KR20170113284A - Resin sheet - Google Patents

Abstract

[PROBLEMS] To provide a resin sheet capable of providing a thin insulating layer excellent in insulating performance.
[MEANS FOR SOLVING PROBLEMS] A resin sheet comprising a support and a resin composition layer bonded to the support, wherein 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 캜, And the dielectric loss tangent at 150 占 폚 is 0.01 or less at a measurement frequency of 10 GHz.

Description

Resin Sheet {RESIN SHEET}

The present invention relates to a resin sheet. Further, the present invention relates to a printed wiring board including a cured product of the resin composition layer of the resin sheet, and a semiconductor device.

In recent years, in order to achieve miniaturization of electronic devices, the printed wiring board is further thinned, and the thickness of the inner layer substrate and the insulating layer tends to be thinner. For example, the resin composition for a thin film described in Patent Document 1 is known in which the inner layer substrate and the insulating layer are made thinner.

Japanese Patent Application Laid-Open No. 2014-152309

In Patent Document 1, the present inventors found that when a thin film is applied to an insulating layer, the roughness tends to increase and the peel strength tends to decrease. In order to solve these problems, the blending amount of the thermoplastic resin It is proposed to do it in a fixed amount. However, this literature does not consider insulation performance (hereinafter also referred to as " thin film insulation property ") when the thickness of the insulating layer is reduced.

When the insulating layer is formed as a thin film, the inorganic filler particles come into contact with each other to easily flow electric current through the interface, or the insulating layer becomes thin, which leads to increase in capacitance and short-circuiting. It becomes difficult.

A problem to be solved by the present invention is to provide a resin sheet capable of providing a thin insulating layer excellent in insulating performance.

As a result of intensive investigations to solve the above problems, the present inventors have found that, in a resin sheet comprising a support and a resin composition layer bonded on the support, the cured product of the resin composition layer satisfies a specific dielectric loss tangent, It is possible to provide an insulating layer having excellent insulation performance (which is excellent in thin film insulation) in spite of being thin. Specifically, the present inventors found that not only the dielectric tangent of the resin composition layer under a normal temperature environment is lowered but also the dielectric tangent of the resin composition layer under a high temperature environment is lowered, an insulating layer having excellent thin film insulation can be provided Thus, the present invention has been completed.

That is, the present invention includes the following contents.

[1] A resin sheet comprising a support and a resin composition layer bonded to the support, wherein 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 캜, And the dielectric loss tangent at 150 占 폚 is 0.01 or less at a measurement frequency of 10 GHz.

[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 minimum melt viscosity of the resin composition layer is 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] The resin composition according to any one of [1] to [4], wherein the resin composition layer contains an inorganic filler and the content of the inorganic filler is 50% by mass or more when the nonvolatile component in the resin composition layer is 100% .

[6] A resin sheet according to any one of [1] to [5], which is used for forming an insulating layer of a printed wiring board.

[7] A 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 more.

[8] A semiconductor device comprising a first conductor layer, a second conductor layer, and an insulating layer insulating the first conductor layer and the second conductor layer, wherein the thickness of the insulating layer between the first conductor layer and the second conductor layer is The resin sheet according to any one of [1] to [7], which is used for forming the insulating layer of a printed wiring board having a thickness of 6 μm or less.

[9] A semiconductor device comprising a first conductor layer, a second conductor layer, and an insulating layer insulating the first conductor layer and the second conductor layer, wherein the thickness of the insulating layer between the first conductor layer and the second conductor layer is 6 탆 or less, wherein the insulating layer is a cured product of the resin composition layer of the resin sheet described in any one of [1] to [8].

[10] A semiconductor device comprising a printed wiring board according to [9].

According to the present invention, it is possible to provide a resin sheet capable of providing a thin insulating layer excellent in insulating performance.

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

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

The resin sheet of the present invention comprises a support and a resin composition layer bonded on the support. The present invention is characterized in that 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 캜 and a dielectric loss tangent at a measurement frequency of 10 GHz and 150 캜 of the cured product of the resin composition layer is 0.01 or less do.

The resin composition layer is formed by a resin composition. First, the resin composition for forming the resin composition layer will be described.

[Resin composition]

The resin composition is not particularly limited, and it is only required that the cured product of the resin composition layer formed by the resin composition satisfies the dielectric loss tangent described above. As the resin composition for imparting a cured product satisfying a predetermined dielectric tangent, for example, a composition containing a curable resin and its curing agent can be mentioned. As the curable resin, conventionally known curable resins used for forming the insulating layer of the printed wiring board can be used, and among them, an epoxy resin is preferable. Accordingly, in one embodiment, the resin composition contains (A) an epoxy resin and (B) a curing agent. It is preferable that the resin composition contains (C) an inorganic filler. The resin composition may further contain, if necessary, additives such as a thermoplastic resin, a curing accelerator, a flame retardant, and an organic filler.

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

≪ (A) Epoxy resin >

Examples of the epoxy resin (A) include epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, Novolak type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, epoxy resin, epoxy resin, epoxy resin, Epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexane dimethanol type epoxy Resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy Resins and the like. The epoxy resin may be used alone or in combination of two or more. The component (A) is preferably at least one selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, and biphenyl type epoxy resin.

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, it is preferable that at least 50% by mass or more of the epoxy resin is an epoxy resin having two or more epoxy groups in one molecule. Among them, an epoxy resin (hereinafter referred to as " liquid epoxy resin ") having two or more epoxy groups in one molecule at a temperature of 20 캜 and an epoxy resin having three or more epoxy groups in one molecule and solid at a temperature of 20 캜 Hereinafter referred to as " solid epoxy resin "). As the epoxy resin, the liquid epoxy resin and the solid epoxy resin are used in combination to have excellent flexibility and to improve the fracture strength of the cured product of the resin composition layer. Particularly, the solid epoxy resin has high heat resistance and makes it easy to lower the dielectric loss tangent of the cured resin composition layer even under high temperature.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolak type epoxy resin, A cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a glycidylamine type epoxy resin, a bisphenol A type epoxy resin, Bisphenol F type epoxy resin, bisphenol AF type epoxy resin and naphthalene type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin), "828US" and "jER828EL" (bisphenol A type) manufactured by Mitsubishi Kagaku (Bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), "630", "630LSD" (glycidyl amine ZX1059 "(a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.," YD-8125G " (Bisphenol A type epoxy resin), EX-721 (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Co., Ltd., CELLOXIDE 2021P (manufactured by Daicel Co., Resin), " PB-3600 " (epoxy resin having a butadiene structure), Shinet Tetsukagaku ZX1658GS "(liquid 1,4-glycidylcyclohexane) manufactured by Mitsubishi Chemical Corporation," 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.

Examples of the solid epoxy resin include naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, An anthracene type epoxy resin, a bisphenol A type epoxy resin and a tetraphenyl ethane type epoxy resin are preferable, and a naphthalene type tetrafunctional epoxy resin, a naphthol type epoxy resin and a biphenyl type epoxy resin are more preferable. Specific examples of the solid epoxy resin include HP4032H (naphthalene type epoxy resin), HP-4700, HP-4710 (naphthalene type tetrafunctional epoxy resin), N-690 HP-7200HH ", " HP-7200H " (dicyclopentadiene type epoxy resin), " EXA EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(naphthylene ether type epoxy resin)," EPPN Quot; NC3000H ", " NC3000L ", " NC3100 " (biphenyl type epoxy resin), Shinnitetsu Sumikinka "ESN475V" (naphthalene type epoxy resin), "ESN485" (naphthol novolak type epoxy resin) manufactured by Kaku K.K., "YX4000H" and "YL6121" manufactured by Mitsubishi Kagaku Co., PG-100 "," CG-500 "manufactured by Osaka Gas Chemical Co., Ltd.)," YX4000HK "(biquileneol type epoxy resin)," YX8800 "(anthracene type epoxy resin), Mitsubishi Kagaku Co., Quot; jL1010 " (solid bisphenol A type epoxy resin) and " jER1031S " (tetraphenyl ethane type epoxy resin) manufactured by Mitsubishi Kagaku Co., Ltd., and the like.

