KR20180099500A - Resin compositions - Google Patents

Abstract

Provided is a resin composition capable of obtaining an insulation layer with the reduction of a dielectric constant and the improvement of adhesion to a conductive layer. The resin composition includes (A) an epoxy resin, (B) an active ester compound, (C) an inorganic filler, and (D) a fluorine-based filler. When the content of nonvolatile components in the resin composition is 100%, the content of the component (D) is 10 mass% to 40 mass%. When the sum of the content of the component (C) and the component (D) is 100%, the component (D) is 20 mass% to 70 mass%.

Description

RESIN COMPOSITIONS [0001]

The present invention relates to a resin composition, an adhesive film, a circuit board, and a semiconductor device.

BACKGROUND ART [0002] As a manufacturing technique of a circuit board, a manufacturing method using a build-up method in which an insulating layer and a conductor layer are alternately stacked 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 discloses a resin composition comprising an epoxy resin, a curing agent, and a fluorine resin filler, wherein the content of the fluorine resin filler is 50% by mass to 85% by mass relative to the solid content of the resin composition And the like.

Japanese Patent Application Laid-Open No. 2016-166347

However, since the resin composition disclosed in Patent Document 1 contains a large amount of the fluororesin filler in an amount of 50% by mass to 85% by mass, the adhesion to the inner-layer circuit substrate is sacrificed, It is difficult to apply it.

Accordingly, it is an object of the present invention to provide a resin composition excellent in dielectric properties and having good adhesion to an inner layer circuit board.

The present inventors have intensively studied the above problems and 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 at a predetermined ratio, and have accomplished the present invention.

That is, the present invention provides the following [1] to [10].

[1] A resin composition comprising (A) an epoxy resin, (B) an active ester compound, (C) an inorganic filler, and (D) a fluorine-

Wherein the content of the component (D) is 10% by mass to 40% by mass when the nonvolatile component in the resin composition is 100% by mass,

Wherein the total amount of the component (C) and the component (D) is 100 mass%, and the component (D) is 20 mass% to 70 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] Component (E) The resin composition according to any one of [1] to [3], further comprising a compound having an unsaturated hydrocarbon group.

[5] The resin composition according to [4], wherein the component (E) is a compound having at least one unsaturated hydrocarbon group selected from the group consisting of an acrylic group, methacrylic group, styryl group, allyl group, vinyl group and propenyl group .

[6] The resin composition according to [5], wherein the component (E) is a compound having a vinyl group and having a cyclic ether structure having 5 or more ring members.

[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 board.

[8] An adhesive film having a support and a resin composition layer comprising the resin composition according to any one of [1] to [6] formed on the support.

[9] A high-frequency circuit board comprising an insulating layer made of a 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].

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a resin composition capable of obtaining an insulating layer having a low dielectric constant, in particular, a low dielectric constant and a low dielectric loss tangent, and excellent adhesion to an inner layer circuit board, particularly a conductor layer.

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

[Resin composition]

The resin composition is a resin composition comprising a component (A) an epoxy resin, a component (B) an active ester compound, a component (C) an inorganic filler, and a component (D) a fluorine- , When 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% % 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 epoxy resins such as biquilene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, A naphthalene type epoxy resin, an anthracene type epoxy resin, a glycidylamine type epoxy resin, a glycidyl ether type epoxy resin, a glycidyl ether type epoxy resin, a glycidyl type epoxy resin, Alicyclic epoxy resins, cycloaliphatic epoxy resins, spiro-ring-containing epoxy resins, cyclohexanedicarboxylic acid esters, cyclohexanedicarboxylic acid esters, cyclohexanedicarboxylic acid esters, A methanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, And tetraphenyl ethane type epoxy resins. The epoxy resins may be used alone or in combination of two or more.

The component (A) is preferably an aromatic skeleton-containing epoxy resin from the viewpoint of lowering the average linear heat expansion coefficient, and is preferably a bisphenol A epoxy resin, a bisphenol F epoxy resin, a naphthalene epoxy resin, A pentadiene type epoxy resin, and more preferably a biphenyl type epoxy resin. Also, the aromatic skeleton is a chemical structure generally defined as aromatic, and 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 nonvolatile component of the epoxy resin is 100% by mass, it is preferable that at least 50% by mass or more of the epoxy resin is an epoxy resin having two or more epoxy groups in one molecule. Among them, it is preferable to include an epoxy resin (referred to as &quot; solid epoxy resin &quot;) having three or more epoxy groups in one molecule and a solid phase at a temperature of 20 캜. The epoxy resin may contain only solid epoxy resin, and may contain a liquid epoxy resin (referred to as a &quot; solid epoxy resin &quot;) and a solid epoxy resin at two or more epoxy groups per molecule at a temperature of 20 캜 There may be. By using a liquid epoxy resin and a solid epoxy resin as an epoxy resin in combination, a resin composition having excellent flexibility can be obtained. Further, the fracture strength of the cured product of the resin composition is also improved.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolak type epoxy resin , An alicyclic epoxy resin having an ester skeleton, a cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a glycidylamine type epoxy resin, a bisphenol A type epoxy resin , Bisphenol F type epoxy resin, bisphenol AF type epoxy resin and naphthalene type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation, "828US", "jER828EL", "825" 630LSD &quot; (glycidyl) epoxy resin, &quot; Epicote 828EL &quot; (bisphenol A type epoxy resin), &quot; jER807 &quot;, &quot; 1750 &quot; (bisphenol F type epoxy resin) Amine type epoxy resin), "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Shinnitetsu Sumikin Kagaku Co., "EX-721" PB-3600 &quot; (an epoxy resin having a butadiene structure), Shinnetsu Tetsukagaku Co., Ltd. (an epoxy resin having an ester skeleton), &quot; Celloxide 2021P &quot; (an alicyclic epoxy resin having an ester skeleton) ) &Quot; ZX1658 &quot;, and &quot; ZX1658GS &quot; (liquid 1,4-glycidyl cyclohexane). These may be used alone, or two or more kinds may be used in combination.

Examples of the solid epoxy resin include naphthalene type tetrafunctional epoxy resins, cresol novolak type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins , An anthracene type epoxy resin, a bisphenol A type epoxy resin and a tetraphenylethane type epoxy resin are preferable, and a naphthalene type tetrafunctional epoxy resin, a naphthol type epoxy resin and a biphenyl type epoxy resin are more preferable.

Specific examples of the solid epoxy resin include HP4032H (naphthalene type epoxy resin), HP-4700, HP-4710 (naphthalene type tetrafunctional epoxy resin), N-690 HP-7200H "," HP-7200H "," EXA-7200H ", and the like)," N-695 "(cresol novolak type epoxy resin) EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(naphthylene ether type epoxy resin)," EPPN-502H "manufactured by Nippon Kayaku Co., NC3000H "," NC3000L "," NC3100 "(biphenyl type epoxy resin), Shinnitetsu Sumikin Kagaku Co., Ltd., "ESN475V" (naphthalene type epoxy resin), "ESN485" (naphthol novolak type epoxy resin) manufactured by Mitsubishi Kagaku KK, "YX4000H", "YX4000", "YL6121" Manufactured by Mitsubishi Chemical Corporation), "YX4000HK" (biquilene type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., "JER1010" (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenyl ethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "YL7760" (bisphenol AF type epoxy resin) Resin). These may be used alone, or two or more kinds may be used in combination.

When a liquid epoxy resin and a solid epoxy resin are used together as the epoxy resin, their ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1: 0.1 to 1:15 in terms of the mass ratio. By setting the ratio of the liquid epoxy resin and the solid epoxy resin within this range, it is possible to make the adhesive property favorable in the case of i) in the form of an adhesive film, and ii) to obtain sufficient flexibility in the case of using in the form of an adhesive film And (iii) a cured product having sufficient breaking 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 more preferably in the range of 1: 0.5 to 1:10, : 1 to 1: 8 is more preferable.

The content of the epoxy resin in the resin composition is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 8% by mass or less, Or more, more preferably 10 mass% or more. The content of the epoxy resin is preferably 40 mass% or less, more preferably 30 mass% or less, further preferably 20 mass% or less, provided that the effect of the present invention can be obtained.

