JP2017149861A - Resin sheet with support body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin sheet with a support body which reduces insertion loss and suppresses variation in the insertion loss; a printed wiring board; and a semiconductor device.SOLUTION: There is provided a resin sheet which has a support body and a resin sheet provided on the support body, where the resin sheet has a first resin composition layer that is provided on a support body side and is formed from a first resin composition, and a second resin composition layer that is provided on an opposite side to the support body side and is formed from a second resin composition, the compositions of the first resin composition and the second resin composition are different from each other, both dielectric constants of a thermoset article of the first resin composition and a thermoset article of the second resin composition are 3.6 or less, both dielectric loss tangents of the thermoset articles of the first and second resin compositions are 0.01 or less, and a difference between the dielectric loss tangents is 0.005 or less.SELECTED DRAWING: Figure 1

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 of manufacturing a printed wiring board (hereinafter also referred to as “wiring board”), a build-up method in which a conductor layer and an insulating layer on which a circuit is formed is alternately stacked is widely used. It is known that it is formed by curing a resin composition layer made of (see, for example, Patent Document 1).

JP 2014-17301 A

  By the way, since the amount of information communication has increased in recent years, a wiring board corresponding to a high frequency band has been demanded. However, 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 two insulating layers is large, the electrical signal changes to heat and / or noise, and the signal and information cannot be accurately transmitted. is there. In addition, even if the insertion loss is small, there is a problem that if the variation in the insertion loss is large, the stability of the high-speed signal is lacking, the device does not operate as designed, and malfunction is likely to 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 variation in insertion loss.

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

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 is provided on the support side, the first resin composition layer formed of the first resin composition,
A second resin composition layer formed by the second resin composition provided on the side opposite to the support side,
The compositions of the first resin composition and the second resin composition are different from each other,
A first thermoset obtained by thermosetting the first resin composition at 200 ° C. for 90 minutes, and a second thermoset obtained by thermosetting the second resin composition at 200 ° C. for 90 minutes Both of which have a dielectric constant at 5.8 GHz at 23 ° C. of 3.6 or less,
The dielectric loss tangent at 5.8 GHz at 23 ° C. of the first and second thermosets is both 0.01 or less,
The resin sheet with a support, wherein the difference in dielectric loss tangent between 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 include (a) an epoxy resin, and the component (a) is an epoxy resin having an aromatic structure. With resin sheet.
[3] The first resin composition and the second resin composition include (b) a curing agent, and at least one of the components (b) is an active ester curing agent, [1] or [2] The resin sheet with a support according to 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 The resin sheet with a support according to any one of [1] to [3], which satisfies a relationship of A1 <A2 when the content of the component (c) in the product is A2.
[5] The resin sheet with a support according to any one of [1] to [4], wherein the first and second thermosets each have a dielectric constant at 5.8 GHz at 23 ° C. of 3.5 or less. .
[6] The resin sheet with a support according to any one of [1] to [5], wherein the first and second thermosets each have a dielectric loss tangent at 5.8 GHz at 23 ° C. of 0.0095 or less. .
[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 more.
[8] A printed wiring board including an insulating layer formed of 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], comprising 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 variation in insertion loss.

Drawing 1 is a mimetic diagram showing one mode of a resin sheet with a support of the present invention. FIG. 2 is a schematic cross-sectional view for explaining a manufacturing process of the wiring board. FIG. 3 is a schematic cross-sectional view for explaining a 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 a 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. 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 a stripline transmission line evaluation board produced 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, in the resin sheet with a support of the present invention, when forming the first resin composition layer and the second resin composition layer included in the resin sheet The first resin composition and the second resin composition used in the above will be described.

(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. As a 1st resin composition, the composition containing curable resin and its hardening | curing agent is mentioned, for example. As curable resin, the conventionally well-known curable resin used when forming the insulating layer of a printed wiring board can be used, and an epoxy resin is especially preferable. Accordingly, in one embodiment, the first resin composition includes (a) an epoxy resin, (b) a curing agent, and (c) an inorganic filler. The 1st resin composition may contain the thermoplastic resin, the hardening accelerator, the flame retardant, and the organic filler further as needed.

  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 epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin, cresol novolac Type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, complex Wherein the epoxy resin, spiro ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. The component (a) is preferably 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. It is more preferable that it is 1 type or more. The aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatics and aromatic heterocycles.

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

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

  Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more preferable. Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” manufactured by DIC Corporation. "(Cresol novolac type epoxy resin)", "N-695" (Cresol novolac type epoxy resin), "HP-7200" (Dicyclopentadiene type epoxy resin), "HP-7200HH", "HP-7200H", "EXA -7311 "," EXA-7311-G3 "," EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(naphthylene ether type epoxy resin)," EPPN "manufactured by Nippon Kayaku Co., Ltd. -502H "(trisphenol type epoxy resin)," NC7000L "(naphthol novolak type) Poxy resin), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ESN475V” (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “ESN485” (naphthol novolak) Type epoxy resin), "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), manufactured by Mitsubishi Chemical Corporation, Osaka Gas Chemical “PG-100”, “CG-500” manufactured by Mitsubishi Chemical Corporation, “YL7760” (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “YL7800” (fluorene type epoxy resin), Mitsubishi Chemical Corporation “JER1010” (solid bisfer Lumpur A type epoxy resin), "jER1031S" (tetraphenyl ethane epoxy resin) and the like. These may be used alone or in combination of two or more.

  When the liquid epoxy resin and the solid epoxy resin are used in combination as the epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 0: 0.1 to 1:15 by mass ratio. preferable. By making the quantity ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is obtained when used in the form of a resin sheet, ii) when used in the form of a resin sheet Sufficient flexibility can be obtained, handling properties can be improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii), the quantitative 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 by mass ratio. Is more preferable, and the range of 0: 0.6 to 1: 8 is even more 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 still more preferably, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. 3% by mass or more. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is show | played, Preferably it is 50 mass% or less, More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less.

