KR102656740B1 - Resin sheet with support - Google Patents

Abstract

[Project] Provision of a resin sheet with a support, a printed wiring board, and a semiconductor device that reduces insertion loss and suppresses variation in insertion loss.
[Solution] Equipped with a support and a resin sheet provided on the support, wherein the resin sheet includes a first resin composition layer formed by a first resin composition provided on the support side, and a second resin composition provided on the side opposite to the support side. It has a second resin composition layer formed by, the compositions of the first resin composition and the second resin composition are each different, and the dielectric constants of the heat-cured product of the first resin composition and the heat-cured product of the second resin composition are both 3.6. A resin sheet with a support body wherein the dielectric loss tangents of the heat-cured products of the first and second resin compositions are both 0.01 or less, and the difference in dielectric loss tangents is 0.005 or less.

Description

Resin sheet with support body {RESIN SHEET WITH SUPPORT}

The present invention relates to a resin sheet with a support. It also relates to printed wiring boards and semiconductor devices.

As a manufacturing method for printed wiring boards (hereinafter also referred to as “wiring boards”), the build-up method of alternately laminating circuit-formed conductor layers and insulating layers is widely used, and the insulating layer is formed by curing a two-layer resin composition layer. It is known that this happens (for example, see Patent Document 1).

Patent Document 1: Japanese Patent Application Laid-Open No. 2014-17301

However, as the amount of information communication has recently increased, wiring boards corresponding to high frequency bands have been required. However, in the high frequency region, it is easy to be influenced by the thickness of the conductor layer and insulating layer, and more precise design is required.

In wiring boards corresponding to high frequency bands, if the insertion loss at the interface of the two-layer insulating layer is large, there is a problem in that the electrical signal is converted into heat and/or noise, making it impossible to accurately transmit signals and information. . In addition, even if the insertion loss is small, if the insertion loss variation is large, the stability of the high-speed signal is lacking, and there is a problem that the device does not operate as designed and is prone to malfunction.

The 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 careful study of the above problem, the present inventors have found that, in a resin sheet with a support body provided with a first resin composition layer and a second resin composition layer having different compositions, the first resin composition constituting the first resin composition layer The heat-cured product of the second resin composition constituting the heat-cured product and the second resin composition layer has a dielectric constant of 3.6 or less at 5.8 GHz at 23°C, a dielectric loss tangent of 0.01 or less at 5.8 GHz at 23°C, and each It was discovered that the above problem could be solved by setting the difference in dielectric loss tangent of the thermosetting product to 0.005 or less, and the present invention was completed.

That is, the present invention includes the following contents.

[1] A resin sheet attached to a support comprising a support and a resin sheet provided on the support,

The resin sheet includes a first resin composition layer provided on the support side and formed of the first resin composition,

It has a second resin composition layer formed of a 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, respectively,

A first heat-cured product obtained by heat-curing a first resin composition at 200°C for 90 minutes, and a second heat-cured product obtained by heat-curing a second resin composition at 200°C for 90 minutes, at 5.8 GHz at 23°C. The dielectric constants are all less than 3.6,

The dielectric loss tangents at 5.8 GHz at 23°C of the first and second heat-cured products are both 0.01 or less,

A resin sheet with a support, characterized in that the difference in dielectric loss tangent of the first and second heat cured products is 0.005 or less.

[2] The resin sheet with a support according to [1], wherein the first resin composition and the second resin composition include (a) an epoxy resin, and component (a) is an epoxy resin having an aromatic structure.

[3] The resin sheet with a support according to [1] or [2], wherein the first resin composition and the second resin composition contain (b) a curing agent, and at least one type of component (b) is an active ester curing agent.

[4] The first resin composition and the second resin composition according to any one of [1] to [3], wherein the first resin composition and the second resin composition contain (c) an inorganic filler, and the content of component (c) in the first resin composition is A1, A resin sheet with a support that satisfies the relationship of A1 < A2 when the content of component (c) in the second resin composition is set to A2.

[5] The resin sheet with a support according to any one of [1] to [4], wherein the first and second heat-cured products both have dielectric constants of 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 both the first and second heat-cured products have dielectric loss tangents 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 comprising an insulating layer formed from a cured product of the resin sheet with a support body according to any one of [1] to [7].

[9] The printed wiring board according to [8], comprising a strip line structure.

[10] A semiconductor device comprising 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.

1 is a schematic diagram showing one form of a resin sheet with a support of the present invention.
Figure 2 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board.
Figure 3 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board.
Figure 4 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board.
Figure 5 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board.
Figure 6 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board.
Figure 7 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board.
Figure 8 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board.
Figure 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.
Figure 13 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board.
FIG. 14 is a schematic cross-sectional view in a direction perpendicular to the cross-section in FIG. 12.
Fig. 15 is a schematic cross-sectional view of the strip line transmission line evaluation board manufactured in the example.

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

Before explaining the resin sheet with a support of the present invention in detail, in the resin sheet with a support of the present invention, the first resin sheet used when forming the first resin composition layer and the second resin composition layer contained in the resin sheet. The resin composition and the second resin composition will be described.

(First resin composition)

The first resin composition forming the first resin composition layer is not particularly limited, as long as its cured product has sufficient insulating properties. Examples of the first resin composition include compositions containing a curable resin and a curing agent. As the curable resin, conventionally known curable resins used when forming the insulating layer of a printed wiring board can be used, and among these, epoxy resin is preferable. Accordingly, in one embodiment, the first resin composition includes (a) an epoxy resin, (b) a curing agent, and (c) an inorganic filler. The first resin composition may further contain a thermoplastic resin, a curing accelerator, a flame retardant, and an organic filler as needed.

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

-(a) Epoxy resin-

Examples of epoxy resins 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, and trisphenol type epoxy resin. , naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl Ester-type epoxy resin, cresol novolac-type epoxy resin, biphenyl-type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. are listed. Epoxy resins may be used individually, or two or more types may be used in combination. The component (a) is preferably an epoxy resin having an aromatic structure, and is selected from bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, and naphthalene type epoxy resin. It is more preferable that there are more than one species. An aromatic structure is a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles.

It is preferable that the epoxy resin contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100% by mass, it is preferable that at least 50% by mass or more is an epoxy resin having two or more epoxy groups in one molecule. Among them, an epoxy resin that has two or more epoxy groups in one molecule and is in a liquid state at a temperature of 20°C (hereinafter referred to as “liquid epoxy resin”), and an epoxy resin that has three or more epoxy groups in one molecule and is in a solid state at a temperature of 20°C. It is preferable to include an epoxy resin (hereinafter referred to as “solid epoxy resin”). As an epoxy resin, a resin composition with excellent plasticity is obtained by using a liquid epoxy resin and a solid epoxy resin in combination. Additionally, the breaking strength of the cured product of the resin composition is also improved.

Liquid epoxy resins include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol AF-type epoxy resin, naphthalene-type epoxy resin, glycidyl ester-type epoxy resin, glycidyl amine-type epoxy resin, and phenol novolak-type epoxy resin. , alicyclic epoxy resins having an ester skeleton, cyclohexanedimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure are preferred, and glycidyl amine type epoxy resins and bisphenol A type epoxy resins. , bisphenol F type epoxy resin, bisphenol AF type epoxy resin, and naphthalene type epoxy resin are more preferable. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC Corporation, and "828US", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation. (bisphenol A type epoxy resin), “jER807”, “1750” (bisphenol F type epoxy resin), “jER152” (phenol novolac type epoxy resin), “630”, “630LSD” (glycidyl amine type epoxy resin) ), “ZX1059” (mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Shinnittetsu Sumikin Chemical Co., Ltd., “EX-721” (glycidyl) manufactured by Nagase Chemtex Co., Ltd. Ester type epoxy resin), “Celoxide 2021P” (alicyclic epoxy resin with an ester skeleton) manufactured by Daicel Co., Ltd., “PB-3600” (epoxy resin with a butadiene structure), Nippon Chemical Co., Ltd. “ZX1658” and “ZX1658GS” (liquid 1,4-glycidylcyclohexane) manufactured by Mitsubishi Chemical Corporation, and “630LSD” (glycidyl amine type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used individually, or two or more types may be used in combination.

As solid epoxy resins, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, and 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 solid epoxy resins include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "N-690" (cresol) manufactured by DIC Co., Ltd. novolak 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 Nihon Kayaku Co., Ltd. -502H” (trisphenol-type epoxy resin), “NC7000L” (naphthol novolak-type epoxy resin), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl-type epoxy resin), Shinnittetsu Sumikin “ESN475V” (naphthalene-type epoxy resin), “ESN485” (naphthol novolak-type epoxy resin) manufactured by Kagaku Co., Ltd., “YX4000H” and “YL6121” (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. ), “YX4000HK” (bixylenol-type epoxy resin), “YX8800” (anthracene-type epoxy resin), “PG-100” and “CG-500” manufactured by Osaka Gas Chemical Co., Ltd., manufactured by Mitsubishi Chemical Co., Ltd. "YL7760" (bisphenol AF type epoxy resin), "YL7800" (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and "jER1031S" (tetraphenylethane) type epoxy resin), etc. are listed. These may be used individually, or two or more types may be used in combination.

