KR20220056810A - Method for manufacturing printed wiring board - Google Patents

Abstract

The present invention provides a method for manufacturing a printed wiring board which can have small-diameter via holes formed therein, have excellent smear removability, and suppress occurrence of a hollowing phenomenon. The method for manufacturing a printed wiring board comprises the processes of: (A) forming an opening part in an insulating layer containing a hardened material of a resin composition, by a laser; and (B) forming a via hole by subjecting the opening part to a sandblasting process using an abrasive grain.

Description

The manufacturing method of a printed wiring board {METHOD FOR MANUFACTURING PRINTED WIRING BOARD}

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

In recent years, in a printed wiring board, the buildup layer is multilayered, and refinement|miniaturization and density increase of wiring are calculated|required. The buildup layer is formed by the buildup method of alternately stacking the insulating layer and the conductor layer, and in the manufacturing method by the buildup method, it is common that the 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. 2017-59779

By the way, in manufacturing a printed wiring board, a via hole may be formed in an insulating layer. A "via hole" usually refers to a hole penetrating an insulating layer. As a method of forming a via hole, a method using a laser can be considered.

When a via hole is formed with a laser, a resin residue called smear may be formed in the via hole. In order to remove such a smear, it is normal to perform the desmear process which removes a smear using a chemical|medical solution after formation of a via hole by a laser. 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 a 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. Further, the deteriorated portion is usually observed as a discolored portion.

Moreover, although the method of suppressing a hollowing phenomenon using a sandblasting process can be considered, it is difficult to form a small-diameter via-hole by sandblasting, and the processing speed of a via-hole may be slow.

The present invention has been made in view of the above circumstances, and is to provide a method for manufacturing a printed wiring board in which a via hole of a small diameter can be formed, the smear removability is excellent, and the occurrence of a hollowing phenomenon is suppressed.

As a result of intensive studies to solve the above problems, the present inventors have found that the smear removability is excellent and the hollowing phenomenon can be suppressed by forming the via hole by sandblasting after forming the opening with the laser. , came to complete the present invention.

That is, the present invention includes the following contents.

[1] (A) a step of forming an opening in an insulating layer containing a cured product of a resin composition by means of a laser;

(B) a step of forming a via hole by sandblasting the opening using an abrasive grain;

A method for manufacturing a printed wiring board, including in this order.

[2] The method for manufacturing a printed wiring board according to [1], wherein the average particle diameter of the abrasive grains is 10 µm or less.

[3] The method for manufacturing a printed wiring board according to [1] or [2], wherein the depth of the opening is 50% or more and 95% or less of the thickness of the insulating layer.

[4] Step (B) is a step of forming a via hole by colliding abrasive grains on the bottom surface of the opening through a mask,

The method for manufacturing a printed wiring board according to any one of [1] to [3], wherein the ratio (total value/opening diameter) of the sum of the thickness of the mask and the depth of the opening to the opening diameter of the via hole is 3 or less.

[5] The method for manufacturing a printed wiring board according to any one of [1] to [4], wherein the insulating layer has an elastic modulus at 23°C of 0.1 GPa or more.

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

[7] The method for producing a printed wiring board according to [6], wherein the content of the inorganic filler is 20% by mass or more when the nonvolatile component in the resin composition is 100% by mass.

[8] The method for producing a printed wiring board according to any one of [1] to [7], wherein the resin composition contains a curable resin.

[9] The method for producing a printed wiring board according to [8], wherein the content of the curable resin is 10% by mass or more when the nonvolatile component in the resin composition is 100% by mass.

[10] The method for producing a printed wiring board according to [8] or [9], wherein the curable resin contains an epoxy resin and a curing agent.

[11] The method for producing a printed wiring board according to [10], wherein the curing agent is at least one selected from a phenol-based resin, an active ester-based resin and a cyanate ester-based resin.

[12] The method for manufacturing a printed wiring board according to any one of [1] to [11], wherein the laser is a CO ₂ laser or a UV-YAG laser.

ADVANTAGE OF THE INVENTION According to this invention, a via hole of a small diameter can be formed, it is excellent in smear removability, and the manufacturing method of the printed wiring board by which generation|occurrence|production of the hollowing phenomenon was suppressed can be provided.

1 is a schematic cross-sectional view showing an example of a mode in which an insulating layer and a support are formed on the main surface of an inner-layer circuit board.
Fig. 2 is a schematic cross-sectional view showing an example of a state after performing the step (A).
Fig. 3 is a schematic cross-sectional view showing an example of a state after performing the step (B).
4 : 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.
5 : is sectional drawing 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.
Fig. 6 is a schematic cross-sectional view showing an example of a mode in which an insulating layer and a metal foil are formed on the main surface of an inner-layer circuit board.
Fig. 7 is a schematic cross-sectional view showing an example of a state after performing a pattern etching process on metal foil.
Fig. 8 is a schematic cross-sectional view showing an example of a state after performing the step (A).
Fig. 9 is a schematic cross-sectional view showing an example of a state after performing the step (B).
[Fig. 10] Fig. 10 is a schematic cross-sectional view showing an example of a state after forming a filled via.
11 is a schematic cross-sectional view showing an example of a mode in which an insulating layer, a metal foil, and a dry film are formed on the main surface of an inner circuit board.
12 is a schematic cross-sectional view showing an example of a state after exposure and development.
13 : is a schematic sectional drawing which shows an example of a mode after performing a process (A).
Fig. 14 is a schematic cross-sectional view showing an example of a state after performing the step (B).
[Fig. 15] Fig. 15 is a schematic cross-sectional view showing an example of a state after forming a filled via.
Fig. 16 is a schematic cross-sectional view showing an example of a state after the dry film is removed.
[Fig. 17] Fig. 17 is a schematic cross-sectional view showing an example of a mode in which an insulating layer and a dry film are formed on the main surface of an inner-layer circuit board.
18 is a schematic cross-sectional view showing an example of a state after exposure and development.
Fig. 19 is a schematic cross-sectional view showing an example of a state after the step (A) is performed.
[ Fig. 20 ] Fig. 20 is a schematic cross-sectional view showing an example of a state after the step (B) is performed.
[Fig. 21] Fig. 21 is a schematic cross-sectional view showing an example of a state after forming a filled via.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment and an illustration are shown and this invention is demonstrated in detail. However, this invention is not limited to the embodiment and exemplification given below, It can be implemented by changing arbitrarily in the range which does not deviate from the range which does not deviate from the claim of this invention and its equivalent.

Before demonstrating in detail the manufacturing method of the printed wiring board of this invention, the "resin composition" and "resin sheet with a support body" used by the manufacturing method of the printed wiring board of this invention are demonstrated.

[resin composition]

The resin composition used for forming the cured body may be one in which an insulating layer, which is a cured product, has sufficient hardness and insulating properties. In one embodiment, the resin composition includes (a) an inorganic filler. The resin composition may further contain (b) curable resin, (c) hardening accelerator, (d) thermoplastic resin, (e) elastomer, and (f) other additives as needed. Hereinafter, each component contained in a resin composition is demonstrated in detail.

<(a) Inorganic filler>

The resin composition contains (a) an inorganic filler. As the material of the inorganic filler, an inorganic compound is used. Examples of the inorganic filler material 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 phosphate tungstate, 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, "UFP-30" by a Denka company, "ASFP-20"; "SP60-05", "SP507-05", "SPH516-05" manufactured by Nittetsu Chemical &Materials; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Adomatex Corporation; "Silly writing NSS-3N", "Silly writing NSS-4N", "Silly writing NSS-5N" by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" by the Adomatex company, etc. are mentioned.

(a) The specific surface area of the component 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 restriction 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.

The average particle diameter of the component (a) is preferably 0.01 µm or more, more preferably 0.05 µm or more, still more preferably 0.1 µm or more, and preferably 5 µm from the viewpoint of significantly obtaining the desired effect of the present invention. Hereinafter, more preferably, it is 2 micrometers or less, More preferably, it is 1 micrometer 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 intermediate diameter into an average particle diameter. As the measurement sample, 100 mg of inorganic filler and 10 g of methyl ethyl ketone were weighed in a vial bottle, and what was dispersed for 10 minutes by ultrasonic wave can be used. Using a laser diffraction particle size distribution measuring device, the measurement sample was measured with a particle size distribution based on the volume of component (a) by a flow cell method using a light source wavelength of blue and red, and from the obtained particle size distribution As the median diameter, the average particle diameter can be calculated. As a laser diffraction type particle size distribution measuring apparatus, "LA-960" by Horiba Corporation, etc. are mentioned, for example.

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 combining two 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 Chemical Industry Co., Ltd. “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. “KBE903” manufactured by Shin-Etsu Chemical Co., Ltd. ” (3-aminopropyltriethoxysilane), “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. “SZ-31” (hexamethyl) manufactured by Shin-Etsu Chemical Co., Ltd. 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 treating 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 treating agent can be evaluated by 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. Further, 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.

(a) The content (mass %) of the component is preferably 20 mass % or more, more preferably 30 mass %, when the non-volatile component in the resin composition is 100 mass % from the viewpoint of significantly obtaining the effect of the present invention. % or more, more preferably 40 mass % or more, and 50 mass % or more, preferably 95 mass % or less, more preferably 90 mass % or less, still more preferably 85 mass % or less, 80 mass % or less. In addition, in this invention, unless otherwise indicated, 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 %.

Content (vol%) of the component (a) is preferably 10% by volume or more, more preferably 30% by volume, when the nonvolatile component in the resin composition is 100% by volume from the viewpoint of significantly obtaining the effect of the present invention It is volume % or more, More preferably, it is 50 volume% or more, Preferably it is 90 volume% or less, More preferably, it is 85 volume% or less, More preferably, it is 80 volume% or less.

<(b) curable resin>

The resin composition may contain (b) curable resin. (b) As curable resin, curable resin which can be used when forming the insulating layer of a printed wiring board can be used, A thermosetting resin 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 and the like. (b) A component may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. Hereinafter, like a phenol-based resin, a naphthol-based resin, a benzooxazine-based resin, an active ester-based resin, a cyanate ester-based resin, a carbodiimide-based resin, an amine-based resin, or an acid anhydride-based resin, the resin composition is reacted with an epoxy resin Resins that can harden are sometimes referred to as "curing agents" together. It is preferable that an epoxy resin and a hardening|curing agent are included as (b) component from a viewpoint of making a dielectric loss tangent low as a resin composition.

(b) As an epoxy resin as a component, For example, a bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin , Trisphenol type epoxy resin, naphthol 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, glycidyl cyclohexane 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, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, phenolphthalimidine type epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

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% by mass of the nonvolatile component of component (b) is preferably 50% by mass or more, more preferably Preferably it is 60 mass % or more, Especially preferably, it is 70 mass % or more.

The epoxy resin includes 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, may be referred to as “solid epoxy resin”). there is The resin composition may contain only the liquid epoxy resin, may contain only the solid epoxy resin, and may contain it combining the liquid epoxy resin and the solid epoxy resin as (b) component.

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 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 , alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and butadiene structure epoxy resin, glycidylcyclohexane type epoxy resin, phenolphthal An imidine type epoxy resin is preferable, and a bisphenol A type epoxy resin, a glycidyl cyclohexane type epoxy resin, and a phenol phthalimidine type epoxy resin are 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) by the Nitetsu Chemical & Materials company, etc. 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 novolac-type epoxy resin, a dicyclopentadiene-type epoxy resin, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, and a non Phenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins are preferable, and biphenyl-type epoxy resins and bixylenol-type epoxy resins , a tetraphenylethane type epoxy resin, a naphthalene type epoxy resin, and a naphthylene ether type epoxy resin are more preferable.

