JP2017177469A - Resin sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin sheet which can impart a thin insulating layer excellent in insulating performance.SOLUTION: There is provided a resin sheet which contains a support body and a resin composition layer bonded to the support body, where a dielectric loss tangent of a cured product of the resin composition layer at 23°C and measuring frequency of 10 GHz is 0.006 or less, and a dielectric loss tangent of a cured product of the resin composition layer at 150°C and measuring frequency of 10 GHz is 0.01 or less.SELECTED DRAWING: None

Description

  The present invention relates to a resin sheet. Furthermore, it is related with the printed wiring board containing the hardened | cured material of the resin composition layer of the said resin sheet, and a semiconductor device.

  In recent years, in order to achieve miniaturization of electronic devices, the printed wiring board has been further reduced in thickness, and the thickness of the inner layer substrate and the insulating layer tends to be further reduced. As a material for reducing the thickness of an inner layer substrate or an insulating layer, for example, a thin film resin composition described in Patent Document 1 is known.

JP 2014-152309 A

  In Patent Document 1, the present inventors have found that when a thin film is applied to an insulating layer, the roughness tends to increase and the peel strength tends to decrease, and in order to solve these problems It has been proposed that the blending amount of the thermoplastic resin is a predetermined amount. However, in this document, no consideration is given to the insulation performance (hereinafter also referred to as “thin film insulation”) when the thickness of the insulating layer is reduced.

  When the insulating layer is a thin film, the inorganic filler particles come into contact with each other and the current easily flows through the interface, or the capacitance of the insulating layer is increased and the short circuit is likely to occur. For example, it becomes difficult to maintain the insulation performance as compared with the conventional one.

  The subject of this invention is providing the resin sheet which can provide the thin insulating layer excellent in the insulation performance.

  As a result of intensive studies to solve the above problems, the present inventors have found that the cured product of the resin composition layer is specific in a resin sheet comprising a support and a resin composition layer bonded on the support. It has been found that by satisfying the dielectric loss tangent, it is possible to provide an insulating layer having excellent insulating performance (excellent in thin film insulating properties) despite its thin thickness. Specifically, the present inventors not only lower the dielectric loss tangent of the cured product of the resin composition layer under a normal temperature environment, but also lower the dielectric loss tangent of the cured product of the resin composition layer under a high temperature environment, The inventors have found that it is possible to provide an insulating layer excellent in thin film insulation, and have completed the present invention.

That is, the present invention includes the following contents.
[1] A resin sheet comprising a support and a resin composition layer bonded on the support, wherein the dielectric loss tangent of the cured product of the resin composition layer at a measurement frequency of 10 GHz and 23 ° C. is 0.00. The resin sheet which is 006 or less and whose dielectric loss tangent in the measurement frequency of 10 GHz and 150 degreeC of the hardened | cured material of this resin composition layer is 0.01 or less.
[2] The resin sheet according to [1], wherein the resin composition layer has a thickness of 15 μm or less.
[3] The resin sheet according to [1] or [2], wherein the resin composition layer has a minimum melt viscosity of 1000 poise or more.
[4] The resin sheet according to any one of [1] to [3], wherein the resin composition layer contains an epoxy resin and a curing agent.
[5] When the resin composition layer contains an inorganic filler and the nonvolatile component in the resin composition layer is 100% by mass, the content of the inorganic filler is 50% by mass or more. [1] -The resin sheet in any one of [4].
[6] The resin sheet according to any one of [1] to [5], which is for forming an insulating layer of a printed wiring board.
[7] The resin sheet according to any one of [1] to [5], which is used for forming an insulating layer of a high-frequency substrate of 1 GHz or higher.
[8] A printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer of 6 μm or less formed between the first conductor layer and the second conductor layer, The resin sheet according to any one of [1] to [7], which is used for forming an insulating layer.
[9] A printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer of 6 μm or less formed between the first conductor layer and the second conductor layer, The insulating layer is a printed wiring board which is a cured product of the resin composition layer of the resin sheet according to any one of [1] to [8].
[10] A semiconductor device including the printed wiring board according to [9].

  ADVANTAGE OF THE INVENTION According to this invention, the resin sheet which can provide the thin insulating layer excellent in insulation performance can be provided.

FIG. 1 is a partial cross-sectional view schematically showing an example of a printed wiring board.

  Hereinafter, a printed wiring board and a semiconductor device provided with the resin sheet of the present invention, and a cured product of the resin composition layer of the resin sheet will be described in detail.

  The resin sheet of this invention contains a support body and the resin composition layer joined on this support body. In the present invention, the dielectric loss tangent of the cured product of the resin composition layer at a measurement frequency of 10 GHz and 23 ° C. is 0.006 or less, and the dielectric constant of the cured product of the resin composition layer at a measurement frequency of 10 GHz and 150 ° C. The tangent is 0.01 or less.

  The resin composition layer is formed of a resin composition. First, the resin composition which forms a resin composition layer is demonstrated.

[Resin composition]
The resin composition is not particularly limited as long as the cured product of the resin composition layer formed of the resin composition satisfies the above-described dielectric loss tangent. As a resin composition which provides the hardened | cured material which satisfy | fills a predetermined dielectric loss tangent, the composition containing curable resin and its hardening | curing agent is mentioned, for example. As curable resin, the conventionally well-known curable resin used when forming the insulating layer of a printed wiring board can be used, and an epoxy resin is especially preferable. Therefore, in one embodiment, the resin composition contains (A) an epoxy resin and (B) a curing agent. The resin composition preferably contains (C) an inorganic filler. The resin composition may further contain additives such as a thermoplastic resin, a curing accelerator, a flame retardant, and rubber particles as necessary.

  Hereinafter, (A) epoxy resin, (B) curing agent, (C) inorganic filler and additive that can be used as the material of the resin composition will be described.

<(A) Epoxy resin>
(A) As an epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type Epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin , Biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro Containing epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. 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 at least one selected from bisphenol A type epoxy resins, bisphenol F type epoxy resins, and biphenyl type epoxy resins.

  The epoxy resin preferably contains 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 or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, it has two or more epoxy groups in one molecule, and has a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and three or more epoxy groups in one molecule, It is preferable to contain a solid epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 20 ° C. By using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin, the epoxy resin has excellent flexibility, and the breaking strength of the cured product of the resin composition layer is also improved. In particular, the solid epoxy resin has high heat resistance, and makes it easy to lower the dielectric loss tangent of the cured product of the resin composition layer even at high temperatures.

  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” (bisphenol A) manufactured by Mitsubishi Chemical Corporation. Type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), "630", "630LSD" (glycidylamine type epoxy) Resin), "ZX1059" (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "YD-8125G" (bisphenol A type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Nagase ChemteX ( "EX-721" (glycidyl ester type epoxy resin) manufactured by Daicel Corporation, "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure) ), “ZX1658”, “ZX1658GS” (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel Chemical Co., Ltd., “630LSD” (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and the like. 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", "HP-7200HH", "HP-7200H" (Dicyclopentadiene type epoxy resin), "EXA" -7311 "," EXA-7311-G3 "," EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(naphthylene ether type epoxy resin)," EPPN "manufactured by Nippon Kayaku Co., Ltd. -502H "(trisphenol type epoxy resin)," NC7000L "(naphthol novolak type) Poxy resin), “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", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), manufactured by Mitsubishi Chemical Corporation, Osaka Gas Chemical “PG-100”, “CG-500” manufactured by Mitsubishi Chemical Corporation, “YL7800” (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “jER1010” manufactured by Mitsubishi Chemical Corporation (solid bisphenol A type) Epoxy resin), "jER1031S" (Tetra Eniruetan epoxy resin) and the like.

