TW201738311A - Resin sheet having an insulation layer with excellent insulation performance - Google Patents

Abstract

To provide a resin sheet having a thinner insulation layer with excellent insulation performance. A resin sheet, which comprises a support body, and a resin sheet of a resin composition layer bonded on the support body, the dielectric tangent of the cured product of the resin composition layer measured at a frequency of 10GHz at 23 DEG C is 0.006 or less, the dielectric tangent of the cured product of the resin composition layer measured at a frequency of 10GHz at 150 DEG C is 0.01 or less. Further, the thickness of the resin composition layer is 15[mu]m or less; the most lower melt viscosity of the resin composition layer is 1000 poise or more; and the resin composition layer comprises an inorganic filler and the content of which is 50 mass% or more when the non-volatile components in the resin composition layer is set as 100 mass%.

Description

Resin sheet

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

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

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2014-152309

In Patent Document 1, the inventors have found that the film is applied In the case of the insulating layer, the roughness tends to increase and the peel strength tends to decrease. In order to solve such problems, it has been proposed to set the blending amount of the thermoplastic resin to a predetermined amount. However, in this document, there is no research on the insulating property (hereinafter also referred to as "thin film insulating property") when the thickness of the insulating layer is made thin.

When the insulating layer is a thin film, the inorganic filler particles are in contact with each other to make the current flow more easily, or the thickness of the insulating layer is thin, and it is more difficult to maintain the insulating performance by increasing the electrostatic capacitance and causing the short circuit.

An object of the present invention is to provide a resin sheet which can impart a thin insulating layer excellent in insulating properties.

In order to solve the problem, the present inventors have found that the cured product of the resin composition layer satisfies the specific resin sheet including the support and the resin composition layer bonded to the support. Dielectric tangent, although thin in thickness, imparts excellent insulating properties (excellent film insulation) to the insulating layer. In particular, the present inventors have found that by not only reducing the dielectric tangent of the cured product of the resin composition layer in a normal temperature environment, but also reducing the dielectric tangent of the cured product of the resin composition layer in a high temperature environment, The insulating layer excellent in insulating property of the film is provided, and the present invention is completed.

That is, the present invention includes the following contents.

[1] A resin sheet comprising a support and a resin sheet bonded to a resin composition layer on the support, the resin composition layer being hard The dielectric tangent of the compound at a measurement frequency of 10 GHz and 23 ° C is 0.006 or less, and the dielectric tangent of the cured product of the resin composition layer at a measurement frequency of 10 GHz and 150 ° C is 0.01 or less.

[2] The resin sheet according to [1], wherein the resin composition layer has a thickness of 15 μm or less.

[3] The resin sheet according to [1] or [2] wherein the resin composition layer has a minimum melt viscosity of 1000 poise or more.

[4] The resin sheet according to any one of [1] to [3] wherein the resin composition layer contains an epoxy resin and a curing agent.

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

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

[7] The resin sheet according to any one of [1] to [5] which is used for forming an insulating layer of a high frequency substrate of 1 GHz or more.

[8] The resin sheet according to any one of [1] to [7], comprising a first conductor layer, a second conductor layer, and an insulating layer that insulates the first conductor layer and the second conductor layer, The insulating layer of the printed wiring board having a thickness of the insulating layer between the first conductor layer and the second conductor layer of 6 μm or less is formed.

[9] A printed wiring board comprising: a first conductor layer, a second conductor layer, and an insulating layer that insulates the first conductor layer and the second conductor layer, and an insulating layer between the first conductor layer and the second conductor layer The thickness of the print is 6μm or less The cured wiring layer is a cured product of a resin composition layer of the resin sheet according to any one of [1] to [8].

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

According to the present invention, it is possible to provide a resin sheet which can impart a thin insulating layer excellent in insulating properties.

5‧‧‧1st conductor layer

51‧‧‧Main surface of the first conductor layer

6‧‧‧2nd conductor layer

61‧‧‧Main surface of the second conductor layer

7‧‧‧Insulation

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

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

The resin sheet of the present invention comprises a support and a resin composition layer bonded to the support. In the present invention, the cured product of the resin composition layer has a dielectric tangent at a measurement frequency of 10 GHz and 23 ° C of 0.006 or less, and a cured tangent of the resin composition layer at a measurement frequency of 10 GHz and 150 ° C. It is 0.01 or less.

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

[Resin composition]

The resin composition is not particularly limited, and the cured product of the resin composition layer formed of the resin composition may be a dielectric tangent that satisfies the above. The resin composition which imparts a cured product satisfying a predetermined dielectric tangent is, for example, a composition comprising a curable resin and a curing agent. As the curable resin, a conventionally known curable resin used in forming an insulating layer of a 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. The resin composition preferably contains (C) an inorganic filler. The resin composition may further contain an additive such as a thermoplastic resin, a hardening accelerator, a flame retardant, and an organic filler, if necessary.

Hereinafter, (A) epoxy resin, (B) hardener, (C) inorganic filler, and an additive which can be used as a material of a resin composition are demonstrated.

<(A) Epoxy Resin>

(A) Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, and dicyclopentadiene type ring. Oxygen resin, phenolic epoxy resin, naphthol novolac epoxy resin, phenol novolak epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol ring Oxygen resin, onion type epoxy resin, epoxy propyl amine type epoxy resin, epoxy propyl ester type epoxy Resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, An epoxy resin containing a spiro ring, a cyclohexanedimethanol type epoxy resin, a naphthyl ether type epoxy resin, a trimethylol type epoxy resin, a tetraphenylethane type epoxy resin, or the like. Epoxy resins may be used alone or in combination of two or more. The component (A) is preferably one or more selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, and biphenyl type epoxy resins.

The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile content of the epoxy resin is 100% by mass, it is preferably at least 50% by mass or more of an epoxy resin having two or more epoxy groups in one molecule. In particular, it is preferably an epoxy resin having two or more epoxy groups in one molecule and having a liquid state at a temperature of 20 ° C (hereinafter referred to as "liquid epoxy resin"), and having 3 molecules in one molecule. One or more epoxy groups and an epoxy resin (hereinafter referred to as "solid epoxy resin") having a solid temperature of 20 ° C. As the epoxy resin, the liquid epoxy resin and the solid epoxy resin are used in combination to have excellent flexibility, and also to improve the breaking strength of the cured product of the resin composition layer. In particular, the solid epoxy resin has high heat resistance, and it is easy to lower the dielectric tangent of the cured product of the resin composition layer even at a high temperature.

As the liquid epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, a epoxy propyl ester type epoxy resin, or the like is preferable. Epoxypropylamine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, Cyclohexane dimethanol type epoxy resin, epoxy propyl amine type epoxy resin, and epoxy resin having butadiene structure, more preferably epoxy propyl amine type epoxy resin, bisphenol A type epoxy Resin, bisphenol F epoxy resin, bisphenol AF epoxy resin and naphthalene epoxy resin. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Co., Ltd., "828US" manufactured by Mitsubishi Chemical Corporation, and "jER828EL". (bisphenol A epoxy resin), "jER807" (bisphenol F epoxy resin), "jER152" (phenol novolak epoxy resin), "YL7760" (bisphenol AF epoxy resin), "630", "630LSD" (epoxypropylamine type epoxy resin), "ZX1059" made by Nippon Steel & Sumitomo Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) "Y--8125G" (bisphenol A type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., "EX-721" (epoxypropyl ester type epoxy resin) manufactured by Nippon Chemical Co., Ltd. "Celoxide 2021P" (an alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure), and "Nippon Steel Chemical Co., Ltd." manufactured by Daicel. ZX1658", "ZX1658GS" (liquid 1,4-epoxypropylcyclohexane), "630LSD" (epoxypropylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used alone or in combination of two or more.

As the solid epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a phenol type epoxy resin, a naphthol type epoxy resin is preferable. , biphenyl type epoxy resin, naphthyl ether type epoxy resin, onion type epoxy resin, bisphenol A type epoxy The resin and the tetraphenylethane type epoxy resin are more preferably a naphthalene type tetrafunctional epoxy resin, a naphthol type epoxy resin, and a biphenyl type epoxy resin. Specific examples of the solid epoxy resin include "HP4032H" (naphthalene epoxy resin), "HP-4700", and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Corporation. "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" ( Dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (stretching naphthyl ether type) "EPPN-502H" (phenolic epoxy resin), "NC7000L" (naphthol novolak type epoxy resin), "NC3000H", "NC3000", "Nippon Chemical Co., Ltd." NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., "ESN485" (naphthol novolac type epoxy resin), "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (Bixylenol type epoxy resin) and "YX8800" (onion type epoxy resin) manufactured by Mitsubishi Chemical Corporation "PG-100" and "CG-" of Osaka Gas Chemical Co., Ltd. 500", "YL7800" (茀-type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1010" (solid bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1031S" (tetraphenyl) Ethane type epoxy resin).