Examples of the solid-state epoxy resin include a naphthalene-type tetrafunctional epoxy resin, a cresol novolac-type epoxy resin, a dicyclopentadiene-type epoxy resin, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, and a naphthylene ether-type epoxy resin. , 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-state 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 novolac 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 novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Corporation resin); "ESN475V" (naphthalene-type epoxy resin), "ESN485" (naphthol novolak-type epoxy resin) by a Nittetsu 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 Chemical, "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); "WHR-991S" (phenolphthalimidine type epoxy resin) by a Nippon Kayaku company, 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 is 1:0.3 to 1:10, particularly preferably 1:0.5 to 1:5. 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 significantly obtained. Moreover, when using in the form of a resin sheet with a support body normally, moderate adhesiveness is formed. Moreover, when using normally in the form of a resin sheet with a support body, sufficient flexibility can be acquired and handleability 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 5,000 g/eq., more preferably 50 g/eq. to 3,000 g/eq., more preferably 80 g/eq. to 2,000 g/eq., even more preferably 110 g/eq. to 1,000 g/eq. By being in such a 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. Such an 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 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500 from the viewpoint of significantly obtaining the desired effect of the present invention. . The weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

(b) 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 non-volatile component in the resin composition is 100% by mass, preferably 1% by mass or more, more preferably is 3% by mass or more, more preferably 5% by mass or more. The upper limit of the content of the epoxy resin is preferably 50% by mass or less, more preferably 45% by mass or less, particularly preferably 40% by mass or less from the viewpoint of significantly obtaining the desired effect of the present invention.

(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 an active ester-based resin containing a novolac benzoyl product. 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. "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); "EXB9416-70BK" and "EXB-8150-65T" (manufactured by DIC Corporation) as active ester-based resins containing a naphthalene structure; "DC808" (made by Mitsubishi Chemical Co., Ltd.) as an active ester resin containing the acetylated product of phenol novolac; "YLH1026" (made by Mitsubishi Chemical Co., Ltd.) as an active ester-type resin containing the benzoyl compound of phenol novolac; "DC808" (manufactured by Mitsubishi Chemical) as an active ester-based resin that is an acetylated product of phenol novolac; Examples of the active ester resin that is a benzoyl product of phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation).

(b) As a phenol-type resin and a naphthol-type resin as a component, what has a novolak structure from a viewpoint of heat resistance and water resistance is preferable. Moreover, from a viewpoint of adhesiveness with a conductor layer, a nitrogen-containing phenol-type hardening|curing agent 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" by Meiwa Kasei Corporation, "NHN" by a Nippon Kayaku Corporation, "CBN", for example, ”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN-495V”, “SN375”, “SN395” manufactured by Nittetsu Chemical & Materials Co., Ltd. ', "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" by DIC company etc. are mentioned.

(b) As a specific example of the 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 Chemical Co., Ltd.; "HFB2006M" by Showa Kobunshi (benzoxazine ring equivalent 432) etc. are mentioned.

(b) As cyanate ester-type resin as a component, bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'- methylene bis is, for example. (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" by Ronza Japan (phenol novolak-type polyfunctional cyanate ester resin); "ULL-950S" (polyfunctional cyanate ester resin); "BA230", "BA230S75" (a prepolymer in which a part or all of bisphenol A dicyanate was triazine-ized and became a trimer), "BADCy" (bisphenol A dicyanate), etc. are mentioned.

(b) As a specific example of the carbodiimide-based resin as a component, 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); Stavacuzol (registered trademark) P (carboimide group equivalent: 302) manufactured by Rhein Chemis Co., Ltd. can be heard

(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 A-A", "Kayahard A-B", "Kayahard A-S" manufactured by Nippon Kayaku Co., Ltd. , "Epicure W" 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 resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, and trialkyltetrahydrophthalic anhydride. , dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trimellitic anhydride, pyromelli anhydride Tonic acid, 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), polymer type acid anhydrides, such as styrene maleic acid resin which copolymerized styrene and maleic acid, etc. are mentioned.

(b) As the curing agent as a component, any one of 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, and an acid anhydride-based resin Preferably, any one of an active ester-based resin, a phenol-based resin, a carbodiimide-based resin, and a naphthol-based resin is preferable, and at least one selected from a phenol-based resin, an active ester-based resin and a cyanate ester-based resin is more desirable.

(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 in the epoxy resin]: [the total number of reactive groups in the curing agent] in a ratio of 1:0.01 to 1 The range of :5 is preferable, 1:0.1 - 1:3 are more preferable, and 1:0.3 - 1:2 are still more preferable. Here, "the number of epoxy groups of an epoxy resin" is the value which added all the value 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 added 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 is preferably 1% by mass or more, more preferably 3% by mass or more, more preferably 1% by mass or more with respect to 100% by mass of the nonvolatile component in the resin composition from the viewpoint of obtaining a cured product having excellent flexibility. Preferably it is 5 mass % or more, Preferably it is 40 mass % or less, More preferably, it is 30 mass % or less, More preferably, it is 20 mass % or less.

(b) The content of the component, from the viewpoint of significantly obtaining the effect of the present invention, with respect to 100 mass% of the nonvolatile component in the resin composition, preferably 10 mass% or more, more preferably 13 mass% or more, still more preferably is 15 mass % or more, Preferably it is 50 mass % or less, More preferably, it is 45 mass % or less, More preferably, it is 40 mass % or less.

<(c) curing accelerator>

The resin composition may contain the (c) hardening accelerator as an arbitrary component. 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, tetrabutylphosphoniumdecanoate, (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-dimethylaminopyridine 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 Imidazole, 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-phenylimida Zolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-unde Silimidazolyl-(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, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1, 2-a] imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline, imidazole compounds and epoxy resins of adducts, and 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, 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.

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

(c) the content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, particularly preferably 0.03% by mass or more, when the nonvolatile component in the resin composition is 100% by mass, Preferably it is 3 mass % or less, More preferably, it is 1 mass % or less, Especially preferably, it is 0.5 mass % or less.

In addition, when the curing agent as the component (b) is not included, the content of the curing accelerator (c) is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, when the nonvolatile component in the resin composition is 100% by mass. It is 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.

<(d) Thermoplastic resin>

The resin composition may contain the (d) thermoplastic resin as an arbitrary component. (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 10,000 or more, More preferably, it is 15,000 or more, More preferably, it is 20,000 or more. The upper limit is preferably 100,000 or less, more preferably 70,000 or less, still more preferably 60,000 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. It can calculate /K-804L using chloroform etc. as a mobile phase, measuring a column temperature at 40 degreeC, and using the standard polystyrene calibration curve.

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. and phenoxy resins having at least one skeleton selected from the group consisting of skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton and trimethylcyclohexane skeleton. Any functional group, such as a phenolic hydroxyl group and an epoxy group, 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), "YX8100" (bisphenol S skeleton-containing phenoxy resin) and "YX6954" (bisphenol acetophenone manufactured by Mitsubishi Chemical Corporation) skeleton-containing phenoxy resin), in addition to "FX280" and "FX293" by Nittetsu Chemical & Materials, "YL7500BH30", "YX6954BH30" by Mitsubishi Chemical, "YX7553", "YX7553BH30" , "YL7553BH30", "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 Chemical Co., Ltd. S-Rec BH series, BX series (eg BX-5Z), KS series (eg KS-1), BL series, BM series, etc. are mentioned. .

As a specific example of polyimide resin, "Ricacoat SN20" and "Ricacoat PN20" by a New 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 (polyimide described in Japanese Patent Application Laid-Open No. 2006-37083), polysiloxane Modified polyimides, such as skeleton containing polyimide (The polyimide described in Unexamined-Japanese-Patent No. 2002-12667, Unexamined-Japanese-Patent No. 2000-319386, etc.) are mentioned.

As a specific example of polyamideimide resin, "Viromax HR11NN" and "Viromax HR16NN" by Toyobo Co., Ltd. are mentioned. Specific examples of the polyamideimide resin include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing polysiloxane skeleton) manufactured by Hitachi Chemical Co., 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 oligophenylene ether styrene resin "OPE-2St1200" by Mitsubishi Gas Chemical Company, etc. are mentioned. As a specific example of polyether ether ketone resin, the Sumitomo Chemical Company "Sumiproy K" etc. are mentioned. Specific examples of the polyetherimide resin include "Urtem" manufactured by GE Corporation.

As a specific example of polysulfone resin, the polysulfone "P1700" by Solvay Advanced Polymers, "P3500", etc. are mentioned.

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. Therefore, 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 10,000 or more is especially preferable.

(d) When content of a thermoplastic resin makes the non-volatile component in a resin composition 100 mass %, Preferably it is 0.1 mass % or more, More preferably, it is 0.3 mass % or more, 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.

<(e) elastomer>

The resin composition may use the (e) elastomer as an arbitrary component other than the said component. (e) A component may be used individually by 1 type, and may use 2 or more types together.

(e) As a component, in a molecule|numerator, a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, a polyester structure, and a poly It is preferable that it is a resin having at least one structure selected from a carbonate structure, and in the molecule, a polybutadiene structure, a poly(meth)acrylate structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyester structure, or a polycarbonate structure It is more preferable that it is a resin which has 1 type(s) or 2 or more types of structures selected, and it is more preferable that it is a resin which has any one of a polybutadiene structure, a polyester structure, and a polycarbonate structure in a molecule|numerator. In addition, "(meth)acrylate" is a term including a methacrylate, an acrylate, and a combination thereof. These structures may be contained in the main chain of the elastomer molecule or may be contained in the side chain.

(e) It is preferable that a component has a high molecular weight from a viewpoint of acquiring the effect of this invention remarkably. (e) The number average molecular weight (Mn) of the component is preferably 1,000 or more, more preferably 1,500 or more, still more preferably 3,000 or more and 5,000 or more. The upper limit is preferably 1,000,000 or less, more preferably 900,000 or less. A number average molecular weight (Mn) is a polystyrene conversion number average molecular weight measured using GPC (gel permeation chromatography).

It is preferable that (e) component has a low glass transition temperature (Tg) from a viewpoint of acquiring the effect of this invention remarkably. (e) The glass transition temperature (Tg) of component becomes like this. Preferably it is 30 degrees C or less, More preferably, it is 20 degrees C or less, More preferably, it is 10 degrees C or less. Preferably it is -60 degreeC or more, More preferably, it is -50 degreeC or more, More preferably, it is -45 degreeC or more.

It is preferable that (e) component has a functional group which can react with the epoxy resin as (b) component from a viewpoint of reacting with the epoxy resin as (b) component, hardening a resin composition, and raising peeling strength. In addition, as a functional group which can react with an epoxy resin, the functional group shown by heating shall be included.

In one suitable embodiment, the functional group capable of reacting with the epoxy resin as component (b) is 1 selected from the group consisting of a hydroxyl group, a carboxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group It is more than a species of functional group. Among them, the functional group is preferably a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group, more preferably a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, or an epoxy group, and a phenolic hydroxyl group is particularly preferred. However, when an epoxy group is included as a functional group, it is preferable that the weight average molecular weight (Mw) of (e) component is 5,000 or more.

(e) A preferred embodiment of the component is a resin containing a polybutadiene structure, and the polybutadiene structure may be contained in the main chain or may be contained in the side chain. In addition, a part or all of polybutadiene structure may be hydrogenated. A resin containing a polybutadiene structure is called a polybutadiene resin.

Specific examples of the polybutadiene resin include "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", "Ricon 184MA6" manufactured by Clay Valle. ” (polybutadiene containing an acid anhydride group), “GQ-1000” (polybutadiene introduced with hydroxyl groups and carboxyl groups) manufactured by Nippon Soda Corporation, “G-1000”, “G-2000”, “G-3000” (both terminals) Hydroxyl group polybutadiene), "GI-1000", "GI-2000", "GI-3000" (polybutadiene hydrogenated with hydroxyl groups at both ends), "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin) manufactured by Nagase Chemtex and the like. As an embodiment, a linear polyimide using a hydroxyl group-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride as raw materials (a polyimide described in Japanese Patent Application Laid-Open Nos. 2006-37083 and International Publication No. 2008/153208) and phenolic hydroxyl group-containing butadiene. The content rate of the butadiene structure of the said polyimide resin becomes like this. Preferably it is 60 mass % - 95 mass %, More preferably, it is 75 mass % - 85 mass %. For the details of the polyimide resin, Japanese Patent Application Laid-Open No. 2006-37083 and International Publication No. 2008/153208 can be considered, the contents of which are incorporated herein by reference.