As an epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used together, their quantity ratio (liquid epoxy resin:solid epoxy resin) is preferably in the range of 1:0.1 to 1:15 in mass ratio. By keeping the ratio of the liquid epoxy resin and the solid epoxy resin within this range, i) appropriate adhesion can be formed when used in the form of a resin sheet, and ii) sufficient flexibility can be obtained when used in the form of a resin sheet. , handling is improved, and iii) a cured product with sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the amount ratio of liquid epoxy resin and solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably in the range of 1:0.3 to 1:10 in mass ratio, and 1: A range of 0.6 to 1:8 is more preferred.

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 even more preferably 3% by mass, from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability. It is more than %. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is achieved, but is preferably 50 mass% or less, more preferably 40 mass% or less, and still more preferably 30 mass% or less.

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

The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, further preferably 80 to 2000, and even more preferably 110 to 1000. By falling within this range, the crosslinking density of the cured product becomes sufficient and an insulating layer with small surface roughness can be formed. In addition, epoxy equivalent can be measured according to JIS K7236 and is the mass of resin containing 1 equivalent of epoxy group.

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

-(b) Hardener-

The curing agent is not particularly limited as long as it has the function of curing the epoxy resin, and examples include phenol-based curing agents, naphthol-based curing agents, activated ester-based curing agents, benzooxazine-based curing agents, cyanate ester-based curing agents, and carbodiimide-based curing agents. Hardeners, etc. are listed. One type of hardening agent may be used individually, or two or more types may be used together. (b) The component is preferably at least one selected from phenol-based curing agents, naphthol-based curing agents, activated ester-based curing agents, carbodiimide-based curing agents, and cyanate ester-based curing agents, and includes phenol-based curing agents, active ester-based curing agents, and carboxylate-based curing agents. It is more preferable that it is at least one type selected from bodyimide-based curing agents, and it is more preferable that it is an active ester-based curing agent from the viewpoint of lowering the dielectric constant and dielectric loss tangent.

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

Specific examples of phenol-based curing agents and naphthol-based curing agents include, for example, “MEH-7700,” “MEH-7810,” and “MEH-7851” manufactured by Meiwa Kasei Co., Ltd. and “NHN” manufactured by Nippon Kayaku Co., Ltd. 」, 「CBN」, 「GPH」, 「SN170」, 「SN180」, 「SN190」, 「SN475」, 「SN485」, 「SN495」, 「SN375」, manufactured by Shin-Niptetsu Sumikin Kagaku Co., Ltd. SN395", "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", and "EXB-9500" manufactured by DIC Co., Ltd. are listed. .

From the viewpoint of obtaining an insulating layer with excellent adhesion to the conductor layer, an active ester-based curing agent is also preferable. There are no particular restrictions on the active ester-based curing agent, but generally it contains two highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. Compounds having the above are preferably used. The active ester-based curing agent is preferably obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. Particularly from the viewpoint of improving heat resistance, active ester-based curing agents obtained from carboxylic acid compounds and hydroxy compounds are preferable, and active ester-based curing agents obtained from carboxylic acid compounds, phenol compounds, and/or naphthol compounds are more preferable. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, and m-cresol. , p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, tri. Hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac, etc. are listed. Here, “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 acetylate of phenol novolac, and a benzoylate of phenol novolak. Active ester compounds are preferable, and among these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure are more preferable. “Dicyclopentadiene-type diphenol structure” refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

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

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

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylenecyanate), and 4,4'-methylenebis(2,6- dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4- Cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanate) Bifunctional cyanate resins such as natephenyl)thioether and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolak and cresol novolac, etc., and some of these cyanate resins are triazinated. Prepolymers, etc. are listed. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (both phenol novolak-type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. Prepolymers in which part or all of the polymer is triazylated to form a trimer) are listed.

Specific examples of the carbodiimide-based 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 a ratio of [total number of epoxy groups of the epoxy resin]:[total number of reactive groups of the curing agent], preferably in the range of 1:0.01 to 1:2, and 1:0.015 to 1:2. 1.5 is more preferable, and 1:0.02 to 1:1 is more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, etc., and varies depending on the type of the curing agent. In addition, the total number of epoxy groups of an epoxy resin is the solid mass of each epoxy resin divided by the epoxy equivalent, which is the sum of all epoxy resins, and the total number of reactive groups of the curing agent is the solid mass of each curing agent divided by the reactor equivalent. The value is the sum of all hardeners. By keeping the amount ratio of the epoxy resin and the curing agent within this range, the heat resistance of the cured product of the resin composition is further improved.

In one embodiment, the first resin composition includes (a) the epoxy resin and (b) the curing agent described above. The resin composition is (a) an epoxy resin, which is a mixture of a liquid epoxy resin and a solid epoxy resin (the mass ratio of liquid epoxy resin:solid epoxy resin is preferably 1:0.1 to 1:15, more preferably 1:0.3 to 1). :12, more preferably 1:0.6 to 1:10), (b) as a curing agent, from the group consisting of phenol-based curing agents, naphthol-based curing agents, activated ester-based curing agents, carbodiimide-based curing agents and cyanate ester-based curing agents. It is preferable to each include at least one selected type (preferably an active ester-based curing agent).

The content of the curing agent in the first resin composition is not particularly limited, but is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. Additionally, 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, but examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, Aluminum hydroxide, 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, oxide Zirconium, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate are listed. Among these, silica is particularly preferable. Additionally, spherical silica is preferred as the silica. One type of inorganic filler may be used alone, or two or more types may be used in combination.

The average particle diameter of the inorganic filler is not particularly limited, but is preferably 2 μm or less, more preferably 1.5 μm or less, and still more preferably from the viewpoint of obtaining an insulating layer with small surface roughness and improving fine wiring formability. is 1㎛ or less. The lower limit of the average particle diameter is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.1 μm or more, and even more preferably 0.3 μm or more. Commercially available inorganic fillers having such an average particle diameter include, for example, "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Adomatex Co., Ltd., and "UFP" manufactured by Denki Kagaku Kogyo Co., Ltd. -30”, “Silpen NSS-3N”, “Silpen NSS-4N”, “Silpen NSS-5N” manufactured by Tokuyama Co., Ltd., “SC2500SQ”, “SO-C4”, “SO” manufactured by Adomatex Co., Ltd. -C2”, “SO-C1”, etc. are listed.

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 using a laser diffraction scattering type particle size distribution measuring device, and the median diameter thereof can be measured as the average particle diameter. The measurement sample can preferably be one in which an inorganic filler is dispersed in methyl ethyl ketone by ultrasonic waves. As a laser diffraction scattering type particle size distribution measuring device, "SALD-2200" manufactured by Shimadzu Sesakusho Co., Ltd., etc. can be used.

From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler is preferably surface treated with at least one surface treatment agent selected from a silane coupling agent, an alkoxysilane compound, and an organosilazane compound. These may be oligomers. Examples of surface treatment agents include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanate coupling agents. Commercially available surface treatment agents include, for example, “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and “KBM803” (3-mercaptopropyl) manufactured by Shin-Etsu Chemical Co., Ltd. Trimethoxysilane), “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Kogyo Co., Ltd., “KBM573” (N-phenyl-3-aminopropyltrimethane) manufactured by Shin-Etsu Chemical Kogyo Co., Ltd. Toxysilane), “SZ-31” (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Kogyo Co., Ltd., “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Kogyo Co., Ltd. ) manufactured by “KBM-4803” (long chain epoxy type silane coupling agent), etc. are listed. One type of surface treatment agent may be used individually, or two or more types may be used in combination.

The degree of surface treatment by a surface treatment agent can be evaluated based on the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and still more preferably 0.2 mg/m 2 or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in sheet form, 1 mg/m 2 or less is preferable, 0.8 mg/m 2 or less is more preferable, and 0.5 mg/m 2 or less is still more 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 a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, “EMIA-320V” manufactured by Horiba Sesakusho Co., Ltd., etc. can be used.

The content of the inorganic filler in the first resin composition is preferably 70% by mass or less, more preferably 70% by mass or less, when the non-volatile component in the first resin composition is 100% by mass, from the viewpoint of improving plating peel properties. is 60 mass% or less, 50 mass% or less, or 40 mass% or less. The lower limit of the content of component (c) in the first resin composition is not particularly limited and may be 0 mass%, but from the viewpoint of reducing the dielectric loss tangent, it may be 5 mass% or more, 10 mass% or more, 20 mass% or more, etc. You can.

-(d) Thermoplastic resin-

The first resin composition contains (d) a thermoplastic resin in addition to components (a) to (c).

Thermoplastic resins include, for example, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamidoimide resin, polyether imide resin, polysulfone resin, polyether sulfone resin, and polyphenyl. Ren ether resin, polycarbonate resin, polyether ether ketone resin, and polyester resin are listed, and phenoxy resin is preferred. Thermoplastic resins may be used individually, or two or more types may be used in combination.