From the viewpoint of lowering the dielectric tangent of the cured product of the resin composition layer even at a high temperature, the epoxy resin is preferably a resin having a high purity (for example, a resin having a small amount of ionic impurities such as chloride ions). As pure For example, "828US", "YL980", "1750", "YL983U" made by Mitsubishi Chemical Corporation, "YD-8125G" manufactured by Nippon Steel & Co., Ltd., "YD" -825GS", "ZX-1658GS", "YDF-8170G", etc.

The liquid epoxy resin is preferably an aromatic epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C, and is preferably a solid epoxy resin. An aromatic epoxy resin having three or more epoxy groups in a molecule and being solid at a temperature of 20 ° C. Further, the term "aromatic epoxy resin" as used in the present invention means an epoxy resin having an aromatic ring structure in its molecule.

In the case of an epoxy resin and a liquid epoxy resin and a solid epoxy resin, the ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.5 to 1:15. The scope. By setting the ratio of the amount of the liquid epoxy resin to the solid epoxy resin to be in this range, i) is obtained in the form of a resin sheet to give an appropriate adhesive property, and ii) when used in the form of a resin sheet. The flexibility is sufficient to improve the workability, and iii) the effect of obtaining a cured product of the resin composition layer having sufficient breaking strength. From the viewpoint of the effects of the above i) to iii), the ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is preferably 1:1.0 by mass ratio. The range of ~1:12 is more preferably in the range of 1:1.3 to 1:10.

The content of the epoxy resin in the resin composition is preferably 5% by mass or more, more preferably 9% by mass or more, more preferably from the viewpoint of obtaining an insulating layer having a low dielectric tangent and exhibiting insulating reliability. For 11 quality %the above. The upper limit of the content of the epoxy resin is not particularly limited as long as it exhibits the effects of the present invention, but is preferably 50% by mass or less, and more preferably 40% by mass or less.

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

The epoxy equivalent of the epoxy resin is preferably from 50 to 5,000, more preferably from 50 to 3,000, still more preferably from 80 to 2,000, still more preferably from 110 to 1,000. By setting it as such a range, it is possible to provide an insulating layer in which the crosslinking density of the cured product of the resin composition layer is small and the surface roughness is small. Further, the epoxy equivalent can be measured in accordance with JIS K7236 and is a mass of a resin containing 1 equivalent of an epoxy group.

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

<(B) hardener>

The curing agent is not particularly limited as long as it has a function of curing the epoxy resin, and examples thereof include a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, and cyanogen. An acid ester curing agent, a carbodiimide curing agent, and the like. The curing agent may be used alone or in combination of two or more.

As a phenolic curing agent and a naphthol-based curing agent, heat resistance From the viewpoint of water resistance, a phenol-based curing agent having a novolac structure or a naphthol-based curing agent having a novolak structure is preferable. Moreover, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferred, and a phenol-based curing agent containing a triazine skeleton is more preferred. Among them, from the viewpoint of satisfying heat resistance, water resistance, and adhesion to a conductor layer, a phenol novolak hardener containing a triazine skeleton is preferable.

Specific examples of the phenolic curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851", and Nippon Chemical Co., Ltd., manufactured by Megumi Kasei Co., Ltd. "SNN", "CBN", "GPH", Nippon Steel & Living Co., Ltd. "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V" "SN-3090", "SN395", "DIC-7", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-" 9500" and so on.

The active ester-based curing agent is not particularly limited, but generally, it is preferable to use phenol esters, thiophenol esters, N-hydroxylamine esters, esters of heterocyclic hydroxy compounds, etc. in one molecule. More than one ester group with high reactivity. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a sulfuric acid compound with a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent derived from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester system derived from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. hardener. Examples of the carboxylic acid compound include benzoic acid and acetic acid. Succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, and methylated double. Phenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1 ,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene Type diphenol compound, phenol novolak, and the like. Here, the "dicyclopentadiene type diphenol compound" means a diphenol compound obtained by condensing a phenol 2 molecule with a molecule of dicyclopentadiene.

Specifically, it is preferably an active ester compound comprising a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetal of a phenol novolac, and a benzaldehyde containing a phenol novolac. The active ester compound of a mercapto compound is more preferably an active ester compound containing a naphthalene structure or an active ester compound containing a dicyclopentadiene type diphenol structure. The "dicyclopentadiene type diphenol structure" is a divalent structural unit composed of a phenyl-bicyclopentyl-phenylene group.

As a commercial product of the active ester-based curing agent, examples of the active ester compound containing a dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and " HPC-8000H-65TM and "EXB-8000L-65TM" (manufactured by DIC), as an active ester compound containing a naphthalene structure, "EXB9416-70BK" (manufactured by DIC), as a phenolic phenolic aldehyde "DC808" (manufactured by Mitsubishi Chemical Corporation), and an active ester compound containing a benzoquinone-based phenol novolak, "YLH1026" (Mitsubishi Chemical Co., Ltd.) And the active ester-based curing agent of the acetal phenol varnish, which is an active ester-based curing agent of benzoquinone-based phenol novolac, "YLH1026" (Mitsubishi Chemical Co., Ltd.), "YLH1030" (Mitsubishi Chemical Co., Ltd.), and "YLH1048" (Mitsubishi Chemical Co., Ltd.) can be cited.

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industries Co., Ltd.

Examples of the cyanate-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylenecyanate), and 4,4'. -methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2- Bis(4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1, 3-bis(4-cyanate phenyl-1-(methylethylidene)) benzene, bis(4-cyanate phenyl) sulfide, and bis(4-cyanate phenyl) ether A polyfunctional cyanate resin derived from a bifunctional cyanate resin, a phenol novolac, a cresol novolak, or the like, and a triazine-based prepolymer such as a cyanate resin. Specific examples of the cyanate-based curing agent include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate resin) manufactured by Lonza Japan Co., Ltd., and "ULL-950S" (polyfunctional cyanic acid). Ester resin), "BA230", "BA230S75" (part of bisphenol A dicyanate or All triazines become prepolymers of terpolymers and the like.

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

The component (B) is preferably one or more selected from the group consisting of a phenolic curing agent, a naphthol curing agent, an active ester curing agent, and a cyanate curing agent. Moreover, from the viewpoint of reducing the dielectric tangent of the cured product of the resin composition layer at a high temperature, it is preferred that the curing agent has high heat stability. Examples of the curing agent having high heat stability include an active ester curing agent, a cyanate curing agent, and a carbodiimide curing agent. Among these, from the viewpoint of high hydrophobicity and lowering the dielectric tangent of the cured product of the resin composition layer at a high temperature, it is more preferably selected from the group consisting of an active ester-based hardener and a cyanate-based hardener. One or more kinds are more preferably an active ester-based curing agent.

The ratio of the amount of the epoxy resin to the hardener is in the range of [the total number of epoxy groups of the epoxy resin]: [the total number of the reactive groups of the hardener], preferably in the range of 1:0.01 to 1:2, The ratio is 1:0.015~1:1.5, and more preferably 1:0.02~1:1. 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 type of the curing agent. Further, the total number of epoxy groups of the epoxy resin is a total value obtained by dividing the solid content of each epoxy resin by the value of the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is The value obtained by dividing the solid content of each hardener by the value of the reactive base equivalent for all the hardeners. By setting the amount ratio of the epoxy resin to the hardener to be in this range, the heat resistance of the cured product of the resin composition layer is further enhanced.

In one embodiment, the resin composition comprises the aforementioned ring Oxygen resin and hardener. The resin composition is preferably used as the (A) epoxy resin, and comprises a mixture of a liquid epoxy resin and a solid epoxy resin (liquid epoxy resin: the quality of the solid epoxy resin is preferably 1:0.1~) 1:15, more preferably 1:0.3 to 1:12, still more preferably 1:0.6 to 1:10), and the (B) hardener is selected from the group consisting of a phenolic hardener, a naphthol hardener, and an active agent. One or more of the group consisting of an ester-based curing agent and a cyanate-based curing agent (preferably one or more selected from the group consisting of an active ester-based curing agent and a cyanate-based curing agent) .

The content of the curing agent in the resin composition is not particularly limited, but is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less. Further, 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 comprise an inorganic filler. The material of the inorganic filler is not particularly limited, and examples thereof include cerium oxide, aluminum oxide, glass, cordierite, cerium oxide, barium sulfate, cerium carbonate, talc, clay, mica powder, zinc oxide, and hydrotalcite. Boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, barium carbonate, barium titanate, calcium titanate, titanic acid Magnesium, barium titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate, and the like. Among these, it is especially suitable for cerium oxide. Examples of the cerium oxide include amorphous cerium oxide, molten cerium oxide, crystalline cerium oxide, and synthetic cerium oxide. Empty ruthenium dioxide and the like. Further, as the cerium oxide, spherical cerium oxide is preferred. The inorganic filler may be used singly or in combination of two or more.

