JP2018141053A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of giving an insulating layer achieving both a reduction in dielectric constant and an improvement in adhesion to a conductor layer.SOLUTION: The resin composition contains 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-based filler. When a nonvolatile component in the resin composition is 100 mass%, the content of the component (D) is 10-40 mass%. When the total content of the component (C) and the component (D) is 100 mass%, the component (D) is 20-70 mass%.SELECTED DRAWING: None

Description

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

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

Japanese Patent Laid-Open No. 2006-166347

  However, since the resin composition disclosed in Patent Document 1 contains a large amount of fluororesin filler of 50% by mass to 85% by mass, the adhesion to the inner circuit board is sacrificed, and the high frequency circuit board and It is difficult to apply to a multilayer wiring board.

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

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

That is, the present invention provides the following [1] to [10].
[1] A resin composition comprising component (A) epoxy resin, component (B) active ester compound, component (C) inorganic filler, and component (D) fluorine-based filler,
When the nonvolatile component in the resin composition is 100% by mass, the content of the component (D) is 10% by mass to 40% by mass,
The resin composition whose said component (D) is 20 mass%-70 mass% when the sum total of content of the said component (C) and the said component (D) is 100 mass%.
[2] The resin composition according to [1], wherein the component (D) is fluoropolymer particles.
[3] The resin composition according to [2], wherein the fluorine-based polymer particles are polytetrafluoroethylene (PTFE) particles.
[4] The resin composition according to any one of [1] to [3], further including a component (E) a compound having an unsaturated hydrocarbon group.
[5] The component (E) is a compound having one or more unsaturated hydrocarbon groups selected from the group consisting of an acryl group, a methacryl group, a styryl group, an allyl group, a vinyl group, and a propenyl group. ] The resin composition as described in.
[6] The resin composition according to [5], wherein the component (E) is a compound having a vinyl group and a cyclic ether structure having a 5-membered ring or more.
[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] provided on the support.
[9] A high-frequency circuit board including 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 board according to [9].

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can obtain the insulating layer which is low in a dielectric characteristic, especially a dielectric constant and a dielectric loss tangent, and is excellent in the adhesiveness with respect to an inner-layer circuit board, especially a conductor layer can be provided.

  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 containing component (A) epoxy resin, component (B) active ester compound, component (C) inorganic filler, and component (D) fluorine-based filler, When the non-volatile component of 100% by mass is used, 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% by mass. In a case, a component (D) is 20 mass%-70 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 a component (A) epoxy resin. Examples of the epoxy resin include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak Type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, complex Wherein the epoxy resin, spiro ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  The component (A) is preferably an aromatic skeleton-containing epoxy resin from the viewpoint of reducing the average linear thermal expansion coefficient. The bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, naphthalene-type epoxy resin, biphenyl-type epoxy resin, and di More preferably, it is at least one selected from cyclopentadiene type epoxy resins, and biphenyl type epoxy resins are more preferable. The aromatic skeleton is a chemical structure generally defined as aromatic, and includes polycyclic aromatics and aromatic heterocycles.

  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, at least 50% by mass is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, it is preferable to contain an epoxy resin having three or more epoxy groups in one molecule and solid at 20 ° C. (referred to as “solid epoxy resin”). The epoxy resin may contain only a solid epoxy resin, and has two or more epoxy groups in one molecule, and is liquid at 20 ° C. (referred to as “liquid epoxy resin”) and solid. And an epoxy resin. By using a liquid epoxy resin and a solid epoxy resin in combination as an epoxy resin, a resin composition having excellent flexibility can be obtained. Moreover, the breaking strength of the cured product of the resin composition is also improved.

  Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, and ester skeletons. Preferred are cycloaliphatic epoxy resins, cyclohexanedimethanol type epoxy resins, glycidylamine type epoxy resins, and epoxy resins having a butadiene structure. Glycidylamine type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, 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” manufactured by Mitsubishi Chemical Corporation. “Epicoat 828EL” (bisphenol A type epoxy resin), “jER807”, “1750” (bisphenol F type epoxy resin), “jER152” (phenol novolac type epoxy resin), “630”, “630LSD” (glycidylamine type epoxy) Resin), “ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin), “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, "Ceroki" manufactured by Daicel Corporation Id 2021P "(alicyclic epoxy resin having an ester skeleton)," PB-3600 "(epoxy resin having a butadiene structure)," ZX1658 "," ZX1658GS "(liquid 1,4-) manufactured by Nippon Steel Chemical Co., Ltd. Glycidylcyclohexane). These may be used alone or in combination of two or more.

  Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and 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” manufactured by DIC Corporation. (Cresol novolac type epoxy resin), “N-695” (cresol novolac type epoxy resin), “HP-7200” (dicyclopentadiene type epoxy resin), “HP-7200HH”, “HP-7200H”, “EXA-” 7311 "," EXA-7311-G3 "," EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(naphthylene ether type epoxy resin)," EPPN-502H "manufactured by Nippon Kayaku Co., Ltd. "(Trisphenol type epoxy resin)", "NC7000L" (Naphthol novolak type epoxy) ), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ESN475V” (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “ESN485” (naphthol novolak type) Epoxy resin), “YX4000H”, “YX4000”, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), “YX8800” (anthracene type epoxy resin), manufactured by Mitsubishi Chemical Corporation “PG-100”, “CG-500” manufactured by Gas Chemical Co., Ltd., “YL7760” (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “YL7800” (fluorene type epoxy resin), Mitsubishi Chemical Co., Ltd. "JER1010" (solid screw Phenol A type epoxy resin), "jER1031S" (tetraphenyl ethane epoxy resin) and the like. These may be used alone or in combination of two or more.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1:15 in terms of mass ratio. preferable. By making the quantitative ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) the adhesiveness can be made suitable when used in the form of an adhesive film, and ii) the adhesive film is used in the form of an adhesive film. In some cases, sufficient flexibility can be obtained, handling properties can be improved, and iii) an effect that a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii) above, the quantitative ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is 1: 0.5 to 1:10 by mass ratio. A range is more preferable, and a range of 1: 1 to 1: 8 is even more preferable.

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

  The epoxy equivalent of an epoxy resin becomes like this. Preferably it is 50-5000, More preferably, it is 50-3000, More preferably, it is 80-2000, More preferably, it is 110-1000. By setting it as this range, the crosslinked density of hardened | cured material is enough and it can be set as an insulating layer with small surface roughness. The epoxy equivalent is the mass of a resin containing 1 equivalent of an epoxy group, and can be measured according to JIS K7236.

