JP6011079B2 - Resin sheet with support - Google Patents

Description

  The present invention relates to a resin sheet with a support. Furthermore, it is related with the multilayer printed wiring board and semiconductor device containing the said resin sheet with a support body.

  In recent years, miniaturization and high performance of electronic devices have progressed, and in a semiconductor package substrate, a build-up layer has been formed into multiple layers, and miniaturization and high density of wiring have been demanded.

  Various efforts were made against this. For example, Patent Document 1 discloses a resin composition containing an epoxy resin and an active ester resin. It is described that the insulating layer formed of these compositions can achieve both dielectric properties and heat resistance. However, its performance was not always satisfactory.

JP 2009-235165 A

  In a resin composition, it is preferable to add a large amount of an active ester compound to obtain a cured product having excellent dielectric properties, and a large amount of an inorganic filler to reduce the coefficient of thermal expansion. In the formation, a new problem has been found that laser processability and smear removability are likely to deteriorate. On the other hand, if the amount of the active ester compound is reduced, the smear removability is improved, but the dielectric loss tangent increases, and there is a problem that the plating peel strength tends to decrease with respect to the copper plating formed after desmearing. confirmed.

  The present invention has been made in view of the above circumstances, and the problem to be solved by the present invention is a support excellent in smear removability and plating peel strength despite a low dielectric loss tangent and linear thermal expansion coefficient. It is to provide a resin sheet with a body.

  As a result of earnest research to solve the above problems, the present inventor has found a support, a specific first layer formed on the support, and a specific second layer formed on the first layer. Thus, the present invention has been completed by using a resin sheet with a support characterized by having.

That is, the present invention includes the following contents.
[1] A first layer containing a support and an epoxy resin, an active ester compound and an inorganic filler formed on the support, wherein the nonvolatile component in the first layer is 100% by mass A second layer containing an epoxy resin, an active ester compound and an inorganic filler formed on the first layer, the first layer having an active ester compound content of 5% by mass or more, A resin sheet with a support, comprising: a second layer in which the active ester compound is 5% by mass or less when the nonvolatile component in the layer is 100% by mass.
[2] The resin sheet with a support according to [1], wherein the inorganic filler has an average particle size of 0.01 to 3 μm.
[3] The resin sheet with a support according to [1] or [2], wherein the content of the inorganic filler is 40 to 90% by mass.
[4] The resin sheet with a support according to any one of [1] to [3], wherein the inorganic filler is surface-treated with a surface treatment agent.
[5] The resin sheet with a support according to [4], wherein the inorganic filler has a carbon amount per unit surface area of 0.02 to 1 mg / m ² .
[6] The resin sheet with a support according to any one of [1] to [5], wherein the thickness of the second layer is 2 μm or more.
[7] The support according to any one of [1] to [6], wherein the resin sheet is thermoset to form an insulating layer, and the linear thermal expansion coefficient of the insulating layer is 25 ppm or less. With resin sheet.
[8] The resin sheet is thermally cured to form an insulating layer, and a dielectric loss tangent (measurement frequency: 5.8 GHz) of the insulating layer is 0.0065 or less [1] to [7] The resin sheet with a support body in any one of these.
[9] The resin sheet is thermally cured to form an insulating layer, and the arithmetic average roughness (Ra) after roughening the surface of the insulating layer is 150 nm or less, and the root mean square roughness (Rq) is The resin sheet with a support according to any one of [1] to [8], which is 220 nm or less.
[10] The resin sheet is thermally cured to form an insulating layer, the surface of the insulating layer is roughened, and the peel strength between the conductive layer obtained by plating and the insulating layer is 0.5 kgf / cm or more The resin sheet with a support according to any one of [1] to [9], wherein
[11] The resin sheet with a support according to any one of [1] to [10], which is a resin sheet with a support for an insulating layer of a multilayer printed wiring board.
[12] The resin sheet with a support according to any one of [1] to [11], which is a resin sheet with a support for a buildup layer of a multilayer printed wiring board.
[13] (A) A step of laminating the resin sheet with a support according to any one of [1] to [12] on one or both surfaces of the inner circuit board, (B) insulating the resin sheet with a support by thermosetting A step of forming a layer, (C) a step of drilling the insulating layer to form a via hole, (D) a step of peeling the support, (E) a step of roughening the surface of the insulating layer, (F) roughening A process for forming a conductor layer by plating on the surface of the insulating layer after the treatment, wherein (C) in the step of drilling the insulating layer to form a via hole, A method for producing a multilayer printed wiring board, wherein a top diameter (diameter) of a via hole of a layer is 65 μm or less.
[14] A semiconductor device using a multilayer printed wiring board manufactured by the method according to [13].

  Use of a resin sheet with a support comprising a support, a specific first layer formed on the support, and a specific second layer formed on the first layer Accordingly, it is possible to provide a resin sheet with a support excellent in smear removability and plating peel strength even though the dielectric loss tangent and the coefficient of linear thermal expansion are low.

[Resin sheet with support]
The resin sheet with a support of the present invention is a first layer containing a support and an epoxy resin, an active ester compound and an inorganic filler formed on the support, the nonvolatile layer in the first layer When the component is 100% by mass, the first layer containing 5% by mass or more of the active ester compound, and the second layer containing the epoxy resin, the active ester compound and the inorganic filler formed on the first layer. And when the non-volatile component in the said 2nd layer is 100 mass%, it has the 2nd layer whose active ester compound is 5 mass% or less, It is characterized by the above-mentioned. In addition, you may have a protective film in the exposed surface side of a 2nd layer in order to prevent adhesion of refuse etc.