The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By setting this range, an insulating layer having sufficient cross-linking density of the cured product and having a small surface roughness can be obtained. 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 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

<Component (B) Active ester compound>

Component (B) The active ester compound is a compound having at least one active ester group in one molecule. Usually, the active ester compound can function as a curing agent for curing the resin composition by reacting with the above-described component (A) epoxy resin. Component (B) By using the active ester compound, the dielectric tangent of the cured product of the resin composition can be lowered, and in general, an insulating layer with a small surface roughness can be obtained.

Component (B) The active ester compound preferably has two or more active ester groups in one molecule. Examples of such active ester compounds include ester groups having high reactivity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, And the like. The active ester compound (B) may be used alone, or two or more kinds thereof may be used in combination at an arbitrary ratio.

From the viewpoint of improving the heat resistance, the active ester compound (B) is more preferably an active ester compound obtained by condensation reaction of a carboxylic acid compound and / or thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. Among them, an active ester compound obtained by reacting a carboxylic acid compound with at least one 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 per molecule, obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group, is more preferable. Among them, an aromatic compound having at least two active ester groups in one molecule is particularly preferable as an aromatic compound obtained by reacting a carboxylic acid compound having at least two carboxyl groups in one molecule with an aromatic compound having a phenolic hydroxyl group. The active ester compound (B) may be linear or branched. In addition, if a carboxylic acid compound having two or more carboxyl groups in one molecule contains a compound having an aliphatic chain, compatibility with the resin composition can be enhanced, and heat resistance can be enhanced if the compound has an aromatic ring.

Examples of the carboxylic acid compound include aliphatic carboxylic acids having 1 to 20 (preferably 2 to 10, more preferably 2 to 8) carbon atoms, aromatic groups having 7 to 20 carbon atoms (preferably 7 to 10) 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 pyromellitic acid. Among them, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid and terephthalic acid are preferable from the viewpoint of heat resistance, and isophthalic acid and terephthalic acid are more preferable. The carboxylic acid compound may be used alone, or two or more kinds may be used in combination at an arbitrary ratio.

The thiocarboxylic acid compound includes, for example, thioacetic acid and thiobenzoic acid. The thiocarboxylic acid compound may be used singly or in combination of two or more at any ratio.

Examples of the phenol compound include a phenol compound having 6 to 40 carbon atoms (preferably 6 to 30, more preferably 6 to 23, and still more preferably 6 to 22) carbon atoms. Suitable specific examples of the phenol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenol phthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o- Cresol, catechol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzene triol, and dicyclopentadiene type diphenol. Here, "dicyclopentadiene-type diphenol" refers to a phenol compound obtained by condensing two molecules of phenol in one molecule of dicyclopentadiene. As the phenol compound, a phenol novolak, a phosphorus atom-containing oligomer having a phenolic hydroxyl group described in JP-A-2013-40270 may be used. The phenol compounds may be used alone, or two or more phenol compounds may be used in combination at an arbitrary ratio.

The naphthol compound includes, for example, a naphthol compound having 10 to 40 (preferably 10 to 30, more preferably 10 to 20) carbon atoms. Suitable specific examples of the naphthol compound include? -Naphthol,? -Naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene and 2,6-dihydroxynaphthalene. As the naphthol compound, naphthol novolak may also be used. The naphthol compound may be used singly or in combination of two or more at any ratio.

Among them, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol,? -Naphthol,? -Naphthol, 1,5-dihydroxy Naphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzene triol, dicyclopenta Diene type diphenols, phenol novolacs, and phosphorus atom-containing oligomers having a phenolic hydroxyl group are preferable. Further, it is also possible to use catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, More preferred are phosphorus atom-containing oligomers having fluoroglycine, benzenetriol, dicyclopentadiene type diphenol, phenol novolac, and phenolic hydroxyl group. Among them, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclo Pentadien-type diphenol, phenol novolac, and phosphorus atom-containing oligomers having a phenolic hydroxyl group are more preferable. Further, it is also possible to use a phosphorus atom-containing oligomer having 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene type diphenol, phenol novolak, Is more preferable. Among them, a phosphorus atom-containing oligomer having 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene type diphenol or phenolic hydroxyl group is even more preferable Do. Dicyclopentadiene type diphenols are also particularly preferred.

Examples of the thiol compound include benzene dithiol and triazinedithiol. The thiol compound may be used alone, or two or more thiol compounds may be used in combination at an arbitrary ratio.

Suitable specific examples of the active ester compound include active ester compounds containing a dicyclopentadiene type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated phenol novolak, benzoyl phenol novolak An active ester compound containing a cargo, 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, an active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group is more preferable Do. Here, the "dicyclopentadiene type diphenol structure" refers to a divalent structural unit comprising phenylene-dicyclopentylene-phenylene.

Particularly suitable specific examples of the active ester compound having a dicyclopentadiene type diphenol structure include compounds represented by the following formulas.

In the above formulas, R represents, independently of each other, a phenyl group or a naphthyl group. Among them, R is preferably a naphthyl group from the viewpoint of lowering dielectric tangent and improving heat resistance.

In the above formula, k represents 0 or 1. In particular, from the viewpoint of lowering dielectric tangent and improving heat resistance, k is preferably 0.

In the above formula, n is an average number of repeating units of 0.05 to 2.5. Among them, n is preferably 0.25 to 1.5 from the viewpoint of lowering dielectric tangent and improving heat resistance.

Component (B) As the active ester compound, the active ester compound disclosed in Japanese Patent Application Laid-Open No. 2004-277460 or Japanese Patent Application Laid-Open No. 2013-40270 may be used. As the active ester compound (B), commercially available active ester compounds may be used. EXB9451 "," EXB9460 "," EXB9460S "," HPC-8000-65T "," HPC-8000L-65M "(dicyclopentadiene-type diphenol structure &Lt; / RTI &gt; "EXB9416-70BK" (active ester compound containing a naphthalene structure) manufactured by DIC Corporation; &Quot; DC808 &quot; (active ester compound containing acetylated phenol novolak), manufactured by Mitsubishi Kagaku; &Quot; YLH1026 &quot; (active ester compound containing benzoylated phenol novolak) manufactured by Mitsubishi Kagaku; &Quot; EXB9050L-62M &quot; (phosphorus atom-containing active ester compound) manufactured by DIC Corporation; .

The active group equivalent of the active ester compound (B) is preferably 120 to 500, more preferably 150 to 400, and particularly preferably 180 to 300. When the equivalent of the active group of the component (B) active ester compound is within the above range, the crosslinked density of the cured product of the resin composition becomes sufficient, and an insulating layer with a small surface roughness can be obtained. Here, the active group equivalent represents the mass of the resin containing one equivalent of an active group.

The active ester compound may be used alone, or two or more kinds thereof may be used in combination at an arbitrary ratio.

The content of the active ester compound (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 or more, relative to 100% by mass of the nonvolatile component in the resin composition And particularly preferably 15 mass% or more, more preferably 40 mass% or less, more preferably 35 mass% or less, and still more preferably 30 mass% or less. If the content of the component (B) active ester compound is lower than the lower limit of the above range, the adhesiveness between the conductor layer and the insulating layer can be particularly enhanced. If the content is less than the upper limit of the above range, the heat resistance can be improved, Or the like.

When the number of epoxy groups in the epoxy resin of the component (A) is 1, the number of active groups of the active ester compound (B) is preferably 0.1 or more, more preferably 0.2 or more, from the viewpoint of obtaining an insulating layer having a good mechanical strength. More preferably not less than 0.3, particularly preferably not less than 0.4, preferably not more than 2, more preferably not more than 1.5, and even more preferably not more than 1. [ Here, the "number of epoxy groups of the epoxy resin" is a value obtained by dividing the value obtained by dividing the amount of non-volatile component of the epoxy resin present in the resin composition by the epoxy equivalent, to the total epoxy resin. The term &quot; active group &quot; means a functional group capable of reacting with an epoxy group. The term &quot; number of active groups of the active ester compound &quot; means the sum of values obtained by dividing the amount of non-volatile components in the active ester compound present in the resin composition to be.

<Component (C) inorganic filler>

The resin composition contains component (C) inorganic filler. The material of the inorganic filler is not particularly limited. As the material of the inorganic filler, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, A metal oxide such as magnesium, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, Barium, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly suitable. As the silica, spherical silica is preferable. The inorganic fillers may be used singly or in combination of two or more kinds.