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

  The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By becoming this range, the crosslinked density of hardened | cured material becomes sufficient and it can bring about an insulating layer with small surface roughness. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

  The weight average molecular weight of an epoxy resin becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

-(B) Curing agent-
The curing agent is not particularly limited as long as it has a function of curing the epoxy resin. For example, a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, a cyanate ester curing agent, and Examples thereof include carbodiimide curing agents. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together. The component (b) is preferably at least one selected from a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a carbodiimide curing agent, and a cyanate ester curing agent, a phenol curing agent, One or more selected from an active ester curing agent and a carbodiimide curing agent is more preferable, and an active ester curing agent is more preferable 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 novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Moreover, from a viewpoint of adhesiveness with a conductor layer, a nitrogen-containing phenol type hardening | curing agent is preferable and a triazine frame | skeleton containing phenol type hardening | curing agent is more preferable. Among these, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “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.

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

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

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

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

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

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

  The amount ratio of the epoxy resin and the curing agent is preferably a ratio of [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of the curing agent] in the range of 1: 0.01 to 1: 2. 1: 0.015 to 1: 1.5 are more preferable, and 1: 0.02 to 1: 1 are more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like, and varies depending on the type of the curing agent. Moreover, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the value obtained by dividing the solid mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is: The value obtained by dividing the solid mass of each curing agent by the reactive group equivalent is the total value for all curing agents. By 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 includes the aforementioned (a) epoxy resin and (b) a curing agent. The resin composition is a mixture of a liquid epoxy resin and a solid epoxy resin (a) as an epoxy resin (mass ratio of liquid epoxy resin: solid epoxy resin is preferably 0: 0.1 to 1:15, more preferably 0: 0.3-1: 12, more preferably 0: 0.6-1: 10), (b) a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a carbodiimide curing as a curing agent One or more selected from the group consisting of an agent and a cyanate ester curing agent (preferably an active ester curing agent) are preferably included.

  Although content of the hardening | curing agent in a 1st resin composition is not specifically limited, Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less. The lower limit is not particularly limited but is preferably 2% by mass or more.

-(C) Inorganic filler-
The material of the inorganic filler is not particularly limited. For example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly preferred. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

  The average particle size of the inorganic filler is not particularly limited, but is preferably 2 μm or less, more preferably 1.5 μm or less, and even more 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. Although the minimum of this average particle diameter is not specifically limited, Preferably it is 0.01 micrometer or more, More preferably, it is 0.1 micrometer or more, More preferably, it is 0.3 micrometer or more. Examples of commercially available inorganic fillers having such an average particle size include, for example, “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C” manufactured by Admatechs, manufactured by Denki Kagaku Kogyo Co., Ltd. “UFP-30”, “Silfil NSS-3N”, “Silfil NSS-4N”, “Silfil NSS-5N” manufactured by Tokuyama Corporation, “SC2500SQ”, “SO-C4”, “SO-C4” manufactured by Admatechs Co., Ltd. -C2 "," SO-C1 "and the like.

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

  The inorganic filler is preferably surface-treated with at least one surface treatment agent of a silane coupling agent, an alkoxysilane compound, and an organosilazane compound from the viewpoint of improving moisture resistance and dispersibility. These may be oligomers. Examples of the surface treatment agent include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents, and the like. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM803” (3-mercaptopropyltrimethoxy manufactured by Shin-Etsu Chemical Co., Ltd.). Silane), Shin-Etsu Chemical "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical "SZ-31" (hexamethyldisilazane) manufactured by KK, "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type) Silane coupling agent). A surface treating agent may be used individually by 1 type, and may be used in combination of 2 or more types.

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

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

  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 plating peelability. More preferably, it is 60 mass% or less, 50 mass% or less, or 40 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 from the viewpoint of reducing the dielectric loss tangent, it is 5% by mass or more and 10% by mass. As mentioned above, it may be 20 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 include ether ketone resins and polyester resins, and phenoxy resins are preferred. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

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

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). In addition to these, “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” and the like.

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

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

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

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

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

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

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

  When the 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 still more 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 a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, a metal-based curing accelerator, and the like. A curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are preferable, and an amine curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2 Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl Examples include imidazole compounds such as -3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, such as 2-ethyl-4-methylimidazole and 1-benzyl-2- Phenylimidazole is preferred.

  Commercially available products may be used as the imidazole curing accelerator, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation.

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

  As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned, for example. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

  Although content of the hardening accelerator in a 1st resin composition is not specifically limited, 0.01 mass%-3 mass% are preferable when the non-volatile component of an epoxy resin and a hardening | curing agent is 100 mass%.

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

  Commercially available products may be used as the flame retardant, for example, “HCA-HQ” manufactured by Sanko Co., Ltd., “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd., and the like.

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

-(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 in forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles.

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

  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 still more 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 as necessary. Examples of such other additives include organic copper compounds, organic zinc compounds, and organic cobalt compounds. Examples of the metal compound include thickeners, antifoaming agents, leveling agents, adhesion imparting agents, and resin additives such as coloring agents.

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

  As a 2nd resin composition, content of an inorganic filler when the non-volatile component in a 2nd resin composition is 100 mass% from a viewpoint which suppresses curvature and reduces a dielectric loss tangent is 60 mass. % Or more, preferably 70% by mass or more, 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.

  Examples of the inorganic filler in the second resin composition include the same inorganic filler as described in the section (First resin composition). 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%), the relationship of A1 <A2 It is preferable to satisfy. Moreover, 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% by mass or less, 80% by mass or less, and the like.

  In one embodiment, the second resin composition includes an epoxy resin and a curing agent together with an 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 as necessary.

  The epoxy resin, curing agent and additive contained in the second resin composition are the same as the (a) epoxy resin, (b) curing agent and additive described in the (first resin composition) column. Is mentioned.

