JP6728760B2 - Resin sheet with support - Google Patents

Description

The present invention relates to a resin sheet with a support. Furthermore, the present invention relates to a printed wiring board and a semiconductor device.

As a method for manufacturing a printed wiring board (hereinafter, also referred to as “wiring board”), a build-up method of alternately stacking circuit-formed conductor layers and insulating layers is widely used. Two insulating layers are used. It is known to be formed by curing a resin composition layer made of (for example, refer to Patent Document 1).

JP, 2014-17301, A

By the way, since the amount of information communication has been increasing in recent years, a wiring board corresponding to a high frequency band has been demanded, but in the high frequency region, it is easily affected by the thickness of the conductor layer and the insulating layer. , More precise design is needed.

In a wiring board corresponding to a high frequency band, if the insertion loss at the interface between the two insulating layers is large, the electric signal changes to heat and/or noise, which makes it impossible to accurately transmit the signal and information. is there. Further, even if the insertion loss is small, if the variation of the insertion loss is large, the stability of the high-speed signal will be lacking, and the device will not operate as designed, and a malfunction will easily occur.

An object of the present invention is to provide a resin sheet with a support, a printed wiring board, and a semiconductor device that reduce insertion loss and suppress variations in insertion loss.

As a result of diligent studies on the above problems, the present inventors have found that in a resin sheet with a support including a first resin composition layer and a second resin composition layer having different compositions, the first resin composition layer is The thermosetting product of the first resin composition and the thermosetting product of the second resin composition forming the second resin composition layer have a dielectric constant of 3.6 or less at 5.8 GHz at 23° C., The dielectric loss tangent at 23° C. at 5.8 GHz is 0.01 or less, and the difference in the dielectric loss tangent of each thermosetting product is set to 0.005 or less. It came to completion.

That is, the present invention includes the following contents.
[1] A resin sheet with a support, comprising a support and a resin sheet provided on the support,
The resin sheet includes a first resin composition layer formed of the first resin composition, which is provided on the support side,
A second resin composition layer formed of the second resin composition, which is provided on the side opposite to the support side,
The first resin composition and the second resin composition have different compositions,
First thermosetting product obtained by thermosetting the first resin composition at 200° C. for 90 minutes, and second thermosetting product obtained by thermosetting the second resin composition at 200° C. for 90 minutes , The dielectric constant at 5.8 GHz at 23° C. is both 3.6 or less,
The dielectric loss tangents of the first and second thermosetting products at 23° C. at 5.8 GHz are both 0.01 or less,
A resin sheet with a support, wherein the difference in dielectric loss tangent of the first and second thermosets is 0.005 or less.
[2] The support according to [1], wherein the first resin composition and the second resin composition contain (a) an epoxy resin, and the (a) component is an epoxy resin having an aromatic structure. With resin sheet.
[3] The first resin composition and the second resin composition contain (b) a curing agent, and at least one component (b) is an active ester curing agent [1] or [2]. The resin sheet with a support as described in 1.
[4] The first resin composition and the second resin composition include (c) an inorganic filler, the content of the component (c) in the first resin composition is A1, and the second resin composition is When the content of the component (c) in the product is A2, the resin sheet with a support according to any one of [1] to [3], which satisfies the relationship of A1<A2.
[5] The resin sheet with a support according to any one of [1] to [4], wherein both the first and second thermosetting products have a dielectric constant at 23° C. at 5.8 GHz of 3.5 or less. ..
[6] The resin sheet with a support according to any one of [1] to [5], wherein both the first and second thermosetting products have a dielectric loss tangent of 0.0095 or less at 23° C. at 5.8 GHz. ..
[7] The resin sheet with a support according to any one of [1] to [6], which is used in a high frequency band of 1 GHz or higher.
[8] A printed wiring board including an insulating layer formed by a cured product of the resin sheet in the resin sheet with a support according to any one of [1] to [7].
[9] The printed wiring board according to [8], which has a stripline structure.
[10] A semiconductor device including the printed wiring board according to [8] or [9].

According to the present invention, it is possible to provide a resin sheet with a support, a printed wiring board, and a semiconductor device that reduce insertion loss and suppress variations in insertion loss.

FIG. 1 is a schematic view showing one embodiment of the resin sheet with a support of the present invention. FIG. 2 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 3 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 4 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 5 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 6 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 7 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 8 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 9 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 10 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 11 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 12 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 13 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 14 is a schematic cross-sectional view in a direction orthogonal to the cross section of FIG. FIG. 15 is a schematic cross-sectional view of the stripline transmission line evaluation board manufactured in the example.

Hereinafter, the resin sheet with a support, the printed wiring board, and the semiconductor device of the present invention will be described in detail.

Before describing the resin sheet with a support of the present invention in detail, when forming the first resin composition layer and the second resin composition layer included in the resin sheet in the resin sheet with a support of the present invention The 1st resin composition and 2nd resin composition used for are demonstrated.

(First resin composition)
The first resin composition forming the first resin composition layer is not particularly limited as long as the cured product has sufficient insulation. Examples of the first resin composition include a composition containing a curable resin and a curing agent therefor. As the curable resin, a conventionally known curable resin used when forming an insulating layer of a printed wiring board can be used, and among them, an epoxy resin is preferable. Thus, in one embodiment, the first resin composition comprises (a) epoxy resin, (b) curing agent and (c) inorganic filler. The first resin composition may further contain a thermoplastic resin, a curing accelerator, a flame retardant, and an organic filler, if necessary.

Hereinafter, each component that can be used as the material of the first resin composition will be described in detail.

-(A) Epoxy resin-
Examples of the epoxy resin include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac Type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene Examples thereof include ether type epoxy resins, trimethylol type epoxy resins, and tetraphenylethane type epoxy resins. The epoxy resins may be used alone or in combination of two or more. The component (a) is preferably an epoxy resin having an aromatic structure and is selected from a bixylenol type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a biphenyl type epoxy resin, and a naphthalene type epoxy resin. More preferably, it is one or more. The aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatic and aromatic heterocyclic rings.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Above all, having two or more epoxy groups in one molecule, having a liquid epoxy resin at a temperature of 20° C. (hereinafter referred to as “liquid epoxy resin”), and having three or more epoxy groups in one molecule, It is preferable to include a solid epoxy resin at a temperature of 20° C. (hereinafter referred to as “solid epoxy resin”). By using a liquid epoxy resin and a solid epoxy resin together as the epoxy resin, a resin composition having excellent flexibility can be obtained. Further, the breaking strength of the cured product of the resin composition is also improved.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton. Preferred are alicyclic epoxy resins, cyclohexanedimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure. Glycidyl amine type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF Type epoxy resin and naphthalene type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D” and “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “828US”, “jER828EL” and “825” manufactured by Mitsubishi Chemical Corporation. "(Bisphenol A type epoxy resin), "jER807", "1750" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidyl amine type epoxy resin), "ZX1059" (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Co., Ltd., ( "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure) manufactured by Daicel Corporation, "ZX1658", "ZX1658GS" manufactured by Nippon Steel Chemical Co., Ltd. (Liquid 1,4-glycidyl cyclohexane), “630LSD” (glycidyl amine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and the like. These may be used alone or in combination of two or more.

As the solid epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin and tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin and biphenyl type epoxy resin are more preferable. Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "N-690" manufactured by DIC Corporation. "(Cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "HP-7200HH", "HP-7200H", "EXA" -7311, "EXA-7331-G3", "EXA-7331-G4", "EXA-7331-G4S", "HP6000" (naphthylene ether type epoxy resin), "EPPN" manufactured by Nippon Kayaku Co., Ltd. -502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V" (naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol) manufactured by Mitsubishi Chemical Corporation. Type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemicals Co., Ltd., "YL7760" (bisphenol AF type epoxy manufactured by Mitsubishi Chemical Corporation). Resin), "YL7800" (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1031S" (tetraphenylethane type epoxy resin) and the like. These may be used alone or in combination of two or more.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, their mass ratio (liquid epoxy resin:solid epoxy resin) is in the range of 0:0.1 to 1:15 by mass ratio. preferable. By setting the amount ratio of the liquid epoxy resin and the solid epoxy resin in such a range, i) a suitable adhesiveness is brought about when used in the form of a resin sheet, and ii) when used in the form of a resin sheet Sufficient flexibility is obtained, handleability is improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the above effects i) to iii), the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin:solid epoxy resin) is in the range of 0:0.3 to 1:10. Is more preferable, and the range of 0:0.6 to 1:8 is further preferable.

The content of the epoxy resin in the first resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably from the viewpoint of obtaining an insulating layer having good mechanical strength and insulation reliability. It is 3% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

In the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass, unless otherwise specified.

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

The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and further preferably 400 to 1500. 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) Curing agent-
The curing agent is not particularly limited as long as it has a function of curing an epoxy resin, and examples thereof include a phenol curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, a cyanate ester curing agent, and Examples include carbodiimide type curing agents. The curing agents may be used alone or in combination of two or more. The component (b) is preferably one or more selected from a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a carbodiimide-based curing agent and a cyanate ester-based curing agent, and a phenol-based curing agent, It is more preferably at least one selected from an active ester-based curing agent and a carbodiimide-based curing agent, and further preferably an active ester-based curing agent from the viewpoint of lowering the dielectric constant and dielectric loss tangent.