  In the resin sheet with a support of the present invention, when the nonvolatile component in the first layer is 100% by mass, the active ester compound is 5% by mass or more, so that the dielectric loss tangent is lowered and the plating peel strength is improved. can do. And when the non-volatile component in a 2nd layer is 100 mass%, an active ester compound is 5 mass% or less, a thermal expansion coefficient is made low and the smear removal property in a carbon dioxide laser processing is made favorable. be able to. Therefore, the multilayer printed wiring board is excellent in interlayer conduction reliability, and is suitable as a resin sheet with a support for an insulating layer of the multilayer printed wiring board. Furthermore, it can be used more suitably as a resin sheet with a support for a buildup layer of a multilayer printed wiring board or a resin sheet with a support for forming a conductor layer by plating.

[Support]
Examples of the support of the present invention include plastic films and metal foils. Specifically, as the plastic film, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, acrylic, cyclic polyolefin, triacetyl cellulose, polyether sulfide, polyether ketone And polyimide. Among these, a polyethylene terephthalate film and a polyethylene naphthalate film are preferable, and an inexpensive polyethylene terephthalate film is particularly preferable. Examples of the metal foil include copper foil and aluminum foil. From the viewpoint of versatility, a plastic film is preferable, and when a plastic film is used, it is preferable to use a support having a surface that is in contact with the first layer, in order to improve releasability. The release agent used for the release treatment is not particularly limited as long as the first layer can be peeled from the support. For example, a silicon release agent, an alkyd resin release agent, a polyolefin resin, a urethane resin, A fluororesin etc. are mentioned. In addition, you may use the plastic film with a release layer marketed as a preferable thing, For example, SK-1, AL which is a PET film which has a release layer which has an alkyd resin type release agent as a main component, for example -5, AL-7 (manufactured by Lintec Corporation) and the like. Further, the plastic film may be subjected to mat treatment or corona treatment, and a release layer may be formed on the treated surface. On the other hand, the metal foil can be removed by an etching solution, or the metal foil may be used as a conductor layer without being removed. Although the thickness of a support body is not specifically limited, The range of 10-150 micrometers is preferable and the range of 25-50 micrometers is more preferable.

  When it has a protective film, the plastic film similar to a support body can be used. The protective film may be subjected to a surface treatment such as a mud treatment or a corona treatment, or may be subjected to a mold release treatment similar to the above. As for the thickness of a protective film, 3-30 micrometers is preferable.

[Resin composition]
The first layer and the second layer of the present invention are resin sheets formed by layering a resin composition. The resin composition can be used without particular limitation as long as it contains an epoxy resin, an active ester compound, and an inorganic filler. Further, a thermoplastic resin, a curing accelerator, and other components can be blended. Hereinafter, the blending components will be described.

(A) Epoxy resin Although it does not specifically limit as an epoxy resin used for this invention, It is preferable to contain the epoxy resin which has a 2 or more epoxy group in 1 molecule. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthol type epoxy resin, naphthalene Type epoxy resin, naphthylene ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, butadiene structure Epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halo Emissions epoxy resins. These may be used alone or in combination of two or more.

  Among these, from the viewpoint of improving heat resistance, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, glycidyl ester type epoxy resin An anthracene type epoxy resin and an epoxy resin having a butadiene structure are preferable. Specifically, for example, bisphenol A type epoxy resin (“Epicoat 828EL”, “YL980” manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (“jER806H”, “YL983U” manufactured by Mitsubishi Chemical Corporation), Naphthalene type bifunctional epoxy resin (“HP4032”, “HP4032D”, “HP4032SS”, “EXA4032SS” manufactured by DIC Corporation), naphthalene type tetrafunctional epoxy resin (“HP4700”, “HP4710” manufactured by DIC Corporation), Naphthol type epoxy resin (“ESN-475V” manufactured by Nippon Steel Chemical Co., Ltd.), epoxy resin having butadiene structure (“PB-3600” manufactured by Daicel Chemical Industries, Ltd.), epoxy resin having biphenyl structure (Nipponization) “NC3000H”, “NC3000L”, “NC31” manufactured by Yakuhin Co., Ltd. "00", "YX4000", "YX4000H", "YX4000HK", "YL6121") manufactured by Mitsubishi Chemical Corporation, anthracene type epoxy resin ("YX8800" manufactured by Mitsubishi Chemical Corporation), naphthylene ether type epoxy resin (DIC) “EXA-7310”, “EXA-7311”, “EXA-7311L”, “EXA7311-G3”), glycidyl ester type epoxy resin (“EX711”, “EX721” manufactured by Nagase ChemteX Corp.) ("R540" manufactured by Printec Co., Ltd.).

  The epoxy resin can improve the handleability of the resin sheet by including a liquid epoxy resin. Furthermore, it is preferable to use a liquid epoxy resin and a solid epoxy resin in combination. The liquid epoxy resin is preferably an aromatic epoxy resin having two or more epoxy groups in one molecule and a liquid at a temperature of 20 ° C. The solid epoxy resin has three or more epoxy groups in one molecule. And an aromatic epoxy resin that is solid at a temperature of 20 ° C. is preferable. In addition, the aromatic epoxy resin as used in the field of this invention means the epoxy resin which has an aromatic ring structure in the molecule | numerator. When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, the blending ratio (liquid epoxy resin: solid epoxy resin) is 1: The range of 0.1 to 1: 2 is preferable, the range of 1: 0.3 to 1: 1.8 is more preferable, and the range of 1: 0.6 to 1: 1.5 is still more preferable.

  The liquid epoxy resin is preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, glycidyl ester type epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene. A type epoxy resin is more preferable. You may use these 1 type or in combination of 2 or more types. Solid epoxy resins include tetrafunctional naphthalene type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, biphenyl type epoxy resins, and naphthylene ethers. Type epoxy resin is preferable, and naphthol type epoxy resin and biphenyl type epoxy resin are more preferable. You may use these 1 type or in combination of 2 or more types.