From the viewpoint that the dielectric tangent of the cured resin composition layer can be lowered even at a high temperature, the epoxy resin is preferably a resin having high purity (for example, a resin having little ionic impurities such as chloride ion). Examples of the high-purity epoxy resin include "828US", "YL980", "1750", "YL983U" manufactured by Mitsubishi Kagaku Co., Ltd., "YD-8125G" manufactured by Shinnitetsu Sumikin Kagaku Co., , "YD-825GS", "ZX-1658GS", and "YDF-8170G".

The liquid epoxy resin is preferably a liquid aromatic epoxy resin having two or more epoxy groups in one molecule and having a temperature of 20 DEG C. The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule and having a temperature of 20 DEG C . The term "aromatic epoxy resin" in the present invention means an epoxy resin having an aromatic ring structure in its molecule.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the amount ratio (liquid epoxy resin: solid epoxy resin) thereof is preferably in the range of 1: 0.5 to 1:15 in terms of the mass ratio. By setting the proportions of the liquid epoxy resin and the solid epoxy resin in this range, it is possible to obtain sufficient flexibility when i) the resin is used in the form of a resin sheet, and ii) when it is used in the form of a resin sheet Handling property is improved, and (iii) a cured product of the resin composition layer having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii), the ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably in the range of 1: 1.0 to 1:12, : 1.3 to 1:10 is 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, further preferably 11% by mass or more, from the viewpoint of obtaining an insulating layer exhibiting low dielectric tangent and exhibiting insulation reliability. Or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 50 mass% or less, more preferably 40 mass% or less.

In the present invention, the content of each component in the resin composition is a value obtained by assuming that the nonvolatile component in the resin composition is 100% by mass, unless otherwise specified.

The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, still more preferably 110 to 1000. With this range, the cross-linking density of the cured product of the resin composition layer becomes sufficient, resulting in an insulating layer having a small surface roughness. The epoxy equivalent can be measured in accordance with JIS K7236, and is the mass of the resin containing one equivalent of an epoxy group.

The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

<(B) Hardener>

The curing agent is not particularly limited as long as it has a function of curing the epoxy resin. Examples of the curing agent include phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents, benzoxazine based curing agents, cyanate ester- And the like. The curing agent may be used singly or in combination of two or more kinds.

As the phenol-based curing agent and 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 viewpoints of heat resistance and water resistance. From the viewpoint of adhesion with the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Among them, a phenazine novolac curing agent containing a triazine skeleton is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesiveness to a conductor layer.

Specific examples of the phenol-based curing agent and naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., SN190 "," SN190 "," SN475 "," SN485 "," SN495 ", and" SN-495V "manufactured by Shinnitetsu Sumikin Kagaku Co., "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500 &Quot; and the like.

The active ester-based curing agent is not particularly limited, but generally, an ester group having a high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of a heterocyclic hydroxy compound, A compound having two or more is preferably used. It is preferable that the active ester-based curing agent is obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. From the viewpoint of heat resistance improvement, an active ester type curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester type 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, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o- Cresol, catechol, alpha -naphthol, beta -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzene triol, dicyclopentadiene type diphenol compounds, phenol novolak, and the like. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol in one dicyclopentadiene molecule.

Specifically, there can be mentioned 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 phenol novolac, a benzoyl compound of phenol novolac Active ester compounds are preferable, and active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

EXB9451 "," EXB9460 "," EXB9460S "," HPC-8000-65T "," HPC-8000H-65TM "as the active ester compound containing a dicyclopentadiene type diphenol structure as a commercially available product of the active ester type curing agent EXB9416-70BK "(manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolak," EXB-8000L-65TM " , YLH1026 (manufactured by Mitsubishi Chemical Corp.) as the active ester compound containing benzoylate of phenol novolac, active ester compound as the acetylated product of phenol novolak YLH1026 &quot; (manufactured by Mitsubishi Kagaku Co., Ltd.), and &quot; YLH1030 &quot; (manufactured by Mitsubishi Kagaku K.K.) as the active ester curing agent, which is a benzoylate of phenol novolak, , &Quot; YLH1048 &quot; (Mitsubishi Kao Manufacturing ku Ltd.) and the like.

Specific examples of the benzoxazine type curing agent include "HFB2006M" manufactured by Showa Kobunshi Co., Ltd., "P-d" and "F-a" manufactured by Shikoku Seiko Kogyo Co.,

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'- Dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1- Cyanate phenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis Bifunctional cyanate resins derived from phenolic novolacs and cresol novolacs such as bis (4-cyanophenyl) thioether and bis (4-cyanate phenyl) ether, and polyfunctional cyanate resins derived from these cyanate resins, And prepolymers. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (phenol novolak type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin) manufactured by Lone Japan Co., Quot; BA230 &quot;, &quot; BA230S75 &quot; (a prepolymer obtained by trimerizing a part or all of bisphenol A dicyanate to form a trimer), and the like.

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

The component (B) is preferably at least one selected from phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents and cyanate ester-based curing agents. From the viewpoint of lowering the dielectric tangent at a high temperature of the cured product of the resin composition layer, it is preferable that the curing agent has high heat stability. Examples of the curing agent having high heat stability stability include an active ester curing agent, a cyanate ester curing agent, and a carbodiimide curing agent. Of these, from the viewpoint of high hydrophobicity and low dielectric tangent at a high temperature of the cured product of the resin composition layer, it is more preferable to use at least one selected from active ester curing agents and cyanate ester curing agents, Is more preferable.

The ratio of the epoxy resin to the curing agent is preferably in the range of 1: 0.01 to 1: 2, more preferably in the range of 1: 0.015 to 1: 1.5, in the ratio of [the total number of epoxy groups of epoxy resin]: [the total number of reactors of the curing agent] , More preferably from 1: 0.02 to 1: 1. 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 kind of the curing agent. The total number of epoxy groups in the epoxy resin is a value obtained by dividing the solid component mass of each epoxy resin by the epoxy equivalent in terms of all epoxy resins and the total number of reactors in the curing agent is the same as the mass Divided by the total amount of the curing agent. By setting the ratio of the epoxy resin and the curing agent to this range, the heat resistance of the cured product of the resin composition layer is further improved.

In one embodiment, the resin composition comprises the above-mentioned epoxy resin and a curing agent. The resin composition preferably comprises (A) a mixture of a liquid epoxy resin and a solid epoxy resin (the mass ratio of the liquid epoxy resin: solid epoxy resin is preferably from 1: 0.1 to 1:15, more preferably from 1: 0.3 to 1: (B) at least one member selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent and a cyanate ester-based curing agent as the curing agent (preferably , At least one selected from the group consisting of an active ester-based curing agent and a cyanate ester-based curing agent).

The content of the curing agent in the resin composition is not particularly limited, but is preferably 30 mass% or less, more preferably 25 mass% or less, further preferably 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 contain an inorganic filler. The material of the inorganic filler is not particularly limited, and examples thereof include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Magnesium 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 titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. As the silica, spherical silica is preferable. The inorganic fillers may be used singly or in combination of two or more kinds.