The average particle diameter of the inorganic filler is preferably 1.5 μm or less, more preferably 1.3 μm or less, still more preferably 1.0 μm or less, from the viewpoint of improving the insulating properties of the high-filled inorganic filler. Below 0.9 μm. The lower limit of the average particle diameter is preferably 0.05 μm or more, more preferably 0.06 μm or more, and still more preferably 0.07 μm or more from the viewpoint of improving the dispersibility in the resin composition layer. As a commercially available product of the inorganic filler having such an average particle diameter, for example, "UFP-30" manufactured by the Electrochemical Industry Co., Ltd., "SPH516-05" manufactured by Nippon Steel & Sumitomo Metal Co., Ltd., and Nippon Steel & Sumitomo Metal Co., Ltd. Material (stock) system "SP507-05" and so on.

The average particle size of the inorganic filler can be determined by laser diffraction and scattering according to the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter can be determined by setting the median diameter to an average particle diameter. As the measurement sample, those in which the inorganic filler is dispersed in methyl ethyl ketone by ultrasonic waves can be preferably used. As the laser diffraction scattering type particle size distribution measuring apparatus, "SALD-2200" manufactured by Shimadzu Corporation can be used.

The specific surface area of the inorganic filler, the melt viscosity of the lowest point of view of said resin composition layer is reduced from the point of view, is preferably 40m ² / g or less, more preferably 37m ² / g or less, and still more preferably 33m ² / g the following. The lower limit of the specific surface area is preferably 1 m ² /g or more, more preferably 2 m ² /g or more, and still more preferably 5 m ² /g or more from the viewpoint of maintaining proper viscoelasticity of the resin composition layer. The specific surface area can be measured, for example, using a BET fully automatic specific surface area measuring device (manufactured by Mountech Co., Ltd., Macsorb HM-1210).

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 true density is preferably 1 g/cm ³ or more, more preferably 1.5 g/cm ³ or more, still more preferably 2.0 g/cm ³ or more. The true density can be measured, for example, using a micro-superdensimeter (Conta Instruments Japan, MUPY-21T).

The inorganic filler is preferably subjected to surface treatment with at least one surface treatment agent such as a decane coupling agent, an alkoxydecane compound, or an organic decazane compound from the viewpoint of improving moisture resistance and dispersibility. These may be oligomers. Examples of the surface treatment agent include a decane-based coupling agent such as an amino decane-based coupling agent, an epoxy decane-based coupling agent, and a mercapto decane-based coupling agent, an alkoxydecane compound, an organic decazane compound, and a titanate. Coupling agent, etc. For example, "KBM403" (3-glycidoxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" manufactured by Shin-Etsu Chemical Co., Ltd. (3) are commercially available as a surface treatment agent. "Methyl propyl trimethoxy decane", "KBE903" (3-aminopropyltriethoxy decane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-based) manufactured by Shin-Etsu Chemical Co., Ltd. "3-Aminopropyltrimethoxydecane", "SZ-31" (hexamethyldioxane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd.矽 )), "KBM-4803" (long-chain epoxy decane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd. The surface treatment agent may be used alone or in combination of two or more.

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 amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, still more preferably 0.2 from the viewpoint of improving the dispersibility of the inorganic filler. Mg/m ² or more. On the other hand, from the viewpoint of suppressing the melt viscosity of the resin varnish and the increase in the melt viscosity of the sheet form, 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.

The amount of carbon per unit surface area of the inorganic filler can be measured by washing the surface-treated inorganic filler with a solvent such as methyl ethyl ketone (MEK). Specifically, as a solvent, a sufficient amount of MEK was added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning was performed at 25 ° C for 5 minutes. After removing the supernatant and drying the solid portion, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.

The content (filling amount) of the inorganic filler in the resin composition is from the viewpoint of improving the thickness stability of the resin composition layer and reducing the dielectric tangent of the insulating layer (hardened material of the resin composition layer). When the nonvolatile content in the composition is 100% by mass, it is 50% by mass or more, preferably 55% by mass or more, and more preferably 60% by mass or more. The upper limit of the content of the inorganic filler in the resin composition is preferably 85% by mass or less, and more preferably 80% by mass or less from the viewpoint of improving the insulating properties of the film.

<(D) Thermoplastic Resin>

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

Examples of the thermoplastic resin include a phenoxy resin, a polyvinyl acetal resin, a polyolefin resin, a polybutadiene resin, a polyimine resin, a polyamidimide resin, a polyether phthalimide resin, and a poly An anthracene resin, a polyether oxime resin, a polyphenylene ether resin, a polycarbonate resin, a polyether ether ketone resin, a polyester resin, preferably a phenoxy resin. The thermoplastic resin may be used singly or in combination of two or more.

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

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

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 "electrodinated butyral 4000-2", "electrodinated butyral 5000-A", and "electrodinated butyral 6000-C" manufactured by Electrochemical Industry Co., Ltd. "S-LEC BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, BM series, etc., manufactured by Sekisui Chemicals Co., Ltd.".

Specific examples of the polyimine resin include "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Nippon Chemical and Chemical Co., Ltd. Specific examples of the polyimine resin include a linear polyimine obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (JP-A-2006-37083) Polyimine described), polyimine containing polyoxyalkylene skeleton (Japanese special open A modified polyimine such as polyethylenimine described in JP-A-2000-319386, and the like.

Specific examples of the polyamidoximine resin include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Further, as a specific example of the polyamidoximine resin, a modification of "KS9100" and "KS9300" (polyamide containing a polyoxyalkylene skeleton) manufactured by Hitachi Chemical Co., Ltd. Polyamidoximine.

Specific examples of the polyether oxime resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Specific examples of the polybenzazole resin include polydiprene "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd.

Specific examples of the polyphenylene ether resin include oligophenylene styrene resin and styrene resin "OPE-2St1200", "OPE-2St2200" manufactured by Mitsubishi Gas Chemical 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. According to one embodiment, the thermoplastic resin is one or more selected from the group consisting of a phenoxy resin, a polyphenylene ether resin, and a polyvinyl acetal resin. From the viewpoint of high hydrophobicity and a reduction in the dielectric tangent of the cured product of the resin composition layer at a high temperature, a phenoxy resin or a polyphenylene ether resin is more preferable.

When the resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably from 0.5% by mass to 10% by mass, more preferably 0.6% by mass. The mass % to 6 mass%, and more preferably 0.7 mass% to 5 mass%.

<(E) hardening accelerator>

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

Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, an lanthanum-based curing accelerator, a metal-based curing accelerator, and an organic peroxide-based curing accelerator. The phosphorus-based curing accelerator, the amine-based curing accelerator, the imidazole-based curing accelerator, and the metal-based curing accelerator are more preferably an amine-based curing accelerator, an imidazole-based curing accelerator, or a metal-based curing accelerator. The curing accelerator may be used alone or in combination of two or more.

Examples of the phosphorus-based hardening accelerator include triphenylphosphine, bismuth borate compound, tetraphenylphosphonium tetraphenyl borate, n-butyl phosphotetraphenyl borate, and tetrabutyl decanoic acid. a salt, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., preferably triphenylphosphine, tetrabutyl Sulfate.

Examples of the amine-based curing accelerator include a trialkylamine such as triethylamine or tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, and a ginseng. (dimethylaminomethyl) phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine, 1,8-di Azabicyclo(5,4,0)-undecene.

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl group. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyl Imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2- Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidinium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-Methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]- Ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4 -diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a] Imidazole compound of benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, etc., and an imidazole compound and an epoxy resin An adduct, preferably 2-ethyl-4-methylimidazole , 1-benzyl-2-phenylimidazole.

As the imidazole-based hardening accelerator, a commercially available product can be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation and "1B2PZ" manufactured by Shikoku Chemical Industries Co., Ltd.

Examples of the oxime-based hardening accelerator include dicyandiamide, 1-methyl hydrazine, 1-ethyl hydrazine, 1-cyclohexyl hydrazine, 1-phenyl fluorene, 1-(o-methylphenyl) fluorene, and dimethyl Base, diphenyl hydrazine, trimethyl hydrazine, tetramethyl hydrazine, pentamethyl hydrazine, 1,5,7-triazabicyclo[4.4.0]non-5-ene, 7-methyl-1 , 5,7-triazabicyclo[4.4.0]non-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-di Ethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenylbiguanide, 1-(o-methylphenyl)biguanide, etc., preferably dicyandiamide, 1,5,7-triaza Bicyclo [4.4.0] 癸-5-ene.

Examples of the metal-based curing accelerator include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt(II) acetylacetonate, cobalt(III) acetoacetate, and copper (II) such as copper(II) pyruvate. Organic zinc complex such as zinc acetylate (II), organic iron complex such as iron(III) pyruvate, and organic nickel complex of nickel(II) acetate An organic manganese complex such as acetaminophen (II) pyruvate or the like. Examples of the organic metal salt include zinc octoate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

Examples of the organic peroxide-based hardening accelerator include dicumyl peroxide, cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, and dicumyl. Peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, and the like. A commercially available product can be used as the organic peroxide-based hardening accelerator, and examples thereof include "PERCUMYL D" manufactured by Nippon Oil Co., Ltd., and the like.