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

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, and naphthalene. Phenoxy resins having one or more skeletons selected from the group consisting of anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton are listed. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. One type of phenoxy resin may be used alone, or two or more types may be used in combination. Specific examples of phenoxy resins include "1256" and "4250" (both phenoxy resins containing a bisphenol A skeleton), "YX8100" (phenoxy resins containing a bisphenol S skeleton), and "YX6954" (both bisphenol A skeleton-containing phenoxy resins) manufactured by Mitsubishi Chemical Corporation. acetophenone skeleton-containing phenoxy resins) are listed, and in addition, "FX280" and "FX293" manufactured by Shin-Niptetsu Sumikin Chemical Co., Ltd., "YX6954BH30", "YX7553BH30", and "YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd. “YX7553BH30”, “YL7769BH30”, “YL6794”, “YL7213”, “YL7290”, “YL7891BH30” and “YL7482”, etc. are listed.

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

Specific examples of the polyimide resin include “Rica Coat SN20” and “Rica Coat PN20” manufactured by Nippon Rika Co., Ltd. Specific examples of polyimide resins include linear polyimides obtained by reacting bifunctional hydroxyl group-terminated polybutadiene, diisocyanate compounds, and tetrabasic acid anhydrides (polyimides described in Japanese Patent Application Laid-Open No. 2006-37083); Modified polyimides such as polysiloxane skeleton-containing polyimides (polyimides described in Japanese Patent Application Laid-Open No. 2002-12667 and Japanese Patent Application Laid-Open No. 2000-319386, etc.) are listed.

Specific examples of polyamidoimide resin include “Viromax HR11NN” and “Viromax HR16NN” manufactured by Toyobo Seki Co., Ltd. Specific examples of polyamideimide resins include modified polyamideimides such as “KS9100” and “KS9300” (polyamideimide containing a polysiloxane skeleton) manufactured by Hitachi Kasei Kogyo Co., Ltd.

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

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

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

Among them, phenoxy resin and polyvinyl acetal resin are preferable as thermoplastic resins. Accordingly, in one suitable embodiment, the thermoplastic resin includes at least one selected from the group consisting of phenoxy resin and 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 0.7% by mass to 5% by mass. It is mass%.

-(e) Curing accelerator-

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

Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and organic peroxide-based curing accelerators. Phosphorus-based curing accelerators, amine-based curing accelerators, Imidazole-based curing accelerators and metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are more preferable. A hardening accelerator may be used individually by 1 type, or may be used in combination of 2 or more types.

Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenyl borate, n-butylphosphonium tetraphenyl borate, tetrabutylphosphonium decanoate, and (4-methylphenyl)triphenylphosph. Phonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc. are listed, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

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

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Midazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole Sol, 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 tri. Melitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl Midazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-tri Azine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2 -Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a] Imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins ( adduct) are listed, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

As the imidazole-based curing accelerator, commercial products may be used, for example, “P200-H50” manufactured by Mitsubishi Chemical Corporation.

Examples of guanidine-based curing accelerators 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]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]deca -5-N, 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-(o-tolyl) biguanide, etc. are listed, dicyandiamide, 1, 5,7-triazabicyclo[4.4.0]deca-5-ene is preferred.

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

Examples of organic peroxide-based curing accelerators include dicumyl peroxide, cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, and di-tert-butyl peroxide. oxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, etc. are listed. As an organic peroxide-based curing accelerator, a commercial product may be used, for example, "Percumil D" manufactured by Nichiyu Corporation.

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

-(f) Flame retardant-

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

As the flame retardant, a commercially available product may be used, for example, “HCA-HQ” manufactured by Sanko Co., Ltd., “PX-200” manufactured by Daihachi Chemical Co., Ltd., etc. are listed.

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, and still more preferably 0.5% by mass. to 10% by mass is more preferable.

-(g) Organic filler-

The resin composition may contain (g) an organic filler from the viewpoint of improving stretching. As the organic filler, any organic filler that can be used when forming the insulating layer of a printed wiring board may be used. Examples include rubber particles, polyamide fine particles, and silicon particles.

As the rubber particles, commercially available products may be used, for example, “EXL2655” manufactured by Dow Chemical Nippon Co., Ltd., “AC3816N” manufactured by Gantz Kasei Co., Ltd., etc.

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 0.3% by mass to 5% by mass. mass%, or 0.5 mass% to 3 mass%.

-(h) Optional additives-

The first resin composition may further contain other additives as needed. Examples of such other additives include organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, and thickeners, antifoaming agents, and leveling agents. Resin additives such as agents, adhesion imparting agents, and colorants are listed.

(Second resin composition)

The second resin composition forming the second resin composition layer may have a different composition from the first resin composition and is not particularly limited, but the second resin composition preferably contains an inorganic filler, and the inorganic filler and the epoxy resin are It is more desirable to include it.

As for the second resin composition, from the viewpoint of suppressing warping and reducing the dielectric loss tangent, the content of the inorganic filler when the non-volatile component in the second resin composition is 100% by mass is preferably 60% by mass or more, and is 70% by mass. It is more preferable that it is % or more, and it is still more preferable that it is 72 mass % or more, 74 mass % or more, or 76 mass % or more. The upper limit of the content of the inorganic filler in the second resin composition is preferably 95 mass% or less, more preferably 90 mass% or less.

Examples of the inorganic filler in the second resin composition include those similar to the inorganic filler described in the (first resin composition) column. 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 %), it is preferable to satisfy the relationship of A1 < A2. Additionally, the difference between A1 and A2 (A2-A1) is preferably 5 mass% or more, more preferably 8 mass% or more, and even more preferably 10 mass% or more. The upper limit of the difference (A2-A1) is not particularly limited, but can usually be 90% by mass or less, 80% by mass or less, etc.

In one embodiment, the second resin composition includes an epoxy resin and a curing agent along 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 needed.

The epoxy resin, curing agent, and additives contained in the second resin composition include the same ones as (a) the epoxy resin, (b) curing agent, and additives described in the (first resin composition) column.

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

When the epoxy resin in the second resin composition contains a solid epoxy resin and a liquid epoxy resin, the ratio of the mass M _S of the solid epoxy resin to the mass M _L of the liquid epoxy resin (M _S /M _L ) is 1 to 10. A range of is desirable. By setting M _S / M _L to this range, i) appropriate viscosity is formed when used in the form of a resin sheet, ii) sufficient flexibility is obtained when used in the form of a resin sheet, and handling is improved. and iii) effects such as obtaining a cured product with sufficient breaking strength are obtained. In addition, in order to reduce the melt viscosity, it is preferable to include 2 parts by mass or more of the liquid epoxy resin when the inorganic filler is 100 parts by mass.

In addition, the appropriate ranges of the epoxy equivalent weight of the epoxy resin in the second resin composition and the weight average molecular weight of the epoxy resin are the same as those of the epoxy resin contained in the first resin composition.

The content of the curing agent in the second resin composition is not particularly limited, but from the viewpoint of obtaining an insulating layer with a low dielectric loss tangent, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass. That's it. The upper limit of the content of the curing agent is not particularly limited as long as the effect of the present invention is achieved, but is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 12% by mass or less. Therefore, the content of the curing agent in the second resin composition is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 5 to 12% by mass.

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

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

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

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

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.

The second resin composition, like the first resin composition, optionally contains optional additives, for example, organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, and organic fillers, thickeners, antifoaming agents, and leveling agents. It may also contain resin additives such as adhesives, adhesion imparting agents, and colorants.

[Resin sheet with support]

The resin sheet with a support of the present invention is a resin sheet with a support, comprising a support and a resin sheet provided on the support, wherein the resin sheet includes a first resin composition layer formed of a first resin composition provided on the support side, and a resin sheet on the support side. It has a second resin composition layer formed by a second resin composition provided on the opposite side, the compositions of the first resin composition and the second resin composition are different, and the first resin composition is heat-cured at 200 ° C. for 90 minutes. The dielectric constants of the first heat-cured product obtained and the second heat-cured product obtained by heat-curing the second resin composition at 200°C for 90 minutes are both 3.6 or less at 5.8 GHz at 23°C, and the first and second heat cured materials are Both dielectric loss tangents at 5.8 GHz at 23°C of the cured product are 0.01 or less, and the difference between the dielectric loss tangent of the first and second heat cured products is 0.005 or less.

An example of the resin sheet with a support body of the present invention is shown in Fig. 1. In Fig. 1, the resin sheet 10 with a support body includes a support body 11 and a resin sheet 12 provided on the support body 11. In Fig. 1, the resin sheet 12 consists of a first resin composition layer 13 provided on the side of the support and a second resin composition layer 14 provided on the side opposite to the support. In addition, as will be described later, in the resin sheet with a support body 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.

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 films made of plastic materials, metal foils, and release papers, and films and metal foils made of plastic materials are preferred.

When using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”) .), polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), acrylic, polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), and polyether sulfide (PES). ), polyether ketone, polyimide, etc. are listed. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is especially preferable.

When using a metal foil as a support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferable. As the copper foil, a foil made of the simple metal of copper may be used, or a foil made of an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. good night.

The support may be subjected to mat treatment or corona treatment on the surface joined to the first resin composition layer.