  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 exhibiting good mechanical strength and insulation reliability. Preferably it is 10 mass% or more. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is show | played, Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 22 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 still more 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 A range of 1 to 10 is preferred. The M S _/ M _L, With such a range, i) moderate tackiness is brought when used in the form of a resin sheet, ii) sufficient flexibility when used in the form of a resin sheet Is obtained, the handleability is improved, and iii) a cured product having sufficient breaking strength can be obtained. Moreover, in order to reduce melt viscosity, when an inorganic filler is 100 mass parts, it is preferable that 2 mass parts or more of liquid epoxy resins are included.

  In addition, the suitable range of the epoxy equivalent of an epoxy resin and the weight average molecular weight of an epoxy resin in a 2nd resin composition is the same as that of the epoxy resin contained in a 1st resin composition.

  The content of the curing agent in the second resin composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably, from the viewpoint of obtaining a low dielectric loss tangent insulating layer. It is 5 mass% or more. Although the upper limit of content of a hardening | curing agent is not specifically limited as long as the effect of this invention is show | played, Preferably it is 20 mass% or less, More preferably, it is 15 mass% or less, More preferably, it is 12 mass% or less. Therefore, content of the hardening | curing agent in 2nd resin composition becomes like this. Preferably it is 0.1-20 mass%, More preferably, it is 1-15 mass%, More preferably, it is 5-12 mass%.

  The amount ratio of the epoxy resin and the curing agent in the second resin composition is a ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of curing agent], which is 1: 0.2. The range of ˜1: 2 is preferable, 1: 0.3 to 1: 1.5 is more preferable, and 1: 0.4 to 1: 1 is more preferable. By making the quantity ratio of an epoxy resin and a hardening | curing agent into such a range, the heat resistance of the hardened | cured material of a 2nd resin composition improves more.

  Although content of the thermoplastic resin in a 2nd resin composition is not specifically limited, Preferably it is 0 mass%-10 mass%, More preferably, it is 0.2 mass%-8 mass%, More preferably, it is 0.5. It is 5 mass%-5 mass%.

  Although content of the hardening accelerator in a 2nd resin composition is not specifically limited, It is preferable to use in 0.001 mass%-3 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 still more preferably 0.8%. More preferably, 10% by mass to 10% by mass.

  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.

  Similarly to the first resin composition, the second resin composition may be optionally added, for example, an organic metal compound such as an organic copper compound, an organic zinc compound and an organic cobalt compound, and an organic filler, A resin additive such as a thickener, an antifoaming agent, a leveling agent, an adhesion imparting agent, and a coloring agent may be included.

[Resin sheet with support]
The resin sheet with a support according to the present invention is a resin sheet with a support including a support and a resin sheet provided on the support, and the resin sheet is provided on the support side. A first resin composition layer formed by the resin composition, and a second resin composition layer formed by the second resin composition provided on the side opposite to the support side, The first resin composition and the second resin composition are different from each other, and the first thermoset obtained by thermosetting the first resin composition at 200 ° C. for 90 minutes, and the second resin The second thermosetting product obtained by thermosetting the composition at 200 ° C. for 90 minutes has a dielectric constant of 3.6 or less at 5.8 GHz at 23 ° C., and the first and second thermosetting products The dielectric loss tangent at 5.8 GHz at 23 ° C. is 0.01 or less, and the first and second The difference in dielectric loss tangent of the heat cured product 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 consists of the 1st resin composition layer 13 provided in the support body side, and the 2nd resin composition layer 14 provided in the opposite side to a support body. 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, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). .) Polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), polymethyl methacrylate (PMMA) and other acrylics, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

  The support may be subjected to mat treatment and corona treatment on the surface to be bonded 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 bonded to the first resin composition layer may be used. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used. For example, “SK-1” manufactured by Lintec Corporation, which is a PET film having a release layer mainly composed of an alkyd resin release agent. , “AL-5”, “AL-7”, and the like.

  Although it does not specifically limit as thickness of a support body, The range of 5 micrometers-75 micrometers is preferable, and the range of 10 micrometers-60 micrometers is more preferable. In addition, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

<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 of the support and forming the first resin composition layer. And a second resin composition layer formed of the second resin composition.

  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 1st resin composition layer which consists of a 1st resin composition becomes like this. Preferably it is 6 micrometers or less, More preferably, it is 5 micrometers or less. Although the minimum of the thickness of a 1st resin composition layer is not specifically limited, From a viewpoint of obtaining the insulating layer which exhibits the outstanding peeling strength with respect to a conductor layer after a roughening process, from a viewpoint of the ease of manufacture of the resin sheet with a support body. Usually, it may be 0.05 μm or more, 0.1 μm or more, and the like. The presence of the first resin composition layer can improve the plating peel strength.

  The thickness of the 2nd resin composition layer which consists of a 2nd resin composition is not specifically limited, The thickness of the 1st resin composition layer and the additional resin composition layer (if it exists) mentioned later is considered. However, what is necessary is just to determine so that the thickness of the resin sheet obtained may become 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. Warpage is suppressed by the presence of the second resin composition layer.

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

  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 the prevention of scratches and adhesion of dust and the like on the surface of the resin sheet. As the material for the protective film, the same materials as described for the support may be used. Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. The resin sheet with a support can be used by peeling off the protective film when producing a printed wiring board.

  A first thermoset obtained by thermosetting the first resin composition at 200 ° C. for 90 minutes, and a second thermoset 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., thus providing an insulating layer capable of suppressing insertion loss to a low level. The dielectric constant at 5.8 GHz at 23 ° C. of the first and second thermosets 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. Although a lower limit is not specifically limited, It can be set to 0 or more, 1.0 or more, etc. 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 thermosets have a low dielectric loss tangent at 5.8 GHz at 23 ° C., an insulating layer that can keep the insertion loss low is provided. The dielectric loss tangent at 5.8 GHz at 23 ° C. of the first and second thermosets is both 0.01 or less, preferably 0.0095 or less, more preferably 0.009 or less, or 0.008 or less, or 0.007 or less is more preferable. Although a lower limit is not specifically limited, It can be set to 0 or more, 0.001 or more, etc. The dielectric loss tangent can be measured according to the procedure described later (measurement of dielectric constant and dielectric loss tangent of each cured product).