  From the viewpoint that the dielectric loss tangent of the cured product of the resin composition layer can be lowered even at high temperatures, the epoxy resin is preferably a high-purity resin (for example, a resin having a small amount of ionic impurities such as chlorine ions). Examples of high-purity epoxy resins include “828US”, “YL980”, “1750”, “YL983U” manufactured by Mitsubishi Chemical Corporation, “YD-8125G”, “YD-825GS” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ”,“ ZX-1658GS ”,“ YDF-8170G ”, and the like.

  The liquid epoxy resin is preferably an aromatic epoxy resin having two or more epoxy groups in one molecule and a liquid at a temperature of 20 ° C. The solid epoxy resin has three or more epoxy groups in one molecule. And an aromatic epoxy resin that is solid at a temperature of 20 ° C. is preferable. In addition, the aromatic epoxy resin as used in the field of this invention means the epoxy resin which has an aromatic ring structure in the molecule | numerator.

  When the liquid epoxy resin and the solid epoxy resin are used in combination as the epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.5 to 1:15 by mass ratio. preferable. By making the quantity ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is obtained when used in the form of a resin sheet, ii) when used in the form of a resin sheet Sufficient flexibility is obtained, handling properties are improved, and iii) a cured product of the resin composition layer having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii) above, the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 1.0 to 1:12. Is more preferable, and the range of 1: 1.3 to 1:10 is even more preferable.

  The content of the epoxy resin in the resin composition is preferably 5% by mass or more, more preferably 9% by mass or more, and still more preferably 11% by mass from the viewpoint of obtaining an insulating layer having a low dielectric loss tangent and insulation reliability. That's it. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is show | played, Preferably it is 50 mass% or less, More preferably, it is 40 mass% or less.

  In addition, in this invention, content of each component in a resin composition is a value when the non-volatile component in a resin composition is 100 mass% unless there is separate description.

  The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By being in this range, the crosslinked density of the cured product of the resin composition layer is sufficient, and an insulating layer having a small surface roughness can be provided. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

  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.

<(B) Curing agent>
The curing agent is not particularly limited as long as it has a function of curing an epoxy resin. For example, a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, a cyanate ester Examples thereof include a curing agent and a carbodiimide curing agent. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Moreover, from a viewpoint of adhesiveness with a conductor layer, a nitrogen-containing phenol type hardening | curing agent is preferable and a triazine frame | skeleton containing phenol type hardening | curing agent is more preferable. Among these, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN-495V”, “SN375” manufactured by Nippon Steel & Sumikin Co., Ltd. ”,“ SN395 ”,“ TD-2090 ”,“ LA-7052 ”,“ LA-7054 ”,“ LA-1356 ”,“ LA-3018-50P ”,“ EXB-9500 ”manufactured by DIC Corporation, etc. Is mentioned.

  Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally 1 molecule of ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of a heterocyclic hydroxy compound, are carried out. A compound having two or more thereof is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac and the like can be mentioned. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  Specifically, 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 a phenol novolac, and an active ester compound containing a benzoylated product of a phenol novolac are preferred, Of these, active ester compounds having a naphthalene structure and active ester compounds having a dicyclopentadiene type diphenol structure are more preferred. The “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

  Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-" as active ester compounds containing a dicyclopentadiene type diphenol structure. 65TM "," EXB-8000L-65TM "(manufactured by DIC Corporation)," EXB9416-70BK "(manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, and as an active ester compound containing an acetylated product of phenol novolac “DC808” (manufactured by Mitsubishi Chemical Corporation), “YLH1026” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolac, and “DC808” as an active ester curing agent which is an acetylated product of phenol novolac. "( "YLH1026" (Mitsubishi Chemical Corporation), "YLH1030" (Mitsubishi Chemical Corporation), "YLH1048" (Mitsubishi Chemical Corporation) as active ester-based curing agents that are benzoylated phenol novolaks Chemical Co., Ltd.).

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd., “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Novolac and K Polyfunctional cyanate resin derived from tetrazole novolac, these cyanate resins and partially triazine of prepolymer. Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (phenol novolac type polyfunctional cyanate ester resin), “ULL-950S” (polyfunctional cyanate ester resin) manufactured by Lonza Japan Co., Ltd., “ BA230 "," BA230S75 "(a prepolymer in which a part or all of bisphenol A dicyanate is triazine-modified into a trimer) and the like.

  Specific examples of the carbodiimide curing agent include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.

  (B) As a component, it is preferable that it is 1 or more types selected from a phenol type hardening | curing agent, a naphthol type hardening | curing agent, an active ester type hardening | curing agent, and a cyanate ester type hardening | curing agent. Moreover, as a hardening | curing agent, a thing with high heat stability is preferable from a viewpoint that the dielectric loss tangent under the high temperature of the hardened | cured material of a resin composition layer can be made low. Examples of the curing agent having high heat stability include an active ester curing agent, a cyanate ester curing agent, and a carbodiimide curing agent. Of these, one or more selected from an active ester curing agent and a cyanate ester curing agent from the viewpoint of high hydrophobicity and low dielectric loss tangent of the cured product of the resin composition layer at high temperatures It is more preferable that it is an active ester type curing agent.

  The amount ratio of the epoxy resin and the curing agent is preferably a ratio of [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of the curing agent] in the range of 1: 0.01 to 1: 2. 1: 0.015 to 1: 1.5 are more preferable, and 1: 0.02 to 1: 1 are more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like, and varies depending on the type of the curing agent. Moreover, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the value obtained by dividing the solid mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is: The value obtained by dividing the solid mass of each curing agent by the reactive group equivalent is the total value for all curing agents. By making the quantity ratio of an epoxy resin and a hardening | curing agent into such a range, the heat resistance of the hardened | cured material of a resin composition layer improves more.

  In one embodiment, the resin composition includes the aforementioned epoxy resin and a curing agent. The resin composition is a mixture of a liquid epoxy resin and a solid epoxy resin (A) as an epoxy resin (mass ratio of liquid epoxy resin: solid epoxy resin is preferably 1: 0.1 to 1:15, more preferably 1: 0.3-1: 12, more preferably 1: 0.6-1: 10), (B) a phenolic curing agent, a naphthol curing agent, an active ester curing agent and a cyanate ester One or more selected from the group consisting of curing agents (preferably one or more selected from the group consisting of active ester curing agents and cyanate ester curing agents) are preferably included.

  Although content of the hardening | curing agent in a resin composition is not specifically limited, Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less. The lower limit is not particularly limited but is preferably 2% by mass or more.

<(C) Inorganic filler>
In one embodiment, the resin composition may include an inorganic filler. The material of the inorganic filler is not particularly limited. For example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water Aluminum oxide, 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. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, spherical silica is preferable as the silica. 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 1.5 μm or less, more preferably 1.3 μm or less, still more preferably 1.0 μm or less, from the viewpoint of improving the thin film insulation by highly filling the inorganic filler. 9 μm or less is even more preferable. From the viewpoint of improving dispersibility in the resin composition layer, the lower limit of the average particle diameter is preferably 0.05 μm or more, more preferably 0.06 μm or more, and further preferably 0.07 μm or more. Examples of commercially available inorganic fillers having such an average particle diameter include “UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd., “SPH516-05” manufactured by Nippon Steel & Sumikin Materials Co., Ltd., and Nippon Steel & Sumikin Materials. “SP507-05” manufactured by Co., Ltd. and the like can be mentioned.

