KR20220029428A - Process for producing printed wiring board - Google Patents

Abstract

The present invention provides a method for manufacturing a printed wiring board, which can suppress a hollowing phenomenon and suppress the occurrence of irregularities on the side surfaces and bottom surfaces of via holes and trenches. The method for manufacturing a printed wiring board includes the processes of: (A) forming an insulating layer containing a cured material of a resin composition, on an inner-layer circuit board; and (B) performing plasma treatment on the surface of the insulating layer, to form via holes or trenches. A resin composition contains an inorganic filler, the content of the inorganic filler is 60 mass% or greater with respect to 100 mass% of a non-volatile component in the resin composition, and the gas used for the plasma treatment contains SF_6.

Description

The manufacturing method of a printed wiring board {PROCESS FOR PRODUCING PRINTED WIRING BOARD}

This invention relates to the manufacturing method of a printed wiring board, and the resin composition for via-hole or trench formation by plasma processing.

In recent years, in a printed wiring board, the buildup layer is multilayered, and refinement|miniaturization of wiring and density increase are calculated|required. A buildup layer is formed by the buildup method which piles up an insulating layer and a conductor layer alternately, and in the manufacturing method by a buildup method, it is common that an insulating layer is formed by thermosetting a resin composition.

Many proposals of a resin composition suitable for formation of the insulating layer of an inner-layer circuit board are made including the resin composition described in patent document 1, for example.

Japanese Patent Laid-Open No. 2017-059779

However, there are cases in which a via hole or a trench is formed in the insulating layer when manufacturing a printed wiring board. A "via hole" usually refers to a hole penetrating an insulating layer. In addition, a "trench" shows the groove|channel which does not penetrate an insulating layer normally. As a method of forming a via hole or a trench, a method using a laser is conceivable.

The inventors of the present invention have discovered that heat is generated when laser is irradiated, and the heat is transmitted to the underlying metal of the insulating layer and the inner layer circuit board, thereby causing the hollowing phenomenon. The hollowing phenomenon means that peeling occurs between the insulating layer and the inner circuit board around the via hole. Such a hollowing phenomenon usually occurs when the resin around the via hole is deteriorated by heat, and the deteriorated portion is eroded by a chemical solution such as a roughening solution. In addition, said deteriorated part is observed normally as a discoloration part.

Furthermore, the present inventors discovered that when a via hole is formed by using a laser, the hardened|cured material of a resin component and an inorganic filler are excavated from the side surface and the bottom surface of a via hole, unevenness|corrugation generate|occur|produces, and it becomes a non-uniform|heterogenous surface. For this reason, it was found that when the conductor layer was formed in the via hole by sputtering, the thickness of the conductor layer became non-uniform.

The object of the present invention is to provide a method for manufacturing a printed wiring board capable of suppressing the hollowing phenomenon and suppressing the occurrence of irregularities on the side and bottom surfaces of via holes and trenches, and for forming via holes or trenches by plasma treatment To provide a resin composition of

MEANS TO SOLVE THE PROBLEM As a result of earnest examination in order to solve the said subject, this inventor discovered that the said subject could be solved by forming a via hole or a trench by plasma processing, and came to complete this invention.

That is, the present invention includes the following contents.

[1] (A) a step of forming an insulating layer containing a cured product of a resin composition on an inner-layer circuit board; and

(B) performing plasma treatment on the surface of the insulating layer to form via holes or trenches;

When a resin composition contains an inorganic filler and content of an inorganic filler makes the non-volatile component in a resin composition 100 mass %, it is 60 mass % or more,

The manufacturing method of the printed wiring board in which the gas used for plasma processing contains _SF6 .

[2] (A) a step of forming an insulating layer containing a cured product of a resin composition on an inner-layer circuit board; and

(B) performing plasma treatment on the surface of the insulating layer to form via holes or trenches;

When a resin composition contains an inorganic filler and content of an inorganic filler makes the nonvolatile component in a resin composition 100 volume%, it is 38 volume% or more,

The manufacturing method of the printed wiring board in which the gas used for plasma processing contains _SF6 .

[3] (D) The method for manufacturing a printed wiring board according to [1] or [2], further comprising a step of forming a conductor layer.

[4] The method for manufacturing a printed wiring board according to [3], wherein the step (D) forms a conductor layer by sputtering.

[5] The printed wiring board according to any one of [1] to [4], wherein the gas used for the plasma treatment contains a mixed gas containing SF ₆ and at least one gas selected from Ar and O ₂ manufacturing method.

[6] The method for producing a printed wiring board according to any one of [1] to [5], wherein the resin composition contains a curable resin.

[7] A resin composition for forming an insulating layer of a printed wiring board, comprising:

containing inorganic fillers;

When content of an inorganic filler makes the non-volatile component in a resin composition 100 mass %, the resin composition for forming the via hole or trench by a plasma processing in the insulating layer of a printed wiring board which is 60 mass % or more.

[8] A resin composition for forming an insulating layer of a printed wiring board, comprising:

containing inorganic fillers;

The resin composition for forming the via hole or trench by plasma processing in the insulating layer of a printed wiring board whose content of an inorganic filler makes the nonvolatile component in a resin composition 100 volume%, 38 volume% or more.

[9] The resin composition according to [7] or [8], further comprising a curable resin.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a printed wiring board which can suppress a hollowing phenomenon and generation|occurrence|production of the unevenness|corrugation of the side surface and bottom surface of a via hole and a trench, and a via hole or trench formation by plasma processing A resin composition can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows an example of a mode that a via hole is formed in a process (C).
It is a top view which shows typically the insulating layer immediately before forming a conductor layer of the printed wiring board in which the via hole is formed by the conventional laser processing.
It is sectional drawing which shows typically the insulating layer immediately before forming a conductor layer of the printed wiring board in which a via hole is formed by the conventional laser processing.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment and an illustration are shown and this invention is demonstrated in detail. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily changed and implemented without departing from the scope of the claims of the present invention and their equivalents.

Before demonstrating in detail the manufacturing method of the printed wiring board of this invention, the "resin composition" and "resin sheet" used by the manufacturing method of the printed wiring board of this invention are demonstrated. The resin composition is suitable for forming a via hole or trench in the insulating layer of a printed wiring board by plasma processing. In addition, a resin composition contains an inorganic filler, when content of an inorganic filler makes the non-volatile component in a resin composition 100 mass %, it is 60 mass % or more, and content of an inorganic filler is a non-volatile component in a resin composition. is 100% by volume, either 38% by volume or more or 40% by volume or more. By using such a resin composition, in forming a via hole or a trench by plasma processing, a hollowing phenomenon can be suppressed, and it can suppress that the side wall and the bottom surface of a via hole and a trench become non-uniform|heterogenous surfaces.

[resin composition]

The resin composition used for forming the cured body may be one used in a process of forming a via hole or a trench by plasma-treating the surface of an insulating layer that is a cured product of the resin composition. In one embodiment, the resin composition includes (a) an inorganic filler. In addition to (a) component, the resin composition may further contain (b) curable resin, (c) hardening accelerator, (d) thermoplastic resin, and (e) other additives as needed. Hereinafter, each component contained in a resin composition is demonstrated in detail.

<(a) Inorganic filler>

A resin composition contains (a) inorganic filler, and content of (a) inorganic filler is 60 mass % or more, when content of (a) inorganic filler makes the non-volatile component in a resin composition 100 mass %. Since the resin composition (a) contains a large amount of inorganic filler, even if the inorganic filler is scraped by plasma irradiation with a predetermined gas and the cured product of the resin component is dug out, it is desirable to reduce the frequency of irregularities on the bottom surface and sidewall of the via hole. It becomes possible, and it can suppress that a side wall and a bottom surface become a non-uniform surface. As a result, it becomes possible to make the thickness of the conductor layer uniform. Here, unless otherwise indicated, a "resin component" means components other than the inorganic filler in the nonvolatile component contained in a resin composition.

(a) The content of the component is 60 mass % or more, preferably 63 mass %, when the nonvolatile component in the resin composition is 100 mass % from the viewpoint of reducing the unevenness of the bottom surface and side wall of the via hole or trench. % or more, more preferably 65 mass % or more, preferably 95 mass % or less, more preferably 90 mass % or less, still more preferably 80 mass % or less. In addition, in this invention, content of each component in a resin composition is a value at the time of making the non-volatile component in a resin composition 100 mass %, unless otherwise indicated.

(a) The content of the component is 38% by volume or more, preferably 40% by volume, when the nonvolatile component in the resin composition is 100% by volume from the viewpoint of reducing the unevenness of the bottom surface and sidewall of the via hole or trench. % or more, more preferably 42 volume% or more, preferably 70 mass% or less, more preferably 65 mass% or less, still more preferably 60 mass% or less.

(a) As a material of an inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include silica, alumina, aluminosilicate, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, Magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, zirconate titanate Barium acid, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungsten phosphate, etc. are mentioned. Among these, calcium carbonate and silica are suitable, and silica is especially suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as a silica, spherical silica is preferable. (a) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

(a) As a commercial item of a component, For example, "SP60-05" by a Shin-Nittetsu Sumikin Materials company, "SP507-05"; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Adomatex Corporation; "UFP-30" by Denka Corporation; "Silly writing NSS-3N", "Silly writing NSS-4N", "Silly writing NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "SC2050-SXF", etc. by the Adomatex company are mentioned.

The average particle diameter of the component (a) is preferably more than 0.1 µm, more preferably 0.15 µm or more, particularly preferably 0.2 µm or more, from the viewpoint of remarkably obtaining the desired effect of the present invention, preferably is 5 µm or less, more preferably 2 µm or less, still more preferably 1 µm or less.

