JP2014007403A - Method for manufacturing multilayer printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a multilayer printed wiring board capable of reducing a dielectric dissipation factor of an insulating layer and a root mean square roughness Rq of a surface of the insulating layer after roughening treatment despite the fact that smear after roughening treatment in a via hole of the insulating layer can be suppressed.SOLUTION: There is provided a method for manufacturing a printed wiring board including specific steps in which a resin composition containing an epoxy resin, an active ester compound, and an inorganic filler is used.

Description

  The present invention relates to a method for manufacturing a multilayer printed wiring board.

  In recent years, electronic devices have become smaller and higher in performance, and in multilayer printed wiring boards, the build-up layer has been multilayered, miniaturization and higher density of wiring are required, and dielectrics are also required to reduce transmission loss. There is a need for an insulating material having a low tangent.

  Patent Document 1 discloses a method of manufacturing a multilayer printed wiring board by irradiating an insulating layer containing 35% by mass or more of an inorganic filler with a carbon dioxide laser from above a plastic film. However, smear, dielectric loss tangent, and root mean square roughness Rq are not disclosed or directed at all.

International Publication No. 2009/0666759

  When drilling an insulating layer of a multilayer printed wiring board, smear (resin residue) is generated in the via hole, and it is necessary to remove the smear in the roughening process. However, according to the knowledge of the present inventors, when a multilayer printed wiring board was produced using a low dielectric loss tangent resin composition containing an active ester compound, the inside of the via hole was roughened after the insulating layer was drilled. Even so, a new problem has arisen that it is difficult to remove smear (resin residue) in the via hole. Further, if the roughening treatment conditions are increased to remove these smears, the problem that the surface of the insulating layer becomes too rough occurs.

  Therefore, the problem to be solved by the present invention is to reduce the dielectric loss tangent of the insulating layer and reduce the roughness after the roughening treatment, although the smear after the roughening treatment in the via hole of the insulating layer can be suppressed. An object of the present invention is to provide a method for manufacturing a multilayer printed wiring board that can reduce the root mean square roughness Rq of the surface of the insulating layer.

  As a result of earnest research to solve the above problems, the present inventor has adopted a method for producing a printed wiring board having specific steps in a resin composition containing an epoxy resin, an active ester compound and an inorganic filler. The present invention has been completed.

That is, the present invention includes the following contents.
[1] (A) A step of laminating a resin composition sheet with a base so that the resin composition layer is in contact with both sides or one side of the circuit board,
(B) a step of thermally curing the resin composition layer to form an insulating layer;
(C) forming a via hole by drilling from above the base material on the surface of the insulating layer;
(D) a step of peeling the substrate;
(E) a step of roughening the surface of the insulating layer;
In a method for producing a multilayer printed wiring board containing
The resin composition layer contains an epoxy resin, an active ester compound and an inorganic filler,
The method for producing a multilayer printed wiring board, wherein the root mean square roughness Rq of the surface of the insulating layer after the roughening treatment is 500 nm or less.
[2] The method for producing a multilayer printed wiring board according to the above [1], wherein the epoxy resin is 1 to 40% by mass when the nonvolatile component in the resin composition is 100% by mass.
[3] The multilayer printed wiring board according to [1] or [2], wherein the active ester compound is 3 to 40% by mass when the nonvolatile component in the resin composition is 100% by mass. Production method.
[4] The multilayer print as described in any one of [1] to [3] above, wherein the inorganic filler is 30 to 85% by mass when the nonvolatile component in the resin composition is 100% by mass. A method for manufacturing a wiring board.
[5] The multilayer print according to any one of the above [1] to [4], wherein the inorganic filler is 55 to 85% by mass when the nonvolatile component in the resin composition is 100% by mass. A method for manufacturing a wiring board.
[6] The method for producing a multilayer printed wiring board according to any one of [1] to [5], wherein the inorganic filler has an average particle size of 0.01 to 2 μm.
[7] The method for producing a multilayer printed wiring board according to any one of [1] to [6], wherein the inorganic filler has a carbon amount per unit weight of 0.02 to 3%.
[8] The method for producing a multilayer printed wiring board according to any one of [1] to [7], wherein the resin composition layer further contains a smear suppressing component.
[9] The method for producing a multilayer printed wiring board according to any one of [1] to [8], wherein the substrate is a plastic film.
[10] The method for producing a multilayer printed wiring board according to any one of [1] to [9], wherein the thickness of the substrate is 10 to 150 μm.
[11] The method for producing a multilayer printed wiring board according to any one of [1] to [10], wherein the dielectric tangent of the insulating layer is 0.05 or less.
[12] The method for producing a multilayer printed wiring board according to any one of [1] to [11], wherein the top diameter (diameter) of the via hole is 70 μm or less.
[13] The multilayer print according to any one of [1] to [12] above, wherein an opening ratio of the via hole (the diameter of the bottom of the via hole / the top diameter (diameter) of the via hole) is 70 to 100%. A method for manufacturing a wiring board.
[14] The multilayer printed wiring according to any one of [1] to [13], wherein in the step of roughening treatment, the roughening treatment with an oxidizing agent is performed at 60 to 80 ° C. for 10 to 30 minutes. A manufacturing method of a board.
[15] The multilayer printed wiring according to any one of [1] to [14], further comprising (F) a step of plating the surface of the insulating layer after the roughening treatment to form a conductor layer A manufacturing method of a board.
[16] The method for producing a multilayer printed wiring board according to the above [15], wherein the peel strength between the conductor layer and the insulating layer is 0.35 kgf / cm or more.
[17] A semiconductor device using a multilayer printed wiring board manufactured by the method according to any one of [1] to [16].

  In a resin composition containing an epoxy resin, an active ester compound and an inorganic filler, by adopting a method for producing a printed wiring board having a specific process, smearing after roughening treatment in the via hole of the insulating layer is suppressed. In spite of this, it is possible to provide a method for manufacturing a printed wiring board in which the dielectric loss tangent of the insulating layer can be lowered and the root mean square roughness Rq of the surface of the insulating layer after the roughening treatment can be reduced. Became.

The present invention
(A) A step of laminating a resin composition sheet with a substrate so that the resin composition layer is in contact with both sides or one side of the circuit board,
(B) a step of thermally curing the resin composition layer to form an insulating layer;
(C) forming a via hole by drilling from above the base material on the surface of the insulating layer;
(D) a step of peeling the substrate;
(E) a step of roughening the surface of the insulating layer;
In a method for producing a multilayer printed wiring board containing
The resin composition layer contains an epoxy resin, an active ester compound and an inorganic filler,
The method for producing a multilayer printed wiring board, wherein the root mean square roughness Rq of the surface of the insulating layer after the roughening treatment is 500 nm or less,
It is.

<(A) Process>
(A) A process is a process of laminating | stacking a resin composition sheet | seat with a base material so that the resin composition layer may touch the both surfaces or single side | surface of a circuit board. In the resin composition sheet with a substrate of the present invention, a resin composition layer is formed on a substrate. The resin composition layer is formed using a resin composition containing (a) an epoxy resin, (b) an active ester compound, and (c) an inorganic filler. Details will be described below.