  The weight average molecular weight of an epoxy resin becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. 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>
The component (B) active ester compound is a compound having one or more active ester groups in one molecule. Usually, the active ester compound can function as a curing agent that reacts with the component (A) epoxy resin already described to cure the resin composition. By using the component (B) active ester compound, the dielectric loss tangent of the cured product of the resin composition can be lowered, and more usually, an insulating layer having a small surface roughness can be obtained.

  The component (B) active ester compound preferably has two or more active ester groups in one molecule. Examples of such active ester compounds include two ester groups having high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. The compound which has the above is mentioned. Moreover, a component (B) active ester compound may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  From the viewpoint of improving heat resistance, the active ester compound (B) is more preferably an active ester compound obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. . Among these, an active ester compound obtained by reacting a carboxylic acid compound with one or more selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound is more preferable. Furthermore, an aromatic compound having two or more active ester groups in one molecule obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group is more preferable. Among them, an aromatic compound obtained by reacting a carboxylic acid compound having at least two or more carboxy groups in one molecule with an aromatic compound having a phenolic hydroxyl group, wherein two or more in one molecule An aromatic compound having an active ester group is particularly preferred. Further, the component (B) active ester compound may be linear or branched. Furthermore, if the carboxylic acid compound having two or more carboxy groups in one molecule is a compound containing an aliphatic chain, the compatibility with the resin composition can be enhanced, and any compound having an aromatic ring can be used. Heat resistance can be increased.

  Examples of the carboxylic acid compound include an aliphatic carboxylic acid having 1 to 20 carbon atoms (preferably 2 to 10 and more preferably 2 to 8) and an aromatic having 7 to 20 carbon atoms (preferably 7 to 10). Carboxylic acid is mentioned. 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 these, 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. Moreover, a carboxylic acid compound may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  Examples of the thiocarboxylic acid compound include thioacetic acid and thiobenzoic acid. Moreover, a thiocarboxylic acid compound may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  Examples of the phenol compound include phenol compounds having 6 to 40 carbon atoms (preferably 6 to 30, more preferably 6 to 23, and still more preferably 6 to 22). Preferable specific examples of the phenol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Examples include cresol, p-cresol, catechol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, and dicyclopentadiene type diphenol. Here, “dicyclopentadiene type diphenol” refers to a phenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene. As the phenol compound, a phenol novolak or a phosphorus atom-containing oligomer having a phenolic hydroxyl group described in JP2013-40270A may be used. Moreover, a phenol compound may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.

  Examples of the naphthol compound include naphthol compounds having 10 to 40 carbon atoms (preferably 10 to 30, more preferably 10 to 20). Preferable specific examples of the naphthol compound include α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene. A naphthol novolak may also be used as the naphthol compound. Moreover, a naphthol compound may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  Among them, from the viewpoint of improving heat resistance and solubility, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5 -Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene diphenol, phenol novolac, phosphorus with phenolic hydroxyl group Atom-containing oligomers are preferred. Further, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol, phenol More preferred are novolak and phosphorus atom-containing oligomers having a phenolic hydroxyl group. Among them, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene type diphenol, phenol novolak, phenolic hydroxyl group A phosphorus atom-containing oligomer is more preferable. Furthermore, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene type diphenol, phenol novolac, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are even more preferable. Among them, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene type diphenol, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are particularly preferable. Furthermore, dicyclopentadiene type diphenol is particularly preferable.

  Examples of the thiol compound include benzenedithiol and triazinedithiol. Moreover, a thiol compound may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  Preferable specific examples of the active ester compound include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoylated product of phenol novolac. Examples include active ester compounds, active ester compounds obtained by reacting aromatic carboxylic acids with phosphorus atom-containing oligomers having phenolic hydroxyl groups. Among these, an active ester compound having a dicyclopentadiene type diphenol structure, an active ester compound having a naphthalene structure, and an active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferable. . Here, the “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

  As a particularly preferable specific example of the active ester compound containing a dicyclopentadiene type diphenol structure, a compound represented by the following formula may be mentioned.

  In said formula, R represents a phenyl group or a naphthyl group each independently. Among these, R is preferably a naphthyl group from the viewpoint of reducing the dielectric loss tangent and improving the heat resistance.

In the above formula, k represents 0 or 1. Among these, k is preferably 0 from the viewpoint of reducing the dielectric loss tangent and improving the heat resistance.
In the above formula, n is the average number of repeating units and is 0.05 to 2.5. Especially, it is preferable that n is 0.25-1.5 from a viewpoint of reducing a dielectric loss tangent and improving heat resistance.

  As the component (B) active ester compound, an active ester compound disclosed in JP-A No. 2004-277460 or JP-A No. 2013-40270 may be used. Moreover, as a component (B) active ester compound, you may use a commercially available active ester compound. Examples of commercially available active ester compounds include “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T”, “HPC-8000L-65M” (dicyclopentadiene type diphenol structure manufactured by DIC). Active ester compound containing DIC; “EXB9416-70BK” manufactured by DIC (active ester compound including naphthalene structure); “DC808” manufactured by Mitsubishi Chemical Corporation (active ester compound including acetylated phenol novolac); “YLH1026 manufactured by Mitsubishi Chemical Corporation” "(Active ester compound containing a benzoylated product of phenol novolac)"; "EXB9050L-62M" (phosphorus atom-containing active ester compound) manufactured by DIC.

  The active group equivalent of the component (B) active ester compound is preferably 120 to 500, more preferably 150 to 400, and particularly preferably 180 to 300. When the active group equivalent of the component (B) active ester compound is in the above-described range, the crosslinked density of the cured product of the resin composition becomes sufficient, and an insulating layer having a small surface roughness can be obtained. Here, an active group equivalent shows the mass of resin containing 1 equivalent of active groups.

  Moreover, an active ester compound may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  The content of the component (B) active ester compound in the resin composition is preferably 1% by mass or more and more preferably 5% by mass or more with respect to 100% by mass of the nonvolatile component in the resin composition. It is more preferably 10% by mass or more, particularly preferably 15% by mass or more, more preferably 40% by mass or less, more preferably 35% by mass or less, and 30% by mass or less. More preferably. When the content of the component (B) active ester compound is equal to or higher than the lower limit of the above range, the adhesion between the conductor layer and the insulating layer can be particularly enhanced, and when it is equal to or lower than the upper limit of the above range, the heat resistance is increased. Can be improved, and the occurrence of smear can be suppressed.