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

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., manufactured by Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. , "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" and the like manufactured by DIC Corporation.

An active ester curing agent is also preferable from the viewpoint of obtaining an insulating layer having excellent adhesion to the conductor layer. The active ester curing agent is not particularly limited, but generally one molecule of ester group having high reaction activity such as phenol ester, thiophenol ester, N-hydroxyamine ester, and ester of heterocyclic hydroxy compound is used. A compound having two or more of them is preferably used. The active ester type curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester type curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester type curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Examples thereof include benzenetriol, dicyclopentadiene type diphenol compound, and phenol novolac. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specifically, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferable. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

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

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Highpolymer Co., Ltd., "Pd" and "Fa" manufactured by Shikoku Chemicals Co., Ltd.

Examples of the cyanate ester-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis(2,6-dimethylphenyl cyanate), 4,4. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenyl propane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethyl) Phenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bifunctional cyanate resin such as bis(4-cyanatephenyl)ether, phenol Examples thereof include polyfunctional cyanate resins derived from novolac and cresol novolac, and prepolymers obtained by partially converting these cyanate resins into triazine. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" manufactured by Lonza Japan Co., Ltd. (both are phenol novolac type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (of bisphenol A dicyanate). Prepolymers) which are partially or wholly triazined to form trimers, and the like.

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

The amount ratio of the epoxy resin and the curing agent is preferably [the total number of epoxy groups of the epoxy resin]:[the total number of reactive groups of the curing agent] in the range of 1:0.01 to 1:2, 1:0.015 to 1:1.5 is more preferable, and 1:0.02 to 1:1 is further preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like, and varies depending on the type of the curing agent. The total number of epoxy groups of the epoxy resin is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is It is a value obtained by summing the values obtained by dividing the solid content mass of each curing agent by the reactive group equivalent for all curing agents. By setting the amount ratio of the epoxy resin and the curing agent in such a range, the heat resistance of the cured product of the resin composition is further improved.

In one embodiment, the first resin composition contains the above-mentioned (a) epoxy resin and (b) curing agent. The resin composition is a mixture of liquid epoxy resin and solid epoxy resin as (a) epoxy resin (mass ratio of liquid epoxy resin:solid epoxy resin is preferably 0:0.1 to 1:15, more preferably 0:0.3 to 1:12, more preferably 0:0.6 to 1:10), (b) as a curing agent, a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a carbodiimide curing agent It is preferable to include one or more types (preferably active ester type curing agents) selected from the group consisting of agents and cyanate ester type curing agents, respectively.

The content of the curing agent in the first resin composition is not particularly limited, but is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less. The lower limit is not particularly limited, but is preferably 2% by mass or more.

-(C) Inorganic filler-
The material of the inorganic filler is not particularly limited, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium phosphate tungstate. Among these, silica is particularly suitable. Spherical silica is preferable as the silica. The inorganic fillers may be used alone or in combination of two or more.

The average particle diameter of the inorganic filler is not particularly limited, but preferably 2 μm or less, more preferably 1.5 μm or less, and further preferably 1 μm from the viewpoint of obtaining an insulating layer having a small surface roughness and improving the fine wiring formability. It is as follows. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.1 μm or more, still more preferably 0.3 μm or more. Examples of commercially available inorganic fillers having such an average particle diameter include "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatechs Co., Ltd., manufactured by Denki Kagaku Kogyo Co., Ltd. "UFP-30", "Silfill NSS-3N", "Silfill NSS-4N", "Silfill NSS-5N" manufactured by Tokuyama Corporation, "SC2500SQ", "SO-C4", "SO" manufactured by Admatechs Co., Ltd. -C2", "SO-C1", etc. are mentioned.

The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis using a laser diffraction/scattering particle size distribution measuring device, and the median size can be used as the average particle size for measurement. As the measurement sample, an inorganic filler dispersed in methyl ethyl ketone by ultrasonic waves can be preferably used. As the laser diffraction/scattering particle size distribution measuring device, "SALD-2200" manufactured by Shimadzu Corporation can be used.

The inorganic filler is preferably surface-treated with at least one surface treatment agent selected from the group consisting of a silane coupling agent, an alkoxysilane compound, and an organosilazane compound, from the viewpoint of improving moisture resistance and dispersibility. These may be oligomers. Examples of the surface treatment agent include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents and the like. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and "KBM803" (3-mercaptopropyltrimethoxy manufactured by Shin-Etsu Chemical Co., Ltd.). Silane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type) Silane coupling agent) and the like. The surface treatment agents may be used alone or in combination of two or more.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, 1 mg/m ² or less is preferable, 0.8 mg/m ² or less is more preferable, and 0.5 mg/m ² or less is further preferable. preferable.

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

The content of the inorganic filler in the first resin composition is preferably 70% by mass or less when the nonvolatile component in the first resin composition is 100% by mass, from the viewpoint of improving the plating peelability. It is more preferably 60% by mass or less, 50% by mass or less, or 40% by mass or less. The lower limit of the content of the component (c) in the first resin composition is not particularly limited and may be 0% by mass, but 5% by mass or more and 10% by mass from the viewpoint of decreasing the dielectric loss tangent. As described above, it may be 20% by mass or more.

-(D) Thermoplastic resin-
The first resin composition may contain (d) a thermoplastic resin in addition to the components (a) to (c).

Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, and polyether. Examples thereof include ether ketone resins and polyester resins, and phenoxy resins are preferable. The thermoplastic resins may be used alone 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, and even 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 gel permeation chromatography (GPC) method. Specifically, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P/K-manufactured by Showa Denko KK as a column. 804L/K-804L can be calculated by using chloroform as a mobile phase, measuring column temperature at 40° C., and using a calibration curve of standard polystyrene.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene. Examples include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group. 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 are bisphenol A skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Corporation, "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" ( Bisphenol acetophenone skeleton-containing phenoxy resin), and in addition, "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "YX6954BH30", "YX7553BH30", "YX7553BH30" manufactured by Mitsubishi Chemical Corporation, "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7891BH30", "YL7482", etc. are mentioned.

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, "Electrical butyral 4000-2", "Electrical butyral 5000-A", "Electrical butyral 6000-C", and "Electrical butyral 6000-EP" manufactured by Denki Kagaku Kogyo Co., Ltd. , Sekisui Chemical Co., Ltd. S-REC BH series, BX series (eg BX-5Z), KS series (eg KS-1), BL series, BM series and the like.

Specific examples of the polyimide resin include "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin also include a linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (polyimide described in JP 2006-37083 A), a polysiloxane skeleton. Modified polyimides such as contained polyimides (polyimides described in JP-A-2002-12667 and JP-A-2000-319386) can be mentioned.

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

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

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

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

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

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

-(E) Curing accelerator-
The first resin composition may contain (e) a curing accelerator in addition to the components (a) to (c).

Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, phosphorus-based curing accelerators, amine-based curing accelerators, and the like. A curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are preferable, and an amine curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are more preferable. The curing accelerator may be used alone or in combination of two or more.

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

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl Imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds and epoxy resins are mentioned, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 Examples thereof include allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, and dicyandiamide, 1,5,7-triazabicyclo[4.4.0]dec-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 and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. And the like, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.

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

-(F) Flame retardant-
The first resin composition may include (f) a flame retardant. Examples of the flame retardant include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, metal hydroxides and the like. The flame retardants may be used alone or in combination of two or more.

As the flame retardant, a commercially available product may be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd. and "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd.

When the first resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, More preferably, it is more preferably 0.5% by mass to 10% by mass.

-(G) Organic filler-
The resin composition may include (g) an organic filler from the viewpoint of improving elongation. As the organic filler, any organic filler that can be used when forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles.

As the rubber particles, commercially available products may be used, and examples thereof include "EXL2655" manufactured by Dow Chemical Japan Co., Ltd. and "AC3816N" manufactured by Ganz Kasei Co., Ltd.

When the first resin composition contains an organic filler, the content of the organic filler is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass, and further preferably Is 0.3% by mass to 5% by mass, or 0.5% by mass to 3% by mass.

-(H) Optional additives-
The first resin composition may further contain other additives, if necessary. Examples of such other additives include organic copper compounds, organic zinc compounds, organic cobalt compounds, and other organic compounds. Examples thereof include metal compounds and resin additives such as thickeners, defoamers, leveling agents, adhesion promoters, and colorants.

(Second resin composition)
The second resin composition forming the second resin composition layer is not particularly limited as long as it has a composition different from that of the first resin composition, but the second resin composition contains an inorganic filler. Those containing an inorganic filler and an epoxy resin are more preferable.

As the second resin composition, the content of the inorganic filler is 60 mass when the nonvolatile component in the second resin composition is 100 mass% from the viewpoint of suppressing warpage and decreasing the dielectric loss tangent. % Or more, more preferably 70% by mass or more, still more preferably 72% by mass or more, 74% by mass or more, or 76% by mass or more. The upper limit of the content of the inorganic filler in the second resin composition is preferably 95% by mass or less, more preferably 90% by mass or less.

