Industry Co., Ltd." -DOG (number average molecular weight 326) corresponds to the above formula (8)" and "KAYARAD R-604 by Nippon Kayaku Co., Ltd., which corresponds to the above formula (8)".

The number-average molecular weight of the component (E) is preferably in the range of 100 to 10,000, and preferably 200 to 3,000, from the viewpoint of preventing volatilization during drying of the resin varnish and preventing excessive increase in the melt viscosity of the resin composition. range. Further, the number average molecular weight in the present invention can be measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). As the number average molecular weight by the GPC method, for example, "LC-9A/RID-6A" manufactured by Shimadzu Corporation can be used as a measuring device, and "Shodex K-800P/K-804L/K-804L" manufactured by Showa Denko Co., Ltd. The column, chloroform or the like was used as a mobile phase, and the measurement was performed by a column temperature of 40 ° C, and was calculated using a calibration curve of standard polystyrene.

When the content of the component (E) is 100% by mass, the dielectric tangent of the cured product is preferably 1% by mass or more, and more preferably 3% by mass or more. Moreover, from the viewpoint of improving the compatibility of the resin varnish, it is preferably 15% by mass or less, and more preferably 10% by mass.

The mass ratio of the component (A) epoxy resin to the component (E) (the mass of the epoxy resin: the mass of the component (E)) is preferably in the range of 1:0.01 to 1:100, and is 1:0.1 to 1 The range of 90 is more preferable, and the range of 1:0.1 to 1:80 is further preferable. By setting it as such a range, compatibility can be improved.

The resin composition can improve the compatibility by containing the component (E), and the fluorine-based filler of the component (D) described above can be more uniformly dispersed in the resin composition. As a result, since the uniformity of the resin composition is improved, the adhesion of the cured product to the conductor layer can be further enhanced, and the dielectric tangent can be further reduced. As a result, the physical properties and electrical characteristics of the formed insulating layer can be improved, and the reliability of the device can be improved.

<Component (F) Hardening Accelerator> The resin composition may further contain a component (F) hardening accelerator. Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a lanthanum-based curing accelerator, a metal-based curing accelerator, and a peroxide-based curing accelerator. The curing accelerator is preferably a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, or a metal-based curing accelerator, and an amine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based hardening accelerator. The agent is also preferred. The curing accelerator may be used alone or in combination of two or more.

Examples of the phosphorus-based hardening accelerator include triphenylphosphine, a barium borate compound, phenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonate, and (4- Methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate. As the phosphorus-based hardening accelerator, triphenylphosphine or tetrabutylphosphonate is preferred.

Examples of the amine-based curing accelerator include a trialkylamine such as triethylamine or tributylamine, 4-dimethylaminopyridine (DMAP), dimethylbenzylamine, 2,4,6, and a ginseng. (dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene. As the amine-based curing accelerator, 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-methyl group. Imidazole, 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-alkylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecane Imidazo-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl -s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenyl Imidazoisocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H- Pyrrole [1,2-a]benzimidazole, 1-dodecyl-2-methyl-3- An imidazole compound such as benzylimidazolium chloride, 2-methylimidazoline or 2-phenylimidazoline, or an adduct of an imidazole compound and an epoxy resin. As the imidazole-based hardening accelerator, 2-ethyl-4-methylimidazole or 1-benzyl-2-phenylimidazole is preferred.

A commercially available product can also be used as an imidazole-based hardening accelerator. As a commercially available imidazole-based hardening accelerator, for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation can be used.

Examples of the oxime-based hardening accelerator include dicyandiamide, 1-methyl hydrazine, 1-ethyl hydrazine, 1-cyclohexyl hydrazine, 1-phenyl fluorene, 1-(o-methylphenyl) fluorene, and Methyl hydrazine, diphenyl hydrazine, trimethyl hydrazine, tetramethyl hydrazine, pentamethyl hydrazine, 1,5,7-triazabicyclo[4.4.0]non-5-ene, 7-methyl- 1,5,7-triazabicyclo[4.4.0]non-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allyl biguanide, 1-phenylbiguanide, 1-(o-methylphenyl)biguanide. As the lanthanide hardening accelerator, dicyandiamide or 1,5,7-triazabicyclo[4.4.0]non-5-ene is preferred.

The metal-based hardening accelerator may, for example, be an organometallic complex or an organic metal salt of a metal such as cobalt, copper, zinc, iron, nickel, manganese or tin. Specific examples of the organic metal complex include an organic cobalt complex such as cobalt (II) acetate, acetylacetonatocobalt (III), and an organic copper complex such as copper (II). , an organic zinc complex such as acetonitrile zinc(II), an organic iron complex such as iron(III) acetate, an organic nickel complex such as acetonitrile acetone (II), or manganese acetylacetonate. (II) Organic manganese complexes. The organic metal salt may, for example, be zinc octoate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate or zinc stearate.

Examples of the peroxide-based hardening accelerator include cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, and tert-. Butyl cumene peroxide, di-tert-butyl peroxide, dicumyl hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide.

A commercially available product can be used as the peroxide-based hardening accelerator. For example, "Percumyl D" manufactured by Nippon Oil Co., Ltd. is used as the peroxide-based hardening accelerator.