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

<(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-based flame retardant, a phosphorus compound containing an organic nitrogen, a nitrogen compound, a xenon-based flame retardant, and a metal hydroxide. The flame retardant may be used alone or in combination of two or more.

As a flame retardant, a commercially available product can be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd., and "PX-200" manufactured by Daiha Chemical Industry Co., Ltd., and the like. As the flame retardant, those which are difficult to be hydrolyzed are preferable, and for example, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide or the like is 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, even more preferably 0.5% by mass to 10% by mass is more preferable.

<(G) organic filler>

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

Commercially available products can be used as the rubber particles, and examples thereof include "EXL 2655" manufactured by Dow Chemical Co., Ltd., "AC3401N" manufactured by AICA Industrial Co., Ltd., and "AC3816N".

The rubber particles are preferably low in ionicity and can reduce the dielectric tangent of the cured product of the resin composition layer. "AC3816N" and "AC3401N" manufactured by AICA Industrial Co., Ltd.

When the resin composition contains an organic filler, the content of the organic filler is preferably from 0.1% by mass to 20% by mass, more preferably from 0.2% by mass to 10% by mass, even more preferably from 0.3% by mass to 5% by mass, Or 0.5% by mass to 3% by mass.

<(H) Other additives>

The resin composition may further contain other additives as necessary, and examples of the other additives include organometallic compounds such as an organic copper compound, an organic zinc compound, and an organic cobalt compound, and an adhesion promoter, an antifoaming agent, and a leveling agent. A resin additive such as a tackifier or a coloring agent.

The resin sheet of the present invention provides an insulating layer (hardened product of a resin composition layer) excellent in film insulating properties. Accordingly, 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 more suitably used as an interlayer insulating layer for forming a printed wiring board. The resin sheet (resin sheet for the interlayer insulating layer of the printed wiring board) is used. Further, for example, in the printed wiring board including the first conductor layer, the second conductor layer, and the insulating layer provided between the first conductor layer and the second conductor layer, the insulating layer can be formed of the resin sheet of the present invention. The thickness of the insulating layer between the first and second conductor layers is 6 μm or less (preferably 5.5 μm or less, more preferably 5 μm or less) and the insulating property is excellent. In a preferred embodiment, the resin sheet of the present invention comprises a first conductor layer, a second conductor layer, and an insulating first conductor layer and The insulating layer of the two-conductor layer is formed of an insulating layer of a printed wiring board having a thickness of an insulating layer between the first conductor layer and the second conductor layer of 6 μm 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 μm or less, more preferably 12 μm or less, still more preferably 10 μm or less, still more preferably 8 μm or less from the viewpoint of thickness reduction 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 μm or more, 1.5 μm or more, 2 μm or more.

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

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter, Polyester, polycarbonate (hereinafter sometimes abbreviated as "PC"), polymethyl methacrylate (PMMA), etc., etc. Mercapto cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimine, and the like. Among them, polyethylene terephthalate or polyethylene naphthalate is preferred, and polyethylene terephthalate is particularly preferred.

In the case of using a metal foil as the support, examples of the metal foil include a copper foil, an aluminum foil, and the like, and a copper foil is preferable. As a copper foil, A foil composed of a single metal of copper may be used, or a foil composed of an alloy of copper and other metals such as tin, chromium, silver, magnesium, nickel, zirconium, hafnium, titanium, or the like may be used.

The support can be subjected to matting treatment, corona treatment, and antistatic treatment on the surface joined to the resin composition layer.

Further, as the support, a support for releasing the release layer having a release layer can be provided on the surface to be bonded to the resin composition layer. The release agent used for the release layer of the support to which the mold release layer is attached may, for example, be selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin. One or more release agents. A commercially available product can be used as the support for the mold release layer. For example, "SK-1" and "AL" manufactured by Lintec Co., Ltd., which is a release film having a release layer containing an alkyd resin release agent as a main component, can be used. -5", "AL-7", "LumilarT6AM" and "LumilarR80" made by Toray (share).

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support having a release layer is used, the thickness of the entire support having the release layer is preferably in the above range.

The resin sheet can be produced, for example, by preparing a resin varnish which dissolves the resin composition in an organic solvent, and applying the resin varnish to a support using a die coater or the like, followed by drying to form a resin composition layer.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl ether acetate. B, such as carbitol acetate Carboxyl alcohols such as acid esters, cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide (DMAc) and N- A guanamine-based solvent such as methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

Drying can be carried out by a known method of heating, blowing hot air or the like. The drying condition is not particularly limited, but the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it is different in the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the resin can be formed by drying at 50 ° C to 150 ° C for 3 minutes to 10 minutes. Composition layer.

In the resin sheet, a protective film according to the support may be further laminated on a surface that is not bonded to the support of the resin composition layer (that is, a surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion or scratching of dust or the like on the surface of the resin composition layer can be prevented. The resin sheet can be wound into a roll to be stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

The lowest melt viscosity of the resin composition layer of the resin sheet is preferably 12,000 poise (1200 Pa.s) or less, more preferably 10,000 poise (1000 Pa.s) or less, from the viewpoint of obtaining good wiring embedding property, and further Preferably, it is 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 from the viewpoint that the resin composition layer is thin and the thickness is maintained and maintained. Preferably, it is preferably 1000 poise (100 Pa.s) or more, more preferably 1500 poise (150 Pa.s) or more, and even more preferably 2000 poise (200 Pa.s) or more.

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 layer is heated at a constant temperature increase rate to melt the resin, the melt viscosity in the initial stage decreases as the temperature rises, and then rises more than a certain degree as the temperature increases the melt viscosity. The lowest melt viscosity refers to the melt viscosity of the minimum point. The lowest melt viscosity of the resin composition layer can be measured by a dynamic viscoelastic method, and can be measured, for example, by the method described in <Measurement of the lowest melt viscosity> described later.

[hardened material]

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

The cured product of the resin composition layer satisfying the specific dielectric tangent as described above, which is contained in the resin composition (for example, an epoxy resin and a hardener), can be used by using a resin having a high purity or being difficult to be hydrolyzed. The resin is used, or a resin having high heat resistance or a resin having high hydrophobicity (for example, an active ester-based curing agent or an oligo-phenylene ether) or the like is used.

The thermosetting condition of the resin composition layer of the resin sheet of the present invention is not particularly limited, and for example, a printed wiring board to be described later can be used. The conditions normally used for insulation. Further, preliminary heating may be performed before the thermosetting resin composition layer, and heating under thermal curing conditions may include preliminary heating for a plurality of times. As an example of the thermosetting condition, the resin composition layer is first thermally cured at 100 ° C for 30 minutes, secondly at 180 ° C for 30 minutes, and further at 200 ° C 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 a resin composition layer at 100 ° C for 30 minutes, followed by 180 ° C for 30 minutes, and further at 200 ° C for 90 minutes) The dielectric tangent at a frequency of 10 GHz and 23 ° C is preferably 0.005 or less, more preferably 0.004 or less, still more preferably 0.003 or less from the viewpoint of an insulating layer which is excellent in film insulating properties.

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 a resin composition layer at 100 ° C for 30 minutes, followed by 180 ° C for 30 minutes, and further at 200 ° C for 90 minutes) The dielectric tangent at a frequency of 10 GHz and 150 ° C is preferably 0.009 or less, more preferably 0.008 or less, still more preferably 0.007 or less from the viewpoint of an insulating layer which is excellent in film insulating properties.

The cured product of the resin composition layer has a dielectric tangent at a measurement frequency of 10 GHz and 23 ° C and a dielectric tangent at a measurement frequency of 10 GHz and 150 ° C, and can be, for example, a method described in <Measurement of dielectric tangent of a cured product> which will be described later. Determination.

A cured product obtained by thermally curing the resin composition layer of the resin sheet of the present invention (for example, a cured product obtained by thermally curing a resin composition layer at 100 ° C for 30 minutes and then at 180 ° C for 30 minutes), even at 130 ° C, A good insulation resistance value was also exhibited after 100 hours in an application environment of 85 RH% and 3.3 V. That is, an insulating layer exhibiting a good insulation resistance value is provided. The upper limit of the insulation resistance value is preferably 10 ¹² Ω or less, more preferably 10 ¹¹ Ω or less, still more preferably 10 ¹⁰ Ω or less. The lower limit is not particularly limited, but is preferably 10 ⁶ Ω or more, and more preferably 10 ⁷ Ω or more. The measurement of the insulation resistance value can be measured in accordance with the method described in <Evaluation of Insulation Reliability and Measurement of Thickness of Insulating Layer Between Conductive Layers> to be described later.