[Resin composition]
(A) Epoxy resin Although it does not specifically limit as (a) 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, bisphenol A type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy from the viewpoint of improving heat resistance, insulation reliability, and adhesion to metal foil. Resins, glycidyl ester type epoxy resins, anthracene type epoxy resins, and epoxy resins having a butadiene structure are preferred. 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 Toto Kasei Co., Ltd.), epoxy resin having a butadiene structure (“PB-3600” manufactured by Daicel Chemical Industries, Ltd.), biphenyl type epoxy resin (Nippon Kayaku Co., Ltd.) "NC3000H", "NC3000L", "NC3100", Mitsubishi Chemical "YX4000", "YX4000H", "YX4000HK", "YL6121"), anthracene type epoxy resin (Mitsubishi Chemical Corporation "YX8800"), naphthylene ether type epoxy resin (DIC Corporation) “EXA-7310”, “EXA-7311”, “EXA-7311L”, “EXA7311-G3”), glycidyl ester type epoxy resin (“EX711”, “EX721” manufactured by Nagase ChemteX Corporation), Purin Co., Ltd. Tech "R540").

  In particular, when the resin composition is made into a sheet form, it has moderate flexibility and excellent handleability, so that it has two or more epoxy groups in one molecule and is a liquid fragrance at a temperature of 20 ° C. It is preferable to contain a group epoxy resin (hereinafter referred to as “liquid epoxy resin”). Further, in terms of improving smear suppression, the liquid epoxy resin and three or more epoxy groups in one molecule and a solid aromatic epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 20 ° C. )) In combination. 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 an epoxy resin is used, a liquid epoxy resin is preferable in terms of having an appropriate flexibility when the resin composition is used in the form of an adhesive film. When a solid epoxy resin is used, a cured product of the resin composition is appropriate. Is preferable in that it has a high breaking strength. When the liquid epoxy resin and the solid epoxy resin are used in combination, the blending ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1: 0.1 to 1:15 by mass ratio, and 1: 0.1 A range of ˜1: 2 is more preferred, a range of 1: 0.3 to 1: 1.8 is still more preferred, and a range of 1: 0.6 to 1: 1.5 is even more preferred.

  In the resin composition of the present invention, from the viewpoint of improving the cured properties of the resin composition, when the nonvolatile component in the resin composition is 100% by mass, the epoxy resin content is preferably 40% by mass or less, 35 The mass% or less is more preferable, and 30 mass% or less is still more preferable. 1 mass% or more is preferable, as for the minimum of content of an epoxy resin, 3 mass% or more is more preferable, and 5 mass% or more is still more preferable. In one embodiment, the content of the epoxy resin in the resin composition is preferably 1 to 40% by mass, more preferably 3 to 40% by mass, when the nonvolatile component in the resin composition is 100% by mass. 35 mass% is still more preferable, and 5-30 mass% is still more preferable. In particular, when the resin composition is made into a sheet form, it has moderate flexibility and is excellent in handleability, so the content of the liquid epoxy resin is 100% by mass of the nonvolatile component in the resin composition. In this case, 1 to 25% by mass is preferable, 5 to 20% by mass is more preferable, and 10 to 20% by mass is still more preferable.

(B) Active ester compound The (b) active ester compound in the present invention is a compound having one or more active ester groups in one molecule, lowers the dielectric loss tangent of the resin composition, and sets the root mean square roughness Rq. Can be small. (B) 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 by 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 carboxylic acid compound having at least two or more carboxy groups 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. Further, if the carboxylic acid compound having at least two or more carboxy groups in a molecule is a compound containing an aliphatic chain, the compatibility with the resin composition can be increased, and any compound having an aromatic ring can be used. Heat resistance 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, dicyclopentadienyldiphenol, 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.

  More specifically, the active ester compound containing a dicyclopentadienyl diphenol structure includes a compound represented by the following formula (1).

(In the formula, R represents a phenyl group or a naphthyl group, k represents 0 or 1, and n represents an average number of repeating units of 0.05 to 2.5.)

  From the viewpoint of reducing the dielectric loss tangent and improving the heat resistance, R is preferably a naphthyl group, k is preferably 0, and n is preferably 0.25 to 1.5.

  (B) As an active ester compound, the active ester compound currently disclosed by Unexamined-Japanese-Patent No. 2004-277460 may be used, and a commercially available active ester compound can also be used. Specific examples of commercially available active ester compounds include an active ester curing agent containing a dicyclopentadienyl structure, an active ester curing agent containing a naphthalene structure, and an active ester curing containing an acetylated product of phenol novolac. An active ester type curing agent containing a benzoylated product of a phenol novolac is preferable, and an active ester type curing agent containing a naphthalene structure and an active ester type curing agent containing a dicyclopentadienyl diphenol structure are more preferable. EXB9451, EXB9460, EXB9460S, HPC-8000-65T (manufactured by DIC Corporation) as an active ester type curing agent containing a dicyclopentadienyl diphenol structure, EXB9416-70BK as an active ester type curing agent containing a naphthalene structure ( DIC Corporation), DC808 (manufactured by Mitsubishi Chemical Corporation) as an active ester-based curing agent containing an acetylated product of phenol novolac, and YLH1026 (Mitsubishi Chemical Corporation) as an active ester-based curing agent containing a benzoylated product of phenol novolac. Manufactured), and the like.

  (B) The content of the active ester compound is preferably 40% by mass or less when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of improving heat resistance and further suppressing the occurrence of smear. More preferably, it is more preferably 30% by mass or less, still more preferably 25% by mass or less. On the other hand, from the viewpoint of improving the peel strength, when the nonvolatile component in the resin composition is 100% by mass, it is preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 7% by mass or more. The mass% or more is even more preferable.

  Moreover, when the number of epoxy groups of (a) the epoxy resin is 1, from the viewpoint of improving the mechanical properties of the resin composition, the number of reactive groups of the (b) active ester compound is preferably 0.2 to 2, 3-1.5 are more preferable and 0.4-1 are 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 of the active ester compound” means the solid content mass of the active ester compound present in the resin composition. This is the total value of all values divided by equivalents.

(C) Inorganic filler (c) Inorganic filler used in the present invention is not particularly limited, and for example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, carbonic acid Examples include calcium, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Of these, silica is preferable. As silica, amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica and hollow silica are preferred, and fused silica is more preferred. Moreover, spherical silica is preferable as the silica. You may use these 1 type or in combination of 2 or more types. Examples of commercially available spherical fused silica include “SO-C2” and “SO-C1” manufactured by Admatechs.

  (C) Although the average particle diameter of the inorganic filler is not particularly limited, the upper limit of the average particle diameter of the inorganic filler is the viewpoint that fine wiring is formed on the insulating layer, the total of the inorganic filler From the viewpoint of suppressing the occurrence of smear during drilling by increasing the surface area, it is preferably 2 μm or less, more preferably 1 μm or less, still more preferably 0.8 μm or less, even more preferably 0.6 μm or less, and even more preferably 0.5 μm. The following is particularly preferable, 0.4 μm or less is particularly preferable, and 0.3 μm or less is particularly preferable. On the other hand, the lower limit of the average particle size of the inorganic filler is preferably 0.01 μm or more from the viewpoint of preventing the viscosity of the varnish from increasing and handling properties from being lowered when the resin composition is a varnish. 0.03 μm or more is more preferable, 0.05 μm or more is further preferable, 0.07 μm or more is particularly preferable, and 0.1 μm or more is particularly 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 particle size distribution measuring apparatus, LA-750 manufactured by Horiba, Ltd. or the like can be used.