The content of the hardening accelerator in the resin composition is not particularly limited. When the nonvolatile content is 100% by mass, the content of the curing accelerator is usually 0.01% by mass to 3% by mass, preferably 0.05% by mass to 2% by mass, and preferably 0.1% by mass to 1% by mass. good.

<Component (G) Thermoplastic Resin> The resin composition may contain the component (G) thermoplastic resin. Examples of the thermoplastic resin include a phenoxy resin, a polyvinyl acetal resin, a polyolefin resin, a polybutadiene resin, a polyimide resin, a polyamidimide resin, a polyether quinone resin, and the like. Polyanthrene resin, polyether oxime resin, polycarbonate resin, polyether ether ketone resin, polyester resin. A phenoxy resin is preferred as the thermoplastic resin. The thermoplastic resin may be used alone or in combination of two or more.

The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and even more preferably in the range of 20,000 to 60,000. The polystyrene-equivalent weight average molecular weight of the thermoplastic resin can be measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin can be obtained by using "LC-9A/RID-6A" manufactured by Shimadzu Corporation as a measuring device and using "Shodex K-800P" by Showa Denko Co., Ltd. /K-804L/K-804L" was used as a mobile column using chloroform or the like as a mobile phase, and the column temperature was measured at 40 ° C, and was calculated using a calibration curve of standard polystyrene.

The phenoxy resin may, for example, be a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, an anthracene skeleton, or a dicyclopentadiene skeleton. A phenoxy resin having one or more selected ones selected from the group consisting of a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal group of the phenoxy resin may be any one of a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (all are phenoxy resins containing a bisphenol A skeleton) and "YX8100" (including a bisphenol S skeleton) manufactured by Mitsubishi Chemical Corporation. "Phenoxy resin" and "YX6954" (phenoxy resin containing a bisphenol acetophenone skeleton), and "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., Mitsubishi Chemical Corporation "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7891BH30" and "YL7482".

Examples of the polyvinyl acetal resin include a polyethylene formaldehyde resin and a polyvinyl butyral resin. As the polyvinyl acetal resin, a polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", and "Denka Butyral 6000-EP" manufactured by Electrochemical Industry Co., Ltd. S-LEC BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series, manufactured by Sekisui Chemical Co., Ltd.

Specific examples of the polyimide resin include "Rikacoat SN20" and "Rikacoat PN20" manufactured by Nippon Chemical and Chemical Co., Ltd. Specific examples of the polyimine resin include a linear polyimine obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (JP-2006) Polyimine, which is described in JP-A-37083, and polyimine which contains a polyoxyalkylene skeleton (polyimine described in JP-A-2002-12667, JP-A-2000-319386, etc.) Modified polyimine.

A commercially available product can also be used as the polyamidoximine resin. Specific examples of the commercially available polyamidoximine resin include "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamidoximine resin include modified polymers such as "KS9100" and "KS9300" (polyamidoquinone containing a polyoxyalkylene skeleton) manufactured by Hitachi Chemical Co., Ltd. Amidoxime.

A commercially available product can also be used as the polyether oxime resin. As a specific example of a commercially available polyether oxime resin, "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. is mentioned.

Commercially available products can also be used as the polyamide resin. Specific examples of the commercially available polyfluorene resin include "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd.

Among them, a phenoxy resin or a polyvinyl acetal resin is preferred as the thermoplastic resin. In a preferred embodiment, the thermoplastic resin is one or more selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin.

When the resin composition contains a thermoplastic resin, when the nonvolatile content is 100% by mass, the content of the thermoplastic resin is preferably 0.5% by mass to 15% by mass, and more preferably 0.6% by mass to 12% by mass. %, more preferably 0.7% by mass to 10% by mass.

<Component (H) Flame Retardant> The resin composition may also contain a component (H) flame retardant. Examples of the flame retardant include an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a polyfluorene-based flame retardant, and a metal hydroxide. The flame retardant may be used alone or in combination of two or more.

Commercially available products can also be used as the flame retardant. For the commercially available flame retardant, for example, "HCA-HQ" manufactured by Sanko Co., Ltd. and "PX-200" manufactured by Daiwa Chemical Industry Co., Ltd. are mentioned.

When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited. When the nonvolatile content is 100% by mass, the content of the flame retardant is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, still more preferably 0.5% by mass to 10% by mass. .

<Component (I) Optional Additive> Further, the resin composition may contain any additive as needed. Examples of the above-mentioned additives include an organic metal compound such as an organic copper compound, an organic zinc compound, and an organic cobalt compound, and a thickener, an antifoaming agent, a leveling agent, an adhesion imparting agent, and a coloring agent. Resin additive.

<Continuing Film> Next, the film system is provided with a support and a resin composition layer containing the resin composition described above provided on the support.

Supporting body As the support, for example, a film made of a plastic material, a metal foil, or a release paper can be mentioned. As the support system, a film or a metal foil made of a plastic material is preferable.