As the inorganic filler in the second resin composition, the same inorganic fillers as those described in the (first resin composition) section can be mentioned. When the content of the inorganic filler in the first resin composition is A1 (mass %) and the content of the inorganic filler in the second resin composition is A2 (mass %), A1<A2 It is preferable to satisfy. The difference (A2-A1) between A1 and A2 is preferably 5% by mass or more, more preferably 8% by mass or more, and further preferably 10% by mass or more. The upper limit of the difference (A2-A1) is not particularly limited, but can be usually 90 mass% or less, 80 mass% or less, and the like.

In one embodiment, the second resin composition includes an epoxy resin and a curing agent together with the inorganic filler. The second resin composition may further contain additives such as a thermoplastic resin, a curing accelerator, a flame retardant and an organic filler, if necessary.

The epoxy resin, the curing agent and the additive contained in the second resin composition are the same as the (a) epoxy resin, the (b) curing agent and the additive described in the (first resin composition) section. Are listed.

The content of the epoxy resin in the second resin composition is preferably 0.1% by mass or more, more preferably 5% by mass or more, from the viewpoint of obtaining an insulating layer having good mechanical strength and insulation reliability. It is preferably 10% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 22% by mass or less. Therefore, the content of the (a) epoxy resin in the second resin composition is preferably 0.1 to 30% by mass, more preferably 5 to 25% by mass, and further preferably 10 to 22% by mass.

Epoxy resin of the second resin composition is, if it contains solid epoxy resin and a liquid epoxy resin, the ratio of the mass M _S of a solid epoxy resin to the weight M _L of the liquid epoxy resin (M S _{/ M L)} is The range of 1 to 10 is preferable. By setting M _S /M _L in such a range, i) a suitable tackiness is provided when used in the form of a resin sheet, and ii) sufficient flexibility when used in the form of a resin sheet And the handling property is improved, and iii) a cured product having sufficient breaking strength can be obtained. Further, in order to reduce the melt viscosity, when the inorganic filler is 100 parts by mass, it is preferable that the liquid epoxy resin is contained in an amount of 2 parts by mass or more.

In addition, the suitable range of the epoxy equivalent of the epoxy resin and the weight average molecular weight of the epoxy resin in the second resin composition is the same as that of the epoxy resin contained in the first resin composition.

The content of the curing agent in the second resin composition is not particularly limited, but from the viewpoint of obtaining an insulating layer having a low dielectric loss tangent, preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably It is 5 mass% or more. The upper limit of the content of the curing agent is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 12% by mass or less. Therefore, the content of the curing agent in the second resin composition is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and further preferably 5 to 12% by mass.

The amount ratio of the epoxy resin and the curing agent in the second resin composition is 1:0.2 in the ratio of [total number of epoxy groups of epoxy resin]:[total number of reactive groups of curing agent]. The range is preferably from 1:2 to 1:2, more preferably from 1:0.3 to 1:1.5, even more preferably from 1:0.4 to 1:1. By setting the amount ratio of the epoxy resin and the curing agent in such a range, the heat resistance of the cured product of the second resin composition is further improved.

The content of the thermoplastic resin in the second resin composition is not particularly limited, but is preferably 0% by mass to 10% by mass, more preferably 0.2% by mass to 8% by mass, further preferably 0.5% by mass. It is from 5% by mass to 5% by mass.

The content of the curing accelerator in the second resin composition is not particularly limited, but it is preferably used in the range of 0.001% by mass to 3% by mass.

The content of the flame retardant in the second resin composition is not particularly limited, but is preferably 0.2% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and further preferably 0.8% by mass. The mass% to 10 mass% is more preferable.

The content of the organic filler in the second resin composition is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass.

As with the first resin composition, the second resin composition may optionally contain any additive, for example, an organometallic compound such as an organocopper compound, an organozinc compound and an organocobalt compound, and an organic filler, It may contain a resin additive such as a thickener, a defoaming agent, a leveling agent, an adhesion-imparting agent, and a coloring agent.

[Resin sheet with support]
A resin sheet with a support of the present invention is a resin sheet with a support including a support and a resin sheet provided on the support, wherein the resin sheet is provided on the support side. A first resin composition layer formed of the resin composition, and a second resin composition layer formed of the second resin composition, which is provided on the side opposite to the support side, The first resin composition and the second resin composition have different compositions, and a first thermosetting product obtained by thermosetting the first resin composition at 200° C. for 90 minutes, and a second resin The second thermosetting product obtained by thermosetting the composition at 200° C. for 90 minutes has a dielectric constant at 5.8 GHz at 23° C. of both 3.6 or less, and the first and second thermosetting products. The dielectric loss tangent at 23° C. at 5.8 GHz is 0.01 or less, and the difference between the dielectric loss tangents of the first and second thermosetting products is 0.005 or less.

An example of the resin sheet with a support of the present invention is shown in FIG. In FIG. 1, a resin sheet 10 with a support includes a support 11 and a resin sheet 12 provided on the support 11. In FIG. 1, the resin sheet 12 includes a first resin composition layer 13 provided on the support side and a second resin composition layer 14 provided on the opposite side to the support. As will be described later, in the resin sheet with a support of the present invention, the resin sheet may include an additional resin composition layer between the first resin composition layer and the second resin composition layer. Good.

Hereinafter, the support and the resin sheet of the resin sheet with a support of the present invention will be described in detail.

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

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as “PET”) or polyethylene naphthalate (hereinafter abbreviated as “PEN”). .) and the like, polycarbonate (hereinafter sometimes abbreviated as “PC”), acrylic such as polymethylmethacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether. Examples include ketones and polyimides. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

The support may be matt-treated or corona-treated on the surface to be joined to the first resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be joined to the first resin composition layer may be used. Examples of the release agent used in the release layer of the support with release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. The support with release layer may be a commercially available product, for example, "SK-1" manufactured by Lintec Co., Ltd., which is a PET film having a release layer containing an alkyd resin release agent as a main component. , "AL-5", "AL-7" and the like.

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

<Resin sheet>
The resin sheet has a composition different from the first resin composition layer provided on the support side and the first resin composition provided on the opposite side to the support and forming the first resin composition layer. A second resin composition layer formed of the second resin composition of.

In the resin sheet with a support of the present invention, the thickness of the resin sheet is preferably 3 μm or more, more preferably 5 μm or more. The upper limit of the thickness of the resin sheet is considered from the viewpoint of setting the thickness of the resin layer on the conductor, but is preferably 70 μm or less, more preferably 50 μm or less.

The thickness of the first resin composition layer made of the first resin composition is preferably 6 μm or less, more preferably 5 μm or less. The lower limit of the thickness of the first resin composition layer is not particularly limited, but from the viewpoint of obtaining an insulating layer exhibiting excellent peel strength with respect to the conductor layer after the roughening treatment and from the viewpoint of ease of manufacturing the resin sheet with a support. Usually, it can be 0.05 μm or more, 0.1 μm or more. The presence of the first resin composition layer can improve the plating peel strength.

The thickness of the second resin composition layer made of the second resin composition is not particularly limited, and the thicknesses of the first resin composition layer and additional resin composition layers (if any) described later are taken into consideration. Meanwhile, the thickness of the obtained resin sheet may be determined so as to fall within a desired range. In one embodiment, the thickness of the second resin composition layer is preferably 3 μm or more, more preferably 5 μm or more, still more preferably 7 μm or more, 8 μm or more, 9 μm or more or 10 μm or more. The upper limit of the thickness of the second resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, 50 μm or less, or 40 μm or less. The presence of the second resin composition layer suppresses warpage.

In the present invention, the resin sheet includes the first and second resin composition layers between the first resin composition layer (support side) and the second resin composition layer (opposite side of the support). A resin composition layer (not shown) having a composition different from that may be included. Such an additional resin composition layer may be formed using the same materials as the components described in the (first resin composition) section.

The resin sheet with a support of the present invention may further include a protective film on the surface of the resin sheet that is not joined to the support (that is, the surface opposite to the support). The protective film contributes to preventing dust and the like from adhering to the surface of the resin sheet and preventing scratches. As the material of the protective film, the same material as that described for the support may be used. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. The resin sheet with a support can be used by removing the protective film when manufacturing a printed wiring board.

First thermosetting product obtained by thermosetting the first resin composition at 200° C. for 90 minutes, and second thermosetting product obtained by thermosetting the second resin composition at 200° C. for 90 minutes Has a low dielectric constant at 5.8 GHz at 23° C., and thus provides an insulating layer capable of suppressing insertion loss. The dielectric constant at 5.8 GHz at 23° C. of the first and second thermosetting products is 3.6 or less, preferably 3.5 or less, 3.4 or less, 3.3 or less, or 3.2 or less. Is more preferable. The lower limit value is not particularly limited, but may be 0 or more, 1.0 or more, and the like. The dielectric constant can be measured according to the procedure described later (measurement of dielectric constant and dielectric loss tangent of each cured product).

Since the first and second thermosetting products have low dielectric loss tangents at 23° C. and 5.8 GHz, they provide an insulating layer capable of suppressing insertion loss. The dielectric loss tangents of the first and second thermosetting products at 23° C. at 5.8 GHz are both 0.01 or less, preferably 0.0095 or less, more preferably 0.009 or less, and 0.008 or less, or It is more preferably 0.007 or less. The lower limit value is not particularly limited, but may be 0 or more, 0.001 or more, and the like. The dielectric loss tangent can be measured according to the procedure described below (measurement of dielectric constant and dielectric loss tangent of each cured product).

