WO2015098601A1 - 配線板の製造方法 - Google Patents
配線板の製造方法 Download PDFInfo
- Publication number
- WO2015098601A1 WO2015098601A1 PCT/JP2014/083176 JP2014083176W WO2015098601A1 WO 2015098601 A1 WO2015098601 A1 WO 2015098601A1 JP 2014083176 W JP2014083176 W JP 2014083176W WO 2015098601 A1 WO2015098601 A1 WO 2015098601A1
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- WIPO (PCT)
- Prior art keywords
- layer
- main surface
- wiring
- molecular bonding
- epoxy resin
- Prior art date
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Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/422—Plated through-holes or plated via connections characterised by electroless plating method; pretreatment therefor
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
- H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
- H05K2203/0796—Oxidant in aqueous solution, e.g. permanganate
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/429—Plated through-holes specially for multilayer circuits, e.g. having connections to inner circuit layers
Definitions
- the present invention relates to a method for manufacturing a wiring board.
- a technique for joining the wiring layer and the insulating layer by a bonding force generated by using the unevenness of the surface of the insulating layer formed by roughening the surface of the insulating layer is known. It has been. However, when the unevenness on the surface of the insulating layer is formed by a roughening process, it is difficult to form a wiring with high accuracy due to the presence of the unevenness, and thus it is difficult to make further fine wiring.
- a method for manufacturing a wiring board is known in which a molecular bonding layer is formed on the surface of an insulating layer for further miniaturization of wiring on the wiring board, and the molecular bonding layer is used to bond the wiring layer and the insulating layer by chemical adhesion.
- a molecular bonding layer is formed on the surface of an insulating layer for further miniaturization of wiring on the wiring board, and the molecular bonding layer is used to bond the wiring layer and the insulating layer by chemical adhesion.
- molecular bonding agents for constituting such a molecular bonding layer compounds having various structures are known (see Patent Document 1).
- a molecular bonding layer is formed after a hole is provided in an insulating layer (polyimide film). Therefore, in addition to the inner wall of the hole, when the hole is a via hole, a molecular bonding layer is also formed on the surface of the wiring exposed from the hole, so that electrical connection by a filled via formed thereafter May not be established or electrical resistance may increase.
- the present invention provides a method for manufacturing a wiring board that can realize further miniaturization of wiring and can more reliably make electrical connection through holes provided in an insulating layer. Objective.
- Step (A) Insulating layer having a first main surface and a second main surface facing the first main surface, and only the first main surface or the first main surface and the second main surface Preparing a structure including a molecular bonding layer provided on both surfaces;
- Step (B) forming a metal layer bonded to the molecular bonding layer;
- Step (C) performing laser irradiation to form a hole that penetrates the metal layer, the molecular bonding layer, and the insulating layer;
- Step (D) performing a desmear treatment on the hole;
- Step (E) forming a conductor layer;
- a step (F) of forming a wiring layer
- the step (A) provides a structure in which the insulating layer is a cured prepreg and the molecular bonding layer is provided on both the first main surface and the second main surface of the insulating layer.
- the manufacturing method of the wiring board as described in [1] which is a process to perform.
- the insulating layer is provided on the circuit board, and the molecular bonding layer is formed only on the first main surface opposite to the second main surface to which the circuit board is bonded.
- the step (A) is a step of preparing a structure further including a protective film to be bonded to the molecular bonding layer.
- Method. [5] The step (A) further includes a step of providing a protective film to be bonded to the molecular bonding layer.
- the process (B) is a process according to any one of [1] to [3], wherein the protective film is peeled from the structure to form a metal layer to be bonded to the molecular bonding layer.
- the method further includes a step (G) of removing the metal layer after the step (D) and before the step (E).
- step (E) is a step of forming a conductor layer in the exposed molecular bonding layer and the hole.
- step (B) is a step of forming a metal layer by an electroless plating step.
- a wiring board of the present invention it is possible to realize further fine wiring while maintaining good peel strength without performing a roughening treatment step as in the prior art, and provided in the insulating layer. It is possible to provide a wiring board that can ensure electrical connection through the hole.
- FIG. 1 is a schematic diagram showing a cut end face of a wiring board cut along a cutting line passing through a hole.
- FIG. 2 is a schematic view of a structure used for manufacturing a wiring board.
- FIG. 3 is a schematic diagram for explaining a manufacturing process of the wiring board.
- FIG. 4 is a schematic diagram for explaining a manufacturing process of the wiring board.
- FIG. 5 is a schematic diagram for explaining a manufacturing process of the wiring board.
- FIG. 6 is a schematic diagram for explaining a manufacturing process of the wiring board.
- FIG. 7 is a schematic diagram showing an end face of the wiring board cut along a cutting line passing through the hole.
- FIG. 8 is a schematic view of a structure used for manufacturing a wiring board.
- FIG. 9 is a schematic diagram for explaining a manufacturing process of the wiring board.
- FIG. 10 is a schematic diagram for explaining a manufacturing process of the wiring board.
- FIG. 11 is a schematic diagram for explaining a manufacturing process of a wiring board.
- FIG. 12 is a schematic diagram for explaining a manufacturing process of the wiring board.
- FIG. 13 is a schematic diagram for explaining the manufacturing process of the wiring board.
- the method for manufacturing a wiring board according to the present invention includes a step (A) an insulating layer having a first main surface and a second main surface facing the first main surface, and only the first main surface or the first main surface.
- FIG. 1 is a schematic view of a wiring board cut along a cutting line passing through a hole.
- the wiring board 10 includes an insulating layer 20.
- the insulating layer 20 has a first main surface 20a and a second main surface 20b opposite to the first main surface 20a.
- the insulating layer 20 of the first embodiment is a cured prepreg 22 in which the prepreg is cured.
- the molecular bonding layer 30 is provided on both the first main surface 20a and the second main surface 20b.
- the molecular bonding layer 30 has a function of bonding the insulating layer 20 and the metal layer 42 formed of different materials with a chemical adhesive force.
- a structure in the middle of manufacturing the wiring board 10 including the insulating layer 20 and the molecular bonding layer 30 may be simply referred to as a “structure”.
- a metal layer 42 is provided on both the molecular bonding layers 30 on the first main surface 20a side and the second main surface 20b side.
- the material of the metal layer 42 is not particularly limited as long as the material can withstand a desmear process in the step (D) described later.
- Examples of the material of the metal layer 42 include copper (Cu) and nickel (Ni).
- the thickness of the metal layer 42 can prevent damage due to a process performed after the process of forming the metal layer 42 on the molecular bonding layer 30 and can be removed by a removal process such as a flash etching process in a wiring formation process described later. It is not particularly limited as long as it can be performed.
- the thickness of the metal layer 42 is generally 0.1 ⁇ m to 5 ⁇ m, preferably 0.3 ⁇ m to 2 ⁇ m.
- the metal layer 42 is intended to prevent damage to the molecular bonding layer 30 due to a process performed after the process of forming the metal layer 42, and can be removed after the purpose has been achieved. Therefore, the wiring board 10 of the first embodiment includes a form in which the metal layer 42 is not provided.
- the wiring board 10 includes a hole 26.
- the hole portion 26 according to the first embodiment includes the insulating layer 20, the molecular bonding layer 30 on both the first main surface 20a side and the second main surface 20b side, the first main surface 20a side and the second main surface 20b side. This is a through hole that penetrates both of the metal layers 42.
- the wiring board 10 has a wiring layer 40.
- the wiring board 10 of the first embodiment includes a first wiring layer 46 provided on the first main surface 20a side and a second wiring layer 48 provided on the second main surface 20b side.
- the first wiring layer 46 is bonded to the first region 42a which is a partial region of the metal layer 42 on the first main surface 20a side and the first region 42a of the metal layer 42.
- the first region 44a which is a partial region on the first main surface 20a side
- the first main portion of the electroplated layer 45 that is joined to the first region 44a of the conductor layer 44.
- a first region 45a which is a partial region on the surface 20a side.
- the second wiring layer 48 is bonded to the second region 42b, which is a partial region of the metal layer 42 on the second main surface 20b side, and the second region 42b of the metal layer 42.
- the second main region 20b of the electroplating layer 45 joined to the second region 44b which is a partial region of the conductive layer 44 on the second main surface 20b side and the second region 44b of the conductive layer 44.
- a second region 45b which is a partial region on the surface 20b side.
- the first wiring layer 46 is configured by laminating the first region 42 a of the metal layer 42, the first region 44 a of the conductor layer 44, and the first region 45 a of the electrolytic plating layer 45.
- the second wiring layer 48 is configured by laminating the second region 42 b of the metal layer 42, the second region 44 b of the conductor layer 44, and the second region 45 b of the electrolytic plating layer 45.
- first wiring layer 46 and the second wiring layer 48 may include not only a linear wiring but also an electrode pad (land) on which an external terminal can be mounted, for example.