When a film made of a plastic material is used as the support, the plastic material may, for example, be polyethylene terephthalate (hereinafter sometimes referred to as "PET") or polyethylene naphthalate. Polyesters such as polyesters (hereinafter sometimes referred to as "PEN"), polycarbonates (hereinafter sometimes referred to as "PC"), acrylic polymers such as polymethyl methacrylate (PMMA), and rings Polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimine. Among them, polyethylene terephthalate or polyethylene naphthalate is preferred because it is inexpensive and excellent in availability, so polyethylene terephthalate is particularly preferred.

When a metal foil is used as the support, the metal foil may, for example, be a copper foil or an aluminum foil. Copper foil is preferred as the support system. As the copper foil, a foil made only of copper may be used, or a foil made of a copper alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, hafnium, titanium, or the like) may be used.

A polishing treatment, a corona treatment, and an antistatic treatment may be applied to the surface of the support that is bonded to one side of the resin composition layer.

Further, as the support, a support having a release layer may be used, which is a release layer on the surface joined to the resin composition layer. The release agent to be used in the release layer of the support having the release layer may be, for example, an alkyd resin, a polyolefin resin, a urethane resin, or a polyoxymethylene resin. One or more release agents selected from the group. As a support system with a release layer, a commercially available product can be used, and, for example, a "PET-1" manufactured by LINTEC Co., Ltd., which has a release film having an alkyd-based release agent as a main component, can be used. "Al-5", "AL-7", and Toray (share) "Lumirror T6AM".

The thickness of the support is not particularly limited. 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. In the case where a support having a release layer is used, the thickness of the entire support having the release layer is preferably in the above range.

Resin Composition Layer The resin composition layer of the film is a film obtained by semi-curing a coating film of a resin varnish. Then, the film can be produced by dissolving a resin composition in an organic solvent to prepare a resin varnish, applying the resin varnish to a support using a die coater or the like, and then coating the resin varnish. The film was dried to some extent to form a resin composition layer.

Examples of the organic solvent used for the formation of the resin composition layer include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol. Acetate such as monomethyl ether acetate and carbitol acetate, cellosolve, carbitol such as butyl carbitol, aromatic hydrocarbon such as toluene and xylene, dimethyl A guanamine-based solvent such as formamide, dimethylacetamide (DMAc) or N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

The drying of the coating film of the resin varnish can be carried out by a known method such as heating or blowing hot air. The drying condition is not particularly limited, but the content of the organic solvent in the resin composition layer is 10% by mass or less, and preferably is 5% by mass or less. Depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the coating film of the resin varnish can be used at 50 ° C to 150 ° C. It is allowed to dry for 3 minutes to 10 minutes to form a resin composition layer.

In the film, a protective film corresponding to the support can be further laminated on the surface (the side opposite to the support side) on one side of the surface of the resin composition layer that is not bonded to the support. The thickness of the protective film is not particularly limited. The thickness of the protective film is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion or damage to the surface of the resin composition layer such as dust can be suppressed. The film can then be wound up in a roll to be stored. When the film has a protective film, it can be used by peeling off and removing the protective film.

The lowest melt viscosity of the resin composition layer (or the resin composition) in the film is preferably 1000 poise or more from the viewpoint of stably maintaining the thickness of the resin composition layer even if it is thin. More than 1,500 poise is more preferred, and more preferably 2,000 poise or more. The lowest melt viscosity of the resin composition layer is preferably 12,000 poise or less, more preferably 10,000 poise or less, more preferably 8,000 poise or less, and particularly preferably 5,000 poise or less from the viewpoint of good embedding of the circuit. .

The "lowest melt viscosity of the resin composition layer" means the lowest viscosity exhibited when the resin composition layer is melted. Specifically, when the resin composition layer is heated and melted at a constant temperature increase rate, the initial melt viscosity decreases as the temperature rises, and then, after a certain period of time, with the temperature Ascending, while the melt viscosity will also rise. The so-called minimum melt viscosity refers to the melt viscosity of the minimum point at which the melt viscosity is the lowest. The lowest melt viscosity of the resin composition layer can be measured by a dynamic viscoelastic method.

<Prepreg> The insulating layer associated with the high-frequency circuit substrate can be formed using a prepreg instead of the illustrated adhesive film. The prepreg system can be formed by impregnating a resin composition described later on a sheet-like fibrous base material.

The sheet-like fibrous base material used in the prepreg is not particularly limited. As the sheet-like fibrous base material, a glass cloth, an aromatic polyamide nonwoven fabric, a liquid crystal polymer nonwoven fabric or the like can be used as a substrate for a prepreg. The thickness of the sheet-like fibrous base material is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, and still more preferably 600 μm or less from the viewpoint of the reduction in thickness of the high-frequency circuit substrate. Since the plating submersion depth of the plating layer at the time of formation of the conductor layer can be suppressed to a low level, it is preferably 30 μm or less, more preferably 20 μm or less, and still more preferably 10 μm or less. The thickness of the sheet-like fibrous base material can be usually 1 μm or more, 1.5 μm or more, and 2 μm or more.

The prepreg system can be produced by a known method such as a hot melt method or a solvent method.

The thickness of the prepreg can be set to the same range as the resin composition layer in the above-mentioned film.