  When the number of epoxy groups of component (A) epoxy resin is 1, from the viewpoint of obtaining an insulating layer with good mechanical strength, the number of active groups of component (B) active ester compound is preferably 0.1 or more, more Preferably it is 0.2 or more, more preferably 0.3 or more, particularly preferably 0.4 or more, preferably 2 or less, more preferably 1.5 or less, and even more preferably 1 or less. is there. Here, the “number of epoxy groups of the epoxy resin” is a value obtained by dividing the value obtained by dividing the amount of nonvolatile components of the epoxy resin present in the resin composition by the epoxy equivalent for all epoxy resins. Further, “active group” means a functional group capable of reacting with an epoxy group, and “the number of active groups of the active ester compound” means the amount of non-volatile components of the active ester compound present in the resin composition. This is the total value of all values divided by the active group equivalent.

<Component (C) Inorganic filler>
The resin composition contains a component (C) inorganic filler. The material of the inorganic filler is not particularly limited. Examples of the inorganic filler material include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, Magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide , Barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly preferred. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

  The average particle size of the inorganic filler is preferably 5 μm or less, more preferably 2.5 μm or less, and even more preferably from the viewpoint of improving the embedding property of the conductor layer and obtaining an insulating layer having a low surface roughness. It is 2 μm or less, and more preferably 1.5 μm or less. The average particle diameter is preferably 0.01 μm or more, more preferably 0.05 μm or more, and further preferably 0.1 μm or more, 0.5 μm or more, or 1 μm or more. Examples of commercially available inorganic fillers having such an average particle size include, for example, “SP60-05”, “SP507-05” manufactured by Nippon Steel & Sumikin Materials Co., Ltd., “YC100C” manufactured by Admatechs Corporation, “ “YA050C”, “YA050C-MJE”, “YA010C”, “UFP-30” manufactured by Denka Corporation, “Sylfil NSS-3N”, “Sylfil NSS-4N”, “Sylfil NSS-5N” manufactured by Tokuyama Corporation, Examples include “SC2500SQ”, “SO-C4”, “SO-C2”, and “SO-C1” manufactured by Admatechs Corporation.

  The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As a 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 particle size distribution measuring apparatus, “LA-500” manufactured by Horiba, Ltd. or the like can be used.

  Inorganic fillers are aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, alkoxysilane compounds, organosilazane compounds, titanate coupling agents, etc., from the viewpoint of improving moisture resistance and dispersibility. It is preferable to treat with one or more surface treatment agents. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM803” (3-mercaptopropyltrimethoxy manufactured by Shin-Etsu Chemical Co., Ltd.). Silane), Shin-Etsu Chemical "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical "SZ-31" (hexamethyldisilazane) manufactured by Co., Ltd., "KBM-103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long chain) Epoxy type silane coupling agent).

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably at 0.02 mg / ^{m 2} or more, more preferably 0.1 mg / ^{m 2} or more, More preferably, it is 0.2 mg / m ² or more. On the other hand, from the viewpoint of preventing the melt viscosity of the resin varnish and the melt viscosity when the resin varnish is in sheet form, the amount of carbon per unit surface area of the inorganic filler is preferably 1 mg / m ² or less, It is more preferably 0.8 mg / m ² or less, and further 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 the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. Next, after removing the supernatant and drying the non-volatile components, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by Horiba, Ltd. can be used.

  The content of the inorganic filler in the resin composition is preferably 10% by mass or more when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer having a low coefficient of thermal expansion. Preferably it is 15 mass% or more, More preferably, it is 20 mass% or more. The content of the inorganic filler in the resin composition is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably, from the viewpoint of improving the mechanical strength of the insulating layer, particularly the elongation. It is 50 mass% or less.

<Component (D) Fluorine-based filler>
The resin composition contains component (D) a fluorine-based filler. Here, “fluorine-based” means containing a fluorine atom. The “fluorine-based filler” refers to a filler containing a compound containing a fluorine atom as a material. Component (D) is in the form of particles, and the particle size is not particularly limited. The average particle size of the component (D) is excellent in dispersibility in the resin composition, is preferably 5 μm or less, more preferably 4 μm or less, and further preferably 3 μm or less. The average particle diameter of the component (D) is preferably 0.05 μm or more, more preferably 0.08 μm or more, and further preferably 0.10 μm or more. Therefore, the component (D) preferably has an average particle size of 0.05 μm to 5 μm, more preferably 0.08 μm to 4 μm, and even more preferably 0.10 μm to 3 μm.

  As a component (D), the particle | grains containing the material chosen from a fluororesin and fluororubber are mentioned, for example.

  Component (D) is preferably fluorine-based polymer particles containing a fluororesin 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), and tetrafluoroethylene-perfluorodioxide. Sole copolymer (TFE / PDD), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polyvinyl fluoride (PVF). These resins may be used alone or in combination of two or more.

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

  The weight average molecular weight of PTFE is preferably 5000000 or less, more preferably 4000000 or less, and still more preferably 3000000 or less.

  Commercial products may be used as the fluorine-based polymer particles. Specific examples of PTFE particles, which are commercially available fluoropolymer particles, include “Lublon L-2” manufactured by Daikin Industries, Ltd., “Lublon L-5” manufactured by Daikin Industries, Ltd., and “Lublon manufactured by Daikin Industries, Ltd.” L-5F ", Asahi Glass Co., Ltd." FluonPTFE L-170JE ", Asahi Glass Co., Ltd." FluonPTFEEL-172JE ", Asahi Glass Co., Ltd." FluonPTFE L-173JE ", Kitamura" KTL-500F " "KTL-2N" manufactured by Kitamura Co., Ltd., "KTL-1N" manufactured by Kitamura Co., Ltd., and "TLP10F-1" manufactured by Mitsui DuPont Fluorochemical Co., Ltd.

  Component (D) may contain, for example, surface-treated particles. Examples of the surface treatment include surface treatment with a surface treatment agent. The surface treatment agent is not particularly limited. In addition to surfactants such as nonionic surfactants, amphoteric surfactants, cationic surfactants and anionic surfactants, the surface treatment agents include inorganic fine particles. From the viewpoint of affinity, it is preferable to use a fluorosurfactant as the surface treatment agent. Specific examples of the fluorosurfactant include “Surflon S-243” (perfluoroalkyl ethylene oxide adduct) manufactured by AGC Seimi Chemical Co., Ltd., “Megafac F-251” manufactured by DIC Corporation, DIC Corporation ) "Megafuck F-477", DIC Corporation "Megafuck F-553", DIC Corporation "Megafuck R-40", DIC Corporation "Megafuck R-43", DIC “Megafac R-94” manufactured by Co., Ltd., “FTX-218” manufactured by Neos Co., Ltd., “Furgent 610FM” manufactured by Neos Co., Ltd., and “Futgent 730LM” manufactured by Neos Co., Ltd. may be mentioned.