A suitable embodiment of the component (e) is a resin containing a poly(meth)acrylate structure. A resin containing a poly(meth)acrylate structure is called a poly(meth)acrylic resin. As poly(meth)acrylic resin, "ME-2000", "W-116.3", "W-197C", "KG-25", "KG by Nagase Chemtex Co., Ltd. Teisan Resin, Negami Kogyo Co., Ltd. make -3000" and the like.

A preferred embodiment of the component (e) is a resin containing a polycarbonate structure. A resin containing a polycarbonate structure is called a polycarbonate resin. As polycarbonate resin, "T6002", "T6001" (polycarbonate diol) by Asahi Kasei Corporation, "C-1090", "C-2090", "C-3090" (polycarbonate diol) by Kuraray Corporation, etc. can be heard Moreover, the linear polyimide which uses a hydroxyl-terminated polycarbonate, a diisocyanate compound, and a tetrabasic acid anhydride as raw materials can also be used. The content rate of the carbonate structure of the said polyimide resin becomes like this. Preferably it is 60 mass % - 95 mass %, More preferably, it is 75 mass % - 85 mass %. For details of the polyimide resin, the description of International Publication No. 2016/129541 may be taken into consideration, the content of which is incorporated herein by reference.

Moreover, as another embodiment of (e) component, it is resin containing a polysiloxane structure. A resin containing a polysiloxane structure is referred to as a siloxane resin. As the siloxane resin, for example, "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone Co., Ltd., an amine group-terminated polysiloxane, and a linear polyimide using a tetrabasic acid anhydride as raw materials (International Publication) 2010/053185, Japanese Patent Application Laid-Open No. 2002-12667, and Japanese Patent Application Laid-Open No. 2000-319386) and the like.

(e) As another embodiment of a component, it is resin containing a polyalkylene structure and a polyalkyleneoxy structure. A resin containing a polyalkylene structure is called a polyalkylene resin, and a resin containing a polyalkyleneoxy structure is called a polyalkyleneoxy resin. The polyalkyleneoxy structure preferably has a polyalkyleneoxy structure having 2 to 15 carbon atoms, more preferably a polyalkyleneoxy structure having 3 to 10 carbon atoms, and polyalkylene having 5 to 6 carbon atoms. The oxy structure is more preferred. As a specific example of polyalkylene resin and polyalkyleneoxy resin, "PTXG-1000", "PTXG-1800" by Asahi Kasei Seni Co., Ltd., etc. are mentioned.

(e) Another embodiment of the component is a resin containing a polyisoprene structure. A resin containing a polyisoprene structure is called a polyisoprene resin. As a specific example of polyisoprene resin, "KL-610", "KL613" by a Kuraray company, etc. are mentioned.

(e) As another embodiment of a component, it is resin containing a polyisobutylene structure. A resin containing a polyisobutylene structure is called a polyisobutylene resin. Specific examples of the polyisobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) manufactured by Kaneka Corporation, "SIBSTAR-042D" (styrene-isobutylene diblock copolymer), etc. can be heard

(e) A preferred embodiment of the component is a resin containing a polyester structure. A resin containing a polyester structure is called a polyester resin. As a polyester resin, "Byron 600", "Byron 560", "Byron 230" by Toyobo Corporation, "Byron GK-360", "Byron BX-1001", "LP-035" by Mitsubishi Chemical Corporation, " LP-011", "TP-220", "TP-249", "SP-185", etc. are mentioned.

(e) the content of the elastomer is preferably 5% by mass or more, more preferably 10% 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 Preferably it is 15 mass % or more. An upper limit becomes like this. Preferably it is 50 mass % or less, More preferably, it is 45 mass % or less, More preferably, it is 40 mass % or less.

<(f) other additives>

The resin composition may further contain other additives as arbitrary components other than the said component. Examples of such additives include flame retardants; organic fillings; 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.

Examples of the flame retardant include a phosphazene compound, an organophosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide, and a phosphazene compound is preferable. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

Although a phosphazene compound will not be specifically limited if it is a cyclic compound which has nitrogen and phosphorus as structural elements, It is preferable that a phosphazene compound is a phosphazene compound which has a phenolic hydroxyl group.

As a specific example of a phosphazene compound, "SPH-100", "SPS-100", "SPB-100" "SPE-100" by Otsuka Chemical Co., Ltd. make, "FP-100" by Fushimi Seyakusho Corporation, for example, as a specific example of a phosphazene compound, ', "FP-110", "FP-300", "FP-400", etc. are mentioned, "SPH-100" by the Otsuka Chemical Company is preferable.

As a flame retardant other than a phosphazene compound, you may use a commercial item, For example, "HCA-HQ" by Sanko Corporation, "PX-200" by a Daihachi Chemical Industry, etc. are mentioned. As the flame retardant, one that is difficult to hydrolyze is preferable, and for example, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like are preferable.

When content of a flame retardant makes the nonvolatile component in a resin composition 100 mass %, Preferably it is 0.1 mass % or more, More preferably, it is 0.2 mass % or more, More preferably, it is 0.3 mass % or more. An upper limit becomes like this. Preferably it is 15 mass % or less, More preferably, it is 10 mass % or less, More preferably, it is 5 mass % or less.

As an organic filler, you may use arbitrary organic fillers which can be used when forming the insulating layer of a printed wiring board, For example, a rubber particle, polyamide microparticles|fine-particles, a silicone particle, etc. are mentioned. As a rubber particle, you may use a commercial item, For example, "EXL2655" by a Dow Chemical Nippon company, "AC3401N" by Aika Corporation, "AC3816N", etc. are mentioned. An organic filler may be used individually by 1 type, or may use 2 or more types together.

When content of an organic filler makes the nonvolatile component in a resin composition 100 mass %, Preferably it is 0.1 mass % or more, More preferably, it is 0.15 mass % or more, More preferably, it is 0.2 mass % or more. An upper limit becomes like this. Preferably it is 10 mass % or less, More preferably, it is 5 mass % or less, More preferably, it is 3 mass % or less.

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 with Support]

The resin sheet with a support body 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 150 µm or less, more preferably 100 µm or less, more preferably 150 µm or less, more preferably 100 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. Preferably it is 50 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, may be abbreviated as “PET”), polyethylene naphthalate (hereinafter, abbreviated as “PEN”). Polyester such as ), polycarbonate (hereinafter, may be abbreviated as “PC”), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide ( PES), polyether ketone, polyimide, etc. are mentioned. Among them, 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. good.

A support body may give a mat treatment, a corona treatment, and an antistatic treatment to the surface to join with 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 on the surface to join with the 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 the 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 mold release layer which has alkyd resin mold release agents, such as "Purex" manufactured by manufacture and "Uni-Peel" by a Unichika company, 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 with a support body may further contain the other layer as needed. As such another layer, the protective film according to the support body etc. which were provided on the surface which is not joined to the support body of a resin composition layer (namely, 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 with a support is prepared by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying this resin varnish on a support using a die coater or the like, and further drying to form a resin composition layer can do.

As an organic solvent, For example, ketones, such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetic acid 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 varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of an organic solvent, the resin composition layer is dried at 50°C to 150°C for 3 minutes to 10 minutes. can form.

The resin sheet with a support body can be wound up and preserve|saved in roll shape. When the resin sheet with a support body has a protective film, it becomes usable by peeling off a protective film.

[Manufacturing method of printed wiring board]

The method for manufacturing a printed wiring board of the present invention comprises:

(A) a step of forming an opening in an insulating layer containing a cured product of a resin composition by means of a laser; and

(B) Sandblasting the opening using an abrasive grain to form a via hole in this order.

As described above, as a method of forming a via hole in the insulating layer, a method using a laser can be considered. When a via hole is formed using only a laser, a hollowing phenomenon may occur due to heat generated by irradiating the laser. In addition to the method of forming the via hole using a laser, there is a method of forming the via hole by sand blasting. If the via hole is formed only by sand blasting, the occurrence of the hollowing phenomenon can be suppressed, but it is difficult to form a small diameter via hole, and the processing speed of the via hole may be slow.

In the present invention, a small-diameter via hole can be formed by first forming an opening in the insulating layer by means of a laser, and then forming a via hole by colliding abrasive grains on the bottom surface of the opening by sandblasting. It is excellent in property, and it becomes possible to suppress generation|occurrence|production of a hollowing phenomenon. In addition, since the opening as a part of the via hole is formed by the laser and not the entire via hole is formed, the number of laser shots can be reduced. In addition, since the via hole is formed by sandblasting in the opening formed by the laser, deterioration of the resin around the bottom of the via hole can be suppressed, so the occurrence of the hollowing phenomenon can be suppressed, and the processing time can be reduced. It also becomes possible to shorten it (via workability).

Before performing the step (A), the manufacturing method of the printed wiring board,

(1) a process of preparing an inner-layer circuit board; and

(3) The step of forming an insulating layer on the main surface of the inner-layer circuit board may be included.

In addition, in order to use it for formation of the insulating layer in the said process (3), the manufacturing method of a printed wiring board,

(2) The step of preparing a resin sheet with a support including a support and a resin composition layer provided on the support and formed of a resin composition may be further included.

Hereinafter, each process of the manufacturing method of a printed wiring board is demonstrated.

<Process (1)>

Step (1) is a step of preparing an inner-layer circuit board. An inner-layer circuit board is usually provided with a support substrate and a metal layer provided on the surface of the support substrate. The metal layer is exposed on the main surface of the inner circuit board, and a via hole is formed in the region where the metal layer is located. Accordingly, the region in which the via hole is formed on the main surface of the inner-layer circuit board is formed of the metal layer.

As a material of a support substrate, a glass epoxy board|substrate, a metal board|substrate, a polyester board|substrate, a polyimide board|substrate, a BT resin board|substrate, a thermosetting polyphenylene ether board|substrate etc. are mentioned, for example. 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.

The arithmetic mean roughness Ra of the main surface of the inner circuit board is preferably 500 nm or less, more preferably 450 nm or less, still more preferably 400 nm or less and 350 nm or less. By setting the arithmetic mean roughness Ra of the main surface of the inner circuit board to 500 nm or less, it is possible to suppress the insulating layer formed on the main surface from entering deep into the inner circuit board, and it is possible to improve the workability of the via hole. Although it does not specifically limit about a lower limit, Preferably it is 10 nm or more, More preferably, it is 50 nm or more, More preferably, it is 100 nm or more. The arithmetic mean roughness (Ra) of the principal surface is a value measured based on ISO 25178, and can be measured using a non-contact type surface roughness meter. The main surface of the inner-layer circuit board refers to the surface of the inner-layer circuit board on which the insulating layer is provided.

In addition, when the arithmetic mean roughness (Ra) is not constant in the main surface, the arithmetic mean roughness (Ra) of the main surface in the region where the metal layer is formed should just be in the above range, and the main surface in the region where the via hole is formed. It is preferable that the arithmetic mean roughness Ra is in the above range.

As a 10-point average roughness Rz of the main surface of an inner-layer circuit board, Preferably it is 5,000 nm or less, More preferably, it is 4,500 nm or less, More preferably, it is 4,000 nm or less. By setting the 10-point average roughness Rz of the main surface of the inner circuit board to 5,000 nm or less, the insulating layer formed on the main surface can be suppressed from entering deep into the inner circuit board, and the insulation reliability can be improved. Although it does not specifically limit about a minimum, Preferably it is 50 nm or more, More preferably, it is 100 nm or more, More preferably, it is 1,000 nm or more. The 10-point average roughness (Rz) of the main surface is a value measured based on ISO 25178, and can be measured using a non-contact type surface roughness meter.