  From the viewpoint of reducing the linear thermal expansion coefficient of the cured product of the resin sheet, the content of the epoxy resin is preferably 3 to 40% by mass when the nonvolatile component in the first layer is 100% by mass. More preferably, it is 5-30 mass%, and it is still more preferable that it is 7-20 mass%. The same range is preferable for the second layer.

(B) Active ester compound The active ester compound used in the present invention is a compound having one or more active ester groups in one molecule. The active ester compound can react with an epoxy resin or the like, and a compound having two or more active ester groups in one molecule is preferable. In general, compounds having two or more ester groups with high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferably used. .

 From the viewpoint of improving heat resistance, an active ester compound obtained from a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound is more preferable. An active ester compound obtained by reacting a carboxylic acid compound with one or more selected from a phenol compound, a naphthol compound, and a thiol compound is more preferable. An aromatic compound having two or more active ester groups in one molecule obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group is even more preferable. And an aromatic compound obtained by reacting a compound having at least two or more carboxylic acids in one molecule with an aromatic compound having a phenolic hydroxyl group, and in one molecule of the aromatic compound. Especially preferred are aromatic compounds having two or more active ester groups. Further, it may be linear or multi-branched. In addition, if the compound having at least two carboxylic acids in one molecule is a compound containing an aliphatic chain, the compatibility with the resin composition can be increased, and if it is a compound having an aromatic ring, it is heat resistant. Sexuality can be increased.

 Specific examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Of these, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid and terephthalic acid are preferred, and isophthalic acid and terephthalic acid are more preferred from the viewpoint of heat resistance. Specific examples of the thiocarboxylic acid compound include thioacetic acid and thiobenzoic acid.

 Specific examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenol phthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, and o-cresol. , M-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone Phloroglucin, benzenetriol, dicyclopentadienyl diphenol, phenol novolac and the like. Among them, from the viewpoint of improving heat resistance and solubility, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5 -Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, phenol novolac are preferred, catechol, 1 , 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophene Non-tetrahydrobenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, and phenol novolak are more preferable. 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxy More preferred are hydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, phenol novolac, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadienyl diphenol, Phenol novolac is even more preferred, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthal Emissions, dicyclopentadienyl diphenol especially preferred, dicyclopentadienyl diphenol is particularly preferred. Specific examples of the thiol compound include benzenedithiol and triazinedithiol. The active ester compound may be used alone or in combination of two or more.

 Specifically, an active ester compound containing a dicyclopentadienyl diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of a phenol novolak, and an active ester compound containing a benzoylated product of a phenol novolak are preferred. Of these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadienyl diphenol structure are more preferred. Commercially available products include EXB9451, EXB9460, EXB9460S, HPC-8000-65T (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadienyl diphenol structure, and EXB9416-70BK as an active ester compound containing a naphthalene structure. (Manufactured by DIC Corporation), DC808 (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac, YLH1026 (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolac, Etc.

  The content of the active ester compound contained in the first layer is that the dielectric loss tangent is lowered and the plating peel strength is improved, and further, sufficient peel strength can be exhibited even when thermally cured with a support. Therefore, when the nonvolatile component in the first layer is 100% by mass, the content is 5% by mass or more. Preferably it is 5-30 mass%, More preferably, it is 5-25 mass%, More preferably, it is 5-20 mass%. On the other hand, the content of the active ester compound contained in the second layer lowers the linear thermal expansion coefficient and improves the smear removability in the carbon dioxide laser processing from 100% of the non-volatile component in the second layer. In the case of mass%, it is 5 mass% or less. Preferably it is 0-5 mass%, More preferably, it is 0.5-5 mass%, More preferably, it is 1-4 mass%.

  Moreover, when the number of epoxy groups of the (a) epoxy resin is 1, the reactive group number of the active ester compound (b) is preferably 0.2 to 2 from the viewpoint of improving the mechanical properties of the cured product. -1.5 is more preferable, and 0.4-1 is still more preferable. Here, “the number of epoxy groups of the epoxy resin” is a value obtained by totaling the values obtained by dividing the solid mass of each epoxy resin present in the resin composition by the epoxy equivalent for all epoxy resins. The “reactive group” means a functional group capable of reacting with an epoxy group, and the “reactive group number” means the solid content mass of the active ester compound present in the resin composition in terms of the reactive group equivalent. This is the sum of all the divided values.

(C) Inorganic filler Examples of the inorganic filler used in the present invention include silica, alumina, mica, mica, silicate, barium sulfate, magnesium hydroxide, and titanium oxide, and silica and alumina are preferable. In particular, silica such as amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica is preferable, and spherical silica and fused silica are more preferable. From the viewpoint of improving the filling property to the resin sheet, spherical fused silica is more preferable. These can use 1 type (s) or 2 or more types. Examples of commercially available spherical fused silica include “SOC2” and “SOC1” manufactured by Admatechs.

  Although the average particle diameter of the inorganic filler is not particularly limited, it is possible to suppress the occurrence of smear during drilling by increasing the total surface area of the inorganic filler from the viewpoint of forming fine wiring on the insulating layer. In view of the above, it is preferably 3 μm or less, more preferably 2 μm or less, still more preferably 1 μm or less, still more preferably 0.8 μm or less, and even more preferably 0.6 μm or less. On the other hand, when the resin composition is a varnish, it is preferably 0.01 μm or more, more preferably 0.03 μm or more, more preferably 0.07 μm, from the viewpoint of preventing the viscosity of the varnish from increasing and handling properties from decreasing. The above is more preferable, and 0.1 μm or more is even more preferable. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-950 manufactured by Horiba, Ltd. or the like can be used.