Additionally, as the support, a support with a release layer having a release layer on the surface bonded to the first resin composition layer may be used. Examples of the release agent used in the release layer of the support with a release layer include at least one release agent selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. The support with the release layer may be a commercially available product, for example, "SK-1", "AL-5", and "AL" manufactured by Lintech Co., Ltd., which are PET films having a release layer containing an alkyd resin-based release agent as a main component. -7”, etc. are listed.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In addition, when using a support body with a release layer, it is preferable that the entire thickness of the support body with a release layer is within the above range.

＜Resin sheet＞

The resin sheet is formed of a first resin composition layer provided on the support side and a second resin composition provided on the side opposite to the support and having a different composition from the first resin composition forming the first resin composition layer. It has a resin composition layer.

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, and is preferably 70 μm or less, more preferably 50 μm or less.

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

The thickness of the second resin composition layer made of the second resin composition is not particularly limited, and the thickness of the resulting resin sheet is desired, taking into account the thickness of the first resin composition layer and the additional resin composition layer (if any) described later. It would be good to decide on a range. In one embodiment, the thickness of the second resin composition layer is preferably 3 μm or more, more preferably 5 μm or more, even 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, and still more preferably 60 μm or less, 50 μm or less, or 40 μm or less. Warping is suppressed by the presence of the second resin composition layer.

In the present invention, the resin sheet is provided between the first resin composition layer (support side) and the second resin composition layer (opposite side to the support), a resin composition layer ( (not shown) may be included. This additional resin composition layer may be formed using the same materials as those 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 side of the resin sheet that is not bonded to the support (that is, the side opposite to the support). The protective film contributes to preventing adhesion of dust or the like to the surface of the resin sheet and prevention of scratches. As the material for the protective film, you may use the same material as the material described for the support. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. The resin sheet with the support can be used by peeling off the protective film when manufacturing a printed wiring board.

The first heat-cured product obtained by heat-curing the first resin composition at 200°C for 90 minutes, and the second heat-cured product obtained by heat-curing the second resin composition at 200°C for 90 minutes were 5.8GHz at 23°C. Since the dielectric constant is low, an insulating layer is formed that can suppress insertion loss to a low level. The dielectric constant at 5.8 GHz at 23°C of the first and second heat-cured products is 3.6 or less, preferably 3.5 or less, and more preferably 3.4 or less, 3.3 or less, or 3.2 or less. The lower limit is not particularly limited, but 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 heat-cured materials have a low dielectric loss tangent at 5.8 GHz at 23° C., they form an insulating layer capable of suppressing insertion loss to a low level. The dielectric loss tangent at 5.8GHz at 23°C of the first and second heat-cured products is both 0.01 or less, preferably 0.0095 or less, more preferably 0.009 or less, and even more preferably 0.008 or less, or 0.007 or less. The lower limit is not particularly limited, but can be 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 the present invention, since the difference in dielectric loss tangent between the first and second heat cured materials is small, an insulating layer capable of suppressing variation in insertion loss is formed. The difference in dielectric loss tangent of the first and second heat cured products is 0.005 or less, preferably 0.0045 or less, and more preferably 0.004 or less, 0.003 or less, 0.002 or less, or 0.0015 or less. The lower limit is not particularly limited, but can be set to 0 or more. The difference in dielectric loss tangent can be measured according to the procedure (measurement of dielectric constant and dielectric loss tangent of each cured material) described later.

Since the resin sheet with a support body of the present invention can reduce insertion loss and suppress variation in insertion loss, it can be used as an insulating layer of a printed wiring board used in a high frequency band. In addition, since the resin sheet with a support of the present invention can form an insulating layer capable of forming fine wiring thereon, it can be used to form an insulating layer in the manufacture of printed wiring boards by the build-up method for high frequency applications. It can be suitably used (for a build-up insulating layer of a printed wiring board), and can be more suitably used for forming a conductor layer by plating (for a build-up insulating layer of a printed wiring board that forms a conductor layer by plating). Additionally, the high frequency band means a high frequency band of 1 GHz or more (preferably 1.5 GHz or more, more preferably 3 GHz or more).

[Method for manufacturing resin sheet with support]

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

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

Examples of methods for forming the first resin composition layer and the second resin composition layer include a method of laminating the first resin composition layer and the second resin composition layer so that they are bonded to each other. A method of laminating the first resin composition layer and the second resin composition layer so as to bond them to each other includes, for example, applying the first resin composition to a support, drying the coating film to form the first resin composition layer, and then forming the first resin composition layer. A method of applying a second resin composition on the layer and drying the coating film to form a second resin composition layer is listed.

In this method, the first resin composition layer can be produced by preparing a resin varnish in which the first resin composition is dissolved in an organic solvent, applying this resin varnish on a support using a die coater or the like, and drying the resin varnish.

Organic solvents include, for example, ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl. Examples include carbitols such as carbitol, aromatic hydrocarbons such as toluene and xylene, and amide-based solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Organic solvents may be used individually, or two or more types may be used in combination.

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

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 this resin varnish is applied on the first resin composition layer formed on a support using a die coater or the like, It can be produced by drying the resin varnish. By weakening the drying conditions, the melt viscosity can also be reduced.

The organic solvent used in preparing the resin varnish in which the second resin composition is dissolved may be the same as that used in the preparation of the resin varnish in which the first resin composition is dissolved, and the resin varnish in which the second resin composition is dissolved may be prepared by dissolving the first resin composition. It can be dried using the same method as drying the dissolved resin varnish.

In addition to the above coating method, the resin sheet may be formed by a random coating method in which two types of resin varnishes are sequentially applied on one coating line. In addition, the resin sheet includes a method of applying a first resin composition on a second resin composition layer and drying the coating film to form a first resin composition layer, and a method of forming a first resin composition layer and a separately prepared first resin composition layer and a second resin composition layer. It can also be formed by a method of stacking so as to be joined to each other.

In addition, in the present invention, for example, after forming the second resin composition layer and the first resin composition layer sequentially on the protective film, a support may be laminated on the first resin composition layer to produce a resin sheet with a support.

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 substrate used for the prepreg is not particularly limited, and commonly used prepreg substrates such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used.

Prepreg can be manufactured by known methods such as hot melt method and solvent method.

The thickness of the prepreg can be within the same range as that of the second resin composition layer in the above-mentioned resin sheet.

[Printed wiring board]

The printed wiring board of the present invention includes an insulating layer formed from a cured product of the resin sheet with a support body of the present invention. In addition, the resin sheet with a support used in the printed wiring board of the present invention is preferably provided with a conductor layer of a strip line structure that operates in a high frequency band because it can reduce insertion loss and suppress variation in insertion loss. .

The printed wiring board of the present invention can be manufactured, for example, by a method including the steps (1) to (4) below using the resin sheet with the support described above.

(1) A process of preparing a base material with a wiring layer (inner layer circuit board) having a base material and a wiring layer formed on at least one side of the base material,

(2) A step of laminating the resin sheet with a support of the present invention on a substrate with a wiring layer so that the second resin composition layer is bonded to the substrate with a wiring layer, and heat curing to form an insulating layer,

(3) a process of roughening the insulating layer, and

(4) It includes a process of forming a conductor layer.

＜Process (1)＞

Step (1) is a step of preparing a substrate with a wiring layer having a substrate and a wiring layer formed on at least one side of the substrate. As an example is shown in FIG. 2 , the substrate 20 with a wiring layer has a wiring layer 22 that is a part of the substrate 21 on at least one side of the substrate 21 .

As an example of step (1) is shown in FIG. 3, patterning is performed on the wiring layer of the substrate with a wiring layer. The patterned wiring layer 22' can be formed by a known method using, for example, photolithography using a dry film, a drill, a laser, a plasma, an etching medium, etc., taking into account the characteristics of the substrate 21. .

The material used for the wiring layer is not particularly limited. In a suitable embodiment, the wiring layer includes one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The wiring layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (e.g., nickel/chromium alloy, copper/nickel alloy, and copper/titanium alloy). Those formed are listed, copper being preferred.

The base material is not particularly limited as long as steps (1) to (4) can be performed. Examples of substrates include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. A metal layer such as copper foil is formed on the surface of the substrate. It's okay if it's done.

The thickness of the base material is preferably thinner from the viewpoint of thinning, and is preferably less than 1000 μm, more preferably 800 μm or less, further 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 from the viewpoint of improving handling during transportation, it is preferably 30 μm or more, more preferably 50 μm or more, and even more preferably 100 μm or more.

From the viewpoint of thinning, the thickness of the wiring layer is preferably 40 μm or less, more preferably 35 μm or less, further preferably 30 μm or less, even more preferably 25 μm or less, particularly preferably 20 μm or less, 19 It is ㎛ or less, or 18 ㎛ or less. 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, or 5 μm or more.

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

The substrate with the wiring layer may be cut into a predetermined size as needed and then subjected to the following process.

＜Process (2)＞

Step (2) is a step of laminating the resin sheet with a support of the present invention on a substrate with a wiring layer so that the second resin composition layer is bonded to the substrate with a wiring layer, and thermally curing it to form an insulating layer. In detail, as an example shown in FIG. 4, the second resin composition layer 14 of the resin sheet 10 with a support body is embedded so as to bury the wiring layer 22' of the substrate with a wiring layer obtained in the above-described step (1). ) are laminated, and the resin sheet 12 of the support-attached resin sheet 10 is heat-cured.