  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 the measurement sample, an inorganic filler dispersed in methyl ethyl ketone by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, “SALD-2200” manufactured by Shimadzu Corporation can be used.

The specific surface area of the inorganic filler is preferably 40 m ² / g or less, more preferably 37 m ² / g or less, and even more preferably 33 m ² / g or less, from the viewpoint of lowering the minimum melt viscosity of the resin composition layer described later. is there. The lower limit of the specific surface area is preferably 1 m ² / g or more, more preferably 2 m ² / g or more, and still more preferably 5 m ² / g or more, from the viewpoint of maintaining appropriate viscoelasticity of the resin composition layer. The specific surface area can be measured using, for example, a BET fully automatic specific surface area measuring apparatus (manufactured by Mountec, Macsorb HM-1210).

From the viewpoint of improving dispersibility in the resin composition layer, the true density of the inorganic filler is preferably 15 g / cm ³ or less, more preferably 10 g / cm ³ or less, and even more preferably 5 g / cm ³ or less. The lower limit of the true density is preferably 1 g / cm ³ or more, more preferably 1.5 g / cm ³ or more, and still more preferably 2.0 g / cm ³ or more. The true density can be measured using, for example, a micro-ultra pycnometer (manufactured by Cantachrome Instruments Japan, MUPY-21T).

  The inorganic filler is preferably surface-treated with at least one surface treatment agent of a silane coupling agent, an alkoxysilane compound, and an organosilazane compound from the viewpoint of improving moisture resistance and dispersibility. These may be oligomers. Examples of the surface treatment agent include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents, and the like. 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 KK, "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type) Silane coupling agent). A surface treating agent may be used individually by 1 type, and may be used in combination of 2 or more types.

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 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is more preferable from the viewpoint of suppressing the increase in melt viscosity of the resin varnish and the sheet form. preferable.

  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, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid, 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.

  From the viewpoint of improving the thickness stability of the resin composition layer and reducing the dielectric loss tangent of the insulating layer (cured product of the resin composition layer), the content (filling amount) of the inorganic filler in the resin composition is as follows. When the nonvolatile component in the resin composition is 100% by mass, it is 50% by mass or more, preferably 55% by mass or more, more preferably 60% by mass or more. The upper limit of the content of the inorganic filler in the resin composition is preferably 85% by mass or less, more preferably 80% by mass or less, from the viewpoint of improving thin film insulation.

<(D) Thermoplastic resin>
The resin composition of the present invention may further contain (D) 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, polyphenylene ether resin, polycarbonate resin, and polyether. Examples include ether ketone resins and polyester resins, and phenoxy resins are preferred. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

  The weight average molecular weight in terms of polystyrene of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. 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-reduced weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be calculated using a standard polystyrene calibration curve by measuring the column temperature at 40 ° C. using chloroform or the like as a mobile phase.

  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” (manufactured by Mitsubishi Chemical Corporation). In addition, "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "YX6954BH30", "YX7553", "YX7553BH30" manufactured by Mitsubishi Chemical Corporation, “YL7769BH30”, “YL6794”, “YL7213”, “YL7290”, “YL7482” and the like.

  Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and 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”, and “Electrical butyral 6000-EP” manufactured by Denki Kagaku Kogyo Co., Ltd. , Sreck 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 hydroxyl 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).

  Specific examples of the polyamide-imide resin include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as “KS9100” and “KS9300” (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Chemical Co., Ltd.

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.

  Specific examples of the polyphenylene ether resin include oligophenylene ether / styrene resins “OPE-2St1200” and “OPE-2St2200” manufactured by Mitsubishi Gas Chemical Co., Ltd., “NORYL SA90” manufactured by SABIC, and the like.

  As the thermoplastic resin, phenoxy resin, polyphenylene ether resin, and polyvinyl acetal resin are preferable. Accordingly, in a preferred embodiment, the thermoplastic resin includes one or more selected from the group consisting of a phenoxy resin, a polyphenylene ether resin, and a polyvinyl acetal resin. From the viewpoints of high hydrophobicity and low dielectric loss tangent of the cured product of the resin composition layer at high temperature, phenoxy resins and polyphenylene ether resins are more preferable.

  When the resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 0.5% by mass to 10% by mass, more preferably 0.6% by mass to 6% by mass, and still more preferably 0.8%. It is 7 mass%-5 mass%.

<(E) Curing accelerator>
The resin composition of the present invention may further contain (E) a curing accelerator.

  Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, a metal-based curing accelerator, and the like. A 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 are more preferable. 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, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

  Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo. (5,4,0) -undecene and the like are mentioned, and 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 Examples include imidazole compounds such as -3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, such as 2-ethyl-4-methylimidazole and 1-benzyl-2- Phenylimidazole is preferred.

  Commercially available products may be used as the imidazole curing accelerator, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation, “1B2PZ” manufactured by Shikoku Kasei Kogyo Co., Ltd., and the like.

  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) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned, for example. 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.

  Although content of the hardening accelerator in a resin composition is not specifically limited, 0.01 mass%-3 mass% are preferable when the non-volatile component of an epoxy resin and a hardening | curing agent is 100 mass%.

<(F) Flame retardant>
The resin composition of the present invention may further contain (F) a flame retardant. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

  Commercially available products may be used as the flame retardant, for example, “HCA-HQ” manufactured by Sanko Co., Ltd., “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd., and the like. As the flame retardant, those which are difficult to hydrolyze are preferable, and for example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like are preferable.

  When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and still more preferably. 0.5 mass%-10 mass% are further more preferable.

<(G) Organic filler>
The resin composition may contain (G) an organic filler from the viewpoint of lowering the dielectric loss tangent of the cured product of the resin composition layer. As the organic filler, any organic filler that can be used in forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles.

  As the rubber particles, commercially available products may be used, and examples thereof include “EXL2655” manufactured by Dow Chemical Japan Co., Ltd., “AC3401N” and “AC3816N” manufactured by Aika Industry Co., Ltd.

  As the rubber particles, for example, “AC3816N” and “AC3401N” manufactured by Aika Industry Co., Ltd. are preferable from the viewpoint that the ionicity is low and the dielectric loss tangent of the cured product of the resin composition layer can be lowered.

  When the resin composition contains an organic filler, the content of the organic filler is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass, and still more preferably 0.8%. 3% by mass to 5% by mass, or 0.5% by mass to 3% by mass.

<(H) Optional additive>
The resin composition may further contain other additives as necessary. Examples of such other additives include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, And resin additives such as thickeners, antifoaming agents, leveling agents, adhesion-imparting agents, and coloring agents.

  The resin sheet of the present invention provides an insulating layer (cured product of the resin composition layer) having excellent thin film insulation. Therefore, the resin sheet of the present invention can be suitably used as a resin sheet (for forming an insulating layer of a printed wiring board) for forming an insulating layer of a printed wiring board, and forms an interlayer insulating layer of the printed wiring board. Therefore, it can be used more suitably as a resin sheet (resin sheet for an interlayer insulating layer of a printed wiring board). Further, for example, in a printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer provided between the first conductor layer and the second conductor layer, the resin of the present invention. By forming the insulating layer with a sheet, the insulating layer between the first and second conductor layers has a thickness of 6 μm or less (preferably 5.5 μm or less, more preferably 5 μm or less), and excellent insulation performance. be able to.