  The content of the inorganic filler is not particularly limited, but from the viewpoint of preventing the flexibility of the sheet form from being reduced, when the nonvolatile component in the first layer is 100% by mass, the content is 90% by mass or less. Preferably, 85 mass% or less is more preferable, and 80 mass% or less is still more preferable. The same range is preferable for the second layer. In addition, from the viewpoint of reducing the thermal expansion coefficient of the insulating layer, increasing the total surface area of the inorganic filler to suppress smearing during drilling, and making it easier to remove smear during roughening treatment, When the nonvolatile component in one layer is 100% by mass, 40% by mass or more is preferable, 50% by mass or more is more preferable, 60% by mass or more is further preferable, and 65% by mass or more is even more preferable. The same range is preferable for the second layer.

  The inorganic filler is preferably surface-treated with a surface treatment agent in order to improve moisture resistance and dispersibility. As the surface treatment agent, one or more selected from an epoxysilane coupling agent, an aminosilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an organosilazane compound, and a titanate coupling agent are preferable. . Of these, aminosilane coupling agents are preferred because of their excellent moisture resistance, dispersibility, and properties of cured products. Commercially available products include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" manufactured by Shin-Etsu Chemical Co., Ltd. ”(Phenyltrimethoxysilane),“ SZ-31 ”(hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

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

Carbon content per unit surface area of the inorganic filler, in terms of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is preferable in terms of preventing an increase in the melt viscosity of the resin varnish or the film form. Further preferred.

(D) Thermoplastic resin Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyethersulfone resin, and polysulfone resin, and phenoxy resin and polyvinyl acetal resin are preferable. A thermoplastic resin may be used individually by 1 type, or may use 2 or more types together.

  The polystyrene-reduced weight average molecular weight of the thermoplastic resin is preferably in the range of 8000 to 70000, more preferably in the range of 10,000 to 60000, and still more preferably in the range of 20000 to 60000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-reduced weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, And a phenoxy resin having one or more skeletons selected from a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, or may use 2 or more types together. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), “YX6954” (bisphenolacetophenone) manufactured by Mitsubishi Chemical Corporation. Skeleton-containing phenoxy resin), "YL7553" (fluorene skeleton-containing phenoxy resin), "FX280", "FX293" manufactured by Tohto Kasei Co., Ltd., "YL6794", "YL7213", "YL7290", "YL7290", " YL7482 "etc. are mentioned.

  Specific examples of the polyvinyl acetal resin include: Electric Butyral 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., S-Lec BH Series, BX Series manufactured by Sekisui Chemical Co., Ltd. KS series, BL series, BM series, etc. are mentioned.

  As for content of a thermoplastic resin, 0.5-15 mass% is preferable with respect to 100 mass% of non-volatile components in a 1st layer. The same range is preferable for the second layer.

(E) Curing accelerator Examples of the curing accelerator include organic phosphine compounds, imidazole compounds, amine adduct compounds, and tertiary amine compounds. The content of the curing accelerator is preferably used in the range of 0.01 to 3% by mass when the total of the nonvolatile components of the epoxy resin and the active ester compound is 100% by mass. A hardening accelerator may be used individually by 1 type, or may use 2 or more types together.

 The resin composition of the present invention further includes a curing agent such as phenol resin, cyanate ester resin, benzoxazine resin, a flame retardant such as phosphorus compound, metal hydroxide, silicon powder, nylon powder, fluorine powder, rubber particles, etc. Organic fillers, organic solvents, additives and the like can be appropriately blended.

  The resin composition of the present invention is appropriately mixed with the above components and, if necessary, kneaded or mixed by a kneading means such as a three-roll, ball mill, bead mill, or sand mill, or a stirring means such as a super mixer or a planetary mixer. By doing so, it can be produced as a resin varnish.

[First layer]
The first layer of the present invention can be produced as a resin composition layer in which a resin composition is formed on a support. The resin composition layer can be formed, for example, by preparing a resin composition containing an organic solvent, applying the resin composition on a support, drying and heating. The drying and heating conditions can be set as appropriate within a range of 1 to 60 minutes at 80 to 170 ° C, but preferably 1 to 30 minutes at 80 to 130 ° C.

  In order to reduce the dielectric loss tangent of the resin sheet and improve the plating peel strength, the thickness of the first layer is preferably 2 μm or more. More preferably, it is 2-50 micrometers, More preferably, it is 4-35 micrometers.

[Second layer]
The second layer of the present invention can be produced as a resin composition layer in which a resin composition is formed on the first layer. The drying conditions and the like can be appropriately set in the same manner as in the first layer.

  In order to reduce the thermal expansion coefficient of the resin sheet and improve the smear removability, the thickness of the second layer is preferably 2 μm or more. More preferably, it is 2-50 micrometers, More preferably, it is 4-35 micrometers.

[Production method of resin sheet with support]
Various methods can be used as a method for producing the resin sheet with a support. For example, a resin composition layer as a first layer can be formed on a support, a resin composition can be applied thereon, and a resin composition layer as a second layer can be formed by drying. Moreover, after producing what formed the resin composition layer which is the 1st layer on the support body, and what formed the resin composition layer which is the 2nd layer on another support body, respectively, each resin composition A method of laminating the layer surfaces by lamination is also mentioned. The conditions for laminating together are preferably a laminating temperature of 70 to 110 ° C., a laminating time of 5 to 30 seconds, and a laminating pressure of 1 to 10 kgf / cm ² . Further, while applying the resin composition on the support, another resin composition may be simultaneously applied thereon and then dried to simultaneously produce the first layer and the second layer.

 The ratio of the thickness of the first layer and the second layer can be appropriately set according to the required performance, but is preferably 1: 9 to 9: 1, and is 3: 7 to 7: 3. Is more preferable.

[Multilayer printed wiring board using resin sheet with support]
Hereinafter, an example of the manufacturing method of the multilayer printed wiring board using the resin sheet with a support body of this invention is explained in full detail.