In the present invention, the cured product of the resin composition layer also includes a cured product having a dielectric tangent of 10 GHz and 23 ° C at a measurement frequency of 0.006 or less and a dielectric tangent of 10 GHz and 150 ° C at a measurement frequency of 0.01 or less. The cured product has the same constitution as the cured product of the resin composition layer of the resin sheet of the present invention. Further, the curing conditions of the resin composition for forming a cured product are the same as those of the resin sheet. The cured product of the present invention (for example, a cured product obtained by thermally curing a resin composition layer at 100 ° C for 30 minutes, followed by 180 ° C for 30 minutes, and further at 200 ° C for 90 minutes) has a dielectric frequency of 10 GHz and 23 ° C. The preferred range of the tangent and the preferred range of the dielectric tangent at the measurement frequency of 10 GHz and 150 ° C are the same as those of the above-mentioned resin sheet. The preferred range of the insulation resistance value of the cured product is also the same as that of the above-mentioned cured resin sheet.

Since the resin sheet of the present invention can reduce the dielectric tangent at a high temperature, the occurrence of heat or noise due to an electrical signal can be suppressed even in 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 so-called high frequency band means 1 GHz or more (preferably 1.5 GHz or more, more preferably High frequency band of 3 GHz or higher.

[Manufacturing method of printed wiring board and printed wiring board]

The printed wiring board of the present invention includes the insulating layer, the first conductor layer, and the second conductor layer formed of the cured product of the resin composition layer of the resin sheet of the present invention. The printed wiring board of the present invention may be provided with the cured product of the present invention as an insulating layer. The insulating layer is provided between the first conductor layer and the second conductor layer, and insulates the first conductor layer and the second conductor layer (the conductor layer is also referred to as a wiring layer). Since the insulating layer formed of the cured product of the resin composition layer of the resin sheet of the present invention is excellent in film insulating properties, the insulating layer between the first and second conductor layers has a thickness of 6 μm or less and is excellent in insulation properties.

The thickness of the insulating layer between the first and second conductor layers is preferably 6 μm or less, more preferably 5.5 μm or less, still more preferably 5 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more. The thickness of the insulating layer between the first and second conductor layers is, as shown in Fig. 1, the thickness t1 of the insulating layer 7 between the main surface 51 of the first conductor layer 5 and the main surface 61 of the second conductor layer 6. . The first and second conductor layers are adjacent to each other through the insulating layer, and the main surface 51 and the main surface 61 face each other. The thickness of the insulating layer between the first and second conductor layers can be measured by the method described in the following section: "Evaluation of insulation reliability and measurement of thickness of insulating layer between conductor layers".

Further, the thickness t2 of the entire insulating layer is preferably 20 μm or less, more preferably 15 μm or less, still more preferably 12 μm or less. The lower limit is not particularly limited, but may be 1 μm or more.

The printed wiring board of the present invention uses the above-mentioned resin thin The sheet can be produced by a method comprising the steps of the following (I) and (II).

(I) a step of laminating a resin composition layer of a resin sheet and an inner layer substrate on an inner substrate

(II) Step of forming a heat insulating resin composition layer to form an insulating layer

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

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating the resin sheet from the side of the support to the inner layer substrate. As a member for heating the resin sheet to the inner layer substrate (hereinafter also referred to as "heating and pressing member"), for example, a heated metal plate (such as a SUS mirror plate) or a metal roll (SUS roll) may be mentioned. In addition, it is preferable that the heating and pressing member is not directly pressed into the resin sheet, and the surface unevenness of the inner layer substrate is pressed through the elastic material such as heat-resistant rubber so as to sufficiently follow the resin sheet.

The lamination of the inner substrate and the resin sheet can be carried out by vacuum lamination. In the vacuum lamination, the heating and pressing temperature is preferably in the range of 60 ° C to 160 ° C, more preferably in the range of 80 ° C to 140 ° C, and the heating pressing pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa. The range of heating and pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds. A range of 300 seconds. The lamination is preferably carried out under reduced pressure of 26.7 hPa or less.

Lamination can be carried out by means of a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum press laminator manufactured by Nihon Seiki Co., Ltd., and a vacuum applicator made of a daylight and material.

After the lamination, the smoothing treatment of the laminated resin sheet can be performed under normal pressure (at atmospheric pressure) by, for example, pressing the heating and pressing member from the support side. The pressing conditions of the smoothing treatment may be the same conditions as the above-described laminated heating and pressing conditions. The smoothing treatment can be carried out by a commercially available laminator. Still, lamination and smoothing can be carried out using the commercially available vacuum laminator continuity described above.

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

In the step (II), the thermosetting resin composition layer forms an insulating layer.

The thermosetting condition of the resin composition layer is not particularly limited, and conditions generally employed in forming an insulating layer of a printed wiring board can be used.

For example, the thermosetting conditions of the resin composition layer differ depending on the type of the resin composition, etc., but the curing temperature may be in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 220 ° C, more preferably 170 ° C). In the range of ~200 ° C), the hardening 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).

Prior to thermally hardening the resin composition layer, the resin composition layer may be preheated at a temperature lower than the hardening temperature. For example, the resin composition layer may be subjected to 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) before the thermosetting resin composition layer. The above (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes) is prepared for heating.

When the printed wiring board is manufactured, the steps of (III) drilling the insulating layer, (IV) roughening the insulating layer, and (V) forming the conductor layer may be further performed. These steps (III) to (V) can be carried out in accordance with various methods well known to those skilled in the art for use in the manufacture of printed wiring boards. Further, in the case where the support body is removed after the step (II), the removal of the support may be between the step (II) and the step (III), between the step (III) and the step (IV), or the step ( Implemented between IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductor layer of the steps (II) to (V) may be repeated to form a multilayer wiring board. In this case, it is preferable that the thickness of the insulating layer between the individual conductor layers (t1 in Fig. 1) is within the above range.

The step (III) is a step of drilling a hole in the insulating layer, whereby a hole of a through hole, a through hole or the like can be formed in the insulating layer. The step (III) can be carried out using, for example, drilling, laser, plasma, or the like in accordance with the composition of the resin composition used for the formation of the insulating layer. The size or shape of the hole may be appropriately determined depending on the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. The order and conditions of the roughening treatment are not particularly limited, and well-known procedures and conditions that are generally used when forming an insulating layer of a printed wiring board can be employed. For example, in order The insulating layer is roughened by a swelling treatment of the swelling liquid, a roughening treatment by an oxidizing agent, and a neutralization treatment by a neutralizing liquid. The swelling solution is not particularly limited, and examples thereof include an alkali solution and a surfactant solution, and an alkali solution is preferred. As the alkali solution, a sodium hydroxide solution or a potassium hydroxide solution is more preferred. Examples of the commercially available swelling liquid include "Swelling Dip Securiganth P" manufactured by Atotek Japan Co., Ltd., "Swelling Dip Securiganth SBU", and the like. The swelling treatment by the swelling liquid is not particularly limited. For example, the insulating layer may be immersed in a swelling liquid at 30° C. to 90° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferred that the insulating layer is immersed in a swelling liquid at 40 ° C to 80 ° C for 5 minutes to 15 minutes. The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60 ° C to 80 ° C for 10 minutes to 30 minutes. Further, the concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of the commercially available oxidizing agent include an alkaline permanganic acid solution such as "Concentrate. Compact CP" manufactured by Atotek Japan Co., Ltd., and "Dosing solution. Securiganth P". In addition, as a neutralizing liquid, an acidic aqueous solution is preferable, and a "Reduction solution Securigant P" by Atotek Japan Co., Ltd. is mentioned as a commercial item, for example. The treatment with the neutralizing solution can be carried out by immersing the treated surface subjected to roughening treatment with an oxidizing agent at 30 ° C to 80 ° C for 5 minutes to 30 minutes. From the point of view of workability, etc. Preferably, the object to be subjected to roughening treatment by an oxidizing agent is immersed in a liquid at 40 ° C to 70 ° C for 5 minutes to 20 minutes.

In one embodiment, the arithmetic mean roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, still more preferably 300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less, or 100 nm or less. . The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact type surface roughness meter. Specific examples of the non-contact surface roughness meter include "WYKO NT3300" manufactured by Wyco Instruments.

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

The conductor material used for the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer comprises one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Above the metal. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include alloys of two or more metals selected from the group (for example, nickel chrome alloy, copper cum nickel alloy, and copper cum). Titanium alloy). Among them, from the viewpoint of versatility, cost, ease of pattern formation, and the like of the formation of the conductor layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or Alloy layer of nickel and chromium alloy, copper and nickel alloy, copper and titanium alloy, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel and chromium alloy The alloy layer is more preferably a single metal layer of copper.

The conductor layer may have a single layer structure, or may be a multi-layer structure in which two or more layers of a single metal layer or an alloy layer composed of different kinds of metals or alloys are laminated. In the case where the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium or an alloy layer of nickel and chromium alloy.