The average particle diameter of the inorganic filler is preferably 1.5 占 퐉 or less, more preferably 1.3 占 퐉 or less, further preferably 1.0 占 퐉 or less, and further preferably 0.9 占 퐉 or less from the viewpoint of enhancing the thin film insulation property by highly filling the inorganic filler desirable. From the viewpoint of improving the dispersibility in the resin composition layer, the lower limit of the average particle diameter is preferably 0.05 mu m or more, more preferably 0.06 mu m or more, and still more preferably 0.07 mu m or more. Examples of the commercially available inorganic filler having such an average particle diameter include "UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd., "SPH516-05" manufactured by Shinnitetsu Sumikin Materials Co., Ltd., SP507-05 &quot; manufactured by Material Sciences Co., Ltd., and the like.

The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured with a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter is determined as the average particle diameter. The sample to be measured is preferably an inorganic filler dispersed in methyl ethyl ketone by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring apparatus, "SALD-2200" manufactured by Shimadzu Corporation may 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, still more preferably 33 m 2 / g or less, from the viewpoint of lowering the minimum melt viscosity of the resin composition layer described later . The lower limit of the specific surface area is preferably 1 m2 / g or more, more preferably 2 m2 / g or more, and further preferably 5 m2 / g or more, from the viewpoint of proper viscoelastic maintenance of the resin composition layer. The specific surface area can be measured using, for example, a BET automatic specific surface area measuring apparatus (Macsorb HM-1210, manufactured by Mounet Co., Ltd.).

The true density of the inorganic filler is preferably 15 g / cm 3 or less, more preferably 10 g / cm 3 or less, still more preferably 5 g / cm 3 or less, from the viewpoint of improving the dispersibility in the resin composition layer. The lower limit of the density is preferably 1 g / cm &lt; 3 &gt; More preferably not less than 1.5 g / cm 3, and further preferably not less than 2.0 g / cm 3. The true density can be measured using, for example, a micro-ultra-peak furnace (MUPY-21T, manufactured by Quanta Chromium Instrument, Japan).

The inorganic filler is preferably surface-treated with at least one surface treatment agent such as 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 silane coupling agents such as amino silane coupling agents, epoxy silane coupling agents and mercaptosilane coupling agents, alkoxysilane compounds, organosilazane compounds and titanate coupling agents. Examples of commercially available products of the surface treatment agent include KBM403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM803 (3-mercapto- KBE903 "(3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.," KBM573 "(manufactured by Shin-Etsu Chemical Co., SZ-31 (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM103 (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin- KBM-4803 &quot; (long-chain epoxy type silane coupling agent). One kind of surface treatment agent may be used alone, or two or more kinds of surface treatment agents may be used in combination.

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

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 a surface treatment agent, and ultrasonically cleaned at 25 占 폚 for 5 minutes. After the supernatant is removed and the solid content is dried, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba Seisakusho Co., Ltd. and the like can be used.

From the viewpoint of improving the thickness stability of the resin composition layer and lowering the dielectric loss tangent of the insulating layer (cured product of the resin composition layer), the content (fill amount) of the inorganic filler in the resin composition is preferably 100 mass% %, Preferably not less than 55 mass%, more preferably not less than 60 mass%. 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 improvement of the thin film insulation property.

&Lt; (D) Thermoplastic resin >

The resin composition of the present invention may further contain (D) a thermoplastic resin.

Examples of the thermoplastic resin include thermoplastic resins such as phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyether sulfone resin, Ether resins, polycarbonate resins, polyether ether ketone resins, and polyester resins. Phenoxy resins are preferred. The thermoplastic resins may be used singly or in combination of two or more.

The weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably in the range of 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 of the thermoplastic resin in terms of polystyrene is measured by gel permeation chromatography (GPC). Specifically, the weight average molecular weight of the thermoplastic resin in terms of polystyrene was measured using LC-9A / RID-6A manufactured by Shimadzu Corporation, Shodex K-800P / K (manufactured by Showa Denko K.K.) -804L / K-804L can be measured using a calibration curve of standard polystyrene at a column temperature of 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, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, A phenoxy resin having at least one skeleton selected from the group consisting of a skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethyl cyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used singly or in combination of two or more kinds. Specific examples of the phenoxy resin include "1256" and "4250" (both phenol resins containing a bisphenol A skeleton), "YX8100" (phenoxy resin containing a bisphenol S skeleton), and "YX6954" manufactured by Mitsubishi Chemical Corporation (Phenoxy resin containing a bisphenol acetophenone skeleton). In addition, "FX280" and "FX293" manufactured by Sinetettsu Sumikin Kagaku Co., Ltd., "YX6954BH30" and "YX7553" manufactured by Mitsubishi Kagaku , "YL7569BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", and "YL7482".

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, "Telephone (electrification) butyral 4000-2", "Telephone Butyral 5000-A", "Telephone Butyral 6000-C" manufactured by Denki Kagaku Co., (For example, BX-5Z), KS series (for example, KS-1), BL series, BM series (for example, Series, and the like.

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

Specific examples of the polyamide-imide resin include "Bioromax HR11NN" and "Bioromax HR16NN" manufactured by Toyo Boseki K.K. Specific examples of the polyamide-imide resin include modified polyamideimides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Chemical Co., Ltd.

Specific examples of the polyether sulfone resin include "PES 5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

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 an oligophenylene ether styrene resin "OPE-2St1200", "OPE-2St2200" manufactured by Mitsubishi Gas Sagaku Co., Ltd., and "NORYL SA90" manufactured by SABIC.

The thermoplastic resin is preferably a phenoxy resin, a polyphenylene ether resin, or a polyvinyl acetal resin. Accordingly, in a preferred embodiment, the thermoplastic resin includes at least one 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 tangent of the cured product of the resin composition layer at a high temperature, a phenoxy resin and a polyphenylene ether resin 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 0.7% by mass to 5% by mass .

<(E) Curing accelerator>

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

Examples of the curing accelerator include phosphorus hardening accelerator, amine hardening accelerator, imidazole hardening accelerator, guanidine hardening accelerator, metal hardening accelerator, and organic peroxide hardening accelerator. Examples of the hardening accelerator include phosphorus hardening accelerator, Accelerators, imidazole-based curing accelerators and metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators and metal-based curing accelerators are more preferable. The curing accelerator may be used singly or in combination of two or more kinds.

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

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl- Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- Phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] -ethyl-s-triazine, 2,4- diamino-6- [ Imidazolyl- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- Triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl- 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3 Methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, etc. And imidazole compounds of imidazole compounds and epoxy resins, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As the imidazole-based curing accelerator, a commercially available product may be used, and for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation, "1B2PZ" manufactured by Shikoku Seiko Co., Ltd., and the like can be given.

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

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

Examples of the organic peroxide-based curing accelerator include dicumylperoxide, cyclohexanoneperoxide, tert-butylperoxybenzoate, methylethylketoneperoxide, dicumylperoxide, tert-butylcumylperoxide, di- Peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, and the like. As the organic peroxide curing accelerator, a commercially available product may be used, and for example, &quot; PERCUMIL D &quot;

The content of the curing accelerator in the resin composition is not particularly limited, but it is preferably 0.01% by mass to 3% by mass based on 100% by mass of the nonvolatile component of the epoxy resin and the curing agent.

<(F) Flame Retardant>

The resin composition of the present invention may further comprise (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 silicon-based flame retardant, a metal hydroxide, and the like. The flame retardant may be used alone or in combination of two or more.