 In the method for producing a multilayer printed wiring board of the present invention, (A) a step of laminating a resin sheet with a support on one or both sides of an inner circuit board, (B) an insulating layer by thermosetting the resin sheet with a support Forming step, (C) forming a via hole by drilling in the insulating layer, (D) removing the support, (E) roughening the surface of the insulating layer, (F) after the roughing treatment A step of plating the surface of the insulating layer to form a conductor layer, and the like.

 (A) In the step of laminating the resin sheet with a support on one or both sides of the inner layer circuit board (step (A)), the second layer of the resin sheet with the support is on the inner layer circuit board side, and one side of the inner layer circuit board Or laminate on both sides. As used herein, the inner layer circuit board refers to a conductive layer patterned (circuit formed) on one or both sides of a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, or a thermosetting polyphenylene ether board. And an intermediate product in which an insulating layer and a conductor layer are to be formed when a multilayer printed wiring board is manufactured. In addition, it is preferable from the viewpoint of improving the adhesion between the insulating layer and the inner circuit board that the surface of the conductor layer has been previously roughened by blackening or the like.

In the step (A), when the resin sheet with a support has a protective film, the protective film is removed, and then the resin sheet with the support and the inner layer circuit board are preheated as necessary, with the support. The resin sheet is pressed against the inner circuit board while being pressurized and heated. In the resin sheet with a support of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used. Lamination conditions are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., and the pressure bonding pressure (laminating pressure) is preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ), the pressure bonding time (laminating time) is preferably 5 to 180 seconds, and the lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch method or a continuous method using a roll. The vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Meiki Seisakusho Co., Ltd., a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.

 (B) In the step of thermally curing the resin sheet with a support to form an insulating layer (step (B)), the resin sheet with the support is laminated on the inner circuit board, and then the inner layer is formed by thermosetting the resin sheet. An insulating layer (cured product) can be formed on the circuit board. The thermosetting conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. to 210 ° C. It is selected in the range of 30 to 120 minutes at ° C. Further, by thermosetting without peeling off the support, it is possible to prevent adhesion of foreign matters such as dust and dust during thermosetting.

  The resin sheet is thermally cured to form an insulating layer, and the linear thermal expansion coefficient of the insulating layer is preferably 25 ppm or less, and more preferably 20 ppm or less. The lower limit is not particularly limited, but is generally 4 ppm. Thereby, distortion with a buildup layer and wiring can be prevented and a highly reliable multilayer printed wiring board can be obtained.

  The resin sheet is thermally cured to form an insulating layer, and the dielectric loss tangent (measurement frequency 5.8 GHz) of the insulating layer is preferably 0.0065 or less, and 0.006 or less is more preferably a lower limit, although not particularly limited. Generally, it is 0.001. Thereby, a multilayer printed wiring board with little electric signal loss can be obtained.

 (C) In the step of forming a via hole by drilling the insulating layer (step (C)), the via hole is formed by drilling the insulating layer. The drilling can be performed by a known method such as drilling, laser, or plasma, or a combination of these methods if necessary. However, drilling by a laser such as a carbon dioxide laser or YAG laser is preferable and versatile. In view of the above, a carbon dioxide laser is more preferable.

  When forming a via hole with a carbon dioxide laser, the number of shots is usually selected from 1 to 5 shots, although it depends on the depth and hole diameter of the via hole to be formed. In order to increase the processing speed of the via hole and improve the productivity of the multilayer printed wiring board, it is better that the number of shots is small, and the number of shots is preferably 1 to 3. When processing with a plurality of shots, a burst mode that is continuous shots or a cycle mode that is a plurality of shots with time intervals may be used.

  The pulse width of the carbon dioxide laser is not particularly limited, and can be selected in a wide range from a middle range of 28 μs to a short pulse of 4 μs. From the viewpoint of efficiency, 10 μs to 26 μs is more preferable.

 When drilling with a carbon dioxide laser, in the resin sheet with a support of the present invention, it is preferable to adjust the laser energy to 0.1 to 3 W from the viewpoint of improving smear removability. It is more preferable to adjust to 2W.

  Since the resin sheet with a support of the present invention has improved smear removability, good drilling can be achieved even if the top diameter (diameter) of the via hole in the insulating layer is made small in order to reduce the thickness of the multilayer printed wiring board. Processing is possible. Specifically, in step (C), the top diameter (diameter) of the via hole in the insulating layer is preferably 65 μm or less, more preferably 60 μm or less, and even more preferably 55 μm or less. On the other hand, the top diameter (diameter) of the via hole is preferably set to 15 μm or more in order to prevent the roughening process in the via hole from being difficult to be performed.

 (D) In the step of peeling the support (step (D)), the support is peeled off. When the substrate is a plastic film, the substrate can be peeled by mechanical removal with a manual or automatic peeling device. When the substrate is a metal foil, the metal foil can be peeled and removed by dissolving the metal foil with an etching solution or the like. In addition, although (D) process may be performed before (C) process and may be performed after (C) process, from the point of smear removal improvement, (C) process is changed to (D) process. Preferably it is done before.

  (E) In the step of roughening the surface of the insulating layer (step (E)), the surface of the insulating layer is roughened after peeling off the support. In the case of dry-type roughening treatment, plasma treatment or the like can be mentioned. It is done. The wet roughening treatment is preferable in that smear in the via hole can be removed while forming an uneven anchor on the surface of the insulating layer.

  The swelling treatment with the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 to 80 ° C. for 5 to 20 minutes (preferably at 55 to 70 ° C. for 8 to 15 minutes). Examples of the swelling liquid include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Securiganth P (Swelling Dip Securiganth S) and Swelling Dip Securiganth SBU (ABUTEC Japan). be able to.

  The roughening treatment with an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60 to 80 ° C. for 10 to 30 minutes (preferably at 70 to 80 ° C. for 15 to 25 minutes). Examples of the oxidizing agent include alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. it can. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by weight. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact CP and Dosing Solution Securigans P manufactured by Atotech Japan.