[Resin sheet]
The resin sheet of the present invention includes a support and a resin composition layer provided on the support, and the resin composition layer is formed from the resin composition.

  The thickness of the resin composition layer is preferably 15 μm or less, more preferably 12 μm or less, still more preferably 10 μm or less, and even more preferably 8 μm or less, from the viewpoint of reducing the thickness of the printed wiring board. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, it may be 1 micrometer or more, 1.5 micrometers or more, 2 micrometers or more, etc.

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

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). .) Polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), polymethyl methacrylate (PMMA) and other acrylics, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

  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 used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . 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., “Lumirror R80”, and the like.

  Although it does not specifically limit as thickness of a support body, The range of 5 micrometers-75 micrometers is preferable, and the range of 10 micrometers-60 micrometers is more preferable. 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.

  The resin sheet is prepared by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish on a support using a die coater or the like, and further drying to form a resin composition layer. Can be manufactured.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol, etc. Carbitols, 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 may be performed 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 using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the resin composition is dried at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes. A physical layer can be formed.

  In the resin sheet, a protective film according to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The resin sheet can be stored in a roll. When the resin sheet has a protective film, it can be used by peeling off the protective film.

  The minimum melt viscosity of the resin composition layer in the resin sheet is preferably 12000 poise (1200 Pa · s) or less, more preferably 10,000 poise (1000 Pa · s) or less, and even more preferably 8000 poise (800 Pa) from the viewpoint of obtaining good wiring embedding properties. S) or less, 5000 poise (500 Pa · s) or less, or 4000 poise (400 Pa · s) or less. The lower limit of the minimum melt viscosity is preferably 1000 poise (100 Pa · s) or more, more preferably 1500 poise (150 Pa · s) or more, and 2000 poise (200 Pa · s) from the viewpoint of stably maintaining the thickness even if the resin composition layer is thin. -S) or more is more preferable.

  The minimum melt viscosity of the resin composition layer refers to the minimum viscosity exhibited by the resin composition layer when the resin of the resin composition layer is melted. Specifically, when the resin composition layer is heated at a constant temperature increase rate to melt the resin, the melt viscosity decreases in the initial stage as the temperature rises, and then exceeds a certain level, the melt viscosity increases as the temperature rises. To do. The minimum melt viscosity refers to the melt viscosity at such a minimum point. The minimum melt viscosity of the resin composition layer can be measured by a dynamic viscoelastic method, and can be measured, for example, according to the method described in <Measurement of minimum melt viscosity> described later.

[Hardened product]
The cured product obtained by thermally curing the resin composition layer of the resin sheet of the present invention has a dielectric loss tangent at a measurement frequency of 10 GHz and 23 ° C. of 0.006 or less, and a dielectric loss tangent at a measurement frequency of 10 GHz and 150 ° C. 0.01 or less. According to this invention, the hardened | cured material of a resin composition layer can bring about the insulating layer excellent in thin film insulation by satisfy | filling the above specific dielectric loss tangent.

  The cured product of the resin composition layer satisfying the specific dielectric loss tangent as described above uses a high-purity resin or is not easily hydrolyzed as a component (for example, an epoxy resin and a curing agent) contained in the resin composition. It can be realized by using a resin, using a resin having high heat resistance, or using a resin having high hydrophobicity (for example, an active ester curing agent or oligophenylene ether).

  The thermosetting conditions of the resin composition layer of the resin sheet of the present invention are not particularly limited, and for example, conditions usually employed when forming an insulating layer of a printed wiring board described later may be used. In addition, the resin composition layer may be preheated before thermosetting, and the heating under the thermosetting conditions may be performed a plurality of times including preheating. As an example of heat curing conditions, first, the resin composition layer is thermally cured at 100 ° C. for 30 minutes, then at 180 ° C. for 30 minutes, and further at 200 ° C. for 90 minutes.

  Cured product of the resin composition layer of the resin sheet of the present invention (for example, a cured product obtained by thermally curing the resin composition layer at 100 ° C. for 30 minutes, then at 180 ° C. for 30 minutes, and further at 200 ° C. for 90 minutes) The dielectric loss tangent at a measurement frequency of 10 GHz and 23 ° C. is preferably 0.005 or less, more preferably 0.004 or less, from the viewpoint that an insulating layer excellent in thin film insulation can be provided. More preferably, it is 0.003 or less.

  Cured product of the resin composition layer of the resin sheet of the present invention (for example, a cured product obtained by thermally curing the resin composition layer at 100 ° C. for 30 minutes, then at 180 ° C. for 30 minutes, and further at 200 ° C. for 90 minutes) The dielectric loss tangent at a measurement frequency of 10 GHz and 150 ° C. is preferably 0.009 or less, more preferably 0.008 or less, from the viewpoint that an insulating layer having excellent thin film insulation can be provided. More preferably, it is 0.007 or less.

  The dielectric loss tangent of the cured product of the resin composition layer at a measurement frequency of 10 GHz and 23 ° C. and the dielectric loss tangent at a measurement frequency of 10 GHz and 150 ° C. are measured, for example, according to the method described in <Measurement of dielectric loss tangent of cured product> described later. Can do.

A cured product obtained by thermally curing the resin composition layer of the resin sheet of the present invention (for example, a cured product obtained by thermally curing the resin composition layer at 100 ° C. for 30 minutes and then at 180 ° C. for 30 minutes), The insulation resistance value after 100 hours under 130 ° C, 85RH%, 3.3V applied environment shows a good result. That is, an insulating layer exhibiting a good insulation resistance value is provided. The upper limit of the insulation resistance value is preferably 10 ¹² Ω or less, more preferably 10 ¹¹ Ω or less, and further preferably 10 ¹⁰ Ω or less. The lower limit is not particularly limited, but is preferably 10 ⁶ Ω or more, more preferably 10 ⁷ Ω or more. The insulation resistance value can be measured according to the method described in <Evaluation of insulation reliability, measurement of thickness of insulating layer between conductor layers> described later.

  In the present invention, the cured product of the resin composition layer has a dielectric loss tangent of 0.006 or less at a measurement frequency of 10 GHz and 23 ° C., and a dielectric loss tangent of 0.01 or less at a measurement frequency of 10 GHz and 150 ° C. Some cured products are also included. A hardened | cured material is the structure similar to the hardened | cured material of the resin composition layer of the resin sheet of this invention. Moreover, the curing conditions of the resin composition for forming the cured product are the same as the curing conditions of the resin sheet. In a cured product of the present invention (for example, a cured product obtained by thermally curing a resin composition layer at 100 ° C. for 30 minutes, then at 180 ° C. for 30 minutes, and further at 200 ° C. for 90 minutes) at a measurement frequency of 10 GHz and 23 ° C. The preferred range of dielectric loss tangent and the preferred range of dielectric loss tangent at a measurement frequency of 10 GHz and 150 ° C. are the same as those of the cured resin sheet described above. The preferable range of the insulation resistance value of the cured product is also the same as that of the cured product of the resin sheet described above.

  Since the resin sheet of the present invention can reduce the dielectric loss tangent at high temperatures, it is possible to suppress the generation of heat and noise due to electrical signals even in a high temperature environment. Therefore, the resin sheet of this invention can be used conveniently for the insulating layer of a printed wiring board used in a high frequency band. The high frequency band means a high frequency band of 1 GHz or more (preferably 1.5 GHz or more, more preferably 3 GHz or more).