Lamination of the wiring layer and the resin sheet with a support can be performed by, for example, heat-pressing the resin sheet with a support on the wiring layer from the support side after removing the protective film of the resin sheet with a support. Examples of members for heat-pressing the support-attached resin sheet to the wiring layer (hereinafter also referred to as “heat-pressing member”) include heated metal plates (SUS head plates, etc.) or metal rolls (SUS rolls). In addition, it is preferable not to press the heat-pressed member directly onto the support-attached resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the support-attached resin sheet sufficiently follows the surface irregularities of the wiring layer.

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

Lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Nikko Materials Co., Ltd., a vacuum pressurized laminator manufactured by Meiki Sesakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., etc. These are listed.

After lamination, the laminated resin sheet with the support may be smoothed under normal pressure (under atmospheric pressure), for example, by pressing a heat-pressing member from the support side. The press conditions for the smoothing treatment can be the same as the heat-pressing conditions for the above-described lamination. Smoothing treatment can be performed using a commercially available laminator. Additionally, the lamination and smoothing treatment may be performed continuously using the commercially available vacuum laminator described above.

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

For example, the heat curing conditions of the resin sheet vary depending on the types of the first and second resin compositions, etc., 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 (eg, 170°C to 200°C), and the curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

Before thermally curing the resin sheet, the resin sheet may be preheated at a temperature lower than the curing temperature. For example, prior to heat curing the resin sheet, the resin sheet is cured for 5 minutes at a temperature of 50°C to 120°C (preferably 60°C to 110°C, more preferably 70°C to 100°C). You may preheat it for more than 5 minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

The support of the resin sheet with a support body may be peeled off after laminating the resin sheet with a support body on a substrate with a wiring layer and heat curing, or the support may be peeled before laminating the resin sheet with a support body on a substrate with a wiring layer. Additionally, the support may be peeled off before the roughening treatment process described later.

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

＜Process (3)＞

Process (3) is a process of roughening the insulating layer. The procedures and conditions of the roughening treatment are not particularly limited, and known procedures and conditions normally used when forming the insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order. The swelling liquid is not particularly limited, but is an alkaline solution. Surfactant solutions and the like are listed, and alkaline solutions are preferable. Sodium hydroxide solution and potassium hydroxide solution are more preferable as the alkaline solution. Examples of commercially available swelling liquids include “Swelling Deep Securiganth P” and “Swelling Deep Securiganth SBU” manufactured by Atotech Japan Co., Ltd. The swelling treatment using the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the cured body in a swelling liquid of 40°C to 80°C for 5 to 15 minutes. The oxidizing agent is not particularly limited, but examples include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 80°C for 10 to 30 minutes. Additionally, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securigant P” manufactured by Atotech Japan Co., Ltd. Additionally, an acidic aqueous solution is preferable as the neutralizing liquid, and examples of commercially available products include "Reduction Solution/Securigant P" manufactured by Atotech Japan Co., Ltd. Treatment with a neutralizing liquid can be performed by immersing the treated surface, which has undergone roughening treatment with an oxidizing agent, in a neutralizing liquid at 30°C to 80°C for 5 to 30 minutes. In terms of workability, etc., a method of immersing the object that has been roughened with an oxidizing agent in a neutralizing liquid at 40°C to 70°C for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness Ra of the surface of the insulating layer after roughening is preferably 400 nm or less, more preferably 350 nm or less, even more preferably 300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less, or 100 nm or less. . The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact surface roughness meter. Specific examples of non-contact surface roughness meters include “WYKO NT3300” from Vico Instruments.

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

The formation of the via hole is not particularly limited, but may be performed using, for example, a drill, laser, plasma, etc., depending on the composition of the first and second resin compositions used to form the insulating layer. The size and shape of the hole may be determined appropriately 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 suitable embodiment, the conductor layer comprises one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. do. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (e.g., nickel/chromium alloy, copper/nickel alloy, and copper/titanium alloy) ) are listed. Among them, from the viewpoint of versatility of forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, a copper-nickel alloy , an alloy layer of a copper-titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single metal layer of copper is more preferable. This is more preferable.

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

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

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

In detail, a plating seed layer is formed on the surface of an insulating layer formed by heat curing a resin sheet by electroless plating. Next, on the formed plating seed layer, a mask pattern is formed to expose a portion of the plating seed layer corresponding to the desired wiring pattern. After forming an electric field plating layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer with a desired wiring pattern.

As an example shown in Figure 5, bonded to the surface of the exposed insulating layer 12' consisting of the heat-cured first resin composition layer 13' and the heat-cured second resin composition layer 14'. A plating seed layer 31 is formed. First, alkaline cleaning is performed to clean the surface of the insulating layer 12' and adjust the charge. Next, a soft etching process is performed (if there is a via hole, a soft etching process is performed to clean the inside of the via hole). Specifically, the treatment may be performed under any suitable conditions using an etchant such as an aqueous sulfuric acid acidic sodium peroxodisulfate solution. Next, a pre-dip process is performed to adjust the electric charge on the surface of the insulating layer 12' in order to apply Pd (palladium) to the surface of the insulating layer 12'. Next, Pd, which is an activator, is applied to the surface, and the 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 a via hole is formed, the plating seed layer 31 is formed within the via hole, that is, to cover the side wall and the wiring layer exposed from the via hole.

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

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

As an example shown in FIG. 7, the electroplating layer 32 is formed on the exposed plating seed layer 31 by electrolytic plating. If via holes are formed, the via holes are buried together through electroplating to form filled vias.

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

In the present invention, the formation of the insulating layer and the conductor layer in steps (2) to (4) may be repeated to form a multilayer wiring board having a plurality of insulating layers and a plurality of conductor layers. Hereinafter, a method for manufacturing a multilayer wiring board will be described, but descriptions of parts that overlap with the above will be omitted as appropriate.

As an example is shown in Figure 9, the second resin composition layer of the resin sheet with a support is laminated on the conductor layer 30 so as to be bonded to the produced conductor layer 30, and is heat-cured to form a second insulating layer 12". ) is formed. That is, step (2) is carried out. The resin sheet with a support body of the present invention used in this step may be the same as the resin sheet with a support body of the present invention laminated on a substrate with a wiring layer. You may also use

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

In addition, as an example 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, and soldering treatment. Necessary surface treatment such as the like may be performed.

As an example is shown in FIG. 14, the multilayer wiring board manufactured in this way has a strip line structure in which the conductor layer is embedded in the insulating layer 12' and is arranged according to a predetermined pattern. That is, a conductor layer is disposed inside the insulating layer. With this configuration, even when used in a high frequency band, fluctuations in characteristic impedance can be suppressed and insertion loss can be reduced. Additionally, FIG. 14 is a schematic cross-sectional view showing a portion of a direction perpendicular to the cross-section shown in FIG. 12.

Above, a printed wiring board having a wiring layer, an insulating layer, and a conductor layer on one side of the base material has been described, but a printed wiring board having a wiring layer, an insulating layer, and a conductor layer on both sides of the base material may also be used. Additionally, a multilayer wiring board having a plurality of insulating layers and conductor layers on both sides of the substrate may be used.

[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.

As semiconductor devices, various semiconductor devices provided in electrical appliances (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, aircraft, etc.) are listed. .

The semiconductor device of the present invention can be manufactured by mounting components (semiconductor chips) in conductive locations of a printed wiring board. A “continuity point” is a “point that transmits an electric signal on a printed wiring board,” and the location may be on the surface or buried. Additionally, 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 when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically includes a wire bonding mounting method, a flip chip mounting method, and a bumpless build-up ( A mounting method using a bumpless build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), etc. are listed. Here, the “mounting method using a bumpless build-up layer (BBUL)” refers to a “mounting method in which a semiconductor chip is directly embedded in a recessed portion of a printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board.”

[Example]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In addition, in the following description, “part” and “%” mean “part by mass” and “% by mass”, respectively, unless otherwise specified.

[Production of resin sheet with support]

Resin sheets with supports of examples and comparative examples were produced using a resin varnish (resin composition) prepared according to the following procedures.

(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 A mixture of 15 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Co., Ltd., a 1:1 solution of cyclohexanone:methyl ethyl ketone (MEK) with a solid content of 30% by mass), 12 parts of solvent naphtha, and 5 parts of cyclohexanone. It was dissolved in a solvent by heating while stirring. After cooling to room temperature, 6 parts of a phenol novolak-based curing agent containing a triazine skeleton (hydroxyl equivalent 125, “LA-7054” manufactured by DIC Co., Ltd., MEK solution with a solid content of 60%) and an active ester compound (DIC 20 parts of “HPC-8000-65T” manufactured by Co., Ltd., a toluene solution containing 65% by mass of non-volatile content with a weight average molecular weight of about 2700 and an active group equivalent of about 223), an amine-based curing accelerator (4-dimethylaminopyridine (DMAP), 2 parts of MEK solution with a solid content of 5% by mass), 1 part of imidazole-based curing accelerator (“P200-H50” manufactured by Mitsubishi Chemical Corporation, propylene glycol monomethyl ether solution with a solid content of 50% by mass), 1 part of aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) Surface-treated spherical silica (“SO-C2” manufactured by Adomatex Co., Ltd., average particle diameter 0.5 μm, carbon content per unit surface area: 0.38 mg/m2) 60 parts were mixed and uniformly dispersed with a high-speed rotating mixer, and then filtered with a cartridge filter (“SHP050” manufactured by ROKITECHNO) to prepare Resin Varnish 1.