The average particle diameter of the inorganic filler is preferably not more than 5 mu m, more preferably not more than 2.5 mu m, more preferably not more than 2 mu m, from the viewpoint of improving the filling property of the conductor layer and obtaining an insulating layer with low surface roughness Mu m or less, and even more preferably 1.5 mu m or less. The average particle diameter is preferably 0.01 占 퐉 or more, more preferably 0.05 占 퐉 or more, still more preferably 0.1 占 퐉 or more, 0.5 占 퐉 or more, or 1 占 퐉 or more. Examples of the commercially available inorganic filler having such an average particle diameter include SP60-05, SP-507-05, YD100C manufactured by Adomatex Co., Ltd., Shin-Tetsu Sumikin Materials Co., , "YA050C", "YA050C-MJE", "YA010C", "UFP-30" manufactured by Denka Corporation, "Silphil NSS-3N" manufactured by Tokuyama Corporation, "Silphil NSS- 5N "manufactured by Nippon Sheet Glass Co., Ltd.," SC2500SQ "manufactured by Adomex Co., Ltd.," SO-C4 "," SO-C2 "and" 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 measured with a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter of the inorganic filler is determined as the average particle diameter. As the measurement sample, a sample in which an inorganic filler is dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction scattering type particle size distribution measuring apparatus, "LA-500" manufactured by Horiba Seisakusho Co., Ltd. and the like can be used.

From the viewpoint of improving the moisture resistance and dispersibility, the inorganic filler is preferably selected from the group consisting of an amino silane coupling agent, an epoxy silane coupling agent, a mercaptosilane coupling agent, an alkoxysilane compound, an organosilazane compound and a titanate coupling agent It is preferable that the surface treatment agent is treated with at least two kinds of surface treatment agents. As commercially available products of surface treatment agents, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercapto KBE903 "(3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.," KBM573 "(manufactured by Shin-Etsu Chemical Co., SZ-31 (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM-103 (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., KBM-4803 &quot; (long chain epoxy type silane coupling agent) manufactured by Kagyo KK.

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

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, first, a sufficient amount of MEK as a solvent is added to an inorganic filler surface-treated with a surface treatment agent, and ultrasonically cleaned at 25 ° C for 5 minutes. Subsequently, the supernatant liquid is removed, and the nonvolatile component is dried, and then 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 Seisakusho Co., Ltd. and the like can be used.

The content of the inorganic filler in the resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 15% by mass or less, Or more, and more preferably 20 mass% or more. The content of the inorganic filler in the resin composition is preferably 70 mass% or less, more preferably 60 mass% or less, further preferably 50 mass% or less, from the viewpoint of improving the mechanical strength of the insulating layer, Respectively.

<Component (D) Fluorine-based filler>

The resin composition contains a fluorine-based filler as the component (D). Here, the term &quot; fluorine-based &quot; means a fluorine-containing one. The "fluorine-based filler" refers to a filler containing a fluorine atom-containing compound as a material. The component (D) is in a particulate form, and its particle diameter is not particularly limited. The average particle diameter of the component (D) is preferably 5 占 퐉 or less, more preferably 4 占 퐉 or less, and even more preferably 3 占 퐉 or less because of its excellent dispersibility in the resin composition. The average particle diameter of the component (D) is preferably 0.05 mu m or more, more preferably 0.08 mu m or more, and further preferably 0.10 mu m or more. Therefore, the component (D) preferably has an average particle diameter of 0.05 탆 to 5 탆, more preferably 0.08 탆 to 4 탆, and further preferably 0.10 탆 to 3 탆.

As the component (D), for example, particles containing a material selected from a fluorine resin and a fluorine rubber may be mentioned.

As the component (D), fluorine-based polymer particles containing a fluorine resin are preferable from the viewpoint of reducing the dielectric constant of the insulating layer.

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

From the viewpoint of further reducing the dielectric constant of the insulating layer, it is preferable to use PTFE as the fluorine resin. In other words, as the component (D), it is preferable to use PTFE particles which are fluoropolymer particles containing PTFE as the fluororesin.

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.

Specific examples of PTFE particles that are commercially available fluorine-based polymer particles include "Lubron L-2" manufactured by Daikin Industries Ltd., "Lubron L-2" manufactured by Daikin Industries, Ltd. -5 "manufactured by Asahi Glass Co., Ltd.," Lubron L-5F "manufactured by Daikin Kogyo Co., Ltd.," FluonPTFE L-170JE "manufactured by Asahi Glass Co., Ltd.," FluonPTFE L-172JE " KTL-1N "manufactured by Kitamura Co., Ltd.," Mitsui DuPont "(trade name) manufactured by KITAMURA CO., LTD.," FluonPTFE L-173JE " TLP10F-1 &quot; manufactured by Fluoro Chemical Co., Ltd. can be mentioned.

The component (D) may contain, for example, surface-treated particles. The surface treatment includes, for example, surface treatment with a surface treatment agent. The surface treatment agent is not particularly limited. In addition to the surfactants such as nonionic surfactants, amphoteric surfactants, cationic surfactants and anionic surfactants, the surface treating agent includes inorganic fine particles and the like. From the viewpoint of affinity, it is preferable to use a fluorine-based surfactant as the surface treatment agent. Specific examples of the fluorine-based surfactant include "SURFON S-243" (perfluoroalkyl ethylene oxide adduct) manufactured by AGC Seiyam Chemical Co., "Megapak F-251" manufactured by DIC Co., Megapak F-477 "manufactured by DIC Corporation," Megapark F-553 "manufactured by DIC Corporation," Megapark R-40 "manufactured by DIC Corporation," Megapark R-43 " FTX-218 "manufactured by Neos Corporation," Pertigent 610FM "manufactured by Neos Corporation, and" Pectigent 730LM "manufactured by Neos Co., Ltd. can be mentioned.

From the viewpoint of effectively reducing the dielectric constant of the insulating layer and maintaining the adhesion strength, the content of the component (D) is preferably such that when the nonvolatile component in the resin composition is 100 mass%, the content of the component (D) 10% by mass to 40% by mass. From the viewpoint of effectively reducing the dielectric constant of the insulating layer, 15 mass% or more is preferable, and 20 mass% or more is more preferable. But is preferably 35 mass% or less, more preferably 30 mass% or less, and still more preferably 25 mass% or less, from the viewpoint of maintaining the adhesion strength.

When the total content of the component (C) and the component (D) is 100 mass%, the component (D) is preferably 20 mass% from the viewpoint of effectively reducing the dielectric constant of the insulating layer, % To 70% by mass. From the viewpoint of effectively reducing the dielectric constant of the insulating layer, 25 mass% or more is preferable, and 30 mass% or more is more preferable. But is preferably 60 mass% or less, more preferably 50 mass% or less, still more preferably 40 mass% or less, from the viewpoint of maintaining the adhesion strength.

Particular attention is paid to the dielectric constant of the cured product of the resin composition. In the present embodiment, the fluorine-based filler (D) used for reducing the dielectric constant of the cured product is preferably PTFE particles which are fluoropolymer particles containing PTFE.

Here, the dielectric constant of PTFE is 2.1. Therefore, for example, when PTFE particles are used as the components of the resin composition, even if the target of reduction of the dielectric constant of the cured product is about 0.1, the dielectric constant is reduced and the physical properties of the resin composition, It is extremely difficult to make it good. This is because, in order to reduce the dielectric constant, when a large amount of PTFE particles are compounded in the resin composition as described in the above-mentioned Patent Document 1, the dielectric constant of the cured product can surely be reduced, but the PTFE particles tend to aggregate in the resin composition This is because, as a result, the PTFE particles can not be uniformly distributed in the resin composition and the cured product, the adhesion to the semiconductor layer is significantly lowered, and the physical properties and electrical properties of the cured product are impaired.

However, the resin composition according to the present embodiment finds a solution for adjusting the content of the component (C) and the component (D) in the resin composition to the above-mentioned numerical range, and by considering the blending of other components, Even if the content of the component (D) is further reduced, reduction of the dielectric constant of the cured product can be realized, not only the reduction of the dielectric constant and the improvement in the adhesiveness to the conductor layer can be achieved, but also the dielectric loss tangent of the cured product can be lowered Effect can be obtained.