  (C) Although content in particular of an inorganic filler is not restrict | limited, From a viewpoint of preventing that the flexibility when a resin composition is made into a film form prevents 100 mass of non-volatile components in a resin composition. % Is preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less. In addition, from the viewpoint of lowering the thermal expansion coefficient of the insulating layer, increasing the total surface area of the inorganic filler to suppress the occurrence of smear during drilling, and making it easier to remove smear during the roughening treatment, When the nonvolatile component in the resin composition is 100% by mass, 30% by mass or more is preferable, 40% by mass or more is more preferable, 50% by mass or more is further preferable, 55% by mass or more is even more preferable, and 60% by mass. The above is particularly preferable.

  (C) Inorganic fillers are aminosilane coupling agents, ureidosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, and silane couplings from the viewpoint of improving moisture resistance and dispersibility. Agents, vinyl silane coupling agents, styryl silane coupling agents, acrylate silane coupling agents, isocyanate silane coupling agents, sulfide silane coupling agents, organosilazane compounds, titanate coupling agents, etc. It is preferable that the surface treatment is performed. In particular, after the surface treatment of the inorganic filler with an organosilazane compound, the surface treatment with a silane coupling agent further improves the moisture resistance and dispersibility of the inorganic filler. These may be used alone or in combination of two or more.

  Specifically, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane Aminosilane coupling agents such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane, 3-ureidopropyltriethoxysilane, etc. Ureidosilane coupling agent, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane Epoxysilane coupling agents such as glycidylbutyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyl Mercaptosilane-based coupling agents such as dimethoxysilane, 11-mercaptoundecyltrimethoxysilane, methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazolesilane, triazinesilane, tert- Silane coupling agents such as butyltrimethoxysilane, vinyl silamines such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane Coupling agent, styrylsilane coupling agent such as p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-methacryloxy Acrylate silane coupling agents such as propyltriethoxysilane and 3-methacryloxypropyldiethoxysilane, isocyanate silane coupling agents such as 3-isocyanatopropyltrimethoxysilane, bis (triethoxysilylpropyl) disulfide, bis (tri Ethoxysilylpropyl) sulfidesilane coupling agents such as tetrasulfide, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, hexa Enyldisilazane, trisilazane, cyclotrisilazane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, hexabutyldisilazane, hexaoctyldisilazane, 1,3-diethyltetramethyldi Silazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1,3-diethyltetramethyldisilazane, 1,1, Organosilazane compounds such as 3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, dimethylaminotrimethylsilazane, tetramethyldisilazane, tetra-n -Butyl titanate dimer, tita Um-i-propoxyoctylene glycolate, tetra-n-butyl titanate, titanium octylene glycolate, diisopropoxy titanium bis (triethanolamate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium, bis (dioctyl pyro) Phosphate) ethylene titanate, bis (dioctylpyrophosphate) oxyacetate titanate, tri-n-butoxy titanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, Tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) ) Phosphite titanate, isopropyl trioctanoyl titanate, isopropyl tricumyl phenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tridodecylbenzenesulfonyl Examples thereof include titanate coupling agents such as titanate, isopropyl tris (dioctyl pyrophosphate) titanate, and isopropyl tri (N-amidoethyl / aminoethyl) titanate. Of these, aminosilane coupling agents are preferred because they are excellent in moisture resistance, dispersibility, and properties of cured products, and organosilazane compounds are preferred because they are excellent in improving dispersibility of resin varnishes. Commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) 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 weight of the inorganic filler after being washed with a solvent (for example, methyl ethyl ketone). Here, “the amount of carbon per unit weight of the inorganic filler” is the percentage of the amount of carbon (g) bonded to 1 g of the inorganic filler. 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 content, the carbon amount per unit weight of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. can be used.

  The amount of carbon per unit weight of the inorganic filler is preferably 0.02% or more in terms of improving the dispersibility of the inorganic filler and stabilizing the root mean square roughness after the roughening treatment of the cured product. 05% or more is more preferable, and 0.1% or more is still more preferable. On the other hand, it is preferably 3% or less, more preferably 2% or less, and even more preferably 1% or less from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the adhesive film.

(D) Curing accelerator The resin composition of the present invention may further contain (d) a curing accelerator for the purpose of adjusting the curing time and the curing temperature. (D) Although it does not specifically limit as a hardening accelerator, An imidazole type hardening accelerator, an amine type hardening accelerator, an organic phosphine compound, an organic phosphonium salt compound, etc. are mentioned. These may be used alone or in combination of two or more.

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2- Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1- Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2- Feni Imidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- ( 1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6 -[2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4 -Methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-be Jill imidazolium chloride, 2-methyl-imidazoline, adduct of 2-phenyl-imidazo imidazole compounds such as phosphorus and imidazole compound and an epoxy resin. These may be used alone or in combination of two or more.

  Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,5). And amine compounds such as 4,0) -undecene (hereinafter abbreviated as DBU). These may be used alone or in combination of two or more.

  Examples of organic phosphine compounds and organic phosphonium salt compounds include TPP, TPP-K, TPP-S, TPTP-S, TBA-DA, TPP-SCN, and TPTP-SCN (trade names of Hokuko Chemical Co., Ltd.). . These may be used alone or in combination of two or more.

  (D) The content of the curing accelerator is preferably 0.01 to 3% by mass with respect to 100% by mass of the non-volatile component in the resin composition from the viewpoint of storage stability of the resin varnish and efficiency of curing. More preferably, the content is 1-2% by mass.

(E) Thermoplastic resin In the resin composition of the present invention, by further containing (e) a thermoplastic resin, the viscosity of the resin varnish obtained from the resin composition can be adjusted to a suitable range, Moreover, the flexibility of the cured product can be increased. The thermoplastic resin is not particularly limited, and examples thereof include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyamide resin, polyethersulfone resin, polysulfone resin, polybutadiene resin, and ABS resin. Of these, phenoxy resins and polyvinyl acetal resins are preferred, and phenoxy resins are more preferred from the viewpoint of enhancing the flexibility of the cured product and contributing to adhesion. These may be used alone or in combination of two or more. The thermoplastic resin preferably has a glass transition temperature of 80 ° C. or higher.

  The weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 800,000, more preferably in the range of 10,000 to 200,000, still more preferably in the range of 15,000 to 150,000, and in the range of 20,000 to 100,000. Is even more preferred. By being in this range, the effect of improving the film forming ability and the mechanical strength is sufficiently exhibited, and the compatibility with the epoxy resin can also be improved. In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the weight average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -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, Examples thereof include those having one or more skeletons selected from a trimethylcyclohexane skeleton. Two or more phenoxy resins may be mixed and used. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Examples of commercially available products include 1256, 4250 (bisphenol A skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Corporation, YX8100 (bisphenol S skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Corporation, and YX6954 (bisphenol manufactured by Mitsubishi Chemical Corporation). Acetophenone skeleton-containing phenoxy resin). Examples of commercially available products include FX280 and FX293 manufactured by Nippon Steel Chemical Co., Ltd., YL7553, YL6954, YL6794, YL7213, YL7290, and YL7482 manufactured by Mitsubishi Chemical Corporation.