(Preparation of Resin Varnish 2)

5 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Tetsu Sumikin Chemical Co., Ltd., epoxy equivalent weight approximately 169, 1:1 mixture of bisphenol A type and bisphenol F type), bixylenol type epoxy resin (Mitsubishi Chemical Co., Ltd. “YX4000HK” manufactured by Co., Ltd., epoxy equivalent approximately 185) 5 parts, bisphenol AF type epoxy resin (“YL7760” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 238) 5 parts, naphthalene type epoxy resin (Shinnittetsu Sumikin Car) 20 parts of “ESN475V” manufactured by Kagaku Co., Ltd., epoxy equivalent 330), and 1 part of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Co., Ltd., cyclohexanone:methyl ethyl ketone (MEK) with a solid content of 30% by mass. 1 solution) 5 parts were dissolved by heating while stirring in a mixed solvent of 25 parts solvent naphtha and 5 parts cyclohexanone. After cooling to room temperature, 5 parts of a cresol novolak-based curing agent containing a triazine skeleton (hydroxyl equivalent weight 151, “LA-3018-50P” manufactured by DIC Co., Ltd., 2-methoxypropanol solution with a solid content of 50%) , 20 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC Co., Ltd., a toluene solution containing 65% by mass of non-volatile matter with a weight average molecular weight of about 2700 and an active group equivalent of about 223), carbodiimide resin (Nisshinbo Chemical) 10 parts of “V-03” manufactured by Co., Ltd., toluene solution with 50% by mass of non-volatile components), 2 parts of amine-based curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with 5% by mass of solids), flame retardant ( “HCA-HQ” manufactured by Sanko Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter 2 μm) 2 Part, spherical silica (“SO-C2” manufactured by Adomatex Co., Ltd.) surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), average particle diameter 0.5 ㎛, per unit surface area. 170 parts (carbon amount: 0.38 mg/m2) were mixed and uniformly dispersed with a high-speed rotating mixer, and then filtered with a cartridge filter (“SHP050” manufactured by ROKITECHNO) to prepare Resin Varnish 2.

(Preparation of Resin Varnish 3)

5 parts of liquid naphthalene-type epoxy resin (epoxy equivalent 144, “HP4032SS” manufactured by DIC Co., Ltd.), 5 parts of xylenol-type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent approximately 185), 5 parts naphthalene-type epoxy 15 parts of resin (“ESN475V” manufactured by Shinnittetsu Sumikin Chemical Co., Ltd., epoxy equivalent 330), and phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Co., Ltd., cyclohexanone:methylethyl with a solid content of 30% by mass) 7 parts of a 1:1 solution of ketone (MEK) were dissolved by heating while stirring in a mixed solvent of 20 parts of solvent naphtha and 5 parts of cyclohexanone. After cooling to room temperature, 10 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC Co., Ltd., a toluene solution with a mass average molecular weight of about 2700, an active group equivalent of about 223, and a non-volatile content of 65% by mass), Carbodi. 5 parts of mid resin (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., toluene solution with 50% by mass of non-volatile components), prepolymer of bisphenol A dicyanate (“BA230S75” manufactured by Lonza Japan Co., Ltd., cyanate) Equivalent weight: about 232, MEK solution with 75% by mass of non-volatile matter) 20 parts, curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with 5% by mass of solid content) 1.2 parts, curing accelerator (manufactured by Tokyo Kasei Co., Ltd., cobalt) (Ⅲ) 3.5 parts of acetylacetonate [Co (Ⅲ) Ac, MEK solution with a solid content of 1% by mass]), 3.5 parts of rubber particles (PARALOID EXL2655 manufactured by Dow Chemical Nippon Co., Ltd.), 3 parts of phenylaminosilane-based coupling agent ( Spherical silica surface-treated with “KBM573” manufactured by Shin-Etsu Chemical Co., Ltd. (average particle diameter: 0.24 μm, “SO-C1” manufactured by Adomatex Co., Ltd., carbon content per unit area: 0.36 mg/m2) 80 The parts were mixed and uniformly dispersed with a high-speed rotating mixer, and then filtered with a cartridge filter (“SHP030” manufactured by ROKITECHNO) to prepare Resin Varnish 3.

(Preparation of Resin Varnish 4)

5 parts of bixylenol-type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 5 parts of bisphenol AF-type epoxy resin (“YL7760” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 238), naphthalene 15 parts of a type epoxy resin (“ESN475V” manufactured by Nippon Chemical Co., Ltd., epoxy equivalent 330), and phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Co., Ltd., cyclohexanone with a solid content of 30% by mass: 5 parts of methyl ethyl ketone (MEK) (1:1 solution) were dissolved by heating while stirring in a mixed solvent of 20 parts of solvent naphtha and 5 parts of cyclohexanone. After cooling to room temperature, 10 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC Co., Ltd., a toluene solution with a weight average molecular weight of about 2700, an active group equivalent of about 223, and a non-volatile content of 65% by mass), bisphenol A 20 parts of dicyanate prepolymer (“BA230S75” manufactured by Lonza Japan Co., Ltd., cyanate equivalent weight of about 232, MEK solution with 75% by mass of non-volatile matter), curing accelerator (4-dimethylaminopyridine (DMAP), solid content of 5% by mass) % MEK solution) 0.5 part, curing accelerator (manufactured by Tokyo Kasei Co., Ltd., cobalt (Ⅲ) acetylacetonate [Co (Ⅲ) Ac, MEK solution with a solid content of 1% by mass]) 3 parts, flame retardant (Sanko Co., Ltd.) Manufactured as “HCA-HQ”, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter 2㎛) 2 parts, aminosilane Spherical silica (“SO-C2” manufactured by Adomatex Co., Ltd.) surface-treated with a coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), average particle diameter 0.5 μm, carbon content per unit surface area: 0.38 mg /m2) 120 parts were mixed and uniformly dispersed with a high-speed rotating mixer, and then filtered with a cartridge filter (“SHP050” manufactured by ROKITECHNO) to prepare Resin Varnish 4.

(Preparation of Resin Varnish 5)

12 parts of biphenyl-type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288), 8 parts of naphthalene-type epoxy resin (“ESN475V” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 330), and 6 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 5 parts of cyclohexanone. It was dissolved in a mixed solvent by heating while stirring. After cooling to room temperature, 22 parts of an activated ester-based curing agent (“HPC-8000-65T” manufactured by DIC Co., Ltd., an active group equivalent of about 223, a toluene solution containing 65% by mass of non-volatile components), and an amine-based curing accelerator. (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5% by mass) 1 part, phosphorus-based curing accelerator (“TBP-DA” tetrabutylphosphonium decanoate manufactured by Hokko Kagaku Kogyo Co., Ltd.) 0.3 parts, rubber particles (PARALOID EXL2655, manufactured by Dow Chemical Nippon Co., Ltd.) 2 parts, spherical silica (average particle diameter 0.24 ㎛, Co., Ltd.) surface-treated with a phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) ) 30 parts of “SO-C1” manufactured by Adomatex, carbon content per unit area of 0.36 mg/m2), and spherical silica (average particle) surface-treated with phenyltrimethoxysilane (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd. 40 parts of diameter 0.1㎛, "UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd., carbon amount per unit surface area 0.19mg/㎡) were mixed and uniformly dispersed with a high-speed rotating mixer, and then filtered using a cartridge filter (ROKITECHNO manufactured by "UFP-30"). Resin varnish 5 was prepared by filtration through "SHP020").

(Preparation of Resin Varnish 6)

4 parts bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Tetsu Sumikin Chemical Co., Ltd., epoxy equivalent weight approximately 169, 1:1 mixture of bisphenol A type and bisphenol F type), bisphenol AF type epoxy resin (Mitsubishi Chemical Co., Ltd. “YL7760” manufactured by Co., Ltd., epoxy equivalent 238) 12 parts, naphthalene type epoxy resin (“ESN475V” manufactured by Nippon-Steel Chemical Co., Ltd., epoxy equivalent 330) 4 parts, and phenoxy resin (Mitsubishi Chemical Co., Ltd.) Note) 6 parts of the manufactured “YL7891BH30” (1:1 solution of cyclohexanone:methyl ethyl ketone (MEK) with a solid content of 30% by mass), 20 parts of solvent naphtha, and 5 parts of cyclohexanone were heated and dissolved while stirring. After cooling to room temperature, 24 parts of an active ester-based curing agent (“HPC-8000-65T” manufactured by DIC Co., Ltd., an active group equivalent of about 223, a toluene solution containing 65% by mass of non-volatile components), oligophenylene ether, 10 parts of styrene resin (“OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Co., Ltd., toluene solution with 72% by mass of solids), amine-based curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with 5% by mass of solids) ) 2 parts, imidazole-based curing accelerator (“1B2PZ” 1-benzyl-2-phenylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd., MEK solution with 5% solid content) 0.5 part, aminosilane-based coupling agent (Shinetsu Chemical) Mix 150 parts of spherical silica (“SO-C4” manufactured by Adomatex Co., Ltd., average particle diameter of 1 μm, carbon content per unit surface area of 0.31 mg/m2) surface-treated with “KBM573” manufactured by Kogyo Co., Ltd. After uniformly dispersing with a high-speed rotating mixer, it was filtered with a cartridge filter (“SHP050” manufactured by ROKITECHNO) to prepare Resin Varnish 6.