(a) The average particle diameter of the component can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, it can measure by creating the particle diameter distribution of an inorganic filler on a volume basis with a laser diffraction scattering type particle diameter distribution measuring apparatus, and making the median diameter into an average particle diameter. As the measurement sample, 100 mg of inorganic filler and 10 g of methyl ethyl ketone were measured and placed in a vial bottle and dispersed for 10 minutes by ultrasonication can be used. For the measurement sample, using a laser diffraction particle size distribution analyzer, the wavelength of the light source to be used is blue and red, the volume-based particle size distribution of the inorganic filler is measured by a flow cell method, and the median diameter from the obtained particle size distribution to calculate the average particle diameter. As a laser diffraction type particle diameter distribution measuring apparatus, "LA-960" by Horiba Corporation, "SALD-2200" by Shimadzu Corporation, etc. are mentioned, for example.

The specific surface area of component (a) is preferably 1 m 2 /g or more, more preferably 2 m 2 /g or more, particularly preferably 3 m 2 /g or more. Although there is no particular limitation on the upper limit, it is preferably 60 m 2 /g or less, 50 m 2 /g or less, or 40 m 2 /g or less. The specific surface area can be obtained by adsorbing nitrogen gas to the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec) according to the BET method, and calculating the specific surface area using the BET multi-point method.

It is preferable that the component (a) is treated with a surface treating agent from a viewpoint of improving moisture resistance and dispersibility. As the surface treatment agent, for example, a vinylsilane coupling agent, a (meth)acrylic coupling agent, a fluorine-containing silane coupling agent, an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, An alkoxysilane, an organosilazane compound, a titanate type coupling agent, etc. are mentioned. Especially, from a viewpoint of acquiring the effect of this invention remarkably, a vinylsilane-type coupling agent, a (meth)acrylic-type coupling agent, and an aminosilane-type coupling agent are preferable, and an aminosilane-type coupling agent is more preferable. In addition, a surface treatment agent may be used individually by 1 type, and may be used in combination of 2 or more types arbitrarily.

As a commercial item of a surface treatment agent, Shin-Etsu Chemical Co., Ltd. make "KBM1003" (vinyl triethoxysilane), Shin-Etsu Chemical Co., Ltd. make "KBM503" (3-methacryloxypropyl triethoxysilane), Shin-Etsu, for example, “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Kagaku Industries, “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. “KBE903” manufactured by Shin-Etsu Chemical Co., Ltd. ' (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyl) disilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane coupling agent), Shin-Etsu Chemical Co., Ltd. "KBM" -7103" (3,3,3-trifluoropropyl trimethoxysilane), etc. are mentioned.

It is preferable that the grade of the surface treatment by a surface treatment agent falls within a predetermined range from a viewpoint of the dispersibility improvement of an inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 parts by mass to 5 parts by mass of a surface treatment agent, preferably at 0.2 parts by mass to 3 parts by mass, and 0.3 parts by mass to 2 parts by mass. It is preferable that it is surface-treated.

The grade of the surface treatment by a surface treatment agent can be evaluated according to the amount of carbon per unit surface area of an inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and still more preferably 0.2 mg/m 2 or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in sheet form, 1 mg/m 2 or less is preferable, 0.8 mg/m 2 or less is more preferable, and 0.5 mg/m 2 or less is still more preferable.

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

<(b) curable resin>

The resin composition may contain (b) curable resin. (b) Although a thermosetting resin and a photocurable resin are mentioned as curable resin, When forming the insulating layer of a printed wiring board, the thermosetting resin which can be used is preferable.

As the thermosetting resin, for example, an epoxy resin, a phenol-based resin, a naphthol-based resin, a benzoxazine-based resin, an active ester-based resin, a cyanate ester-based resin, a carbodiimide-based resin, an amine-based resin, an acid anhydride-based resin, etc. can be heard (b) A component may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. Hereinafter, such as phenol-based resins, naphthol-based resins, benzooxazine-based resins, active ester-based resins, cyanate ester-based resins, carbodiimide-based resins, amine-based resins, and acid anhydride-based resins, the resin composition by reacting with an epoxy resin A resin capable of curing the resin may be collectively referred to as a “curing agent”. The resin composition preferably contains an epoxy resin and a curing agent as component (b) from the viewpoint of forming an insulating layer, and more preferably contains any one of an epoxy resin, an active ester-based resin, and a phenol-based resin. And, it is more preferable to include an epoxy resin and an active ester-based resin.

(b) Examples of the epoxy resin as a component include a bixylenol-type epoxy resin, a bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, a bisphenol S-type epoxy resin, a bisphenol AF-type epoxy resin, and a dicyclopentadiene-type epoxy resin. , Trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type Epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, butadiene structure epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy Resin, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. are mentioned. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

It is preferable that the resin composition contains the epoxy resin which has two or more epoxy groups in 1 molecule as (b) component. From the viewpoint of significantly obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule to 100 mass% of the nonvolatile component of the component (b) is preferably 50 mass% or more, more Preferably it is 60 mass % or more, Especially preferably, it is 70 mass % or more.

Epoxy resins include an epoxy resin that is liquid at a temperature of 20°C (hereinafter sometimes referred to as “liquid epoxy resin”), and an epoxy resin that is solid at a temperature of 20°C (hereinafter sometimes referred to as “solid epoxy resin”). . The resin composition may contain only a liquid epoxy resin or only a solid epoxy resin as component (b), but from a viewpoint of acquiring the effect of this invention remarkably, a resin composition is a liquid epoxy resin and a solid phase It is preferable to include an epoxy resin in combination.

As a liquid epoxy resin, the liquid epoxy resin which has two or more epoxy groups in 1 molecule is preferable.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin , an alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure are preferred, bisphenol A type epoxy resin, bisphenol An F-type epoxy resin is more preferable.

As a specific example of a liquid epoxy resin, "HP4032", "HP4032D", "HP4032SS" by DIC company (naphthalene type epoxy resin); "828US", "jER828EL", "825", "Epicoat 828EL" by Mitsubishi Chemical Corporation (bisphenol A epoxy resin); "jER807", "1750" by Mitsubishi Chemical Corporation (bisphenol F-type epoxy resin); "jER152" by Mitsubishi Chemical (phenol novolak type epoxy resin); "630" and "630LSD" by Mitsubishi Chemical (glycidylamine type epoxy resin); "ZX1059" (mixture of a bisphenol A epoxy resin and a bisphenol F type epoxy resin) by the Nitetsu Chemical & Materials company; "EX-721" by the Nagase Chemtex company (glycidyl ester type epoxy resin); "Celoxide 2021P" by Daicel (alicyclic epoxy resin which has ester skeleton); "PB-3600" by Daicel (epoxy resin which has a butadiene structure); "ZX1658", "ZX1658GS" (liquid 1, 4- glycidyl cyclohexane type epoxy resin), etc. by the Nitetsu Chemical & Materials company are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

As a solid epoxy resin, the solid epoxy resin which has 3 or more epoxy groups in 1 molecule is preferable, and the aromatic solid epoxy resin which has 3 or more epoxy groups in 1 molecule is more preferable.

Examples of the solid-state epoxy resin include a bixylenol-type epoxy resin, a naphthalene-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a cresol novolak-type epoxy resin, a dicyclopentadiene-type epoxy resin, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, and a non A phenyl-type epoxy resin, a naphthylene ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol A-type epoxy resin, a bisphenol AF-type epoxy resin, and a tetraphenylethane-type epoxy resin are preferable, and a naphthalene-type epoxy resin is more preferable.

Examples of the solid-state epoxy resin include naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, and naphthylene ether-type epoxy resins. , an anthracene-type epoxy resin, a bisphenol A-type epoxy resin, and a tetraphenylethane-type epoxy resin are preferable, and a naphthalene-type tetrafunctional epoxy resin, a naphthol-type epoxy resin, and a biphenyl-type epoxy resin are more preferable. As a specific example of a solid epoxy resin, "HP4032H" (naphthalene type epoxy resin) manufactured by DIC, "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolac) type epoxy resin), “N-695” (cresol novolak type epoxy resin), “HP-7200”, “HP-7200HH”, “HP-7200H” (dicyclopentadiene type epoxy resin), “EXA-7311” ", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolak type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Corporation profit); "ESN475V" (naphthalene-type epoxy resin), "ESN485" (naphthol novolac-type epoxy resin) by the Nitetsu Chemical & Materials company; "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin) by Mitsubishi Chemical Corporation; "PG-100", "CG-500" manufactured by Osaka Gas Chemicals, "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical, "YL7800" (fluorene type epoxy resin), "jER1010" (solid phase) Bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

(b) When a liquid epoxy resin and a solid epoxy resin are used in combination as a component, their ratio (liquid epoxy resin:solid epoxy resin) is a mass ratio, preferably 1:0.1 to 1:20 , more preferably 1:0.3 to 1:15, particularly preferably 1:0.5 to 1:10. When the amount ratio of the liquid epoxy resin and the solid epoxy resin is within such a range, the desired effect of the present invention can be obtained remarkably. Moreover, when using in the form of a resin sheet normally, moderate adhesiveness is formed. Moreover, when using in the form of a resin sheet normally, sufficient flexibility is acquired and handling property improves. Moreover, usually, the hardened|cured material which has sufficient breaking strength can be obtained.

(b) The epoxy equivalent of the epoxy resin as a component becomes like this. Preferably it is 50 g/eq. to 5000 g/eq., more preferably 50 g/eq. to 3000 g/eq., more preferably 80 g/eq. to 2000 g/eq., even more preferably 110 g/eq. to 1000 g/eq. By setting it as this range, the hardening body with sufficient crosslinking density of the hardened|cured material of a resin composition can be formed. Epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of an epoxy group. This epoxy equivalent can be measured according to JISK7236.

(b) The weight average molecular weight (Mw) of the epoxy resin as a component is preferably 100 to 5000, more preferably 250 to 3000, still more preferably 400 to 1500, from the viewpoint of remarkably obtaining the desired effect of the present invention. am. The weight average molecular weight of an epoxy resin is a weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) method.