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

  At this time, when the total content of the component (C) and the component (D) is 100% by mass, the component (D) maintains the viewpoint of effectively reducing the dielectric constant of the insulating layer and the adhesion strength. From this point of view, it is 20% by mass to 70% by mass. From the viewpoint of effectively reducing the dielectric constant of the insulating layer, it is preferably 25% by mass or more, and more preferably 30% by mass or more. From the viewpoint of maintaining the adhesion strength, it is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less.

  Paying particular attention to the dielectric constant of the cured product of the resin composition, the component (D) fluorine-based filler used for reducing the dielectric constant of the cured product in this embodiment is preferably a fluorine-based polymer particle containing PTFE. It is a PTFE particle.

  Here, the dielectric constant of PTFE is 2.1. Thus, for example, when PTFE particles are used as a component of the resin composition, the dielectric constant is reduced and the physical properties of the resin composition are reduced even if the target for reducing the dielectric constant of the cured product is about 0.1. As a result, it is extremely difficult to improve the physical properties and electrical characteristics of the cured product. Because, in order to reduce the dielectric constant, if a large amount of PTFE particles are blended in the resin composition as described in Patent Document 1, the dielectric constant of the cured product can surely be reduced. The PTFE particles tend to aggregate in the resin composition, and the PTFE particles cannot be uniformly distributed in the resin composition and the cured product. As a result, the adhesion to the conductor layer is significantly reduced. Moreover, it is because there exists a possibility that the physical property and electrical property of hardened | cured material may be impaired.

  However, according to the resin composition according to the present embodiment, a solution means for adjusting the contents of the component (C) and the component (D) in the resin composition in accordance with the above numerical range is found. Considering the blending of components, even if the content of component (D) is further reduced, the dielectric constant of the cured product can be reduced, and the dielectric constant can be reduced and the adhesion to the conductor layer can be improved. As well as an effect that the dielectric loss tangent of the cured product can be reduced.

<Component (E) Compound having an unsaturated hydrocarbon group>
The resin composition may contain a component (E). When the cured product has a molecular structure site formed by the reaction of the unsaturated bond site of the component (E), the polarity of the cured product is reduced, and the value of the dielectric loss tangent can be reduced.

  The component (E) is not particularly limited as long as it has an unsaturated hydrocarbon group. By using an unsaturated hydrocarbon group, the dielectric loss tangent of the cured product can be reduced. The unsaturated hydrocarbon group is preferably an acrylic 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 the molecule. For example, an allyl group, a vinyl group, and a propenyl group are mentioned. That is, the component (E) is preferably a compound having one or more unsaturated hydrocarbon groups selected from the group consisting of an acryl group, a methacryl group, a styryl group, an allyl group, a vinyl group, and a propenyl group.

  As a component (E), the compound represented by following formula (2), following formula (7), and following formula (8) is more preferable.

In formula (2), R < ¹ > -R < ⁶ > represents a hydrogen atom or a C1-C4 alkyl group each independently, Preferably it is a hydrogen atom. A represents a structure (divalent group) represented by the following formula (3) or the following formula (4).

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

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

In formula (5), R ^{7 to} R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and preferably a hydrogen atom or a methyl group. 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 (a divalent group) represented by the following formula (B-1), (B-2) or (B-3).

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

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

Wherein ^(6), R 1 to R ^6, the formula (2) has the same meaning as ^R 1 to R ⁶ in, B has the same meaning as B in the formula (3) in, a, b is , Are the same as a and b in the formula (5).

  As the component (E), “a compound having a cyclic ether structure of 5 or more members” represented by the following formula (8) is more preferable.

In the above formula, ring F represents a divalent group having a cyclic ether structure of 5 or more members. B ¹ and B ² each independently represents a single bond or a divalent linking group. C ¹ and C ² represent functional groups which may be the same or different from each other.

  A cyclic ether having a 5-membered ring or more has a property that the dielectric loss tangent can be lowered because the movement of the molecule is restricted. The carbon-carbon unsaturated bond may be contained in the cyclic ether structure or may be contained outside the cyclic ether structure. There may be a plurality of carbon-carbon unsaturated bonds.

  The number of oxygen atoms contained in the cyclic ether structure according to the “compound having a 5-membered or higher cyclic ether structure” is preferably 1 or more, more preferably 2 or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. Yes, preferably 5 or less, more preferably 4 or less, still more preferably 3 or less.

  The cyclic ether structure having 5 or more members is not particularly limited as long as the cyclic ether has a multi-membered structure having 5 or more members. The cyclic ether structure having 5 or more members may be a monocyclic ring, a polycyclic ring or a condensed ring. In addition, the “compound having a cyclic ether structure having 5 or more 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 further preferably a 5- to 6-membered ring. Specific examples of the cyclic ether structure having five or more members include a furan structure, a tetrahydrofuran structure, a dioxolane structure, a pyran structure, a dihydropyran structure, a tetrahydropyran structure, and a dioxane structure. Among these, from the viewpoint of improving the compatibility, the compound having a cyclic ether structure having a 5-membered ring or more preferably includes 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.

  Moreover, substituents, such as an alkyl group and an alkoxy group, may couple | bond with the cyclic ether structure 5 or more membered. The number of carbon atoms of the substituent is usually 1 to 6, preferably 1 to 3.

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

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

The meaning of such a substituent _{"C 1-6"} and _{"C 6-10",} explain these words to generalize as _{"C p-q".} “C _p-q ” (where p and q are positive integers and p <q is satisfied) means that the number of carbon atoms of the organic group described immediately after this wording is p to q. Represents. Specifically, for example, “C _1-6 alkyl group” represents “an alkyl group having 1 to 6 carbon atoms”.

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

Among these, B ¹ and B ² are represented by an alkylene group which may have a substituent, an alkynylene group which may have a substituent, a group represented by —COO—, and —O—. A group in which two or more arbitrary groups are selected and combined is preferable, and an alkylene group which may have a substituent, or two or more arbitrary groups are selected from a group represented by —COO— Thus, the combined group is more preferable.

C ¹ and C ² represent functional groups that may be the same or different from each other. Examples of the functional group include a vinyl group, a methacryl group, an acrylic group, an allyl group, a styryl group, a propenyl group, and an epoxy group. As the functional group, a vinyl group is preferable.

  Specific examples of the “compound having a cyclic ether structure having 5 or more members” include compounds represented by the following formulae.

  Examples of the component (E) include a styrene-modified polyphenylene ether resin (“OPE-2St 1200 (number average molecular weight 1200)” manufactured by Mitsubishi Gas Chemical Co., Ltd., equivalent to the above formula (6)), bixylenol diallyl ether resin (Mitsubishi Chemical Corporation). “YL7776 (number average molecular weight 331)” manufactured by Shin-Nakamura Chemical Co., Ltd. “A-DOG (number average molecular weight 326), equivalent to formula (8)” “KAYARAD R-604, equivalent to the formula (8)” manufactured by Nippon Kayaku Co., Ltd. can be mentioned.