[High-frequency circuit board] The high-frequency circuit board of the present invention is used for forming an insulating layer of a high-frequency circuit board, and includes an insulating layer formed of a cured product of the resin composition described above.

Here, the "high-frequency circuit board" means a circuit board that can operate even in the case of a high-frequency electric signal. Here, the "high frequency band" means a frequency band of 1 GHz or more, and is particularly effective in the frequency band of 28 GHz to 80 GHz in the present invention.

The inner layer circuit board provided in the high-frequency circuit board and the insulating layer provided on the inner layer circuit board will be described separately.

<Inner layer circuit board> The term "inner layer circuit board" means a core substrate (for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, or a thermosetting type polymerization). On the single-sided side or the double-sided side main surface of the substrate such as a phenylene ether substrate, a conductor layer (wiring layer) (that is, an electrical circuit) that is patterned into a predetermined pattern is directly or indirectly formed. The substrate.

The thickness of the inner layer circuit board used for the high-frequency circuit board is usually 50 μm to 4000 μm, and is preferably 200 μm to 3200 μm from the viewpoint of improving the mechanical strength and the low-profile (thickness reduction) of the high-frequency circuit board. .

In the inner layer circuit board, in order to electrically connect the two-layer conductor layers (and the conductor layers provided on the insulating layer) provided on the inner layer circuit board to each other, one or more main surfaces may be provided. The through hole to the other main surface may be provided with any suitable further constituent elements such as passive components.

<Insulating Layer> The insulating layer related to the high-frequency circuit board is a layer of a cured product obtained by thermally curing a resin composition described later. The insulating layer formed of the cured product is particularly suitable for use as an insulating layer for a high-frequency circuit substrate.

In the high-frequency circuit substrate, the insulating layer may be provided in only one layer or may be provided in two or more layers. When two or more insulating layers are provided, it can be provided in a build-up manner in which a conductor layer (wiring) and an insulating layer are laminated to each other.

The thickness of the insulating layer associated with the high-frequency circuit substrate is usually 20 μm to 200 μm, and is preferably 50 μm to 150 μm from the viewpoint of improving electrical characteristics and low-profile of the high-frequency circuit substrate.

The insulating layer may have one or more via holes for electrically connecting the conductor layer provided in the inner layer circuit board to the conductor layer provided on the insulating layer or to be provided in two or more layers. The conductor layers of the insulating layer are electrically connected to each other.

The dielectric constant of the insulating layer is as low as possible. From the viewpoint of further reducing the transmission loss of the high-frequency electric signal, the dielectric constant is preferably 3.0 or less, more preferably 2.9 or less, and still more preferably 2.8 or less. The lower limit of the dielectric constant is not particularly limited, but is usually 1 or more.

The insulating layer is preferably to exhibit a lower dielectric tangent. The dielectric tangential system is preferably 0.0049 or less, more preferably 0.0048 or less, and more preferably 0.0047 or less from the viewpoint of preventing heat generation during transmission of a high-frequency signal, reducing signal delay, and signal noise. The lower limit of the dielectric tangent is not particularly limited, but is usually 0.0001 or more.

The dielectric tangent and the dielectric constant can be measured by the method described in "Measurement and Evaluation of Dielectric Rate and Dielectric Tangent" which will be described later.

The insulating layer associated with the high-frequency circuit substrate has good adhesion to the conductor layer, that is, exhibits excellent peel strength for the conductor layer. The peel strength of the conductor layer is preferably 0.4 kgf/cm or more, more preferably 0.5 kgf/cm or more, and still more preferably 0.6 kgf/cm or more. The upper limit of the peel strength of the conductor layer is not particularly limited, but is usually 2 kgf/cm or less. The evaluation of the peel strength of the conductor layer can be carried out according to the method described in "Measurement and Evaluation of Peel Strength" to be described later.

[Method of Manufacturing High-Frequency Circuit Board] Next, a method of manufacturing a high-frequency circuit board will be described.

The high-frequency circuit substrate can be produced by using the above-described adhesive film and by a production method comprising the following steps (I) and (II). Step (I): a step of laminating an adhesive film to an inner layer circuit substrate by bonding a resin composition layer of the adhesive film to an inner layer circuit substrate; and (II): thermally hardening the resin composition layer The step of forming an insulating layer.

The lamination of the film on the inner layer circuit board can be carried out, for example, by pressing the film on the inner layer circuit board from the side of the support body while heating and pressing. Examples of the member for heating the pressure-bonding step (also referred to as "heating and pressure-bonding member") include a heated metal plate (such as a SUS mirror plate) or a metal roll (SUS roll). In addition, the heating and pressure-bonding member is not directly pressed against the support of the film, and the elastic material such as heat-resistant rubber is interposed so that the adhesive film sufficiently follows the main surface of the inner layer circuit substrate. It is preferable that the unevenness is pressed.

The lamination of the inner layer circuit substrate and the subsequent film can be carried out by vacuum lamination. In the vacuum lamination, the temperature at which the pressure is applied is preferably in the range of 60 ° C to 160 ° C, and preferably in the range of 80 ° C to 140 ° C. The pressure of the heating and pressing is preferably in the range of 0.098 MPa to 1.77 MPa, and preferably in the range of 0.29 MPa to 1.47 MPa, and the time of heating and pressing is preferably in the range of 20 seconds to 400 seconds. Good range from 30 seconds to 300 seconds. The lamination system is preferably carried out under reduced pressure of 26.7 hPa or less.