(b) The content of the epoxy resin as a component, from the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, when the nonvolatile component in the resin composition is 100% by mass, preferably 10% by mass or more, more preferably Preferably it is 15 mass % or more, More preferably, it is 20 mass % or more. The upper limit of the content of the epoxy resin is preferably 45% by mass or less, more preferably 40% by mass or less, and particularly preferably 35% by mass or less from the viewpoint of remarkably obtaining the desired effect of the present invention.

(b) As content of the epoxy resin as a component, when the resin component in a resin composition is 100 mass % from a viewpoint of acquiring the effect of this invention remarkably, Preferably it is 50 mass % or more, More preferably, it is 60 mass %. More preferably, it is 70 mass % or more, Preferably it is 95 mass % or less, More preferably, it is 90 mass % or less, More preferably, it is 88 mass % or less. A resin component means the component except (a) an inorganic filler among the non-volatile components in a resin composition.

(b) As the active ester-based resin as a component, a resin having one or more active ester groups in one molecule can be used. Among them, as the active ester-based resin, phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds having two or more ester groups with high reactive activity in one molecule Resin is preferred. It is preferable that the said active ester resin is obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound, and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester resin obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is more preferable.

Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac, etc. are mentioned. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol to one molecule of dicyclopentadiene.

Preferred specific examples of the active ester resin include an active ester resin containing a dicyclopentadiene-type diphenol structure, an active ester resin containing a naphthalene structure, an active ester resin containing an acetylated product of phenol novolac, phenol and active ester-based resins containing novolac benzoylate. Among them, an active ester-based resin containing a naphthalene structure and an active ester-based resin containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Commercially available active ester resins are active ester resins containing a dicyclopentadiene type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H- 65TM", "EXB-8000L-65TM" (manufactured by DIC Corporation); As a naphthalene-type active ester-based resin containing a naphthalene structure, "EXB9416-70BK", "EXB-8100L-65T", "EXB-8150L-65T", "EXB-8150-65T", "HPC-8150-60T", "HPC-8150-62T" (manufactured by DIC Corporation), and "PC1300-02-65T" (manufactured by Air Water Corporation); "DC808" (made by Mitsubishi Chemical) as an active ester-type resin containing the acetylated product of phenol novolak; "YLH1026" (made by Mitsubishi Chemical) as an active ester-type resin containing the benzoyl compound of phenol novolak; "DC808" (manufactured by Mitsubishi Chemical) as an active ester-based resin that is an acetylated product of phenol novolac; As an active ester resin which is a benzoyl product of phenol novolac, "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); "EXB-8500-65T" (made by DIC) etc. are mentioned.

(b) Content of the active ester resin as a component is from a viewpoint of acquiring the effect of this invention remarkably with respect to 100 mass % of non-volatile components in a resin composition, Preferably it is 1 mass % or more, More preferably, 3 mass % or more, more preferably 5 mass % or more, preferably 20 mass % or less, more preferably 15 mass % or less, still more preferably 10 mass % or less.

(b) The content of the active ester-based resin as a component is preferably 3% by mass or more, more preferably 5% by mass, when the resin component in the resin composition is 100% by mass from the viewpoint of significantly obtaining the effect of the present invention. It is mass % or more, More preferably, it is 8 mass % or more, Preferably it is 25 mass % or less, More preferably, it is 20 mass % or less, More preferably, it is 15 mass % or less.

(b) As a phenol-type resin and a naphthol-type resin as a component, it is preferable from a viewpoint of heat resistance and water resistance to have a novolak structure. Moreover, from a viewpoint of adhesiveness with a conductor layer, a nitrogen-containing phenol-type resin is preferable, and a triazine skeleton containing phenol-type resin is more preferable.

As a specific example of a phenol-type resin and a naphthol-type resin, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Corporation, "NHN" manufactured by Nippon Kayaku, "CBN", for example, ', "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN170" manufactured by Nittetsu Chemical & Materials. SN395", "TD-2090" manufactured by DIC, "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", etc. are mentioned.

(b) As a specific example of a benzoxazine-based resin as a component, "JBZ-OD100" (benzoxazine ring equivalent 218), "JBZ-OP100D" (benzoxazine ring equivalent 218), "ODA-BOZ" ( benzoxazine ring equivalent 218); "P-d" (benzoxazine ring equivalent 217), "F-a" (benzooxazine ring equivalent 217) manufactured by Shikoku Kasei Kogyo Co., Ltd.; "HFB2006M" by Showa Kobunshi (benzoxazine ring equivalent 432) etc. are mentioned.

(b) Examples of the cyanate ester-based resin as a component include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), and 4,4'-methylene bis. (2,6-dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1 -bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bifunctional cyanate resins such as bis(4-cyanatephenyl)thioether and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially triazined. As a specific example of cyanate ester type resin, "PT30", "PT30S" and "PT60" (phenol novolak type polyfunctional cyanate ester resin) manufactured by Ronza Japan, "ULL-950S" (polyfunctional cyanate ester resin) ), "BA230", and "BA230S75" (prepolymer in which a part or all of bisphenol A dicyanate was triazineized and trimerized), etc. are mentioned.

(b) Specific examples of the carbodiimide-based resin as a component include Nisshinbo Chemical Co., Ltd. Carbodilite (registered trademark) V-03 (carbodiimide group equivalent: 216), V-05 (carbodiimide group equivalent: 216), V-07 (carbodiimide group equivalent: 200); V-09 (carbodiimide group equivalent: 200); Stavaxol (registered trademark) P (carbodiimide group equivalent: 302) manufactured by Rheinchemi Co., Ltd. is mentioned.

(b) Examples of the amine-based resin as a component include resins having at least one amino group in one molecule, for example, aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, and the like. Among them, aromatic amines are preferable from the viewpoint of exhibiting the desired effect of the present invention. Primary amine or secondary amine is preferable and, as for amine-type resin, primary amine is more preferable. Specific examples of the amine curing agent include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone , 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4, 4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl ) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4- (4-amino) Phenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4 ,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. are mentioned. Commercially available amine resins may be used, for example, "KAYABOND C-200S", "KAYABOND C-100", "Kayahard AA", "Kayahard AB", "Kayahard AS" manufactured by Nippon Kayaku Co., Ltd. , "Epicure W" manufactured by Mitsubishi Chemical Corporation, etc. are mentioned.

(b) Examples of the acid anhydride-based resin as a component include resins having at least one acid anhydride group in one molecule. Specific examples of the acid anhydride-based resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride , dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trimellitic anhydride, pyromellitic anhydride , benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a , 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione, ethylene glycol bis ( anhydrotrimellitate) and polymer-type acid anhydrides, such as styrene maleic acid resin which copolymerized styrene and maleic acid, etc. are mentioned.

(b) In the case of containing an epoxy resin and a curing agent as a component, the amount ratio of the epoxy resin and all curing agents is [the total number of epoxy groups of the epoxy resin]: [the total number of reactive groups of the curing agent] in a ratio of 1:0.01 to 1 The range of :5 is preferable, 1:0.05 - 1:3 are more preferable, and 1:0.1 - 1:2 are still more preferable. Here, "the number of epoxy groups of an epoxy resin" is the value which summed up all the values obtained by dividing the mass of the nonvolatile component of the epoxy resin present in the resin composition by the epoxy equivalent. In addition, "the number of active groups of a hardening|curing agent" is the value which summed up all the value obtained by dividing the mass of the nonvolatile component of the hardening|curing agent which exists in a resin composition by the active group equivalent. (b) As a component, by making the ratio of an epoxy resin and a hardening|curing agent into this range, the hardening body excellent in flexibility can be obtained.

(b) the content of the curing agent as a component, from the viewpoint of significantly obtaining the effect of the present invention, with respect to 100% by mass of the nonvolatile component in the resin composition, preferably 1% by mass or more, more preferably 3% by mass or more, More preferably, it is 5 mass % or more, Preferably it is 20 mass % or less, More preferably, it is 15 mass % or less, More preferably, it is 10 mass % or less.

(b) Content of the hardening|curing agent as a component, when the resin component in a resin composition is 100 mass % from a viewpoint of acquiring the effect of this invention remarkably, Preferably it is 5 mass % or more, More preferably, it is 10 mass % or more. , More preferably, it is 15 mass % or more, Preferably it is 40 mass % or less, More preferably, it is 30 mass % or less, More preferably, it is 25 mass % or less.

<(c) curing accelerator>

The resin composition may contain the (c) hardening accelerator. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators, and amine-based curing accelerators and imidazole-based curing accelerators are preferred. , an amine-based curing accelerator is more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the phosphorus curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenyl Phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc. are mentioned, Triphenyl phosphine and tetrabutyl phosphonium decanoate are preferable.

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl Imidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s- Triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazineisocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid adduct Water, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2 -a] an imidazole compound such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and an imidazole compound and an epoxy resin An adduct body is mentioned, 2-ethyl- 4-methylimidazole and 1-benzyl- 2-phenylimidazole are preferable.

As an imidazole-type hardening accelerator, you may use a commercial item, For example, "P200-H50" by a Mitsubishi Chemical company, etc. are mentioned.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, and diphenylguanidine. , trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc. are mentioned, dicyandiamide, 1,5,7-triazabicyclo[4.4.0]deca-5-ene is preferred.

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

(c) Content of hardening accelerator, when making the nonvolatile component in a resin composition 100 mass % from a viewpoint of acquiring the effect of this invention remarkably, Preferably it is 0.01 mass % or more, More preferably, it is 0.02 mass % or more. , Especially preferably, it is 0.03 mass % or more, Preferably it is 3 mass % or less, More preferably, it is 1 mass % or less, Especially preferably, it is 0.5 mass % or less.

(c) the content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, when the resin component in the resin composition is 100% by mass from the viewpoint of significantly obtaining the effect of the present invention; More preferably, it is 0.1 mass % or more, Preferably it is 3 mass % or less, More preferably, it is 2 mass % or less, More preferably, it is 1 mass % or less.