- the hole 26 that is a through hole has its inner wall covered with the third region 44c of the conductor layer 44, and is embedded by the embedded region 45c of the electrolytic plating layer 45 that is joined to the third region 44c.
- the through-hole wiring 50 that electrically connects the first wiring layer 46 and the second wiring layer 48 is formed.
- the first region 44 a, the second region 44 b, and the third region 44 c of the conductor layer 44 may be integrally configured so as to be electrically connected, and the first region 45 a and the second region of the electrolytic plating layer 45. 45b and the third region 45c may be integrally configured so as to be electrically connected.
- the step (A) according to the method for manufacturing a wiring board of the present invention includes an insulating layer having a first main surface and a second main surface facing the first main surface, only the first main surface or the first main surface. This is a step of preparing a structure including molecular bonding layers provided on both the main surface and the second main surface.
- FIG. 2 is a schematic view of a structure used for manufacturing a wiring board.
- the insulating layer 20 is a cured prepreg, and the molecular bonding layer 30 is provided on both the first main surface 20a and the second main surface 20b of the insulating layer 20. This is a step of preparing the body 60.
- the insulating layer 20 of the first embodiment is a cured prepreg.
- the cured prepreg 22 that is the insulating layer 20 will be described.
- the cured prepreg 22 is a structure obtained by curing a sheet-like prepreg obtained by impregnating a sheet-like fiber base material with a resin composition.
- the cured prepreg 22 can be formed using any suitable prepreg according to the use of the wiring board 10.
- the sheet-like fiber base material that can be contained in the cured prepreg 22 and the prepreg that is a material thereof is not particularly limited, and a base material commonly used as a sheet-like fiber base material for prepregs such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric. Can be used.
- the thickness of the cured prepreg 22 and the prepreg can be set to any suitable thickness depending on the use of the wiring board 10. From the viewpoint of further reducing the thickness of the wiring board 10, a sheet-like fiber base material having a thickness of 10 ⁇ m to 150 ⁇ m is preferably used, particularly a sheet-like fiber base material having a thickness of 10 ⁇ m to 100 ⁇ m, and a thickness of 10 ⁇ m to 50 ⁇ m.
- a sheet-like fiber substrate and a sheet-like fiber substrate having a thickness of 10 ⁇ m to 30 ⁇ m are preferably used.
- glass cloth that can be used as the sheet-like fiber base material
- style 1027MS manufactured by Asahi Schavel Co., Ltd.
- Style 1037MS manufactured by Asahi Schubel Co., Ltd.
- 1078 manufactured by Arisawa Manufacturing Co., Ltd.
- liquid crystal polymer non-woven fabric examples include “Veculus” (weight per unit area: 6 g / m 2 to 15 g / m 2 ) and “Vectran” manufactured by Kuraray Co., Ltd. by the melt blow method.
- the components of the resin composition that can be used for forming the prepreg and the content thereof are not particularly limited on the condition that the cured prepreg has sufficient hardness and insulating properties.
- content of the component of a resin composition is shown as an amount when the sum total of the non-volatile component in a resin composition is 100 mass%.
- the resin composition used as the material of the prepreg may contain an inorganic filler, an epoxy resin, a curing agent, an organic filler, a curing accelerator, a thermoplastic resin, a flame retardant, and the like as components. Good.
- each of the said component which a resin composition may contain is demonstrated.
- the resin composition is an inorganic filler from the viewpoint of reducing the coefficient of thermal expansion when cured, suppressing the occurrence of defects such as cracks and circuit distortion due to the difference in coefficient of thermal expansion, and suppressing the excessive decrease in melt viscosity. It is preferable to contain.
- the material of the inorganic filler is not particularly limited.
- silica such as amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica is particularly suitable.
- spherical silica is preferable as the silica.
- An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type. Examples of commercially available spherical (fused) silica include “SOC1”, “SOC2”, “SOC4”, “SOC5”, and “SOC6” manufactured by Admatechs Co., Ltd.
- the average particle diameter of the inorganic filler is preferably in the range of 0.01 ⁇ m to 4 ⁇ m, more preferably in the range of 0.05 ⁇ m to 2.5 ⁇ m, from the viewpoint of improving the fluidity of the resin composition. More preferably, it is in the range of 1 ⁇ m to 1.5 ⁇ m, and still more preferably in the range of 0.3 ⁇ m to 1.0 ⁇ m.
- the average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter.
- a measurement sample in which an inorganic filler is dispersed in water by ultrasonic waves can be preferably used.
- a laser diffraction / scattering particle size distribution measuring apparatus “LA-500” manufactured by Horiba, Ltd. or the like can be used.
- Inorganic fillers are aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents from the viewpoint of improving moisture resistance and dispersibility. It is preferable that it is processed with 1 or more types of surface treating agents. Examples of such commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM803” (3-Mercapto) manufactured by Shin-Etsu Chemical Co., Ltd. Propyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.
- KBE903 (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.
- KBM573 N-phenyl-3-aminopropyltrimethoxysilane
- Examples include “SZ-31” (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd.
- the inorganic filler surface-treated with the surface treatment agent can be washed with a solvent (for example, methyl ethyl ketone (MEK)), and then the amount of carbon per unit surface area of the inorganic filler can be measured.
- a solvent for example, methyl ethyl ketone (MEK)
- MEK methyl ethyl ketone
- a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes.
- the carbon amount per unit surface area of an inorganic filler can be measured using a carbon analyzer.
- EMIA-320V manufactured by Horiba, Ltd. can be used.
- Carbon content per unit surface area of the inorganic filler is preferably at 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, More preferably, it is 0.2 mg / m 2 or more.
- amount of carbon per unit surface area of the inorganic filler is preferably at 1 mg / m 2 or less, more preferably 0.8 mg / m 2 or less, 0 More preferably, it is 5 mg / m 2 or less.
- a resin composition contains an organic filler from a viewpoint of improving adhesiveness with the layer formed by a plating process.
- the organic filler include rubber particles.
- the rubber particles that are organic fillers for example, rubber particles that do not dissolve in an organic solvent described later and are incompatible with an epoxy resin, a curing agent, a thermoplastic resin, and the like described later are used.
- Such rubber particles are generally prepared by increasing the molecular weight of the rubber particle components to such an extent that they do not dissolve in organic solvents or resins, and making them into particles.
- Examples of rubber particles that are organic fillers include core-shell type rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles.
- the core-shell type rubber particles are rubber particles having a core layer and a shell layer.
- a two-layer structure in which an outer shell layer is made of a glassy polymer and an inner core layer is made of a rubbery polymer or Examples thereof include a rubber particle having a three-layer structure in which an outer shell layer is made of a glassy polymer, an intermediate layer is made of a rubbery polymer, and an inner core layer is made of a glassy polymer.
- the glassy polymer layer is made of, for example, methyl methacrylate polymer
- the rubbery polymer layer is made of, for example, butyl acrylate polymer (butyl rubber).
- examples of rubber particles that can be used include “Staffyroid AC3816N” manufactured by Ganz Corporation. A rubber particle may be used individually by 1 type, or may use 2 or more types together.
- the average particle diameter of the rubber particles as the organic filler is preferably in the range of 0.005 ⁇ m to 1 ⁇ m, more preferably in the range of 0.2 ⁇ m to 0.6 ⁇ m.
- the average particle diameter of the rubber particles can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and the particle size distribution of the rubber particles is measured on a mass basis using a concentrated particle size analyzer (“FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.). It can be measured by making the median diameter as an average particle diameter.
- epoxy resin examples include 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 epoxy resin, naphthol novolac epoxy resin, phenol novolac.
- Type epoxy resin tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin , Linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro-ring containing epoxy Shi resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins and trimethylol type epoxy resins.
- An epoxy resin may be used individually by 1 type, or may use 2 or more types together.
- the epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule.
- the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass is preferably an epoxy resin having two or more epoxy groups in one molecule.
- it has two or more epoxy groups in one molecule and has a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and three or more epoxy groups in one molecule.
- a solid epoxy resin at a temperature of 20 ° C.
- liquid epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, bifunctional aliphatic epoxy resin, or naphthalene type epoxy resin, and bisphenol A type epoxy resin and bisphenol F type.
- Type epoxy resin or naphthalene type epoxy resin is preferred.
- Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “jER828EL”, “jER1007” (bisphenol A type epoxy manufactured by Mitsubishi Chemical Corporation).
- the solid epoxy resin examples include a crystalline bifunctional epoxy resin, a tetrafunctional naphthalene type epoxy resin, a cresol novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol epoxy resin, a naphthol novolak type epoxy resin, and a biphenyl type epoxy. Examples thereof include resins and naphthylene ether type epoxy resins. Specific examples of the solid epoxy resin include “HP-4700”, “HP-4710” (tetrafunctional naphthalene type epoxy resin), “N-690” (cresol novolac type epoxy resin), “N” manufactured by DIC Corporation.