Lamination can be carried out by a commercially available vacuum laminator. As a commercially available vacuum laminating machine, for example, a vacuum press type laminator manufactured by Nikko Seiki Co., Ltd. or a vacuum laminator made of Nikko-materials can be used.

After lamination, the laminated resin composition layer may be subjected to smoothing treatment under normal pressure (at atmospheric pressure) by pressing from the support side by, for example, heating the pressure-sensitive adhesive member. The pressing condition of the smoothing treatment can be set under the same conditions as the conditions of the above-described laminated heating and pressure bonding. The smoothing treatment can be carried out by a commercially available laminating machine. Further, the lamination and smoothing treatment can be carried out continuously using the commercially available vacuum laminator described above.

The support system can be removed between step (I) and step (II) or removed after step (II).

In the step (II), the resin composition layer laminated (and smoothed) is thermally cured to form an insulating layer.

The conditions for thermal curing of the resin composition layer are not particularly limited, and conditions generally employed when forming an insulating layer of a high-frequency circuit substrate can be employed.

The thermosetting condition of the resin composition layer may be, for example, a curing temperature of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 220 ° C, preferably in the range of 170 ° C to 200 ° C). The hardening time can be set in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, and preferably 15 minutes to 90 minutes).

The resin composition layer may be preheated by a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, before the resin composition layer is thermally cured, it is preheated by a temperature of 50 ° C or more and less than 120 ° C (preferably 60 ° C or more and 110 ° C or less, preferably 70 ° C or more and 100 ° C or less). The hot resin composition layer may be used for 5 minutes or more (preferably 5 minutes to 150 minutes, preferably 15 minutes to 120 minutes).

When the high-frequency circuit substrate is manufactured, any one of (III) the step of opening the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming the conductor layer may be further performed. These steps (III) to (V) can be carried out in accordance with various methods known to the industry for use in the manufacture of high-frequency circuit boards. Further, if the support is removed after the step (II), the support may be removed between the step (II) and the step (III), between the step (III) and the step (IV), or The step (IV) is carried out between the step (V) and the step (V).

In other embodiments, the insulating layer associated with the high-frequency circuit substrate of the present invention may be formed using the prepreg described above instead of the adhesive film. The formation of the insulating layer using the prepreg can be basically carried out by the same steps as in the case of using the adhesive film.

The step (III) is a step of opening a hole in the insulating layer, whereby a hole of a through hole, a through hole or the like can be formed for the insulating layer. The step (III) can be carried out using, for example, drilling, laser, plasma, or the like in accordance with the composition of the resin composition used in the formation of the insulating layer, and the like. The size or shape of the holes can be appropriately determined in accordance with the design of the high-frequency circuit substrate.

Step (IV) is a step of roughening the insulating layer. The procedure and conditions of the roughening treatment are not particularly limited, and can be used in well-known procedures and conditions that are generally used when forming an insulating layer of a high-frequency circuit board. For example, the insulating layer may be subjected to a roughening treatment by a swelling treatment using a swelling liquid, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralization liquid. The swelling liquid is not particularly limited. Examples of the swelling solution include an alkali solution and a surfactant solution. The swelling liquid is preferably an alkali solution, and the alkali solution is preferably a sodium hydroxide solution or a potassium hydroxide solution. As a commercially available swelling liquid, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan Co., Ltd. can be mentioned. The swelling treatment by the swelling liquid is not particularly limited. The swelling treatment can be carried out, for example, by immersing the insulating layer in a swelling liquid at 30 ° C to 90 ° C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferred to immerse the insulating layer in a swelling liquid at 40 ° C to 80 ° C for 5 minutes to 15 minutes. The oxidizing agent is not particularly limited. The oxidizing agent may, for example, be an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment by an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C for 10 minutes to 30 minutes. Further, the concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. The commercially available oxidizing agent may, for example, be an alkaline permanganic acid solution such as "Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd. or "Dosing solution Securiganth P". Further, it is preferred that the neutralizing liquid is an acidic aqueous solution. A commercially available product of the neutralizing liquid is, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd. By the treatment of the neutralizing liquid, the treated surface of the insulating layer which has been subjected to the roughening treatment by the oxidizing agent is immersed in the neutralizing liquid at 30 ° C to 80 ° C for 5 minutes to 30 minutes. In terms of workability and the like, it is preferred to immerse the insulating layer which has been subjected to the roughening treatment of the oxidizing agent in a neutralizing liquid of 40 ° C to 70 ° C for 5 minutes to 20 minutes.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 280 nm or less, more preferably 250 nm or less, still more preferably 200 nm or less, 140 nm or less, 130 nm or less, or 120 nm or less. 110 nm or less, 100 nm or less, 95 nm or less, or 90 nm or less. The Ra value is preferably 0.5 nm or more, and more preferably 1 nm or more. The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact type surface roughness meter. Specific examples of the non-contact surface roughness meter include "WYKO NT3300" manufactured by Veeco Instruments.