<(d) Thermoplastic resin>

The resin composition may contain (d) a thermoplastic resin. (d) As the thermoplastic resin, for example, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether Resin, polyether ether ketone resin, polyester resin, etc. are mentioned, A phenoxy resin is preferable. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

(d) The weight average molecular weight of a thermoplastic resin in terms of polystyrene becomes like this. Preferably it is 38000 or more, More preferably, it is 40000 or more, More preferably, it is 42000 or more. The upper limit is preferably 100000 or less, more preferably 70000 or less, still more preferably 60000 or less. (d) The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, (d) the weight average molecular weight in terms of polystyrene of the thermoplastic resin is LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P/K-804L manufactured by Showa Denko as a column as a column. /K-804L can be calculated using a standard polystyrene calibration curve by measuring the column temperature at 40°C using chloroform or the like as a mobile phase.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton , an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a phenoxy resin having at least one skeleton selected from the group consisting of trimethylcyclohexane skeleton. Any functional group in a phenolic hydroxyl group, an epoxy group, etc. may be sufficient as the terminal of a phenoxy resin. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the phenoxy resin include "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resins) manufactured by Mitsubishi Chemical Corporation, "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" (bisphenol aceto) phenoxy resin) containing a phenone skeleton), and in addition, "FX280" and "FX293" manufactured by Nittetsu Chemical & Materials, "YL7500BH30", "YX6954BH30", "YX7553", and " YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", etc. are mentioned.

As polyvinyl acetal resin, polyvinyl formal resin and polyvinyl butyral resin are mentioned, for example, Polyvinyl butyral resin is preferable. As a specific example of polyvinyl acetal resin, "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", "Denka Butyral" manufactured by Denki Chemical Co., Ltd. as a specific example, for example, 6000-EP", Sekisui Kagaku Co., Ltd. S-Rec BH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series, etc. are mentioned. .

As a specific example of polyimide resin, "Ricacoat SN20" and "Ricacoat PN20" by a Shin-Nippon Rica company are mentioned. Specific examples of the polyimide resin include a linear polyimide obtained by reacting a difunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (a polyimide described in Japanese Patent Application Laid-Open No. 2006-037083), polysiloxane Modified polyimides, such as skeleton containing polyimide (The polyimide described in Unexamined-Japanese-Patent No. 2002-012667, Unexamined-Japanese-Patent No. 2000-319386, etc.) are mentioned.

Specific examples of the polyamideimide resin include "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo Corporation. Specific examples of the polyamideimide resin include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing polysiloxane skeleton) manufactured by Hitachi Kasei Industries, Ltd.

As a specific example of polyether sulfone resin, the Sumitomo Chemical Company "PES5003P" etc. are mentioned. As a specific example of polyphenylene ether resin, the Mitsubishi Gas Chemical company oligophenylene ether styrene resin "OPE-2St1200" etc. are mentioned. As a specific example of polyether ether ketone resin, the Sumitomo Chemical Company "Sumiproy K" etc. are mentioned. As a specific example of polyetherimide resin, "Ultem" by GE, etc. are mentioned.

Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

Examples of the polyolefin resin include ethylene-based copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; Polyolefin-type elastomers, such as a polypropylene and an ethylene-propylene block copolymer, etc. are mentioned.

Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethyl tere. A phthalate resin etc. are mentioned.

Especially, as (d) a thermoplastic resin, a phenoxy resin and polyvinyl acetal resin are preferable. Accordingly, in one suitable embodiment, the thermoplastic resin includes at least one selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin. Especially, as a thermoplastic resin, a phenoxy resin is preferable, and a phenoxy resin with a weight average molecular weight of 40,000 or more is especially preferable.

(d) The content of the thermoplastic resin is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of significantly obtaining the effect of the present invention. , More preferably, it is 0.5 mass % or more. An upper limit becomes like this. Preferably it is 5 mass % or less, More preferably, it is 4 mass % or less, More preferably, it is 3 mass % or less.

(d) the content of the thermoplastic resin is preferably 0.5 mass% or more, more preferably 1 mass% or more, when the resin component in the resin composition is 100 mass% from the viewpoint of significantly obtaining the effect of the present invention; More preferably, it is 1.5 mass % or more, Preferably it is 10 mass % or less, More preferably, it is 5 mass % or less, More preferably, it is 3 mass % or less.

<(e) other additives>

The resin composition may further contain other additives as arbitrary components other than the component mentioned above. Examples of such additives include flame retardants; organic fillers; organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds; thickener; antifoam; leveling agent; adhesion imparting agent; Resin additives, such as a coloring agent, are mentioned. These additives may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. Each content can be suitably set by a person skilled in the art.

The preparation method of a resin composition is not specifically limited, For example, the method of mixing and dispersing a compounding component using a rotary mixer etc. with a solvent etc. as needed is mentioned.

[Resin Sheet]

A resin sheet contains a support body and the resin composition layer provided on the said support body and formed from the resin composition. The resin composition is as described in the [Resin composition] column.

The thickness of the resin composition layer is preferably 100 µm or less, more preferably 50 µm or less, from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product excellent in insulation even if the cured product of the resin composition is a thin film; More preferably, they are 40 micrometers or less, 30 micrometers or less, and 20 micrometers or less. Although the lower limit of the thickness of a resin composition layer is not specifically limited, Usually, it can be 1 micrometer or more, 5 micrometers or more, etc.

As a support body, the film which consists of a plastic material, metal foil, and a release paper are mentioned, for example, The film which consists of a plastic material, and metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material is, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”). ) such as polyester, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), Polyether ketone, polyimide, etc. are mentioned. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

The support may be subjected to a matte treatment, a corona treatment, or an antistatic treatment on the surface to be bonded to the resin composition layer.

Moreover, as a support body, you may use the support body with a mold release layer which has a mold release layer in the surface to join with a resin composition layer. As a mold release agent used for the mold release layer of a support body with a mold release layer, 1 or more types of mold release agents are mentioned from the group which consists of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin, for example. A commercial item may be used for a support body with a mold release layer, For example, "SK-1", "AL-5", "AL-7" by Lintec Corporation, "Lumira T60" by Tore Corporation, Teijin Corporation PET film which has a release layer which has alkyd resin type mold release agents, such as "Purex" manufactured by manufacture and "Unipil" manufactured by Unitica Corporation, as a main component; "U2-NR1" by DuPont Films, etc. are mentioned.

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

In one embodiment, the resin sheet may further contain other layers as needed. As such another layer, the protective film according to the support body etc. which were provided in the surface which is not joined to the support body of a resin composition layer (that is, the surface on the opposite side to a support body), etc. are mentioned, for example. Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer - 40 micrometers. By laminating|stacking a protective film, adhesion of dust, etc. to the surface of a resin composition layer, and a flaw can be suppressed.

A resin sheet can be produced by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying this resin varnish to a support using a die coater, and further drying to form a resin composition layer. there is.

As an organic solvent, For example, ketones, such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

You may perform drying by well-known methods, such as a heating and hot-air spraying. Although drying conditions are not specifically limited, Content of the organic solvent in a resin composition layer is 10 mass % or less, Preferably it is made to dry so that it may become 5 mass % or less. Although it also changes depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30 mass % to 60 mass % of an organic solvent, by drying at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes, A resin composition layer can be formed.

The resin sheet can be wound and stored in roll shape. When a resin sheet has a protective film, it becomes usable by peeling off a protective film.

[Manufacturing method of printed wiring board]

The manufacturing method of the printed wiring board of this invention is

(A) a step of forming an insulating layer containing a cured product of a resin composition on an inner-layer circuit board; and

(B) Plasma treatment is performed on the surface of the insulating layer to form a via hole or a trench, and the gas used for the plasma treatment contains SF ₆ .

In the present invention, a via hole or trench is formed in the insulating layer by plasma processing instead of laser processing. Accordingly, it is possible to suppress the hollowing phenomenon, and it is possible to suppress the occurrence of irregularities in the side surfaces and bottom surfaces of via holes and trenches.

In addition, in the manufacturing method of the printed wiring board of this invention, in addition to a process (A) and a process (B), if necessary,

(C) a step of roughening the surface of the insulating layer;

(D) Step of forming a conductor layer on the surface of the insulating layer

may contain

It is preferable to perform a process (A) and a process (B) in this order, and it is more preferable to carry out in this order of a process (A), a process (B), a process (C), and a process (D). Hereinafter, each process of the manufacturing method of a printed wiring board is demonstrated.

<Process (A)>

A process (A) is a process of forming the insulating layer containing the hardened|cured material of a resin composition on an inner-layer circuit board. In the step (A), an insulating layer is usually formed on the main surface of the inner-layer circuit board. The main surface of the inner-layer circuit board indicates the surface of the inner-layer circuit board on which the insulating layer is provided. The resin composition used herein is the resin composition described above.

In performing the step (A), the step of (A-1) preparing the inner-layer circuit board may be included. An inner-layer circuit board is normally equipped with a support substrate and the metal layer provided in the surface of the support substrate. The metal layer is exposed on the main surface of the inner-layer circuit board.

Examples of the material for the support substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. As a material of a metal layer, copper foil, copper foil with a carrier, the material of the conductor layer mentioned later, etc. are mentioned, Copper foil is preferable.

Moreover, in performing a process (A), you may include the process of (A-2) preparing a resin sheet. The resin sheet is as described above.

In a process (A), the insulating layer is formed by laminating|stacking the resin composition layer of a resin sheet on the main surface of an inner-layer circuit board, and thermosetting the resin composition layer, for example.

Lamination of the inner circuit board and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner circuit board from the support side. As a member (hereinafter also referred to as "thermal compression member") for heat-bonding the resin sheet to the inner-layer circuit board, for example, a heated metal plate (SUS head plate, etc.) or a metal roll (SUS roll), etc. are mentioned. In addition, it is preferable not to press the thermocompression-bonding member directly to the resin sheet, but to press through an elastic material, such as a heat-resistant rubber, in order that the resin sheet may fully follow the surface unevenness|corrugation of an inner-layer circuit board.