<Component (E) Compound Having Unsaturated Hydrocarbon Group>

The resin composition may contain the component (E). By having the cured product in the 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 dielectric loss tangent value 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, dielectric tangent of the cured product can be lowered. The unsaturated hydrocarbon group is preferably an acryl group, a methacryl group, a styryl group, or an olefin group. Here, the "olefin group" refers to an aliphatic hydrocarbon group having a carbon-carbon double bond in a molecule. For example, an allyl group, a vinyl group, or a propenyl group. That is, the component (E) is preferably a compound having at least one unsaturated hydrocarbon group selected from the group consisting of an acryl group, a methacryl group, a styryl group, an allyl group, a vinyl group and a propenyl group.

As the component (E), compounds represented by the following formulas (2), (7) and (8) are more preferable.

(2)

In the above 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. A represents a structure (divalent group) represented by the following formula (3) or (4).

(3)

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

(4)

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

(5)

In the above 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, preferably a hydrogen atom or a methyl group. In particular, R ⁷ , R ⁸ , R ¹³ and R ¹⁴ are more preferably a methyl group. a and b are integers of 0 to 100, at least one of which is not 0. B represents a structure (divalent group) represented by the following formula (B-1), (B-2) or (B-3)

The formula (B-1)

(B-2)

(B-3)

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

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

In the above 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, preferably a hydrogen atom or a methyl group. E represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

As the compound represented by the above formula (2), a compound represented by the following formula (6) is more preferable.

(6)

In the formula (6), R ¹ to R ⁶ are, and R ¹ to R ⁶ and copper in the above formula (2), B is a B and agreement in the formula (3), a, b, the formula (A) and (b) in (5).

The compound represented by the formula (7) is as follows.

(7)

As the component (E), "a compound having a cyclic ether structure having five or more ring members" represented by the following formula (8) is more preferable.

(8)

In the above formula (8), the ring F represents a divalent group having a cyclic ether structure having five or more ring members. B ¹ and B ² each independently represent a single bond or a divalent linking group. C ¹ and C ² represent the same or different functional groups.

The cyclic ethers having five or more ring members have a property that the dielectric tangent can be lowered because the movement of molecules is limited. The carbon-carbon unsaturated bond may be contained in the cyclic ether structure or may be contained only in the cyclic ether structure. A plurality of carbon-carbon unsaturated bonds may be present.

The number of oxygen atoms contained in the cyclic ether structure according to the &quot; compound having a cyclic ether structure having five or more ring members &quot; is preferably at least 1, more preferably at least 2, and more preferably at least 2 from the viewpoint of obtaining a desired effect of the present invention Is preferably 5 or less, more preferably 4 or less, and further preferably 3 or less.

The cyclic ether structure having five or more ring members is not particularly limited as long as the cyclic ether has a multiple ring structure of five-membered rings or more. The cyclic ether structure having five or more ring members may be a monocyclic, polycyclic or condensed ring. The "compound having a cyclic ether structure having five or more ring members" may have a plurality of cyclic ether structures. The cyclic ether structure is preferably a 5- to 10-membered ring, more preferably a 5- to 8-membered ring, and even more preferably a 5- to 6-membered ring. Specific examples of the cyclic ether structure having five or more ring members include a furan structure, a tetrahydrofuran structure, a dioxolane structure, a pyran structure, a dihydropyran structure, a tetrahydropyran structure, and a dioxane structure. Among them, from the viewpoint of improving the compatibility, the compound having a cyclic ether structure having five or more rings is preferable to include a dioxane structure. The dioxane structure includes a 1,2-dioxane structure, a 1,3-dioxane structure and a 1,4-dioxane structure, and a 1,3-dioxane structure is preferable.

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

Specific examples of the divalent group having a cyclic ether structure having five or more ring members include a furan-2,5-diyl group, a tetrahydrofuran-2,5-diyl group, a dioxolane-2,5-diyl group, Diyl group, dihydropyran-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,2-dioxane-3,6-diyl group, 1,3-dioxane-2,5 -Diol group, 1,4-dioxane-2,5-diyl group, and 5-ethyl-1,3-dioxane-2,5-diyl group. As the divalent group having a cyclic ether structure having 5 or more ring members, 5-ethyl-1,3-dioxane-2,5-diyl group is preferable.

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

The substituent is not particularly limited. Examples of the substituent include a halogen atom, a group represented by -OH, a -OC _1-6 alkyl group, -N (C _1-6 alkyl group) ₂ , a C _1-6 alkyl group, a C _6-10 aryl group, -NH ₂ , a group represented by -CN, a group represented by -C (O) OC _1-6 alkyl, a group represented by -COOH, a group represented by -C (O) H, or -NO ₂ , .

_Quot ; C _1-6 &quot; and &quot; C _6-10 &quot; according to the above substituents are _generically referred to as &quot; C _pq &quot; &_Quot; C _pq &quot; (where p and q are positive integers and p &lt; q is satisfied) indicates that the number of carbon atoms of the organic group described immediately after this word is p to q. Specifically, for example, the "C _1-6 alkyl group" represents "an alkyl group having 1 to 6 carbon atoms".

The substituent may also have a substituent (hereinafter sometimes referred to as "secondary substituent"). As the secondary substituent, for example, there can be mentioned the same group as the substituent described above.

Of these, B ¹ and B ² are selected from an alkylene group which may have a substituent, an alkynylene group which may have a substituent, a group represented by -COO-, and two or more arbitrary groups selected from the group represented by -O- And a group obtained by selecting two or more arbitrary groups from the group represented by -COO-, which may have a substituent, is more preferable.

C ¹ and C ² represent the same or different functional groups. Examples of the functional group include a vinyl group, a methacrylic group, an acrylic group, an allyl group, a styryl group, a propenyl group, and an epoxy group. As the functional group, a vinyl group is preferable.

Specific examples of the &quot; compound having a cyclic ether structure having five or more ring members &quot; include compounds represented by the following formulas.

As the component (E), for example, a styrene-modified polyphenylene ether resin (OPE-2St 1200 (number average molecular weight 1200) manufactured by Mitsubishi Gas Kagaku Co., (A-DOG (number average molecular weight: 326) manufactured by Shin-Nakamura Kagaku Co., Ltd.), "YL7776 (number average molecular weight 331)" manufactured by Mitsubishi Kagaku Co., Equivalent to the above formula (8) ", KAYARAD R-604 manufactured by Nippon Kayaku Co., Ltd., and the above formula (8) equivalent.

The number average molecular weight of the component (E) is preferably in the range of from 100 to 10000, more preferably from 200 to 10000, from the viewpoint of preventing the volatilization of the resin varnish during drying and preventing the melt viscosity of the resin composition from rising too high, 3000 &lt; / RTI &gt; In addition, the number average molecular weight in the present invention is 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, and "Shodex K-800P / K-804L / K-804L "as a mobile phase, chloroform at a column temperature of 40 ° C, and using a standard polystyrene calibration curve.

The content of the component (E) is preferably 1% by mass or more, and more preferably 3% by mass or more, from the viewpoint of lowering the dielectric loss tangent of the cured product when the nonvolatile component is 100% by mass. From the viewpoint of improving the compatibility of the resin varnish, the content is preferably 15% by mass or less, and more preferably 10% by mass.

Component (A) The mass ratio of the epoxy resin to the component (E) (mass of the epoxy resin: mass of the component (E)) is preferably in the range of 1: 0.01 to 1: 100, , More preferably in the range of 1: 0.1 to 1: 80. Within this range, compatibility can be improved.

By including the component (E), the resin composition can improve the compatibility and disperse the fluorine-based filler (D) already described more uniformly 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 improved, and the dielectric loss tangent can be lowered. As a result, the physical properties and electrical characteristics of the insulating layer to be formed can be improved and the reliability of the device can be improved.

&Lt; Curing accelerator of component (F)

The resin composition may contain a component (F) curing accelerator. Examples of the curing accelerator include a phosphorus hardening accelerator, an amine hardening accelerator, an imidazole hardening accelerator, a guanidine hardening accelerator, a metal hardening accelerator and a peroxide hardening accelerator. As the hardening accelerator, phosphorus hardening accelerator, amine hardening accelerator, imidazole hardening accelerator and metal hardening accelerator are preferable, and amine hardening accelerator, imidazole hardening accelerator and metal hardening accelerator are more preferable. The curing accelerator may be used singly or in combination of two or more kinds.