- the quantitative ratio thereof is in the range of 1: 0.1 to 1: 4 by mass ratio.
- the quantitative ratio of liquid epoxy resin and the solid epoxy resin is in the range of 1: 0.3 to 1: 3.5 by mass ratio. More preferably, it is more preferably in the range of 1: 0.6 to 1: 3, and particularly preferably in the range of 1: 0.8 to 1: 2.5.
- the content of the epoxy resin in the resin composition is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 45% by mass, and further preferably 5% by mass to 40% by mass. More preferably, the content is 7% by mass to 35% by mass.
- the weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500.
- 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.
- the epoxy equivalent of the epoxy resin is preferably in the range of 50 to 3000, more preferably in the range of 80 to 2000, and still more preferably in the range of 110 to 1000. By setting it as such a range, the hardening body with sufficient crosslinking density can be obtained.
- the epoxy equivalent can be measured according to a method standardized as JIS K7236.
- the epoxy equivalent is the mass of an epoxy resin containing 1 equivalent of an epoxy group.
- the curing agent is not particularly limited as long as it has a function of curing the epoxy resin.
- curing agent is mentioned.
- curing agent may be used individually by 1 type, or may use 2 or more types together.
- phenol-based curing agent and naphthol-based curing agent examples include a phenol-based curing agent having a novolak structure, a naphthol-based curing agent having a novolak structure, a nitrogen-containing phenol-based curing agent, a triazine skeleton-containing cresol-based curing agent, and a triazine skeleton-containing A phenol type hardening
- curing agent is mentioned.
- phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., “NHN” manufactured by Nippon Kayaku Co., Ltd. ”,“ CBN ”,“ GPH ”,“ SN170 ”,“ SN180 ”,“ SN190 ”,“ SN475 ”,“ SN485 ”,“ SN495 ”,“ SN375 ”,“ SN395 ”, DIC (manufactured by Tohto Kasei Co., Ltd.) "LA7052", “LA7054”, “LA3018”, etc. manufactured by Corporation.
- the active ester curing agent is not particularly limited, but generally an ester group having high reaction activity such as phenol ester, thiophenol ester, N-hydroxyamine ester, heterocyclic hydroxy compound ester in one molecule.
- a compound having two or more in the above is preferably used.
- the active ester curing agent is preferably a curing agent obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound.
- an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable.
- the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
- phenol compound or naphthol compound examples 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, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Examples thereof include benzenetriol, dicyclopentadiene type diphenol compound, and phenol novolac.
- the active ester curing agent examples include an active ester compound containing a dicyclopentadiene type diphenol condensation structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoyl of phenol novolac. And active ester compounds containing compounds.
- active ester curing agents include, for example, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-” manufactured by DIC Corporation as active ester compounds having a dicyclopentadiene type diphenol condensation structure. 65T “,” EXB9416-70BK “manufactured by DIC Corporation as an active ester compound containing a naphthalene structure,” DC808 “manufactured by Mitsubishi Chemical Corporation as an active ester compound containing an acetylated product of phenol novolac, and a benzoylated product of phenol novolac Examples of the active ester compound include “YLH1026” manufactured by Mitsubishi Chemical Corporation.
- benzoxazine-based curing agent examples include “HFB2006M” manufactured by Showa Polymer Co., Ltd. and “Pd” and “Fa” manufactured by Shikoku Chemicals Co., Ltd.
- cyanate ester curing agent examples include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4 '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Novolac and Examples thereof include polyfunctional cyanate resins derived from resol novolac, etc., prepolymers in which these cyanate resins are
- cyanate ester-based curing agents include “PT30” and “ PT60 "(both phenol novolac-type polyfunctional cyanate ester resins),” BA230 "(a prepolymer in which a part or all of bisphenol A dicyanate is triazine-modified into a trimer) and the like.
- carbodiimide curing agent examples include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.
- the amount ratio between the epoxy resin and the curing agent is a ratio of [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of the curing agent] and should be in the range of 1: 0.2 to 1: 2. Is more preferable, and the range of 1: 0.3 to 1: 1.5 is more preferable, and the range of 1: 0.4 to 1: 1 is more preferable.
- the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like, and varies depending on the type of the curing agent.
- the total number of epoxy groups of the epoxy resin is a value obtained by totaling the values obtained by dividing the mass of the nonvolatile component of each epoxy resin by the epoxy equivalent for all epoxy resins
- the total number of reactive groups of the curing agent is The value obtained by dividing the mass of the non-volatile component of each curing agent by the reactive group equivalent is the total value for all curing agents.
- the ratio of the total number of epoxy groups of the epoxy resin and the total number of reactive groups of the curing agent is preferably in the range of 1: 0.2 to 1: 2, more preferably The range is from 1: 0.3 to 1: 1.5, and more preferably from 1: 0.4 to 1: 1.
- the resin composition is a mixture of a liquid epoxy resin and a solid epoxy resin as an epoxy resin (the mass ratio of liquid epoxy resin: solid epoxy resin is preferably in the range of 1: 0.1 to 1: 4. : More preferably in the range of 0.3 to 1: 3.5, still more preferably in the range of 1: 0.6 to 1: 3, and in the range of 1: 0.8 to 1: 2.5.
- a curing agent preferably a phenol curing agent, a naphthol system
- One or more selected from the group consisting of curing agents more preferably one or more selected from the group consisting of a phenolic novolak resin containing a triazine skeleton and a naphthol-based curing agent, and more preferable.
- Ku is a curing agent) containing a triazine skeleton-containing phenol novolak resin, it is preferable to include, respectively.
- thermoplastic resin examples include phenoxy resin, acrylic resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyethersulfone resin, and polysulfone resin.
- a thermoplastic resin may be used individually by 1 type, or may use 2 or more types together.
- the weight average molecular weight in terms of polystyrene of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000.
- the weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method.
- GPC gel permeation chromatography
- the polystyrene-converted weight average molecular weight of the thermoplastic resin is “LC-9A / RID-6A” manufactured by Shimadzu Corporation as a measuring device, and “Shodex K-800P” manufactured by Showa Denko KK as a column.
- / K-804L / K-804L can be calculated using a standard polystyrene calibration curve by measuring the column temperature at 40 ° C using chloroform or the like as the mobile phase.
- phenoxy resin examples include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene
- the terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.
- a phenoxy resin may be used individually by 1 type, or may use 2 or more types together.
- Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (bisphenol) manufactured by Mitsubishi Chemical Corporation.
- Other examples include “FX280” and “FX293” manufactured by Toto Kasei Co., Ltd., “YL7553”, “YL6794”, “YL7213”, “YL7290” manufactured by Mitsubishi Chemical Corporation, and the like. "YL7482” etc. are mentioned.
- the acrylic resin is preferably a functional group-containing acrylic resin, more preferably an epoxy group-containing acrylic resin having a glass transition temperature of 25 ° C. or lower, from the viewpoint of further reducing the thermal expansion coefficient and the elastic modulus.
- the number average molecular weight (Mn) of the functional group-containing acrylic resin is preferably 10,000 to 1,000,000, more preferably 30,000 to 900,000.
- the functional group equivalent of the functional group-containing acrylic resin is preferably 1000 to 50000, more preferably 2500 to 30000.
- an epoxy group-containing acrylic ester copolymer resin having a glass transition temperature of 25 ° C. or lower is preferable. Specific examples thereof are manufactured by Nagase ChemteX Corporation.
- SG-80H epoxy group-containing acrylate copolymer resin (number average molecular weight Mn: 350,000 g / mol, epoxy value 0.07 eq / kg, glass transition temperature 11 ° C.)), manufactured by Nagase ChemteX Corporation SG-P3 ”(epoxy group-containing acrylate copolymer resin (number average molecular weight Mn: 850000 g / mol, epoxy value 0.21 eq / kg, glass transition temperature 12 ° C.)).
- polyvinyl acetal resin examples include electrified butyral “4000-2”, “5000-A”, “6000-C”, “6000-EP” manufactured by Denki Kagaku Kogyo Co., Ltd., and Sekisui Chemical Co., Ltd. SK series, BL series, BM series, etc. are available.
- polyimide resin examples include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd.
- polyimide resin examples include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide resin described in JP-A-2006-37083). And modified polyimides such as polysiloxane skeleton-containing polyimides (polyimide resins described in JP-A Nos. 2002-12667 and 2000-319386).
- polyamide-imide resin examples include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd.
- polyamideimide resin also include modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd.
- polyethersulfone resin examples include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.
- polysulfone resin examples include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.
- the content of the thermoplastic resin in the resin composition is preferably 0.1% by mass to 20% by mass. By setting the content of the thermoplastic resin within such a range, the viscosity of the resin composition becomes appropriate, and a uniform resin composition layer having a thickness and a bulk property can be formed.
- curing accelerator examples include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and guanidine-based curing accelerators.
- Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like.
- amine curing accelerator examples include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8 -Diazabicyclo (5,4,0) -undecene and the like.