  The number average molecular weight of the component (E) is preferably in the range of 100 to 10,000, more preferably 200, from the viewpoint of preventing volatilization when drying the resin varnish and preventing the melt viscosity of the resin composition from excessively increasing. It is in the range of ~ 3000. In addition, the number average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). As the number average molecular weight by the GPC method, for example, “LC-9A / RID-6A” manufactured by Shimadzu Corporation is used as a measuring device, and “Shodex K-800P / K-804L / K-804L” manufactured by Showa Denko KK is used as a column. Is measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated 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. Moreover, from a viewpoint of improving the compatibility of a resin varnish, 15 mass% or less is preferable and 10 mass% is more preferable.

  The mass ratio of the component (A) epoxy resin to the component (E) (the mass of the epoxy resin: the mass of the component (E)) is preferably in the range of 1: 0.01 to 1: 100, and 1: 0 More preferably, it is in the range of 1 to 1:90, and more preferably in the range of 1: 0.1 to 1:80. By making it in such a range, compatibility can be improved.

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

<Component (F) Curing Accelerator>
The resin composition may contain a component (F) curing accelerator. Examples of the curing accelerator include a phosphorus curing accelerator, an amine curing accelerator, an imidazole curing accelerator, a guanidine curing accelerator, a metal curing accelerator, and a peroxide curing accelerator. As the curing accelerator, a phosphorus curing accelerator, an amine curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are preferable, and an amine curing accelerator, an imidazole curing accelerator, and a metal curing accelerator include More preferred. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

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

  A commercially available product may be used as the imidazole curing accelerator. Examples of commercially available imidazole-based curing accelerators include “P200-H50” manufactured by Mitsubishi Chemical Corporation.

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

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

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

  A commercially available product can be used as the peroxide curing accelerator. Examples of the peroxide curing accelerator include “Park Mill D” manufactured by NOF Corporation.

  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, when the nonvolatile component is 100% by mass, More preferably, the content is 1% by mass to 1% by mass.

<Component (G) thermoplastic resin>
The resin composition may contain a component (G) a thermoplastic resin. Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polycarbonate resin, polyetheretherketone resin, A polyester resin is mentioned. As the thermoplastic resin, a phenoxy resin is preferable. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

  The polystyrene-reduced weight average molecular weight of the thermoplastic resin is preferably in the range of 8000 to 70000, more preferably in the range of 10,000 to 60000, and still more preferably in the range of 20000 to 60000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene equivalent weight average molecular weight of the thermoplastic resin is “LC-9A / RID-6A” manufactured by Shimadzu Corporation as a measuring device, and “Shodex K-” manufactured by Showa Denko KK as a column. 800P / K-804L / K-804L ", using chloroform or the like as the mobile phase, measuring the column temperature at 40 ° C, and calculating using a standard polystyrene calibration curve.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (bisphenol) manufactured by Mitsubishi Chemical Corporation. Other examples include “FX280” and “FX293” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “YX6954BH30”, “YX7553”, “YX7553BH30”, “YL7769BH30” manufactured by Mitsubishi Chemical Corporation. , “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, for example, “Electrical butyral 4000-2”, “Electrical butyral 5000-A”, “Electrical butyral 6000-C”, “Electrical butyral 6000-EP” manufactured by Denki Kagaku Kogyo Co., Ltd., Examples include SRECEC BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxy group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (polyimides described in JP-A Nos. 2002-12667 and 2000-319386).

  A commercially available product may be used as the polyamideimide resin. Specific examples of commercially available polyamide-imide resins include “Vilomax HR11NN” and “Vilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin include modified polyamideimides such as “KS9100” and “KS9300” (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Chemical Co., Ltd.

  A commercially available product may be used as the polyethersulfone resin. Specific examples of commercially available polyethersulfone resins include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  A commercially available product may be used as the polysulfone resin. Specific examples of commercially available polysulfone resins that can be used include “P1700” and “P3500” manufactured by Solvay Advanced Polymers.

  Of these, phenoxy resin and polyvinyl acetal resin are preferable as the thermoplastic resin. In a preferred embodiment, the thermoplastic resin includes one or more selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin.

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

<Component (H) Flame Retardant>
The resin composition may contain a component (H) flame retardant. Examples of the flame retardant include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

  A commercially available product may be used as the flame retardant. Examples of commercially available flame retardants include “HCA-HQ” manufactured by Sanko Co., Ltd. and “PX-200” manufactured by Daihachi Chemical Industry 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 further preferably 0 when the nonvolatile component is 100% by mass. 0.5 mass% to 10 mass%.

<Component (I) Optional Additive>
The resin composition may further contain an optional additive as necessary. Examples of such optional additives include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, and resins such as thickeners, antifoaming agents, leveling agents, adhesion promoters, and colorants. An additive is mentioned.

<Adhesive film>
The adhesive film includes a support and a resin composition layer that is provided on the support and includes the resin composition described above.

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

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as “PET”) and polyethylene naphthalate (hereinafter sometimes referred to as “PEN”). Examples include polyester, polycarbonate (hereinafter sometimes referred to as “PC”), acrylic polymer such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. It is done. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and polyethylene terephthalate is particularly preferable because it is inexpensive and excellent in availability.

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

  The support may be subjected to mat treatment, corona treatment, and antistatic treatment on the surface to be bonded to the resin composition layer.

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. Examples of the release agent that can be used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Is mentioned. As the support with a release layer, a commercially available product may be used. For example, “SK-1” manufactured by Lintec Corporation, which is a PET film having a release layer mainly composed of an alkyd resin release agent. , “AL-5”, “AL-7”, “Lumirror T6AM” manufactured by Toray Industries, Inc.

  The thickness of the support is not particularly limited. The thickness of the support is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In addition, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

Resin Composition Layer The resin composition layer provided in the adhesive film is a thin film obtained by semi-curing a resin varnish coating. The adhesive film is prepared, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish to a support using a die coater or the like, and drying the resin varnish coating film to some extent. It can manufacture by setting it as a physical layer.