  Specific examples of the polyvinyl acetal resin include those manufactured by Denki Kagaku Kogyo Co., Ltd., electrified butyral 4000-2, 5000-A, 6000-C, 6000-EP, and Sekisui Chemical Co., Ltd., ESREC BH series, BX series, and KS. Series, BL series, BM series and the like. Specific examples of the polyimide resin include polyimide “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Also, a linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (as described in JP 2006-37083 A), a polysiloxane skeleton-containing polyimide (JP 2002-2002). And modified polyimides such as those described in JP-A No. 12667 and JP-A No. 2000-319386. Specific examples of the polyamideimide resin include polyamideimides “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. In addition, modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd. may be mentioned. Specific examples of the polyethersulfone resin include polyethersulfone “PES5003P” manufactured by Sumitomo Chemical Co., Ltd. Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solven Advanced Polymers Co., Ltd.

  Although the content of the thermoplastic resin is not particularly limited, it is 0 with respect to 100% by mass of the nonvolatile component in the resin composition from the viewpoint of adjusting the melt viscosity of the sheet-shaped laminated material and adjusting the resin varnish viscosity. 5-30 mass% is preferable, and 1-20 mass% is more preferable.

(F) Smear suppressing component The resin composition of the present invention may further contain (f) a smear suppressing component. Thereby, smear suppression of via holes can be further increased. Here, smear suppression includes both meanings of reducing the amount of smear generated during drilling and making it easier to remove smear during roughening. The smear suppressing component is capable of suppressing smear after the hole is processed and roughened in the cured product of the resin composition. Examples of the smear suppressing component include an organic smear suppressing component and an inorganic smear suppressing component, and an organic smear suppressing component is preferable from the viewpoint of improving insulation reliability. Specifically, examples of the organic smear suppressing component include pigments, dyes, rubber particles, antioxidants, infrared absorbers, and the like, and examples of the inorganic smear suppressing component include metal compound powder and metal powder. . As the smear suppressing component, it is preferable to use one or more selected from the group consisting of pigments, dyes, rubber particles, antioxidants and infrared absorbers. Of these, pigments and / or rubber particles are more preferable, and pigments are more preferable from the viewpoints of excellent smear suppression ability and excellent peel strength. These may be used alone or in combination of two or more.

  Examples of the pigment include a blue pigment, a yellow pigment, a red pigment, a black pigment, and a green pigment. Examples of blue pigments include phthalocyanine, anthraquinone, and dioxazine pigments. Examples of yellow pigments include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone pigments. Examples of red pigments include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone pigments. Examples of the black pigment include carbon black and graphite. Examples of the green pigment include phthalocyanine-based pigments. One or more pigments may be used in combination, and one or more pigments selected from the group consisting of blue pigments, yellow pigments, red pigments, black pigments, and green pigments can be appropriately blended. Especially, it is preferable to use 1 or more types selected from the group which consists of a blue pigment, a yellow pigment, a red pigment, and a green pigment from the point which can improve insulation reliability further, and a blue pigment, a yellow pigment, and red It is more preferable to use a mixed pigment obtained by mixing pigments. In preparing a mixed pigment comprising a mixture of a blue pigment, a yellow pigment and a red pigment, the blue pigment and the yellow pigment can be effectively absorbed from the laser during drilling and smearing can be further suppressed. And the mass ratio of the red pigment is preferably 2 to 6: 5 to 9: 6 to 10, more preferably 3 to 5: 5 to 8: 7 to 10, and further preferably 3 to 5: 6 to 8: 7 to 9. preferable.

  As dyes, azo (monoazo, disazo, etc.) dyes, azo-methine dyes, anthraquinone dyes, quinoline dyes, ketone imine dyes, fluorone dyes, nitro dyes, xanthene dyes, acenaphthene dyes, quinophthalone dyes, aminoketone dyes, methine dyes, perylenes And dyes, coumarin dyes, perinone dyes, triphenyl dyes, triallylmethane dyes, phthalocyanine dyes, incrophenol dyes, azine dyes, or mixtures thereof.

  Examples of the rubber particles include core-shell type rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, a two-layer structure in which an outer shell layer is made of a glassy polymer and an inner core layer is made of a rubbery polymer, or Examples include a three-layer structure in which the outer shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer.

  Examples of the antioxidant include hindered phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Commercially available products include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (“IRGANOX 1010” manufactured by Ciba Japan Co., Ltd.), 2,2-thio-diethylenebis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (“IRGANOX 1035” manufactured by Ciba Japan Co., Ltd.), 1,3,5-tris [[3,5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl] methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione ("IRGANOX 3114" manufactured by Ciba Japan Co., Ltd.) Can be mentioned.

  Examples of infrared absorbers include phthalocyanine compounds, anthraquinone compounds, nickel complexes, and the like. Examples of commercially available products include IR-14 (manufactured by Nippon Shokubai Co., Ltd.), TX-HA-1 (manufactured by Nippon Shokubai Co., Ltd.), and the like.

  As metal compound powder, titania such as titanium oxide, magnesia such as magnesium oxide, iron oxide such as iron oxide, nickel oxide such as nickel oxide, zinc oxide such as manganese dioxide and zinc oxide, silicon dioxide, Aluminum oxide, rare earth oxide, cobalt oxide such as cobalt oxide, tin oxide such as tin oxide, tungsten oxide such as tungsten oxide, silicon carbide, tungsten carbide, boron nitride, silicon nitride, titanium nitride, aluminum nitride, sulfuric acid Examples thereof include powders of barium, rare earth oxysulfides, or mixtures thereof.

  Examples of metal powders include silver, aluminum, bismuth, cobalt, copper, iron, magnesium, manganese, molybdenum, nickel, palladium, antimony, silicon, tin, titanium, vanadium, tungsten, zinc, or alloys or mixtures thereof. Is mentioned.

  The content of the smear suppressing component is preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 4% by mass with respect to 100% by mass of the nonvolatile component in the resin composition from the viewpoint of preventing a decrease in the cured properties. % Or less is more preferable, 3% by mass or less is further more preferable, and 2% by mass or less is particularly preferable. Further, from the viewpoint of improving the smear suppressing ability, 0.001% by mass or more is preferable, 0.01% by mass or more is more preferable, and 0.02% by mass with respect to 100% by mass of the nonvolatile component in the resin composition. The above is more preferable, 0.05% by mass or more is still more preferable, 0.08% by mass or more is particularly preferable, and 0.1% by mass or more is particularly preferable.

(G) Other components The resin composition of the present invention may further comprise a phenol resin, a cyanate ester resin, a benzoxazine resin, a maleimide compound, a bisallylnadiimide compound, a vinyl as long as the effects of the present invention are not impaired. Thermosetting components such as benzyl resin and vinyl benzyl ether resin, organic fillers such as silicon powder, nylon powder and fluorine powder, thickeners such as olben and benton, silicone-based, fluorine-based and polymer-based antifoaming agents or Examples thereof include leveling agents, thiazole-based and triazole-based adhesion imparting agents, flame retardants such as aluminum hydroxide, and organic solvents.