- DMAP 4-dimethylaminopyridine
- benzyldimethylamine 2,4,6-tris (dimethylaminomethyl) phenol
- 1,8 -Diazabicyclo (5,4,0) -undecene examples include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8 -Diazabicyclo (5,4,0) -undecene and the like.
- DMAP 4-dimethylamin
- imidazole curing accelerator examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2- Phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6 -[ '-Methylimidazolyl- (1
- guanidine curing accelerator examples 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] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- o- tolyl) biguanide
- a hardening accelerator may be used individually by 1 type, or may be used in combination of 2 or more type.
- the content of the curing accelerator in the resin composition may be used in the range of 0.05% by mass to 3% by mass when the total amount of nonvolatile components of the epoxy resin and the curing agent is 100% by mass. preferable.
- the flame retardant examples include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide.
- Examples of the flame retardant that can be used include “HCA-HQ-HST” manufactured by Sanko Co., Ltd.
- a flame retardant may be used individually by 1 type, or may use 2 or more types together.
- the content of the flame retardant in the resin composition layer is not particularly limited, but is preferably in the range of 0.5% by mass to 10% by mass, more preferably in the range of 1% by mass to 9% by mass, More preferably, it is in the range of 1.5% by mass to 8% by mass.
- the resin composition may contain other additives for the purpose of adjusting the properties of the resin composition or its cured body, as necessary.
- other additives include organic copper.
- examples include compounds, organic metal compounds such as organic zinc compounds and organic cobalt compounds, and resin additives such as thickeners, antifoaming agents, leveling agents, adhesion-imparting agents, and coloring agents.
- the prepreg can be produced by a known method such as a hot melt method or a solvent method.
- the resin composition is not dissolved in an organic solvent, but once coated on a release paper having good releasability from the resin composition, it is laminated on a sheet-like fiber base material, or is formed into a sheet by a die coater.
- a prepreg is manufactured by, for example, coating directly on a fiber base material.
- the sheet-like fiber base material is immersed in a resin varnish in which the resin composition is dissolved in an organic solvent to impregnate the sheet-like fiber base material and then dried to form a prepreg. ing.
- the prepreg may be formed by continuously heat laminating by sandwiching a sheet-like fiber base material from both sides with two resin sheets made of a resin composition and heating under pressure. it can.
- Examples of the organic solvent used in preparing the resin varnish for forming the prepreg include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate.
- Examples thereof include acetate esters such as carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
- An organic solvent may be used individually by 1 type, or may use 2 or more types together.
- the prepreg forming step may be performed by a roll-to-roll method or a batch method using a long sheet-like fiber base material.
- the cured prepreg 22 can be formed by heat-treating the prepreg under predetermined conditions. Specifically, a vacuum hot press process is mentioned as an example of the formation method of the cured prepreg 22. Hereinafter, a vacuum hot press process that can be used in the process of forming the cured prepreg 22 will be described.
- the vacuum hot pressing step can be performed, for example, by pressing the prepreg from both sides with a metal plate such as a heated stainless steel plate (SUS plate).
- a metal plate such as a heated stainless steel plate (SUS plate).
- the vacuum hot pressing step is preferably performed with cushion paper, a release sheet or the like interposed on both sides of the metal plate to be used.
- cushion paper for example, “AACP-9N” (800 ⁇ m thickness) manufactured by Awa Paper Co., Ltd. can be used.
- release sheet for example, “Aflex 50N NT” (thickness 50 ⁇ m) manufactured by Asahi Glass Co., Ltd. can be used.
- the conditions of the vacuum hot pressing step are, for example, the atmospheric pressure is usually 1 ⁇ 10 ⁇ 2 MPa or less, preferably 1 ⁇ 10 ⁇ 3 MPa or less, the heating temperature is 150 ° C. to 250 ° C., and the pressing force is 10 kgf / cm 2 to 70 kgf / cm 2 may be used.
- the temperature increase from the normal temperature to the predetermined heating temperature and the temperature decrease from the predetermined heating temperature to the normal temperature are performed while maintaining the predetermined temperature increase rate and temperature decrease rate.
- the temperature increase rate and the temperature decrease rate are preferably about 5 ° C./min.
- the vacuum hot press process can be performed using a vacuum hot press apparatus common in this field.
- the vacuum heat press apparatus include “MNPC-V-750-5-200” manufactured by Meiki Seisakusho Co., Ltd. and “VH1-1603” manufactured by Kitagawa Seiki Co., Ltd.
- the molecular bonding layer 30 provided on both the first main surface 20a and the second main surface 20b of the cured prepreg 22 is obtained by a method suitable for the molecular bonding agent selected as a material for forming the molecular bonding layer 30. Can be formed.
- the molecular bonding agent that is a material of the molecular bonding layer 30 is not particularly limited, and for example, a commercially available molecular bonding agent containing a conventionally known compound as described in Patent Document 1 can be used.
- molecular bonding agents include fluorinated alkyl group type “X-24-9453” of triazine thiol functional silicone alkoxy oligomer manufactured by Shin-Etsu Chemical Co., Ltd., aminotriazine novolak resin (for example, DIC Corporation).
- epoxy silane coupling agents for example, 3-glycidoxypropyltrimethoxysilane, "KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.
- a molecular bonding agent for example, 3-glycidoxypropyltrimethoxysilane, "KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.
- the molecular bonding layer 30 is formed, for example, in a molecular bonding agent solution obtained by dissolving the cured prepreg 22 in a predetermined solvent (for example, a mixed solvent obtained by mixing water, isopropyl alcohol and acetic acid) at a predetermined concentration (temperature, For example, the cured prepreg 22 taken out after being dipped in time etc. and dried under predetermined conditions can be formed on the surface including the first main surface 20a and the second main surface 20b.
- a predetermined solvent for example, a mixed solvent obtained by mixing water, isopropyl alcohol and acetic acid
- the step (A) is preferably a step of preparing a structure 60 that further includes a protective film 110 that is bonded to the molecular bonding layer 30.
- the molecular bonding layer 30 is thus covered with the protective film 110, the molecular bonding layer 30 can be effectively protected. Moreover, since the structure 60 provided with the protective film 110 can be stored, for example, the implementation timing after the step (B) can be set to an arbitrary timing.
- polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA), cyclic polyolefins, and triacetyl cellulose (TAC).
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA)
- cyclic polyolefins such as polycarbonate (PC) and polymethyl methacrylate (PMMA)
- TAC triacetyl cellulose
- PES Polyether sulfide
- polyether ketone polyimide and the like.
- the protective film 110 containing the above-described material may be subjected to a mat treatment or a corona treatment on the surface to be bonded to the cured prepreg 22.
- a “protective film with a release layer” having a release layer on the side to which the cured prepreg 22 is bonded may be used.
- a mold release agent used for forming a mold release layer of a protective film with a mold release layer for example, one or more mold release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins are used. Can be mentioned.
- the release layer can be formed, for example, by applying a solution containing a release agent to the surface of the protective film 110 and drying it.
- the protective film with a release layer for example, “SK-1”, “AL-5”, “AL-5” manufactured by Lintec Corporation, which is a PET film having a release layer mainly composed of an alkyd resin release agent. AL-7 "and the like.
- the thickness of the protective film 110 is not particularly limited, but is preferably in the range of 5 ⁇ m to 75 ⁇ m, more preferably in the range of 10 ⁇ m to 60 ⁇ m, and still more preferably in the range of 12.5 ⁇ m to 55 ⁇ m.
- the protective film with a release layer it is preferable that the whole thickness of the protective film with a release layer is the said range.
- the protective film 110 may be laminated by a laminating process according to an ordinary method so as to cover both the first main surface 20a side and the second main surface 20b side of the cured prepreg 22. Lamination of the protective film 110 to the cured prepreg 22 can be performed using a conventionally known laminator apparatus.
- FIG. 3 is a schematic diagram for explaining a manufacturing process of the wiring board.
- Step (B) is a step of forming a metal layer to be bonded to the molecular bonding layer. As shown in FIG. 2 and FIG. 3, in the step (B) according to the first embodiment, when the protective film 110 is provided, the protective film 110 is peeled off from the structure 60 and exposed molecules. A metal layer 42 to be bonded to the bonding layer 30 may be formed.
- the metal layer 42 can be formed by a plating process such as an electroless plating process using the suitable material already described.
- the step (B) is preferably a step of forming the metal layer 42 by an electroless plating step (first electroless plating step) using copper as a material.
- the metal layer 42 is formed as a copper layer by an electroless plating process.
- Step (C) is a step of forming a hole that penetrates the metal layer, the molecular bonding layer, and the insulating layer by laser irradiation.
- the laser irradiation is performed from the first main surface 20a side of the structure 60 obtained in the above-mentioned ⁇ Step (B)>, whereby the metal layer 42 and the molecular bonding are performed.
- a hole 26 that is a through hole in the first embodiment and penetrates the layer 30 and the insulating layer 20 is formed.