Commercially available products may be used as the flame retardant, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd., "PX-200" manufactured by Daihachi Chemical Co., As the flame retardant, it is preferable that hydrolysis is difficult, 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, further preferably 0.5% by mass to 10% % By mass is preferable.

&Lt; (G) Organic filler >

The resin composition may contain (G) an organic filler in view of lowering the dielectric tangent of the resin composition layer cured product. 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 silicon particles.

As the rubber particles, a commercially available product may be used, for example, "EXL2655" manufactured by Dow Chemical Co., Ltd., "AC3401N" manufactured by Aika Kogyo Co., Ltd., and "AC3816N".

As the rubber particles, for example, "AC3816N" and "AC3401N" manufactured by Aikogyo Co., Ltd. are preferable from the viewpoint of low ionicity and low dielectric tangent of the resin composition layer cured product.

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, further preferably 0.3% by mass to 5% Or 0.5% by mass to 3% by mass.

<(H) Other additives>

The resin composition may further contain other additives as required. Examples of such other additives include organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds, and thickeners, defoaming agents, leveling agents, And a resin additive such as an imparting agent and a coloring agent.

The resin sheet of the present invention results in an insulating layer (cured resin composition layer) excellent in 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 can be suitably used as a resin sheet for forming an interlayer insulating layer of a printed wiring board A resin sheet for an interlayer insulating layer of a wiring board). Further, for example, in a printed wiring board comprising a first conductor layer, a second conductor layer, and an insulation layer provided between the first conductor layer and the second conductor layer, The insulation performance between the first and second conductor layers can be made to be excellent while the thickness of the insulation layer is set to 6 m or less (preferably 5.5 m or less, more preferably 5 m or less). In a preferred embodiment, the resin sheet of the present invention comprises a first conductor layer, a second conductor layer, and an insulating layer insulating the first conductor layer and the second conductor layer, And the thickness of the insulating layer between the two conductor layers is 6 占 퐉 or less.

[Resin sheet]

The resin sheet of the present invention comprises a support and a resin composition layer provided on the support, and the resin composition layer is formed of a resin composition.

The thickness of the resin composition layer is preferably 15 占 퐉 or less, more preferably 12 占 퐉 or less, further preferably 10 占 퐉 or less, and still more preferably 8 占 or less, from the viewpoint of reducing the thickness of the printed wiring board. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 1 占 퐉 or more, 1.5 占 퐉 or more, 2 占 퐉 or more, or the like.

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

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter may be abbreviated as "PET"), polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN" (TAC), polyether sulfide (PES), polyether sulfide (PES), polyether sulfone (PES), polyether sulfone Polyether ketone, polyimide, and the like. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

In the case of using a metal foil as a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. The copper foil may be a foil made of a single metal of copper or an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, You may use foil.

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

As the support, a support having a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the release agent used for the release layer of the release layer-adherend support include at least one release agent selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin. SK-1, &quot; &quot; AL-5, &quot; and &quot; AL-5, &quot; manufactured by Lintec Corporation, each of which is a PET film having a releasing layer mainly composed of an alkyd resin-based releasing agent, 7, &quot; Lumirror T6AM &quot;, &quot; Lumirror R80 &quot;, manufactured by Toray Industries, Inc. and the like.

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

The resin sheet can be produced, for example, by preparing a resin varnish obtained by dissolving a resin composition in an organic solvent, coating the resin varnish on a support using a die coater or the like, and drying the resin varnish to form a resin composition layer.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, Carbitol such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used singly or in combination of two or more kinds.

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

In the resin sheet, a protective film corresponding to the support may be further laminated on the surface of the resin composition layer not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 m to 40 m. By laminating a protective film, it is possible to prevent adhesion of dust or the like on the surface of the resin composition layer and scarring. The resin sheet can be rolled and stored. 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 10000 poise (1000 Pa · s) or less, still more preferably 8000 poise (800 Pa · 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 higher, more preferably 1500 poise (150 Pa · s) or higher, and still more preferably 2000 poise (200 Pa · s) or higher from the viewpoint of stably maintaining the thickness even if the resin composition layer is thin. s) or more is more preferable.

The lowest melt viscosity of the resin composition layer means the lowest viscosity exhibited by the resin composition layer when the resin of the resin composition layer is melted. Specifically, when the resin composition is heated by heating at a constant heating rate to melt the resin, the melt viscosity of the resin is lowered along with the temperature rise in the initial stage, and thereafter, the melt viscosity increases with the temperature rise . The lowest melt viscosity refers to the melt viscosity of such a minimum point. The minimum melt viscosity of the resin composition layer can be measured by a dynamic viscoelasticity method and can be measured, for example, by the method described in &quot; Measurement of Minimum Melting Viscosity &quot;

[Cured goods]

The cured product obtained by thermally curing the resin composition layer of the resin sheet of the present invention has a dielectric loss tangent of 0.006 or less at a measurement frequency of 10 GHz and 23 deg. C, and a dielectric loss tangent of 0.01 or less at a measurement frequency of 10 GHz and 150 deg. According to the present invention, the cured product of the resin composition layer satisfies the specific dielectric tangent as described above, which can result in an insulating layer having excellent thin film insulation.

The cured product of the resin composition layer satisfying the specific dielectric tangent as described above can be obtained by using a resin having high purity as a component (for example, an epoxy resin and a curing agent) contained in the resin composition or by using a resin Or a resin having high heat resistance or a resin having high hydrophobicity (for example, an active ester type curing agent or oligophenylene ether) may be used.

The thermosetting condition of the resin composition layer of the resin sheet of the present invention is not particularly limited and may be, for example, a condition which is generally adopted when forming an insulating layer of a printed wiring board described later. Further, the preliminary heating may be performed before thermosetting the resin composition layer, and the heating under the thermosetting condition may be performed a plurality of times including preheating. As an example of the thermosetting condition, the resin composition layer is thermally cured at 100 占 폚 for 30 minutes, then at 180 占 폚 for 30 minutes, and further at 200 占 폚 for 90 minutes.

The 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 DEG C for 30 minutes, then at 180 DEG C for 30 minutes and further at 200 DEG C for 90 minutes) From the viewpoint that dielectric loss tangent at a measurement frequency of 10 GHz and 23 deg. C may lead to an insulating layer having excellent thin film insulation property, it is preferably 0.005 or less, more preferably 0.004 or less, and still more preferably 0.003 or less.

The 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 占 폚 for 30 minutes, then at 180 占 폚 for 30 minutes and at 200 占 폚 for 90 minutes) From the viewpoint that dielectric tangent at a frequency of 10 GHz and 150 占 폚 may result in an insulating layer having excellent thin film insulation property, it is preferably 0.009 or less, more preferably 0.008 or less, still more preferably 0.007 or less.

The dielectric loss tangent of the cured product of the resin composition layer at 10 GHz and 23 deg. C and the dielectric loss tangent at a measurement frequency of 10 GHz and 150 deg. C can be measured, for example, according to the method described in & .

The 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 캜 for 30 minutes and then at 180 캜 for 30 minutes) 85RH%, and 3.3V, and exhibits good insulation resistance even after 100 hours elapse. That is, an insulation layer showing a good insulation resistance value. 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 higher, more preferably 10 ⁷ Ω or higher. The measurement of the insulation resistance value can be performed according to the method described in &quot; Evaluation of insulation reliability and measurement of insulation layer thickness between conductor layers &quot;.