You may perform lamination|stacking of an inner-layer circuit board and a resin sheet by the vacuum lamination method. In the vacuum laminating method, the thermocompression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, and the thermocompression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to It is the range of 1.47 MPa, The heat compression time becomes like this. Preferably it is 20 second - 400 second, More preferably, it is the range of 30 second - 300 second. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

Lamination can be performed with a commercially available vacuum laminator. As a commercially available vacuum laminator, the vacuum pressure laminator by the Meiki Seisakusho company, the vacuum applicator by the Nikko Materials company, a batch type vacuum pressure laminator etc. are mentioned, for example.

After lamination, under normal pressure (under atmospheric pressure), for example, a smoothing process of the laminated resin sheet may be performed by pressing the thermocompression-bonding member from the support body side. The press conditions of the smoothing process can be made into the conditions similar to the thermocompression-bonding conditions of the said lamination|stacking. A smoothing process can be performed with a commercially available laminator. In addition, you may perform lamination|stacking and a smoothing process continuously using the said commercially available vacuum laminator.

A support body may be removed before thermosetting a resin sheet after lamination|stacking, and may be removed after a process (A).

After laminating the resin sheet on the inner-layer circuit board, the resin composition layer is thermosetted to form an insulating layer. The thermosetting conditions of a resin composition layer are not specifically limited, When forming the insulating layer of a printed wiring board, you may use the conditions normally employ|adopted.

For example, although the thermosetting conditions of the resin composition layer also differ depending on the kind of resin composition, etc., a curing temperature becomes like this. Preferably it is 120 degreeC - 240 degreeC, More preferably, it is 150 degreeC - 220 degreeC, More preferably, it is 170 degreeC. ℃ to 210 ℃. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, still more preferably 15 minutes to 100 minutes.

Before thermosetting a resin composition layer, you may preheat a resin composition layer at temperature lower than hardening temperature. For example, prior to thermosetting the resin composition layer, at a temperature of 50 ° C or more and less than 120 ° C (preferably 60 ° C or more and 115 ° C or less, more preferably 70 ° C or more and 110 ° C or less), the resin composition layer is You may preheat for 5 minutes or more (preferably for 5 minutes - 150 minutes, More preferably, it is 15 minutes - 120 minutes, More preferably, it is 15 minutes - 100 minutes).

The thickness of the insulating layer is preferably 100 µm or less, more preferably 50 µm or less, still more preferably 40 µm or less, 30 µm or less, 20 µm or less, preferably 1 µm or more, more preferably 5 µm or less. More than that.

In addition, instead of using a resin sheet to form an insulating layer, you may apply|coat a resin composition directly on the main surface of an inner-layer circuit board, and you may form an insulating layer. The conditions for forming the insulating layer in that case are the same as the conditions for forming the insulating layer using the resin sheet. In addition, the resin composition to be applied is as described above.

After the completion of the step (A) and before the step (B), in order to effectively form a via hole or a trench in the insulating layer, (A-3) a step of laminating a dry film on the insulating layer or on a support, and (A- 4) The dry film may be exposed and developed using a photomask, and the process of obtaining a patterned dry film may be included.

In the step (A-3), the dry film is laminated on the insulating layer or the support formed on the main surface of the inner circuit board. Lamination conditions of the insulating layer and the dry film may be the same as the lamination conditions of the inner circuit board and the resin sheet.

As the dry film used in the step (A-3), a patterned dry film may be obtained by exposure and development, and a film resistant to the plasma treatment in the step (B) is more preferable. Moreover, as a dry film, the photosensitive dry film which consists of a photoresist composition can be used. As such a dry film, the dry film formed from resin, such as a novolak resin and an acrylic resin, can be used, for example.

The thickness of the dry film is preferably 10 µm or more, more preferably 15 µm or more, still more preferably 20 µm or more, preferably 100 µm or less, more preferably from the viewpoint of improving the workability of the via hole. It is 70 micrometers or less, More preferably, it is 50 micrometers or less.

In the step (A-4), exposure is performed by irradiating an active energy ray through a photomask having a predetermined pattern. As for the detail of exposure, an active energy ray is irradiated to the surface of a dry film through a photomask, and the exposure part of a dry film is photocured. As an active energy ray, an ultraviolet-ray, a visible ray, an electron beam, X-ray etc. are mentioned, for example, An ultraviolet-ray is preferable. The irradiation amount and irradiation time of an ultraviolet-ray can be set suitably according to a dry film. Examples of the exposure method include a contact exposure method in which a mask pattern is brought into close contact with the dry film and exposed, and a non-contact exposure method in which a mask pattern is exposed using parallel light without being in close contact with the dry film.

After exposure, one of the exposed part and the non-exposed part of a dry film (normally, a non-exposed part) is removed by developing, and a pattern dry film is formed. Image development may perform either wet image development or dry image development. As a method of image development, a dip method, a paddle method, a spray method, a brushing method, a scraping method etc. are mentioned, for example.

In the process (B) mentioned later, plasma processing is performed using the pattern dry film as a mask, and a via hole or a trench is formed.

<Process (B)>

The step (B) is a step of forming a via hole or a trench in the surface of the insulating layer by performing plasma treatment on the surface of the insulating layer. (B) As an example is shown in FIG. 1, as for the detail of a process, the removal of the hardened|cured material 1020 of the resin composition contained in the insulating layer 100 by plasma by a predetermined gas, and the inorganic filler 1010 are shaved. Thus, the via hole 110 is formed. Usually, the hardened|cured material 1020 of a resin component and the inorganic filler 1010 are etched by plasma. When plasma processing is continued in order to etch the inorganic filler 1010, a part of the hardened|cured material 1020 of a resin component is dug out. The excavated cured product 1020 of the resin component falls off from the sidewall or bottom surface of the via hole 110 , and the portion 1030 where the cured resin component 1020 is dug out on the sidewall or bottom surface of the via hole 110 . ) (irregularities) may occur. Usually, a dent is not formed in the part by which the inorganic filler 1010 was etched. The content of the inorganic filler 1010 is 60% by mass or more when the nonvolatile component in the resin composition is 100% by mass, and the content of the inorganic filler 1010 is greater than the resin component, so the bottom surface of the via hole 110 and The frequency of the location 1030 in which the hardened|cured material 1020 of the resin component of a side wall was excavated can be reduced. That is, the number of unevenness|corrugation of a bottom surface and a side wall can be reduced, and formation of a non-uniform|heterogenous surface is suppressed. As a result, it becomes possible to make the thickness of the conductor layer formed in the via hole 110 uniform in the step (D) to be described later.

In the plasma treatment, a via hole or trench is formed in the surface of the insulating layer by treating the surface of the insulating layer with plasma generated by introducing a gas into the plasma generating device. The plasma generation method is not particularly limited, and includes microwave plasma generating plasma by microwaves, high frequency plasma using high frequency waves, atmospheric pressure plasma generated under atmospheric pressure, atmospheric pressure plasma generated under vacuum, and the like, and atmospheric pressure generated under vacuum. Plasma is preferred.

Moreover, it is preferable that the plasma used in a process (C) is RF plasma excited by high frequency.

As gas to be plasma-ized, the gas containing _SF6 which can etch the resin component and inorganic filler in an insulating layer is used. As the gas to be converted into plasma, SF ₆ may be included. For example, in addition to SF ₆ , a mixed gas containing other gases such as Ar and O ₂ may be used. As the gas to be converted into plasma, a mixed gas containing SF ₆ and at least any one of Ar and O ₂ is preferable, and a mixed gas containing SF ₆ , Ar and O ₂ is more preferable.

The mixing ratio of SF ₆ and other gases to the mixed gas (SF ₆ /other gases: unit is sccm) is preferably 1/0.01 to 1/1 from the viewpoint of making the thickness of the conductor layer formed in the via hole or trench uniform. , More preferably, it is 1/0.05 to 1/1, More preferably, it is 1/0.1 to 1/1.

When the gas to be plasmaized is a mixed gas containing SF ₆ , Ar and O ₂ , the mixing ratio of Ar and O ₂ (Ar/O ₂ : unit sccm) is 1 from the viewpoint of significantly obtaining the effects of the present invention. /0.01 to 1/1, more preferably 1/0.05 to 1/1, still more preferably 1/0.1 to 1/1.

Although the irradiation time in plasma processing is not specifically limited, 1 minute or more is preferable, 2 minutes or more are more preferable, 3 minutes or more are still more preferable. Although it does not specifically limit about an upper limit, 20 minutes or less are preferable, 15 minutes or less are more preferable, and 10 minutes or less are more preferable.

In the present invention, since the via hole or trench is formed by plasma processing, the diameter of the opening of the via hole or trench can be reduced. As said opening diameter, Preferably they are 50 micrometers or less, More preferably, they are 40 micrometers or less, More preferably, they are 30 micrometers or less and 20 micrometers or less. The lower limit is not particularly limited, but may be 1 µm or more.

<Process (C)>

The step (C) is a step of roughening the surface of the insulating layer, and in detail, foreign substances such as solids of the resin component of the resin composition dropped by the step (B) are removed from the via hole or trench with the treatment solution. it is fair Foreign matter exists on the surface of the insulating layer after a process (B). This foreign material may contain the solid material of the resin component of the resin composition excavated by plasma processing, for example. This foreign material may cause a decrease in the adhesion strength of the conductor layer. Then, the process (C) for removing these foreign materials is performed. The detail of step (C) is a process of removing said foreign material by making the surface of an insulating layer contact a process liquid after completion|finish of process (B). A process (C) may be performed once and may be performed multiple times.