[Printed wiring board, printed wiring board manufacturing method]
The printed wiring board of the present invention includes an insulating layer, a first conductor layer, and a second conductor layer formed from a cured product of the resin composition layer of the resin sheet of the present invention. The printed wiring board of the present invention may be provided with the cured product of the present invention as an insulating layer. The insulating layer is provided between the first conductor layer and the second conductor layer, and insulates the first conductor layer and the second conductor layer (the conductor layer is also referred to as a wiring layer). . Since the insulating layer formed from the cured product of the resin composition layer of the resin sheet of the present invention is excellent in thin film insulating properties, it is insulative even if the thickness of the insulating layer between the first and second conductor layers is 6 μm or less. Excellent.

The thickness of the insulating layer between the first and second conductor layers is preferably 6 μm or less, more preferably 5.5 μm or less, and even more preferably 5 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more. The thickness of the insulating layer between the first and second conductor layers is the insulation between the main surface 51 of the first conductor layer 5 and the main surface 61 of the second conductor layer 6 as shown in FIG. This refers to the thickness t1 of the layer 7. The first and second conductor layers are conductor layers adjacent to each other with an insulating layer interposed therebetween, and the main surface 51 and the main surface 61 face each other. The thickness of the insulating layer between the first and second conductor layers can be measured according to the method described in <Evaluation of insulation reliability, measurement of the thickness of the insulating layer between conductor layers> described later.
The total thickness t2 of the insulating layer is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 12 μm or less. The lower limit is not particularly limited, but may be 1 μm or more.

The printed wiring board of this invention can be manufactured by the method including the process of following (I) and (II) using the above-mentioned resin sheet.
(I) The process of laminating | stacking so that the resin composition layer of a resin sheet may join to an inner layer board | substrate on an inner layer board | substrate (II) The process of thermosetting a resin composition layer and forming an insulating layer

  The “inner layer substrate” used in step (I) is mainly a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or one or both surfaces of the substrate. A circuit board on which a patterned conductor layer (circuit) is formed. Further, when the printed wiring board is manufactured, an inner layer circuit board of an intermediate product in which an insulating layer and / or a conductor layer is further formed is also included in the “inner layer board” in the present invention. When the printed wiring board is a circuit board with a built-in component, an inner layer board with a built-in component can be used.

  Lamination | stacking of an inner layer board | substrate and a resin sheet can be performed by heat-pressing a resin sheet to an inner layer board | substrate from the support body side, for example. Examples of the member that heat-presses the resin sheet to the inner layer substrate (hereinafter, also referred to as “heat-pressing member”) include a heated metal plate (SUS end plate) or a metal roll (SUS roll). It is preferable that the thermocompression-bonding member is not pressed directly on the resin sheet, but is pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

  Lamination of the inner layer substrate and the resin sheet may 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 80 ° C to 140 ° C, and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably 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., a vacuum applicator manufactured by Nikko Materials Co., Ltd., and the like.

  After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same conditions as the thermocompression bonding conditions for the laminate. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform lamination | stacking and a 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 resin composition layer is thermally cured to form an insulating layer.

  The thermosetting conditions for the resin composition layer are not particularly limited, and the conditions normally employed when forming the insulating layer of the printed wiring board may be used.

  For example, although the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition, the curing temperature is 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 the curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

  Before the resin composition layer is thermally 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 printed wiring board, you may further implement (III) the process of drilling in an insulating layer, (IV) the process of roughening an insulating layer, and (V) the process of forming a conductor layer. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used in the production of printed wiring boards. In addition, when removing a support body after process (II), removal of this support body is performed between process (II) and process (III), between process (III) and process (IV), or process ( It may be carried out between IV) and step (V). Moreover, if necessary, the multilayer wiring board may be formed by repeatedly forming the insulating layer and the conductor layer in the steps (II) to (V). In this case, the thickness of the insulating layer between the respective conductor layers (t1 in FIG. 1) is preferably within the above range.

  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) may be performed using, for example, a drill, laser, plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring 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 usually used when forming an insulating layer of a printed wiring board can be employed. 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. Although it does not specifically limit as a swelling liquid, An alkaline solution, surfactant solution, etc. are mentioned, Preferably it is an alkaline solution, As this alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan Co., Ltd. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer for 1 minute-20 minutes in 30 degreeC-90 degreeC swelling liquid. 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. Although it does not specifically limit as an oxidizing agent, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. 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. The neutralizing solution is preferably an acidic aqueous solution. Examples of commercially available products include “Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be performed by immersing the treated surface 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, a method of immersing an object subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

  In one embodiment, the arithmetic average roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, further preferably 300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less, or 100 nm or less. It is. The arithmetic average roughness (Ra) of the insulating layer surface 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 is cited.

  Step (V) is a step of forming a conductor layer. When the conductor layer is not formed on the inner layer substrate, the step (V) is a step of forming the first conductor layer. When the conductor layer is formed on the inner layer substrate, the conductor layer is the first conductor layer. Step (V) is a step of forming the second conductor layer.

  The conductor 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). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel / chromium alloy, copper / An alloy layer of nickel alloy or copper / titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel / chromium alloy is more preferable, and a single layer of copper is preferable. A 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.

  Although the thickness of a conductor layer is based on the design of a desired printed wiring board, generally it is 3 micrometers-35 micrometers, Preferably it is 5 micrometers-30 micrometers.

  In one embodiment, the conductor layer may be formed by plating. For example, the surface of the insulating layer can be plated by a conventionally known technique 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 a semi-additive method will be described.

  First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. 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.

  Since the resin sheet of the present invention provides an insulating layer having a good wiring embedding property, it can be suitably used even when the printed wiring board is a component built-in circuit board. The component built-in circuit board can be manufactured by a known manufacturing method.

  A printed wiring board manufactured using the resin sheet of the present invention includes an insulating layer that is a cured product of the resin composition layer of the resin sheet of the present invention, and an embedded wiring layer embedded in the insulating layer. It may be.

The printed wiring board manufactured using the resin sheet of the present invention exhibits a characteristic that the insulation reliability is excellent even when the thickness of the insulating layer between the first and second conductor layers is 6 μm or less. The upper limit of the insulation resistance value after 100 hours has elapsed under 130 ° C, 85RH%, 3.3V applied environment is preferably 10 ¹² Ω or less, more preferably 10 ¹¹ Ω or less, and even more preferably 10 ¹⁰ Ω or less. The lower limit is not particularly limited, but is preferably 10 ⁶ Ω or more, more preferably 10 ⁷ Ω or more. The insulation resistance value can be measured according to the method described in <Evaluation of insulation reliability, measurement of thickness of insulating layer between conductor layers> described later.

[Semiconductor device]
The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring 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 of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The “conduction location” is a “location where an electrical signal is transmitted on a printed wiring board”, and the location may be a surface or an embedded location. 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, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive 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 recess of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. It is.

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.
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.

[Method for measuring physical properties of inorganic filler]
First, a method for measuring physical properties of inorganic fillers used in Examples and Comparative Examples will be described.

<Measurement of average particle size>
100 mg of inorganic filler, 0.1 g of a dispersant (“SN9228” manufactured by San Nopco Co., Ltd.) and 10 g of methyl ethyl ketone were weighed in a vial and dispersed with an ultrasonic wave for 20 minutes. A particle size distribution was measured by a batch cell method using a laser folding particle size distribution measuring device (“SALD-2200” manufactured by Shimadzu Corporation), and an average particle size based on the median diameter was calculated.