In the present invention, the difference in dielectric loss tangent of the first and second thermosetting products is small, so that an insulating layer capable of suppressing variations in insertion loss is provided. The difference in dielectric loss tangent of the first and second thermosetting products is 0.005 or less, preferably 0.0045 or less, and 0.004 or less, 0.003 or less, 0.002 or less, or 0.0015 or less. More preferable. The lower limit value is not particularly limited, but may be 0 or more. The difference in dielectric loss tangent can be measured according to the procedure described below (measurement of dielectric constant and dielectric loss tangent of each cured product).

INDUSTRIAL APPLICABILITY The resin sheet with a support of the present invention can be used for an insulating layer of a printed wiring board used in a high frequency band because it can reduce insertion loss and suppress variations in insertion loss. be able to. Further, since the resin sheet with a support of the present invention can provide an insulating layer on which fine wiring can be formed, an insulating layer is formed in the production of a printed wiring board by a build-up method in high frequency applications. Therefore, it can be suitably used for (for build-up insulating layer of printed wiring board), and more suitable for forming the conductor layer by plating (for build-up insulating layer of printed wiring board forming conductor layer by plating). Can be used. The high frequency band means a high frequency band of 1 GHz or higher (preferably 1.5 GHz or higher, more preferably 3 GHz or higher).

[Method for producing resin sheet with support]
Hereinafter, an example of the method for producing the resin sheet with a support of the present invention will be described.

First, a first resin composition layer made of a first resin composition and a second resin composition layer made of a second resin composition are formed on a support.

As a method of forming the first resin composition layer and the second resin composition layer, for example, a method of laminating the first resin composition layer and the second resin composition layer so as to be bonded to each other is known. Can be mentioned. As a method of laminating the first resin composition layer and the second resin composition layer so as to bond them to each other, for example, the first resin composition is applied to a support, the coating film is dried, and the first resin composition is dried. After forming the first resin composition layer, a method of applying the second resin composition on the first resin composition layer and drying the applied film to provide the second resin composition layer can be mentioned.

In this method, for the first resin composition layer, a resin varnish prepared by dissolving the first resin composition in an organic solvent is prepared, and the resin varnish is applied onto a support by using a die coater or the like, It can be produced by drying the varnish.

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

The resin varnish may be dried by a known drying method such as heating or blowing hot air. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the support is dried at 50°C to 150°C for 3 minutes to 10 minutes. A first resin composition layer can be formed on top.

In the above method, for the second resin composition layer, a resin varnish prepared by dissolving the second resin composition in an organic solvent is prepared, and the resin varnish is formed on a support using a die coater or the like. It can be prepared by applying the composition on the resin composition layer and drying the resin varnish. By weakening the drying conditions, the melt viscosity can be lowered.

As the organic solvent used for preparing the resin varnish in which the second resin composition is dissolved, the same organic solvent as that used in preparing the resin varnish in which the first resin composition is dissolved can be used. The resin varnish in which the composition is dissolved can be dried by the same method as the method for drying the resin varnish in which the first resin composition is dissolved.

The resin sheet may be formed by a tandem coating method in which two types of resin varnish are sequentially coated on one coating line, in addition to the above coating method. Further, the resin sheet is formed by applying the first resin composition on the second resin composition layer, drying the applied film to provide the first resin composition layer, and the first prepared separately. It can also be formed by a method of laminating the resin composition layer and the second resin composition layer so as to be bonded to each other.

Further, in the present invention, for example, after the second resin composition layer and the first resin composition layer are sequentially formed on the protective film, a support is laminated on the first resin composition layer to support it. You may produce a resin sheet with a body.

The second resin composition layer may be a prepreg. The prepreg is formed by impregnating a sheet-shaped fiber base material with a second resin composition.

The sheet-shaped fiber base material used for the prepreg is not particularly limited, and those commonly used as a base material for prepreg such as glass cloth, aramid non-woven fabric and liquid crystal polymer non-woven fabric can be used.

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

The thickness of the prepreg may be in the same range as the second resin composition layer in the above resin sheet.

[Printed wiring board]
The printed wiring board of the present invention includes an insulating layer formed by a cured product of the resin sheet in the resin sheet with a support of the present invention. In addition, the resin sheet with a support used in the printed wiring board of the present invention can reduce the insertion loss and suppress the variation of the insertion loss. Therefore, a conductor layer having a stripline structure that operates in a high frequency band can be provided. It is preferable to provide.

The printed wiring board of the present invention can be manufactured, for example, using the above-mentioned resin sheet with a support by a method including the following steps (1) to (4).
(1) a step of preparing a base material with a wiring layer (inner layer circuit board) having a base material and a wiring layer provided on at least one surface of the base material;
(2) The resin sheet with a support of the present invention is laminated on a base material with a wiring layer so that the wiring layer is bonded to the base material with a wiring layer so that the second resin composition layer is bonded to the base material with a wiring layer, and the resin sheet is thermally cured to form an insulating layer. The step of forming
(3) A step of roughening the insulating layer, and (4) a step of forming a conductor layer are included.

<Step (1)>
The step (1) is a step of preparing a base material with a wiring layer having a base material and a wiring layer provided on at least one surface of the base material. As shown in an example in FIG. 2, the base material 20 with a wiring layer has a wiring layer 22 which is a part of the base material 21 on at least one surface of the base material 21.

For details of the step (1), as shown in an example in FIG. 3, the wiring layer of the base material with the wiring layer is patterned. The patterned wiring layer 22' can be formed in consideration of the characteristics of the substrate 21 by, for example, a known method using photolithography using a dry film, drill, laser, plasma, etching medium, or the like.

The material used for the wiring layer is not particularly limited. In a preferred embodiment, the wiring layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Including metal. The wiring layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more kinds of metals selected from the above group (for example, nickel-chromium alloy, copper Examples thereof include those formed from nickel alloys and copper/titanium alloys, with copper being preferred.

The base material is not particularly limited as long as the steps (1) to (4) can be carried out. Examples of the base material include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like, and a metal layer such as a copper foil is formed on the substrate surface. May be.

From the viewpoint of thinning, the thickness of the base material is preferably thin, and is preferably less than 1000 μm, more preferably 800 μm or less, still more preferably 700 μm or less, still more preferably 600 μm or less. The lower limit of the thickness of the substrate is not particularly limited, but is preferably 30 μm or more, more preferably 50 μm or more, still more preferably 100 μm or more, from the viewpoint of improving the handling property during transportation.

The thickness of the wiring layer is preferably 40 μm or less, more preferably 35 μm or less, even more preferably 30 μm or less, still more preferably 25 μm or less, particularly preferably 20 μm or less, 19 μm or less, or 18 μm or less from the viewpoint of thinning. .. The lower limit of the thickness of the surface wiring is not particularly limited, but is usually 1 μm or more, 3 μm or more, 5 μm or more.

The line (circuit width)/space (width between circuits) ratio of the wiring layer is not particularly limited, but is preferably 100/100 μm or less (that is, the pitch is 200 μm or less), preferably 25/25 μm or less (pitch 50 μm or less), preferably Is 20/20 μm or less (that is, the pitch is 40 μm or less), more preferably 18/18 μm or less (pitch 36 μm or less), and further preferably 15/15 μm or less (pitch 30 μm or less). The lower limit of the line/space ratio of the wiring layer is not particularly limited, but is preferably 0.5/0.5 μm or more, more preferably 1/1 μm or more. The pitch need not be the same throughout the wiring layer.

The substrate with a wiring layer may be cut into a predetermined size as necessary, and then the next step may be performed.

<Step (2)>
In the step (2), the resin sheet with a support of the present invention is laminated on the base material with a wiring layer so that the wiring layer is bonded to the base material with a wiring layer, and heat-cured. Is a step of forming an insulating layer. For details, as shown in an example in FIG. 4, the second resin composition of the resin sheet with a support 10 is embedded so as to embed the wiring layer 22 ′ of the base material with a wiring layer obtained in the above step (1). The layers 14 are laminated and the resin sheet 12 of the resin sheet 10 with a support is thermoset.

The wiring layer and the resin sheet with a support can be laminated by removing the protective film of the resin sheet with a support and then thermocompression bonding the resin sheet with a support to the wiring layer from the support side, for example. Examples of the member for heating and pressure-bonding the resin sheet with a support to the wiring layer (hereinafter, also referred to as “thermo-compression-bonding member”) include a heated metal plate (SUS end plate or the like) or metal roll (SUS roll). To be Note that the thermocompression-bonding member is not directly pressed onto the resin sheet with a support, but is pressed via an elastic material such as heat-resistant rubber so that the resin sheet with a support sufficiently follows the surface irregularities of the wiring layer. preferable.

The wiring layer and the resin sheet with a support may be laminated by a vacuum laminating method after removing the protective film of the resin sheet with a support. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of 0.29 MPa to 1.47 MPa, and the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 13 hPa or less.

Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum press laminator manufactured by Nikko Materials Co., Ltd., a vacuum press laminator manufactured by Meiki Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., and the like. Can be mentioned.