The procedure and conditions of a process (C) are not specifically limited, When forming the insulating layer of a printed wiring board, the well-known procedure and conditions normally used are employable. For example, the insulating layer can be roughened by performing the swelling process by a swelling liquid, the roughening process by an oxidizing agent, and the neutralization process by a neutralizing liquid in this order. Although it does not specifically limit as a swelling liquid used for a roughening process, An alkali solution, surfactant solution, etc. are mentioned, Preferably it is an alkali solution, As said alkali solution, sodium hydroxide solution and potassium hydroxide solution are more preferable. As a commercially available swelling liquid, "Swelling Deep Securiganth P", "Swelling Deep Securiganth SBU", "Swelling Deep Securigant P" manufactured by Atotech Japan, etc. are mentioned, for example. . Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer in 30 degreeC - 90 degreeC swelling liquid for 1 minute - 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent used for a roughening process, For example, the alkaline permanganic acid solution which melt|dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. It is preferable to perform the roughening process by oxidizing agents, such as alkaline permanganic acid solution, by making the insulating layer immerse for 10 minutes - 30 minutes in the oxidizing agent solution heated to 60 degreeC - 100 degreeC. Moreover, as for the density|concentration of the permanganate in an alkaline permanganic acid solution, 5 mass % - 10 mass % are preferable. As a commercially available oxidizing agent, alkaline permanganic acid solutions, such as "Concentrate Compact CP" and "Dosing Solution Securigans P" by Atotech Japan, are mentioned, for example. Moreover, as a neutralization liquid used for a roughening process, an acidic aqueous solution is preferable, and as a commercial item, "reduction solution securigant P" by Atotech Japan company is mentioned, for example. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in a neutralizing solution at 30°C to 80°C for 1 minute to 30 minutes. The method of immersing the target object in which the roughening process by the oxidizing agent was made|formed from points, such as workability|operativity, in the neutralization liquid of 40 degreeC - 70 degreeC for 5 minutes - 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness Ra of the insulating layer surface after roughening is preferably 500 nm or less, more preferably 400 nm or less, still more preferably 300 nm or less. Although a lower limit is not specifically limited, Preferably it is 30 nm or more, More preferably, it is 40 nm or more, More preferably, it is 50 nm or more. The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact type surface roughness meter.

<Process (D)>

A process (D) is a process of forming a conductor layer on the surface of an insulating layer. The conductor material used for a conductor layer is not specifically limited. In a suitable embodiment, the conductor layer comprises at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. do. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer is, for example, an alloy of two or more metals selected from the group described above (eg, nickel-chromium alloy, copper-nickel alloy, and copper-titanium). a layer formed of an alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, a copper-nickel alloy , a copper/titanium alloy alloy layer is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel/chromium alloy is more preferable, and a single metal layer of copper This is more preferable.

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

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

As one preferred embodiment of the step (D), the conductor layer is formed by sputtering. In this invention, since the inorganic filler whose average particle diameter is 0.1 micrometer or less is included as a resin composition, the unevenness|corrugation difference of the location where the inorganic filler of the bottom surface of a via hole and a side wall was dug out becomes small. As a result, it becomes possible to make the thickness of the conductor layer formed in the via hole or trench uniform.

When forming the conductor layer by sputtering, normally, first, the conductor seed layer is formed on the surface of the insulating layer by sputtering, and then the conductor sputter layer is formed on the conductor seed layer by sputtering. Before formation of the conductor seed layer by sputtering, the surface of the insulating layer may be cleaned by reverse sputtering. As the gas used for the reverse sputtering, various gases can be used, and among them, Ar, O ₂ , and N ₂ are preferable. If the seed layer is Cu and Cu alloy, it is Ar or O ₂ or Ar, O ₂ mixed gas, if the seed layer is Ti, it is Ar or N ₂ or Ar, N ₂ mixed gas, and the seed layer is Cr and Cr alloy (Nichrome). etc.), Ar or O ₂ or Ar, O ₂ mixed gas is preferable. Sputtering can be performed using various sputtering apparatuses, such as a magnetron sputtering and a mirrortron sputtering. Examples of the metal forming the conductor seed layer include Cr, Ni, Ti, and nichrome. In particular, Cr and Ti are preferable. The thickness of the conductor seed layer is usually preferably 5 nm or more, more preferably 10 nm or more, preferably 1000 nm or less, and more preferably 500 nm or less. Cu, Pt, Au, Pd, etc. are mentioned as a metal which forms a conductor sputtering layer. In particular, Cu is preferable. The thickness of the conductor sputtering layer is usually preferably 50 nm or more, more preferably 100 nm or more, preferably 3000 nm or less, and more preferably 1000 nm or less.

After forming a conductor layer by sputtering, you may form a copper plating layer on the said conductor layer by electrolytic copper plating further. Usually, the thickness of a copper plating layer becomes like this. Preferably it is 5 micrometers or more, More preferably, it is 8 micrometers or more, Preferably it is 75 micrometers or less, More preferably, it is formed so that it may become 35 micrometers or less. Well-known methods, such as a subtractive method and a semi-additive method, can be used for circuit formation.

The manufacturing method of the printed wiring board of this invention shows the characteristic that a hollowing phenomenon is suppressed. Hereinafter, a hollowing phenomenon is demonstrated with reference to drawings.

Fig. 2 shows a surface 100U of a conventional printed wiring board in which a via hole is formed with a laser, opposite to the metal layer 210 (not shown in Fig. 2) of the insulating layer 100 immediately before the conductor layer is formed. ) is a schematic representation of 3 is a cross-sectional view schematically showing the insulating layer 100 just before the conductor layer is formed, together with the metal layer 210 of the inner circuit board 200 of a conventional printed wiring board in which via holes are formed with a laser. In FIG. 3 , a cross section of the insulating layer 100 is shown as a plane passing through the center 120C of the via bottom 120 of the via hole 110 and parallel to the thickness direction of the insulating layer 100 .

As shown in FIG. 2 , when a via hole is formed with a laser, the discoloration portion 140 may be generated due to deterioration of the resin due to the heat of the laser. The discoloration portion 140 is subjected to chemical erosion during the roughening treatment, the insulating layer 100 is peeled off from the metal layer 210 , and a gap portion 160 continuous from the edge 150 of the via bottom 120 . may be formed (a hollowing phenomenon).

In the present invention, since the via hole or trench is formed by plasma treatment that hardly generates heat, deterioration of the resin can be suppressed. Accordingly, peeling of the insulating layer 100 from the metal layer 210 can be suppressed, the size of the gap portion 160 can be reduced, and ideally, the discoloration portion 140 and the gap portion 160 can be eliminated. can

The size of the discoloration part 140 may be evaluated by the hollowing distance Wt of the via hole 110 from the edge 180 of the via top 130 .

The edge 180 of the via top 130 corresponds to the inner peripheral edge of the discoloration portion 140 . The hollowing distance Wt from the edge 180 of the via top 130 is the distance from the edge 180 of the via top 130 to the edge 190 on the outer periphery of the discoloration part 140 . indicates. As the hollowing distance Wt from the edge 180 of the via top 130 is smaller, it can be evaluated that the formation of the discoloration portion 140 can be effectively suppressed.

For example, plasma is irradiated to the insulating layer 100 obtained by curing the resin sheet formed on the copper foil by heating at 100° C. for 30 minutes and then at 180° C. for 30 minutes to cure, and a via having a top diameter (Lt) of about 15 μm. A hole 110 is formed. The hollowing distance Wt of the insulating layer 100 obtained in this way from the edge 180 of the via top 130 is preferably 15 µm or less, more preferably 10 µm or less, still more preferably 5 µm or less. It can be done below. Although the lower limit is not particularly limited, it can be set to 0 µm or more, 0.01 µm or more, or the like.

The hollowing distance Wt from the edge 180 of the via top 130 can be measured by observation with an optical microscope.

Further, according to the study of the present inventor, it has been found that, in general, the larger the diameter of the via hole 110 is, the larger the size of the discoloration portion 140 tends to be. Accordingly, the degree of suppression of formation of the discoloration portion 140 may be evaluated by the ratio of the size of the discoloration portion 140 to the diameter of the via hole 110 . For example, it can be evaluated by the hollowing ratio (Ht) to the top radius (Lt/2) of the via hole (110). Here, the top radius Lt/2 of the via hole 110 refers to the radius of the via top 130 of the via hole 110 . In addition, the hollowing ratio Ht to the top radius Lt/2 of the via hole 110 is the hollowing distance Wt from the edge 180 of the via top 130, It is a ratio obtained by dividing by the saw radius (Lt/2). The smaller the hollowing ratio Ht to the top radius Lt/2 of the via hole 110 is, the more effectively the formation of the discoloration portion 140 can be suppressed.

For example, plasma is irradiated to the insulating layer 100 obtained by heating and curing a resin sheet formed on copper foil at 100° C. for 30 minutes, then 180° C. for 30 minutes, and a via having a top diameter (Lt) of about 15 μm. A hole 110 is formed. The hollowing ratio (Ht) to the top radius (Lt/2) of the via hole 110 formed in the insulating layer 100 obtained in this way is preferably 35% or less, more preferably 25% or less, still more preferably may be 10% or less and 5% or less. Although the lower limit is not particularly limited, it can be set to 0% or more, 0.01% or more, or the like.

The hollowing ratio (Ht) to the top radius (Lt/2) of the via hole 110 is the top diameter (Lt) of the via hole 110 , and the edge ( 180) from the hollowing distance (Wt) can be calculated.

The edge 150 of the via bottom 120 corresponds to the inner peripheral edge of the gap portion 160 . Accordingly, the distance ( Wb) corresponds to the size of the gap portion 160 in the in-plane direction. Here, the in-plane direction refers to a direction perpendicular to the thickness direction of the insulating layer 100 . In the following description, the distance Wb is sometimes referred to as a hollowing distance Wb from the edge 150 of the via bottom 120 of the via hole 110 .

The size of the discoloration portion 140 can be evaluated by the degree of suppression of the hollowing phenomenon by the hollowing distance Wb from the edge 150 of the via bottom 120 . Specifically, it can be evaluated that the hollowing phenomenon can be effectively suppressed as the hollowing distance Wb from the edge 150 of the via bottom 120 is smaller.