  The neutralization treatment with the neutralizing solution is performed by immersing in a neutralizing solution at 30 to 50 ° C. for 3 to 10 minutes (preferably at 35 to 45 ° C. for 3 to 8 minutes). As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, Reduction Solution / Secligant P manufactured by Atotech Japan Co., Ltd. may be mentioned.

  The surface roughness after heat-curing the resin sheet to form an insulating layer and roughening the surface of the insulating layer has an arithmetic average roughness (Ra) of 150 nm or less in order to improve the formation of fine wiring. Is preferable, and it is more preferably 100 nm or less. The lower limit value of the arithmetic average roughness (Ra) is not limited, but is generally 10 nm or more. The root mean square roughness (Rq) is preferably 220 nm or less, more preferably 200 nm or less, even more preferably 150 nm or less, and even more preferably 100 nm or less. The lower limit value of the root mean square roughness (Rq) is not limited, but is generally 20 nm or more. Since the root mean square roughness (Rq) reflects the local state of the insulating layer surface, it can be confirmed that the surface of the insulating layer is denser and smoother by grasping Rq.

  (F) In the step of forming the conductor layer by plating on the surface of the insulating layer after the roughening treatment ((F step)), the conductor layer can be formed on the surface of the insulating layer. As a method for forming the plating, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. As wet plating, a method of forming a conductor layer by combining electroless plating and electrolytic plating after the roughening treatment, a method of forming a plating resist having a pattern opposite to that of the conductor layer, and forming the conductor layer only by electroless plating , Etc. As a subsequent pattern formation method, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.

  The peel strength between the insulating layer and the conductor layer obtained by thermosetting the resin sheet to form an insulating layer, roughening the surface of the insulating layer, and plating is preferably 0.5 kgf / cm or more. The upper limit is not particularly limited, but is generally 1.2 kgf / cm.

  By repeating the above-described series of steps a plurality of times, a multilayer printed wiring board in which build-up layers are laminated in multiple stages is obtained. In the present invention, although it has a low dielectric loss tangent and linear thermal expansion coefficient, it is excellent in smear removability and plating peel strength, so it can be suitably used as a resin sheet with a support for a buildup layer of a multilayer printed wiring board. Can do.

<Semiconductor device>
A semiconductor device can be manufactured by using the multilayer printed wiring board manufactured by the method of the present invention. A semiconductor device can be manufactured by mounting a semiconductor chip in a conductive portion of the multilayer printed wiring board of the present invention. The “conduction location” is a “location where an electrical signal is transmitted in a multilayer printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

    EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, “part” means “part by mass”.

  First, measurement methods and evaluation methods in the physical property evaluation in this specification will be described.

<Preparation of samples for measurement of arithmetic average roughness (Ra value), root mean square roughness (Rq value), peel strength>
(1) Underlayer treatment of inner layer circuit board Both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Works R5715ES) on which an inner layer circuit is formed The copper surface was roughened by etching 1 μm with CZ8100 manufactured by MEC Co., Ltd.

(2) Lamination of resin sheet with support Using the batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Co., Ltd.) as an inner layer circuit, the resin sheets with support prepared in Examples and Comparative Examples were used. Laminated on both sides of the substrate. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding for 30 seconds at 100 ° C. and a pressure of 0.74 MPa.

(3) Curing of Resin Composition The laminated adhesive film was continuously cured at 80 ° C. for 30 minutes under the curing conditions of 170 ° C. for 30 minutes to form an insulating layer.

(4) Via hole formation Using a CO ₂ laser processing machine (LC-2E21B / 1C) manufactured by Hitachi Via Mechanics, mask diameter 1.60 mm, focus offset value 0.050, pulse width 25 μs, power 0.66 W, The insulating layer was drilled under the conditions of aperture 13, number of shots 2 and burst mode to form a via hole having a top diameter (diameter) of 50 μm on the surface of the insulating layer. Thereafter, the PET film was peeled off.

(5) Roughening treatment The inner layer circuit board on which the insulating layer is formed is a swelling liquid, diethylene glycol monobutyl ether-containing swelling dip securigant P (glycol ethers, aqueous solution of sodium hydroxide) of Atotech Japan Co., Ltd. Immerse at 60 ° C for 10 minutes, and then as a roughening solution, immerse in Atotech Japan's Concentrate Compact P (KMnO4: 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C for 20 minutes. As a neutralizing solution, it was immersed in Atotech Japan Co., Ltd. Reduction Sholyshin Securigant P (aqueous solution of sulfuric acid) at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 30 minutes. This substrate was designated as evaluation substrate A.

(6) Plating by semi-additive method Evaluation board A was immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C. for 20 minutes. After annealing for 30 minutes at 150 ° C., an etching resist was formed. After pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm. Next, annealing was performed at 200 ° C. for 60 minutes. This substrate was designated as evaluation substrate B.