  In this invention, since the difference of the dielectric loss tangent of the 1st and 2nd thermosetting products is small, the insulating layer which can suppress the dispersion | variation in insertion loss is brought about. The difference in dielectric loss tangent between the first and second thermosets is 0.005 or less, preferably 0.0045 or less, 0.004 or less, 0.003 or less, 0.002 or less, or 0.0015 or less. Further preferred. The lower limit is not particularly limited, but may be 0 or more. The difference in dielectric loss tangent can be measured according to the procedure described later (measurement of dielectric constant and dielectric loss tangent of each cured product).

  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. Moreover, 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 for high frequency applications. Therefore, it can be suitably used for (for a build-up insulating layer of a printed wiring board) and more suitably for forming a conductor layer by plating (for a build-up insulating layer of a printed wiring board in which a conductor layer is formed 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 manufacturing method of 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, there is a method of laminating the first resin composition layer and the second resin composition layer so as to be bonded to each other. Can be mentioned. As a method of laminating the first resin composition layer and the second resin composition layer so as to be bonded to each other, for example, the first resin composition is applied to a support, the coating film is dried, After forming the 1 resin composition layer, the 2nd resin composition is apply | coated on the 1st resin composition layer, the coating film is dried and the method of providing a 2nd resin composition layer is mentioned.

  In this method, the first resin composition layer is prepared by preparing a resin varnish obtained by dissolving the first resin composition in an organic solvent, and applying the resin varnish on a support 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, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol. And aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, or may use 2 or more types together.

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

  In the above method, the second resin composition layer is prepared by preparing a resin varnish in which the second resin composition is dissolved in an organic solvent, and forming the resin varnish on a support using a die coater or the like. It can apply | coat on the resin composition layer of this, and can produce it by drying a resin varnish. The melt viscosity can also be lowered by weakening the drying conditions.

  As the organic solvent used for the preparation of the resin varnish in which the second resin composition is dissolved, the same organic solvent as that used for the preparation of 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. The resin sheet is a method in which the first resin composition is applied on the second resin composition layer, the coating film is dried to provide the first resin composition layer, and the first prepared separately. The resin composition layer and the second resin composition layer can also be formed by a method of laminating them so as to be bonded to each other.

  Furthermore, in the present invention, for example, after the second resin composition layer and the first resin composition layer are formed in order on the protective film, a support is laminated on the first resin composition layer for support. 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-like fiber base material with the second resin composition.

  The sheet-like fiber base material used for a prepreg is not specifically limited, What is used normally as base materials for prepregs, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, can be used.

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

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

[Printed wiring board]
The printed wiring board of the present invention includes an insulating layer formed of 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 insertion loss and suppress variation in insertion loss, so that 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 this invention can be manufactured by the method including the process of following (1)-(4), for example using the above-mentioned resin sheet with a support body.
(1) A step of preparing a substrate with a wiring layer (inner layer circuit board) having a substrate and a wiring layer provided on at least one surface of the substrate;
(2) The resin sheet with a support of the present invention is laminated on a substrate with a wiring layer so that the second resin composition layer of the wiring layer is bonded to the substrate with the wiring layer, and is thermally cured to be an insulating layer. Forming a process,
(3) a step of roughening the insulating layer, and (4) a step of forming a conductor layer.

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

  The details of the step (1) are performed by patterning the wiring layer of the substrate with the wiring layer as shown in FIG. The patterned wiring layer 22 ′ can be formed by a known method using, for example, photolithography using a dry film, drill, laser, plasma, etching medium or the like in consideration of the characteristics of the substrate 21.

  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. Contains 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 metals selected from the above group (for example, nickel-chromium alloy, copper- A nickel alloy and a copper / titanium alloy), and copper is preferable.

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

  The thickness of the substrate is preferably thinner from the viewpoint of thinning, and is preferably less than 1000 μm, more preferably 800 μm or less, still more preferably 700 μm or less, and even 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, and even more preferably 100 μm or more, from the viewpoint of improving the handleability 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, even 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, and the like.

  The line (circuit width) / space (inter-circuit width) 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 even more 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 step (2), the resin sheet with a support of the present invention is laminated on a substrate with a wiring layer and thermally cured so that the wiring layer is bonded to the substrate with the wiring layer. And forming an insulating layer. For details, as shown in FIG. 4, the second resin composition of the resin sheet 10 with the support so as to embed the wiring layer 22 ′ of the substrate with wiring layer obtained in the above-described step (1). The layer 14 is laminated | stacked and the resin sheet 12 of the resin sheet 10 with a support body is thermosetted.

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

  Lamination of the wiring layer and the resin sheet with a support may be performed by vacuum lamination 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. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 13 hPa or less.

  Lamination can be performed with a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressure laminator manufactured by Nikko Materials, a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, etc. Can be mentioned.

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

  After laminating the second resin composition layer on the substrate with the wiring layer so that the wiring layer is embedded, the resin sheet is thermoset to form an insulating layer. The thermosetting conditions for the resin sheet are not particularly limited, and the conditions normally employed when forming the insulating layer of the wiring board may be used.