After laminating, the smoothing treatment of the laminated resin sheet with a support may be performed under normal pressure (under atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same as the above-mentioned thermocompression bonding conditions for the lamination. The smoothing treatment can be performed with a commercially available laminator. The lamination and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

The second resin composition layer is laminated on the base material with a wiring layer so that the wiring layer is embedded, and then the resin sheet is thermoset to form an insulating layer. The thermosetting conditions of the resin sheet are not particularly limited, and the conditions usually adopted when forming the insulating layer of the wiring board may be used.

For example, the thermosetting conditions of the resin sheet differ depending on the types of the first and second resin compositions and the like, but the curing temperature is in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably in the range of 120°C to 220°C). Is in the range of 170° C. to 200° C.) and the curing time is in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

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

The support of the resin sheet with a support may be peeled after laminating the resin sheet with a support on a base material with a wiring layer and thermosetting, or laminating the resin sheet with a support on a base material with a wiring layer. The support may be peeled off before. In addition, the support may be peeled off before the treatment step for hardening described later.

The thickness of the insulating layer is the same as the thickness of the resin sheet, and the preferred range is also the same.

<Step (3)>
Step (3) is a step of roughening the insulating layer. The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions usually used when forming an insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order. The swelling liquid is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, preferably an alkaline solution, and the alkaline solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan Co., Ltd. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the 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 preferable to immerse the cured product 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 permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 80°C for 10 minutes to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Atotech Japan Co., Ltd. The neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be performed by immersing the treated surface, which has been subjected to the roughening treatment with the oxidizing agent, in the neutralizing solution at 30° C. to 80° C. for 5 minutes to 30 minutes. From the viewpoint of workability and the like, it is preferable to immerse the object roughened with the oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

In one embodiment, the arithmetic average roughness Ra of the insulating layer surface 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. Is. The arithmetic average roughness (Ra) of the surface of the insulating layer can be measured using a non-contact surface roughness meter. A specific example of the non-contact type surface roughness meter is "WYKO NT3300" manufactured by Bee Coin Instruments.

Before performing the roughening treatment of the step (3), for example, a step of forming a via hole in the insulating layer may be performed. As a result, holes such as via holes and through holes can be formed in the insulating layer.

The formation of the via hole is not particularly limited, but may be performed by using, for example, a drill, a laser, plasma or the like depending on the composition of the first and second resin compositions used for forming the insulating layer. The size and shape of the hole may be appropriately determined according to the design of the printed wiring board.

<Step (4)>
Step (4) is a step of forming a conductor layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Including metal. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more kinds of metals selected from the above group (for example, nickel-chromium alloy, copper. Layers formed from nickel alloys and copper-titanium alloys). Among them, from the viewpoint of versatility of forming a conductor layer, cost, easiness of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper. A nickel alloy or an alloy layer of copper/titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel/chromium alloy is more preferable, and a single layer of copper is Metal layers are more preferred.

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

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

The conductor layer can be formed by any conventionally known and suitable method such as plating, sputtering and vapor deposition, and is preferably formed by plating. In a preferred embodiment, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. Further, when the support in the resin sheet with the support is a metal foil, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method.

Specifically, a plating seed layer is formed by electroless plating on the surface of an insulating layer formed by thermosetting a resin sheet. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. An electrolytic plating layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. After that, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

As shown in FIG. 5 as an example, a plating seed to be bonded to the surface of the insulating layer 12′ which is composed of the exposed and thermoset first resin composition layer 13′ and the thermoset second resin composition layer 14′. The layer 31 is formed. First, the surface of the insulating layer 12' is cleaned and alkali cleaning is performed to adjust the charge. Next, a soft etching process is performed (if there is a via hole, a soft etching process is performed to clean the via hole). Specifically, the treatment may be performed under any suitable condition using an etchant such as a sulfuric acid sodium peroxodisulfate aqueous solution. Then, a pre-dip step of adjusting the charge on the surface of the insulating layer 12' is performed in order to apply Pd (palladium) to the surface of the insulating layer 12'. Next, Pd which is an activator is applied to the surface to reduce the Pd applied to the insulating layer 12'. Next, copper (Cu) is deposited on the surface of the insulating layer 12' to form the plating seed layer 31. When the via hole is formed, the plating seed layer 31 is formed so as to cover the inside of the via hole, that is, the side wall and the wiring layer exposed from the via hole.

As shown in an example in FIG. 6, after forming the plating seed layer 31, a mask pattern 40 exposing a part of the plating seed layer 31 is formed. The mask pattern 40 can be formed, for example, by bonding a dry film to the plating seed layer 31 and performing exposure, development and cleaning under predetermined conditions.

The dry film that can be used in the step (4) is not particularly limited as long as it is a photosensitive dry film made of a photoresist composition, and for example, a dry film of novolac resin, acrylic resin or the like can be used. A commercially available product may be used as the dry film, and for example, a dry film with a PET film, “ALPHO 20A263” manufactured by Nikko Materials Co., Ltd., “RD1225” manufactured by Hitachi Chemical Co., Ltd., or the like can be used.

As shown in an example in FIG. 7, an electrolytic plating layer 32 is formed on the exposed plating seed layer 31 by electrolytic plating. When the via hole is formed, the via hole is also embedded by electroplating to form a filled via.

As shown in an example in FIG. 8, the mask pattern is then peeled off and removed, and flash etching is performed under any suitable condition to remove only the exposed plating seed layer 31 to form the conductor layer 30.

In the present invention, the formation of the insulating layer and the conductor layer in the steps (2) to (4) may be repeatedly performed to form a multilayer wiring board including a plurality of insulating layers and a plurality of conductor layers. Hereinafter, a method of manufacturing a multilayer wiring board will be described, but the description of the portions overlapping the above description will be omitted as appropriate.

As shown in FIG. 9 as an example, the second resin composition layer of the resin sheet with a support is laminated on the conductor layer 30 so as to be bonded to the prepared conductor layer 30, and heat-cured to form the second insulation. Form layer 12''. That is, the step (2) is performed. The support-attached resin sheet of the present invention used in this step may be the same as the support-attached resin sheet of the present invention, which is laminated on the wiring layer-attached base material, or different ones may be used. May be.

As shown in an example in FIG. 10, after forming a via hole 50 in the second insulating layer 12 ″, a roughening process is performed, and a plating seed layer 31 is formed as an example in FIG. 11. After forming the plating seed layer 31, as shown in an example in FIG. 12, a mask pattern (not shown) that exposes a part of the plating seed layer 31 is formed, and an electroplating layer is formed on the exposed plating seed layer 31. 32 is formed, and at the same time, the filled via 51 is formed by filling the via hole by the electroplating process, thereby forming the conductor layer 30′.

Further, as shown in FIG. 13 as an example, a solder resist film 60 is formed on the outermost surface of the printed wiring board of the present invention, and the conductor layer exposed from the solder resist film 60 is subjected to nickel treatment, plating treatment, solder treatment, etc. You may give required surface treatment.

The multilayer wiring board thus manufactured has a stripline structure in which conductor layers are embedded in an insulating layer 20' and arranged according to a predetermined pattern, as shown in FIG. That is, the conductor layer is arranged inside the insulating layer. With such a configuration, it is possible to suppress the fluctuation of the characteristic impedance and reduce the insertion loss even when used in a high frequency band. Note that FIG. 14 is a schematic cross-sectional view showing a part of a direction orthogonal to the cross section shown in FIG.

Although the printed wiring board having the wiring layer, the insulating layer, and the conductor layer on one surface of the base material has been described above, the printed wiring board having the wiring layer, the insulating layer, and the conductor layer on the both surfaces of the base material has been described. It may be. Further, it may be a multilayer wiring board having a plurality of insulating layers and conductor layers on both sides of the base material.

[Semiconductor device]
The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

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

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conducting portion" is "a portion of the printed wiring board for transmitting an electric signal", and the location may be a surface or an embedded portion. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively. Specifically, the wire bonding mounting method, the flip chip mounting method, and the bumpless method are used. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, "mounting method using bump-up build-up layer (BBUL)" means "mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board to connect the semiconductor chip and wiring on the printed wiring board". Is.

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

[Production of resin sheet with support]
Using the resin varnish (resin composition) prepared by the following procedure, resin sheets with a support of Examples and Comparative Examples were produced.

(Preparation of resin varnish 1)
10 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 25 parts of biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 288), and phenoxy resin (YX7553BH30 manufactured by Mitsubishi Chemical Co., Ltd., a 1:1 solution of cyclohexanone:methyl ethyl ketone (MEK) having a solid content of 30 mass%) 15 parts was dissolved by heating in a mixed solvent of 12 parts solvent naphtha and 5 parts cyclohexanone while stirring. Let After cooling to room temperature, there were added triazine skeleton-containing phenol novolac-based curing agent (hydroxyl group equivalent 125, "LA-7054" manufactured by DIC Corporation, MEK solution having a solid content of 60%) 6 parts, active ester compound (DIC). "HPC-8000-65T" manufactured by K.K., 20 parts by weight of a weight average molecular weight of about 2700, a toluene solution having a nonvolatile content of about 223 and a nonvolatile content of 65% by mass, an amine curing accelerator (4-dimethylaminopyridine (DMAP). ), MEK solution having a solid content of 5% by mass), 2 parts, imidazole-based curing accelerator ("P200-H50" manufactured by Mitsubishi Chemical Corporation, propylene glycol monomethyl ether solution having a solid content of 50% by mass), 1 part, aminosilane-based cup Spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd.) surface-treated with a ring agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), average particle diameter 0.5 μm, carbon amount per unit surface area 0.38 mg /M ² ) 60 parts were mixed and uniformly dispersed with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP050” manufactured by ROKITECHNO) to prepare a resin varnish 1.