The cured product of the resin composition layer includes a cured product having a dielectric loss tangent of 0.006 or less at a measurement frequency of 10 GHz and 23 占 폚 and a dielectric loss tangent of 0.01 or less at a measurement frequency of 10 GHz and 150 占 폚. The cured product has the same structure as the cured product of the resin composition layer of the resin sheet of the present invention. The curing conditions of the resin composition for forming the cured product are the same as the curing conditions for the resin sheet. The curing temperature of the cured product of the present invention (for example, a cured product obtained by thermally curing the resin composition layer at 100 占 폚 for 30 minutes and then at 180 占 폚 for 30 minutes and further at 200 占 폚 for 90 minutes) And the preferable range of dielectric loss tangent at 150 deg. C and 10 GHz are the same as those of the above-mentioned cured resin sheet. The preferable range of the insulation resistance value of the cured product is the same as the above-mentioned cured product of the resin sheet.

The resin sheet of the present invention can lower the dielectric loss tangent at high temperature, and it is therefore possible to suppress the generation of heat or noise due to an electric signal even under a high temperature environment. Therefore, the resin sheet of the present invention can be suitably used for an 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 higher (preferably 1.5 GHz or higher, more preferably 3 GHz or higher).

[Printed wiring board, manufacturing method of printed wiring board]

The printed wiring board of the present invention comprises an insulating layer, a first conductor layer and a second conductor layer formed by curing 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 to insulate the first conductor layer from the second conductor layer (the conductor layer is also referred to as a wiring layer). Since the insulating layer formed by the cured product of the resin composition layer of the resin sheet of the present invention is excellent in thin film insulation, the insulating property is excellent even if the thickness of the insulating layer between the first and second conductor layers is 6 탆 or less.

The thickness of the insulating layer between the first and second conductor layers is preferably 6 占 퐉 or less, more preferably 5.5 占 퐉 or less, and further preferably 5 占 퐉 or less. The lower limit is not particularly limited, but may be 0.1 탆 or more. The thickness of the insulating layer between the first and second conductor layers means the thickness of the main surface 51 of the first conductor layer 5 and the major surface 51 of the second conductor layer 6 (T1) of the insulating layer (7) between the insulating layer The first and second conductor layers are adjacent conductor layers through the insulating layer, and the main surface 51 and the main surface 61 are opposed to each other. The thickness of the insulating layer between the first and second conductor layers can be measured according to the method described in &quot; Evaluation of insulation reliability and measurement of thickness of insulating layer between conductor layers &quot;.

The total thickness t2 of the insulating layer is preferably 20 占 퐉 or less, more preferably 15 占 퐉 or less, and further preferably 12 占 퐉 or less. The lower limit is not particularly limited, but may be 1 占 퐉 or more.

The printed wiring board of the present invention can be produced by a method including the following steps (I) and (II) using the resin sheet described above.

(I) a step of laminating a resin composition layer of a resin sheet to be laminated on an inner layer substrate on an inner layer substrate

(II) a step of thermally curing the resin composition layer to form an insulating layer

The term &quot; inner layer substrate &quot; used in the step (I) refers mainly to a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, (Circuits) formed by patterning on one side (one side) or both sides of the circuit board. Further, when manufacturing a printed wiring board, an inner layer circuit board of an intermediate product in which an insulating layer and / or a conductor layer is to be formed is also included in the &quot; inner layer board &quot; When the printed wiring board is a component built-in circuit board, an inner-layer board containing components can be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet from the support side to the inner layer substrate. Examples of the member for heating and pressing the resin sheet to the inner layer substrate (hereinafter also referred to as "hot pressing member") include a heated metal plate (SUS hard plate) or a metal roll (SUS roll). Further, it is preferable to press the heat-press member through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface unevenness of the inner layer substrate, not directly press the resin sheet.

The lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum laminating method, the heat pressing temperature is preferably in the range of 60 占 폚 to 160 占 폚, more preferably 80 占 폚 to 140 占 폚, and the heat pressing pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa, and the heat pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably performed under a reduced pressure of 26.7 hPa or less.

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

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

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

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

The thermosetting conditions of the resin composition layer are not particularly limited, and conditions that are generally 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 are different depending on the type of the resin composition and the like, the curing temperature is in the range of 120 캜 to 240 캜 (preferably in the range of 150 캜 to 220 캜, 200 占 폚), and the curing time may be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

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

In the production of a printed wiring board, (III) a step of piercing the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further carried out. 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. When the support is removed after the step (II), the removal of the support is carried out between the steps (II) and (III), between the steps (III) and (IV) ). If necessary, the multilayer wiring board may be formed by repeating the formation of the insulating layer and the conductor layer in the steps (II) to (V). In this case, it is preferable that the thickness of the insulating layer (t1 in Fig. 1) between the respective conductor layers is within the above range.

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

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

In one embodiment, the arithmetic average roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 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, 100 nm or less. The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact surface roughness meter. As a specific example of the non-contact surface roughness meter, "WYKO NT3300" manufactured by Vico Instrument Co., Ltd. can be mentioned.

Step (V) is a step of forming a conductor layer. Step (V) is a step of forming the first conductor layer when the conductor layer is not formed on the inner layer substrate, and when the conductor layer is formed on the inner layer substrate, the conductor layer is the first conductor layer, 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 comprises at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium . The conductor layer may be either 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, a nickel-chromium alloy, a copper- Titanium alloy). Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper or a nickel-chromium alloy, a copper-nickel alloy And an alloy layer of a 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 a nickel-chromium alloy is more preferable, Is more preferable.

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

The thickness of the conductor layer depends on the design of the desired printed wiring board, but is generally from 3 탆 to 35 탆, preferably from 5 탆 to 30 탆.

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a conventionally known technique such as a semi-custom method or a pull-on method. Hereinafter, an example in which the conductor layer is formed by the semi-specific method is described.

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

Since the resin sheet of the present invention leads to a good insulation layer in terms of wiring embedding property, the resin sheet 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.

The printed wiring board manufactured using the resin sheet of the present invention may have an insulating layer which is a cured product of the resin composition layer of the resin sheet of the present invention and a buried wiring layer embedded in the insulating layer.

The printed wiring board manufactured using the resin sheet of the present invention exhibits excellent insulation reliability even when the thickness of the insulating layer between the first and second conductor layers is 6 mu m or less. The upper limit of the insulation resistance value after lapse of 100 hours under the conditions of 130 캜, 85 RH% and 3.3 V is preferably 10 ¹² Ω or less, more preferably 10 ¹¹ Ω or less, further preferably 10 ¹⁰ Ω or less. The lower limit is not particularly limited, but is preferably 10 ⁶ Ω or higher, more preferably 10 ⁷ Ω or higher. The measurement of the insulation resistance value can be performed according to the method described in &quot; Evaluation of insulation reliability and measurement of insulation layer thickness between conductor layers &quot;.

[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 by using the printed wiring board of the present invention.

Examples of the semiconductor device include various semiconductor devices provided in an electric product (such as a computer, a mobile phone, a digital camera and a television) and a vehicle (such as a motorcycle, a car, a train, have.

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion (conductive portion) of a printed wiring board. The &quot; conduction site &quot; is a &quot; location where electrical signals are transmitted from the printed wiring board &quot;, and the location may be a surface or a buried site. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor material.

The method for mounting the semiconductor chip in manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip can function effectively. Specifically, the method can be applied to a wire bonding mounting method, a flip chip mounting method, a bump- A mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), and the like. Here, the "mounting method using the bumpless buildup layer (BBUL)" is a "mounting method in which the semiconductor chip is directly embedded in the concave portion of the printed wiring board to connect the wiring on the semiconductor chip and the printed wiring board".

Example

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

[Measurement method of physical property value of inorganic filler]

First, a method of measuring the physical property values of the inorganic filler used in Examples and Comparative Examples will be described.