  For example, the thermosetting conditions of the resin sheet vary depending on the types of the first and second resin compositions, 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. 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 the resin sheet is thermally cured, 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 ( (Preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

  The support of the resin sheet with the support may be peeled after the resin sheet with the support is laminated on the substrate with the wiring layer and thermally cured, or the resin sheet with the support is laminated on the substrate with the wiring layer. You may peel a support body previously. Moreover, you may peel a support body before the taxation process process mentioned 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 for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. Although it does not specifically limit as a swelling liquid, An alkaline solution, surfactant solution, etc. are mentioned, Preferably it is an alkaline solution, As this alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan Co., Ltd. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer for 1 minute-20 minutes in 30 degreeC-90 degreeC swelling liquid. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the cured body in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan Co., Ltd. The neutralizing solution is preferably an acidic aqueous solution. Examples of commercially available products include “Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

  In one embodiment, the arithmetic average roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, further preferably 300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less, or 100 nm or less. It is. The arithmetic average roughness (Ra) of the insulating layer surface can be measured using a non-contact type surface roughness meter. As a specific example of the non-contact type surface roughness meter, “WYKO NT3300” manufactured by Becoins Instruments is cited.

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

  Although formation of a via hole is not specifically limited, For example, a drill, a laser, plasma, etc. may be used according to the composition etc. of the 1st and 2nd resin composition used for formation of an insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.

<Process (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. Contains metal. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A layer formed from a nickel alloy and a copper / titanium alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel / chromium alloy, copper / An alloy layer of nickel alloy or copper / titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel / chromium alloy is more preferable, and a single layer of copper is preferable. A metal layer is more preferred.

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

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

  The conductor layer can be formed by any suitable method known in the art, such as plating, sputtering, or vapor deposition, and is preferably formed by plating. In a preferred embodiment, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern. Moreover, when the support body in a resin sheet with a support body is metal foil, the conductor layer which has a desired wiring pattern can be formed by conventionally well-known techniques, 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 electroplating layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

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

  As shown in FIG. 6, after forming the plating seed layer 31, a mask pattern 40 that exposes 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 washing 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. For example, a dry film such as a novolak resin or an acrylic resin can be used. Commercially available products may be used as the dry film, for example, “ALPHO 20A263” manufactured by Nikko Materials Co., Ltd., “RD1225” manufactured by Hitachi Chemical Co., Ltd., etc., which are dry films with a PET film.

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

  Next, as shown in FIG. 8, the conductor pattern 30 is formed by removing the mask pattern and removing the mask pattern, and performing flash etching under any suitable conditions for removing only the exposed plating seed layer 31.

  In the present invention, the formation of the insulating layer and the conductor layer in 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, although the manufacturing method of a multilayer wiring board is demonstrated, description of the location which overlaps with the above-mentioned content is abbreviate | omitted suitably.

  As shown in an example in FIG. 9, the second resin composition layer of the resin sheet with a support is laminated on the conductor layer 30 so as to be joined to the produced conductor layer 30, and is thermally cured to provide the second insulation. Layer 12 '' is formed. That is, step (2) is performed. The resin sheet with a support of the present invention used in this step may be the same as the resin sheet with a support of the present invention laminated on a substrate with a wiring layer, or a different one. May be.

  As shown in FIG. 10, the via hole 50 is formed in the second insulating layer 12 ″ and then roughening is performed, and as shown in FIG. 11, the plating seed layer 31 is formed. After forming the plating seed layer 31, as shown in FIG. 12, a mask pattern (not shown) for exposing a part of the plating seed layer 31 is formed, and the electroplating layer is formed on the exposed plating seed layer 31. 32 is formed, and the via hole is buried by electroplating to form the filled via 51, thereby forming the conductor layer 30 ′.

  Further, as shown in FIG. 13, 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, plating treatment, solder treatment, and the like. Necessary surface treatment may be applied.

  The multilayer wiring board manufactured as described above has a stripline structure in which a conductor layer is embedded in an insulating layer 20 'and arranged according to a predetermined pattern, as shown in FIG. That is, the conductor layer is disposed inside the insulating layer. By adopting such a configuration, fluctuations in characteristic impedance can be suppressed even when used in a high frequency band, and insertion loss can be reduced. FIG. 14 is a schematic cross-sectional view showing a part in a direction orthogonal to the cross section shown in FIG.

  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. However, the printed wiring board having the wiring layer, the insulating layer, and the conductive layer on both surfaces of the base material, respectively. There may be. Moreover, the multilayer wiring board which has a some insulating layer and conductor layer on both surfaces of a base material may be sufficient.

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

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

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

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, “a mounting method using a build-up layer without a bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. It is.

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

[Preparation of resin sheet with support]
Using the resin varnish (resin composition) prepared by the following procedure, resin sheets with supports 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 (Mitsubishi Chemical Corporation "YX7553BH30", 30 parts by weight of cyclohexanone: methyl ethyl ketone (MEK) 1: 1 solution) 15 parts is heated and dissolved in a mixed solvent of 12 parts of solvent naphtha and 5 parts of cyclohexanone with stirring. I let you. After cooling to room temperature, 6 parts of a triazine skeleton-containing phenol novolac curing agent (hydroxyl equivalent: 125, “LA-7054” manufactured by DIC Corporation, MEK solution having a solid content of 60%), active ester compound (DIC) "HPC-8000-65T" manufactured by KK, 20 parts of a toluene solution having a weight average molecular weight of about 2700 and an active group equivalent of about 223 with a non-volatile content of 65% by mass, an amine curing accelerator (4-dimethylaminopyridine (DMAP) ), 2 parts by weight of MEK solution with a solid content of 5% by weight, 1 part of an imidazole curing accelerator ("P200-H50" manufactured by Mitsubishi Chemical Corporation, propylene glycol monomethyl ether solution with a solid content of 50% by weight), an aminosilane cup Spherical silica surface-treated with a ring agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("SO-" manufactured by Admatechs Co., Ltd.) 2 ", average particle size 0.5 [mu] m, the carbon amount 0.38 mg ^/ m 2) 60 parts were mixed per unit surface area, after uniformly dispersed in a high-speed rotary mixer, filtered through a cartridge filter (ROKITECHNO manufactured" SHP050 ") Thus, a resin varnish 1 was prepared.