Although the thickness of the conductor layer varies depending on the design of the desired printed wiring board, it is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one embodiment, the conductor layer can 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 conventional technique such as a semi-additive method or a full additive method. Hereinafter, an example in which the conductor layer is formed by a semi-additive method will be described.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern for exposing a portion of the plated seed layer to the desired wiring pattern is formed on the formed plating seed layer. After the metal layer is formed by electrolytic plating on the exposed plated seed layer, the mask pattern is removed. Then, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

The resin sheet of the present invention can be suitably used even when the printed wiring board is a component-embedded circuit board because of an insulating layer which is excellent in wiring embedding property. The built-in circuit board of the part can be produced by a well-known manufacturing method.

The printed wiring board produced by using the resin sheet of the present invention may be an insulating layer containing a cured resin composition layer of the resin sheet of the present invention and a buried wiring layer in which the insulating layer is buried.

In the printed wiring board manufactured by using the resin sheet of the present invention, even when the thickness of the insulating layer between the first and second conductor layers is 6 μm or less, the insulating reliability is excellent. The upper limit of the insulation resistance value after 100 hours in an application environment of 130 ° C, 85 RH %, and 3.3 V is preferably 10 ¹² Ω or less, more preferably 10 ¹¹ Ω or less, still more preferably 10 ¹⁰ Ω or less. Although the lower limit is not particularly limited, it is preferably 10 ⁶ Ω or more, and more preferably 10 ⁷ Ω or more. The measurement of the insulation resistance value can be measured in accordance with the method described in <Evaluation of Insulation Reliability and Measurement of Thickness of Insulating Layer Between Conductive Layers> to be described later.

[semiconductor device]

The semiconductor device of the present invention comprises the printed wiring board of the present invention. The semiconductor device of the present invention can be fabricated using the printed wiring board of the present invention.

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

The semiconductor device of the present invention can be fabricated by a conductive dot mounting component (semiconductor wafer) of a printed wiring board. The "conducting point" is the "point of transmission of electrical signals to the printed wiring board". The location can be either a surface or a buried point. Further, the semiconductor wafer is not particularly limited as long as it is an electrical circuit element using a semiconductor as a material.

In the method of mounting a semiconductor wafer in the manufacture of the semiconductor device of the present invention, the semiconductor wafer is not particularly limited as long as it is effective, but specifically, a wire bonding mounting method and a flip chip mounting method are provided. Bump-free layering (BBUL) mounting method, by direction A method for mounting an anisotropic conductive film (ACF), a method for mounting a non-conductive film (NCF), and the like. Here, the "mounting method by the bump-free layer-adding layer (BBUL)" is a method of mounting a semiconductor wafer directly in a concave portion of a printed wiring board, and connecting a semiconductor wafer and a wiring on a printed wiring board.

[Examples]

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

[Method for Measuring Physical Property Value of Inorganic Filler]

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

<Measurement of average particle size>

Into the container, 100 mg of an inorganic filler, 0.1 g of a dispersant ("S992" manufactured by San Nopco Co., Ltd.), and 10 g of methyl ethyl ketone were weighed and dispersed in an ultrasonic wave for 20 minutes. The particle size distribution was measured by a batch tank method using a laser-type particle size distribution measuring apparatus ("SALD-2200" manufactured by Shimadzu Corporation), and the average particle diameter by the median diameter was calculated.

<Measurement of specific surface area>

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

<Measurement of carbon amount>

The amount of carbon per unit surface area of the inorganic filler was measured in the following order. The inorganic filler prepared in the preparation example was added as a solvent to a sufficient amount of MEK, and ultrasonically washed at 25 ° C for 5 minutes. Next, the supernatant is removed to dry the solids. The amount of carbon was measured using a carbon analyzer ("EMIA-320V" manufactured by Horiba, Ltd.). The amount of carbon per unit surface area of the inorganic filler was calculated from the measured value of the amount of carbon and the mass and specific surface area of the inorganic filler used.

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

The resin sheets of the examples and the comparative examples were produced using the resin composition (resin varnish) prepared in the following order.

(Modulation of Resin Composition 1)

The bisphenol A type epoxy resin (YD-8125G, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), epoxy equivalent (about 174), 3 parts, and bisxylenol type epoxy resin (Mitsubishi Chemical Co., Ltd.) YX4000HK", epoxy equivalent of about 185) 3 parts, bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238) 8 parts, naphthalene type epoxy resin (Nippon Steel & Sumitomo Chemical Co., Ltd. (ESN475V), epoxy equivalent (about 330), 12 parts, phenoxy resin ("XX7553BH30" manufactured by Mitsubishi Chemical Corporation, 30% by mass of cyclohexanone: methyl ethyl ketone (MEK) The 1:1 solution) 10 parts, and a mixed solvent of 12 parts of a solvent oil and 10 parts of cyclohexanone were stirred and heated and dissolved. After cooling to room temperature, an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Co., Ltd., a toluene solution having a reactive base equivalent of about 225 and a nonvolatile content of 65 mass%) was mixed with 20 parts of phenylene oxide. Base ether and styrene resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., toluene solution of 72% by mass solids) 10 parts, amine hardening accelerator (4-dimethylaminopyridine (DMAP)) 2 parts by mass of MEK solution), imidazole-based hardening accelerator ("1B2PZ" 1-benzyl-2-phenylimidazole manufactured by Shikoku Chemical Industry Co., Ltd., solid solution 5% MEK solution) 0.4 2 parts of rubber particles (made by AICA Industrial Co., Ltd., AC-3401N) in 10 parts of solvent oil and swelled at room temperature for 12 hours, and an amine decane-based coupling agent (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) ) Surface-treated spheroidal cerium oxide (SP507-05, manufactured by Nippon Steel & Sumitomo Metal Co., Ltd.), average particle diameter of 0.91 μm, specific surface area of 6.5 m ² /g, and carbon content per unit surface area of 0.34 mg/m ² ) 160 parts were uniformly dispersed by a high-speed rotary mixer, and then filtered through a cartridge filter ("SHP030" manufactured by ROKITECHNO) to prepare a resin composition 1.

(Modulation of Resin Composition 2)

Bisphenol A type epoxy resin (YD-8125G, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy resin equivalent: 174) 2 parts, bisxylenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000HK""Epoxy equivalent: 185) 5 parts, a naphthyl ether type epoxy resin ("EXA-7311-G4" manufactured by DIC Co., Ltd., epoxy equivalent: about 213) 5 parts, biphenyl type epoxy resin (Japan) Chemical plant (stock) "NC3000L", epoxy equivalent of about 272) 15 parts, epoxidized polybutadiene ("PB3600" (made by Daicel), epoxy equivalent of about 193) 2 parts, phenoxy resin (Mitsubishi Chemical (stock) "YX7553BH30", solid content 30% by mass of cyclohexanone: methyl ethyl ketone (MEK) 1:1 solution) 10 parts of solvent oil 15 parts and cyclohexanone 10 parts mixed solvent Stir and heat to dissolve. After cooling to room temperature, a cresol novolak-based hardener containing a triazine skeleton ("LA3018-50P" manufactured by DIC Co., Ltd., 2-hydroxyl group having a hydroxyl equivalent of about 151 and a solid content of 50%) was mixed. Solution) 5 parts, active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Co., Ltd., toluene solution having a reactive base equivalent of about 225 and a nonvolatile content of 65 mass%) 12 parts, carbodiimide resin (Nisshinbo 10 parts of "V-03", carbodiimide equivalent 216, non-volatile content 50% by mass of toluene solution), amine-based hardening accelerator (4-dimethylaminopyridine (DMAP), solid form 1.5 parts by mass of MEK solution) 1.5 parts, flame retardant ("HCA-HQ" manufactured by Sanguang Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10- 2 parts of phosphaphenanthrene-10-oxide, an average particle diameter of 1.2 μm), spherical cerium oxide surface treated with an amine decane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) "SPH516-05" made of a material (stock), an average particle diameter of 0.29 μm, a specific surface area of 16.3 m ² /g, and a carbon content of 0.43 mg/m ² per unit surface area, 110 parts, and uniformly dispersed by a high-speed rotary mixer. Filtered by cartridge filter (SHP020 manufactured by ROKITECHNO) The resin composition 2 was prepared.