  Examples of the organic solvent used for forming the resin composition layer include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate. Mention may be made of esters, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

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

  In the adhesive film, a surface of the resin composition layer that is not bonded to the support (the surface opposite to the support) may be further laminated with a protective film according to the support. it can. The thickness of the protective film is not particularly limited. The thickness of the protective film is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion or scratches of dust or the like to the surface of the resin composition layer. The adhesive film can be stored in a roll. When an adhesive film has a protective film, it can be used by peeling off 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 from the viewpoint of stably maintaining the thickness even when the resin composition layer is thin. More preferably, it is 1500 poise or more, and further preferably 2000 poise 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, particularly preferably, from the viewpoint of improving circuit embedding properties. It is less than 5000 poise.

  The “minimum melt viscosity of the resin composition layer” refers to the minimum viscosity exhibited when the resin composition layer is melted. Specifically, when the resin composition layer is heated and melted at a constant rate of temperature increase, the melt viscosity initially decreases as the temperature rises, and then the melt viscosity increases as the temperature rises over a period of time. . The lowest melt viscosity is the minimum melt viscosity at which the melt viscosity is the lowest. The minimum melt viscosity of the resin composition layer can be measured by a dynamic viscoelastic method.

<Prepreg>
The insulating layer on the high-frequency circuit board may be formed using a prepreg instead of the adhesive film described above. The prepreg can be formed by impregnating a sheet-like fiber base material with a resin composition described later.

  The sheet-like fiber base material used for the prepreg is not particularly limited. As the sheet-like fiber substrate, 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 reducing the thickness of the high-frequency circuit board, the thickness of the sheet-like fiber base material is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, and even more preferably 600 μm or less. is there. Since the depth of plating for forming the conductor layer can be kept small, it is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 10 μm or less. The thickness of the sheet-like fiber base material can usually be 1 μm or more, 1.5 μm or more, and 2 μm or more.

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

  The thickness of the prepreg can be in the same range as the resin composition layer in the adhesive film described above.

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

  Here, the “high frequency circuit board” means a circuit board that can be operated even with an electric signal in a high frequency band. Here, the “high frequency band” 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.

  Each of the inner layer circuit board and the insulating layer provided on the inner layer circuit board provided in the high frequency circuit board will be described.

<Inner layer circuit board>
“Inner layer circuit board” is a main surface of one or both sides of a substrate such as a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, a thermosetting polyphenylene ether board, which is a core base material, A conductor layer (wiring layer) patterned directly or indirectly into a predetermined pattern, that is, a substrate having an electrical circuit.

  The thickness of the inner layer circuit board that can be used for the high-frequency circuit board is usually 50 μm to 4000 μm. From the viewpoint of improving the mechanical strength and reducing the height (reducing the thickness) of the high-frequency circuit board, preferably 200 μm to 3200 μm.

  In order to electrically connect the two conductor layers (and the conductor layer provided on the insulating layer) on both sides of the inner layer circuit board to the inner layer circuit board, the inner layer circuit board is connected from one main surface to the other main surface. One or more through-holes may be provided, and any suitable additional components such as passive elements may be provided.

<Insulating layer>
The insulating layer concerning a high frequency circuit board is a layer of the hardened | cured material which heat-cured the resin composition mentioned later. Such an insulating layer made of a cured product can be suitably applied particularly to an insulating layer for a high-frequency circuit board.

  In the high-frequency circuit board, only one insulating layer may be provided, or two or more layers may be provided. In the case where two or more insulating layers are provided, the insulating layer can be provided as a buildup layer in which conductor layers (wirings) and insulating layers are alternately stacked.

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

  The insulating layer is for electrically connecting a conductor layer provided in the inner layer circuit board and a conductor layer provided in the insulating layer, or for electrically connecting conductor layers provided in two or more insulating layers. One or more via holes may be provided.

  The dielectric constant of the insulating layer is preferably 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 further reducing transmission loss of high-frequency electrical signals. The lower limit value of the dielectric constant 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 more preferably 0.0047 or less, from the viewpoint of preventing heat generation during transmission of a high-frequency signal, reducing signal delay and signal noise. More preferably it is. The lower limit value of the dielectric loss tangent is not particularly limited, but is usually 0.0001 or more.

  The dielectric loss tangent and dielectric constant can be measured according to the method described in “Evaluation and evaluation of dielectric constant and dielectric loss tangent” described later.

  The insulating layer applied to the high-frequency circuit board exhibits good adhesion to the conductor layer, that is, excellent peel strength to the conductor layer. The peel strength with respect to 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. Although the upper limit of the peel strength with respect to the conductor layer is not particularly limited, it is usually 2 kgf / cm or less. The peel strength of the conductor layer can be evaluated according to the method described in “Measurement and evaluation of peel strength” described later.

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

A high frequency circuit board can be manufactured by the manufacturing method including the following process (I) and process (II) using the adhesive film already demonstrated.
Step (I) Step of laminating an adhesive film on the inner layer circuit board so that the resin composition layer of the adhesive film is bonded to the inner layer circuit substrate Step (II) Forming an insulating layer by thermosetting the resin composition layer Process

  Lamination | stacking of the adhesive film to an inner layer circuit board can be performed by the thermocompression bonding process heated, for example, pressing an adhesive film to an inner layer circuit board from a support body side. Examples of the member for the thermocompression bonding process (also referred to as “thermocompression bonding member”) include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). Instead of pressing the thermocompression bonding member directly against the support of the adhesive film, an elastic material such as heat-resistant rubber is used so that the adhesive film sufficiently follows the irregularities on the main surface of the inner circuit board. It is preferable to press through.

  Lamination of the inner circuit board and the adhesive film can be performed by a vacuum laminating method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C to 160 ° C, more preferably in the range of 80 ° C to 140 ° C. The pressure for thermocompression bonding 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 for thermocompression bonding is preferably in the range of 20 seconds to 400 seconds. More preferably, it is in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

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

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

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

  In step (II), the laminated (and smoothing) resin composition layer is thermoset to form an insulating layer.

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

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

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

  When manufacturing a high-frequency circuit board, any one of (III) a step of drilling an insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer is further performed. May be. These steps (III) to (V) can be performed 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 step (II), the support is removed between step (II) and step (III), between step (III) and step (IV), or step It can be carried out between (IV) and step (V).

  In another embodiment, the insulating layer according to the high-frequency circuit board of the present invention may be formed using the prepreg already described instead of the adhesive film. The formation of the insulating layer using the prepreg can be basically performed by the same process as in the case of using the adhesive film.