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

(Preparation of resin varnish 3)
5 parts of liquid naphthalene type epoxy resin (epoxy equivalent 144, “HP4032SS” manufactured by DIC Corporation), 5 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), naphthalene type epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V", epoxy equivalent 330) 15 parts, and phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", solid content 30 mass% cyclohexanone: methyl ethyl ketone (MEK) 1: 1 solution 7) was 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, a toluene solution having a weight average molecular weight of about 2700 and an active group equivalent of about 223 with a nonvolatile content of 65% by mass), carbodiimide 5 parts of resin (Nisshinbo Chemical Co., Ltd. “V-03”, 50 mass% non-volatile toluene solution), bisphenol A dicyanate prepolymer (Lonza Japan Co., Ltd. “BA230S75”, cyanate equivalent of about 232, non-volatile content 75 parts by mass of MEK solution (75% by mass), 1.2 parts of curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass), curing accelerator (manufactured by Tokyo Chemical Industry Co., Ltd., cobalt ( III) 3.5 parts of acetylacetonate [Co (III) Ac, MEK solution having a solid content of 1% by mass], rubber particles (Dow Chemica) 3 parts of PARALOID EXL2655 manufactured by Japan Co., Ltd., spherical silica surface treated with phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle size 0.24 μm, AD Co., Ltd.) After mixing 80 parts of Matex “SO-C1” (carbon amount 0.36 mg / m ² ) per unit area and uniformly dispersing with a high-speed rotary mixer, filter with a cartridge filter (“SHP030” made by ROKITECHNO) Resin varnish 3 was prepared.

(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 Resin (Nippon Steel & Sumikin Chemical Co., Ltd. “ESN475V”, epoxy equivalent 330) 15 parts, and phenoxy resin (Mitsubishi Chemical Co., Ltd. “YX7553BH30”, solid content 30 mass% cyclohexanone: methyl ethyl ketone (MEK) 1: 1 5 parts of the solution) was 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 (“PCC-8000-65T” manufactured by DIC Corporation, a toluene solution having a weight average molecular weight of about 2700 and an active group equivalent of about 223 and having a nonvolatile content of 65% by mass), bisphenol Prepolymer of A dicyanate (“BA230S75” manufactured by Lonza Japan Co., Ltd., cyanate equivalent of about 232, MEK solution with non-volatile content of 75% by mass), 20 parts of curing accelerator (4-dimethylaminopyridine (DMAP), solid content of 5 mass) % Of MEK solution) 0.5 part, curing accelerator (manufactured by Tokyo Chemical Industry Co., Ltd., cobalt (III) acetylacetonate [Co (III) Ac, MEK solution having a solid content of 1% by mass)) 3 parts, flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaf Spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd.) surface-treated with 2 parts of nanthrene-10-oxide, average particle size 2 [mu] m, and an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) , 120 parts of an average particle size of 0.5 μm and carbon amount per unit surface area of 0.38 mg / m ² ) were mixed and dispersed uniformly with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP050” manufactured by ROKITECHNO). Resin varnish 4 was prepared.

(Preparation of resin varnish 5)
12 parts biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. “NC3000L”, epoxy equivalent 288), 8 parts naphthalene type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 330), and phenoxy resin ( It was heated and dissolved in a mixed solvent of “YX7553BH30” manufactured by Mitsubishi Chemical Corp., 6 parts of a cyclohexanone: methyl ethyl ketone (MEK) 1: 1 solution having a solid content of 30% by mass, 25 parts of solvent naphtha and 5 parts of cyclohexanone with stirring. . After cooling to room temperature, 22 parts of an active ester curing agent (“HPC-8000-65T” manufactured by DIC Corporation, a toluene solution having an active group equivalent of about 223 and a non-volatile component of 65% by mass), amine-based curing Accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5 mass%), phosphorus-based curing accelerator (“TBP-DA” tetrabutylphosphonium decanoate manufactured by Hokuko Chemical Co., Ltd.) 0 .3 parts, 2 parts of rubber particles (manufactured by Dow Chemical Japan Co., Ltd., PARALOID EXL2655), spherical silica surface treated with phenylaminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573”) (average) particle size 0.24 .mu.m, (Ltd.) Admatechs Ltd., "SO-C1," carbon content 0.36 mg ^/ m 2) 30 parts per unit area, and phenyl Spherical silica (average particle size 0.1 μm, Denki Kagaku Kogyo Co., Ltd. “UFP-30” surface treated with Limethoxysilane (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd.), amount of carbon per unit surface area 0 .19 mg / m ² ) 40 parts were mixed and dispersed uniformly with a high-speed rotary mixer, and then filtered through a cartridge filter (“SHP020” manufactured by ROKITETECHNO) to prepare a resin varnish 5.

(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 (manufactured by Mitsubishi Chemical Corporation) 12 parts of “YL7760”, epoxy equivalent 238), 4 parts of naphthalene type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 330), and phenoxy resin (“YL7891BH30” manufactured by Mitsubishi Chemical Corporation), solid content 30 parts by mass of cyclohexanone: methyl ethyl ketone (MEK) 1: 1 solution), 6 parts of solvent naphtha and 5 parts of cyclohexanone were dissolved by heating with stirring. After cooling to room temperature, 24 parts of an active ester curing agent (“HPC-8000-65T” manufactured by DIC Corporation, a toluene solution having an active group equivalent of about 223 and a non-volatile component of 65% by mass), oligophenylene ether -10 parts of styrene resin (Mitsubishi Gas Chemical Co., Ltd. "OPE-2St 1200", toluene solution with a solid content of 72% by mass), amine curing accelerator (4-dimethylaminopyridine (DMAP), solid content of 5% by mass MEK solution) 2 parts, imidazole-based curing accelerator ("1B2PZ" 1-benzyl-2-phenylimidazole, 5% solid MEK solution manufactured by Shikoku Kasei Kogyo Co., Ltd.) 0.5 part, aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd. “KBM573”) surface treated spherical silica (manufactured by Admatechs “SO-C4”, average particle size 1 μm, Position carbon content 0.31 mg ^/ m 2 per surface area) were mixed 150 parts, after uniformly dispersed in a high-speed rotary mixer, and filtered through a cartridge filter (ROKITECHNO manufactured "SHP050"), the resin varnish 6 was prepared.