<Measurement of Average Particle Diameter>

, 0.1 g of a dispersing agent (&quot; SN9228 &quot;, manufactured by Sanno Fuco Co., Ltd.) and 10 g of methyl ethyl ketone were placed in a vial bottle and dispersed by ultrasonic wave for 20 minutes. The particle size distribution was measured in a batch cell system using a laser diffraction particle size distribution analyzer (&quot; SALD-2200 &quot;, manufactured by Shimadzu Seisakusho Co., Ltd.) to calculate the average particle diameter based on the median diameter.

&Lt; Measurement of specific surface area &

The specific surface area of the inorganic filler was measured using a BET automatic specific surface area measuring apparatus ("Macsorb HM-1210" manufactured by Mantec 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 the Preparation Example and ultrasonically cleaned at 25 캜 for 5 minutes. The supernatant was then removed and the solids dried. The amount of carbon was measured using a carbon analyzer (&quot; EMIA-320V &quot;, manufactured by Horiba Seisakusho Co., Ltd.) for the obtained solid. The amount of carbon per unit surface area of the inorganic filler was calculated based on the measured value of the amount of carbon and the mass and specific surface area of the used inorganic filler.

&Lt; Production of resin sheet (Examples 1 to 3, Comparative Examples 1 and 2)

Using the resin composition (resin varnish) prepared in the following procedure, resin sheets of Examples and Comparative Examples were prepared.

(Preparation of Resin Composition 1)

3 parts of a bisphenol A type epoxy resin ("YD-8125G", manufactured by Shin-Nettetsu Sumikin Kagaku Co., Ltd., epoxy equivalent weight: about 174), 3 parts of a bisacylenol type epoxy resin "YX4000HK" manufactured by Mitsubishi Chemical Corporation, 8 parts of a bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 238), 3 parts of a naphthalene type epoxy resin ("ESN475V" manufactured by Shinnitetsu Sumikin Kagaku Co., 10 parts), 10 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30 mass%), 12 parts of solvent naphtha And 10 parts of cyclohexanone in a mixed solvent. After cooling to room temperature, 20 parts of an active ester type curing agent ("HPC-8000-65T" manufactured by DIC Corporation, an active equivalent weight of about 225, and a toluene solution of a nonvolatile component of 65 mass%) 20 parts of an oligophenylene ether 10 parts of a styrene resin ("OPE-2St 1200" manufactured by Mitsubishi Chemical Corporation, a toluene solution of a solid content of 72 mass%), 10 parts of an amine curing accelerator (4-dimethylaminopyridine (DMAP), 5 mass% ), 0.4 part of an imidazole-based curing accelerator (&quot; 1B2PZ &quot; 1-benzyl-2-phenylimidazole manufactured by Shikoku Chemicals Corp., MEK solution of 5% in solid content) 2 parts of AC-3401N) were swollen in 10 parts of solvent naphtha at room temperature for 12 hours and spherical silica surface treated with an aminosilane coupling agent (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) Average particle diameter of 0.91 mu m, specific surface area of 6.5 m &lt; 2 &gt; / g, unit surface area of carbon (SP507-05 manufactured by Kinematerials Co., 0.34mg / ㎡) After mixing 160 parts of and, uniformly dispersed in a high-speed rotary mixer, the mixture was filtered through a cartridge filter (produced ROKITECHNO "SHP030") to prepare a resin composition 1.

(Preparation of Resin Composition 2)

2 parts of a bisphenol A type epoxy resin ("YD-8125G", manufactured by Shin-Nettetsu Sumikin Kagaku Co., Ltd., epoxy equivalent weight: about 174), 2 parts of a bisacylenol type epoxy resin "YX4000HK" manufactured by Mitsubishi Chemical Corporation, 5), 5 parts of naphthylene ether type epoxy resin ("EXA-7311-G4" manufactured by DIC Corporation, epoxy equivalent weight of about 213), 5 parts of biphenyl type epoxy resin (NC3000L manufactured by Nippon Kayaku Co., 2 parts of epoxidized polybutadiene (&quot; PB3600 &quot; manufactured by Daicel Co., Ltd., epoxy equivalent of about 193), phenoxy resin (YX7553BH30 manufactured by Mitsubishi Chemical Corp., solid content 30% Of 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK)) was dissolved by heating in a mixed solvent of 15 parts of solvent naphtha and 10 parts of cyclohexanone while heating. After cooling to room temperature, 5 parts of a triazine skeleton-containing cresol novolac curing agent ("LA3018-50P" manufactured by DIC Corporation, hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%), 12 parts of an ester type curing agent ("HPC-8000-65T" manufactured by DIC Corporation, an active agent equivalent of about 225, and a toluene solution of a nonvolatile component of 65% by mass), 12 parts of a carbodiimide resin (V- , 10 parts of a carbodiimide equivalent 216, and 50% by mass of a toluene solution of a nonvolatile component), 1.5 parts of an amine curing accelerator (4-dimethylaminopyridine (DMAP), 5% (Average particle diameter: 1.2 mu m) &quot; HCA-HQ &quot;, 10- (2,5- dihydroxyphenyl) -10-hydro-9-oxa-10- phosphaphenanthrene- (SPH516-05 manufactured by Shin-Nettetsu Sumikin Materials Co., Ltd.) surface-treated with an aminosilane-based coupling agent (KBM573, manufactured by Shin-Etsu Chemical Co., (Specific surface area: 16.3 m 2 / g, carbon content per unit surface area: 0.43 mg / m 2) were mixed and uniformly dispersed with a high-speed rotary mixer, followed by filtration through a cartridge filter ("SHP020" manufactured by ROKITECHNO) To prepare Resin Composition 2.

(Preparation of Resin Composition 3)

, 4 parts of naphthalene type epoxy resin (HP4032SS manufactured by DIC Corporation, epoxy equivalent weight: about 144), 8 parts of naphthylene ether type epoxy resin (EXA-7311-G4 manufactured by DIC Corporation, epoxy equivalent weight: about 213) 15 parts of a naphthalene type epoxy resin ("ESN475V", manufactured by Shin-Nettetsu Sumikin Kagaku Co., Ltd., epoxy equivalent weight 330), 15 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, (1: 1 solution of methyl ethyl ketone (MEK)) 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 Lonsa Japan K.K., a cyanate equivalent weight of about 232, and a nonvolatile matter-containing 75 mass% MEK solution), 20 parts of a polyfunctional cyanate 6 parts of an ester resin ("ULL-950S" manufactured by Lone Japan Co., Ltd., cyanate equivalent of about 230, 75% by mass of nonvolatile content of MEK solution), 6 parts of active ester type curing agent "HPC- 6 parts by weight of a carbodiimide resin ("V-03" manufactured by Nissinbo Chemical Co., Ltd., carbodiimide equivalent weight 216, 50% by weight of a nonvolatile component , 0.4 part of an amine-based curing accelerator (4-dimethylaminopyridine (DMAP), 5% by mass of solid content of MEK solution), 5 parts of a curing accelerator (Cobalt (III) acetylacetonate (III) Ac), 3 parts by mass of a solid content of MEK solution), 3 parts of an aminosilane coupling agent (KBM573 manufactured by Shin-Etsu Chemical Co., (SPH516-05, manufactured by Shin-Nettetsu Sumikin Materials Co., Ltd., average particle diameter: 0.29 mu m, specific surface area: 16.3 m2 / g, carbon amount per unit surface area: 0.43 mg / , Homogeneously dispersed in 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 a bisphenol A type epoxy resin ("828EL" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 186), 15 parts of a biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight: 272) , 5 parts of epoxidized polybutadiene ("PB3600" manufactured by Daicel Co., Ltd., epoxy equivalent of about 193), 5 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation), cyclohexanone in methyl ethyl ketone (1: 1 solution of methyl ethyl ketone (MEK)) was heated and dissolved in a mixed solvent of 10 parts of solvent naphtha and 10 parts of cyclohexanone with stirring. After cooling to room temperature, 5 parts of a triazine skeleton-containing cresol novolac curing agent ("LA3018-50P" manufactured by DIC Corporation, hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%), 12 parts of an ester type curing agent ("HPC-8000-65T" manufactured by DIC Corporation, an active agent equivalent of about 225, and a toluene solution of a nonvolatile component of 65% by mass), 12 parts of a carbodiimide resin (V- , 10 parts of a carbodiimide equivalent 216, and 50% by mass of a toluene solution of a nonvolatile component), 1.5 parts of an amine curing accelerator (4-dimethylaminopyridine (DMAP), 5% (Average particle diameter: 1.2 mu m) &quot; HCA-HQ &quot;, 10- (2,5- dihydroxyphenyl) -10-hydro-9-oxa-10- phosphaphenanthrene- , 2 parts of rubber particles (AC-3355, manufactured by Aika Corp.), 8 parts of solvent naphtha at room temperature for 12 hours, an aminosilane coupling agent (Shinetsu Kagakukogyo Co., Ltd.) (Adomapine SO-C1, manufactured by Adomex Co., Ltd.) having an average particle diameter of 0.63 탆, a specific surface area of 11.2 m 2 / g, a carbon amount of 0.35 mg / m 2 per unit surface area ) Were mixed and homogeneously dispersed with a high-speed rotary mixer, followed by filtration through a cartridge filter ("SHP030" manufactured by ROKITECHNO) to prepare Resin Composition 4.