<Measurement and Evaluation of Arithmetic Average Roughness (Ra Value) and Root Mean Square Roughness (Rq Value)>
Using a non-contact type surface roughness meter (WYKO NT3300, manufactured by Bee Coins Instruments Co., Ltd.), Ra value and Rq value are obtained from numerical values obtained with a measurement range of 121 μm × 92 μm using a 50 × lens. It was. Each was measured by determining the average value of 10 points selected at random. The evaluation is as follows.
○: Ra value is 150 nm or less ×: Ra value is greater than 150 nm ○: Rq value is 220 nm or less ×: Rq value is greater than 220 nm

<Measurement and Evaluation of Peeling Strength (Peel Strength) of Plating Conductor Layer>
Cut the 10mm width and 100mm length into the conductor layer of the evaluation board B, peel off one end and grasp it with a gripping tool (TSE Co., Ltd., Autocom type testing machine AC-50C-SL). The load (kgf / cm) when 35 mm was peeled off in the vertical direction at a speed of 50 mm / min at room temperature was measured. The evaluation is as follows.
○: Peel strength is 0.5 kgf / cm or more ×: Peel strength is less than 0.5 kgf / cm

<Evaluation of smear removability at the bottom of via hole>
The periphery of the via hole bottom was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the via hole bottom was measured from the obtained image. The evaluation is as follows.
○: Maximum smear length is less than 3 μm ×: Maximum smear length is 3 μm or more

<Measurement and evaluation of linear thermal expansion coefficient>
The resin sheet with a support obtained in Examples and Comparative Examples was thermally cured by heating at 200 ° C. for 90 minutes, and a sheet-like cured product was obtained by peeling the PET film. The cured product was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer Thermo Plus TMA8310 (manufactured by Rigaku Corporation). After mounting the test piece on the apparatus, the test piece was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. The average linear thermal expansion coefficient (ppm) from 25 ° C. to 150 ° C. in the second measurement was calculated. The evaluation is as follows.
○: Average linear thermal expansion coefficient is less than 20 ppm Δ: Average linear thermal expansion coefficient is 20 ppm or more and 25 ppm or less
X: Average linear thermal expansion coefficient is larger than 25 ppm

<Measurement and evaluation of dielectric loss tangent>
The resin sheet with a support obtained in Examples and Comparative Examples was cured by heating at 200 ° C. for 90 minutes, and the support was peeled to obtain a sheet-like cured product. The cured product was cut into a length of 80 mm and a width of 2 mm and used as an evaluation sample. The dielectric loss tangent of this evaluation sample was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using an HP 8362B apparatus manufactured by Agilent Technologies. Two test pieces were measured, and the average value was calculated. The evaluation is as follows.
○: Dissipation factor is 0.0065 or less ×: Dissipation factor is greater than 0.0065

<Adjustment of resin varnish 1>
5 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type), crystalline bifunctional epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation) , Epoxy equivalent of about 185), 10 parts of biphenyl type epoxy resin (“NC3000H” manufactured by Nippon Kayaku Co., Ltd.), phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK solution having a solid content of 30% by mass) 10 parts were dissolved by heating in 30 parts of solvent naphtha with stirring. After cooling to room temperature, 40 parts of an active ester compound (“HPC8000-65T” manufactured by DIC Corporation, a toluene solution having a nonvolatile content of 65% by mass with an active group equivalent of about 223), a curing accelerator (4-dimethylamino) 7 parts of pyridine, MEK solution having a solid content of 2% by mass, flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd.), 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phos 2 parts of faphenanthrene-10-oxide (average particle size 2 μm), spherical silica (average particle size 0.5 μm) surface-treated with a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) , “SOC2” manufactured by Admatechs Co., Ltd., 160 parts of carbon per unit area 0.39 mg / m ² , were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 1. The active ester compound was 12% by mass.

<Adjustment of resin varnish 2>
5 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type), crystalline bifunctional epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation) , Epoxy equivalent of about 185), 10 parts of biphenyl type epoxy resin (“NC3000H” manufactured by Nippon Kayaku Co., Ltd.), phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK solution having a solid content of 30% by mass) 10 parts were dissolved by heating in 30 parts of solvent naphtha with stirring. After cooling to room temperature, 20 parts of an active ester compound (“HPC8000-65T” manufactured by DIC Corporation, a toluene solution having a nonvolatile content of 65% by mass with an active group equivalent of about 223), a naphthol-based curing agent (hydroxyl group equivalent of 215) 12 parts of MEK solution with a solid content of 60%, manufactured by Nippon Steel Chemical Co., Ltd., 4 parts of curing accelerator (4-dimethylaminopyridine, MEK solution with a solid content of 2% by mass), flame retardant (“Sanko Co., Ltd.“ HCA-HQ ”, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm) 2 parts , Spherical silica (average particle size 0.5 μm, Admatex Co., Ltd. “SOC2”, carbon per unit area, surface-treated with a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) Quantity 0. The resin varnish 2 was prepared by mixing 150 parts of 39 mg / m ² ) and uniformly dispersing with a high-speed rotary mixer. The active ester compound was 6.5% by mass.

<Adjustment of resin varnish 3>
5 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type), crystalline bifunctional epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation) , Epoxy equivalent of about 185), 10 parts of biphenyl type epoxy resin (“NC3000H” manufactured by Nippon Kayaku Co., Ltd.), phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK solution having a solid content of 30% by mass) 10 parts were dissolved by heating in 30 parts of solvent naphtha with stirring. After cooling to room temperature, 10 parts of an active ester compound (“HPC8000-65T” manufactured by DIC Corporation, a toluene solution having a nonvolatile content of 65% by mass with an active group equivalent of about 223), a triazine-containing phenolic curing agent (hydroxyl group) Equivalent 146, 10 parts of MEK solution with 60% solid content of “LA-1356” manufactured by DIC Corporation), 3 parts of curing accelerator (4-dimethylaminopyridine, 2% by weight MEK solution with solid content), flame retardant ( “HCA-HQ” manufactured by Sanko Co., Ltd., 2 parts of 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm), Spherical silica surface treated with a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle size 0.5 μm, “SOC2” manufactured by Admatechs Co., Ltd.) -Bon amount 0.39 mg / m ² ) 140 parts were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish 3. The active ester compound was 3.6% by mass.