- This laser irradiation can be performed using any suitable laser processing machine using a carbon dioxide gas laser, a YAG laser, an excimer laser or the like as a light source.
- the laser processing machine which may be used, for example, by Hitachi Via Mechanics Co., Ltd. CO 2 laser processing machine "LC-2k212 / 2C", Mitsubishi Electric Corporation “ML605GTWII”, Matsushita Welding Systems Co., Ltd. A laser processing machine is mentioned.
- Laser irradiation conditions are not particularly limited, and laser irradiation can be performed by any suitable process according to a conventional method according to the selected means.
- the shape of the hole 26, that is, the shape of the outline of the opening when viewed in the extending direction is not particularly limited, but is generally circular (substantially circular).
- the “diameter” of the hole 26 refers to the diameter (diameter) of the outline of the opening when viewed in the extending direction.
- the top diameter refers to the contour diameter r1 of the hole 26 on the first main surface 20a side
- the bottom diameter refers to the contour diameter r2 of the hole 26 on the second main surface 20b side.
- a process (D) is a process of performing a desmear process with respect to a hole.
- the desmear process is performed to remove smear in the hole 26.
- This desmear process may be a wet desmear process or a dry desmear process.
- the specific process and conditions of the desmear treatment are not particularly limited as long as the function of the molecular bonding layer 30 is not impaired.
- known processes and conditions that are usually used in forming an insulating layer of a multilayer printed wiring board Can be adopted.
- Examples of the dry desmear treatment include plasma treatment, and examples of the wet desmear treatment include a method of performing a swelling treatment with a swelling liquid, a desmear treatment with an oxidizing agent, and a desmear treatment with a neutralizing solution in this order.
- the wet desmear process will be described.
- the swelling liquid used in the wet desmear treatment is not particularly limited.
- the swelling liquid include an alkaline solution and a surfactant solution, and an alkaline solution is preferable.
- a sodium hydroxide solution and a potassium hydroxide solution are more preferable as the alkaline solution.
- the commercially available swelling liquid include “Swelling Dip Securigans P”, “Swelling Dip Securigans SBU” manufactured by Atotech Japan Co., Ltd., and the like.
- the swelling treatment with the swelling liquid is not particularly limited, and can be performed, for example, by immersing the structure 60 provided with the hole 26 in the swelling liquid at 30 ° C. to 90 ° C. for 1 minute to 20 minutes.
- the swelling treatment is preferably a treatment in which the structure 60 is immersed in a swelling liquid at 40 ° C. to 80 ° C. for 5 seconds to 15 minutes.
- the oxidizing agent used in the wet desmear treatment is not particularly limited.
- the oxidizing agent include an alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide.
- the desmear treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the structure 60 in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes.
- the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass.
- oxidizing agents examples include alkaline permanganate solutions such as “Concentrate Compact P” and “Dosing Solution Securigans P” manufactured by Atotech Japan Co., Ltd.
- the neutralizing solution is preferably an acidic aqueous solution, and as a commercially available product, for example, “Reduction Solution Securigans P” manufactured by Atotech Japan Co., Ltd. may be mentioned.
- the treatment with the neutralizing solution can be performed by immersing the structure 60 treated with the oxidizing agent in a neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to desmear treatment with an oxidant solution in a neutralizing solution at 40 ° C. to 70 ° C. for 5 to 20 minutes is preferable.
- the metal layer 42 covering the molecular bonding layer 30 is formed and the hole 26 is formed in a state where the molecular bonding layer 30 is protected by the metal layer 42, the molecular bonding between the metal layer 42 and the insulating layer 20 is performed. A decrease in bonding force due to the layer 30 can be prevented. Therefore, the metal layer 42 and the insulating layer 20 can be firmly bonded.
- the formed hole 26 is subjected to a desmear process, even if the hole 26 has a relatively small top diameter r1 and bottom diameter r2 and a relatively large aspect ratio, molecular bonding is performed from within the hole 26. It is possible to form a clean hole 26 from which the material such as the layer 30 and a residue such as a reaction product generated in the step of forming the hole 26 are removed. Therefore, the conduction by the hole 26 provided in the insulating layer 20 can be improved.
- Step (E) is a step of forming a conductor layer.
- a conductor layer 44 is formed on the surface of the metal layer 42 and the hole 26 of the structure 60 obtained in the above-described ⁇ Step (C)>. That is, the first region 44a joined to the metal layer 42 on the first main surface 20a side, the second region 44b joined to the metal layer 42 on the second main surface 20b side, and the third region 44c joined to the inner wall of the hole 26 are formed. A conductor layer 44 is formed.
- the conductor layer 44 can be formed by a process similar to the process of forming the metal layer 42 already described. Therefore, detailed description of the conductor layer 44 is omitted.
- the conductor layer 44 is preferably formed by an electroless plating process.
- the metal layer 42 is formed by an electroless plating process, that is, a first electroless plating process
- the metal layer 42 may be referred to as a first electroless plating layer.
- the conductor layer 44 formed by the plating process may be referred to as a second electroless plating layer.
- the metal layer 42 can be removed after achieving the purpose of preventing damage to the molecular bonding layer 30 due to a process performed after the process of forming the metal layer 42. Therefore, the step (E) may be performed after removing the metal layer 42. That is, if the conductor layer 44 is formed after the metal layer 42 is removed after the desmear process, the amount of removal in the subsequent flash etching process (the removal process of the metal layer 42 and the conductor layer 44) can be reduced, and the milder Since the removal process can be performed under appropriate conditions, further miniaturization can be realized.
- FIG. 5 and 6 are schematic views for explaining a manufacturing process of the wiring board.
- Step (F) is a step of forming a wiring layer.
- the first wiring layer 46 and the second wiring layer 48 that are the wiring layers 40 may be formed by performing a single process at the same time, or may be formed as separate processes.
- a protective layer such as a resist layer in order to protect the surface on the side formed at a later timing.
- the protective layer is removed and the processing on the side formed at the later timing may be performed.
- a mask pattern 100 is formed.
- the mask pattern 100 is formed as a pattern that covers a region of the conductor layer 44 that is a seed layer where a wiring is not formed and exposes a region where the wiring is formed.
- the mask pattern 100 can be formed using a conventionally known dry film (photosensitive resist film).
- a dry film photosensitive resist film
- As the dry film for example, “ALPHA NIT3025” (trade name) manufactured by Nichigo-Morton Co., Ltd., which is a dry film with a PET film, can be used.
- the mask pattern 100 can be formed, for example, by bonding a dry film to the conductor layer 44 and performing an exposure process, a development process, and a cleaning process under predetermined conditions.
- an electrolytic plating process is performed under the condition that the hole 26 that is a through hole is filled with a material, and the structure 60 in which the mask pattern 100 is formed is bonded to the conductor layer 44 by electrolysis. A plating layer 45 is formed. At this time, the through-hole wiring 50 is formed by embedding the hole 26.
- the mask pattern 100 is stripped and removed by any suitable process according to the selected material, and a flash etching process is performed under any suitable conditions to remove the exposed conductor layer 44 and the metal layer 42 immediately below it.
- the first wiring layer 46 is formed on the first main surface 20a side
- the second wiring layer 48 is formed on the second main surface 20b side (see FIG. 1).
- the wiring board 10 having the configuration already described with reference to FIG. 1 can be manufactured.
- the process (G) of removing the metal layer 42 after a process (D) and before a process (E) is carried out. Further, it may be included. Hereinafter, this process (G) is demonstrated.
- Step (G) is a step of removing the metal layer after step (D) and before step (E).
- the step (E) is a step of forming the conductor layer 44 in the exposed molecular bonding layer 30 and the hole 26.
- Process (G) can be any suitable process such as an etching process performed under conditions according to the material of the conductor layer 44.
- the step (G) since the wiring layer 40 is formed using only the conductor layer 44 as a seed layer, the amount of the conductor to be removed when the wiring layer 40 is formed can be reduced. Since the wiring layer 40 can be patterned under milder conditions, further miniaturization of the wiring can be realized.
- FIG. 7 is a schematic diagram showing an end face of the wiring board cut along a cutting line passing through the hole.
- the wiring board 10 of the second embodiment includes a circuit board 24 including an electronic circuit 24a.
- the circuit board 24 is one or both sides of an insulating base material such as a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, and a thermosetting polyphenylene ether board.
- an insulating base material such as a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, and a thermosetting polyphenylene ether board.
- the electronic circuit 24a of the circuit board 24 has a configuration provided on only one side in the illustrated example, but is not limited thereto, and may be provided on both sides.
- the electronic circuit 24a includes wiring, electrode pads, electronic components, and the like, and is configured to exhibit a predetermined function.
- circuit board 24 a conventionally known arbitrary suitable circuit board provided with wiring, electronic parts, etc. having a desired function as the electronic circuit 24a can be used.