In addition, when the 10-point average roughness Rz is not constant in the main surface, the 10-point average roughness Rz of the main surface in the region where the metal layer is formed is preferably in the above range, and in the region where the via hole is formed It is more preferable that the 10-point average roughness (Rz) of the main surface of is in the above range.

The main surface of the inner-layer circuit board can adjust the arithmetic mean roughness Ra and the 10-point mean roughness Rz to the above ranges by, for example, etching and polishing.

<Process (2)>

A process (2) is a process of preparing the resin sheet with a support body containing a support body and the resin composition layer provided on the said support body and formed from the resin composition. About the resin sheet with a support body, it is as having demonstrated above.

<Process (3)>

Step (3) is a step of forming an insulating layer on the main surface of the inner-layer circuit board. At a process (3), for example, on the main surface of an inner-layer circuit board, the resin composition layer of the resin sheet with a support body is laminated|stacked, and an insulating layer is formed by thermosetting the resin composition layer.

As an example is shown in FIG. 1 , the inner-layer circuit board 10 includes a support substrate 11 and a metal layer 12 provided on the surface of the support substrate 11 . In the step (3), the insulating layer 22 is formed by laminating a resin sheet (not shown) with a support body on the main surface 10a of the inner circuit board 10 and thermosetting the resin composition layer. Usually, since the insulating layer 22 is provided on the surface of the metal layer 12, the surface of the metal layer 12 on the opposite side to the surface on the side of the support substrate 11 is the main surface 10a. In addition, although the metal layer 12 is provided on one surface of the support substrate 11 in FIG. 1, you may provide on both surfaces of the support substrate 11. As shown in FIG.

Lamination of the inner-layer circuit board and the resin sheet with a support can be performed by, for example, thermocompressing the resin sheet with a support to the inner-layer circuit board from the support side. As a member (hereinafter also referred to as "thermal compression member") for heat-bonding the resin sheet with a support to the inner circuit board, for example, a heated metal plate (SUS head plate, etc.) or metal roll (SUS roll), etc. are mentioned. . In addition, it is preferable not to press the thermocompression-bonding member directly to the resin sheet with a support, but to press through an elastic material, such as a heat-resistant rubber, so that the resin sheet with a support 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 the resin sheet with a support body by the vacuum lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, and the thermocompression compression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably is in the range of 0.29 MPa to 1.47 MPa, and the heat compression time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination|stacking becomes like this. Preferably it is performed under reduced pressure conditions of pressure 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 Sesakusho company, the vacuum applicator by the Nikko Materials company, a batch type vacuum pressure laminator etc. are mentioned, for example.

After lamination, the laminated resin sheet with a support body may be smoothed under normal pressure (under atmospheric pressure), for example, 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.

After laminating the resin sheet with a support body on an inner-layer circuit board, the resin composition layer is thermosetted and the insulating layer is formed. 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 vary depending on the type of resin composition, etc., the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, still more preferably 170°C to 210°C. 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 the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing 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 heated 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 25 µm or less, preferably 20 µm or less, more preferably 15 µm or less, still more preferably 10 µm or less from the viewpoint of forming a small-diameter via hole. Although the lower limit of the thickness of an insulating layer is not specifically limited, Usually, it can be 1 micrometer or more, 5 micrometers or more, etc.

In addition, in the process (3), instead of the method of using a resin sheet, 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 at this time are the same as the conditions for forming the insulating layer using the resin sheet with a support body.

The elastic modulus at 23° C. of the insulating layer obtained by curing the resin composition layer at 200° C. for 90 minutes is preferably 0.1 GPa or more, more preferably 1 GPa or more, more preferably 3 GPa or more, from the viewpoint of improving the via processability. , Preferably it is 30 GPa or less, More preferably, it is 25 GPa or less, More preferably, it is 20 GPa or less. An elastic modulus can be measured by the method described in the Example mentioned later.

The support may be removed after laminating and thermosetting the resin sheet with a support, may be removed after completion of step (A), may be removed after laminating and thermosetting the resin sheet with support, or sandblasting in step (B) You may remove it after using it as a mask by a process.

<Process (A)>

A process (A) is a process of forming an opening part in the insulating layer containing the hardened|cured material of a resin composition with a laser. As an embodiment of the step (A), as an example is shown in FIG. 2 , a laser is irradiated to the insulating layer 22 formed on the main surface 10a of the inner circuit board 10 to form the opening 30 . .

It is preferable to perform laser irradiation in the state which provided the mask for a sandblasting process on the insulating layer 22. Accordingly, the step (A) may include a step of forming a mask on the insulating layer 22 before laser irradiation. As a mask, a dry film, metal foil, these combinations, etc. are mentioned, for example. These masks can be provided on the insulating layer 22 by, for example, laminating either a dry film or a metal foil on the insulating layer after peeling the support.

As a dry film, a thing which can obtain a patterned dry film by exposure and image development is preferable, and if it is a film with tolerance with respect to the sandblasting process in the process (B) mentioned later, it 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.

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. good.

The thickness of the mask 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. Preferably it is 70 micrometers or less, More preferably, it is 50 micrometers or less.

The thickness of the mask such as metal foil is preferably 1 µm or more, more preferably 2 µm or more, still more preferably 3 µm or more, preferably 40 µm or less, more preferably from the viewpoint of improving the workability of the via hole. Preferably it is 20 micrometers or less, More preferably, it is 15 micrometers or less.

In addition, you may use the support body 21 as a mask. When the support body 21 is used as a mask, since the process of providing a mask different from the support body 21 can be omitted, the manufacturing method can be simplified. In this embodiment, as shown in FIG. 2, the example which used the support body 21 as a mask is shown and demonstrated.

The depth (a) of the opening is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more of the thickness of the insulating layer from the viewpoint of significantly obtaining the effect of the present invention. As an upper limit, it is preferable that it is 95 % or less of the thickness of an insulating layer, More preferably, it is 90 % or less, More preferably, it is 85 % or less. The depth of the opening refers to the distance from the surface of the insulating layer on the side in contact with the mask (the support body 21 in FIG. 2 ) to the bottom of the opening. The depth of the opening can be obtained by observing the cross-section and calculating the difference between the deepest part of the non-processed part and the non-insulating part of the insulating layer.

The opening diameter (b) of the opening may be the opening diameter (via diameter) of the via hole. The opening diameter (b) is preferably 100 µm or less, more preferably 75 µm or less, still more preferably 55 µm or less, preferably 5 µm or more, more Preferably it is 10 micrometers or more, More preferably, it is 15 micrometers or more. In addition, the opening diameter b shows the diameter in the upper end of the insulating layer 22, as shown in FIG.

The ratio of the depth (a) of the opening to the diameter (b) of the opening (depth (a) of the opening/diameter (b) of the opening of the opening) is preferably 0.1 or more from the viewpoint of significantly obtaining the effects of the present invention. , More preferably, it is 0.3 or more, More preferably, it is 0.5 or more, Preferably it is 3 or less, More preferably, it is 1 or less, More preferably, it is 0.7 or less.

As a laser light source which can be used for formation of an opening part, _a CO2 laser (carbon dioxide gas laser), a UV-YAG laser, a UV laser, a YAG laser, an excimer laser, etc. are mentioned, for example. Among them, a CO ₂ laser or a UV-YAG laser is preferable from the viewpoint of processing speed and cost.

When irradiating a CO ₂ laser, the number of shots is preferably 2 or less, more preferably 1, from the viewpoint of improving the via processability. In order to keep the number of shots within the above range, it is preferable to set the energy and pulse width of the CO ₂ laser to a certain value or more. The energy of the CO ₂ laser is preferably 0.3 W or more, more preferably 0.5 W or more, still more preferably 1.0 W or more, preferably 30 W or less, more preferably 20 W or less, still more preferably 15 W or less. am. Further, the pulse width of the CO ₂ laser is preferably 3 μsec or more, more preferably 5 μsec or more, still more preferably 8 μsec or more, preferably 40 μsec or less, more preferably 30 μsec or less, still more preferably 20 μsec or less. am.

When irradiating a UV-YAG laser, the number of shots is preferably 20 or less, more preferably 15, from the viewpoint of improving the via processability. In order to keep the number of shots within the above range, it is preferable to set the energy and pulse width of the UV-YAG laser to a certain value or more. The energy of the UV-YAG laser is preferably 0.05 W or more, more preferably 0.10 W or more, still more preferably 0.15 W or more, preferably 20 W or less, more preferably 10 W or less, still more preferably 5 W or less. is below.

The via hole can be formed using a commercially available laser device. As a commercially available carbon dioxide laser apparatus, "LC-2E21B/1C" by Hitachi Via Mechanics, "ML605GTWII" by Mitsubishi Electric Corporation, and a substrate punching laser processing machine by Matsushita Yosetsu Systems, Inc. are mentioned, for example. Moreover, as a UV-YAG laser apparatus, "LU-2L212/M50L" by Via Mechanics, etc. is mentioned, for example.

In the step (A), as described above, it is preferable to form the opening 30 by irradiating a laser to the insulating layer 22 provided with a mask such as the support 21 . Therefore, preferably, the opening 30 is formed in communication with not only the insulating layer 22 but also the mask. Therefore, when the support body 21 is used as a mask like the example shown in FIG. 2, the opening part 30 can be formed continuously in the insulating layer 22 and the support body 21. As shown in FIG. In this case, the ratio (total value) of the total value (c) of the thickness of the mask (the thickness of the support body 21 in Fig. 2) and the depth (a) of the opening, and the diameter of the opening of the via hole formed in the step (B). (c)/aperture diameter) is preferably 3 or less, more preferably 2.5 or less, still more preferably 2 or less, preferably 0.1 or more, more preferably from the viewpoint of significantly obtaining the effect of the present invention. It is 0.3 or more, More preferably, it is 0.5 or more. Here, the thickness of a mask means the thickness of the mask before performing a process (B).

In addition, the ratio (sum value (c)/aperture diameter (b)) of the total value (c) of the thickness of the mask and the depth (a) of the opening, and the opening diameter (b) of the opening 30 before the step (B) ) is, from the viewpoint of significantly obtaining the effects of the present invention, preferably 3 or less, more preferably 2.5 or less, still more preferably 2 or less, preferably 0.1 or more, more preferably 0.3 or more, still more preferably is greater than or equal to 0.5.

The total value (c) of the thickness of the mask and the depth of the opening is preferably 50% or more of the total thickness of the mask and the insulating layer from the viewpoint of significantly obtaining the effect of the present invention, more preferably 60% or more, still more preferably more than 70%. As an upper limit, it is preferable that it is 95 % or less of the total thickness of a mask and an insulating layer, More preferably, it is 90 % or less, More preferably, it is 80 % or less.

<Process (B)>

The step (B) is a step of forming a via hole in the opening by sandblasting using an abrasive grain. As a detailed embodiment of the step (B), a via hole is formed by colliding an abrasive grain on the bottom surface of the opening through a mask. As a mask, it is preferable that it is at least any one of the support body opened by the process (A), a dry film, and metal foil, and a support body is more preferable.

In the step (B), sand blasting is performed to make the abrasive grains collide with the bottom surface of the opening 30 (that is, the exposed surface of the insulating layer) as shown in FIG. 2 to form the via hole 40 (after the via hole formation). An example is shown). Here, in the sandblasting treatment, abrasive grains or slurry solutions of abrasive grains are sprayed from a nozzle on the surface of a location not covered by a mask such as a support, dry film, or metal foil by air sprayed at a predetermined pressure, and the abrasive grains are insulated It refers to a process in which a via hole is formed by colliding with a layer. The sand blasting treatment in the step (B) may be either a dry blasting treatment for spraying abrasive grains or a wet blasting treatment for spraying a slurry solution of abrasive grains, but from the viewpoint of forming small-diameter via holes, it is preferable to perform a wet blasting treatment. .