(Preparation of Resin Composition 5)

, 10 parts of a bisphenol A type epoxy resin ("828EL" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight of about 186), 15 parts of a naphthalene type epoxy resin ("ESN475V" manufactured by Shin Nitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent weight: about 330) , 2 parts of epoxidized polybutadiene ("PB3600" manufactured by Daicel Co., Ltd., epoxy equivalent of about 193), 2 parts of phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Corp.), cyclohexanone Ketone (1: 1 solution of MEK)) was dissolved by heating 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 Lonsa Japan K.K., a cyanate equivalent weight of about 232, and a nonvolatile matter-containing 75 mass% MEK solution), 20 parts of a polyfunctional cyanate 6 parts of an ester resin ("ULL-950S" manufactured by Lone Japan Co., Ltd., cyanate equivalent of about 230, 75% by mass of nonvolatile content of MEK solution), 6 parts of active ester type curing agent "HPC- , 6 parts of a toluene solution of a nonvolatile component of about 225, an active agent equivalent of about 225, and 5 parts of a block type isocyanate resin ("Barnock D-500" manufactured by DIC Corporation, 65% by mass ethyl acetate solution of a nonvolatile component) , 0.4 part of an amine-based curing accelerator (4-dimethylaminopyridine (DMAP), 5 mass% of a solid content MEK solution), 0.4 part of curing accelerator (Co (III) Ac) , 3 parts by mass of a solid content of MEK solution), 3 parts of an aminosilane coupling agent (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) 100 parts of the treated spherical silica (Adomapine SO-C1, manufactured by Adomex, Ltd., average particle diameter 0.63 占 퐉, specific surface area 11.2 m2 / g, carbon amount per unit surface area 0.35 mg / m2) The mixture was uniformly dispersed with a rotary mixer and then filtered through a cartridge filter ("SHP030" manufactured by ROKITECHNO) to prepare Resin Composition 5.

The components used in the preparation of Resin Compositions 1 to 5 and their blending amount (parts by mass of nonvolatile matter) are shown in Table 1 below.

(Production of Resin Sheet of Examples 1 to 3 and Comparative Examples 1 and 2)

(Lamier R80, thickness 38 占 퐉, softening point 130 占 폚, "release PET" manufactured by TORAY CO., LTD.) Which had been subjected to release treatment with an alkyd resin releasing agent (AL- Prepared.

Each of the resin compositions was uniformly coated on the mold release PET with a die coater so that the thickness of the resin composition layer after drying was 40 占 퐉 and dried at 70 占 폚 at 100 占 폚 for 4.5 minutes or 60 占 폚 to 90 占 폚 for 2 minutes Thereby forming a resin composition layer. Subsequently, a roughened surface of a polypropylene film ("ALPAN MA-411" manufactured by Oji-Fetch Co., Ltd., thickness 15 μm) as a protective film was laminated on the surface of the resin sheet not bonded to the support, Respectively. As a result, a resin sheet for dielectric tangent measurement in the order of a support, a resin composition layer and a protective film was obtained.

A resin sheet for measuring the lowest melt viscosity and for measuring insulation reliability was obtained in the same manner as in the resin sheet for measurement of dielectric loss tangent, except that each resin composition was applied on the release PET so that the thickness of the resin composition layer after drying was 13 占 퐉 Respectively.

<Measurement of Minimum Melting Viscosity>

Using a resin sheet having a resin composition layer thickness of 13 占 퐉, only the resin composition layer was peeled off from the release type PET (support) and compressed into a mold to prepare pellets for measurement (diameter 18mm, 1.2 to 1.3g).

Using a parallel plate having a diameter of 18 mm, 1 g of the sample resin composition layer was measured by using a dynamic viscoelasticity measuring apparatus (Rheosol-G3000 manufactured by U. &amp; B / M Co., Ltd.) The dynamic viscoelasticity was measured under the measurement conditions of a temperature interval of 2.5 캜, a frequency of 1 Hz, and a deformation of 1 deg, and the lowest melt viscosity (poise) was calculated.

&Lt; Measurement of dielectric loss tangent of cured product &

(R5715ES, manufactured by Matsushita Electric Industrial Co., Ltd., thickness: 0.7 mm, thickness: 38 mm, 240 mm square) having a thickness of 0.7 mm and an untreated PET film ("501010" 255 mm square), and the four sides of the release PET film were fixed with a polyimide adhesive tape (width 10 mm).

A resin sheet (200 mm square) having a thickness of 40 占 퐉 of the resin composition layer prepared in Examples and Comparative Examples was laminated using a batch type vacuum pressure laminator (2 stage built-up laminator, CVP700, Nikko Corporation) , And the resin composition layer was laminated at the center so as to be in contact with the release surface of a release PET film ("501010" manufactured by Lintec Corporation). The lamination treatment was carried out by reducing the pressure for 30 seconds to bring the air pressure to 13 hPa or less, followed by compression at 100 DEG C and a pressure of 0.74 MPa for 30 seconds.

Subsequently, the resultant was placed in an oven at 100 ° C. for 30 minutes, then transferred to an oven at 180 ° C. at a temperature of 180 ° C., and thermally cured for 30 minutes. Thereafter, the substrate was taken out under a room temperature atmosphere, and the releasing PET (support) was peeled from the resin sheet. Then, the substrate was put into an oven at 200 캜 and thermally cured under a curing condition for 90 minutes.

The above-mentioned &quot; cured product for evaluation &quot; was cut into test pieces having a width of 1.5 mm and a length of 80 mm. Using the HP8362B manufactured by Agilent Technologies, the test piece was measured at a measurement frequency of 10 GHz using a cavity resonance perturbation method Deg.] C, or 150 [deg.] C. The dielectric loss tangent (Df) was measured at a measurement frequency of 10 GHz, a measurement temperature of 23 캜, or 150 캜. Three test specimens were subjected to measurement, and average values were calculated. The results are shown in Table 2.