The hollowing distance Wb of the via hole 110 of the insulating layer 100 from the edge 150 of the via bottom 120 is preferably 10 µm or less, more preferably 5 µm or less, still more preferably is 4.5 µm or less, particularly preferably 4 µm or less. Although the lower limit is not particularly limited, it can be set to 0 µm or more, 0.01 µm or more, or the like. The hollowing distance Wb is a cross section of the insulating layer 100 using a FIB (focused ion beam) that is parallel to the thickness direction of the insulating layer 100 and passes through the center 120C of the via bottom 120 . It can measure by observing the cross section with an electron microscope after cutting so that this may appear.

In addition, it has been found that, in the conventional method using a laser, the size of the gap portion 160 tends to increase as the diameter of the via hole increases. Accordingly, the degree of suppression of the hollowing phenomenon may be evaluated according to the ratio of the size of the gap portion 160 to the diameter of the via hole 110 . For example, it can be evaluated by the hollowing ratio Hb to the bottom radius Lb/2 of the via hole 110 . Here, the bottom radius Lb/2 of the via hole 110 refers to the radius of the via bottom 120 of the via hole 110 . In addition, the hollowing ratio (Hb) to the bottom radius (Lb/2) of the via hole 110 is the hollowing distance Wb from the edge 150 of the via bottom 120 , the It is a ratio obtained by dividing by the bottom radius (Lb/2). The smaller the hollowing ratio Hb to the bottom radius Lb/2 of the via hole 110 is, the more effectively the hollowing phenomenon can be suppressed.

The hollowing ratio (Hb) can be preferably set to 35% or less, more preferably 30% or less, still more preferably 25% or less. The hollowing ratio (Hb) to the bottom radius (Lb/2) of the via hole 110 is the bottom diameter (Lb) of the via hole 110 and the edge ( 150) from the hollowing distance (Wb).

In the manufacturing process of the printed wiring board, the via hole 110 is usually formed in a state in which another conductor layer (not shown) is not provided on the surface 100U of the insulating layer 100 opposite to the metal layer 210 . , is formed Therefore, if the manufacturing process of the printed wiring board is known, the structure in which the via bottom 120 is on the side of the metal layer 210 and the via top 130 is opened on the side opposite to the metal layer 210 can be clearly recognized. can However, in the completed printed wiring board, there may be cases in which conductor layers are provided on both sides of the insulating layer 100 . In this case, it may be difficult to distinguish the via bottom 120 from the via top 130 due to the positional relationship with the conductor layer. However, normally, the top diameter Lt of the via top 130 is larger than the bottom diameter Lb of the via bottom 120 . Accordingly, in the above case, it is possible to distinguish the via bottom 120 and the via top 130 according to the size of the diameter.

The manufacturing method of the printed wiring board of this invention can reduce the frequency of the location where the resin component was dug out of the bottom face and side wall of a via hole. For this reason, a conductor layer of uniform thickness can be formed in the via hole. When the cross-section of the insulating layer is observed using SEM, it can be confirmed that the copper layer is formed uniformly and without interruption on the wall surfaces of the trench and via hole formed in the insulating layer.

[Semiconductor device]

The semiconductor device of the present invention includes a printed wiring board. The semiconductor device of this invention can be manufactured using the printed wiring board obtained by the manufacturing method of this invention.

Examples of the semiconductor device include various semiconductor devices provided for electric appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trams, ships, and aircraft). there is.

The semiconductor device of this invention can be manufactured by mounting a component (semiconductor chip) in the conduction|electrical_connection location of a printed wiring board. A "conduction location" is "a location through which an electrical signal is transmitted on a printed wiring board", and the location may be on the surface or at an embedded location. In addition, a semiconductor chip will not be specifically limited if it is an electric circuit element which uses a semiconductor as a material.

The semiconductor chip mounting method in manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively, and specifically, a wire bonding mounting method, a flip chip mounting method, and a bumpless build-up layer (BBUL) The mounting method by , the mounting method by the anisotropic conductive film (ACF), the mounting method by the non-conductive film (NCF), etc. are mentioned. Here, the "mounting method using a bumpless build-up layer (BBUL)" is "a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board to connect the semiconductor chip and wiring on the printed wiring board".

[Example]

EXAMPLES Hereinafter, an Example is shown and this invention is demonstrated concretely. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" indicating quantities mean "parts by mass" and "% by mass", respectively, unless otherwise specified. In addition, the operation demonstrated below was performed in the environment of normal temperature and normal pressure, unless otherwise indicated.

<Used inorganic filler>

Inorganic filler 1: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical) with respect to 100 parts of spherical silica ("SC2500SQ" manufactured by Adomatex Co., Ltd., average particle diameter 0.63 µm, specific surface area 11.2 m 2 /g) Manufactured by Kogyo, KBM573) surface treated with 1 copy.

Inorganic filler 2: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical) with respect to 100 parts of spherical silica ("SC1500SQ" manufactured by Adomatex Co., Ltd., average particle diameter 0.3 µm, specific surface area 11 m 2 /g) Kogyo Co., Ltd., KBM573) surface treated with 2 parts.

Inorganic filler 3: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical) with respect to 100 parts of spherical silica (“SC4500SQ” manufactured by Adomatex Co., Ltd., average particle diameter of 1.0 μm, specific surface area of 4.5 m 2 /g) Manufactured by Kogyo, KBM573) surface treated with 1 copy.

<Preparation of resin composition 1>

6 parts of bixylenol-type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical, about 185 epoxy equivalent), 5 parts of naphthalene-type epoxy resin ("ESN475V" manufactured by Shin-Nippon Sumikin Chemical, about 332 epoxy equivalent), bisphenol AF-type epoxy 15 parts of resin ("YL7760" manufactured by Mitsubishi Chemical, about 238 epoxy equivalent), 2 parts of naphthylene ether type epoxy resin ("HP6000L" manufactured by DIC, about 213 epoxy equivalent), cyclohexane type epoxy resin (made by Mitsubishi Chemical) "ZX1658GS", epoxy equivalent about 135) 2 parts, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., cyclohexanone of 30 mass% solid content: 1:1 solution of methyl ethyl ketone (MEK), Mw = 35000) 2 Part was heated and dissolved in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone while stirring. After cooling to room temperature, thereto, 4 parts of a triazine skeleton-containing cresol novolac curing agent ("LA-3018-50P" manufactured by DIC, about 151 hydroxyl equivalent, a 50% solid content 2-methoxypropanol solution); 6 parts of active ester resin ("EXB-8000L-65TM" manufactured by DIC, about 220 active group equivalents, a 1:1 solution of toluene:methyl ethyl ketone (MEK) containing 65 mass% of nonvolatile components), inorganic filler 1 85 Part, 0.05 parts of an amine-based curing accelerator (4-dimethylaminopyridine (DMAP)) are mixed and uniformly dispersed with a high-speed rotary mixer, followed by filtration with a cartridge filter (“SHP020” manufactured by ROKITECHNO) to prepare a resin composition 1 did.

<Preparation of resin composition 2>

In the preparation of the resin composition 1,

6 parts of active ester-based resin (“EXB-8000L-65TM” manufactured by DIC, about 220 active group equivalents, a 1:1 solution of toluene:methylethylketone (MEK) containing 65% by mass of nonvolatile components), active ester-based resin ( "EXB-8200L-65T" manufactured by DIC, about 233 active group equivalents, toluene solution with a solid content of 65% by mass) was changed to 6 parts,

85 parts of inorganic filler 1 was changed to 82 parts of inorganic filler 2.

Except for the above, it carried out similarly to preparation of the resin composition 1, and prepared the resin composition 2.

<Preparation of resin composition 3>

In the preparation of the resin composition 1,

2 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, 1:1 solution of cyclohexanone:methylethyl ketone (MEK) having a solid content of 30% by mass, Mw = 35000), 2 parts of phenoxy resin ("YL7500BH30" manufactured by Mitsubishi Chemical Corporation) ", a 1:1 solution of cyclohexanone: methyl ethyl ketone (MEK) with a solid content of 30% by mass, Mw = 44000) is changed to 2 parts,

85 parts of inorganic filler 1 was changed to 110 parts of inorganic filler 3.

Except for the above, it carried out similarly to preparation of the resin composition 1, and prepared the resin composition 3.

<Preparation of resin composition 4>

Preparation of the resin composition 1 WHEREIN: The quantity of the inorganic filler 1 was changed from 85 parts to 48 parts. Except for the above, it carried out similarly to preparation of the resin composition 1, and prepared the resin composition 4.

The component and the compounding quantity (mass part of a non-volatile matter) used for preparation of the resin compositions 1-4 were shown in the following table|surface. In addition, content of a hardening|curing agent and active ester type resin shows content at the time of making the resin component in a resin composition 100 mass %, and content of (a) component is 100 mass % or 100 volume of non-volatile components in a resin composition. The content in the case of % is shown.

<Production of resin sheets A and B>

As the support, a PET film (“Lumira R80” manufactured by Toray Corporation, 38 μm thick, 130° C. softening point, “Releasable PET”) was prepared with an alkyd resin mold release agent (“AL-5” manufactured by Lintec). Each resin composition was uniformly applied with a die coater on the mold release agent of the support so that the thickness of the resin composition layer after drying was 35 µm, and dried at 70 ° C. to 95 ° C. for 2 minutes to obtain a resin composition layer on mold release PET. Next, a rough surface of a polypropylene film ("Alpan MA-411" manufactured by Ouji Ftex, 15 µm in thickness) as a protective film was applied to the surface of the resin sheet that is not bonded to the support, and the resin composition layer and laminated to bond. Thereby, the resin sheet A which consists of mold release PET (support body), a resin composition layer, and a protective film in order was obtained.

Moreover, it carried out similarly to the resin sheet A, and the resin sheet B was obtained except having apply|coated each resin composition uniformly with the die coater so that the thickness of the resin composition layer after drying might be set to 15 micrometers.