(Preparation of resin varnish 2)
Bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169, 1:1 mixture of bisphenol A type and bisphenol F type) 5 parts, bixylenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation) "YX4000HK", 5 parts of epoxy equivalent 185), 5 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, 238 of epoxy equivalent), naphthalene type epoxy resin (ESN475V manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) , Epoxy equivalent 330), and phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, 1:1 solution of cyclohexanone:methyl ethyl ketone (MEK) having a solid content of 30% by mass), 25 parts of solvent naphtha and cyclohexanone. It was heated and dissolved in 5 parts of the mixed solvent with stirring. After cooling to room temperature, 5 parts of a triazine skeleton-containing cresol novolac-based curing agent (hydroxyl group equivalent 151, "LA-3018-50P" manufactured by DIC Corporation, 2-methoxypropanol solution having a solid content of 50%), 20 parts of active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, toluene solution having a weight average molecular weight of about 2700, an active group equivalent of about 223 and a nonvolatile content of 65 mass%), a carbodiimide resin (Nisshinbo Chemical Co., Ltd.) Manufactured by "V-03", non-volatile component 50 mass% toluene solution) 10 parts, amine curing accelerator (4-dimethylaminopyridine (DMAP), solid content 5 mass% MEK solution) 2 parts, flame retardant (Sanko) "HCA-HQ", 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm) 2 parts, aminosilane Spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd.) surface-treated with a base coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), average particle diameter 0.5 μm, and carbon amount per unit surface area 0 Resin varnish 2 was prepared by mixing 170 parts of 0.38 mg/m ² ) and uniformly dispersing with a high-speed rotary mixer, and then filtering with a cartridge filter (“SHP050” manufactured by ROKITECHNO).

(Preparation of resin varnish 3)
Liquid naphthalene type epoxy resin (epoxy equivalent 144, DIC KK "HP4032SS") 5 parts, bixylenol type epoxy resin (Mitsubishi Chemical KK "YX4000HK", epoxy equivalent 185) 5 parts, naphthalene epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V", epoxy equivalent 330) 15 parts, and phenoxy resin (Mitsubishi Chemical Co., Ltd. "YX7553BH30", solid content 30% by mass cyclohexanone:methyl ethyl ketone (MEK) 1:1 solution. ) 7 parts were dissolved by heating in a mixed solvent of 20 parts of solvent naphtha and 5 parts of cyclohexanone with stirring. After cooling to room temperature, 10 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC Corporation, weight average molecular weight of about 2700, toluene solution of nonvolatile content 65% by mass of active group equivalent of about 223), carbodiimide 5 parts of resin ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., a toluene solution containing 50% by mass of non-volatile components), bisphenol A dicyanate prepolymer ("BA230S75" manufactured by Lonza Japan Co., Ltd., cyanate equivalent of about 232, non-volatile content) 75 mass% MEK solution) 20 parts, curing accelerator (4-dimethylaminopyridine (DMAP), solid content 5 mass% MEK solution) 1.2 parts, curing accelerator (Tokyo Kasei Co., Ltd., cobalt ( III) Acetylacetonate [Co(III)Ac, MEK solution with a solid content of 1% by mass] 3.5 parts, rubber particles (Dow Chemical Japan Co., Ltd., PARALOID EXL2655) 3 parts, phenylaminosilane coupling agent (Shin-Etsu Chemical Co., Ltd., “KBM573”) surface-treated spherical silica (average particle size 0.24 μm, Admatex Co., Ltd. “SO-C1”, carbon amount per unit area 0.36 mg/ 80 parts of m ² ) were mixed and uniformly dispersed with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP030” manufactured by ROKITECHNO) to prepare a resin varnish 3.

(Preparation of resin varnish 4)
5 parts of bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 5 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 238), naphthalene type epoxy 15 parts of resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 330), and phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Co., Ltd., 1:1 of cyclohexanone:methyl ethyl ketone (MEK) having a solid content of 30% by mass. 5 parts of the solution) was heated and dissolved in a mixed solvent of 20 parts of solvent naphtha and 5 parts of cyclohexanone while stirring. After cooling to room temperature, 10 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC Corporation, a toluene solution having a nonvolatile content of 65% by mass with a weight average molecular weight of about 2700 and an active group equivalent of about 223). 20 parts of A dicyanate prepolymer (“BA230S75” manufactured by Lonza Japan Co., MEK solution having a cyanate equivalent of about 232 and a nonvolatile content of 75% by mass), a curing accelerator (4-dimethylaminopyridine (DMAP), solid content of 5% by mass) % MEK solution) 0.5 part, curing accelerator (manufactured by Tokyo Kasei Co., Ltd., cobalt (III) acetylacetonate [Co(III)Ac, MEK solution with solid content of 1% by mass]) 3 parts, flame retardant (Sanko KK "HCA-HQ", 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm) 2 parts , Spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd.) surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), average particle diameter 0.5 μm, carbon per unit surface area A resin varnish 4 was prepared by mixing 120 parts of an amount of 0.38 mg/m ² ), uniformly dispersing with a high-speed rotary mixer, and then filtering with a cartridge filter (“SHP050” manufactured by ROKITECHNO).

(Preparation of resin varnish 5)
12 parts of biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288), 8 parts of naphthalene type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 330), and phenoxy resin ( “YX7553BH30” manufactured by Mitsubishi Chemical Corporation, 6 parts of a 1:1 solution of cyclohexanone:methyl ethyl ketone (MEK) having a solid content of 30% by mass, 6 parts of solvent naphtha and 5 parts of cyclohexanone were dissolved by heating while stirring. .. After cooling to room temperature, 22 parts of an active ester type curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent: 223, toluene solution containing 65% by mass of non-volatile components), amine type curing agent 1 part of accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass), phosphorus-based curing accelerator (“TBP-DA” tetrabutylphosphonium decanoate manufactured by Kitako Chemical Co., Ltd.) 0 .3 parts, rubber particles (Powdered by Dow Chemical Japan Ltd., PARALOID EXL2655) 2 parts, spherical silica surface treated with phenylaminosilane coupling agent (Shin-Etsu Chemical Co., Ltd., "KBM573") (average) Particle size 0.24 μm, “SO-C1” manufactured by Admatechs Co., Ltd., 30 parts of carbon amount per unit area 0.36 mg/m ² ), and phenyltrimethoxysilane (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd.) )) surface-treated spherical silica (average particle size 0.1 μm, “UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd., carbon amount per unit surface area 0.19 mg/m ² ) 40 parts, and mixed at high speed. The resin varnish 5 was prepared by uniformly dispersing with a rotary mixer and then filtering with a cartridge filter (“SHP020” manufactured by ROKITECHNO).

(Preparation of resin varnish 6)
Bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169, 1:1 mixture of bisphenol A type and bisphenol F type) 4 parts, bisphenol AF type epoxy resin (Mitsubishi Chemical Co., Ltd.) "YL7760", epoxy equivalent 238) 12 parts, naphthalene type epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V", epoxy equivalent 330) 4 parts, and phenoxy resin (Mitsubishi Chemical Co., Ltd. "YL7891BH30", solid content. 6 parts of a 30% by mass cyclohexanone:methyl ethyl ketone (MEK) solution, 20 parts of solvent naphtha and 5 parts of cyclohexanone were dissolved by heating while stirring. After cooling to room temperature, 24 parts of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution of an active group equivalent of about 223, and a nonvolatile component of 65 mass%), oligophenylene ether. -Styrene resin (Mitsubishi Gas Chemical Co., Inc. "OPE-2St 1200", toluene solution having a solid content of 72 mass%) 10 parts, amine curing accelerator (4-dimethylaminopyridine (DMAP), solid content 5 mass% MEK solution), imidazole-based curing accelerator ("1B2PZ" 1-benzyl-2-phenylimidazole manufactured by Shikoku Chemicals Co., Ltd., MEK solution with a solid content of 5%) 0.5 part, aminosilane-based coupling agent (Shin-Etsu Chemical Co., Ltd. “KBM573”) surface-treated spherical silica (Admatex Co., Ltd. “SO-C4”, average particle size 1 μm, carbon amount per unit surface area 0.31 mg/m ² ). The resin varnish 6 was prepared by mixing 150 parts and uniformly dispersing with a high-speed rotary mixer, and then filtering with a cartridge filter (“SHP050” manufactured by ROKITECHNO).