(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”, 10 parts of 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 Corporation), solid 20 parts of a cyclohexanone: methyl ethyl ketone (MEK) 1: 1 solution having a content of 30% by mass was dissolved in a mixed solvent of 15 parts of solvent naphtha and 5 parts of cyclohexanone with stirring. After cooling to room temperature, 12 parts of a triazine skeleton-containing phenol novolac curing agent (hydroxyl equivalent 125, “LA-7054 manufactured by DIC Corporation, MEK solution with a solid content of 60%) 12 parts, naphthol curing agent ( “SN-485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 15 parts of MEK solution having a hydroxyl equivalent weight of 215 and a solid content of 60%, polyvinyl butyral resin (glass transition temperature of 105 ° C., “KS-1” manufactured by Sekisui Chemical Co., Ltd.) ) 10 parts of a 1: 1 mixed solution of ethanol and toluene with a solid content of 15%, 1 part of an amine curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5% by mass), imidazole-based curing Accelerator (Mitsubishi Chemical Corporation “P200-H50”, 50 mass% solid content propylene glycol monomethyl ether solution) 2 parts, rubber particles (Dow Chemi 2 parts manufactured by Le Nippon Co., Ltd., PARALOID EXL2655), spherical silica surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C2” manufactured by Admatechs Co., Ltd.) 90 parts of an average particle size of 0.5 μm and carbon amount per unit surface area of 0.38 mg / m ² ) are mixed and dispersed uniformly with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP050” manufactured by ROKITECHNO) Resin varnish 7 was prepared.

(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 (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288) 12 parts, naphthalene type epoxy resin (“HP-4710” manufactured by DIC Corporation) 5 parts of an 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% by mass), 20 parts of solvent naphtha and The mixture was dissolved in 10 parts of cyclohexanone by heating with stirring. After cooling to room temperature, 10 parts of a triazine skeleton-containing phenol novolac curing agent (hydroxyl equivalent 125, “LA-7054” manufactured by DIC Corporation, MEK solution with a solid content of 60%), naphthol curing agent ( “SN-485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 10 parts of a MEK solution having a hydroxyl equivalent weight of 215 and a solid content of 60%, an imidazole curing accelerator (“1B2PZ” 1-benzyl-2-2, manufactured by Shikoku Kasei Kogyo Co., Ltd.) Phenylimidazole, 0.5% solid content MEK solution) 0.5 part, flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd.), 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10 -Phosphophenanthrene-10-oxide, average particle size 2 μm) 3 parts, surface treated with aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) Spherical silica (Co. Admatechs Ltd., "SO-C4", average particle size 1 [mu] m, the carbon amount 0.31 mg ^/ m 2 per unit surface area) 120 parts, and, phenylamino silane coupling agent (Shin-Etsu Chemical ( Co., Ltd., “KBM573”) spherical alumina (“DAW-01” manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 1.5 μm, carbon amount per unit surface area 0.1 mg / m ² ) 60 The parts were mixed and uniformly dispersed 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 blending amount (mass part of non-volatile content) are shown in the following table.

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

  By uniformly applying the resin varnish 1 on the release PET with a die coater so that the thickness of the first resin composition layer after drying is 3 μm, and drying at 80 ° C. to 160 ° C. for 5 minutes, A first resin composition layer was obtained on the release PET. Next, the resin varnish 2 is applied on the first resin composition layer so that the thickness combined with the first resin composition layer after drying is 40 μm, and is adjusted to 70 ° C. to 110 ° C. (average 95 ° C.). And dried for 5 minutes to form two resin composition layers (resin sheets). Next, a polypropylene film (Oji F-Tex Co., Ltd.) is used as a protective film 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). The rough surface of “Alphan MA-411” (thickness: 15 μm) was laminated so as to be bonded to the second resin composition layer. Thereby, the resin sheet 1 with a support body which consists of a support body, the 1st resin composition layer (resin varnish 1 origin), the 2nd resin composition layer (resin varnish 2 origin), and the order of a protective film was obtained. .

<Example 2: Production 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 instead of the resin varnish 1 and the resin varnish 4 was used instead of the resin varnish 2.

<Example 3: Production 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 instead of the resin varnish 1 and the resin varnish 6 was used instead of the resin varnish 2.

<Comparative Example 1: Production of resin sheet 4 with support>
In Example 1, a resin sheet 4 with a support was obtained in the same manner as in Example 1 except that the resin varnish 7 was used instead of the resin varnish 1.

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

<Comparative Example 3: Production of Resin Sheet 6 with Support>
In Example 1, 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 instead of the resin varnish 1 and the resin varnish 8 was used instead of the resin varnish 2.

<Comparative Example 4: Production of Resin Sheet 7 with Support>
In Example 1, except that the resin varnish 8 was used in place of the resin varnish 2, a resin sheet 7 with a support was obtained in the same manner as in Example 1.

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

  Each resin varnish 1-8 is uniformly coated on the release PET film with 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 a resin composition layer was made into a resin composition layer / release PET film / glass cloth base epoxy resin double-sided copper-clad laminate (“R5715ES” manufactured by Matsushita Electric Works, Ltd., thickness 0.7 mm, 255 mm). (Corner) was placed on a glass cloth base epoxy resin double-sided copper-clad laminate, and the four sides of the film were fixed with a polyimide adhesive tape (width 10 mm).