<Measurement of thickness of resin composition layer etc.>

The thickness of the resin composition layer was measured using a contact-type film thickness meter (manufactured by Mitsutoyo, MCD-25MJ).

- Preparation of evaluation boards A and B -

(1) Preparation of copper clad laminate

As a copper clad laminate, a glass cloth-based epoxy double-sided copper clad laminate (copper foil thickness 3 μm, substrate thickness 0.15 mm, Mitsubishi Gas Chemical Co., Ltd. “HL832NSF LCA”, 255 × 340 mm size) in which copper foil layers are laminated on both sides was prepared, 130 It was put in an oven at ℃ and dried for 30 minutes.

(2) Lamination of resin sheets

Peel off the protective film from each produced resin sheet A, and use a batch vacuum pressurization laminator (manufactured by Nikko Materials, two-stage build-up laminator, CVP700) so that the resin composition layer is in contact with the copper clad laminate on both sides of the copper clad laminate laminated to Lamination was performed by pressure-reducing for 30 second, making atmospheric pressure 13 hPa or less, and crimping|bonding at 130 degreeC and pressure 0.74 MPa for 45 second. Subsequently, hot pressing was performed at 120°C and a pressure of 0.5 MPa for 75 seconds.

(3) thermosetting of the resin composition layer

The copper clad laminate on which the resin sheet A was laminated was put into an oven at 100° C. for 30 minutes, then transferred to an oven at 180° C. for 30 minutes, thermosetted to form an insulating layer, and the support was peeled off. Thereby, the copper clad laminated board A with a 35 micrometers insulating layer was obtained.

Moreover, except using the resin sheet B, it carried out similarly to preparation of the copper clad laminated board A, and obtained the copper clad laminated board B with a 15 micrometers insulating layer.

(4) Pattern formation of dry film

A dry film (“ALPHO 20A263” manufactured by Nikko Materials Co., Ltd.) having a thickness of 20 μm was bonded to the surface of the insulating layer of the copper clad laminate A with the insulating layer formed thereon. Lamination of the dry film was carried out using a batch-type vacuum pressurization laminator (“MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.) for 30 seconds to reduce the pressure to 13 hPa or less, then at a pressure of 0.1 MPa and a temperature of 70° C., 20 It was carried out by pressing for a second. Then, the glass mask which has a trench pattern was put on the polyethylene terephthalate film which is a protective layer of a dry film, and UV irradiation was performed with the irradiation intensity|strength of 150 mJ/cm<2> with a UV lamp. After UV irradiation, spray treatment was performed for 30 seconds at a spray pressure of 0.15 MPa using a 1% sodium carbonate aqueous solution at 30°C. Then, it washed with water and patterned so that a trench pattern with a wiring width of 20 micrometers might be formed, and, thereby, the trench process board|substrate was obtained.

Further, using a glass mask having a via pattern, patterning was performed on the copper clad laminate B in the same manner as in the copper clad laminate A to form a via hole having a top diameter of 15 µm to obtain a via processing substrate.

(5) Plasma processing

Examples 1 to 3, Comparative Example 1, using a plasma dry etching apparatus (PlasmaPro100 manufactured by Oxford Instruments Co., Ltd.), Ar/SF ₆ /O ₂ Mixing ratio 10:40:8 (sccm), vacuum degree: 50mTorr, RF Power: 120 W, ICP power: 0 W, processing is performed for 5 minutes, and the top (diameter) is about 15 in the insulating layer on the trench processing substrate, in the trench with a width of about 25 μm, and in the insulating layer on the via processing substrate. After forming a micrometer via hole, the dry film was peeled off after that, and the trench evaluation board|substrate was obtained.

Further, in the same manner as in the preparation of the trench evaluation substrate, a via hole having a top profile (diameter) of about 15 μm was formed in the insulating layer of the via processing substrate, and then the dry film was peeled off to obtain a via evaluation substrate.

(6) Sandblasting

Comparative Example 2 uses silicon carbide (average particle size of 0.6 µm, quartz Mohs hardness 13, "SER-A06" manufactured by Shinano Denki Seiren Co., Ltd.) as an abrasive grain, and is insulating on a trench processed substrate at a processing pressure of 0.2 MPa. A trench was formed by performing the sandblasting process of the layer, after that, the dry film was peeled and the sandblast trench evaluation board|substrate was produced.

Further, in the same manner as in the production of the sand blast trench evaluation substrate, a via hole having a top system (diameter) of about 15 μm was formed in the insulating layer of the via processing substrate, and then the dry film was peeled off to obtain a sand blast via evaluation substrate. .

(7) UV-YAG laser via processing

Comparative Example 3 uses a UV-YAG laser processing machine (“LU-2L212/M50L” manufactured by Via Mechanics Co., Ltd.) to irradiate the insulating layer of the copper clad laminate B with laser light, and the top diameter (diameter) is about A plurality of via holes of 15 μm were formed. The laser beam irradiation conditions were a power of 0.08 W and a number of shots of 25. Let this board|substrate be a laser evaluation board|substrate.

<Observation of trench wall and via wall>

After heating the trench evaluation substrate, the via evaluation substrate, the sand blast trench evaluation substrate, and the sand blast via evaluation substrate at 150° C. for 30 minutes, a sputtering device (“E-400S” manufactured by Canon Anelva Co., Ltd.) was used to form the insulating layer on the insulating layer. A copper layer (thickness 200 nm) was formed. Then, cross-sectional observation was performed using the FIB-SEM composite apparatus ("SMI3050SE" by SII nanotechnology company), and the following reference|standard evaluated.

○: A copper layer is formed uniformly and without interruption on the wall surface of the trench or the wall surface of the via hole formed in the insulating layer.

x: The copper layer is not formed uniformly by unevenness.

<Measurement of via hole dimensions and hollowing distance>

The via evaluation board|substrate, the sand blast via evaluation board|substrate, and the laser evaluation board|substrate were observed with the optical microscope ("KH8700" by Hyrox Corporation). In detail, the insulating layer around the via hole was observed from the top of the via evaluation substrate using an optical microscope (CCD). Observation of the dimensions of the via hole was performed by focusing the optical microscope on the via top. In the observed image, the top diameter (Lt) of the via hole was measured. In the periphery of the via hole, continuous from the edge of the via top of the via hole, it was observed whether a donut-shaped hollow part in which the insulating layer was discolored white was seen. From the observed image, the radius of the via top of the via hole (corresponding to the inner circumferential radius of the hollowing part) (r1) and the outer circumferential radius (r2) of the hollowing part are measured, and the difference (r2) between these radii (r1) and the radius (r2) -r1) was calculated as the hollowing distance from the edge of the via top of the measurement point.

The above measurement was carried out at randomly selected 5 via holes. Then, the average of the measured values of the measured top diameters of the via holes at five locations was employed as the top diameter (Lt1) of the via holes of the sample. In addition, the average of the measured values of the hollowing distances of five via holes was employ|adopted as a hollowing distance (Wt) from the edge of the via top of the sample.

The hollowing ratio (Ht) represents the ratio "Wt/(Lt1/2)" of the hollowing distance Wt from the edge of the via top to the radius (Lt1/2) of the via top of the via hole before the roughening process. When this hollowing ratio (Ht) was 35 % or less, hollowing evaluation was determined as "○", and when hollowing ratio (Ht) was larger than 35%, hollowing evaluation was determined as "x".

* A “-” in the hollowing distance field means that no hollowing is observed.

100 insulating layer
The side of the insulating layer opposite to the 100U conductor layer
110 via hole
120 via bottom
Center of 120C via bottom
130 via top
140 discoloration area
Edge of via bottom of 150 via hole
160 gap
170 End of the gap part on the outer periphery side
Edge of 180 via top
190 Edge of discoloration part
200 inner layer substrate
210 metal layer
1010 Inorganic Filling
Cured product of 1020 resin component
1030 The place where the cured product of the resin component was dug out
Bottom diameter of Lb via hole
Top diameter of Lt via hole
Wb Hollowing distance from the edge of the via bottom
Wt Hollowing distance from the edge of the via top

Claims (9)

(A) a step of forming an insulating layer containing a cured product of a resin composition on an inner-layer circuit board; and
(B) performing plasma treatment on the surface of the insulating layer to form a via hole or trench;
When a resin composition contains an inorganic filler and content of an inorganic filler makes the non-volatile component in a resin composition 100 mass %, it is 60 mass % or more,
The manufacturing method of the printed wiring board in which the gas used for plasma processing contains _SF6 . (A) a step of forming an insulating layer containing a cured product of a resin composition on an inner-layer circuit board; and
(B) performing plasma treatment on the surface of the insulating layer to form a via hole or trench;
When a resin composition contains an inorganic filler and content of an inorganic filler makes the nonvolatile component in a resin composition 100 volume%, it is 38 volume% or more,
The manufacturing method of the printed wiring board in which the gas used for plasma processing contains _SF6 . The manufacturing method of the printed wiring board of Claim 1 or 2 which further includes the process of (D) forming a conductor layer. The manufacturing method of the printed wiring board of Claim 3 in which a process (D) forms a conductor layer by sputtering. The method for manufacturing a printed wiring board according to claim 1 or 2, wherein the gas used for plasma processing contains a mixed gas containing SF ₆ and at least one gas selected from Ar and O ₂ . The manufacturing method of the printed wiring board of Claim 1 or 2 in which a resin composition contains curable resin. A resin composition for forming an insulating layer of a printed wiring board, comprising:
containing inorganic fillers;
When content of an inorganic filler makes the non-volatile component in a resin composition 100 mass %, the resin composition for forming the via hole or trench by a plasma processing in the insulating layer of a printed wiring board which is 60 mass % or more. A resin composition for forming an insulating layer of a printed wiring board, comprising:
containing inorganic fillers;
The resin composition for forming the via hole or trench by plasma processing in the insulating layer of a printed wiring board whose content of an inorganic filler makes the nonvolatile component in a resin composition 100 volume%, 38 volume% or more. The resin composition according to claim 7 or 8, further comprising a curable resin.

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