(Modulation of Resin Composition 3)

4 parts of a naphthalene type epoxy resin ("HP4032SS" manufactured by DIC Co., Ltd., epoxy equivalent: 144), and a naphthyl ether type epoxy resin (EXA-7311-G4 manufactured by DIC), epoxy equivalent About 213) 8 parts, naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent: about 330), 15 parts, phenoxy resin ("XX7553BH30" manufactured by Mitsubishi Chemical Corporation), solid form 5 parts by mass of cyclohexanone: a 1:1 solution of methyl ethyl ketone (MEK), 5 parts, and dissolved by heating while stirring a mixture of 15 parts of a solvent oil and 10 parts of cyclohexanone. After cooling to room temperature, 20 parts of a bisphenol A dicyanate prepolymer ("BA230S75" manufactured by Lonza Japan Co., Ltd., a cyanate equivalent of about 232, and a nonvolatile content of 75 mass% of MEK solution) was added thereto. Polyfunctional cyanate resin ("Lon-950S" manufactured by Lonza Japan Co., Ltd., MEK solution having a cyanate equivalent of about 230 and a nonvolatile content of 75% by mass) 6 parts, active ester-based hardener (DIC) 6 parts of "HPC-8000-65T", a reactive base equivalent of about 225, and a non-volatile content of 65 mass% in toluene), a carbodiimide resin ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide) Equivalent 216, 50% by mass of a toluene solution of a nonvolatile content) 5 parts, an amine-based hardening accelerator (4-dimethylaminopyridine (DMAP), a solid content of 5% by mass of MEK solution) 0.4 parts, and a hardening accelerator ( 3 parts of Tokyo Chemical Co., Ltd., acetonitrile (III) (Co(III)Ac), and 1% by mass of MEK solution), and an amine decane-based coupling agent (Shin-Etsu Chemical Co., Ltd.) "KBM573") Spherical cerium oxide (SPH516-05, manufactured by Nippon Steel & Sumitomo Metal Co., Ltd.) with an average particle diameter of 0.29 μm and a specific surface area of 16.3 m ² /g and a carbon content of 0.43 per unit surface area. mg / m ²⁾ 100 parts, to After uniform dispersion speed rotary mixer to a cartridge filter (ROKITECHNO manufactured "SHP020") filter to prepare the resin composition 3.

(Modulation of Resin Composition 4)

Bisphenol A type epoxy resin ("828EL" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 186), 8 parts, biphenyl type epoxy resin ("30003000" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent) 272) 15 parts, 5 parts of epoxidized polybutadiene ("PB3600" manufactured by Daicel, epoxide equivalent: 193), phenoxy resin ("XX7553BH30" manufactured by Mitsubishi Chemical Corporation, 30% by mass of solid content) 10 parts of cyclohexanone: methyl ethyl ketone (MEK) in a 1:1 solution, and dissolved in a mixed solvent of 10 parts of a solvent oil and 10 parts of cyclohexanone while stirring. After cooling to room temperature, a cresol novolak-based hardener containing a triazine skeleton ("LA3018-50P" manufactured by DIC Co., Ltd., 2-hydroxyl group having a hydroxyl equivalent of about 151 and a solid content of 50%) was mixed. Solution) 5 parts, active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Co., Ltd., toluene solution having a reactive base equivalent of about 225 and a nonvolatile content of 65 mass%) 12 parts, carbodiimide resin (Nisshinbo 10 parts of "V-03", carbodiimide equivalent 216, non-volatile content 50% by mass of toluene solution), amine-based hardening accelerator (4-dimethylaminopyridine (DMAP), solid form 1.5 parts by mass of MEK solution) 1.5 parts, flame retardant ("HCA-HQ" manufactured by Sanguang Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10- 2 parts of phosphaphenanthrene-10-oxide, an average particle diameter of 1.2 μm), and 2 parts of rubber particles (AICA Industrial Co., Ltd., AC-3355) were emulsified at room temperature for 8 hours in a solvent oil for 8 hours. A cerium-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) is a spherical cerium oxide ("ADMAFINE SO-C1" manufactured by Admatex, having an average particle diameter of 0.63 μm and a specific surface area of 11.2 m ² / g, carbon content per unit surface area of 0.35mg / m ²⁾ 110 parts of a high After rotary mixer uniformly dispersed in the filter cartridge (ROKITECHNO manufactured "SHP030") filter to prepare the resin composition 4.

(Modulation of Resin Composition 5)

Bisphenol A type epoxy resin ("828EL" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 186) 10 parts, naphthalene type epoxy resin (ESN475V manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), epoxy equivalent About 330 parts, 15 parts, epoxidized polybutadiene ("PB3600" manufactured by Daicel, epoxide equivalent: 193), 2 parts, phenoxy resin ("XX6954BH30" manufactured by Mitsubishi Chemical Corporation, 30 parts of solid content) 5 parts of cyclohexanone: a 1:1 solution of methyl ethyl ketone (MEK), and dissolved in a mixed solvent of 12 parts of a solvent oil and 10 parts of cyclohexanone while stirring. After cooling to room temperature, 20 parts of a bisphenol A dicyanate prepolymer ("BA230S75" manufactured by Lonza Japan Co., Ltd., a cyanate equivalent of about 232, and a nonvolatile content of 75 mass% of MEK solution) was added thereto. Polyfunctional cyanate resin ("Lon-950S" manufactured by Lonza Japan Co., Ltd., MEK solution having a cyanate equivalent of about 230 and a nonvolatile content of 75% by mass) 6 parts, active ester-based hardener (DIC) 6 parts of a "HPC-8000-65T", a toluene solution having a living base equivalent of about 225 and a nonvolatile content of 65% by mass), a block type isocyanate resin ("BURNOCK D-500" manufactured by DIC Co., Ltd., a nonvolatile component 65 5 parts by mass of ethyl acetate solution), an amine-based hardening accelerator (4-dimethylaminopyridine (DMAP), a solid content of 5% by mass of MEK solution) 0.4 parts, and a hardening accelerator (Tokyo Chemical Co., Ltd.) 3 parts of a solution of cobalt (III) pyruvate (III) (Co(III)Ac) and a solid content of 1% by mass of MEK), and an amine decane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) The treated spherical cerium oxide ("ADMAFINE SO-C1" manufactured by Admatex, having an average particle diameter of 0.63 μm, a specific surface area of 11.2 m ² /g, and a carbon content per unit surface area of 0.35 mg/m ² ) of 100 parts, Rotating mixer at high speed After uniform dispersion, to a cartridge filter (ROKITECHNO manufactured "SHP030") filter to prepare the resin composition 5.

The components used for the preparation of the resin compositions 1 to 5 and the blending amounts thereof (parts by mass of nonvolatile matter) are shown in Table 1 below.

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

As a support, a PET film (Lumilar R80, manufactured by Toray Industries, Ltd.) having a mold release treatment of an alkyd resin release agent ("AL-5" manufactured by Lintec Co., Ltd.), a thickness of 38 μm, and a softening point of 130 ° C was prepared. , "Release PET").

Each of the resin compositions was applied to a release PET, and the resin composition layer after drying was 40 μm, and uniformly coated in a die coater by drying at 70 ° C to 100 ° C for 4.5 minutes or at 60 ° C. After drying at 90 ° C for 2 minutes, a resin composition layer was formed on the release PET. Next, a rough surface of a polypropylene film ("Alfan MA-411" manufactured by Prince Ftex Co., Ltd., thickness: 15 μm) was bonded to the resin composition layer as a protective film on the surface which was not bonded to the support of the resin sheet. Way to laminate. Thereby, a resin sheet for dielectric tangent measurement consisting of a support, a resin composition layer, and a protective film was obtained.

In the same manner as the resin sheet for dielectric tangential measurement, the resin composition was applied to the release PET so that the thickness of the resin composition layer after drying was 13 μm, and the lowest melt viscosity was measured. And a resin sheet for insulation reliability measurement.

<Measurement of the lowest melt viscosity>

A resin sheet having a thickness of 13 μm in the resin composition layer was used, and only the resin composition layer was peeled off from the release PET (support), and the particles for measurement (diameter: 18 mm, 1.2 to 1.3 g) were produced by compression with a mold.

Dynamic viscoelasticity measuring device (made by UBM) "Rheosol-G3000"), using a parallel plate having a diameter of 18 mm for the sample resin composition layer 1g, the temperature was raised from a starting temperature of 60 ° C to 200 ° C at a temperature increase rate of 5 ° C / min, and the measurement temperature interval was 2.5 ° C and the number of vibrations was 1 Hz. The dynamic viscoelasticity was measured by measuring the distortion of 1 deg, and the lowest melt viscosity (poise) was calculated and shown in Table 2.

<Measurement of dielectric tangent of hardened material>

A copper-clad laminate (R5715ES, manufactured by Matsushita Electric Works Co., Ltd.) and a thickness of an untreated surface of a PET film ("501010", a thickness of 38 μm, and a width of 240 mm) and a glass cloth substrate epoxy resin. The contact pattern of 0.7 mm and 255 mm square was set on the copper-clad laminate of the glass cloth substrate epoxy resin, and the four sides of the release PET film were fixed with polyimide and tape (width: 10 mm).

A resin sheet (200 mm square) having a thickness of 40 μm in the resin composition layer prepared in the examples and the comparative examples, using a batch type vacuum pressure laminator (two-stage accumulation laminator made of daylight and material), CVP700 In the case where the resin composition layer is in contact with the release surface of the release PET film ("501010" manufactured by Lintec Co., Ltd.), the laminate treatment is performed at the center. The lamination treatment was carried out by subjecting the gas pressure to 13 hPa or less after performing pressure reduction for 30 seconds, and then pressing at 100 ° C and a pressure of 0.74 MPa for 30 seconds.