&Lt; Evaluation of insulation reliability, measurement of thickness of insulation layer between conductor layers &

(Preparation of substrate for evaluation)

(1) Underlayer treatment of inner layer circuit board

A glass fiber-based epoxy resin double-sided copper clad laminate (copper foil having a thickness of 18 탆 and a thickness of 18 탆) having circuit conductors (copper) formed on both sides of a wiring pattern (with a residual rate of 59% 0.3 mm, "R1515F" manufactured by Panasonic Corporation) was prepared. Both surfaces of the inner layer circuit board were subjected to a roughening treatment (copper etching amount: 0.5 mu m) of copper surface with &quot; CZ8201 &quot;

(2) Laminate of resin sheet

A resin sheet having a thickness of 13 占 퐉 of the resin composition layer prepared in the examples and the comparative examples was applied to a resin composition (thickness: 25 占 퐉) using a batch type vacuum pressure laminator (Nikkiso Materials, 2 stage built- Layer was laminated on both sides of the inner-layer circuit board so as to be in contact with the inner-layer circuit board. The laminate was subjected to pressure reduction for 30 seconds to adjust the air pressure to 13 hPa or less, and pressing at 130 DEG C and a pressure of 0.74 MPa for 45 seconds. Then, hot pressing was performed at 120 DEG C and a pressure of 0.5 MPa for 75 seconds.

(3) Thermal curing of the resin composition layer

The inner-layer circuit board laminated with the resin sheet was placed in an oven at 100 ° C under a temperature condition of 100 ° C and then moved to an oven at 180 ° C for 30 minutes and then at 180 ° C for 30 minutes to form an insulating layer .

(4) Formation of via hole

A CO ₂ laser processing machine "605GTWIII (-P)" manufactured by Mitsubishi Denki K.K. was used, and a laser was irradiated from above the support to form an insulating layer on the conductor of the lattice pattern with a top diameter of 70 Mu m) was formed. The laser irradiation conditions were a burst mode (10 kHz) with a mask diameter of 2.5 mm, a pulse width of 16 μs, an energy of 0.39 mJ / short, and a shot count of 2.

(5) Step of performing harmonic treatment

The support was peeled off from the circuit board provided with the via hole, and subjected to desmear treatment. As the desmear treatment, the following wet desmear treatment was carried out.

Wet desmear treatment:

(Aqueous solution of Swelling Dip ㆍ Securent Gant P, diethylene glycol monobutyl ether and sodium hydroxide solution, manufactured by Atotech Japan Co., Ltd.) at 60 캜 for 5 minutes, and then with an oxidizing agent solution (manufactured by Atotech Japan Co., (Concentrate Compact CP), a potassium permanganate concentration of about 6%, and a sodium hydroxide concentration of about 4%) at 80 DEG C for 10 minutes, and finally with a neutralizing solution (Reduction Solution, Securegant P Sulfuric acid aqueous solution) at 40 DEG C for 5 minutes, and then dried at 80 DEG C for 15 minutes.

(6) Step of forming conductor layer

(6-1) Electroless plating process

In order to form a conductor layer on the surface of the circuit board, a conductor layer was formed by performing a plating process (a copper plating process using a chemical solution manufactured by Atotech Japan) including the following steps 1 to 6.

1. Alkali cleaning (cleaning and charge control of the surface of insulating layer with via hole)

Cleaning was carried out at 60 캜 for 5 minutes using a trade name: Cleaning Cleaner Securiganth 902 (trade name).

2. Soft etching (cleaning in via hole)

Sulfuric acid aqueous solution of sodium peroxodisulfate at 30 DEG C for 1 minute.

3. Pre-dip (adjustment of charge on the surface of insulating layer for Pd application)

Pre.Dip Neoganth B (trade name) was used and treated at room temperature for 1 minute.

4. Providing an activator (imparting Pd to the surface of the insulating layer)

Activator Neoganth 834 (trade name) was used and treated at 35 DEG C for 5 minutes.

5. Reduction (reduction of Pd given to insulating layer)

A mixture of Reducer Neoganth WA (trade name) and Reducer Acceralator 810mod. (Trade name) was used and treated at 30 ° C for 5 minutes.

6. Electroless copper plating process (depositing Cu on the surface of the insulating layer (Pd surface))

Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name) and Reducer Cu (trade name) at 35 ° C for 20 minutes. The thickness of the formed electroless copper plating layer was 0.8 mu m.

(6-2) Electroplating process

Subsequently, an electrolytic copper plating process was performed under the condition that copper was filled in the via hole by using the chemical solution manufactured by Atotech Japan Co., Ltd. Thereafter, as a resist pattern for patterning by etching, a land pattern of 1 mm in diameter, which was conducted to the via hole, and a circular conductor pattern of 10 mm in diameter not connected to the lower layer conductor were used, A conductor layer having a land and a conductor pattern was formed. Next, the annealing was performed at 200 캜 for 90 minutes. This substrate was referred to as substrate A for evaluation.

(7) Measurement of insulation layer thickness between conductor layers

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

(8) Evaluation of insulation reliability of insulating layer

The side of the circular conductor with a diameter of 10 mm of the evaluation substrate A obtained above was used as a positive electrode and the side of the lattice conductor (copper) of the inner-layer circuit board connected to the land having a diameter of 1 mm was used as the negative electrode, (Manufactured by J-RAS Co., Ltd., "PM422" manufactured by ETAC Co., Ltd.) under the conditions of 130 ° C, 85% relative humidity and 3.3V DC voltage, ECM-100 &quot;) (n = 6). The case where the insulation resistance value of all the six test pieces was 10 ⁷ ? Or more was evaluated as &quot;?&Quot;, and in the case where the insulation resistance value was less than 10 ⁷ ?, the evaluation results were shown in Table 2. The insulation resistance values shown in Table 2 are the lowest values of the insulation resistance values of the six test pieces.

5: first conductor layer
51: Main surface of first conductor layer
6: second conductor layer
61: main surface of the second conductor layer
7: Insulation layer

Claims (10)

As a resin sheet comprising a support and a resin composition layer bonded on the support,
The dielectric loss tangent at 23 deg. C of the cured product of the resin composition layer at a measurement frequency of 10 GHz is 0.006 or less,
Wherein the cured product of the resin composition layer has a dielectric loss tangent of 0.01 or less at a measurement frequency of 10 GHz and 150 캜. The resin sheet according to claim 1, wherein the thickness of the resin composition layer is 15 占 퐉 or less. The resin sheet according to claim 1, wherein the minimum melt viscosity of the resin composition layer is 1000 poise or more. The resin sheet according to claim 1, wherein the resin composition layer contains an epoxy resin and a curing agent. The resin sheet according to claim 1, wherein the content of the inorganic filler is 50% by mass or more when the resin composition layer contains an inorganic filler and the nonvolatile component in the resin composition layer is 100% by mass. The resin sheet according to claim 1, which is for forming an insulating layer of a printed wiring board. The resin sheet according to claim 1, wherein the resin sheet is for forming an insulation layer of a high frequency substrate of 1 GHz or more. 8. The semiconductor device according to any one of claims 1 to 7, comprising a first conductor layer, a second conductor layer, and an insulating layer insulating the first conductor layer and the second conductor layer, And the thickness of the insulating layer between the second conductor layers is 6 占 퐉 or less. A first conductor layer, a second conductor layer, and an insulation layer insulating the first conductor layer and the second conductor layer, wherein the insulation layer between the first conductor layer and the second conductor layer has a thickness of 6 m or less As a 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 7. A semiconductor device comprising the printed wiring board according to claim 9.

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