Step (V) is a step of forming a conductor layer.

The material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer includes one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Metal. The conductor layer may be an elemental metal layer or an alloy layer, and examples of the alloy layer include alloys of two or more kinds of metals selected from the above group (for example, nickel, chromium alloy, copper, nickel alloy, copper, titanium). Alloy) layer formed. Among them, in terms of generality of formation of a conductor layer, cost, ease of patterning, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or An alloy layer of nickel, chromium alloy, copper, nickel alloy, copper or titanium alloy is preferred, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/chromium alloy The alloy layer is preferably further preferred, and a copper elemental metal layer is more preferred.

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

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

In one embodiment, the conductor layer is formed of a metal foil used as a support for the film, and may be formed by patterning directly or by plating. As a method of forming the plating, it can be plated onto the surface of the insulating layer by a conventionally known method such as a semi-additive method or a full-addition method to form a conductor layer having a desired wiring pattern. . Hereinafter, an example in which a conductor layer is formed by a semi-additive method will be described.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern in which a part of the plating seed layer is exposed is formed in a manner corresponding to a desired wiring pattern. On the exposed plated seed layer, the metal layer is formed by electrolytic plating, and the mask pattern is removed. Thereafter, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

When the high-frequency circuit board is provided with two or more insulating layers and a wiring layer (addition layer), the step of forming the insulating layer and the step of forming the conductor layer described above can be repeated one or more times. A high-frequency circuit substrate that can function as a high-frequency circuit and has a multilayer wiring structure.

[Semiconductor Device] The semiconductor device includes the high-frequency circuit substrate described above. In other words, the semiconductor device of the present invention can be manufactured using the high-frequency circuit substrate of the present invention.

Examples of the semiconductor device include various semiconductor devices for use in electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, electric cars, ships, airplanes, etc.).

The semiconductor device can be manufactured by mounting a component (semiconductor wafer) on a conductive portion of a high-frequency circuit substrate. The term "conducting portion" means "a portion where an electrical signal can be transmitted in a high-frequency circuit substrate", and the portion may be buried on the surface of the high-frequency circuit substrate or in the thickness direction of the high-frequency circuit substrate. The location of the entry. Further, the semiconductor wafer is not particularly limited as long as it is an electric circuit element using a semiconductor as a material.

In the case of manufacturing the semiconductor device of the present invention, the method of mounting the semiconductor wafer is not particularly limited as long as it can effectively function as a semiconductor wafer. Specific examples of the method of mounting the semiconductor wafer include a wire bonding mounting method, a flip chip mounting method, a bumpless build-up layer (BBUL) mounting method, and an anisotropic conductive film (ACF) mounting method. A non-conductive film (NCF) mounting method is used. Here, the "mounting method using bumpless build-up layer (BBUL)" means that the semiconductor wafer is directly embedded in the high-frequency circuit board, and the semiconductor wafer and the wiring of the high-frequency circuit board are connected. installation method". [Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited to the examples. In the following descriptions, "parts" and "%" mean "parts by mass" and "% by mass" unless otherwise stated.

<Example 1> 20 parts of a terephthalic epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 185) was stirred and melted in 20 parts of a solvent petroleum brain, and then cooled to room temperature. 60 parts of mixed inorganic filler ("SO-C2" manufactured by Admatech Co., Ltd., average particle diameter: 0.5 μm, carbon content per unit surface area: 0.38 mg/m ² ), and PTFE particles (LUBRON L-2, manufactured by Daikin Industries Co., Ltd.) 30 parts of an average particle diameter of 3 μm, and kneaded by a triaxial roll to disperse it. Here, 46.1 parts of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution having a nonvolatile content of 65% of an active group equivalent of about 223) was mixed, and a cyclic ether structure having a ring of 5 or more members was used. 10 parts of the compound (vinyl compound) ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd.), 2 parts of dimethyl MEK solution of 4-dimethylaminopyridine (DMAP) as a curing accelerator, and 2 parts of peroxide A resin varnish 1 was prepared by dispersing 0.13 parts of cumene ("Percumyl D" manufactured by NOF Corporation) and uniformly dispersing it by a rotary mixer.

<Example 2> An inorganic filler ("SO-C2" manufactured by Admatech Co., Ltd., average particle size) was changed to 30 parts by using a bis xylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 185). Changed to 50 parts by a diameter of 0.5 μm and a carbon content per unit surface area of 0.38 mg/m ² ), and changed PTFE particles ("LUBRON L-2" manufactured by Daikin Industries Co., Ltd., average particle diameter: 3 μm) to 21 parts. The active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation, and a 65% toluene solution having a nonvolatile content of about 223 active base equivalent) was changed to 61.5 parts. The resin varnish 2 was prepared in the same manner as in Example 1 except for the above.

<Example 3> An inorganic filler ("SO-C2" manufactured by Admatech Co., Ltd., an average particle diameter of 0.5 μm, and a carbon content per unit surface area of 0.38 mg/m ² ) was changed to 80 parts, and PTFE particles (Dajin Industry ( The stock system "LUBRON L-2", the average particle diameter of 3 μm) was changed to 20 parts. The resin varnish 3 was prepared in the same manner as in Example 1 except for the above.