- the thickness of the electronic circuit 24a patterned on one or both sides of the insulating base material is not particularly limited. From the viewpoint of thinning, it is preferably 70 ⁇ m or less, more preferably 60 ⁇ m or less, further preferably 50 ⁇ m or less, even more preferably 40 ⁇ m or less, particularly preferably 30 ⁇ m or less, 20 ⁇ m or less, 15 ⁇ m or less, or 10 ⁇ m or less. .
- the lower limit of the thickness of the electronic circuit 24a is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and further preferably 5 ⁇ m or more.
- the line / space ratio of the electronic circuit 24a patterned on one or both sides of the insulating base material is not particularly limited. However, from the viewpoint of obtaining a build-up insulating layer having excellent smoothness by reducing surface irregularities, it is usually 900. / 900 ⁇ m or less, preferably 700/700 ⁇ m or less, more preferably 500/500 ⁇ m or less, still more preferably 300/300 ⁇ m or less, and even more preferably 200/200 ⁇ m or less.
- the lower limit of the line / space ratio of the electronic circuit 24a is not particularly limited, but is preferably 1/1 ⁇ m or more from the viewpoint of improving the embedding of the resin composition between the spaces.
- circuit board 24 for example, a circuit board obtained by forming wiring by patterning a copper layer using “R1515A” manufactured by Panasonic Corporation which is a glass cloth base epoxy resin double-sided copper-clad laminate. Is mentioned.
- the insulating layer 20 is provided on the circuit board 24.
- the insulating layer 20 is provided so as to cover the electronic circuit 24 a of the circuit board 24.
- the insulating layer 20 according to the second embodiment is a build-up insulating layer. Therefore, it can form with the material used for a conventionally well-known buildup wiring board.
- the insulating layer 20 of the second embodiment may include a sheet-like fiber substrate such as a glass cloth.
- Examples of the sheet-like fiber substrate that can be used for the insulating layer 20 of the second embodiment include a sheet-like fiber substrate that can be included in the prepreg of the first embodiment already described.
- the insulating layer 20 has a first main surface 20a and a second main surface 20b opposite to the first main surface 20a.
- the molecular bonding layer 30 is provided on the first main surface 20a side.
- the wiring board 10 has a wiring layer 40 that is a build-up wiring layer provided in the molecular bonding layer 30 on the first main surface 20a side.
- the wiring layer 40 has a laminated structure including a conductor layer 44 bonded to the molecular bonding layer 30 and an electroplating layer 45 bonded to the conductor layer 44.
- the wiring board 10 includes a hole 26.
- the hole 26 according to the second embodiment is a via hole that penetrates the insulating layer 20 and the molecular bonding layer 30 on the first main surface 20a side and exposes a part of the electronic circuit 24a.
- the conductor layer 44 defines a first region 44a which is a partial region on the first main surface 20a side, a second region 44b joined to a part of the electronic circuit 24a exposed from the hole 26, and the hole 26. And a third region 44c covering the inner wall, which are electrically connected, that is, integrally formed.
- the electrolytic plating layer 45 is a buried region 45c that fills the hole 26 covered with the first region 45a, which is a partial region on the first main surface 20a side, and the second region 44b and the third region 44c of the conductor layer 44. These are configured to be electrically connected, that is, integrally configured.
- the wiring layer 40 can include not only a linear wiring but also an electrode pad (land) on which an external terminal can be mounted, for example.
- the hole 26 which is a via hole has an inner wall covered with the second region 44b and the third region 44c of the conductor layer 44, and is joined to the second region 44b and the third region 44c.
- the filled via 50 is embedded in the third region 45c of the wiring layer 40 and electrically connects the wiring layer 40 and the electronic circuit 24a.
- the wiring board 10 according to the second embodiment can be a multilayer build-up wiring board in which two or more build-up layers are stacked.
- a configuration example in which the buildup layer including the insulating layer 20 and the wiring layer 40 is provided only on one side is shown, but the present invention is not limited to this. It may be provided.
- FIG. 8 is a schematic view of a structure used for manufacturing a wiring board.
- the insulating layer 20 is provided on the circuit board 24, and the molecular bonding layer 30 is the first main surface opposite to the second main surface 20b to which the circuit board 24 is bonded.
- This is a step of preparing a structure 60 provided only on the surface 20a.
- the insulating layer 20 of the second embodiment is a build-up insulating layer.
- the insulating layer 20 which is a build-up insulating layer will be described.
- an adhesive film used for forming the structure 60 according to the step (A) and a manufacturing process thereof will be described.
- the adhesive film includes an organic support and a resin composition layer provided on one main surface of the organic support.
- Organic support examples of the material for the organic support include the same materials as the protective film 110 described in the first embodiment.
- the glass transition temperature of the organic support is preferably 100 ° C. or higher.
- Examples of the organic support material having a glass transition temperature of 100 ° C. or higher include polyesters such as polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA), cyclic polyolefins, and triacetyl cellulose. (TAC), polyether sulfide (PES), polyether ketone, polyether ether ketone, polyimide and the like. Among these, polyethylene naphthalate and polyimide are preferable from the viewpoint of heat resistance.
- polyesters such as polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA), cyclic polyolefins, and triacetyl cellulose. (TAC), polyether sulfide (PES), polyether ketone, polyether ether ketone, polyimide and the like.
- PET polyethylene naphthalate
- acrylics such as polycarbonate (PC) and polymethyl me
- the organic support containing the above material may be subjected to a mat treatment or a corona treatment on the surface to be bonded to the resin composition layer described later.
- an “organic support with a release layer” having a release layer on the side to which the resin composition layer is bonded, that is, the side on which the resin composition is applied may be used (hereinafter referred to as release layer).
- An organic support with a mold layer may be simply referred to as an organic support).
- a mold release agent used for formation of a mold release layer of an organic support with a mold release layer for example, one or more mold release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins Is mentioned.
- the release layer can be formed, for example, by applying a solution containing a release agent to the surface of the organic support and drying it.
- organic support with a release layer a commercially available product may be used.
- SK-1 manufactured by Lintec Corporation, which is a PET film having a release layer mainly composed of an alkyd resin release agent.
- AL-5 a PET film having a release layer mainly composed of an alkyd resin release agent.
- AL-7 a release layer mainly composed of an alkyd resin release agent.
- the thickness of the organic support is not particularly limited, but is preferably in the range of 5 ⁇ m to 75 ⁇ m, more preferably in the range of 10 ⁇ m to 60 ⁇ m, and still more preferably in the range of 12.5 ⁇ m to 55 ⁇ m.
- the thickness of the resin composition layer is not particularly limited on condition that a wiring can be formed by a plating process.
- the resin composition layer preferably has a thickness of 0.5 ⁇ m to 10 ⁇ m, and more preferably 1 ⁇ m to 5 ⁇ m.
- the components of the resin composition that can be used for forming the resin composition layer and the content thereof are particularly limited on the condition that the resin composition layer has sufficient hardness and insulating properties when cured to form the insulating layer 20. Not.
- the resin composition may contain an inorganic filler, an epoxy resin, a curing agent, an organic filler, a curing accelerator, a thermoplastic resin, a flame retardant, and the like.
- the components that can be contained in the resin composition are the same as the components that can be used in the formation of the cured prepreg 22 described in the first embodiment, and thus description thereof is omitted.
- liquid epoxy resin and a solid epoxy resin are 1: 0 in mass ratio. It is preferably in the range of 1 to 1: 4.
- suitable tackiness is obtained when used in the form of an adhesive film, and ii) when used in the form of an adhesive film. Sufficient flexibility is obtained, the handleability is improved, and iii) it is possible to obtain a cured product having sufficient breaking strength.
- the quantitative ratio of liquid epoxy resin to solid epoxy resin is 1: 0.3 to 1: 3.
- a range of 5 is more preferable, a range of 1: 0.6 to 1: 3 is further preferable, and a range of 1: 0.8 to 1: 2.5 is particularly preferable.
- the resin composition used in the resin composition layer is prepared by appropriately mixing the above-mentioned components and, if necessary, kneading means (three rolls, ball mill, bead mill, sand mill, etc.) or stirring means (super mixer, planetary mixer) Etc.) can be prepared by kneading or mixing.
- the production method of the adhesive film having the resin composition layer is not particularly limited.
- a resin varnish in which the resin composition is dissolved in an organic solvent is prepared, and this resin varnish is applied to an organic support using a die coater or the like. It can produce by apply
- the organic solvent used when preparing the resin varnish is the same as the organic solvent that can be used for forming the prepreg of the first embodiment already described.
- the drying treatment of the coating film made of the resin varnish in the formation of the resin composition layer can be carried out by any known and suitable drying method such as heating and hot air blowing. By this drying treatment, the coating film is made into a resin composition layer.
- the drying conditions for the drying treatment may be arbitrarily suitable in consideration of the boiling point of the organic solvent contained in the resin composition and the resin varnish.