  Step (III) is a step of making a hole in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) can be performed using, for example, a drill, a laser, plasma, or the like according to 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 conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are normally used when forming the insulating layer of the high-frequency circuit board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. The swelling liquid is not particularly limited. Examples of the swelling liquid include an alkaline solution and a surfactant solution. The swelling liquid is preferably an alkaline solution, and the alkaline solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan Co., Ltd. The swelling treatment with the swelling liquid is not particularly limited. The swelling treatment can be performed, for example, by immersing the insulating layer in a swelling liquid at 30 ° C. to 90 ° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. The oxidizing agent is not particularly limited. Examples of the oxidizing agent include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan Co., Ltd. Moreover, as a neutralization liquid, acidic aqueous solution is preferable. As a commercial item of a neutralization liquid, Atotech Japan Co., Ltd. product "Reduction Solution Securigans P" is mentioned, for example. The treatment with the neutralizing solution can be performed by immersing the treated surface of the insulating layer subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, it is preferable to immerse the insulating layer subjected to the roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes.

  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, still more preferably 200 nm or less, 140 nm or less, 130 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, and 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 type surface roughness meter. As a specific example of the non-contact type surface roughness meter, “WYKO NT3300” manufactured by Becoins Instruments Co., Ltd. may be mentioned.

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

  The material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A layer formed from a nickel alloy and a copper / titanium alloy). Above all, from the viewpoint of versatility of forming the conductor layer, cost, easiness of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel / chromium alloy, copper -Nickel alloy, copper-titanium alloy alloy layer is preferable, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal layer, or nickel-chromium alloy alloy layer is more preferable, copper A single metal layer is more preferred.

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

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

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

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

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

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

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

  The semiconductor device can be manufactured by mounting a component (semiconductor chip) on a conductive portion of the high-frequency circuit board. “Conducting part” means “a part where an electric signal can be transmitted in the high-frequency circuit board”, and the part is embedded in the thickness of the high-frequency circuit board even if it is the surface of the high-frequency circuit board. It may be a place. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively. Specifically, the semiconductor chip mounting method includes a wire bonding mounting method, a flip chip mounting method, a mounting method using a bumpless buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a non-conductive property. There is a mounting method using a film (NCF). Here, “a mounting method using a build-up layer without a bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a high-frequency circuit board and the wiring of the semiconductor chip and the high-frequency circuit board are connected”. .

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

<Example 1>
20 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 185) was dissolved in 20 parts of solvent naphtha with stirring and then cooled to room temperature. 60 parts of inorganic filler (“SO-C2” manufactured by Admatechs, average particle size of 0.5 μm, carbon amount per unit surface area of 0.38 mg / m ² ), PTFE particles (“Lublon L- manufactured by Daikin Industries, Ltd.”) 2 ”, average particle diameter 3 μm) 30 parts were mixed, kneaded with three rolls and dispersed. Thereto, an active ester curing agent (“HPC-8000-65T” manufactured by DIC, a toluene solution of 65% non-volatile component having an active group equivalent of about 223) 46.1 parts, a compound having a cyclic ether structure of 5 or more members (Vinyl compound) (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.) 10 parts, 2 parts of a 5% MEK solution of 4-dimethylaminopyridine (DMAP), which is a curing accelerator, and dicumyl peroxide (NOF Corporation) Resin varnish 1 was prepared by mixing 0.13 part (manufactured “Park Mill D”) and uniformly dispersing with a rotary mixer.

<Example 2>
30 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), inorganic filler (“SO-C2” manufactured by Admatechs, average particle size of 0.5 μm, amount of carbon per unit surface area) 0.38 mg / m ² ) was changed to 50 parts, PTFE particles (“Lublon L-2” manufactured by Daikin Industries, Ltd., average particle diameter 3 μm) were changed to 21 parts, and an active ester curing agent (DIC Corporation). “HPC-8000-65T” (a toluene solution of 65% non-volatile component having an active group equivalent of about 223) was changed to 61.5 parts. A resin varnish 2 was prepared in the same manner as in Example 1 except for the above items.

<Example 3>
Inorganic filler (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm, carbon amount per unit surface area 0.38 mg / m ² ) was changed to 80 parts, PTFE particles (Daikin Industries, Ltd.) "Lublon L-2", average particle diameter 3 μm) was changed to 20 parts. A resin varnish 3 was prepared in the same manner as in Example 1 except for the above items.

<Example 4>
Inorganic filler ("Ad-Tex""SO-C2", average particle size 0.5 μm, carbon amount per unit surface area 0.38 mg / m ² ) was changed to 30 parts, PTFE particles (Daikin Kogyo Co., Ltd.) "Lublon L-2", average particle diameter 3 μm) was changed to 60 parts. A resin varnish 4 was prepared in the same manner as in Example 1 except for the above items.

<Comparative Example 1>
Bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) was changed to 30 parts, and inorganic filler (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, per unit surface area) The carbon amount of 0.38 mg / m ² ) was changed to 100 parts, PTFE particles (“Lublon L-2” manufactured by Daikin Industries, Ltd., average particle size 3 μm) were changed to 20 parts, and an active ester curing agent. (“HPC-8000-65T” manufactured by DIC Corporation, a toluene solution of a 65% non-volatile component having an active group equivalent of about 223) was changed to 61.5 parts. A resin varnish 5 was prepared in the same manner as in Example 1 except for the above items.

<Comparative Example 2>
Inorganic filler (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, carbon amount per unit surface area 0.38 mg / m ² ) was changed to 15 parts, and PTFE particles (Daikin Industries, Ltd.) "Lublon L-2", average particle diameter 3 μm) was changed to 50 parts. A resin varnish 6 was prepared in the same manner as in Example 1 except for the above items.

<Comparative Example 3>
The inorganic filler ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size 0.5 µm, carbon amount per unit surface area 0.38 mg / m ² ) was changed to 20 parts, and PTFE particles (Daikin Industries, Ltd.) “Lublon L-2”, average particle size 3 μm) was changed to 5 parts. A resin varnish 7 was prepared in the same manner as in Example 1 except for the above items.

<Comparative example 4>
Inorganic filler ("Ad-Tex""SO-C2", average particle size 0.5 μm, carbon amount per unit surface area 0.38 mg / m ² ) was changed to 35 parts, PTFE particles (Daikin Industries, Ltd.) "Lublon L-2", average particle diameter 3 μm) was changed to 80 parts. A resin varnish 8 was prepared in the same manner as in Example 1 except for the above items.

<Comparative Example 5>
An active ester hardener (“HPC-8000-65T” manufactured by DIC, a toluene solution of 65% non-volatile component having an active group equivalent of about 223) is a naphthol hardener having a novolak structure (phenolic hydroxyl group equivalent 215, NSSMC) "SN-485", MEK solution with 50% non-volatile component) was changed to 40 parts. A resin varnish 9 was prepared in the same manner as in Example 1 except for the above items.