<Measurement of specific surface area>
The specific surface area of the inorganic filler was measured using a BET fully automatic specific surface area measuring device ("Macsorb HM-1210" manufactured by Mountec Co., Ltd.).

<Measurement of carbon content>
The amount of carbon per unit surface area of the inorganic filler was measured according to the following procedure. A sufficient amount of MEK as a solvent was added to the inorganic filler prepared in Preparation Example, and ultrasonic cleaning was performed at 25 ° C. for 5 minutes. Subsequently, the supernatant was removed and the solid content was dried. About the obtained solid, carbon amount was measured using the carbon analyzer ("EMIA-320V" by Horiba, Ltd.). Based on the measured value of the carbon amount and the mass and specific surface area of the inorganic filler used, the carbon amount per unit surface area of the inorganic filler was calculated.

<Production of Resin Sheet (Examples 1-3, Comparative Examples 1-2)>
The resin sheet of an Example and a comparative example was produced using the resin composition (resin varnish) prepared with the following procedures.

(Preparation of resin composition 1)
3 parts of bisphenol A type epoxy resin (“YD-8125G” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 174), 3 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, about 185 of epoxy equivalent) , 8 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238), 12 parts of naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., about 330 of epoxy equivalent), phenoxy Heat while stirring in a mixed solvent of 10 parts of resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass), and 12 parts of solvent naphtha and 10 parts of cyclohexanone. Dissolved. After cooling to room temperature, 20 parts of an active ester curing agent (“HPC-8000-65T” manufactured by DIC Corporation, active group equivalent of about 225, toluene solution with 65% by mass of non-volatile components), oligophenylene ether -10 parts of styrene resin (Mitsubishi Gas Chemical Co., Ltd. "OPE-2St 1200", toluene solution with a solid content of 72% by mass), amine curing accelerator (4-dimethylaminopyridine (DMAP), solid content of 5% by mass MEK solution) 2 parts, imidazole curing accelerator (“1B2PZ” 1-benzyl-2-phenylimidazole, 5% solid MEK solution manufactured by Shikoku Kasei Kogyo Co., Ltd.) 0.4 parts, rubber particles (Aika Industry) Co., Ltd., AC-3401N) 2 parts swollen in 10 parts of solvent naphtha at room temperature for 12 hours, aminosilane coupling agent (Shin-Etsu Chemical) Spherical silica surface-treated with “KBM573” manufactured by Gaku Kogyo Co., Ltd. (“SP507-05” manufactured by Nippon Steel & Sumikin Materials Co., Ltd.), average particle size 0.91 μm, specific surface area 6.5 m ² / g, unit surface area After mixing 160 parts per carbon (0.34 mg / m ² ) and uniformly dispersing with a high-speed rotary mixer, the mixture was filtered with a cartridge filter (“SHP030” manufactured by ROKITETECHNO) to prepare Resin Composition 1.

(Preparation of resin composition 2)
2 parts of bisphenol A type epoxy resin (“YD-8125G” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 174), 5 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, about 185 of epoxy equivalent) , 5 parts of naphthylene ether type epoxy resin (DIC Corporation "EXA-7311-G4", epoxy equivalent of about 213), biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent of about 272) 15 parts, 2 parts of epoxidized polybutadiene ("PB3600" manufactured by Daicel Corporation, epoxy equivalent of about 193), phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation), 30% by mass of cyclohexanone: methyl ethyl ketone (MEK) 1: 1 solution), 10 parts, solvent naphtha and 15 parts cyclohexane. It was dissolved by heating with stirring in a mixed solvent of non 10 parts. After cooling to room temperature, 5 parts of triazine skeleton-containing cresol novolac-based curing agent (“LA3018-50P” manufactured by DIC Corporation, hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%), activity Ester-based curing agent (DIC Corporation "HPC-8000-65T", active group equivalent about 225, non-volatile component 65% by weight toluene solution) 12 parts, carbodiimide resin (Nisshinbo Chemical Co., Ltd. "V-03" , Carbodiimide equivalent 216, 10 parts by weight of a non-volatile component 50% by weight toluene solution, 1.5 parts amine curing accelerator (4-dimethylaminopyridine (DMAP), 5% by weight solid MEK solution) 1.5 parts, flame retardant (Sanko) "HCA-HQ", 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphafe, manufactured by 2 parts of lenthrene-10-oxide (average particle size 1.2 μm), spherical silica surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (manufactured by Nippon Steel & Sumikin Materials Co., Ltd.) SPH516-05 ”, average particle size 0.29 μm, specific surface area 16.3 m ² / g, carbon amount per unit surface area 0.43 mg / m ² ) 110 parts were mixed and uniformly dispersed with a high-speed rotary mixer, The resin composition 2 was prepared by filtering with a cartridge filter (“SHP020” manufactured by ROKITECHNO).

(Preparation of resin composition 3)
4 parts of naphthalene type epoxy resin (DIC Corporation "HP4032SS", epoxy equivalent of about 144), naphthylene ether type epoxy resin (DIC Corporation "EXA-731-G4", epoxy equivalent of about 213), 8 parts, 15 parts of naphthalene type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 330), phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Co., Ltd.), cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass 1: 1 solution) was dissolved by heating in a mixed solvent of 15 parts of solvent naphtha and 10 parts of cyclohexanone with stirring. After cooling to room temperature, 20 parts of a prepolymer of bisphenol A dicyanate ("BA230S75" manufactured by Lonza Japan Co., Ltd., a MEK solution having a cyanate equivalent of about 232 and a non-volatile content of 75% by mass), a polyfunctional cyanate ester resin ( “ULL-950S” manufactured by Lonza Japan Co., Ltd., 6 parts of cyanate equivalent of about 230, MEK solution having a nonvolatile content of 75% by mass, an active ester curing agent (“HPC-8000-65T” manufactured by DIC Corporation), active group Equivalent weight 225, non-volatile component 65% by weight toluene solution) 6 parts, carbodiimide resin (Nisshinbo Chemical Co., Ltd. "V-03", carbodiimide equivalent 216, non-volatile component 50% by weight toluene solution) 5 parts, amine curing Accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass) 0.4 parts Curing accelerator (manufactured by Tokyo Chemical Industry Co., Ltd., cobalt (III) acetylacetonate (Co (III) Ac), 3 mass% MEK solution), aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd.) Spherical silica surface-treated with “KBM573” manufactured by Nippon Steel & Sumikin Materials Co., Ltd. “SPH516-05”, average particle size 0.29 μm, specific surface area 16.3 m ² / g, carbon amount per unit surface area 0 .43 mg / m ² ) 100 parts were mixed and dispersed uniformly with a high-speed rotary mixer, and then filtered through a cartridge filter (“SHP020” manufactured by ROKITECHNO) to prepare Resin Composition 3.