  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.

[Resin composition sheet with substrate]
In the resin composition sheet with a substrate of the present invention, a resin composition layer is formed on a substrate. The resin composition sheet with a substrate is prepared by a method known to those skilled in the art, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, and using this resin varnish on a substrate using a die coater or the like. It can be produced by coating and further drying the organic solvent by heating or blowing hot air to form a resin composition layer.

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

  The drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, for example, a resin composition layer is formed by drying a varnish containing 30 to 60% by mass of an organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. can do.

  The thickness of the resin composition layer is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the resin composition layer preferably has a thickness of 10 to 100 μm. 15-80 micrometers is more preferable from a viewpoint of thin film formation.

  Examples of the base material include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester films such as polyethylene naphthalate, polycarbonate films, and polyimide films. Various plastic films are listed. Moreover, you may use release foil, metal foil, such as copper foil and aluminum foil. Among these, from the viewpoint of versatility, a plastic film is preferable, and a polyethylene terephthalate film is more preferable. The base material and the protective film described later may be subjected to a surface treatment such as a mud treatment or a corona treatment. The release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent.

  The thickness of the base material is not particularly limited. However, when drilling from above the base material, the resin residue is less likely to remain even when the energy of laser irradiation is large, and it is 10 μm or more in that smearing can be suppressed. Preferably, it is 20 μm or more, more preferably 30 μm or more. Moreover, from a viewpoint that an efficient drilling can be performed, 150 micrometers or less are preferable, 100 micrometers or less are more preferable, and 50 micrometers or less are still more preferable.

  A protective film according to the substrate can be further laminated on the surface of the resin composition layer opposite to the surface to which the substrate is in close contact. In this case, the resin composition sheet with a base material includes a base material, a resin composition layer formed on the base material, and a protective film formed on the resin composition layer. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The resin composition sheet with a base material can be wound and stored in a roll shape.

  In addition, the resin composition layer of the present invention may be a prepreg obtained by impregnating a resin composition into a sheet-like reinforcing base material by a hot melt method or a solvent method. As the sheet-like reinforcing substrate, for example, those commonly used as prepreg fibers such as glass cloth and aramid fibers can be used. In the hot melt method, the resin composition is once coated on a support without being dissolved in an organic solvent, and then laminated on a sheet-like reinforcing substrate, or directly applied to a sheet-like reinforcing substrate by a die coater. Thus, a prepreg is manufactured. In the solvent method, a resin varnish is prepared by dissolving a resin in an organic solvent in the same manner as the adhesive film, and a sheet-like reinforcing base material is immersed in the varnish, and then the resin-like varnish is impregnated into the sheet-like reinforcing base material. It is a method of drying. Alternatively, the adhesive film can be prepared by continuously laminating the adhesive film from both sides of the sheet-like reinforcing substrate under heating and pressure conditions.

As described above, in the step (A) of the present invention, the resin composition sheet with a substrate is laminated so that the resin composition layer is in contact with both surfaces or one surface of the circuit board.
Hereinafter, an example of a method for laminating a resin composition sheet with a substrate on a circuit board will be described.

  First, a resin composition sheet with a substrate is laminated using a vacuum laminator so that the resin composition layer is in contact with one or both sides of the circuit board. Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards. Also, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, one of the outermost layers of the multilayer printed wiring board is a conductor layer (circuit) in which one or both sides are patterned. It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

When the resin composition sheet with a substrate has a protective film, after removing the protective film, the resin composition sheet with a substrate and the circuit board are preheated as necessary, and the resin composition with the substrate The object sheet is pressed against the circuit board while being pressurized and heated. In a preferred embodiment, the resin composition sheet with a substrate is laminated on a circuit board under reduced pressure by a vacuum laminating method. 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. Moreover, it can also laminate | stack similarly to the above using a vacuum hot press machine. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho Co., Ltd.), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like. A vacuum laminator is preferable from the viewpoint of versatility and productivity.

<(B) Process>
(B) A process is a process of thermosetting a resin composition layer and forming an insulating layer. Details will be described below.

  After laminating the resin composition sheet with the base material on the circuit board, the insulating layer can be formed on the circuit board by thermosetting the resin composition layer. 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 to 180 minutes, more preferably 160 ° C. to 210 ° C. In the range of 30 to 120 minutes. Moreover, adhesion of foreign matters such as dust and dust can be prevented by thermosetting without peeling off the substrate.

In the step (A), when a resin composition sheet with a substrate is laminated on a circuit board by heating and pressing under reduced pressure using a vacuum hot press machine, the steps (A) and (B) Can be performed simultaneously. For example, a heated metal plate such as a SUS plate is pressed from the substrate side, the pressing temperature is 150 to 200 ° C., the pressing pressure is 1 to 40 kgf / cm ² , the pressing time is 30 to 120 minutes, and the degree of vacuum is 1 ×. It can be carried out at 10 ⁻² MPa or less. Moreover, although heating and pressurization can be performed in one stage, it is preferable to divide the conditions into two or more stages from the viewpoint of controlling the bleeding of the resin. For example, it is preferable that the first-stage press is performed at a temperature of 70 to 150 ° C., a pressure of 1 to 15 kgf / cm ² and a time of 30 to 60 minutes, and the second-stage press is performed under the above conditions. . Thus, an insulating layer can be formed on a circuit board by thermosetting the resin composition layer.

  The dielectric loss tangent of the insulating layer of the present invention can be measured by the method described later in <Measurement of dielectric loss tangent>. Specifically, it can be measured at a frequency of 5.8 GHz and a measurement temperature of 23 ° C. by the cavity resonator perturbation method. From the viewpoints of preventing heat generation at high frequencies, reducing signal delay and signal noise, the dielectric loss tangent is preferably 0.05 or less, more preferably 0.04 or less, still more preferably 0.03 or less, and even more preferably 0.02 or less. preferable. On the other hand, the lower limit value of the dielectric loss tangent is not particularly limited, but is preferably 0.001 or more.

<Process (C)>
Step (C) is a step of forming a via hole by drilling from the base material on the surface of the insulating layer. Details will be described below.

  After forming the insulating layer, a via hole is formed by drilling the insulating layer from above the base material. The drilling can be performed by a known method such as drilling, laser, or plasma, or by combining these methods as necessary. Of these, drilling with a laser such as a carbon dioxide laser or a YAG laser is preferred.

  When forming a via hole with a carbon dioxide laser, a laser with a wavelength of 9.3 to 10.6 μm is generally used. The number of shots is usually selected from 1 to 5 shots, although it varies depending 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. In addition, when processing with multiple shots, the burst mode, which is a continuous shot, is a multi-shot with a time interval because the processing heat is trapped in the hole and the via shape tends to be distorted. Is preferred.

  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 μsec to a short pulse of 4 μsec. However, in the case of high energy, the short pulse is superior in the via processing shape.

  Further, in order to cope with the thinning of the multilayer printed wiring board, the top diameter (diameter) of the via hole is preferably 70 μm or less, more preferably 65 μm or less, and further preferably 60 μm or less. On the other hand, the top diameter (diameter) of the via hole is preferably 15 μm or more, more preferably 20 μm or more, and more preferably 25 μm or more in order to prevent the roughening treatment in the via hole from being difficult. Is more preferable.