(Preparation of resin varnish 7)
Bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169, 1:1 mixture of bisphenol A type and bisphenol F type) 5 parts, bixylenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation) "YX4000HK", epoxy equivalent of about 185) 10 parts, biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent 288) 25 parts, and phenoxy resin (Mitsubishi Chemical Co., Ltd. "YX7553BH30", solid 20 parts of a cyclohexanone:methyl ethyl ketone (MEK) 1:1 solution having a content of 30 mass% was dissolved by heating with stirring in a mixed solvent of 15 parts of solvent naphtha and 5 parts of cyclohexanone. After cooling to room temperature, 12 parts of triazine skeleton-containing phenol novolac-based curing agent (hydroxyl group equivalent 125, "LA-7054" manufactured by DIC Corporation, MEK solution with solid content of 60%), naphthol-based curing agent ( Nippon Steel & Sumikin Chemical Co., Ltd. “SN-485”, hydroxyl equivalent 215, solid content 60% MEK solution 15 parts, polyvinyl butyral resin (glass transition temperature 105° C., Sekisui Chemical Co., Ltd. “KS-1”) 10% of a mixed solution of ethanol and toluene having a solid content of 15% of 1:1 of 1), an amine curing accelerator (4-dimethylaminopyridine (DMAP), a MEK solution having a solid content of 5% by mass) 1 part, and an imidazole curing Accelerator (Mitsubishi Chemical Co., Ltd. "P200-H50", solid content 50 mass% propylene glycol monomethyl ether solution) 2 parts, rubber particles (Dow Chemical Japan Co., PARALOID EXL2655) 2 parts, aminosilane-based Spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd.) surface-treated with a coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), an average particle size of 0.5 μm, and an amount of carbon per unit surface area of 0. After mixing 90 parts of 38 mg/m ² ) and uniformly dispersing with a high-speed rotary mixer, the resin varnish 7 was prepared by filtering with a cartridge filter (“SHP050” manufactured by ROKITECHNO).

(Preparation of resin varnish 8)
Bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169, 1:1 mixture of bisphenol A type and bisphenol F type) 5 parts, bixylenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation) "YX4000HK", epoxy equivalent of about 185) 5 parts, biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent 288) 12 parts, naphthalene type epoxy resin (DIC KK "HP-4710". , Epoxy equivalent of about 170), and 10 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, 1:1 solution of cyclohexanone:methyl ethyl ketone (MEK) having a solid content of 30 mass %), 20 parts of solvent naphtha and It was heated and dissolved in a mixed solvent of 10 parts of cyclohexanone while stirring. After cooling to room temperature, 10 parts of a triazine skeleton-containing phenol novolac-based curing agent (hydroxyl group equivalent 125, "LA-7054" manufactured by DIC Corporation, MEK solution having a solid content of 60%), a naphthol-based curing agent ( Nippon Steel & Sumikin Chemical Co., Ltd. "SN-485", hydroxyl equivalent 215, solid content 60% MEK solution 10 parts, imidazole-based curing accelerator (Shikoku Chemicals "1B2PZ" 1-benzyl-2- Phenylimidazole, MEK solution with a solid content of 5%, 0.5 part, flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd.), 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10. -Phosphaphenanthrene-10-oxide, average particle size 2 μm) 3 parts, spherical silica (manufactured by Admatex Co., Ltd.) surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) “SO-C4”, average particle size 1 μm, carbon amount per unit surface area 0.31 mg/m ² ) 120 parts, and surface with phenylaminosilane coupling agent (Shin-Etsu Chemical Co., Ltd., “KBM573”) 60 parts of the treated spherical alumina (“DAW-01” manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 1.5 μm, carbon amount 0.1 mg/m ² per unit surface area) was mixed and homogenized with a high-speed rotary mixer. And then filtered through a cartridge filter (“SHP050” manufactured by ROKITECHNO) to prepare a resin varnish 8.

The materials used for the production of each resin varnish and the compounding amounts thereof (parts by mass of nonvolatile content) are shown in the following table.

<Example 1: Preparation of resin sheet 1 with support>
As a support, a PET film (“Lumirror R80” manufactured by Toray Industries, Inc., “Lumilar R80” manufactured by Toray Industries, Ltd.) having a release treatment with an alkyd resin-based release agent (“AL-5” manufactured by Lintec Co., Ltd.), a thickness of 38 μm, a softening point of 130° C. Type PET”) was prepared.

The resin varnish 1 is evenly applied on a release PET by a die coater so that the thickness of the first resin composition layer after drying becomes 3 μm, and dried at 80° C. to 160° C. for 5 minutes, A first resin composition layer was obtained on the release PET. Then, the resin varnish 2 was applied onto the first resin composition layer so that the total thickness after drying was 40 μm, and the resin varnish 2 was applied at 70° C. to 110° C. (average 95° C.). And dried for 5 minutes to form a two-layer resin composition layer (resin sheet). Then, on the surface of the resin sheet that is not bonded to the support (that is, the surface of the second resin composition layer that is not bonded to the first resin composition layer), a polypropylene film (Oji Ftex Co., Ltd. The rough surface of "Alphan MA-411" manufactured by ), thickness 15 μm) was laminated so as to be bonded to the second resin composition layer. In this way, a resin sheet 1 with a support was obtained in the order of the support, the first resin composition layer (derived from the resin varnish 1), the second resin composition layer (derived from the resin varnish 2), and the protective film. ..

<Example 2: Preparation of resin sheet 2 with support>
A resin sheet 2 with a support was obtained in the same manner as in Example 1 except that the resin varnish 3 was used in place of the resin varnish 1 and the resin varnish 4 was used in place of the resin varnish 2 in Example 1.

<Example 3: Preparation of resin sheet 3 with support>
A resin sheet 3 with a support was obtained in the same manner as in Example 1 except that the resin varnish 5 was used in place of the resin varnish 1 and the resin varnish 6 was used in place of the resin varnish 2 in Example 1.

<Comparative Example 1: Preparation of resin sheet 4 with support>
A resin sheet with a support 4 was obtained in the same manner as in Example 1 except that the resin varnish 7 was used in place of the resin varnish 1.

<Comparative Example 2: Preparation of resin sheet 5 with support>
A resin sheet with a support 5 was obtained in the same manner as in Example 1 except that the resin varnish 6 was used in place of the resin varnish 2.

<Comparative Example 3: Preparation of resin sheet 6 with support>
A resin sheet 6 with a support was obtained in the same manner as in Example 1 except that the resin varnish 7 was used in place of the resin varnish 1 and the resin varnish 8 was used in place of the resin varnish 2 in Example 1.

<Comparative Example 4: Preparation of resin sheet 7 with support>
A resin sheet with a support 7 was obtained in the same manner as in Example 1 except that the resin varnish 8 was used in place of the resin varnish 2.

<Production of cured product of each resin composition>
A release PET film (“501010” manufactured by Lintec Co., Ltd., thickness 38 μm, 240 mm square) for preparing a cured product was prepared as a support.

Each of the resin varnishes 1 to 8 is evenly applied on the release PET film by a die coater so that the thickness of the resin composition layer after drying is 35 μm, and dried at 70 to 110° C. for 5 minutes. Thus, a resin composition layer was obtained on the release PET film.

The release PET film with the resin composition layer was used as a resin composition layer/release PET film/glass cloth substrate epoxy resin double-sided copper clad laminate (“R5715ES” manufactured by Matsushita Electric Works, Ltd., thickness 0.7 mm, 255 mm It was placed on a glass cloth substrate epoxy resin double-sided copper clad laminate so as to have a square shape, and the four sides of the film were fixed with a polyimide adhesive tape (width 10 mm).

Then, it was thermally cured under curing conditions of 200° C. for 90 minutes. After thermosetting, the polyimide adhesive tape was peeled off, and the release PET film with the resin composition layer was removed from the glass cloth-based epoxy resin double-sided copper-clad laminate. Further, the release PET film (“501010” manufactured by Lintec Co., Ltd.) on which the resin sheet was laminated was peeled off to obtain a sheet-shaped cured product.

(Measurement of dielectric constant and dielectric loss tangent of each cured product)
Each cured product was cut into a test piece having a width of 2 mm and a length of 80 mm, and the test piece was subjected to a cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. using “HP8362B” manufactured by Agilent Technologies. Then, the dielectric constant (Dk) and the dielectric loss tangent (Df) were measured. The measurement was performed on three test pieces, the average value was calculated, and the results are shown in the following table. Further, based on the thus calculated dielectric loss tangent, the difference between the dielectric loss tangents of the first and second thermosetting products in the resin sheets with a support of Examples and Comparative Examples was calculated, and the results are shown in the following table. It was

<Evaluation test>
1. Evaluation of High Frequency Transmission Loss Measurement FIG. 15 is a schematic sectional view of a stripline transmission line evaluation board. Using the resin sheet with a support prepared in Examples and Comparative Examples, a stripline transmission line evaluation board having the configuration of FIG. 15 was prepared according to the following procedure, and high frequency transmission loss measurement was evaluated.

(1) Substrate treatment of inner layer circuit board As an inner layer circuit board, a glass cloth base material epoxy resin double-sided copper clad laminate having a circuit conductor (copper) with through holes formed on both sides (copper foil thickness 18 μm, A thickness of 0.6 mm, "MCL-M-679FGS" manufactured by Hitachi Chemical Co., Ltd.) was prepared.