- the drying conditions may be, for example, 80 ° C. to 150 ° C. for about 3 minutes to 15 minutes.
- the formation process of the adhesive film is preferably performed by a roll-to-roll method using a long support which is an organic support, and may be performed by a batch method.
- the step of forming the adhesive film by the roll-to-roll method is specifically, while continuously conveying a long organic support stretched between at least two rolls including a winding roll and a winding roll, A resin composition is applied to one main surface of the support exposed between the unwinding roll and the winding roll to form a coating film, and the obtained coating film is continuously dried to obtain a resin composition layer This can be done.
- an adhesive film in which a resin composition layer is provided on an organic support can be prepared.
- a protective film bonded to the exposed surface of the resin composition layer that is not bonded to the organic support is further added. It is preferable to provide it.
- This protective film contributes to the prevention of adhesion and scratches of dust and the like to the resin composition layer.
- a protective film a polypropylene film, a polyethylene film, etc. can be used, for example.
- the film which consists of the same material as the material of an organic support body can be used.
- the thickness of the protective film is not particularly limited and is, for example, 1 ⁇ m to 40 ⁇ m. The thickness of the protective film is preferably thinner than the thickness of the organic support.
- the conditions for the laminating step are not particularly limited, and known conditions used for forming an insulating layer (build-up insulating layer) using an adhesive film can be employed.
- it can be performed by pressing a heated metal plate such as a stainless steel mirror plate from the organic support side of the adhesive film.
- the metal plate is not pressed directly, but is pressed through an elastic member made of heat-resistant rubber or the like so that the adhesive film sufficiently follows the irregularities on the surface of the circuit board 24 provided with the electronic circuit 24a. It is preferable to carry out.
- the pressing temperature is preferably in the range of 70 ° C. to 140 ° C.
- the pressing pressure is preferably in the range of 1 kgf / cm 2 to 11 kgf / cm 2 (0.098 MPa to 1.079 MPa)
- the pressing time is preferably 5 The range is from 2 seconds to 3 minutes.
- the laminating step is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less.
- the laminating step can be performed using a commercially available vacuum laminator.
- Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nichigo Morton, and the like.
- a smoothing step of heating and pressurizing the adhesive film laminated on the circuit board 24 may be performed.
- the smoothing step is generally performed by heating and pressing the adhesive film laminated on the circuit board 24 with a heated metal plate or metal roll under normal pressure (atmospheric pressure).
- the conditions for the heating and pressure treatment can be the same as the conditions for the laminating step.
- the laminating step and the smoothing step can be continuously performed using the same vacuum laminator.
- the process which peels the organic support derived from an adhesive film at the arbitrary timings after implementation of the said lamination process or the said smoothing process is performed.
- the step of peeling the organic support can be performed mechanically by, for example, a commercially available automatic peeling device.
- an insulating layer (build-up insulating layer) is formed by performing a thermosetting step of thermosetting the resin composition layer laminated on the circuit board 24.
- the conditions for the thermosetting process are not particularly limited, and conditions usually employed when forming the insulating layer of the multilayer printed wiring board can be applied.
- the conditions of the thermosetting step can be arbitrarily selected depending on the composition of the resin composition used for the resin composition layer.
- the conditions of the heat curing step are, for example, a curing temperature in a range of 120 ° C. to 240 ° C. (preferably in a range of 150 ° C. to 210 ° C., more preferably in a range of 170 ° C. to 190 ° C.), and a curing time of 5 minutes to 90 minutes. (Preferably 10 minutes to 75 minutes, more preferably 15 minutes to 60 minutes).
- a step of preheating the resin composition layer at a temperature lower than the curing temperature may be performed.
- the resin composition layer Prior to carrying out the thermosetting step, the resin composition layer is kept at a temperature of, for example, 50 ° C. or more and less than 120 ° C. (preferably 60 ° C. or more and 110 ° C. or less, more preferably 70 ° C. or more and 100 ° C. or less) for 5 minutes or more (preferably May be preheated for 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).
- Preheating is preferably performed under atmospheric pressure (normal pressure).
- the molecular bonding layer 30 provided on the first main surface 20a of the insulating layer 20 can be formed by a method suitable for the selected molecular bonding agent.
- the example of the molecular bonding agent that is the material of the molecular bonding layer 30 according to the second embodiment and the method of forming the molecular bonding layer 30 are as already described in the first embodiment.
- the step (A) is preferably a step of preparing a structure 60 further including a protective film 110 bonded to the molecular bonding layer 30.
- the protective film 110 may be laminated so as to cover the first main surface 20a side of the insulating layer 20.
- the details of the protective film 110 are the same as those already described in the first embodiment, and a description thereof will be omitted.
- the structure 60 shown in FIG. 8 in which the insulating layer 20 is provided on the circuit board 24 and the molecular bonding layer 30 is provided only on the first main surface 20a of the insulating layer 20 is prepared.
- FIG. 9 is a schematic diagram for explaining a manufacturing process of the wiring board.
- step (B) according to the second embodiment when the protective film 110 is provided, the molecular bonding layer 30 exposed by peeling off the protective film 110 from the structure 60.
- This is a step of forming the metal layer 42 to be bonded to the substrate.
- the metal layer 42 can be formed by a plating process such as an electroless plating process using the suitable material already described.
- the step (B) is preferably a step of forming the metal layer 42 by an electroless plating step (first electroless plating step) using copper as a material.
- the details of the metal layer 42 are the same as those already described in the first embodiment, and a description thereof will be omitted.
- FIG. 10 is a schematic diagram for explaining a manufacturing process of the wiring board.
- the laser irradiation is performed from the first main surface 20a side of the structure 60 obtained in the above-mentioned ⁇ Step (B)>, thereby the metal layer 42 and the molecular bonding.
- a hole 26 that is a via hole in the second embodiment is formed through the layer 30 and the insulating layer 20 to expose a part of the electronic circuit 24a.
- the details of the laser irradiation and the details of the hole 26 are the same as those already described in the first embodiment, and a description thereof will be omitted.
- a process (D) is a process of performing a desmear process with respect to a hole. This desmear process may be a wet desmear process or a dry desmear process.
- the method of manufacturing the wiring board 10 according to the second embodiment it is not necessary to perform the roughening process on the insulating layer 20, and the flatness of the insulating layer 20 is maintained. can do. Further, since the metal layer 42 covering the molecular bonding layer 30 is formed and the hole 26 is formed in a state where the molecular bonding layer 30 is protected by the metal layer 42, the molecular bonding between the conductor layer 44 and the insulating layer 20 is performed. A decrease in bonding force due to the layer 30 can be prevented. Therefore, the conductor layer 44 and the insulating layer 20 can be firmly joined.
- the formed hole 26 is subjected to a desmear process, even if the hole 26 has a relatively small top diameter r1 and bottom diameter r2 and a relatively large aspect ratio, molecular bonding is performed from within the hole 26. It is possible to form a clean hole 26 from which the material such as the layer 30 and a residue such as a reaction product generated in the step of forming the hole 26 are removed. Therefore, the conduction by the hole 26 provided in the insulating layer 20 can be improved.
- Step (E) is a step of forming a conductor layer.
- the exposed molecular bonding layer 30, the inner wall of the hole 26, and a part of the electronic circuit 24 a exposed from the hole 26 are bonded.
- the conductor layer 44 is formed. That is, the first region 44a bonded to the molecular bonding layer 30 on the first main surface 20a side, the second region 44b bonded to a part of the electronic circuit 24a exposed from the hole 26, and the third region bonded to the inner wall of the hole 26 A conductor layer 44 including 44c is formed.
- the conductor layer 44 can be formed by a process similar to the process of forming the metal layer 42 already described in the first embodiment. Therefore, detailed description of the conductor layer 44 is omitted.
- the conductor layer 44 is formed so as to be bonded to the molecular bonding layer 30. Therefore, the process (G) for removing the metal layer 42 is performed before the process (E) is performed. Since this step (G) has already been described in the first embodiment, a description thereof will be omitted.
- the step (G) since the wiring layer 40 is formed using only the conductor layer 44 as a seed layer, the amount of the conductor to be removed when the wiring layer 40 is formed can be reduced. Since the wiring layer can be patterned under milder conditions, further miniaturization of the wiring can be realized. Therefore, the aspect which performs a process (E) following implementation of a process (G) can be applied suitably for formation of the buildup wiring layer in which refinement
- the step (E) can be carried out without carrying out the step (G).
- Step (F) is a step of forming a wiring layer.
- the wiring layer 40 is preferably formed by a semi-additive method using the conductor layer 44 as a seed layer.
- the wiring layer 40 is formed by the semi-additive method will be described.
- a mask pattern 100 is formed.
- the mask pattern 100 is formed as a pattern that covers a region of the conductor layer 44 that is a seed layer where a wiring is not formed and exposes a region where the wiring is formed.
- the mask pattern 100 is the same as that described in the first embodiment, and a description thereof will be omitted.