  Moreover, in order to cope with the thinning of the multilayer printed wiring board as described above, the diameter of the via hole bottom is preferably 60 μm or less, more preferably 55 μm or less, and further preferably 50 μm or less. On the other hand, the diameter of the via hole bottom is preferably 10 μm or more, more preferably 15 μm or more, and even more preferably 20 μm or more from the viewpoint of improving the conduction reliability between layers.

  Furthermore, in order to improve the via shape and improve the conduction reliability between layers, the taper angle of the via hole is preferably 50 to 90 degrees, more preferably 60 to 88 degrees, and further preferably 70 to 86 degrees. Here, the taper angle means an outer angle between the bottom of the via hole and the side surface of the via hole.

  In order to improve the via shape and improve the conduction reliability between layers, the opening ratio of the via hole (the diameter of the bottom of the via hole / the top diameter of the via hole (diameter)) is preferably 70% or more, more preferably 75% or more. 78% or more is more preferable, and 81% or more is further more preferable. On the other hand, 100% or less is preferable at the point which prevents that a plating solution becomes difficult to osmose | permeate.

<(D) Process>
(D) A process is a process of peeling a base material. Details will be described below.

  The substrate is peeled after drilling. 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.

<(E) Process>
Step (E) is a step of roughening the surface of the insulating layer. Details will be described below.

  After peeling off the base material, the surface of the insulating layer is roughened. Examples of the dry roughening treatment include plasma treatment, and examples of the wet roughening treatment include a method in which a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution are performed in this order. In the step (E) of the present invention, either dry or wet roughening treatment may be adopted. However, the wet roughening treatment is more effective in forming the uneven anchor on the surface of the insulating layer, and in the via hole. It is preferable in that smear can be removed.

  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 sodium hydroxide solution and potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Securigans P (Swelling Dip Securigans SBU) and Swelling Dip Securigans SBU manufactured by Atotech Japan Co., Ltd. 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 the insulating layer in the 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.

It is desirable that the surface of the insulating layer after the roughening treatment has fine irregularities in terms of reducing the loss of electrical signals. In the present invention, since smear is suppressed, it is not necessary to perform an excessive roughening treatment in order to remove smear. Therefore, the surface of the insulating layer can be made into a rough surface with fine irregularities, which is excellent in that the opposite characteristics of smear removal and fine rough surface formation can be achieved. The root mean square roughness Rq is an example of the density of the irregularities on the surface of the insulating layer. From this index, it can be seen that the surface of the insulating layer is not a simple average value of the unevenness on the surface of the insulating layer, but has a dense uneven shape. The root mean square roughness Rq of the insulating layer surface after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, further preferably 300 nm or less, still more preferably 250 nm or less, particularly preferably 200 nm or less, and particularly preferably 150 nm or less. Particularly preferred. The lower limit is preferably 5 nm or more, more preferably 10 nm or more, and still more preferably 20 nm or more from the viewpoint of obtaining good adhesion with the plated conductor layer.
The root mean square roughness Rq of the surface of the insulating layer after the roughening treatment can be measured using a non-contact type surface roughness meter. As a specific example of the non-contact type surface roughness meter, “WYKO NT3300” manufactured by Bee Coins Instruments can be cited.

<(F) Process>
In the present invention, a circuit (wiring) can be formed by performing a step ((F) step) of forming a conductor layer by plating on the surface of the insulating layer after the roughening treatment. Details will be described below.

  As a method of forming a conductor layer by plating, a method of forming a conductor layer on an insulating layer by dry plating or wet plating can be mentioned. 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.

  After plating to form the conductor layer, it is desirable that the surface of the insulating layer and the conductor layer are sufficiently adhered. Specifically, the peel strength between the conductor layer obtained by plating on the surface of the insulating layer after the roughening treatment and the insulating layer is preferably 0.35 kgf / cm or more, and more preferably 0.45 kgf / cm or more. On the other hand, the upper limit value is not particularly limited, but is generally 1.2 kgf / cm or less.

  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, since the occurrence of smear is suppressed, the plating adhesion at the bottom of the via hole is improved, the generation of voids at the bottom of the via hole is prevented, and the conduction reliability between layers can be ensured. Therefore, it can be suitably used as a method for producing a multilayer printed wiring board.

<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 Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, these do not restrict | limit this invention in any meaning. In the following description, “part” means “part by mass”.

<Measurement method / Evaluation method>
First, various measurement methods and evaluation methods will be described.

<Smear evaluation>
About the resin composition sheet with a base material obtained by each Example and each comparative example, smear (resin residue) was evaluated according to the following.

(1) Fabrication of circuit board A circuit pattern was formed by etching on both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, board thickness 0.8 mm, R5715ES manufactured by Matsushita Electric Works Co., Ltd.) Further, a roughening treatment was performed with a microetching agent (CZ8100 manufactured by MEC Co., Ltd.), and a circuit board was produced.

(2) Lamination of resin composition sheet with base material The resin composition sheet with base material prepared in each Example and each Comparative Example was batch-type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Co., Ltd.). ) Was laminated on both sides of the circuit board produced in (1) above. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 100 ° C. for 30 seconds at a pressure of 0.74 MPa.

(3) Curing of resin composition layer In Example 1-8 and Comparative Example 1, the resin composition layer was cured as it was under the curing conditions of 170 ° C for 30 minutes. An insulating layer was formed. In Comparative Example 2, the PET film was peeled from the laminated resin composition sheet with a substrate, and then the resin composition layer was cured at 170 ° C. for 30 minutes to form an insulating layer. When the surface of the insulating layer of Comparative Example 2 after curing was visually observed, adhesion of foreign matter (dust) was observed.

(4) Via hole formation Using a CO ₂ laser processing machine (YB-HCS03T04) manufactured by Matsushita Welding Systems Co., Ltd., insulating the insulating layer by processing it in cycle mode conditions with a frequency of 1000 Hz and a pulse width of 13 μs and a shot number of 3 A via hole having a top diameter (diameter) of the via hole on the surface of the layer of 60 μm and a diameter of the bottom of the via hole on the bottom surface of the insulating layer of 50 μm was formed (taper angle is about 83 degrees). In Comparative Example 2, the diameter of the bottom of the via hole was 40 μm. In Example 1-8 and Comparative Example 1, the PET film was peeled after the via hole was formed.

(5) Roughening treatment The circuit board was immersed in a swelling dip securigant P of Atotech Japan Co., Ltd., which is a swelling liquid, at 60 ° C. for 10 minutes. Next, it was immersed for 20 minutes at 80 ° C. in a concentrated compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) of Atotech Japan Co., Ltd., which is a roughening solution (oxidant). Finally, it was immersed for 5 minutes at 40 ° C. in a reduction solution securigant P of Atotech Japan Co., Ltd., which is a neutralizing solution.

(6) Evaluation of residue at bottom of via hole The periphery of the bottom of the via hole was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the bottom of the via hole was measured from the obtained image. ◎: Maximum smear length of less than 2 μm, ◎: Maximum smear length of 2 μm or more and less than 3.5 μm, ○: Maximum smear length of 3.5 μm or more and less than 5 μm, and X: Maximum smear length of 5 μm or more.