Examples of phosphorus hardening accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenyl Phosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. As the phosphorus hardening accelerator, triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl- Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] -ethyl-s-triazine, 2,4- diamino-6- [ Imidazolyl- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- Triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl-s-triazine isocyanate 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2 2-methylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazole, 2-methylimidazolium chloride, Imidazole compounds such as phenol and zolin, and adducts of imidazole compounds and epoxy resins. Examples of imidazole-based curing accelerators include 2-ethyl-4-methylimidazole, 1-benzyl- .

A commercially available imidazole-based curing accelerator may be used. As the imidazole-based curing accelerator which can be used in the market, for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation can be mentioned.

Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, , Trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [ 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1- (o-tolyl) biguanide. As the guanidine curing accelerator, dicyandiamide and 1,5,7-triazabicyclo [4.4.0] deca-5-ene are preferable.

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

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

Commercially available products can be used as the peroxide-based curing accelerator. As the peroxide-based curing accelerator, there can be mentioned, for example, "Percumile D" which is a nich-like preparation.

The content of the curing accelerator in the resin composition is not particularly limited. 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 more preferably 0.1% by mass to 1% by mass, based on 100% by mass of the nonvolatile component desirable.

<Component (G) Thermoplastic resin>

The resin composition may contain the component (G) thermoplastic resin. Examples of the thermoplastic resin include thermoplastic resins such as phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyether sulfone resin, polycarbonate resin , A polyether ether ketone resin, and a polyester resin. As the thermoplastic resin, a phenoxy resin is preferable. The thermoplastic resins may be used alone or in combination of two or more.

The weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably in the range of 8000 to 70000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. The weight average molecular weight of the thermoplastic resin in terms of polystyrene is measured by a gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight of the thermoplastic resin in terms of polystyrene was measured using "LC-9A / RID-6A" manufactured by Shimadzu Corporation as a measuring device and "Shodex (trade name, K-800P / K-804L / K-804L "is used as a mobile phase, chloroform or the like is used as a mobile phase, the column temperature is measured at 40 ° C, and calibration curve of standard polystyrene is used.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, A phenoxy resin having at least one skeleton selected from the group consisting of a skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethyl cyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resins may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (both phenol resins containing a bisphenol A skeleton), "YX8100" (phenoxy resin containing a bisphenol S skeleton), and "YX6954" (Phenoxy resin containing a bisphenol acetophenone skeleton). In addition, "FX280" and "FX293" manufactured by Shin Nitetsu Sumikin Kagaku Co., Ltd., "YX6954BH30", "YX7553" YL7569BH30 "," YL6794 "," YL7213 "," YL7290 "," YL7891BH30 ", and" YL7482 ".

Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin. As the polyvinyl acetal resin, a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include polyvinyl acetal resins such as "Phone Butyral 4000-2", "Phone Butyral 5000-A", "Phone Butyral 6000-C" manufactured by Denki Kagaku Kogyo Co., (For example, KS-1), BL series, and BM series manufactured by Sekisui Chemical Industries, Ltd. under the trade designation "LAL 6000-EP" .

Specific examples of the polyimide resin include "Rika coat SN20" and "Rika coat PN20" manufactured by Shin-Nippon Rikagaku Co., Ltd. Specific examples of the polyimide resin include a linear polyimide (polyimide disclosed in JP-A-2006-37083) obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride, Modified polyimides such as polysiloxane skeleton-containing polyimide (Japanese Patent Application Laid-Open No. 2002-12667 and Japanese Patent Application Laid-Open No. 2000-319386, etc.).

As the polyamide-imide resin, a commercially available product may be used. Specific examples of the polyamide-imide resin that can be used in the market include "Bylomex HR11NN" and "Bylomax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamide-imide resin include modified polyamideimides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Chemical Co., Ltd.

As the polyether sulfone resin, a commercially available product may be used. As a specific example of the polyether sulfone resin that can be used in the market, "PES 5003P" manufactured by Sumitomo Chemical Co., Ltd. may be mentioned.

As the polysulfone resin, a commercially available product may be used. Specific examples of commercially available products include "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd.

Among them, a phenoxy resin and a polyvinyl acetal resin are preferable as the thermoplastic resin. In a preferred embodiment, the thermoplastic resin includes at least one selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin.

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

<Component (H) Flame Retardant>

The resin composition may contain a flame retardant of component (H). Examples of the flame retardant include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants and metal hydroxides. The flame retardant may be used alone, or two or more thereof may be used in combination.

As the flame retardant, a commercially available product may be used. Examples of the flame retardant that can be used for commercial products include "HCA-HQ" manufactured by Sanko Co., Ltd. and "PX-200" manufactured by Daihachi Chemical Co., Ltd.

When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited. 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, and still more preferably 0.5% by mass to 10% by mass, based on 100% by mass of the non- Mass%.

<Component (I) Optional Additive>

The resin composition may further contain optional additives as required. Examples of such optional additives include organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds, and resin additives such as thickeners, defoaming agents, leveling agents, adhesion promoters, and coloring agents.

&Lt; Adhesive film &

The adhesive film comprises a support and a resin composition layer formed on the support and including the resin composition described above.

Support

As the support, for example, a film made of a plastic material, a metal foil, and a release paper can be given. As the support, a film or a metal foil made of a plastic material is preferable.

When a film made of a plastic material is used as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter sometimes referred to as "PEN" (TAC), polyether sulfide (PES), polyether sulfone (PES), polyether sulfone (PES), polyether sulfone , Polyether ketone, and polyimide. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and polyethylene terephthalate is particularly preferable since it is inexpensive and excellent in availability.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil. As the support, copper foil is preferable. As the copper foil, a foil made only of copper may be used, or a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) good.

The support may be subjected to a matte treatment, a corona treatment, and an antistatic treatment on the side bonded to the resin composition layer.

As the support, a support having a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the releasing agent that can be used for the release layer of the release layer-adhered support include at least one release agent selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin. As the support for attaching the releasing layer, a commercially available product may be used. For example, "SK-1", "AL-5" and "PE-5", each of which is a PET film having a releasing layer mainly composed of an alkyd resin- AL-7 "manufactured by Toray Industries, Inc., and" Lumirror T6AM "manufactured by Toray Co., Ltd.

The thickness of the support is not particularly limited. The thickness of the support is preferably in the range of 5 탆 to 75 탆, and more preferably in the range of 10 탆 to 60 탆. When the release layer-adhered support is used, it is preferable that the thickness of the entirety of the release layer-adhered support is in the above range.

The resin composition layer

The resin composition layer included in the adhesive film is a thin film obtained by semi-curing a resin varnish coating film. The adhesive film can be formed, for example, by preparing a resin varnish obtained by dissolving a resin composition in an organic solvent, applying the resin varnish to a support using a die coater or the like, and drying the coating film of the resin varnish to some extent to form a resin composition layer Can be manufactured.

Examples of the organic solvent used for forming the resin composition layer include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, Carbitol such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, amides such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone Solvent. The organic solvents may be used alone, or two or more kinds may be used in combination.

The coating film of the resin varnish can be dried by a known method such as heating or hot air blowing. The drying conditions are not particularly limited, but are dried so that the content of the organic solvent in the resin composition is 10 mass% or less, preferably 5 mass% or less. When using a resin varnish containing an organic solvent in an amount of 30% by mass to 60% by mass, for example, the coating film of the resin varnish may be used at a temperature ranging from 50 ° C to 150 ° C for 3 minutes Followed by drying for 10 minutes, whereby a resin composition layer can be formed.

In the adhesive film, a protective film corresponding to the support may be further laminated on the side of the side of the resin composition layer which is not bonded to the support (the side opposite to the support). The thickness of the protective film is not particularly limited. The thickness of the protective film is, for example, 1 占 퐉 to 40 占 퐉. By laminating a protective film, adherence or scratching of dust or the like to the surface of the resin composition layer can be suppressed. The adhesive film can be rolled and stored. When the adhesive film has a protective film, it can be used by peeling and removing the protective film.