(Preparation of resin composition 4)
8 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation “828EL”, epoxy equivalent of about 186), biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. “NC3000L”, epoxy equivalent of about 272), epoxidation 5 parts of polybutadiene (“PB3600” manufactured by Daicel Corporation, epoxy equivalent of about 193), phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass) 10 parts was dissolved by heating in a mixed solvent of 10 parts of solvent naphtha and 10 parts of cyclohexanone while stirring. After cooling to room temperature, 5 parts of triazine skeleton-containing cresol novolac-based curing agent (“LA3018-50P” manufactured by DIC Corporation, hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%), activity Ester-based curing agent (DIC Corporation "HPC-8000-65T", active group equivalent about 225, non-volatile component 65% by weight toluene solution) 12 parts, carbodiimide resin (Nisshinbo Chemical Co., Ltd. "V-03" , Carbodiimide equivalent 216, 10 parts by weight of a non-volatile component 50% by weight toluene solution, 1.5 parts amine curing accelerator (4-dimethylaminopyridine (DMAP), 5% by weight solid MEK solution) 1.5 parts, flame retardant (Sanko) "HCA-HQ", 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphafe, manufactured by 2 parts of lenthrene-10-oxide, average particle size 1.2 μm), 2 parts of rubber particles (manufactured by Aika Kogyo Co., Ltd., AC-3355) in 8 parts of solvent naphtha for 12 hours at room temperature, aminosilane Spherical silica ("Admafine SO-C1" manufactured by Admatechs Co., Ltd.), average particle size 0.63 [mu] m, specific surface area 11.2m, surface-treated with a coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ² / g, carbon amount per unit surface area 0.35 mg / m ² ) 110 parts are mixed and dispersed uniformly with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP030” manufactured by ROKITECHNO) to obtain a resin composition 4 was prepared.

(Preparation of resin composition 5)
10 parts of bisphenol A-type epoxy resin (Mitsubishi Chemical Corporation “828EL”, epoxy equivalent of about 186), 15 parts of naphthalene type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 330), epoxidation 2 parts of polybutadiene ("PB3600" manufactured by Daicel Corporation, epoxy equivalent of about 193), phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass) 5 parts was heated and dissolved in a mixed solvent of 12 parts of solvent naphtha and 10 parts of cyclohexanone with stirring. After cooling to room temperature, 20 parts of a prepolymer of bisphenol A dicyanate ("BA230S75" manufactured by Lonza Japan Co., Ltd., a MEK solution having a cyanate equivalent of about 232 and a non-volatile content of 75% by mass), a polyfunctional cyanate ester resin ( “ULL-950S” manufactured by Lonza Japan Co., Ltd., 6 parts of cyanate equivalent of about 230, MEK solution having a nonvolatile content of 75% by mass, an active ester curing agent (“HPC-8000-65T” manufactured by DIC Corporation), active group Equivalent weight of about 225, 65 parts by weight non-volatile component in toluene solution) 6 parts, Block-type isocyanate resin (DIC Corporation "Bernock D-500", non-volatile component 65% by weight ethyl acetate solution), 5 parts, amine-based curing acceleration Agent (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5 mass%) (Tokyo Kasei Co., Ltd., Cobalt (III) acetylacetonate (Co (III) Ac), MEK solution with a solid content of 1% by mass), 3 parts, aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd. “KBM573” ") Surface-treated spherical silica (" Admafine SO-C1 "manufactured by Admatechs Co., Ltd.), average particle size 0.63 [mu] m, specific surface area 11.2 m < ² > / g, carbon amount per unit surface area 0.35 mg / m ² ) 100 parts were mixed and dispersed uniformly with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP030” manufactured by ROKITECHNO) to prepare Resin Composition 5.

  Table 1 below shows the components used for the preparation of the resin compositions 1 to 5 and their blending amounts (parts by mass of the nonvolatile content).

(Production of resin sheets of Examples 1 to 3 and Comparative Examples 1 and 2)
As a support, a PET film (“Lumirror R80” manufactured by Toray Industries, Inc.) having a release treatment with an alkyd resin release agent (“AL-5” manufactured by Lintec Corporation), a thickness of 38 μm, a softening point of 130 ° C. Type PET ").

  Each resin composition was uniformly coated on a release PET with a die coater so that the thickness of the resin composition layer after drying was 40 μm, and it was 70 ° C. to 100 ° C. for 4.5 minutes or 60 ° C. to 90 ° C. A resin composition layer was formed on the release PET by drying at 0 ° C. for 2 minutes. Next, a rough surface of a polypropylene film (“Alphan MA-411” manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) as a protective film is bonded to the resin composition layer on the surface of the resin sheet that is not bonded to the support. Laminated so that. This obtained the resin sheet for a dielectric loss tangent measurement which consists of a support body, a resin composition layer, and a protective film in this order.

  For measuring the minimum melt viscosity, in the same manner as the resin sheet for dielectric loss tangent measurement, except that each resin composition was coated on the release PET so that the thickness of the resin composition layer after drying was 13 μm. And the resin sheet for insulation reliability measurement was obtained.

<Measurement of minimum melt viscosity>
Using a resin sheet having a resin composition layer thickness of 13 μm, peeling only the resin composition layer from the release PET (support) and compressing it with a mold (diameter 18 mm, 1.2 to 1.3 g) was produced.

  Using a dynamic viscoelasticity measuring apparatus (“Rheosol-G3000” manufactured by UBM Co., Ltd.), using a parallel plate with a diameter of 18 mm, a starting temperature of 60 ° C. to 200 ° C. is used for 1 g of the sample resin composition layer. The temperature was raised at a rate of 5 ° C./min until the measurement, and the dynamic viscoelasticity was measured under the measurement conditions of a measurement temperature interval of 2.5 ° C., a frequency of 1 Hz, and a strain of 1 deg. The results are shown in Table 2.

<Measurement of dielectric loss tangent of cured product>
The untreated surface of the release PET film (Lintec Co., Ltd. “501010”, thickness 38 μm, 240 mm square) is a glass cloth base epoxy resin double-sided copper-clad laminate (Matsushita Electric Works, Ltd. “R5715ES”, thickness 0. 7 mm, 255 mm square) was placed on a glass cloth base epoxy resin double-sided copper-clad laminate, and the four sides of the release PET film were fixed with polyimide adhesive tape (width 10 mm).

  Using a resin sheet (200 mm square) having a resin composition layer thickness of 40 μm prepared in Examples and Comparative Examples, a batch-type vacuum pressurization laminator (Nikko Materials Co., Ltd. 2-stage buildup laminator, CVP700) The laminate was laminated at the center so that the resin composition layer was in contact with the release surface of the release PET film (“501010” manufactured by Lintec Corporation). The laminating process was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less and then pressing the film at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

  Next, it was cured at 30 ° C. for 30 minutes after being put in a 100 ° C. oven under a temperature condition of 100 ° C., and then for 30 minutes after being transferred to a 180 ° C. oven under a temperature condition of 180 ° C. Thereafter, the substrate was taken out in a room temperature atmosphere, and the release PET (support) was peeled off from the resin sheet. Then, the substrate was put into an oven at 200 ° C. and then cured by curing for 90 minutes.

  The above-mentioned “cured product for evaluation” was cut into a test piece having a width of 1.5 mm and a length of 80 mm, and the test piece was measured using a cavity resonance perturbation method at a measurement frequency of 10 GHz using “HP8362B” manufactured by Agilent Technologies. The dielectric loss tangent (Df) was measured at a temperature of 23 ° C. or 150 ° C. The dielectric loss tangent (Df) was measured at a measurement frequency of 10 GHz and a measurement temperature of 23 ° C. or 150 ° C. Three test pieces were measured, the average value was calculated, and the results are shown in Table 2.

<Evaluation of insulation reliability, measurement of insulation layer thickness between conductor layers>
(Preparation of evaluation substrate)
(1) Base treatment of inner layer circuit board Glass cloth base epoxy resin double-sided copper having circuit conductor (copper) formed on both sides as a 1 mm square lattice wiring pattern (residual copper ratio 59%) as inner layer circuit board A tension laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, “R1515F” manufactured by Panasonic Corporation) was prepared. Both surfaces of the inner layer circuit board were subjected to a copper surface roughening treatment (copper etching amount of 0.5 μm) using “CZ8201” manufactured by MEC.