<Example 4> An inorganic filler ("SO-C2" manufactured by Admatech Co., Ltd., average particle diameter: 0.5 μm, carbon content per unit surface area: 0.38 mg/m ² ) was changed to 30 parts, and PTFE particles (Dajin Industry ( The stock system "LUBRON L-2", the average particle diameter of 3 μm) was changed to 60 parts. The resin varnish 4 was prepared in the same manner as in Example 1 except for the above.

<Comparative Example 1> An inorganic filler ("SO-C2" manufactured by Admatech Co., Ltd., average particle size) was changed to 30 parts by using a bis xylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 185). The amount of carbon (0.38 mg/m ² per unit surface area) was changed to 100 parts, and the PTFE particles ("LUBRON L-2" manufactured by Daikin Industries Co., Ltd., average particle diameter: 3 μm) were changed to 20 parts. The active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation, and a 65% toluene solution having a nonvolatile content of about 223 active base equivalent) was changed to 61.5 parts. The resin varnish 5 was prepared in the same manner as in Example 1 except for the above.

<Comparative Example 2> An inorganic filler ("SO-C2" manufactured by Admatech Co., Ltd., an average particle diameter of 0.5 μm, and a carbon content per unit surface area of 0.38 mg/m ² ) was changed to 15 parts, and PTFE particles (Dajin Industry ( The stock system "LUBRON L-2", the average particle diameter of 3 μm) was changed to 50 parts. The resin varnish 6 was prepared in the same manner as in Example 1 except for the above.

<Comparative Example 3> An inorganic filler ("SO-C2" manufactured by Admatech Co., Ltd., an average particle diameter of 0.5 μm, and a carbon content per unit surface area of 0.38 mg/m ² ) was changed to 20 parts, and PTFE particles (Daijin Industry ( The stock system "LUBRON L-2", the average particle diameter of 3 μm) was changed to 5 parts. The resin varnish 7 was prepared in the same manner as in Example 1 except for the above.

<Comparative Example 4> An inorganic filler ("SO-C2" manufactured by Admatech Co., Ltd., an average particle diameter of 0.5 μm, and a carbon content per unit surface area of 0.38 mg/m ² ) was changed to 35 parts, and PTFE particles (Dajin Industry ( The stock system "LUBRON L-2", the average particle diameter of 3 μm) was changed to 80 parts. The resin varnish 8 was prepared in the same manner as in Example 1 except for the above.

<Comparative Example 5> An active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution having a nonvolatile content of 65% of an active group equivalent of about 223) was changed to a naphthol-based curing agent having a novolak structure. (Phenolic hydroxyl equivalent 215, "SN-485" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., and 50% MEK solution of nonvolatile matter) 40 parts. The resin varnish 9 was prepared in the same manner as in Example 1 except for the above.

<Comparative Example 6> A naphthol-based curing agent having a novolak structure (phenolic hydroxyl equivalent 215, "SN-485" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., and a MEK solution having a nonvolatile content of 50%) was changed to 20 parts. The resin varnish 10 was prepared in the same manner as in Comparative Example 5 except for the above.

[Evaluation Method] Using the resin composition obtained in the above Examples and Comparative Examples, a cured film obtained by curing a resin composition layer was prepared as follows, and evaluated according to the following method.

<Preparation of the cured film (evaluation sample)> The resin varnishes 1 to 10 obtained in the examples and the comparative examples were uniformly formed so that the thickness of the dried resin composition layer was 40 μm by a die coater. It was coated on the main surface of one of the release-treated PET film ("PET501010" manufactured by LINTEC Co., Ltd.), and dried at 80 ° C to 110 ° C (average 95 ° C) for 6 minutes. Thereafter, the film was heat-treated at 200 ° C for 90 minutes, and the cured product film was obtained by peeling and removing the support. The obtained cured film was cut into strips having a length of 80 mm and a width of 2 mm, and a sample for evaluation was prepared.

<Measurement and Evaluation of Dielectric Rate and Dielectric Tangent> For the obtained evaluation sample, "HP8362B" manufactured by Agilent Technologies Co., Ltd. was used and the frequency of the cycle was measured at 10 GHz according to the cavity resonator perturbation method. The dielectric constant and dielectric tangent were measured at 25 °C.

However, if the dielectric constant is 3.0 or less, the evaluation is "good", and if it exceeds 3.0, the evaluation is "bad". In addition, if the value of the dielectric tangent is 0.005 or less, the evaluation is "good", and if it exceeds 0.005, it is evaluated as "bad".

<Measurement and Evaluation of Adhesion (Peel Strength) to Conductor Layer> (1) Roughening treatment of inner layer circuit board Glass cloth substrate epoxy double-sided copper clad laminate (intermediate circuit board) The thickness of the foil was 18 μm, the thickness of the substrate was 0.4 mm, and both sides of Panasonic (R1515A) were immersed in "CZ8101" manufactured by MEC Co., Ltd., and the double-sided copper foil was etched by 1 μm in the thickness direction. Thereby, the roughening treatment of the surface of the copper foil is performed.