The minimum melt viscosity of the resin composition layer (or resin composition) in the adhesive film is preferably 1000 poise or more, more preferably 1500 poise or more, from the viewpoint of stably maintaining the thickness of the resin composition layer, , And more preferably 2,000 poises or more. The minimum melt viscosity of the resin composition layer is preferably 12000 poise or less, more preferably 10,000 poise or less, still more preferably 8000 poise or less, and particularly preferably 8000 poise or less, from the viewpoint of improving the filling property of the circuit 5000 poise or less.

The &quot; minimum melt viscosity of the resin composition layer &quot; refers to the lowest viscosity exhibited when the resin composition layer is melted. Specifically, when the resin composition layer is melted by heating at a constant heating rate, the melt viscosity decreases at the initial stage as the temperature rises. Thereafter, as the temperature rises, the melt viscosity increases with the lapse of a certain period of time. The lowest melt viscosity refers to the melt viscosity at the minimum point where the melt viscosity is the lowest. The minimum melt viscosity of the resin composition layer can be measured by a dynamic viscoelasticity method.

<Prepreg>

The insulating layer along the high frequency circuit board may be formed using a prepreg instead of the adhesive film already described. The prepreg can be formed by impregnating a sheet-like fiber substrate with a resin composition described later.

The sheet-like fibrous substrate used in the prepreg is not particularly limited. As the sheet-like fiber base material, those commonly used as prepreg substrates such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning of the high-frequency circuit board, the thickness of the sheet-like fiber base material is preferably 900 m or less, more preferably 800 m or less, further preferably 700 m or less, and still more preferably 600 m Or less. The penetration depth of the plating due to the formation of the conductor layer can be suppressed to a small value. Therefore, the thickness is preferably 30 占 퐉 or less, more preferably 20 占 퐉 or less, and further preferably 10 占 퐉 or less. The thickness of the sheet-like fibrous base material can be usually 1 占 퐉 or more, 1.5 占 퐉 or more, and 2 占 퐉 or more.

And can be produced by a known method such as prepreg, hot melt method, solvent method and the like.

The thickness of the prepreg can be the same as that of the resin composition layer in the above-mentioned adhesive film.

[High frequency circuit board]

The high-frequency circuit board of the present invention includes an insulating layer formed by a cured product of the resin composition described above for forming an insulating layer of a high-frequency circuit board.

Here, the term &quot; high frequency circuit board &quot; means a circuit board capable of operating even an electric signal of a high frequency band. Here, the &quot; high frequency band &quot; means a band of 1 GHz or more, and is particularly effective in the band of 28 GHz to 80 GHz in the present invention.

An inner layer circuit board and an insulating layer formed on the inner layer circuit board provided in the high frequency circuit board will be described.

<Inner layer circuit board>

The term &quot; inner layer circuit board &quot; means a substrate such as a core substrate, such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate and a thermosetting polyphenylene ether substrate, Refers to a substrate provided with a conductor layer (wiring layer), that is, an electric circuit patterned on a surface in a predetermined pattern, directly or indirectly.

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

In order to electrically connect the two conductor layers on both surfaces of the inner layer circuit board (and the conductor layer formed on the insulating layer) provided on the inner layer circuit board, one Or more through holes may be formed, or may have any suitable additional component such as a passive element.

&Lt; Insulating layer &

The insulating layer along the high frequency circuit board is a layer of a cured product obtained by thermally curing a resin composition described later. The insulating layer made of such a cured product can be suitably applied to an insulating layer particularly for a high-frequency circuit board.

In the high frequency circuit board, the insulating layer may be formed only on one layer, or two or more layers may be formed on the insulating layer. When two or more insulating layers are formed, a buildup layer in which a conductor layer (wiring) and an insulating layer are alternately laminated can be formed.

The thickness of the insulating layer along the high frequency circuit board is usually 20 to 200 占 퐉 and preferably 50 to 150 占 퐉 in view of improvement of electrical characteristics and reduction of the frequency of the high frequency circuit board.

The insulating layer may be formed of at least one via hole for electrically connecting the conductor layer provided in the inner layer circuit board and the conductor layer formed in the insulating layer or for electrically connecting the conductor layers formed in the two or more insulating layers May be provided.

It is preferable that the dielectric constant of the insulating layer is lower. The dielectric constant is preferably 3.0 or less, more preferably 2.9 or less, and even more preferably 2.8 or less from the viewpoint of reducing the transmission loss of the high-frequency electric signal. The lower limit of the permittivity is not particularly limited, but is usually 1 or more.

The insulating layer preferably exhibits a lower dielectric loss tangent. The dielectric loss tangent is preferably 0.0049 or less, more preferably 0.0048 or less, and even more preferably 0.0047 or less from the viewpoints of prevention of generation of heat during transmission of a high-frequency signal, reduction of signal delay, and reduction of signal noise. The lower limit of the dielectric tangent is not particularly limited, but is usually 0.0001 or more.

The dielectric tangent and dielectric constant can be measured according to the method described in &quot; Measurement and evaluation of dielectric constant and dielectric tangent &quot;

The insulating layer with respect to the high frequency circuit board shows good adhesion to the conductor layer, that is, excellent peel strength to the conductor layer. The fill strength of the conductor layer is preferably 0.4 kgf / cm or more, more preferably 0.5 kgf / cm or more, and further preferably 0.6 kgf / cm or more. The upper limit value of the peel strength with respect to the conductor layer is not particularly limited, but is usually 2 kgf / cm or less. The evaluation of the peel strength with respect to the conductor layer can be carried out according to the method described in &quot; Measurement and Evaluation of Peel Strength &quot;

[Manufacturing method of high frequency circuit board]

Next, a method for manufacturing a high-frequency circuit board will be described.

The high-frequency circuit board can be manufactured by a manufacturing method including the following steps (I) and (II) using the adhesive film already described.

Process (I) A step of laminating an adhesive film on the inner layer circuit board and bonding the resin composition layer of the adhesive film to the inner layer circuit board

Process (II) Step of thermally curing the resin composition layer to form an insulating layer

The lamination of the adhesive film to the inner layer circuit board can be performed, for example, by a heat pressing process in which the adhesive film is heated while being pressed against the inner layer circuit board from the support side. Examples of members (also referred to as &quot; hot pressing members &quot;) for a hot pressing process include a heated metal plate (SUS hard plate) or a metal roll (SUS roll). It is also preferable to press the heat resistant compression member through an elastic material such as heat resistant rubber such that the heat resistant compression member does not press directly on the support of the adhesive film and presses the adhesive film sufficiently to the unevenness of the main surface of the inner layer circuit board .

The lamination of the inner layer circuit board and the adhesive film can be carried out by a vacuum lamination method. In the vacuum laminating method, the temperature of hot pressing is preferably in the range of 60 占 폚 to 160 占 폚, and more preferably in the range of 80 占 폚 to 140 占 폚. The pressure of the hot pressing is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the time of the hot pressing is preferably in the range of 20 seconds to 400 seconds, Preferably from 30 seconds to 300 seconds. The lamination is preferably performed under a reduced pressure of 26.7 hPa or less.

The lamination can be performed by a commercially available vacuum laminator. As a commercially available vacuum laminator, there can be mentioned, for example, a vacuum pressurized laminator manufactured by Meikishesakusho Co., Ltd., and a baking applicator manufactured by Nikko Materials Co., Ltd.

After lamination, the laminated resin composition layer may be subjected to a smoothing treatment by further pressing under atmospheric pressure (at atmospheric pressure), for example, from the support side with a hot press member. The pressing condition of the smoothing process may be the same as the condition of the hot pressing of the laminate. The smoothing process can be performed by a commercially available laminator. The lamination and smoothing process may be performed continuously using the commercially available vacuum laminator.

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

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

The conditions of the thermosetting of the resin composition layer are not particularly limited, and conditions that are generally adopted when forming the insulating layer of the high-frequency circuit board can be employed.