(2) Lamination of resin sheet with a support A resin sheet with a support prepared in each of the examples and comparative examples was used as a batch type vacuum pressure laminator (Nikko Materials Co., Ltd., two-stage build-up laminator, CVP700). Was laminated on both surfaces of the inner layer circuit board so that the second resin composition layer was bonded to the inner layer circuit board. Lamination was carried out by reducing the pressure for 30 seconds so that the atmospheric pressure was 13 hPa or less, and then performing pressure bonding for 30 seconds at 100° C. and a pressure of 0.74 MPa. Then, hot pressing was performed for 60 seconds at 100° C. and a pressure of 0.5 MPa.

(3) Thermosetting of Resin Composition Layer The inner layer circuit board laminated with the resin sheet with the support is put in an oven at 100° C. for 30 minutes at a temperature of 100° C., and then at a temperature of 175° C. for 175° C. After transferring to an oven at 0° C., it was thermoset for 30 minutes to form an insulating layer.

(4) Step of performing desmear treatment The support was peeled from the circuit board on which the insulating layer was formed, and desmear treatment was performed. As the desmear treatment, the following wet desmear treatment was performed.

Wet desmear treatment:
Swelling liquid ("Swelling Dip Securigant P" manufactured by Atotech Japan Co., Ltd., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 5 minutes, and then an oxidizing agent solution ("Concentrate manufactured by Atotech Japan Co., Ltd."・Compact CP", an aqueous solution with a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) at 80°C for 20 minutes, and finally a neutralization solution (Atotech Japan KK "Reduction Solution Securigant P" , An aqueous solution of sulfuric acid) at 40° C. for 5 minutes, and then dried at 80° C. for 15 minutes.

(5) Step of forming conductor layer (5-1) Electroless plating step In order to form a conductor layer on the surface of the circuit board, a plating step including the following steps 1 to 6 (chemical solution manufactured by Atotech Japan Co., Ltd.) Was performed to form a conductor layer having a target thickness of 18 μm.

1. Alkaline cleaning (cleaning the surface of the insulating layer and adjusting the charge)
It wash|cleaned for 5 minutes at 60 degreeC using Cleaning Cleaner Security 902 (brand name).
2. Soft etching Treatment was performed at 30°C for 1 minute using an aqueous solution of sodium peroxodisulfate acidified with sulfuric acid.
3. Predip (Adjustment of electric charge on the surface of insulating layer for Pd application)
Pre. Dip Neoganth B (trade name) was used for treatment at room temperature for 1 minute.
4. Activator applied (Pd applied to the surface of the insulating layer)
It was treated with Activator Neoganth 834 (trade name) at 35° C. for 5 minutes.
5. Reduction (reduces Pd applied to the insulating layer)
Reducer Neoganth WA (trade name) and Reducer Accelerator 810 mod. Using a mixed solution with (trade name), the mixture was treated at 30° C. for 5 minutes.
6. Electroless copper plating step (Cu is deposited on the surface of the insulating layer (Pd surface))
Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name), and a mixed solution of 35° C. at Reducer Cu (trade name). It was treated for 20 minutes. The thickness of the formed electroless copper plating layer was 0.8 μm.

(5-2) Formation of dry film pattern Next, a dry film (manufactured by Hitachi Chemical Co., Ltd., "RD1225") is laminated on the formed electroless copper plating layer, and an exposure machine "LI9500" manufactured by Dainippon Screen Mfg. Co., Ltd. (Exposure amount 15 mJ/cm ² ) and development (1% Na ₂ CO ₃ aqueous solution, 30° C., 40 s, spray pressure 0.15 MPa) to form a dry film pattern.

(5-3) Electrolytic plating step Next, an electrolytic copper plating step was performed using the chemical solution "Toprutina α" manufactured by Okuno Chemical Industries Co., Ltd. Thereafter, the dry film pattern was peeled off with a 1% NaOH aqueous solution, and an unnecessary electroless copper plating layer was removed by an etching solution "OPC-HR Soft Etch P" manufactured by Okuno Chemical Industries Co., Ltd. Next, an annealing treatment was performed at 190° C. for 90 minutes to form a conductor layer on the insulating layer.

(6) Lamination of Resin Sheet with Supports Each substrate was immersed in a 10% sulfuric acid aqueous solution for 30 seconds and dried at 130° C. for 15 minutes, and then each resin sheet with support prepared in Examples and Comparative Examples was Lamination was carried out in the same manner as in (2) Lamination of resin sheet with support.

(7) Thermosetting of Resin Composition Layer The inner layer circuit board on which the resin sheet with a support is laminated is put into an oven at 100° C. for 30 minutes at a temperature of 100° C., and then at a temperature of 175° C. for 175° C. After transferring to an oven at 0° C., it was thermoset for 30 minutes to form an insulating layer.

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

(9) Step of Performing Desmear Treatment The support was peeled off from the circuit board provided with the via hole, and the desmear treatment was performed in the same manner as in (4).

(10) Step of forming a conductor layer (5) A conductor layer having a target thickness of 18 μm was formed by the same method as the step of forming a conductor layer. The soft etching was performed for cleaning the inside of the via hole.

(11) Step of forming a solder resist A solder resist "PFR-800 AUS410" manufactured by Taiyo Ink Mfg. Co., Ltd. is laminated and exposed by an exposure machine "LI9500" manufactured by Dainippon Screen Mfg. Co., Ltd. (exposure amount 150 mJ/ cm ² ), development (1% Na ₂ CO ₃ aqueous solution, 30° C., 80 s, spray pressure 0.15 MPa) to form a solder resist.

(Measurement of thickness of insulating layer between conductor layers)
The cross section of the strip line transmission line evaluation board (hereinafter, also referred to as an evaluation board) was observed using a FIB-SEM composite device (“SMI3050SE” manufactured by SII Nano Technology Co., Ltd.). Specifically, a cross section in a direction perpendicular to the surface of the conductor layer was cut out by FIB (Focused Ion Beam), and the thickness of the insulating layer between the conductor layers was measured from the cross section SEM image. For each sample, five randomly selected cross-sectional SEM images were observed, and the average value was used as the thickness of the insulating layer between the conductor layers.

(High frequency transmission loss measurement)
Using the three evaluation boards produced, for an impedance of 50Ω and a wiring length of 34 mm,
VNA (Agilent technology PNA-X): 10 MHz to 50 GHz,
TDR/TDT system (Tektronix DSA8200): Characteristic impedance/eye-pattern
Was used to measure high-frequency transmission loss.

In the table below, three insertion loss values (dB) at 30 GHz are described, and the average value, standard deviation, and cv value of the insertion loss are shown. The cv value of the insertion loss is a value obtained by (standard deviation of insertion loss/average value of insertion loss)×100.

10 Resin Sheet with Support 11 Support 12 Resin Sheet 12′ Insulating Layer 12″ Second Insulating Layer 13 First Resin Composition Layer 13′ Thermosetting First Resin Composition Layer 14 Second Resin Composition Physical layer 14' thermosetting second resin composition layer 20 base material 21 with wiring layer base material 22 wiring layer 22' patterned wiring layer 30 conductor layer 30' conductor layer 31 plating seed layer 32 electric field plating layer 40 mask Pattern 50 Via hole 51 Filled via 60 Solder resist film

Claims (9)

A support-equipped resin sheet comprising a support and a resin sheet provided on the support,
The resin sheet includes a first resin composition layer formed of the first resin composition, which is provided on the support side,
A second resin composition layer formed of the second resin composition, which is provided on the side opposite to the support side,
The first resin composition and the second resin composition have different compositions,
First thermosetting product obtained by thermosetting the first resin composition at 200° C. for 90 minutes, and second thermosetting product obtained by thermosetting the second resin composition at 200° C. for 90 minutes , The dielectric constant at 5.8 GHz at 23° C. is both 3.6 or less,
The first resin composition and the second resin composition include (c) an inorganic filler, and the content of the inorganic filler in the first resin composition is A1 (mass %), the second resin composition. When the content of the inorganic filler in the product is A2 (mass %), the difference between A1 and A2 (A2-A1) is 5 mass% or more and 90 mass% or less,
The dielectric loss tangents of the first and second thermosetting products at 23° C. at 5.8 GHz are both 0.01 or less,
A resin sheet with a support, wherein the difference in dielectric loss tangent of the first and second thermosets is 0.005 or less. The resin sheet with a support according to claim 1, wherein the first resin composition and the second resin composition include (a) an epoxy resin, and the (a) component is an epoxy resin having an aromatic structure. .. The support according to claim 1 or 2, wherein the first resin composition and the second resin composition contain (b) a curing agent, and at least one kind of the component (b) is an active ester curing agent. With resin sheet. Dielectric constant at 5.8GHz at 23 ° C. of the first and second heat cured product are both 3.5 or less, the support coated resin sheet according to any one of claims 1-3. The dielectric loss tangent of the 5.8GHz at 23 ° C. of the first and second thermoset are both 0.0095 or less, the support coated resin sheet according to any one of claims 1-4. 1GHz used in the above high-frequency band, the support coated resin sheet according to any one of claims 1-5. Claim 1 in any one of 6 including an insulating layer formed by the cured product of the resin sheet in the support with a resin sheet, wherein the printed wiring board. The printed wiring board according to claim 7 , comprising a stripline structure. To claim 7 or 8 including a printed wiring board according semiconductor device.

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