<Comparative Example 6>
Bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) was changed to 20 parts, and an active ester curing agent (“HPC-8000-65T” manufactured by DIC Co., Ltd., non-volatile with an active group equivalent of about 223) A naphthol-based curing agent having a novolak structure (a component 65% toluene solution) (phenolic hydroxyl group equivalent 215, “SN-485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., MEK solution having a nonvolatile component 50%) was changed to 20 parts. A resin varnish 10 was prepared in the same manner as in Comparative Example 5 except for the above items.

[Evaluation method]
Using the resin compositions obtained in the above-described Examples and Comparative Examples, cured films obtained by curing the resin composition layers were prepared as described below, and evaluated by the following methods.

<Preparation of cured product film (sample for evaluation)>
Each of the resin varnishes 1 to 10 obtained in Examples and Comparative Examples was dried on the main surface of one of the release-treated PET films ("PET5010" manufactured by Lintec Corporation), and the thickness of the resin composition layer after drying Was uniformly applied by a die coater so as to be 40 μm, and dried at 80 to 110 ° C. (average 95 ° C.) for 6 minutes. Then, it heat-processed for 90 minutes at 200 degreeC, and the hardened | cured material film was obtained by peeling and removing a support body. The obtained cured product film was cut into a strip shape having a length of 80 mm and a width of 2 mm to obtain a sample for evaluation.

<Measurement and evaluation of dielectric constant and dielectric loss tangent>
With respect to the obtained sample for evaluation, dielectric constant and dielectric loss tangent were measured by a cavity resonance perturbation method using “HP8362B” manufactured by Agilent Technologies, under the conditions of a measurement frequency of 10 GHz and a measurement temperature of 25 ° C. .

  A case where the dielectric constant was 3.0 or less was evaluated as “good”, and a case where the dielectric constant exceeded 3.0 was evaluated as “bad”. Moreover, the case where the value of the dielectric loss tangent was 0.005 or less was evaluated as “good”, and the case where it exceeded 0.005 was evaluated as “bad”.

<Measurement and evaluation of adhesion (peel strength) with the conductor layer>
(1) Roughening of inner layer circuit board Glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic Corporation “R1515A”) ) Was immersed in “CZ8101” manufactured by Mec Co., Ltd., and the copper foil on both sides was etched by 1 μm in the thickness direction to roughen the surface of the copper foil.

(2) Lamination of copper foil with resin composition layer Resin varnishes 1 to 10 prepared in Examples and Comparative Examples are each dried on one surface of “MT18Ex” foil manufactured by Mitsui Mining & Smelting Co., Ltd. It apply | coated uniformly with the die-coater so that the thickness of a composition layer might be 40 micrometers, and it was made to dry at 80 to 110 degreeC (average 95 degreeC) for 6 minutes, and produced the copper foil with a resin composition layer. Using the batch-type vacuum pressurization laminator ("MVLP-500" manufactured by Meiki Co., Ltd.), this resin composition layer-attached copper foil is bonded to the inner circuit board (copper foil). Lamination was performed on both sides of the inner circuit board. The laminating process was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Curing treatment of copper foil with resin composition layer The copper foil resin composition layer with a laminated resin composition layer is cured at a temperature of 200 ° C. for 90 minutes to obtain a cured product. A laminated body in which the cured body with foil was laminated on the inner layer circuit board was formed.

(4) Formation of conductor layer (electroplating)
After peeling the copper foil from the cured body with copper foil obtained in the above (3), the exposed surface of the cured body is subjected to copper sulfate electrolytic plating so as to have a thickness of 25 μm, and a conductor layer which is a copper layer Formed. Next, the laminated body on which the conductor layer was formed was annealed at 180 ° C. for 30 minutes to obtain an evaluation circuit board. Using this evaluation circuit board, the peel strength (peel strength) of the conductor layer was measured.

(5) Measurement and evaluation of the peeling strength of the conductor layer A strip-shaped cut having a width of 10 mm and a length of 100 mm was made in the circuit board for evaluation, and one end in the length direction was peeled off to grasp the gripping tool. S.E., an autocom type tester AC-50C-SL), and a load (kgf / cm (N / Cm)).
Here, the case where the measured load was more than 0.3 kgf / cm was evaluated as “good”, and the case where it was 0.3 kgf / cm or less was evaluated as “bad”.

<Result>
The evaluation results are shown in Table 1 below.

  As is apparent from Table 1, according to the resin compositions of Examples 1 to 4, the effects of the dielectric constant of the cured product were obtained by adjusting the contents of the component (C) and the component (D) as described above. The reduction of the dielectric constant, which was considered to be extremely difficult as already explained, and the improvement of the adhesion (peel strength) to the conductor layer as well as the dielectric tangent can be realized. It could be reduced more.

  In Comparative Example 1 in which the ratio of the content of the component (D) to the total amount of the component (C) and the component (D) is low, the dielectric constant of the cured product is high, and the component (C) and the component (D) In Comparative Example 2 in which the ratio of the content of the component (D) to the total amount was too high, the adhesion of the cured body to the conductive layer was low. Therefore, by appropriately adjusting the ratio of the content of the component (D) to the total amount of the component (C) and the component (D) within a predetermined range, the dielectric constant of the cured body and the adhesion of the cured body to the conductive layer are obtained. It turns out that both are compatible.

  In Comparative Example 3 in which the content of component (D) is less than the predetermined range already described, the dielectric constant of the cured product is high, and Comparative Example 4 in which the content of component (D) is greater than the predetermined range. Then, the adhesiveness with respect to the conductive layer of the hardening body has become low. Therefore, it was found that the dielectric constant of the cured body and the adhesion of the cured body to the conductive layer can both be achieved by appropriately adjusting the content of the component (D) within a predetermined range.

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

Claims (10)

A resin composition comprising component (A) epoxy resin, component (B) active ester compound, component (C) inorganic filler, and component (D) fluorine-based filler,
When the nonvolatile component in the resin composition is 100% by mass, the content of the component (D) is 10% by mass to 40% by mass,
The resin composition whose said component (D) is 20 mass%-70 mass% when the sum total of content of the said component (C) and the said component (D) is 100 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 any one of claims 1 to 3, further comprising a component (E) a compound having an unsaturated hydrocarbon group.   The said component (E) is a compound which has a 1 or more unsaturated hydrocarbon group selected from the group which consists of an acryl group, a methacryl group, a styryl group, an allyl group, a vinyl group, and a propenyl group. Resin composition.   The resin composition according to claim 5, wherein the component (E) is a compound having a vinyl group and a cyclic ether structure having a 5-membered ring or more.   The resin composition according to any one of claims 1 to 6, which is used for forming an insulating layer of a high-frequency circuit board.   The adhesive film which has a support body and the resin composition layer containing the resin composition of any one of Claims 1-6 provided on this support body.   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.