  Subsequently, it was heat-cured at 200 ° C. for 90 minutes. After thermosetting, the polyimide adhesive tape was peeled off, and the release PET film with a resin composition layer was removed from the glass cloth base epoxy resin double-sided copper-clad laminate. Further, the release PET film (“501010” manufactured by Lintec Corporation) on which the resin sheet was laminated was peeled off to obtain a sheet-like 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 set to a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using “HP8362B” manufactured by Agilent Technologies. The dielectric constant (Dk) and dielectric loss tangent (Df) were measured. Three test pieces were measured, the average value was calculated, and the results are shown in the following table. Also, based on the calculated dielectric loss tangent, the difference between the dielectric tangents of the first and second thermosets in the resin sheets with support of Examples and Comparative Examples was calculated, and the results are shown in the table below. It was.

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

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

(2) Lamination of resin sheet with support The batch-type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd., two-stage buildup laminator, CVP700) was prepared for each resin sheet with a support prepared in Examples and Comparative Examples. Was laminated on both surfaces of the inner circuit board so that the second resin composition layer was bonded to the inner circuit board. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and pressing the film at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. Next, hot pressing was performed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Thermosetting of resin composition layer The inner layer circuit board on which the resin sheet with the support is laminated is placed in a 100 ° C. oven at 100 ° C. for 30 minutes, and then at 175 ° C. for 175 ° C. After being transferred to an oven at 0 ° C., the insulating layer was formed by thermosetting for 30 minutes.

(4) Process of performing desmear process The support body was peeled from the circuit board in which the insulating layer was formed, and the desmear process was performed. In addition, as a desmear process, the following wet desmear process was implemented.

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

(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.) A copper plating step using the above was performed to form a conductor layer having a target thickness of 18 μm.

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

(5-2) Formation of Dry Film Pattern Next, a dry film (made by Hitachi Chemical Co., Ltd., “RD1225” is laminated on the formed electroless copper plating layer, and an exposure machine “LI9500” made by Dainippon Screen Manufacturing Co., Ltd. A dry film pattern was formed by exposure (exposure 15 mJ / cm ² ) and development (1% Na ₂ CO ₃ aqueous solution, 30 ° C., 40 s, spray pressure 0.15 MPa).

(5-3) Electrolytic Plating Step Next, an electrolytic copper plating step was performed using a chemical solution “Top Lucina α” manufactured by Okuno Pharmaceutical 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 Pharmaceutical Co., Ltd. Next, annealing was performed at 190 ° C. for 90 minutes, and a conductor layer was formed on the insulating layer.

(6) Lamination of resin sheet with support After the substrate is immersed in a 10% sulfuric acid aqueous solution for 30 seconds and dried at 130 ° C. for 15 minutes, each resin sheet with a support prepared in Examples and Comparative Examples is It laminated | stacked by the method similar to the lamination of the resin sheet with a support body of (2).

(7) Thermosetting of resin composition layer The inner layer circuit board on which the resin sheet with the support is laminated is placed in a 100 ° C. oven at 100 ° C. for 30 minutes, and then at 175 ° C. for 175 ° C. After being transferred to an oven at 0 ° C., the insulating layer was formed by thermosetting for 30 minutes.

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

(9) Process of performing desmear process The support body was peeled from the circuit board provided with the via hole, and the desmear process was performed by the method similar to (4).

(10) Step of forming conductor layer (5) A conductor layer having a target thickness of 18 μm was formed by the same method as the step of forming the conductor layer. Soft etching was performed to clean the via hole.

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

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

(High-frequency transmission loss measurement)
Using the three evaluation substrates that were produced, for an impedance of 50Ω setting 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 following table, three insertion loss values (dB) at 30 GHz are described, and the average value, standard deviation, and insertion loss cv value are shown. The cv value of the insertion loss means a value obtained by (standard deviation of insertion loss / average value of insertion loss) × 100.

DESCRIPTION OF SYMBOLS 10 Resin sheet | seat 11 with a support body 12 Resin sheet | seat 12 'Insulating layer 12''2nd insulating layer 13 1st resin composition layer 13' 1st resin composition layer 14 thermosetted 2nd resin composition Material layer 14 ′ Thermoset second resin composition layer 20 Substrate with wiring layer 21 Substrate 22 Wiring layer 22 ′ Patterned wiring layer 30 Conductor layer 30 ′ Conductive layer 31 Plating seed layer 32 Electroplating layer 40 Mask Pattern 50 Via hole 51 Filled via 60 Solder resist film

Claims (10)

A resin sheet with a support comprising a support and a resin sheet provided on the support,
The resin sheet is provided on the support side, the first resin composition layer formed of the first resin composition,
A second resin composition layer formed by the second resin composition provided on the side opposite to the support side,
The compositions of the first resin composition and the second resin composition are different from each other,
A first thermoset obtained by thermosetting the first resin composition at 200 ° C. for 90 minutes, and a second thermoset obtained by thermosetting the second resin composition at 200 ° C. for 90 minutes Both of which have a dielectric constant at 5.8 GHz at 23 ° C. of 3.6 or less,
The dielectric loss tangent at 5.8 GHz at 23 ° C. of the first and second thermosets is both 0.01 or less,
The resin sheet with a support, wherein the difference in dielectric loss tangent between 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 component (a) 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 of the components (b) is an active ester curing agent. With resin sheet.   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 content of the second resin composition is The resin sheet with a support according to any one of claims 1 to 3, which satisfies the relationship of A1 <A2 when the content of the component (c) is A2.   The resin sheet with a support according to any one of claims 1 to 4, wherein the first and second thermosets each have a dielectric constant of 3.5 or less at 23 ° C at 5.8 GHz.   The resin sheet with a support according to any one of claims 1 to 5, wherein a dielectric loss tangent at 5.8 GHz at 23 ° C of the first and second thermosets is 0.0095 or less.   The resin sheet with a support according to any one of claims 1 to 6, which is used in a high frequency band of 1 GHz or more.   The printed wiring board containing the insulating layer formed with the hardened | cured material of the resin sheet in the resin sheet with a support body of any one of Claims 1-7.   The printed wiring board of Claim 8 provided with a stripline structure.   A semiconductor device comprising the printed wiring board according to claim 8.

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