The modified Mohs hardness of the abrasive grains used in the sandblasting treatment is preferably 1 or more, more preferably 5 or more, still more preferably 6 or more, 7 or more from the viewpoint of forming a small-diameter via hole by the sandblasting treatment. am. The upper limit can be set to 15 or less normally. The crystal Mohs hardness of the abrasive grains can be measured using, for example, a Mohs hardness meter.

Examples of the abrasive include inorganic compounds such as silica and glass; metal compounds such as steel, stainless steel, zinc and copper; ceramics such as garnet, zirconia, silicon carbide, alumina, and boron carbide; The particle|grains etc. which have dry ice etc. as a main component are mentioned. Among them, inorganic compounds and ceramics are preferable, and any one of alumina, silicon carbide, and silica is preferable from the viewpoint of remarkably obtaining the desired effect of the present invention. As for silica, crystalline silica is preferable.

A commercial item can be used for the abrasive grain. As a commercial item, For example, the Denka company make "DAW-03", the Nittetsu Chemical & Materials company make "AY2-75" (alumina); "GP#4000", "SER-A06" (silicon carbide) by Shinano Denki Seren Co., Ltd.; "IMSIL A-8" by Tatsumori (crystalline silica); "Fuji Random WA" by Fuji Sesakusho (melted alumina) is mentioned.

As an average particle diameter of the abrasive grains, it is 0.5 micrometer or more, Preferably it is 1 micrometer or more, More preferably, it is 2 micrometers or more. Via workability can be improved by making the lower limit of the average particle diameter of an abrasive grain into this range. In addition, it is possible to suppress blowing against the abrasive grains in the sandblasting process, and it becomes possible to suppress grinding of the mask. The blowing in the opposite direction of the abrasive grains refers to a phenomenon in which the abrasive grains blown into the openings penetrate the openings and reduce the collision speed by the action of the returning airflow, and it is particularly remarkable in the case of abrasive grains having a small average particle diameter. The upper limit of the average particle diameter of the abrasive grains is 20 µm or less, preferably 15 µm or less, and more preferably 10 µm or less. By making the upper limit of the average particle diameter of the abrasive grains within such a range, the workability of the small-diameter via hole can be improved. The average particle diameter of an abrasive grain can be measured by scanning electron microscope observation, for example, The detail can be performed by the method of Unexamined-Japanese-Patent No. 2008-41932.

The pressure (working pressure) for spraying the abrasive grains is preferably 0.05 MPa or more, more preferably 0.1 MPa or more, still more preferably 0.15 MPa or more, preferably 1 MPa or less, more preferably 0.8 MPa or less, further Preferably it is 0.5 MPa or less. By setting the processing pressure within this range, the processing time can be shortened. The working pressure here is a value on the surface of the insulating layer.

The distance between the nozzle and the mask is preferably 200 mm or less, more preferably 190 mm or less, still more preferably 180 mm or less, preferably 10 mm or more, more preferably 15 mm or more, still more preferably 20 mm or more. By setting the distance within this range, the via hole can be efficiently formed.

When the manufacturing method of the present invention is used, it exhibits a characteristic that the processing time of the sand blasting process can be shortened even if the top diameter of the via hole is a small diameter via hole. The processing time is preferably less than 10 minutes, more preferably 8 minutes or less, still more preferably 5 minutes or less and less than 5 minutes. Although the lower limit is not particularly limited, it can be set to 0.1 minutes or more.

Although the example which uses the support body 21 as a mask was shown in FIG. 3, instead of the support body 21, you may use any one of metal foil and a dry film as a mask.

<Other processes>

When manufacturing a printed wiring board, after completion|finish of a process (B), you may further implement the process of (C) roughening an insulating layer, and the process of forming a conductor layer (D). You may implement these process (C) and process (D) according to various methods well-known to those skilled in the art used for manufacture of a printed wiring board. Moreover, you may form a multilayer wiring board by repeating formation of the insulating layer and conductor layer of a process (A) - a process (D) as needed. Moreover, the manufacturing method of a printed wiring board may include the process of removing a mask at an appropriate timing. Usually, a mask is removed after a process (B) and before a process (C).

A process (C) is a process of roughening an insulating layer (it is also mentioned a desmear process). Usually, the removal of the abrasive grain is also performed in this process (C). The procedure and conditions of a roughening process 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 swelling process by a swelling liquid, the roughening process by an oxidizing agent, and the neutralization process by a neutralizing liquid can be performed in this order, and an insulating layer can be roughened. 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. there is. 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" by Atotech Japan, "Dosing Solution Securigans P", are mentioned, for example. Moreover, as a neutralization liquid used for a roughening process, 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 roughened by the oxidizing agent 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, arithmetic mean roughness Ra of the insulating layer surface after a roughening process becomes like this. Preferably it is 500 nm or less, More preferably, it is 400 nm or less, More preferably, it is 300 nm or less. Although it does not specifically limit about a lower limit, 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.

A process (D) is a process of forming a conductor layer, and forms a conductor layer on 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 as the alloy layer, for example, an alloy of two or more metals selected from the group described above (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy) ) can be mentioned. Among them, from the viewpoints of versatility of conductor layer formation, cost, ease of patterning, and the like, single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper or nickel-chromium alloys, copper-nickel alloys, An alloy layer of a copper/titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper or an alloy layer of a nickel/chromium alloy is more preferable, and a single metal layer of copper is further desirable.

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.

In one embodiment, the conductor layer may be formed by plating. For example, by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full additive method, a conductor layer having a desired wiring pattern can be formed. It is preferable to form by the additive method. Hereinafter, an example in which the conductor layer is formed by a semi-additive method is shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Then, on the formed plating seed layer, a mask pattern for exposing a part of the plating seed layer corresponding to the desired wiring pattern is formed. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

Since the manufacturing method of the printed wiring board of this invention performs a process (A) and a process (B), it shows the characteristic that a via hole of a small diameter can be formed. The top diameter (via diameter) of the via hole is preferably 100 µm or less, more preferably 75 µm or less, still more preferably 55 µm or less, preferably 5 µm or more, more preferably 10 µm or more; More preferably, it is 15 micrometers or more. Details of the method for measuring the via diameter and evaluation can be performed by the method described in Examples to be described later.

Since the manufacturing method of the printed wiring board of this invention performs a process (A) and a process (B), it shows the characteristic that it is excellent in smear removability. Therefore, after forming a via hole by the method of this invention, if the desmear process of immersing in this order of a swelling liquid, a roughening liquid, and a neutralizing liquid, a resin residue is not seen in the bottom part of a via hole. Evaluation of smear removability can be performed by the method as described in the Example mentioned later.

The manufacturing method of the printed wiring board of this invention shows the characteristic that a hollowing phenomenon is suppressed. Specifically, even if the via hole diameter is small within the above range, the hollowing phenomenon can be suppressed. Hereinafter, the hollowing phenomenon will be described with reference to the drawings.

4 shows a surface 22U of a conventional printed wiring board in which a via hole is formed with a laser, opposite to the metal layer 12 (not shown in FIG. 4) of the insulating layer 22 immediately before the conductor layer is formed. It is a schematic plan view. 5 : is sectional drawing which shows typically the insulating layer 22 just before the conductor layer is formed of the conventional printed wiring board in which the via hole was formed with a laser, together with the metal layer 12 of an inner-layer circuit board. In FIG. 5 , a cross-section of the insulating layer 22 is shown in a plane that passes through the center 220C of the via bottom 220 of the via hole 40 and is parallel to the thickness direction of the insulating layer 22 .

As shown in FIG. 5, when the via hole 40 is formed with a laser, the discoloration part 240 may arise due to the deterioration of resin by the heat of a laser. The discoloration portion 240 is subjected to chemical erosion during roughening, the insulating layer 22 is peeled off from the metal layer 12 , and a gap portion 260 continuous from the edge 250 of the via bottom 220 . may be formed (a hollowing phenomenon).

In this invention, since the sandblasting process which hardly generates heat|fever after forming an opening part with a laser is employ|adopted, deterioration of resin can be suppressed. Therefore, peeling of the insulating layer 22 from the metal layer 12 can be suppressed, and the size of the gap part 260 can be made small.

The edge 250 of the via bottom (the bottom of the via (via bottom)) 220 corresponds to the inner peripheral edge of the gap portion 260 . Accordingly, the distance ( Wb) corresponds to the size of the gap portion 260 in the in-plane direction. Here, the in-plane direction refers to a direction perpendicular to the thickness direction of the insulating layer 22 . In the following description, the distance Wb is sometimes referred to as a hollowing distance Wb from the edge 250 of the via bottom 220 of the via hole 40 . The degree of suppression of the hollowing phenomenon can be evaluated by the hollowing distance Wb from the edge 250 of the via bottom 220 . Specifically, it can be evaluated that the hollowing phenomenon can be effectively suppressed as the hollowing distance Wb from the edge 250 of the via bottom 220 is smaller.

Using the manufacturing method of the present invention, even when a via hole having a top diameter of 50 μm or less is formed, the hollowing distance Wb of the via hole 40 of the insulating layer 22 from the edge 250 of the via bottom 220 is , preferably 5 µm or less, more preferably 4 µm or less, still more preferably 3 µm or less. The lower limit is not particularly limited, but may be 0 µm or more, 0.1 µm or more, or the like.

The manufacturing method of this invention can manufacture the printed wiring board which has a via hole and a trench, as an example is shown in FIGS. In detail, as an example is shown in FIG. 6, the insulating layer 22 is formed on the inner-layer circuit board 10 before performing a process (A), and the metal foil 60 is further laminated on the insulating layer 22. do. After laminating the metal foil 60, as an example is shown in FIG. 7, the pattern etching process is performed to the metal foil 60, a part of the metal foil 60 is removed, and the hole 61 is formed. Then, as an example is shown in FIG. 8, the process (A) of irradiating a laser to the predetermined location of the metal foil 60 is performed, and the opening part 30 is formed. Next, as an example is shown in Fig. 9, by performing the step (B), the via hole 40 is formed from the opening 30 and the abrasive grains are collided with the bottom of the hole 61 by sand blasting. A trench 50 is formed. Thereafter, as an example is shown in FIG. 10 , the via hole 40 and the trench 50 are filled by electrolytic plating to form a filled via 80 . After the formation of the filled via 80 , the metal foil 60 may be removed if necessary.

Alternatively, a metal foil may be laminated on the resin composition layer of the resin sheet with a support to obtain a metal foil with a resin composition layer, and the metal foil with a resin composition layer may be laminated on an inner circuit board to form an insulating layer and a metal foil on the inner circuit board.

Moreover, the manufacturing method of this invention can manufacture the printed wiring board which has a patterned conductor layer, as an example is shown to FIGS. In detail, as an example is shown in FIG. 11, the insulating layer 22 is formed on the inner-layer circuit board 10 before performing a process (A), and the metal foil 60 and the dry film 70 are further insulated. Laminate over layer 22 . After laminating the metal foil 60 and the dry film 70, as an example is shown in FIG. 12, a part of the dry film 70 is exposed and developed to form a hole 71 from which a part of the dry film 70 is removed. do. Then, as an example is shown in FIG. 13, the process (A) of irradiating a laser to the predetermined location of the dry film 70 is performed, and the opening part 30 is formed. Then, as an example is shown in FIG. 14 , a via hole 40 is formed from the opening 30 by performing the step (B). After the completion of the step (B), as shown in an example in FIG. 15 , the via holes 40 and the holes 71 are filled by electrolytic plating to form a filled via 80 , and dry as an example is shown in FIG. 16 . A film (not shown) is removed to form a patterned conductor layer. As the plating seed layer of the electrolytic plating, the metal foil 60 may be used.

Before removing the dry film, the surface of the filled via 80 may be polished by buffing or the like in order to adjust the height of the filled via 80 if necessary.