The thermosetting condition of the resin composition layer is set, for example, by setting the curing temperature in the range of 120 캜 to 240 캜 (preferably in the range of 150 캜 to 220 캜, more preferably in the range of 170 캜 to 200 캜) The curing time may be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

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

In manufacturing the high-frequency circuit board, either the step of (III) piercing the insulating layer, (IV) the step of roughening the insulating layer, or the step of forming the conductor layer (V) may be further performed. These steps (III) to (V) can be carried out according to various methods known to those skilled in the art, which are used for manufacturing a high-frequency circuit board. When the support is removed after the step (II), the removal of the support is carried out between the step (II) and the step (III), between the step (III) and the step (IV) (V).

In another embodiment, the insulating layer according to the high-frequency circuit board 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 basically be carried out by the same process as in the case of using an adhesive film.

The step (III) is a step of perforating the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. The step (III) can be carried out using, for example, a drill, a laser, a plasma or the like depending on the composition of the resin composition used for forming the insulating layer. The dimensions and shape of the holes can be appropriately determined according to the design of the high-frequency circuit board.

Step (IV) is a step of roughening the insulating layer. The procedure and condition of the roughening treatment are not particularly limited, and known procedures and conditions commonly used in forming the insulating layer of the high-frequency circuit board can be adopted. For example, the swelling treatment by the swelling liquid, the coarsening treatment by the oxidizing agent, and the neutralization treatment by the neutralizing liquid can be performed in this order to roughen the insulating layer. The swelling liquid is not particularly limited. The swelling liquid includes, for example, an alkali solution and a surfactant solution. The swelling liquid is preferably an alkali solution, and as the alkali solution, a sodium hydroxide solution or a potassium hydroxide solution is more preferable. Examples of commercially available swelling solutions include Swelling Deep Securigans P and Swelling Deep Securigans SBU manufactured by Atotech Japan Co., Ltd. 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 solution at 30 占 폚 to 90 占 폚 for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in the swelling liquid at 40 占 폚 to 80 占 폚 for 5 minutes to 15 minutes. The oxidizing agent is not particularly limited. As the oxidizing agent, for example, an alkali permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be mentioned. The roughening treatment with 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 at 60 캜 to 80 캜 for 10 minutes to 30 minutes. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd., and "Dozing Solution Securigans P". As the neutralizing solution, an acidic aqueous solution is preferable. As a commercially available product of the neutralization liquid, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd. may be mentioned. The treatment with the neutralizing liquid can be carried out by immersing the treated surface of the insulating layer subjected to the roughening treatment with an oxidizing agent in a neutralizing solution at 30 ° C to 80 ° C for 5 minutes to 30 minutes. It is preferable to immerse the insulating layer subjected to the roughening treatment with an oxidizing agent in a neutralizing solution at 40 占 폚 to 70 占 폚 for 5 minutes to 20 minutes in terms of workability and the like.

In one embodiment, the arithmetic average 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, further preferably 200 nm or less, 140 nm or less, 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, more preferably 1 nm or more. The arithmetic average roughness (Ra) of the surface of the insulating layer can be measured using a non-contact surface roughness meter. A specific example of the non-contact surface roughness meter is "WYKO NT3300" manufactured by Vico Instruments.

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

The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium do. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include alloys of two or more metals selected from the above-mentioned group (for example, nickel-chromium alloy, copper-nickel alloy and copper- ). &Lt; / RTI &gt; Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper or a nickel-chromium alloy, copper-nickel Alloy or a copper-titanium alloy layer is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy is more preferable, A metal layer is more preferable.

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

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

In one embodiment, the conductor layer can be formed by directly patterning the metal foil used as the support of the adhesive film, or by plating. As a forming method by plating, it is possible to form a conductor layer having a desired wiring pattern by plating on the surface of the insulating layer by a conventionally known method such as a semi-insulating method or a pulling method. Hereinafter, an example in which the conductor layer is formed by the semi-specific method will be described.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Subsequently, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer so as to correspond to the desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

When the high-frequency circuit board has two or more insulating layers and wiring layers (build-up layers), it is possible to function as a high-frequency circuit by repeating the above-described step of forming the insulating layer and the step of forming the conductor layer A high-frequency circuit board having a multilayer interconnection structure can be manufactured.

[Semiconductor device]

The semiconductor device includes the high-frequency circuit board already described. In other words, the semiconductor device of the present invention can be manufactured by using the high frequency circuit board of the present invention.

Examples of the semiconductor device include various semiconductor devices provided in electric products (e.g., a computer, a mobile phone, a digital camera and a TV) and a vehicle (e.g., a motorcycle, an automobile, a tanker, .

The semiconductor device can be manufactured by mounting a component (semiconductor chip) in a conductive portion of the high-frequency circuit board. The &quot; conduction point &quot; is a position where the electric signal can be transmitted from the high-frequency circuit board, and the position may be the surface of the high-frequency circuit board or the portion embedded in the thickness of the high- The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor material.

The method of mounting the semiconductor chip in manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip effectively functions. As a mounting method of the semiconductor chip, specifically, a wire bonding method, a flip chip mounting method, a mounting method using a bumpless buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF) As shown in Fig. Here, the "mounting method using the bumpless buildup layer (BBUL)" means "a mounting method in which a semiconductor chip is directly buried in a high-frequency circuit board to connect the semiconductor chip and the wiring of the high-frequency circuit board".

[Example]

Hereinafter, the present invention will be described concretely with reference to examples, but the present invention is not limited to these examples. In the following description, &quot; part &quot; and &quot;% &quot; mean &quot; part by mass &quot; and &quot;% by mass &quot;, respectively, unless otherwise specified.

&Lt; Example 1 >

20 parts of biquilene-type epoxy resin ("YX4000HK" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent: 185) was dissolved by heating in 20 parts of solvent naphtha with stirring, and then cooled to room temperature. , 60 parts of an inorganic filler ("SO-C2" manufactured by Adomex Co., Ltd., average particle diameter of 0.5 μm, carbon content per unit surface area of 0.38 mg / m 2), 60 parts of PTFE particles ("Lubron L-2" manufactured by Daikin Industries, , Average particle diameter: 3 占 퐉) were mixed and kneaded with three rolls and dispersed. Thereafter, 46.1 parts of an active ester type curing agent ("HPC-8000-65T" manufactured by DIC Co., a toluene solution of a nonvolatile component having an active equivalent of about 223) of 46.1 parts, a compound (vinyl compound) having a cyclic ether structure 10 parts of "A-DOG" manufactured by Shin Nakamura Kagakuko Co., Ltd.), 2 parts of a 5% MEK solution of 4-dimethylaminopyridine (DMAP) as a curing accelerator and 0.1 parts of dicumyl peroxide Were mixed and uniformly dispersed with a rotary mixer to prepare resin varnish 1.

&Lt; Example 2 >

("SO-C2" manufactured by Adomex Co., Ltd., average particle diameter 0.5 mu m, carbon content 0.38 (weight per unit surface area)), 30 parts of bicyclopenol epoxy resin ("YX4000HK" manufactured by Mitsubishi Kagaku Co., ("Lubron L-2" manufactured by Daikin Industries, Ltd., average particle diameter: 3 μm) was changed to 21 parts, and an active ester type curing agent ("HPC -8000-65T &quot;, a toluene solution of 65% of a nonvolatile component having an active equivalent weight of about 223) was changed to 61.5 parts. Resin varnish 2 was prepared in the same manner as in Example 1 except for the above.

&Lt; Example 3 >

Inorganic filler (&quot; SO-C2 &quot; manufactured by Adomex, Inc., average particle diameter 0.5 (Carbon content per unit surface area of 0.38 mg / m 2) was changed to 80 parts, and 20 parts of PTFE particles ("Lubron L-2" manufactured by Daikin Industries, Ltd., average particle diameter 3 μm) were changed. Resin varnish 3 was prepared in the same manner as in Example 1 except for the above.

<Example 4>

, And 80 parts of an inorganic filler ("SO-C2" manufactured by Adomex Co., Ltd., average particle diameter 0.5 μm, carbon amount per unit surface area 0.38 mg / m 2) was changed to 80 parts, and PTFE particles ("Rubron L-2 &quot;, average particle diameter 3 mu m) was changed to 60 parts. Resin varnish 4 was prepared in the same manner as in Example 1 except for the above.