(Preparation of Resin Varnish 7)

5 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Tetsu Sumikin Chemical Co., Ltd., epoxy equivalent weight approximately 169, 1:1 mixture of bisphenol A type and bisphenol F type), bixylenol type epoxy resin (Mitsubishi Chemical Co., Ltd. “YX4000HK” manufactured by Co., Ltd., epoxy equivalent weight approximately 185) 10 parts, biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight 288) 25 parts, and phenoxy resin (Mitsubishi Chemical Co., Ltd. ) 20 parts of the product "YX7553BH30", a 1:1 solution of cyclohexanone:methyl ethyl ketone (MEK) with a solid content of 30% by mass) were dissolved by heating while stirring in a mixed solvent of 15 parts of solvent naphtha and 5 parts of cyclohexanone. After cooling to room temperature, 12 parts of a phenol novolak-based curing agent containing a triazine skeleton (hydroxyl equivalent weight 125, “LA-7054” manufactured by DIC Co., Ltd., 60% solid content MEK solution), and a naphthol-based curing agent (Shinnittetsu Sumi) were added. “SN-485” manufactured by Kin Kagaku Co., Ltd., hydroxyl equivalent weight 215, solid content 60% MEK solution) 15 parts, polyvinyl butyral resin (glass transition temperature 105°C, “KS-” manufactured by Sekisui Kagaku Kogyo Co., Ltd. 1"), 10 parts of a 1:1 mixed solution of ethanol and toluene with a solid content of 15%, 1 part of an amine-based curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5% by mass), and imidazole-based curing. 2 parts of accelerator (“P200-H50” manufactured by Mitsubishi Chemical Co., Ltd., propylene glycol monomethyl ether solution with a solid content of 50% by mass), 2 parts of rubber particles (PARALOID EXL2655 manufactured by Dow Chemical Nippon Co., Ltd.), aminosilane Spherical silica (“SO-C2” manufactured by Adomatex Co., Ltd.) surface-treated with a coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), average particle diameter 0.5 μm, carbon content per unit surface area: 0.38 mg /㎡) 90 parts were mixed and uniformly dispersed with a high-speed rotating mixer, and then filtered with a cartridge filter (“SHP050” manufactured by ROKITECHNO) to prepare Resin Varnish 7.

(Preparation of Resin Varnish 8)

5 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Tetsu Sumikin Chemical Co., Ltd., epoxy equivalent weight approximately 169, 1:1 mixture of bisphenol A type and bisphenol F type), bixylenol type epoxy resin (Mitsubishi Chemical Co., Ltd. “YX4000HK” manufactured by Co., Ltd., epoxy equivalent weight approx. 185) 5 parts, biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight 288) 12 parts, naphthalene type epoxy resin (manufactured by DIC Co., Ltd.) “HP-4710”, epoxy equivalent 170) 5 parts, and 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) 10 parts were dissolved by heating while stirring in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone. After cooling to room temperature, 10 parts of a phenol novolak-based curing agent containing a triazine skeleton (hydroxyl equivalent weight 125, “LA-7054” manufactured by DIC Co., Ltd., MEK solution with a solid content of 60%) was added thereto, and a naphthol-based curing agent (Shinnittetsu). 10 parts of imidazole-based curing accelerator (“SN-485” manufactured by Sumikin Chemical Co., Ltd., hydroxyl equivalent weight 215, MEK solution of 60% solid content), 1-benzyl-2- Phenylimidazole, MEK solution with 5% solid content) 0.5 part, flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10 -Phosphaphenanthrene-10-oxide, average particle diameter 2㎛) 3 parts, spherical silica (Adomatex Co., Ltd.) surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 120 parts of manufactured “SO-C4”, average particle diameter 1㎛, carbon amount per unit surface area 0.31mg/m2), and surface treatment with phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 60 parts of spherical alumina (“DAW-01” manufactured by Denki Kagaku Kogyo Co., Ltd., average particle diameter 1.5 μm, carbon amount per unit surface area 0.1 mg/m2) were mixed and uniformly dispersed with a high-speed rotating mixer. Resin varnish 8 was prepared by filtration with a cartridge filter (“SHP050” manufactured by ROKITECHNO).

The materials used in the production of each resin varnish and their mixing amounts (parts by mass of non-volatile matter) are listed in the table below.

<Example 1: Production of resin sheet 1 with support>

As a support, a PET film (“Lumiror R80” manufactured by Toray Co., Ltd., thickness 38 μm, softening point 130°C, “release PET”) was treated with an alkyd resin-based release agent (“AL-5” manufactured by Lintech Co., Ltd.). Ready.

Resin varnish 1 was uniformly applied with a die coater on release PET so that the thickness of the first resin composition layer after drying was 3 μm, and dried at 80°C to 160°C for 5 minutes to form a first resin composition layer on release PET. Obtained. Next, resin varnish 2 was applied on the first resin composition layer so that the combined thickness of the first resin composition layer after drying was 40㎛, dried at 70°C to 110°C (average 95°C) for 5 minutes, and the second layer was formed. A resin composition layer (resin sheet) was formed. Next, on the side of the resin sheet that is not bonded to the support (i.e., the side that is not bonded to the first resin composition layer of the second resin composition layer), a polypropylene film (manufactured by Oji Ftex Co., Ltd., “Alpan”) is applied as a protective film. MA-411”, a rough surface with a thickness of 15 μm was laminated so as to be bonded to the second resin composition layer. As a result, resin sheet 1 with a support body was obtained, which consists of the support body, the first resin composition layer (derived from the resin varnish 1), the second resin composition layer (derived from the resin varnish 2), and the protective film.

<Example 2: Production of resin sheet 2 with support>

Resin sheet 2 with a support was obtained in the same manner as in Example 1, except that Resin Varnish 3 was used instead of Resin Varnish 1, and Resin Varnish 4 was used instead of Resin Varnish 2.

<Example 3: Production of resin sheet 3 with support>

Resin sheet 3 with a support was obtained in the same manner as in Example 1, except that Resin Varnish 5 was used instead of Resin Varnish 1, and Resin Varnish 6 was used instead of Resin Varnish 2.

<Comparative Example 1: Production of resin sheet 4 with support>

Resin sheet 4 with a support was obtained in the same manner as in Example 1, except that Resin Varnish 7 was used instead of Resin Varnish 1.

<Comparative Example 2: Production of resin sheet 5 with support>

Resin sheet 5 with a support was obtained in the same manner as in Example 1, except that Resin Varnish 6 was used instead of Resin Varnish 2.

<Comparative Example 3: Production of resin sheet 6 with support>

Resin sheet 6 with a support was obtained in the same manner as in Example 1, except that Resin Varnish 7 was used instead of Resin Varnish 1, and Resin Varnish 8 was used instead of Resin Varnish 2.

<Comparative Example 4: Production of resin sheet 7 with support>

Resin sheet 7 with a support was obtained in the same manner as in Example 1, except that Resin Varnish 8 was used instead of Resin Varnish 2.

<Production of cured products of each resin composition>

As a support, a release PET film (“501010” manufactured by Lintech Co., Ltd., thickness 38 μm, 240 mm square) for production of the cured product was prepared.

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

This release PET film with a resin composition layer is made of glass so that it has the structure of a resin composition layer/release PET film/glass cloth base epoxy resin double-sided copper-clad laminate (“R5715ES” manufactured by Matsushita Denko Co., Ltd., thickness 0.7 mm, 255 mm square). It was installed on a fabric-based epoxy resin double-sided copper-clad laminate, and four sides of the film were fixed with polyimide adhesive tape (width 10 mm).

Subsequently, it was heat cured at 200°C for 90 minutes. After heat curing, the polyimide adhesive tape was peeled off, and the release PET film with the resin composition layer was peeled off from the glass cloth-based epoxy resin double-sided copper-clad laminate. Additionally, the release PET film (“501010” manufactured by Lintech Co., Ltd.) on which the resin sheet had been laminated was peeled to obtain a sheet-like cured product.

(Measurement of dielectric constant and dielectric loss tangent of each hardened material)

Each cured product was cut into test pieces with a width of 2 mm and a length of 80 mm, and the test pieces were measured for dielectric constant ( Dk) and dielectric loss tangent (Df) were measured. Three test pieces were measured, the average value was calculated, and the results are listed in the table below. Furthermore, based on the dielectric loss tangent calculated in this way, the difference in dielectric loss tangent of the first and second heat-cured products in the resin sheets with a support body of Examples and Comparative Examples was calculated, and the results are shown in the table below.