(2) Lamination of resin sheet A resin sheet having a resin composition layer thickness of 13 μm prepared in Examples and Comparative Examples was batch-type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd., 2-stage buildup laminator, CVP700) was laminated on both surfaces of the inner layer circuit board so that the resin composition layer was in contact with the inner layer circuit board. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and pressing for 45 seconds at 130 ° C. and a pressure of 0.74 MPa. Next, hot pressing was performed at 120 ° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Thermosetting of resin composition layer The inner layer circuit board on which the resin sheet is laminated is placed in a 100 ° C. oven at 100 ° C. for 30 minutes and then in a 180 ° C. oven at 180 ° C. After the transfer, the thermosetting was performed for 30 minutes to form an insulating layer.

(4) Formation of via holes From above the insulating layer and the support, using a CO ₂ laser processing machine “605GTWIII (-P)” manufactured by Mitsubishi Electric Corporation, a laser is irradiated from above the support to A via hole having a top diameter (70 μm) was formed in the insulating layer on the conductor of the pattern. The laser irradiation conditions were a mask diameter of 2.5 mm, a pulse width of 16 μs, an energy of 0.39 mJ / shot, a shot number of 2, and a burst mode (10 kHz).

(5) Roughening process The support body was peeled from the circuit board provided with the via hole, and the desmear process was performed. In addition, as a desmear process, the following wet desmear process was implemented.

Wet desmear treatment:
Swelling solution (“Swelling Dip Securigant P” manufactured by Atotech Japan Co., Ltd., diethylene glycol monobutyl ether and sodium hydroxide aqueous solution) at 60 ° C. for 5 minutes, and then an oxidant solution (“Concentrate” manufactured by Atotech Japan Co., Ltd.)・ Compact CP ”, aqueous solution with potassium permanganate concentration of about 6%, sodium hydroxide concentration of about 4%) at 80 ° C. for 10 minutes, and finally neutralization solution (“ Reduction Solution Securigant P manufactured by Atotech Japan Co., Ltd.) ”, Immersed in sulfuric acid aqueous solution) at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 15 minutes.

(6) Step of forming conductor layer (6-1) Electroless plating step In order to form a conductor layer on the surface of the circuit board, a plating step including the following steps 1 to 6 (chemical solution manufactured by Atotech Japan Co., Ltd.) The copper plating process using was performed to form a conductor layer.

1. Alkali cleaning (cleaning and charge adjustment of the surface of the insulating layer with via holes)
Product name: Cleaned at 60 ° C. for 5 minutes using Cleaning Cleaner Security 902 (trade name).
2. Soft etching (cleaning inside via holes)
The mixture was treated with an aqueous sodium peroxodisulfate solution at 30 ° C. for 1 minute.
3. Pre-dip (adjustment of surface charge of insulating layer for Pd application)
Pre. Using Dip Neoganth B (trade name), it was treated at room temperature for 1 minute.
4). Activator application (Pd application to the surface of the insulating layer)
Using Activator Neoganth 834 (trade name), it was treated at 35 ° C. for 5 minutes.
5. Reduction (reduction of Pd applied to the insulating layer)
Reducer Neoganth WA (trade name) and Reducer Accelerator 810 mod. Using a mixed solution with (trade name), it was treated at 30 ° C. for 5 minutes.
6). Electroless copper plating process (Cu is deposited on the surface of the insulating layer (Pd surface))
Using a mixture of Basic Solution Print MSK-DK (trade name), Copper solution Print MS MS (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name) at 35 ° C. Treated for 20 minutes. The thickness of the formed electroless copper plating layer was 0.8 μm.

(6-2) Electrolytic plating process Subsequently, the electrolytic copper plating process was performed on the conditions with which a via hole is filled with copper using the chemical solution made from Atotech Japan. Thereafter, as a resist pattern for patterning by etching, a land pattern having a diameter of 1 mm conducted to the via hole and a circular conductor pattern having a diameter of 10 mm not connected to the lower layer conductor are used to form a thickness of 10 μm on the surface of the insulating layer. A conductor layer having lands and conductor patterns was formed. Next, annealing was performed at 200 ° C. for 90 minutes. This substrate was designated as evaluation substrate A.

(7) Measurement of thickness of insulating layer between conductor layers The substrate A for evaluation was subjected to cross-sectional observation using a FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology Co., Ltd.). Specifically, the cross section in the direction perpendicular to the surface of the conductor layer was cut out by FIB (focused ion beam), and the insulating layer thickness between the conductor layers was measured from the cross section SEM image. For each sample, five cross-sectional SEM images selected at random were observed, and the average value was taken as the thickness of the insulating layer between the conductor layers.

(8) Evaluation of insulation reliability of insulating layer Lattice conductor (copper) side of inner layer circuit board connected to a 1 mm diameter land with the circular conductor side of 10 mm diameter of the evaluation board A obtained above as a positive electrode As an electrode, using an advanced accelerated life test apparatus (“PM422” manufactured by ETAC), the insulation resistance value when 200 hours passed under the conditions of 130 ° C., 85% relative humidity, and 3.3 V DC voltage application, Measurement was performed with an electrochemical migration tester (“ECM-100” manufactured by J-RAS Co., Ltd.) (n = 6). In all six test pieces, when the insulation resistance value was 10 ⁷ Ω or more, “◯” was given, and when even one was less than 10 ⁷ Ω, “X” was given. The evaluation results are shown in Table 2. The insulation resistance values listed in Table 2 are the minimum insulation resistance values of the six test pieces.

5 1st conductor layer 51 principal surface 6 of 1st conductor layer 2nd conductor layer 61 principal surface 7 of 2nd conductor layer 7 insulating layer

Claims (10)

A resin sheet comprising a support and a resin composition layer bonded on the support,
The dielectric loss tangent of the cured product of the resin composition layer at a measurement frequency of 10 GHz and 23 ° C. is 0.006 or less,
The resin sheet whose dielectric loss tangent in the measurement frequency of 10 GHz and 150 degreeC of the hardened | cured material of this resin composition layer is 0.01 or less.   The resin sheet according to claim 1, wherein the resin composition layer has a thickness of 15 μm or less.   The resin sheet of Claim 1 or 2 whose minimum melt viscosity of a resin composition layer is 1000 poise or more.   The resin sheet according to any one of claims 1 to 3, wherein the resin composition layer contains an epoxy resin and a curing agent.   The resin composition layer contains an inorganic filler, and when the nonvolatile component in the resin composition layer is 100 mass%, the content of the inorganic filler is 50 mass% or more. The resin sheet of any one of Claims.   The resin sheet according to claim 1, which is for forming an insulating layer of a printed wiring board.   The resin sheet according to any one of claims 1 to 5, which is used for forming an insulating layer of a high-frequency substrate of 1 GHz or more.   Formation of an insulating layer of a printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer of 6 μm or less formed between the first conductor layer and the second conductor layer The resin sheet according to any one of claims 1 to 7, which is for use. A printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer of 6 μm or less formed between the first conductor layer and the second conductor layer,
The printed wiring board, wherein the insulating layer is a cured product of the resin composition layer of the resin sheet according to any one of claims 1 to 8.   A semiconductor device comprising the printed wiring board according to claim 9.

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