&Lt; Comparative Example 1 &

("SO-C2" manufactured by Adomex Co., Ltd., average particle diameter 0.5 mu m, carbon of unit surface area (weight per unit surface area), and the like) was changed to 30 parts, (Lubron L-2 manufactured by Daikin Industries, Ltd., average particle diameter: 3 mu m) was changed to 20 parts, and an active ester type curing agent (manufactured by DIC Corporation) &Quot; HPC-8000-65T &quot;, a toluene solution of 65% of a nonvolatile component having an active equivalent of about 223) was changed to 61.5 parts. Resin varnish 5 was prepared in the same manner as in Example 1 except for the above.

&Lt; Comparative Example 2 &

, 15 parts of an inorganic filler (&quot; SO-C2 &quot; manufactured by Adomex Co., Ltd., average particle diameter of 0.5 mu m, carbon content per unit surface area of 0.38 mg / L-2 &quot;, average particle diameter: 3 mu m) was changed to 50 parts. Resin varnish 6 was prepared in the same manner as in Example 1 except for the above.

&Lt; Comparative Example 3 &

, And 20 parts of an inorganic filler ("SO-C2" manufactured by Adomex Co., Ltd., average particle diameter 0.5 μm, carbon amount per unit surface area 0.38 mg / m 2) was changed to 20 parts, and PTFE particles ("Rubron L-2 &quot;, average particle diameter 3 mu m) was changed to 5 parts. Resin varnish 7 was prepared in the same manner as in Example 1 except for the above.

&Lt; Comparative Example 4 &

, 35 parts of an inorganic filler ("SO-C2" manufactured by Adomex Co., Ltd., average particle diameter of 0.5 μm, carbon content per unit surface area of 0.38 mg / m 2) was changed to 35 parts, and PTFE particles (Lubron L-2 &quot;, average particle diameter 3 mu m) was changed to 80 parts. Resin varnish 8 was prepared in the same manner as in Example 1 except for the above.

&Lt; Comparative Example 5 &

An active ester type curing agent ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution of a nonvolatile component having an active equivalent weight of about 223 of 65%) was mixed with a naphthol type curing agent (phenolic hydroxyl equivalent 215, SN-485 &quot;, manufactured by Kagaku Co., Ltd .; MEK solution of non-volatile component 50%) was changed to 40 parts. Resin varnish 9 was prepared in the same manner as in Example 1 except for the above.

&Lt; Comparative Example 6 >

(Phenolic hydroxyl equivalent 215, SN-485 manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., MEK solution of 50% non-volatile component) having a novolak structure was changed to 20 parts. Resin varnish 10 was prepared in the same manner as in Comparative Example 5 except for the above.

[Assessment Methods]

Using the resin compositions obtained in the above-mentioned Examples and Comparative Examples, a cured film obtained by curing the resin composition layer as described below was prepared and evaluated by the following method.

&Lt; Production of Cured Carrier Film (Evaluation Sample)

Each of the resin varnishes 1 to 10 obtained in Examples and Comparative Examples was applied to one main surface of a release-treated PET film (&quot; PET501010 &quot;, manufactured by LINTEC CO., LTD.) So that the thickness of the resin composition layer after drying was 40 [ Uniformly coated with a coater, and dried at 80 캜 to 110 캜 (average 95 캜) for 6 minutes. Thereafter, the substrate was heat-treated at 200 DEG C for 90 minutes, and the support was peeled and removed to obtain a cured film. The obtained cured film was cut into a rectangular shape having a length of 80 mm and a width of 2 mm to prepare a sample for evaluation.

&Lt; Measurement and evaluation of dielectric constant and dielectric tangent &

Using the "HP8362B" manufactured by Agilent Technologies, the dielectric constant and dielectric loss tangent were measured by the cavity resonance perturbation method under the conditions of a measurement frequency of 10 GHz and a measurement temperature of 25 ° C. .

The case where the dielectric constant was 3.0 or less was evaluated as &quot; good &quot;, and the case where the dielectric constant was 3.0 or more was evaluated as &quot; defective &quot;. The case where the value of dielectric loss tangent was 0.005 or less was evaluated as &quot; good &quot;, and the case of exceeding 0.005 was evaluated as &quot; defective &quot;.

&Lt; Measurement and Evaluation of Adhesion (Peel Strength) to Conductor Layer >

(1) Harmonization of inner layer circuit board

Both surfaces of a glass cloth-based epoxy resin double-sided copper-clad laminate (thickness of copper foil of 18 탆, thickness of substrate: 0.4 mm, "R1515A" manufactured by Panasonic Corporation) which is an inner layer circuit board were immersed in "CZ8101" , And the surface of copper foil was roughened by etching the copper foil on both sides in the thickness direction by 1 mu m.

(2) Lamination of copper foil with resin composition layer

Each of the resin varnishes 1 to 10 prepared in the examples and comparative examples was uniformly applied on one surface of a "MT18Ex" foil manufactured by Mitsui Kinzoku Kogyo Co., Ltd. with a die coater so that the thickness of the resin composition layer after drying became 40 μm And dried at 80 ° C to 110 ° C (average 95 ° C) for 6 minutes to prepare a copper foil with a resin composition layer. The copper foil with the resin composition layer was laminated on both surfaces of the inner-layer circuit board (copper foil) so that the resin composition layer was bonded to the inner-layer circuit board (copper foil) using a batch type vacuum pressure laminator (MVLP- Lt; / RTI &gt; The lamination treatment was carried out by reducing the pressure for 30 seconds to bring the air pressure to 13 hPa or lower, followed by pressing at 100 deg. C and a pressure of 0.74 Mpa for 30 seconds.

(3) Curing treatment of copper foil with resin composition layer

The resin composition layer of the laminated copper foil with the laminated resin composition layer was cured at 200 캜 for 90 minutes to form a cured product to form a laminate in which the copper foil-adhered cured product was laminated on the inner-layer circuit board.

(4) Formation of conductor layer (electroplating)

The copper foil was peeled off from the copper foil-adhered cured product obtained in the above (3), and then copper sulfate electroplating was performed on the surface of the exposed cured product so as to have a thickness of 25 탆 to form a conductor layer as a copper layer. Next, the multilayer body having the conductor layer formed thereon was annealed at 180 캜 for 30 minutes to obtain a circuit board for evaluation.

(5) Measurement and evaluation of peel strength of conductor layer

Using the above evaluation circuit board, the peel strength (peel strength) of the conductor layer was measured.

A rectangular incision of 10 mm in width and 100 mm in length was placed on the circuit board for evaluation and one end in the longitudinal direction was peeled off and picked up with a holding tool (AC-50C-SL, automobile type tester) (Kgf / cm (N / cm)) when 35 mm was peeled off in the vertical direction at a speed of 50 mm / min.

Here, the case where the measured load exceeded 0.3 kgf / cm was evaluated as &quot; good &quot;, and the case where the measured load was 0.3 kgf / cm or less was evaluated as &quot;

<Result>

The evaluation results are shown in Table 1 below.

[Table 1]

As apparent from Table 1, the resin compositions of Examples 1 to 4 can effectively reduce the dielectric constant of the cured product by adjusting the contents of the component (C) and the component (D) as described above, It is possible to achieve both of the reduction of the dielectric constant which has been regarded as extremely difficult and the improvement of the adhesiveness (fill strength) to the conductor layer, as well as to reduce the dielectric loss tangent.

In Comparative Example 1 in which the content ratio of the component (D) to the total amount of the component (C) and the component (D) was low, the dielectric constant of the cured product was high and the component (C) D) was too high, the adhesiveness of the cured body to the conductor layer was lowered in Comparative Example 2. Therefore, it can be seen that the dielectric constant of the cured product and the adhesiveness to the conductive layer of the cured product can be made compatible by appropriately adjusting the ratio of the content of the component (D) to the total amount of the component (C) there was.

In Comparative Example 3 in which the content of the component (D) was smaller than the predetermined range, the dielectric constant of the cured product was high and in Comparative Example 4 in which the content of the component (D) was larger than the predetermined range, the adhesiveness It was low. Therefore, it was found that by adjusting the content of the component (D) to a predetermined range, the dielectric constant of the cured product and the adhesiveness to the conductive layer of the cured product can be both satisfied.

In Comparative Examples 5 and 6 which did not contain the component (B), the dielectric tangent of the cured product was high.

Claims (10)

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