Alternatively, a metal foil may be laminated on the resin composition layer of the resin sheet with a support to obtain a metal foil with a resin composition layer, and the metal foil with a resin composition layer may be laminated on an inner circuit board to form an insulating layer and a metal foil on the inner circuit board.

The manufacturing method of this invention can manufacture the printed wiring board which has a via hole and a trench, as an example is shown in FIGS. 17-21. In detail, as an example is shown in FIG. 17, the insulating layer 22 is formed on the inner-layer circuit board 10 before performing a process (A), and the dry film 70 is laminated on the insulating layer 22 further. do. After laminating the dry film 70, as an example is shown in FIG. 18, the hole 71 from which a part of the dry film 70 was removed by exposing and developing in a part of the dry film 70 is formed. Then, as an example is shown in FIG. 19, the process (A) of irradiating a laser to the predetermined location of the dry film 70 is performed, and the opening part 30 is formed. Then, as an example is shown in Fig. 20, the via hole 40 is formed from the opening 30 by performing the step (B), and at the same time, the abrasive grains are collided with the bottom of the hole 71 by sand blasting. A trench 50 is formed. Thereafter, as an example is shown in FIG. 21 , the via hole 40 and the trench 50 are filled by electrolytic plating to form a filled via 80 . After formation of the filled via 80 , the dry film 70 may be removed if necessary.

Before removing the dry film, if necessary, the surface of the filled via 80 may be polished by buffing or the like to adjust the height of the filled via 80 .

[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 products (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 electric signal is transmitted in a printed wiring board", and the location may be any place, be it a surface or a buried 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 for 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 bump-free buildup layer (BBUL). The mounting method by this, the mounting method by the anisotropic conductive film (ACF), the mounting method by a non-conductive film (NCF), etc. are mentioned. Here, "a mounting method using a bumpless build-up layer (BBUL)" refers to "a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board, and the semiconductor chip and wiring on the printed wiring board are connected".

[Example]

Hereinafter, the present invention will be specifically described by way of Examples. The present invention is not limited to these Examples. In addition, in the following, "part" and "%" which show quantity means "mass part" and "mass %", respectively, unless otherwise indicated. In addition, the operation demonstrated below was performed in the environment of normal temperature and normal pressure, unless otherwise indicated.

<Synthesis Example 1: Synthesis of elastomer>

In a reaction vessel, 69 g of bifunctional hydroxyl group-terminated polybutadiene ("G-3000" manufactured by Nippon Soda Co., Ltd., number average molecular weight = 3,000, hydroxyl group equivalent = 1,800 g/eq.), and an aromatic hydrocarbon-based mixed solvent ( 40 g of "Ifsol 150" manufactured by Idemitsu Sekiyu Chemical Co., Ltd.) and 0.005 g of dibutyltin laurate were added, mixed and uniformly dissolved. When it became uniform, the temperature was raised to 60°C, and 8 g of isophorone diisocyanate ("IPDI" manufactured by Evonik Degusa Japan, isocyanate group equivalent = 113 g/eq.) was added while further stirring, and the reaction was performed for about 3 hours. did

Then, 23 g of cresol novolac resin ("KA-1160" manufactured by DIC, hydroxyl equivalent = 117 g/eq.) and 60 g of ethyldiglycol acetate (made by Daicel) were added to the reaction product, and stirred to 150° C. The temperature was raised and the reaction was performed for about 10 hours. Disappearance of the 2,250 cm ^-1 NCO peak was confirmed by FT-IR. The disappearance of the NCO peak was confirmed and regarded as the end point of the reaction, and the reaction product was cooled to room temperature. Then, the reaction product was filtered with a 100-mesh filter cloth to obtain an elastomer having a butadiene structure and a phenolic hydroxyl group (phenolic hydroxyl group-containing butadiene resin: nonvolatile component 50% by mass). The number average molecular weight of the elastomer was 5,900, and the glass transition point temperature was -7 degreeC.

<Production of resin sheet 1 with support>

10 parts of biphenyl-type epoxy resin ("NC-3000-L" manufactured by Nippon Kayaku, about 269 g/eq. of epoxy equivalent), liquid 1,4-glycidylcyclohexane ("ZX1658" manufactured by Nippon Kayaku Co., Ltd.) , epoxy equivalent about 135 g/eq.) 10 parts, bixylenol type epoxy resin (“YX4000H” manufactured by Mitsubishi Chemical, epoxy equivalent about 185 g/eq.) 10 parts, active ester compound (“HPC-8000-65T” manufactured by DIC) , active group equivalent of about 223 g/eq., toluene solution containing 65 mass% of nonvolatile components) 50 parts, triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC Corporation, hydroxyl equivalent of about 151 g/eq., 6 parts of 2-methoxypropanol solution having a solid content of 50%), 10 parts of a phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK with a solid content of 30% by mass and cyclohexanone) 10 parts, a carbodiimide compound (Nit "V-03" manufactured by Shinbo Chemical, about 216 g/eq. active group equivalent, toluene solution having a solid content of 50% by mass) 10 parts, spherical surface treated with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 220 parts of silica (average particle diameter 0.5 μm, manufactured by Adomatex, “SO-C2”), phosphorus-based flame retardant (“HCA-HQ-HS” manufactured by Sanko Corporation, 10-(2,5-dihydroxyphenyl)-10- Hydro-9-oxa-10-phosphaphenanthrene-10-oxide)) 1 part, rubber particles (manufactured by Aika Kogyo, Staphyloid AC3816N) 1 part, curing accelerator (4-dimethylaminopyridine (DMAP), solid content 5 mass % MEK solution) 5 parts, 25 parts of methyl ethyl ketone, and 15 parts of cyclohexanone were mixed, it disperse|distributed uniformly with a high-speed rotation mixer, and the resin varnish 1 was produced.

Next, on the release surface of the support body, a polyethylene terephthalate film with a release treatment ("AL5" manufactured by Lintec, 38 µm in thickness), the resin varnish 1 is uniformly applied so that the thickness of the resin composition layer is 40 µm, 80 The resin sheet 1 with a support body was produced by drying at thru|or 120 degreeC (average of 100 degreeC) for 6 minutes. Moreover, the resin sheet 1 with a support body whose thickness of the resin composition layer after drying is 20 micrometers and 15 micrometers was also produced by changing the application|coating thickness of the resin varnish 1.

<Production of resin sheet 2 with support>

30 parts of biphenyl type epoxy resin ("NC-3000-L" manufactured by Nippon Kayaku Corporation, epoxy equivalent of about 269 g/eq.), bisphenol A type epoxy resin ("828EL" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 180 g/eq. ) 20 parts, tetraphenylethane type epoxy resin (“jER1031S” manufactured by Mitsubishi Chemical, epoxy equivalent about 198 g/eq.) 5 parts, a phenol novolac curing agent containing a triazine skeleton (“LA-7054” manufactured by DIC, hydroxyl equivalent) About 125 g/eq., MEK solution having a solid content of 60%) 10 parts, phenol novolac curing agent (“TD2090” manufactured by DIC, about 105 g/eq. hydroxyl equivalent) 6 parts phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical) ', 8 parts of a 1:1 solution of MEK and cyclohexanone having a solid content of 30% by mass), spherical silica surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle diameter of 0.5 µm, 140 parts of Domatex "SO-C2"), phosphorus-based flame retardant ("HCA-HQ-HS" manufactured by Sanko Corporation, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10- Phosphaphenanthrene-10-oxide) 5 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5 mass %) 3 parts, methyl ethyl ketone 25 parts, and cyclohexanone 15 parts are mixed, and high-speed It dispersed uniformly with a rotary mixer, and the resin varnish 2 was produced.

Production of the resin sheet 1 with a support body WHEREIN: The resin varnish 1 was replaced with the resin varnish 2. Except for the above, it carried out similarly to preparation of the resin sheet 1 with a support body, and produced the resin sheet 2 with a support body.

<Production of resin sheet 3 with support>

20 parts of bisphenol A epoxy resin ("828EL" manufactured by Mitsubishi Chemical, about 180 g/eq. epoxy equivalent), naphthol-type epoxy resin ("ESN-475V" manufactured by Nittetsu Chemical & Materials, about 332 g/eq. epoxy equivalent). ) 10 parts, a bixylenol type epoxy resin ("YX4000H" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185 g/eq.) 10 parts, a naphthylene ether type epoxy resin ("HP6000" manufactured by DIC), epoxy equivalent of about 260 g/eq. ) 20 parts, cyanate ester curing agent ("BA230S75" manufactured by Lonza Japan, cyanate equivalent of about 235 g/eq., MEK solution containing 75 mass% of nonvolatile components) 10 parts, cyanate ester curing agent (manufactured by Lonza Japan) "BADCy", cyanate equivalent of about 142 g/eq.) 10 parts, active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 223 g/eq., toluene solution containing 65 mass% of nonvolatile components) 20 Part, 8 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical, 1:1 solution of MEK and cyclohexanone having a solid content of 30% by mass), an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 170 parts of treated spherical silica (average particle diameter of 0.5 µm, "SO-C2" manufactured by Adomatex Corporation), 3 parts of a curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass), cobalt ( III) 5 parts of 1 mass % MEK solution of acetylacetonate (made by Tokyo Kasei Co., Ltd.), 40 parts of methyl ethyl ketone, and 20 parts of cyclohexanone were mixed, and it disperse|distributed uniformly with a high-speed rotary mixer, and resin varnish 3 was produced.

Production of the resin sheet 1 with a support body WHEREIN: The resin varnish 1 was changed into the resin varnish 3. Except for the above, it carried out similarly to preparation of the resin sheet 1 with a support body, and produced the resin sheet 3 with a support body.

<Production of resin sheet 4 with support>

5 parts of phenolphthalimidine type epoxy resin ("WHR-991S" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent about 265 g/eq.) 5 parts, biphenyl type epoxy resin ("NC-3000-L" manufactured by Nippon Kayaku, approx. 269 g of epoxy equivalent) /eq.) 20 parts, 50 parts of the elastomer obtained in Synthesis Example 1, and spherical silica surface-treated with a methacrylsilane-based coupling agent (“KBM503” manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle diameter of 0.08 µm, specific surface area of 30.7 m /g, Denka Corporation "UFP-30") 15 parts, phosphorus-based flame retardant (Sanko Corporation "HCA-HQ-HS", 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa- 10-phosphaphenanthrene-10-oxide) 5 parts, hardening accelerator (methyl ethyl ketone solution with a solid content of 10 mass % of 1-benzyl-2-phenylimidazole ("1B2PZ" manufactured by Shikoku Chemical Co., Ltd.)) 2 parts , 20 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 4.

Preparation of the resin sheet 1 with a support body WHEREIN: The resin varnish 1 was replaced with the resin varnish 4 . Except for the above, it carried out similarly to preparation of the resin sheet 1 with a support body, and produced the resin sheet 4 with a support body.

<Preparation of the resin sheet 5 with a support body>

In the production of the resin sheet 1 with a support,

1) 220 parts of spherical silica (average particle diameter of 0.5 µm, "SO-C2" manufactured by Adomatex) surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), an aminosilane-based coupling agent 270 parts of spherical alumina (average particle diameter of 5.3 μm, “DAW-0525” manufactured by Denka Corporation) surface-treated with (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)

2) Furthermore, 50 parts of spherical alumina (average particle diameter of 0.3 µm, "ASFP-20" manufactured by Denka Corporation) surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) was used.

Except for the above, it carried out similarly to preparation of the resin sheet 1 with a support body, and produced the resin sheet 5 with a support body.

The components used for preparation of the resin varnishes 1-5 and the compounding quantity (mass part of a nonvolatile matter) are shown in the following table|surface. In addition, content of (a) component shows content in the case of making the non-volatile component in a resin composition 100 mass %.