<Example 1>
(Preparation of resin sheet 1 with support)
Resin varnish 1 is applied with a die coater on the release surface of ETFE-treated release PET ("Fluoroge RL50KSE" manufactured by Mitsubishi Plastics Co., Ltd., thickness 50 μm) so that the resin composition layer thickness after drying is 15 μm. And dried at 100 ° C. for 1 minute. Furthermore, the resin varnish 3 is applied on the resin composition layer with a die coater so that the total thickness of the resin composition layer after drying is 30 μm, and dried at 80 to 120 ° C. (average 100 ° C.) for 4 minutes. Then, the smooth surface side of a 15 μm thick polypropylene cover film (“Alphan MA-411” manufactured by Oji Specialty Paper Co., Ltd.) is bonded to the resin surface, and the release PET / resin composition layer 1 / resin composition layer 3 / A resin sheet with a support having a structure of a cover film was obtained.

<Example 2>
(Preparation of resin sheet 2 with support)
In the same manner as in Example 1, a resin sheet with a support having a structure of release PET / resin composition layer 2 / resin composition layer 3 / cover film was obtained.

<Comparative Example 1>
(Preparation of resin sheet 3 with support)
Except that the resin varnish 1 was applied with a die coater on the release PET so that the resin composition layer thickness after drying was 30 μm and dried at 80 to 120 ° C. (average 100 ° C.) for 5 minutes, In the same manner as in Example 1, a resin sheet with a support having a structure of release PET / resin composition layer 1 / cover film was obtained.

<Comparative example 2>
(Preparation of resin sheet 4 with support)
Except that the resin varnish 2 was applied with a die coater so that the resin composition layer thickness after drying was 30 μm on the release PET and dried at 80 to 120 ° C. (average 100 ° C.) for 5 minutes, In the same manner as in Example 1, a resin sheet with a support having a structure of release PET / resin composition layer 2 / cover film was obtained.

<Comparative Example 3>
(Preparation of resin sheet 5 with support)
Except that the resin varnish 3 was applied with a die coater so that the resin composition layer thickness after drying was 30 μm on the release PET and dried at 80 to 120 ° C. (average 100 ° C.) for 5 minutes, In the same manner as in Example 1, a resin sheet with a support having a structure of release PET / resin composition layer 3 / cover film was obtained.

  The evaluation results are shown in Table 1.

 As is clear from the results in Table 1, the resin sheets with supports of Examples 1 and 2 have excellent characteristics. On the other hand, in Comparative Examples 1 and 2, the smear removability was poor. In Comparative Example 3, the surface roughness was large, the peel strength was low, and the dielectric loss tangent was also large.

 In the present invention, it has become possible to provide a resin sheet with a support excellent in smear removability and plating peel strength despite having a low dielectric loss tangent and linear thermal expansion coefficient. Furthermore, a multilayer printed wiring board and a semiconductor device using the same can be provided. Furthermore, electric products such as computers, mobile phones, digital cameras, and televisions, and vehicles such as motorcycles, automobiles, trains, ships, and airplanes equipped with these can be provided.

Claims (13)

A support;
When the first layer is formed on the support and contains an epoxy resin, an active ester compound, and an inorganic filler, and the nonvolatile component in the first layer is 100% by mass, the active ester compound is 5 %. A first layer of from 30% to 30% by weight ;
A second layer containing an epoxy resin, an active ester compound and an inorganic filler formed on the first layer, wherein the active ester compound is 100% by mass when the nonvolatile component in the second layer is 100% by mass. A second layer that is 5% by weight or less;
A resin sheet with a support, comprising:   The resin sheet with a support according to claim 1, wherein the inorganic filler has an average particle size of 0.01 to 3 µm.   Content of the said inorganic filler is 40-90 mass%, The resin sheet with a support body of Claim 1 or 2 characterized by the above-mentioned.   The resin sheet with a support according to claim 1, wherein the inorganic filler is surface-treated with a surface treatment agent. The resin sheet with a support according to claim 4, wherein an amount of carbon per unit surface area of the inorganic filler is 0.02 to 1 mg / m ² .   The thickness of the said 2nd layer is 2 micrometers or more, The resin sheet with a support body of any one of Claims 1-5 characterized by the above-mentioned.   The resin sheet with a support according to any one of claims 1 to 6, wherein the resin sheet is thermoset to form an insulating layer, and the coefficient of linear thermal expansion of the insulating layer is 25 ppm or less. .   The resin sheet is thermally cured to form an insulating layer, and a dielectric loss tangent (measurement frequency: 5.8 GHz) of the insulating layer is 0.0065 or less. The resin sheet with a support as described.   The resin sheet is thermally cured to form an insulating layer, and the arithmetic average roughness (Ra) after roughening the surface of the insulating layer is 150 nm or less, and the root mean square roughness (Rq) is 220 nm or less. It is, The resin sheet with a support body of any one of Claims 1-8 characterized by the above-mentioned.   The resin sheet is thermally cured to form an insulating layer, the surface of the insulating layer is roughened, and the peel strength between the conductive layer obtained by plating and the insulating layer is 0.5 kgf / cm or more. The resin sheet with a support according to any one of claims 1 to 9.   It is a resin sheet with the support body for insulating layers of a multilayer printed wiring board, The resin sheet with a support body of any one of Claims 1-10 characterized by the above-mentioned.   It is a resin sheet with a support body for buildup layers of a multilayer printed wiring board, The resin sheet with a support body of any one of Claims 1-11 characterized by the above-mentioned. (A) A step of laminating the resin sheet with a support according to any one of claims 1 to 12 on one side or both sides of an inner circuit board,
(B) a step of thermosetting the support-attached resin sheet to form an insulating layer;
(C) forming a via hole by drilling in the insulating layer;
(D) a step of peeling the support,
(E) a step of roughening the surface of the insulating layer;
(F) a step of plating the surface of the insulating layer after the roughening treatment to form a conductor layer;
A method for producing a multilayer printed wiring board containing
(C) In the step of forming a via hole by drilling a hole in the insulating layer, the top diameter (diameter) of the via hole in the insulating layer is 65 μm or less.