  <Measurement of peel strength (peel strength) of plating conductor layer and measurement of root mean square roughness (Rq)>

(1) Substrate treatment of laminate 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, R5715ES manufactured by Matsushita Electric Works Co., Ltd.) on which an inner layer circuit is formed The copper surface was roughened by dipping in CZ8100 manufactured by MEC.

(2) Lamination of resin composition sheet with substrate The resin composition sheet with substrate prepared in each example and each comparative example is a batch type vacuum pressure laminator MVLP-500 (manufactured by Meiki Seisakusho Co., Ltd., product) Name) and laminated on both sides of the laminate. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Curing of resin composition layer In Example 1-8 and Comparative Example 1, the resin composition layer was cured as it was under the curing conditions of 170 ° C for 30 minutes. Then, an insulating layer was formed, and the PET film was peeled off. In Comparative Example 2, the PET film was peeled from the laminated resin composition sheet with a substrate, and then the resin composition layer was cured at 170 ° C. for 30 minutes to form an insulating layer.

(4) Roughening treatment The laminate is immersed in a swelling dip seculigand P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd. for 10 minutes at 60 ° C., and then the roughening solution (oxidant) As a solution of Atotech Japan Co., Ltd. Concentrate Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 20 minutes, and finally as a neutralizing solution of Atotech Japan Co., Ltd. It was immersed in Reduction Sholysin Securigant P at 40 ° C. for 5 minutes. The laminate after the roughening treatment was designated as sample A.

(5) Plating formation by semi-additive method In order to form a circuit on the surface of the insulating layer, the laminate was immersed in an electroless plating solution containing PdCl ₂ and then immersed in an electroless copper plating solution. 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 180 ° C. for 60 minutes. This laminate was designated as Sample B.

(6) Measurement of root mean square roughness (Rq value) For sample A, using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Becoin Instruments Co., Ltd.), the measurement range is 121 μm × 50 V lens. Rq value was calculated | required by the numerical value obtained as 92 micrometers. And it was set as the measured value by calculating | requiring the average value of 10 each.

(7) Measurement of peel strength (peel strength) of plated conductor layer Cut the conductor layer of sample B into a 10 mm wide and 100 mm long part, peel off one end, and grasping tool (TS Co., Ltd.) -E, auto-comb type tester AC-50C-SL), and 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.

<Measurement of dielectric loss tangent>
The resin composition sheet with a substrate obtained in each Example and each Comparative Example was thermally cured at 190 ° C. for 90 minutes, and the PET film was peeled off to obtain a sheet-like cured product. The cured product was cut into a test piece having a width of 2 mm and a length of 80 mm, and a cavity resonator perturbation method dielectric constant measuring device CP521 manufactured by Kanto Electronics Application Development Co., Ltd. and a network analyzer E8362B manufactured by Agilent Technology Co., Ltd. were used. The dielectric loss tangent (tan δ) was measured at a measurement frequency of 5.8 GHz by the cavity resonator perturbation method. Two test pieces were measured, and the average value was calculated.

<Example 1>
15 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “828” manufactured by Mitsubishi Chemical Corporation), active ester compound (“HPC8000-65T” manufactured by DIC Corporation, active ester equivalent 223, solid content 65% Toluene solution) 18 parts (solid content conversion), spherical silica (average particle size 0.25 μm, “SO-C1” with aminosilane treatment, manufactured by Admatechs Co., Ltd., carbon amount 0.8% per unit weight) 50 parts Then, 1 part of a curing accelerator (manufactured by Shikoku Kasei Co., Ltd., “2E4MZ”) was mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish.
Next, this resin varnish is applied to a release surface of a 38 μm thick PET film (AL5 manufactured by Lintec Corporation) with a die coater so that the resin composition layer thickness after drying is 40 μm. It was made to dry at 6 degreeC (average 100 degreeC) for 6 minutes, and the resin composition sheet with a base material was obtained. The evaluation results are shown in Table 1.

<Example 2>
15 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “828” manufactured by Mitsubishi Chemical Corporation), active ester compound (“HPC8000-65T” manufactured by DIC Corporation, active ester equivalent 223, solid content 65% 13 parts (toluene solution), phenolic curing agent (“SN485” manufactured by Nippon Steel Chemical Co., Ltd., MEK solution with a solid content of 50%) 5 parts (solid content), spherical silica (average particle size) 0.25 μm, “SO-C1” with aminosilane treatment, manufactured by Admatechs Co., Ltd., 50 parts of carbon per unit weight 0.8%, curing accelerator (manufactured by Shikoku Kasei Co., Ltd., “2E4MZ”) 1 The parts were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish. Next, a resin composition sheet with a substrate was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 3>
15 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “828” manufactured by Mitsubishi Chemical Corporation), active ester compound (“HPC8000-65T” manufactured by DIC Corporation, active ester equivalent 223, solid content 65% 9 parts (toluene solution) 9 parts (solid content conversion), phenolic curing agent (“SN485” manufactured by Nippon Steel Chemical Co., Ltd., 50% solid content MEK solution) 9 parts (solid content conversion), spherical silica (average particle size) 0.25 μm, “SO-C1” with aminosilane treatment, manufactured by Admatechs Co., Ltd., 50 parts of carbon per unit weight 0.8%, curing accelerator (manufactured by Shikoku Kasei Co., Ltd., “2E4MZ”) 1 The parts were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish. Next, a resin composition sheet with a substrate was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 4>
1 part of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “828” manufactured by Mitsubishi Chemical Corporation), 14 parts biphenyl type epoxy resin (“NC3000H” manufactured by Nippon Kayaku Co., Ltd.), active ester compound (DIC ( "HPC8000-65T" manufactured by Co., Ltd., 13 parts (in terms of solid content) of active ester equivalent 223, 65% solid content in toluene, spherical silica (average particle size 0.25 μm, "SO-C1" with aminosilane treatment, ( 45 parts by carbon, manufactured by Admatechs Co., Ltd., and 1 part of a curing accelerator (manufactured by Shikoku Kasei Co., Ltd., “2E4MZ”) are mixed and dispersed uniformly with a high-speed rotating mixer. A resin varnish was prepared. Next, a resin composition sheet with a substrate was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 5>
25 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, "828" manufactured by Mitsubishi Chemical Corporation), active ester compound ("HPC8000-65T" manufactured by DIC Corporation), active ester equivalent 223, solid content 65% 29 parts (toluene solution), 50 parts of spherical silica (average particle size 0.25 μm, “SO-C1” with aminosilane treatment, manufactured by Admatechs Co., Ltd., carbon amount 0.8%) Then, 1 part of a curing accelerator (manufactured by Shikoku Kasei Co., Ltd., “2E4MZ”) was mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish. Next, a resin composition sheet with a substrate was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 6>
15 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “828” manufactured by Mitsubishi Chemical Corporation), active ester compound (“HPC8000-65T” manufactured by DIC Corporation, active ester equivalent 223, solid content 65% Toluene solution) 10 parts (in terms of solid content), spherical silica (average particle size 0.25 μm, “SO-C1” with aminosilane treatment, manufactured by Admatechs Co., Ltd., carbon amount 0.8% per unit weight) 50 parts Then, 1 part of a curing accelerator (manufactured by Shikoku Kasei Co., Ltd., “2E4MZ”) was mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish. Next, a resin composition sheet with a substrate was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 7>
15 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “828” manufactured by Mitsubishi Chemical Corporation), active ester compound (“HPC8000-65T” manufactured by DIC Corporation, active ester equivalent 223, solid content 65% Toluene solution) 45 parts (solid content conversion), spherical silica (average particle diameter 0.25 μm, “SO-C1” with aminosilane treatment, manufactured by Admatechs Co., Ltd., carbon amount 0.8% per unit weight) 100 parts Then, 1 part of a curing accelerator (manufactured by Shikoku Kasei Co., Ltd., “2E4MZ”) was mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish. Next, a resin composition sheet with a substrate was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 8>
15 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “828” manufactured by Mitsubishi Chemical Corporation), active ester compound (“HPC8000-65T” manufactured by DIC Corporation, active ester equivalent 223, solid content 65% Toluene solution) 25 parts (solid content conversion), spherical silica (average particle diameter 0.25 μm, “SO-C1” with aminosilane treatment, manufactured by Admatechs Co., Ltd., carbon amount 0.8% per unit weight) 60 parts , 1 part of curing accelerator (manufactured by Shikoku Kasei Co., Ltd., “2E4MZ”) and 10 parts of phenoxy resin (“YL6954” manufactured by Mitsubishi Chemical Co., Ltd.) are mixed and dispersed uniformly with a high-speed rotary mixer, and resin varnish Was made. Next, a resin composition sheet with a substrate was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 9>
15 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “828” manufactured by Mitsubishi Chemical Corporation), active ester compound (“HPC8000-65T” manufactured by DIC Corporation, active ester equivalent 223, solid content 65% Toluene solution) 18 parts (solid content conversion), spherical silica (average particle size 0.25 μm, “SO-C1” with aminosilane treatment, manufactured by Admatechs Co., Ltd., carbon amount 0.8% per unit weight) 50 parts , 1 part of a curing accelerator (manufactured by Shikoku Kasei Co., Ltd., “2E4MZ”), 0.03 part of a blue pigment (manufactured by Dainichi Seika Co., Ltd., cyanine blue 4920) Yellow K1841) 0.03 part and red pigment (Clariant Japan Co., Ltd., PV Fast Pink E01) 0.06 part are mixed and mixed with a high-speed rotary mixer. Dispersed in to prepare a resin varnish. Next, a resin composition sheet with a substrate was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Comparative Example 1>
15 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “828” manufactured by Mitsubishi Chemical Corporation) and phenolic curing agent (“SN485” manufactured by Nippon Steel Chemical Co., Ltd., MEK solution with a solid content of 50%) 18 parts (solid content conversion), spherical silica (average particle size 0.25 μm, “SO-C1” with aminosilane treatment, manufactured by Admatechs Co., Ltd., carbon amount 0.8% per unit weight) 50 parts, curing acceleration 0.1 parts of an agent (“2E4MZ” manufactured by Shikoku Kasei Co., Ltd.) was mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish. Next, a resin composition sheet with a substrate was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Comparative example 2>
The same resin composition sheet with a substrate as in Example 1 was used. The evaluation results are shown in Table 1.