<Evaluation of modulus of elasticity>

(1) Preparation of cured products for evaluation

On the non-release agent-treated side of a PET film treated with a release agent (“501010” manufactured by Lintec, 38 μm thick, 240 mm square), a glass cloth-based epoxy resin double-sided copper clad laminate (“R5715ES” manufactured by Panasonic, 0.7 mm, 255 mm thick) Each) was superimposed and 4 sides were fixed with polyimide adhesive tape (10 mm in width) (Hereinafter, it may say "fixed PET film").

The prepared resin sheets 1 to 5 with a support having a resin thickness of 40 µm were laminated on the release-treated surface of the “fixed PET film”, respectively, using a batch-type vacuum pressure laminator (manufactured by Makey Co., Ltd., MVLP-500). Lamination was performed by pressure-reducing for 30 second, making atmospheric|air pressure 13 hPa or less, and pressing by 100 degreeC and pressure 0.74 MPa for 30 second after that.

Then, the support body was peeled, and the resin sheet with a support body was thermosetted on the curing conditions for 90 minutes after throwing-in to 190 degreeC oven.

After thermosetting, the polyimide adhesive tape was peeled off, the cured product was peeled off from the glass cloth-based epoxy resin double-sided copper clad laminate, and the PET film ("501010" manufactured by Lintec Co., Ltd.) was also peeled off to obtain a sheet-like cured product. The obtained hardened|cured material is called "hardened|cured material for evaluation".

(2) Evaluation of modulus of elasticity

According to Japanese Industrial Standards (JIS K7127), the obtained cured product for evaluation was subjected to a tensile test of the cured product with a Tenshiron universal testing machine (manufactured by A&D), and the elastic modulus at 23°C was measured.

<Example 1>

(1) Lamination of a resin sheet with a support body

The produced resin sheet 1 with a resin thickness of 40 µm with a support was subjected to a micro-etching agent (“CZ8201” manufactured by Mack Corporation) using a batch vacuum pressurized laminator (manufactured by Makey, MVLP-500) to roughen the copper surface. It laminated so that the resin composition layer might contact on both surfaces of the performed laminated board. Lamination was performed by pressure-reducing for 30 second, making atmospheric|air pressure 13 hPa or less, and pressing by 100 degreeC and pressure 0.74 MPa for 30 second after that.

(2) curing of the resin composition layer

An insulating layer was formed by curing the resin composition layer of the laminated resin sheet with a support under curing conditions of 180° C. and 30 minutes.

(3) Formation of via hole

(3-1) Formation of opening by laser

The opening was formed using a CO ₂ laser processing machine (“LC-2E21B/1C” manufactured by Hitachi Via Mechanics). The top diameter (diameter) of the opening on the surface of the insulating layer was 50 mu m, and the depth of the opening was 30 mu m. In addition, the depth of the opening part was calculated|required by calculating the difference between the deepest part of an unprocessed part of an insulating layer and a processed part by cross-sectional observation.

(3-2) Sandblasting

Then, using #2000 alumina abrasive grain slurry (average particle diameter 6.7 µm) as abrasive grains, using the support body opened by the CO ₂ laser as a mask, sandblasting the opening part, via hole (top diameter (diameter ) is 50㎛) was formed. The support body was peeled after sandblasting, and the board|substrate 1 for evaluation was obtained.

<Example 2>

In Example 1, the resin sheet 1 with a support body was replaced with the resin sheet 2 with a support body. Except for the above, it carried out similarly to Example 1, and obtained the board|substrate 2 for evaluation.

<Example 3>

In Example 1, the resin sheet 1 with a support body was replaced with the resin sheet 3 with a support body. Except for the above, it carried out similarly to Example 1, and obtained the board|substrate 3 for evaluation.

<Example 4>

In Example 1, the resin sheet 1 with a support body was replaced with the resin sheet 4 with a support body. Except for the above, it carried out similarly to Example 1, and obtained the board|substrate 4 for evaluation.

<Example 5>

In Example 1, the resin sheet 1 with a support body was replaced with the resin sheet 5 with a support body. Except for the above, it carried out similarly to Example 1, and obtained the board|substrate 5 for evaluation.

<Example 6>

(1) Preparation of copper foil with a resin composition layer

On a copper foil with a carrier (Mitsui Kinzoku Co., Ltd., Microshin MTEx, copper foil thickness 3 µm), the resin varnish 1 is uniformly applied so that the thickness of the resin composition layer is 40 µm, and 80 to 120 ° C. (average 100 ° C.) ) and dried for 6 minutes to prepare a copper foil with a resin composition layer.

(2) Lamination of copper foil with resin composition layer

The obtained copper foil with a resin composition layer was subjected to a vacuum pressurization laminator (manufactured by Makey Corporation, MVLP-500) on both sides of a laminate to which the copper surface was roughened with a micro-etching agent ("CZ8201" manufactured by Mack Corporation), and a resin composition layer It laminated so that it might be in contact with this laminated board. Lamination was performed by pressure-reducing for 30 second, making atmospheric|air pressure 13 hPa or less, and pressing by 100 degreeC and pressure 0.74 MPa for 30 second after that.

(3) curing of the resin composition layer

The resin composition layer on which the copper foil with a carrier was laminated was cured under the curing conditions of 180°C and 30 minutes to form an insulating layer.

(4) Formation of via hole

(4-1) Formation of opening by laser

After peeling off the carrier, an opening was formed using a CO ₂ laser processing machine (“LC-2E21B/1C” manufactured by Hitachi Via Mechanics). The top diameter (diameter) of the opening on the surface of the insulating layer was 50 mu m, and the depth of the opening was 30 mu m.

(4-2) Sandblasting

Next, using #2000 alumina abrasive grain slurry (average particle diameter 6.7 µm) as abrasive grains, using a copper foil opened by a CO ₂ laser as a mask, sandblasting of the openings was performed, and via holes (top diameter (diameter ) is 50㎛) was formed. The copper foil was peeled off after sandblasting, and the board|substrate 6 for evaluation was obtained.

<Example 7>

(1) Lamination of a resin sheet with a support body

The produced resin sheet 1 with a support having a resin thickness of 40 µm was subjected to a batch type vacuum pressurization laminator (manufactured by Meiki Corporation, MVLP-500), and copper foil with a carrier (manufactured by Mitsui Kinzoku Kogyo), Microshin MTEx, copper foil It was laminated so that the resin composition layer was in contact with the thickness of 3 micrometers). The lamination was pressure-reduced for 30 second, the atmospheric pressure was 13 hPa or less, After that, the copper foil with a resin composition layer was obtained by pressing at 100 degreeC and pressure 0.74 Mpa for 30 second.

(2) Lamination of copper foil with resin composition layer

The obtained copper foil with a resin composition layer was subjected to a vacuum pressurization laminator (manufactured by Makey Corporation, MVLP-500) on both sides of a laminate to which the copper surface was roughened with a micro-etching agent ("CZ8201" manufactured by Mack Corporation), and a resin composition layer It laminated so that it might be in contact with this laminated board. Lamination was performed by pressure-reducing for 30 second, making atmospheric|air pressure 13 hPa or less, and pressing by 100 degreeC and pressure 0.74 MPa for 30 second after that.

(3) curing of the resin composition layer

The resin composition layer was cured at 180° C. under curing conditions for 30 minutes to form an insulating layer.

(4) Formation of openings in copper foil

It etched with the said micro-etching agent, and the opening part for trench formation was formed in a part of copper foil with a carrier.

(5) Formation of via hole

(5-1) Formation of opening by laser

The opening was formed using a CO ₂ laser processing machine (“LC-2E21B/1C” manufactured by Hitachi Via Mechanics). The top diameter (diameter) of the opening on the surface of the insulating layer was 50 mu m, and the depth of the opening was 30 mu m.

(5-2) Sandblasting

Next, using #2000 alumina abrasive grain slurry (average particle diameter 6.7 µm) as abrasive grains, using a copper foil opened by a CO ₂ laser as a mask, sandblasting of the openings was performed, and via holes (top diameter ( diameter) was 50 μm). Moreover, the insulating layer was dug out even in the part in which the hole for trench formation was formed by sandblasting, and a trench was formed. The copper foil was peeled off after sandblasting, and the board|substrate 7 for evaluation was obtained.

<Example 8>

In Example 7, (3) the following operation was performed after hardening of the resin composition layer, and formation of the opening part of (4) copper foil was not performed. Except for the above, it carried out similarly to Example 7, and obtained the board|substrate 8 for evaluation.

(4) Lamination of dry film

A dry film (the Nikko Materials company make, NCM325, thickness 25 micrometers) was pasted together on the copper foil surface. Lamination of the dry film was carried out using a batch-type vacuum pressurization laminator (“MVLP-500” manufactured by Meiki Sesakusho 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 20 mJ/cm<2> with a UV lamp. After UV irradiation, a spray treatment was carried out for 50 seconds at a spray pressure of 0.15 MPa using a 1% sodium carbonate aqueous solution at 25°C. Thereafter, water washing was performed to form an opening for forming a trench pattern.

<Example 9>

(1) Preparation of copper foil with a resin composition layer

On a copper foil (JX Kinzoku Co., Ltd., JDLC, thickness 12 μm), the resin varnish 1 is uniformly applied so that the thickness of the resin composition layer is 40 μm, and the resin is dried at 80 to 120° C. (average 100° C.) for 6 minutes, and the resin A copper foil with a composition layer was produced.

(2) Lamination of copper foil with a resin composition layer with copper foil

The obtained copper foil with a resin composition layer was subjected to a vacuum pressurization laminator (manufactured by Makey Corporation, MVLP-500) on both sides of a laminate to which the copper surface was roughened with a micro-etching agent ("CZ8201" manufactured by Mack Corporation), and a resin composition layer It laminated so that it might be in contact with this laminated board. Lamination was performed by pressure-reducing for 30 second, making atmospheric|air pressure 13 hPa or less, and pressing by 100 degreeC and pressure 0.74 MPa for 30 second after that.

(3) curing of the resin composition layer

The resin composition layer was hardened|cured for the laminated board on which the copper foil with a resin composition layer was laminated on 180 degreeC and curing conditions for 30 minutes, the insulating layer was formed, and the copper foil and the laminated board with a hardened layer were obtained.

(4) Half etching of copper foil

The copper foil and the laminated board with a hardened layer were immersed in the iron chloride solution, and the half-etching which made copper thickness from 12 micrometers to 5 micrometers was performed, and the adhering iron chloride solution was washed away with pure water.

(5) Pretreatment of laser processing

Then, the pre-processing for laser processing was performed using the pre-processing liquid for laser processing (the McDermid Performance Solutions Japan company make, "MULTIBOND 100").

(6) Formation of via hole

(6-1) Formation of opening by laser

The opening was formed using a CO ₂ laser processing machine (“LC-2E21B/1C” manufactured by Hitachi Via Mechanics). The top diameter (diameter) of the opening on the surface of the insulating layer was 50 mu m, and the depth of the opening was 30 mu m.

(6-2) Sandblasting

Next, using alumina abrasive grain slurry (average particle diameter of 6.7 µm) of #2000 as abrasive grains, using the copper foil opened by the CO ₂ laser as a mask, sandblasting of the openings is performed, and via holes (top diameter (diameter) ) is 50㎛) was formed. The copper foil was peeled off after sandblasting, and the board|substrate 9 for evaluation was obtained.

<Example 10>

In Example 9, (4) half-etching of the copper foil was not performed. Except for the above, it carried out similarly to Example 9, and obtained the board|substrate 10 for evaluation.

<Example 11>

In Example 1, the resin sheet 1 with a support body with a resin thickness of 40 micrometers was replaced with the resin sheet 1 with a support body with a resin thickness of 20 micrometers,

The via hole was formed as follows. Except for the above, it carried out similarly to Example 1, and obtained the board|substrate 11 for evaluation.

(1) Formation of via hole

(1-1) Formation of openings by laser

The opening was formed using a CO ₂ laser processing machine (“LC-2E21B/1C” manufactured by Hitachi Via Mechanics). The top diameter (diameter) of the opening on the surface of the insulating layer was 30 µm, and the depth of the opening was 15 µm.