Next, it was placed in an oven at 100 ° C for 30 minutes at a temperature of 100 ° C, and then transferred to an oven at 180 ° C for 30 minutes at a temperature of 180 ° C to thermally harden it. Then, the substrate is taken out from the room temperature environment, and the release PET (support) is peeled off from the resin sheet, and then the input is further performed. The hardening condition of the oven at 200 ° C for 90 minutes causes it to be thermally hardened.

The "hardened material for evaluation" was cut into a test piece having a width of 1.5 mm and a length of 80 mm, and "HP8362B" manufactured by Agilent Technologies Co., Ltd. was used for the test piece, and the measurement frequency was measured at a frequency of 10 GHz by a cavity resonance perturbation method. Dielectric tangent (Df) was measured at 23 ° C or 150 ° C. The dielectric tangent (Df) was measured at a measurement frequency of 10 GHz, a measurement temperature of 23 ° C, or 150 ° C. Three test pieces were measured, and the average value was calculated, and the result is shown in Table 2.

<Evaluation of insulation reliability and measurement of thickness of insulating layer between conductor layers> (modulation of the evaluation substrate) (1) Base processing of the inner layer circuit substrate

As an inner layer circuit board, a glass cloth substrate epoxy resin double-sided copper-clad laminate (copper foil) having a circuit conductor (copper) formed on a wiring pattern of 1 mm square grid (residual copper ratio: 59%) is prepared. The thickness is 18 μm, the thickness of the substrate is 0.3 mm, and "R1515F" manufactured by Panasonic Co., Ltd.). The copper surface was roughened (copper etching amount: 0.5 μm) on both sides of the inner layer circuit board by "CZ8201" manufactured by MEC.

(2) Lamination of resin sheets

The resin sheet having a thickness of 13 μm in the resin composition layer prepared in the examples and the comparative examples was subjected to a batch type vacuum pressure laminator (daylight, material, two-stage accumulation laminator, CVP700), and resin. Two layers of the inner layer circuit substrate are laminated in such a manner that the composition layer is in contact with the inner layer circuit substrate surface. The laminating system was carried out by subjecting the pressure to 13 hPa or less after performing pressure reduction for 30 seconds, and then pressing at 130 ° C and a pressure of 0.74 MPa for 45 seconds. Next, hot stamping was performed for 75 seconds at 120 ° C and a pressure of 0.5 MPa.

(3) Thermal hardening of the resin composition layer

The inner layer circuit board of the laminated resin sheet was placed in an oven at 100 ° C for 30 minutes at a temperature of 100 ° C, and then transferred to an oven at 180 ° C for 30 minutes at a temperature of 180 ° C to thermally harden it. Insulation.

(4) Formation of through holes

Above the insulating layer and the support, a CO ₂ laser processing machine "605GTWIII (-P)" manufactured by Mitsubishi Electric Corporation was used to irradiate the laser from above the support to form an insulating layer on the conductor of the lattice pattern. Through hole with a top diameter (70 μm). The laser irradiation conditions were performed with a mask diameter of 2.5 mm, a pulse width of 16 μs, an energy of 0.39 mJ/shot, a number of shots of 2, and a Burst Mode (10 kHz).

(5) Steps of roughening

The support is peeled off from the circuit board on which the through holes are provided, and desmearing is performed. Further, as the desmear treatment, the following wet desmearing treatment was carried out.

Wet desmear treatment: in swelling liquid ("Swelling Dip" by Atotek Japan Co., Ltd. Securiganth P", an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) was immersed at 60 ° C for 5 minutes, followed by an oxidizing agent solution ("Concentrate. Compact CP" manufactured by Atotek Japan Co., Ltd., potassium permanganate concentration 6%, an aqueous solution having a sodium hydroxide concentration of about 4%) was immersed at 80 ° C for 10 minutes, and finally immersed in a neutralizing solution ("Reduction solution Securigant P" manufactured by Atotek Japan Co., Ltd., aqueous sulfuric acid solution) at 40 ° C for 5 minutes. It was further dried at 80 ° C for 15 minutes.

(6) Step of forming a conductor layer (6-1) Electroless plating step

In order to form a conductor layer on the surface of the circuit board, a conductor layer is formed by a plating step (a copper plating step using a chemical liquid manufactured by Atotek Japan Co., Ltd.) including the following steps 1 to 6.

1. Alkali cleaning (washing and charge adjustment of the surface of the insulating layer of the through hole)

It was washed at 60 ° C for 5 minutes using a trade name: Cleaning Cleaner Securiganth 902 (trade name).

2. Soft etching (washing in the through hole)

The aqueous solution of acidic sodium peroxodisulfate was used and treated at 30 ° C for 1 minute.

3. Prepreg (adjustment of the charge applied to the surface of the insulating layer of Pd)

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

4. Activator imparted (giving the Pd of the surface of the insulating layer)

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

5. Reduction (reduction of Pd given by the insulating layer)

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

6. Electroless copper plating step (Cu is deposited on the surface of the insulating layer (Pd surface))

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

(6-2) Electroplating step

Next, an electrolytic copper plating step was carried out using a chemical liquid manufactured by Atotek Japan Co., Ltd. under the condition that copper was filled in the through holes. Then, as a resist pattern for patterning by etching, a land pattern of 1 mm in diameter and a circular conductor having a diameter of 10 mm which is not connected to the lower conductor are used. A conductor layer having a pad and a conductor pattern is formed on the surface of the insulating layer by a thickness of 10 μm. Next, the annealing treatment was carried out at 200 ° C for 90 minutes. This substrate was used as the evaluation substrate A.

(7) Determination of the thickness of the insulating layer between the conductor layers

The evaluation substrate A was subjected to cross-sectional observation using a FIB-SEM composite device (SMI3050SE, manufactured by SII Nanotech Co., Ltd.). Specifically, the cross section perpendicular to the surface of the conductor layer was cut by FIB (bundled ion beam), and the thickness of the insulating layer between the conductor layers was measured from the cross-sectional SEM image. For each sample, a cross-sectional SEM image of five randomly selected spots was observed, and the average value was taken as the thickness of the insulating layer between the conductor layers.

(8) Evaluation of insulation reliability of insulation layer

The circular conductor side having a diameter of 10 mm of the evaluation substrate A obtained above was defined as a + electrode, and the lattice conductor (copper) side of the inner layer circuit substrate connected to the pad having a diameter of 1 mm was defined as a -electrode, and the height was accelerated. The life test device ("PM422" manufactured by ETAC) has an insulation resistance value of 200 hours after being applied at 130 ° C, 85% relative humidity, and 3.3 V DC voltage in an electrochemical migration tester (J). - RAS (share) system "ECM-100") measurement (n = 6). In the case of all the 6-point test pieces, the case where the insulation resistance value is 10 ⁷ Ω or more is set to "○", and the case where one is less than 10 ⁷ Ω is set to "x", and the evaluation result is shown in Table 2. . The insulation resistance value shown in Table 2 is the lowest value of the insulation resistance value of the 6-point test piece.

Claims (10)

A resin sheet comprising a support and a resin sheet bonded to the resin composition layer on the support, wherein the cured product of the resin composition layer has a dielectric tangent of 0.006 or less at a measurement frequency of 10 GHz and 23 ° C. The cured product of the resin composition layer has a dielectric tangent of 0.01 or less at a measurement frequency of 10 GHz and 150 °C. The resin sheet of claim 1, wherein the resin composition layer has a thickness of 15 μm or less. The resin sheet of claim 1, wherein the resin composition layer has a minimum melt viscosity of 1000 poise or more. The resin sheet of claim 1, wherein the resin composition layer contains an epoxy resin and a hardener. The resin sheet according to claim 1, wherein the resin composition layer contains an inorganic filler, and when the nonvolatile component in the resin composition layer is 100% by mass, the content of the inorganic filler is 50% by mass or more. . The resin sheet of claim 1, which is used for forming an insulating layer of a printed wiring board. The resin sheet of claim 1, which is used for forming an insulating layer of a high frequency substrate of 1 GHz or more. The resin sheet according to any one of claims 1 to 7, comprising a first conductor layer, a second conductor layer, and an insulating layer that insulates the first conductor layer and the second conductor layer, the first conductor layer and the second layer The insulating layer of the printed wiring board having a thickness of the insulating layer between the conductor layers of 6 μm or less is formed. A printed wiring board comprising a first conductor layer and a second conductor a printed wiring board having a thickness of 6 μm or less in the insulating layer of the insulating layer between the first conductor layer and the second conductor layer, and the insulating layer is as claimed in claim 1 A cured product of a resin composition layer of the resin sheet of any one of 7. A semiconductor device comprising the printed wiring board of claim 9.