  As apparent from Table 1, in the examples, smear was suppressed, the dielectric loss tangent was low, and Rq was also small. Furthermore, in Examples 4, 6, and 9, particularly excellent results were obtained in suppressing smear. On the other hand, in Comparative Example 1, Rq was large and the surface of the insulating layer was not a dense rough surface, the peel strength was low, and the dielectric loss tangent was also high. Comparative Example 2 resulted in smear remaining.

  Although the smear after the roughening treatment in the via hole of the insulating layer can be suppressed, the dielectric loss tangent of the insulating layer is lowered and the root mean square roughness Rq of the insulating layer surface after the roughening treatment is reduced. It is now possible to provide a method for manufacturing a multilayer printed wiring board that can be used. Furthermore, electric products such as computers, mobile phones, digital cameras, and televisions equipped with this multilayer printed wiring board, and vehicles such as motorcycles, automobiles, trains, ships, and aircraft can be provided.

Claims (17)

(A) A step of laminating a resin composition sheet with a substrate so that the resin composition layer is in contact with both sides or one side of the circuit board,
(B) a step of thermally curing the resin composition layer to form an insulating layer;
(C) forming a via hole by drilling from above the base material on the surface of the insulating layer;
(D) a step of peeling the substrate;
(E) a step of roughening the surface of the insulating layer;
In a method for producing a multilayer printed wiring board containing
The resin composition layer contains an epoxy resin, an active ester compound and an inorganic filler,
The method for producing a multilayer printed wiring board, wherein the root mean square roughness Rq of the surface of the insulating layer after the roughening treatment is 500 nm or less.   The method for producing a multilayer printed wiring board according to claim 1, wherein the epoxy resin is 1 to 40% by mass when the nonvolatile component in the resin composition is 100% by mass.   The method for producing a multilayer printed wiring board according to claim 1 or 2, wherein the active ester compound is 3 to 40% by mass when the nonvolatile component in the resin composition is 100% by mass.   The multilayer printed wiring board according to any one of claims 1 to 3, wherein the inorganic filler is 30 to 85% by mass when the nonvolatile component in the resin composition is 100% by mass. Method.   The multilayer printed wiring board according to any one of claims 1 to 4, wherein the inorganic filler is 55 to 85% by mass when the nonvolatile component in the resin composition is 100% by mass. Method.   The method for producing a multilayer printed wiring board according to claim 1, wherein the inorganic filler has an average particle diameter of 0.01 to 2 μm.   The method for producing a multilayer printed wiring board according to any one of claims 1 to 6, wherein an amount of carbon per unit weight of the inorganic filler is 0.02 to 3%.   The method for producing a multilayer printed wiring board according to any one of claims 1 to 7, wherein the resin composition layer further contains a smear suppressing component.   The method for producing a multilayer printed wiring board according to claim 1, wherein the substrate is a plastic film.   The method for producing a multilayer printed wiring board according to any one of claims 1 to 9, wherein the base material has a thickness of 10 to 150 µm.   The method for producing a multilayer printed wiring board according to any one of claims 1 to 10, wherein a dielectric loss tangent of the insulating layer is 0.05 or less.   The top diameter (diameter) of a via hole is 70 micrometers or less, The manufacturing method of the multilayer printed wiring board of any one of Claims 1-11 characterized by the above-mentioned.   The multilayer printed wiring board according to any one of claims 1 to 12, wherein an opening ratio of the via hole (diameter at the bottom of the via hole / top diameter (diameter) of the via hole) is 70 to 100%. Method.   The method for producing a multilayer printed wiring board according to any one of claims 1 to 13, wherein in the step of roughening treatment, the roughening treatment with an oxidizing agent is performed at 60 to 80 ° C for 10 to 30 minutes. .   The method for producing a multilayer printed wiring board according to claim 1, further comprising (F) a step of plating the surface of the insulating layer after the roughening treatment to form a conductor layer. .   The method for producing a multilayer printed wiring board according to claim 15, wherein a peel strength between the conductor layer and the insulating layer is 0.35 kgf / cm or more.   A multi-layer printed wiring board manufactured by the method according to claim 1 is used.