(1-2) Sandblasting

Next, using an alumina abrasive grain slurry (average particle diameter of 4.0 µm) of #3000 as abrasive grains, using the support body opened by a CO ₂ laser as a mask, sandblasting of the openings was performed, and via holes (top diameter (diameter ) is 30㎛) was formed. The support body was peeled off after sandblasting, and the board|substrate 11 for evaluation was obtained.

<Example 12>

In Example 7, the resin sheet 1 with a support with a resin thickness of 40 micrometers was replaced with the resin sheet 1 with a support body with a resin thickness of 15 micrometers,

The via hole was formed as follows. Except for the above, it carried out similarly to Example 7, and obtained the board|substrate 12 for evaluation.

(1) Formation of via hole

(1-1) Formation of openings by laser

The opening was formed using a UV-YAG laser processing machine ("LU-2L212/M50L" manufactured by Via Mechanics). The top diameter (diameter) of the opening on the surface of the insulating layer was 20 mu m, and the depth of the opening was 12 mu m.

(1-2) Sandblasting

Next, using #3000 alumina abrasive grain slurry (average particle diameter 4.0 µm) as abrasive grains, using the copper foil opened by UV-YAG laser as a mask, sandblasting of the openings was performed, and via holes (top diameter ( diameter) was 20 μm). The copper foil was peeled off after sandblasting, and the board|substrate 12 for evaluation was obtained.

<Example 13>

In Example 12, copper foil with a carrier (manufactured by Mitsui Kinzoku Co., Ltd., Microshin MTEx, copper foil thickness 3 µm) was replaced with a dry film (manufactured by Asahi Kasei, trade name "ATP-10VTDS", thickness 10 µm) it was Except for the above, it carried out similarly to Example 12, and obtained the board|substrate 13 for evaluation.

<Example 14>

In Example 13, openings for trench patterns were formed in the dry film using a mask before forming the openings with the UV-YAG laser. A substrate 14 for evaluation was obtained in the same manner as in Example 13 except for the above.

<Example 15>

In Example 2, the resin sheet 2 with a support with a resin thickness of 40 µm was replaced with a resin sheet 2 with a support with a resin thickness of 25 µm,

The via hole was formed as follows. Except for the above, it carried out similarly to Example 2, and obtained the board|substrate 15 for evaluation.

(1) Formation of via hole

(1-1) Formation of openings by laser

The opening was formed using a CO ₂ laser processing machine (“LC-2E21B/1C” manufactured by Hitachi Via Mechanics). The top diameter (diameter) of the opening on the surface of the insulating layer was 30 mu m, and the depth of the opening was 25 mu m.

(1-2) Via processing by sandblasting

Next, using an alumina abrasive grain slurry (average particle diameter of 4.0 µm) of #3000 as the abrasive grain, sandblasting the openings using the support body opened by the CO ₂ laser as a mask, via holes (top diameter (diameter) ) is 30㎛) was formed. The support body was peeled off after sandblasting, and the board|substrate 15 for evaluation was obtained.

<Comparative Example 1>

In Example 1, the via hole was formed as follows. Except for the above, it carried out similarly to Example 1, and obtained the board|substrate 16 for evaluation.

(1) Formation of via hole

After forming the insulating layer, the PET film as a support was peeled off. A via hole was formed in the insulating layer from which the support was peeled using a UV-YAG laser processing machine ("LU-2L212/M50L" manufactured by Via Mechanics) to obtain a substrate 16 for evaluation. Moreover, the top diameter (diameter) of the via hole in the surface of an insulating layer was 50 micrometers.

<Comparative Example 2>

In Example 1, the via hole was formed as follows. Except for the above, it carried out similarly to Example 1, and obtained the board|substrate 17 for evaluation.

(1) Formation of via hole

Via holes were formed using a CO ₂ laser processing machine (“LC-2E21B/1C” manufactured by Hitachi Via Mechanics) to obtain a substrate 17 for evaluation. Moreover, the top diameter (diameter) of the via hole in the surface of an insulating layer was 50 micrometers.

<Comparative Example 3>

In Example 1, the via hole was formed as follows. Except for the above, it carried out similarly to Example 1, and obtained the board|substrate 18 for evaluation.

(1) Formation of via hole

(1-1) Formation of openings by laser

The opening was formed using a CO ₂ laser processing machine (“LC-2E21B/1C” manufactured by Hitachi Via Mechanics). The top diameter (diameter) of the opening on the surface of the insulating layer was 50 mu m, and the depth of the opening was 35 mu m. Let this be a board|substrate.

(1-2) desmear processing

The substrate is immersed in a swelling liquid, Diethylene glycol monobutyl ether-containing swelling deep-securigand P manufactured by Atotech Japan Co., Ltd., at 60° C. for 5 minutes, and then, as a roughening solution, Atotech Japan Concentrate Immerse in compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) at 80° C. for 30 minutes, and finally, as a neutralizing solution, at 40° C. in reduction Soleucine Securigant P manufactured by Atotech Japan. By immersing for 5 minutes, the bottom of the opening was scraped off to form a via hole.

<Comparative Example 4>

In Example 1, the via hole was formed as follows. Except for the above, it carried out similarly to Example 1, and obtained the board|substrate 19 for evaluation.

(1) Formation of via hole

(1-1) Formation of via pattern by sandblasting resist

Patterning was performed so that vias having a diameter of 50 mu m were formed on the surface of the insulating layer using a sandblasting resist (manufactured by Nikko Materials Co., Ltd., NCM250, thickness 50 mu m).

(1-2) Sandblasting

Next, an alumina abrasive grain slurry of #2000 (average particle diameter of 6.7 µm) was used as the abrasive grain, and a sand blasting resist having a via pattern formed thereon was used as a mask, and the via portion was sandblasted to obtain a substrate 19 for evaluation. .

<Comparative Example 5>

In Comparative Example 4, (1) via holes were formed as follows. Except for the above, it carried out similarly to the comparative example 4, and obtained the board|substrate 20 for evaluation.

(1) Formation of via hole

(1-1) Formation of via pattern by sandblasting resist

Patterning was performed so that vias having a diameter of 150 µm were formed on the surface of the insulating layer using a sand blasting resist (manufactured by Nikko Materials Co., Ltd., NCM250, thickness 50 µm).

(1-2) Via processing by sandblasting

Next, using an alumina abrasive grain slurry of #1200 (average particle diameter of 9.5 µm) as abrasive grains, using a sandblasting resist having a via pattern as a mask, sandblasting of the via portion was performed to obtain a substrate 20 for evaluation. .

<Evaluation of via diameter>

(circle): Formation of a via hole is possible with an opening diameter of 100 micrometers or less.

x: A via hole cannot be formed with an opening diameter of 100 micrometers or less.

<Evaluation of smear removability>

Substrates 1 to 20 for evaluation obtained in Examples and Comparative Examples were immersed in Swelling Deep Securigand P containing diethylene glycol monobutyl ether manufactured by Atotech Japan, which is a swelling solution, at 60° C. for 5 minutes, and then As a roughening liquid, it was made to immerse in Atotech Japan Concentrate Compact P (KMnO4 _: 60g/L, NaOH:40g/L aqueous solution) at 80 degreeC for 15 minutes, and finally, As a neutralizing liquid, Atotech Japan company make It was immersed in reduction Soleucine Securigant P at 40°C for 5 minutes. Then, the via hole was observed with the electron microscope, and the following reference|standard evaluated.

(circle): The resin residue is not seen in the bottom part of a via hole.

x: A resin residue is seen in the bottom part of a via hole.

<Evaluation of Hollowing>

Cross-sectional observation was performed for the board|substrate for evaluation after evaluation of smear removability using the FIB-SEM composite apparatus ("SMI3050SE" by SII nanotechnology company). In detail, using FIB (focused ion beam), the insulating layer was cut so that a cross section parallel to the thickness direction of the insulating layer and passing through the center of the via bottom of the via hole appeared. The cross section was observed by SEM. In the observed image, a gap portion formed by peeling the insulating layer from the copper foil of the inner layer substrate was visible continuously from the edge of the via bottom. Then, the distance from the edge of the via bottom to the edge part on the outer peripheral side of a clearance gap was measured as a hollowing distance, and the following reference|standard evaluated.

(circle): A hollowing distance is 5 micrometers or less.

x: The hollowing distance exceeds 5 micrometers.

<Evaluation of via workability>

(1) Evaluation of via processability by CO ₂ laser

In order to make the depth of an opening part into a predetermined|prescribed depth by CO2 laser processing, _the number of shots required was evaluated, and the following criteria evaluated.

◎: number of shots 1.

○: number of shots 2.

x: The number of shots is 3 or more.

(2) Evaluation of via processability by UV-YAG laser

The UV-YAG laser processing evaluated the number of shots required to set the depth of the opening to a predetermined depth, and evaluated according to the following criteria.

○: The number of shots is 20 or less.

x: The number of shots exceeds 20.

(3) Evaluation of via workability by sand blasting

The insulating layer at the bottom of the opening was removed, and the required sandblasting time until the conductor layer of the laminate was exposed was evaluated according to the following criteria.

(double-circle): processing time is less than 5 minutes.

○: Processing time is 5 minutes or more and less than 10 minutes.

x: processing time is 10 minutes or more.

* In the table|surface, "WB" means a wet blast process. Content of an inorganic filler is a value at the time of making the nonvolatile component in a resin composition 100 mass %.

10 inner layer circuit board
11 support substrate
12 metal layer
10a major surface
21 support
22 insulating layer
30 opening
40 via hole
50 trench
60 metal foil
61 holes
70 dry film
71 hole
80 field via
The surface of the insulating layer opposite to the 22U metal layer
220 via bottom
Center of 220C via bottom
240 discoloration
Edge of via bottom of 250 via hole
260 gap
270 End of the clearance part on the outer peripheral side
a Depth of the opening
b Opening diameter (via hole diameter)
c The sum of the thickness of the mask and the depth of the opening
Wb Hollowing distance from the edge of the via bottom

Claims (12)

(A) a step of forming an opening in an insulating layer containing a cured product of a resin composition by means of a laser; and
(B) a step of forming a via hole by sandblasting the opening using an abrasive grain;
A method for manufacturing a printed wiring board, including in this order. The method for manufacturing a printed wiring board according to claim 1, wherein the abrasive grains have an average particle diameter of 10 µm or less. The method for manufacturing a printed wiring board according to claim 1, wherein the depth of the opening is 50% or more and 95% or less of the thickness of the insulating layer. The method according to claim 1, wherein the step (B) is a step of forming a via hole by colliding an abrasive grain on the bottom surface of the opening through a mask,
The manufacturing method of the printed wiring board whose ratio (total value/opening diameter) of the sum total value of the thickness of a mask and the depth of an opening part, and the opening diameter of a via hole is 3 or less. The method for manufacturing a wiring board according to claim 1, wherein the insulating layer has an elastic modulus at 23°C of 0.1 GPa or more. The manufacturing method of the printed wiring board of Claim 1 in which the resin composition contains an inorganic filler. The manufacturing method of the printed wiring board of Claim 6 whose content of an inorganic filler makes the nonvolatile component in a resin composition 100 mass %, 20 mass % or more. The method for manufacturing a printed wiring board according to claim 1, wherein the resin composition contains a curable resin. The manufacturing method of the printed wiring board of Claim 8 whose content of curable resin is 10 mass % or more, when the non-volatile component in a resin composition makes 100 mass %. The method for manufacturing a printed wiring board according to claim 8, wherein the curable resin contains an epoxy resin and a curing agent. The method for manufacturing a printed wiring board according to claim 10, wherein the curing agent is at least one selected from a phenol-based resin, an active ester-based resin, and a cyanate ester-based resin. The method for manufacturing a printed wiring board according to claim 1, wherein the laser is a CO ₂ laser or a UV-YAG laser.

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