(2) Lamination processing of the copper foil with the resin composition layer The resin varnishes 1 to 10 prepared in the examples and the comparative examples were each dried to a thickness of 40 μm in the resin composition layer by a die coater. The method is uniformly applied to the surface of one side of the "MT18Ex" foil manufactured by Mitsui Mining & Mining Co., Ltd., and dried at 80 ° C to 110 ° C (average 95 ° C) for 6 minutes to prepare a resin composition. Layer of copper foil. A resin composition layer is attached to the inner layer circuit board (copper foil) by using a batch type vacuum pressure bonding machine ("MVLP-500" manufactured by a famous machine) The copper foil is laminated to the both sides of the inner circuit substrate. The lamination treatment was carried out under reduced pressure for 30 seconds and at a gas pressure of 13 hPa or less, followed by pressure-bonding at 100 ° C and a pressure of 0.74 MPa for 30 seconds.

(3) Hardening treatment of copper foil with resin composition layer The resin composition layer of the copper foil with the resin composition layer laminated thereon is hardened at 200 ° C for 90 minutes to form a hardened body. The hardening treatment is performed to form a laminate in which the hardened body with the copper foil is laminated on the inner layer circuit substrate.

(4) Formation of Conductive Layer (Electroplating/electroplating) After the copper foil was peeled off from the hardened body with copper foil obtained in the above (3), the thickness of the exposed hardened body was 25 μm. Copper sulfate electroplating is performed to form a conductor layer as a copper layer. Next, the laminate in which the conductor layer was formed was annealed at 180 ° C for 30 minutes to prepare a circuit board for evaluation.

(5) Measurement and Evaluation of Peel Strength of Conductor Layer The peel strength (peel strength) of the conductor layer was measured using the above-mentioned evaluation circuit board. A strip-shaped slit having a width of 10 mm and a length of 100 mm was cut out on the evaluation circuit board, and one end in the longitudinal direction was peeled off, and clamped by a clipper ((SE) TSE, AUTO COM type tester AC-50C-SL). The load (kgf/cm (N/cm)) at 35 mm in the vertical direction at a temperature of 50 mm/min was measured at room temperature (25 ° C). Here, when the measured load exceeds 0.3 kgf/cm, it is evaluated as "good", and when it is 0.3 kgf/cm or less, it is evaluated as "poor".

<Results> The results of the evaluation are shown in Table 1 below.

As can be seen from Table 1, according to the resin compositions of Examples 1 to 4, the content of the component (C) and the component (D) can be adjusted as described above, and the effectiveness of the dielectric constant of the cured product can be achieved. The reduction can not only reduce the dielectric constant, but also improve the adhesion (peeling strength) to the conductor layer (it is considered to be extremely difficult as described above), and the dielectric tangent can be further reduced.

In Comparative Example 1 in which the ratio of the content of the component (D) is low relative to the total amount of the component (C) and the component (D), the dielectric constant of the cured body becomes high; and the component (C) and the component ( In the total amount of D) and the content of the component (D), the ratio of the content of the component (D) was too high, and the adhesion of the cured body to the conductive layer was low. Therefore, it is understood that the ratio of the content of the component (D) can be appropriately adjusted to a predetermined range with respect to the total amount of the component (C) and the component (D), whereby the dielectric constant and hardening of the cured body can be achieved. The adhesion of the body to the conductive layer.

Comparative Example 3 in which the content of the component (D) was less than the specified range, the dielectric ratio of the hardened body became high, and the content of the component (D) was more than the above specified range, and the hardened body was conductive. The adhesion of the layer is low. Therefore, it can be understood that by appropriately adjusting the content of the component (D) to a predetermined range, the dielectric constant of the cured body and the adhesion of the cured body to the conductive layer can be achieved.

In Comparative Examples 5 and 6 which did not contain the component (B), the dielectric tangent of the hardened bodies became high.

Claims (10)

A resin composition comprising a resin composition of a component (A) epoxy resin, a component (B) active ester compound, a component (C) inorganic filler, and a component (D) fluorine-based filler, and the resin composition When the nonvolatile content is 100% by mass, the content of the component (D) is 10% by mass to 40% by mass; and when the total content of the component (C) and the component (D) is 100% by mass The component (D) is 20% by mass to 70% by mass. The resin composition of claim 1, wherein the component (D) is a fluorine-based polymer particle. The resin composition of claim 2, wherein the fluorine-based polymer particles are polytetrafluoroethylene (PTFE) particles. The resin composition of claim 1, wherein the component (E) further contains a compound having an unsaturated hydrocarbon group. The resin composition of claim 4, wherein the component (E) has one or more selected from the group consisting of an acrylic group, a methacryl group, a styryl group, an allyl group, a vinyl group, and a propylene group. A compound of an unsaturated hydrocarbon group. The resin composition of claim 5, wherein the component (E) is a compound having a vinyl group and having a cyclic ether structure of 5 members or more. The resin composition of claim 1, which is used for forming an insulating layer of a high-frequency circuit substrate. An adhesive film comprising a support and a resin composition layer comprising the resin composition according to any one of claims 1 to 6 provided on the support. A high-frequency circuit substrate comprising an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 6. A semiconductor device comprising the high frequency circuit substrate of claim 9.