＜Evaluation test＞

1. Evaluation of high-frequency transmission loss measurements

Fig. 15 is a schematic cross-sectional view of a strip line transmission line evaluation board. Using the resin sheets with supports produced in Examples and Comparative Examples, a strip line transmission line evaluation board with the configuration shown in Fig. 15 was produced following the following procedure, and high-frequency transmission loss measurement was evaluated.

(1) Base processing of inner layer circuit board

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

(2) Laminate of resin sheet with support

Each support-attached resin sheet produced in the Examples and Comparative Examples was formed using a batch vacuum pressurization laminator (Nikko Materials Co., Ltd., two-stage build-up laminator, CVP700), and the second resin composition layer was formed as an inner layer. To bond it to the circuit board, it was laminated on both sides of the inner layer circuit board. The lamination was performed by reducing the pressure for 30 seconds to bring the atmospheric pressure to 13 hPa or less, and pressing it at 100°C and a pressure of 0.74 MPa for 30 seconds. Next, heat pressing was performed at 100°C and a pressure of 0.5 MPa for 60 seconds.

(3) Thermal curing of the resin composition layer

The inner layer circuit board laminated with the resin sheet attached to the support is insulated by placing it in an oven at 100°C for 30 minutes at a temperature of 100°C, then transferring it to an oven at 175°C at a temperature of 175°C, and heat curing for 30 minutes. A layer was formed.

(4) Process of performing desmear treatment

The support was peeled from the circuit board on which the insulating layer was formed, and desmear treatment was performed. In addition, as the desmear treatment, the following wet desmear treatment was performed.

Wet Desmear Processing:

Swelling liquid (“Swelling Deep Securigant P” manufactured by Atotech Japan Co., Ltd., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 5 minutes, followed by an oxidizing agent solution (manufactured by Atotech Japan Co., Ltd.) “Concentrate Compact CP”, an aqueous solution with a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) at 80°C for 20 minutes, and finally, a neutralizing solution (“Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd. 」, sulfuric acid aqueous solution) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

(5) Process of forming a conductor layer

(5-1) Electroless plating process

In order to form a conductor layer on the surface of the circuit board, a plating process including the following steps 1 to 6 (copper plating process using a chemical solution manufactured by Atotech Japan Co., Ltd.) is performed to produce a conductor with a target thickness of 18 ㎛. A layer was formed.

1. Alkaline cleaning (cleaning and charge adjustment of the surface of the insulating layer)

Cleaning was performed at 60°C for 5 minutes using Cleaning Cleaner Securiganth 902 (brand name).

2. Soft etching

It was treated at 30°C for 1 minute using sulfuric acidic sodium peroxodisulfate aqueous solution.

3. Pre-dip (adjustment of surface charge of insulating layer to impart Pd)

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

4. Provision of activator (provision of Pd to the surface of the insulating layer)

It was treated at 35°C for 5 minutes using Activator Neoganth 834 (brand name).

5. Reduction (reduces Pd given to the insulating layer)

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

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

A mixture of Basic Solution Printganth MSK-DK (brand name), Copper solution Printganth MSK (brand name), Stabilizer Printganth MSK-DK (brand name), and Reducer Cu (brand name) was used to treat at 35°C 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 (“RD1225” manufactured by Hitachi Kasei Co., Ltd.) was laminated on the formed electroless copper plating layer, followed by exposure using an exposure machine “LI9500” manufactured by Dainippon Screen Sezo Co., Ltd. (exposure amount: 15 mJ/c㎡), A dry film pattern was formed by development (1% Na ₂ CO ₃ aqueous solution, 30°C, 40 s, spray pressure 0.15 MPa).

(5-3) Electrolytic plating process

Next, an electrolytic copper plating process was performed using the chemical solution “Topletina α” manufactured by Okuno Seiyaku Kogyo Co., Ltd. Thereafter, the dry film pattern was peeled off with a 1% NaOH aqueous solution, and the unnecessary electroless copper plating layer was removed using the etchant “OPC-HR Soft Etch P” manufactured by Okuno Seiyaku Kogyo Co., Ltd. Next, annealing was performed at 190°C for 90 minutes to form a conductor layer on the insulating layer.

(6) Laminate of resin sheet with support

The substrate was immersed in a 10% aqueous sulfuric acid solution for 30 seconds and dried at 130°C for 15 minutes, and then each support-attached resin sheet produced in the examples and comparative examples was laminated by the same method as the support-attached resin sheet in (2). It was laminated.

(7) Thermal curing of the resin composition layer

The inner layer circuit board on which the resin sheet with the support is laminated is placed in an oven at 100°C for 30 minutes under a temperature condition of 100°C, and then transferred to an oven at 175°C under a temperature condition of 175°C and heat cured for 30 minutes. An insulating layer was formed.

(8) Formation of via hole

The laser is irradiated from the top of the insulating layer and the support using a CO ₂ laser processing machine "605GTWIII(-P)" manufactured by Mitsubishi Denki Co., Ltd., and the insulating layer on the conductor in a grid pattern has a top diameter. A via hole of (70㎛) was formed. 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 number of shots of 2, and burst mode (10 kHz).

(9) Process of performing desmear treatment

The support was peeled off from the circuit board on which the via hole was formed, and desmear treatment was performed in the same manner as (4).

(10) Process of forming a conductor layer

(5) Using the same method as the process for forming the conductor layer, a conductor layer with a target thickness of 18 μm was formed. Additionally, soft etching was performed to clean the via hole.

(11) Process of forming solder resist

Solder resist "PFR-800 AUS410" manufactured by Taiyo Inky Sezo Co., Ltd. was laminated, exposed (exposure amount 150 mJ/cm2) using an exposure machine "LI9500" manufactured by Dainippon Screen Sezo Co., Ltd., and developed (1% Na ₂ A solder resist was formed using CO ₃ aqueous solution, 30°C, 80 s, spray pressure 0.15 MPa).

(Measurement of the thickness of the insulating layer between conductor layers)

A strip line transmission line evaluation board (hereinafter also referred to as an evaluation board) was subjected to cross-sectional observation using a FIB-SEM combination device (“SMI3050SE” manufactured by SII Nano Technology Co., Ltd.). In detail, a cross-section in the direction perpendicular to the surface of the conductor layer was cut using 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, cross-sectional SEM images of five randomly selected locations were observed, and the average value thereof was taken as the thickness of the insulating layer between conductor layers.

(High-frequency transmission loss measurement)

Using three manufactured evaluation boards, VNA (Agilent technology PNA-X): 10 MHz to 50 GHz, TDR/TDT system (Tektronix DSA8200): Characteristic impedance/eye-pattern for an impedance setting of 50Ω and a wiring length of 34 mm. High-frequency transmission loss was measured using .

In the table below, three insertion loss values (dB) at 30 GHz are described, and their average value, standard deviation, and cv value of insertion loss are described. The cv value of insertion loss refers to the value obtained by (standard deviation of insertion loss/average value of insertion loss) x 100.

10: Resin sheet with support body
11: support
12: Resin sheet
12': insulation layer
12": second insulating layer
13: First resin composition layer
13': Heat-cured first resin composition layer
14: Second resin composition layer
14': heat-cured second resin composition layer
20: Wiring layer attachment substrate
21: Description
22: wiring layer
22': patterned wiring layer
30: conductor layer
30': conductor layer
31: Plating seed layer
32: Electroplating layer
40: Mask pattern
50: Via hole
51: field via
60: Solder resist film

Claims (10)

A resin sheet attached to a support, comprising a support and a resin sheet provided on the support,
The resin sheet includes a first resin composition layer provided on the support side and formed of the first resin composition,
It has a second resin composition layer formed of a 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, respectively,
A first heat-cured product obtained by heat-curing a first resin composition at 200°C for 90 minutes, and a second heat-cured product obtained by heat-curing a second resin composition at 200°C for 90 minutes, at 5.8 GHz at 23°C. The dielectric constants are all less than 3.6,
The first resin composition and the second resin composition include (c) an inorganic filler, and the content of the inorganic filler in the first resin composition is A1 (mass %), and the content of the inorganic filler in the second resin composition is A2 (mass %). When , the difference (A2-A1) between A1 and A2 is 5 mass% or more and 90 mass% or less,
The dielectric loss tangents at 5.8 GHz at 23°C of the first and second heat-cured products are both 0.01 or less,
A resin sheet with a support, characterized in that the difference in dielectric loss tangent of the first and second heat cured products 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 component (a) is an epoxy resin having an aromatic structure. The resin sheet with a support according to claim 1, wherein the first resin composition and the second resin composition contain (b) a curing agent, and at least one type of component (b) is an active ester curing agent. The resin sheet with a support according to claim 1, wherein the first and second heat-cured products both have dielectric constants at 5.8 GHz at 23°C of 3.5 or less. The resin sheet with a support according to claim 1, wherein both the first and second heat-cured products have dielectric loss tangents at 5.8 GHz at 23°C of 0.0095 or less. The resin sheet with a support according to claim 1, which is used in a high frequency band of 1 GHz or more. A printed wiring board comprising an insulating layer formed from a cured product of the resin sheet with a support body according to any one of claims 1 to 6. 8. The printed wiring board of claim 7, comprising a strip line structure. A semiconductor device comprising the printed wiring board according to claim 7. delete

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