- an electrolytic plating process is performed under the condition that the hole 26 that is a via hole is filled with a material, and the structure 60 in which the mask pattern 100 is formed is formed on the first main surface 20 a side. Then, an electrolytic plating layer 45 including a first region 45a provided so as to be joined to the first region 44a of the conductor layer 44 and an embedded region 45c in which the hole 26 is embedded is formed. At this time, the filled via 50 is formed by embedding the hole 26.
- the mask pattern 100 is peeled and removed, and a flash etching process is performed under any suitable conditions for removing the exposed conductor layer 44, thereby forming the wiring layer 40 as a build-up wiring layer on the first main surface 20a side. Form.
- the wiring board 10 having the configuration already described with reference to FIG. 7 can be manufactured.
- the wiring board 10 that has been subjected to the step (F) is used. Further, the series of steps from the step (A) to the step (F) may be repeated one more times.
- the wiring board manufactured by the manufacturing method of the present invention can be used as a wiring board for mounting electronic components such as semiconductor chips.
- various types of semiconductor devices can be manufactured.
- a semiconductor device including such a wiring board can be suitably used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts). .
- part means “part by mass”.
- LA-7054 manufactured by DIC Corporation, MEK solution having a hydroxyl equivalent of 125 and a non-volatile component of 60%
- active ester curing agent an active ester curing agent
- HPC8000-65T manufactured by DIC Corporation, active group equivalent of about 223, non-volatile component 65% by weight toluene solution
- curing accelerator (4-dimethylaminopyridine, non-volatile component 5% by mass MEK solution) 4 Part
- spherical silica surface treated with a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle size 0.5 ⁇ m, “SOC2” manufactured by Admatechs Co., Ltd., carbon per unit area) 0.39 mg / m 2 ) 160 parts
- flame retardant (“HCA-HQ-HST” manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphene) Nyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (average particle size 2 ⁇ m) was mixed and dispersed uniformly with a high-speed rotary mixer to prepare resin varnish 1 .
- a glass cloth having a thickness of 30 ⁇ m (“1067NS” manufactured by Arisawa Manufacturing Co., Ltd.) was immersed and impregnated in the resin varnish 1 by heating, and the solvent was volatilized by heating to form a prepreg.
- the prepreg was dried so that the amount of the solvent remaining in the prepreg was 0.5%, and the thickness of the prepreg was 50 ⁇ m, and wound into a roll.
- the thickness of the prepreg was measured using a contact-type thickness gauge (“MCD-25MJ” manufactured by Mitutoyo Corporation).
- the solution was dissolved while heating. After cooling to room temperature (room temperature), there are 12 parts of a triazine skeleton-containing phenol novolak curing agent (“LA-7054” manufactured by DIC Corporation, a hydroxyl group equivalent of 125, a MEK solution with a nonvolatile component of 60%), naphthol curing.
- LA-7054 triazine skeleton-containing phenol novolak curing agent manufactured by DIC Corporation, a hydroxyl group equivalent of 125, a MEK solution with a nonvolatile component of 60%
- SN-485 manufactured by Nippon Steel Chemical Co., Ltd., MEK solution having a hydroxyl equivalent weight of 215 and a nonvolatile component of 60%
- polyvinyl acetal resin solution (“KS-1” manufactured by Sekisui Chemical Co., Ltd.), 25 parts of a 15% nonvolatile component ethanol / toluene mixed solution) 25 parts, 1 part of a curing accelerator (4-dimethylaminopyridine, 5% by weight nonvolatile component MEK solution), phenylaminosilane coupling agent (Shin-Etsu Chemical Co., Ltd. “KBM573”) surface-treated spherical silica (average particle size 0.24 ⁇ m, Admatechs Co., Ltd.
- the resin composition layer after drying has a thickness of 30 ⁇ m on the release layer side of the PET film with an alkyd release layer (“AL5” manufactured by Lintec Co., Ltd., thickness 38 ⁇ m) that is an organic support.
- AL5 alkyd release layer
- the resin varnish 2 was uniformly applied and dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 4 minutes to produce an adhesive film.
- the thickness of the resin composition layer was measured using a contact-type layer thickness meter (“MCD-25MJ” manufactured by Mitutoyo Corporation).
- Example 1 Vacuum hot pressing step
- the prepreg formed in the above ⁇ Formation of prepreg> is cut into a 250 mm square and cushion paper (“ACP-9N” manufactured by Awa Paper Co., Ltd., thickness 800 ⁇ m) / stainless steel (SUS) Plate (thickness 1 mm) / release sheet (“Aflex 50N NT” manufactured by Asahi Glass Co., Ltd., thickness 50 ⁇ m) / prepreg / release sheet / SUS board / cushion paper are stacked in this order to form a vacuum hot press device (Kitakawa Using a “VH1-1603” manufactured by Seiki Co., Ltd., a vacuum hot pressing step was performed to form a cured prepreg.
- ACP-9N manufactured by Awa Paper Co., Ltd., thickness 800 ⁇ m
- SUS stainless steel
- the implementation conditions of the vacuum hot press process are as follows. Temperature: Increased from room temperature (room temperature) to 200 ° C. at a rate of temperature increase of 5 ° C./min, held at 200 ° C. for 90 minutes, and then decreased to room temperature at a rate of temperature decrease of 5 ° C./min. 0 kg / cm 2 ) held for 20 minutes, and when the temperature reaches about 125 ° C., the pressing force is set to 50 kg / cm 2 , and this is held until the end of temperature drop: 70 mm / hg to 74 mm / hg (9.3 ⁇ 10 -3 MPa to 9.9 ⁇ 10 -3 MPa)
- a through-hole penetrating the metal layer and the cured prepreg was formed by drilling using a CO 2 laser processing machine “LC-2k212 / 2C” manufactured by Hitachi Via Mechanics Co., Ltd. .
- the top diameter (diameter) of the through hole on the surface of the cured prepreg was 65 ⁇ m.
- the drilling was performed in a cycle mode with a mask diameter of 3.5 mm, a power of 1 W, a frequency of 2000 Hz, a pulse width of 4 ⁇ s, a shot number of 3, and the like.
- Conductive layer formation process In order to form a conductive layer on the surface of the metal layer and in the through-hole, again in the electroless plating process (the following electroless copper plating process using chemicals manufactured by Atotech Japan Co., Ltd.) A certain second electroless plating step) was performed to form a conductor layer (second electroless plating layer).
- the thickness of the formed conductor layer was 0.8 ⁇ m.
- the total thickness of the metal layer and the conductor layer on the surface of the cured prepreg was about 1.3 ⁇ m.
- Alkali cleaning cleaning of the surface of the metal layer and the surface in the through hole and charge adjustment
- Washing was performed at 60 ° C. for 2 minutes using “Cleaning Cleaner Security 902” (trade name).
- Pre-dip adjustment of the charge on the surface of the metal layer and the surface of the through hole for Pd application
- Pre. Dip Neoganth B (trade name)
- the treatment was performed at room temperature for 1 minute.
- Activator Applying Pd to the surface of the metal layer and the surface of the through hole
- Activator Neoganth 834 (trade name)
- Reduction reduction of Pd applied to the surface of the metal layer and the surface of the through hole
- Electroless copper plating (Cu is deposited on the surface of the metal layer and the surface of the through hole (Pd surface))
- a mixture of "Basic Solution Printganth MSK-DK” trade name
- Copper solution Printganth MSK trade name
- Stabilizer Printganth MSK-DK trade name
- Reducer Cu trade name
- Wiring layer forming step ⁇ Mask pattern forming step> the surface of the structure was treated with 5% sulfuric acid aqueous solution for 30 seconds to form “ALPHON NIT3025” (trade name) manufactured by Nichigo Morton Co., Ltd., which is a dry film with a 25 ⁇ m thick mask pattern forming PET film. It laminated
- MVLP-500 trade name
- L (line: line width of the dry film) / S (space: spacing between the linear dry films) 8 ⁇ m / 8 ⁇ m, that is, 16 ⁇ m pitch comb-tooth pattern (wiring length 15 mm, 16 lines)
- L / S 10 ⁇ m / 10 ⁇ m, that is, 20 ⁇ m pitch comb-teeth pattern (wiring length 15 mm, 16 lines),
- L / S 15 ⁇ m / 15 ⁇ m, ie, 30 ⁇ m pitch comb-teeth pattern (wiring length 15 mm, 16 lines)
- a mask photomask is placed on the PET film side, which is the protective layer of each dry film provided on both sides of the structure, and UV light of 150 mJ / cm 2 is provided on both sides of the structure using a UV lamp. An exposure process for irradiating each dry film was performed to form a mask pattern.
- a spray treatment was performed in which a 1% sodium carbonate aqueous solution at a temperature of 30 ° C. was sprayed onto the structure at a pressure of 0.15 MPa for 30 seconds.
- Electrolytic plating process electrolytic copper plating process
- An electrolytic plating layer electrolytic copper plating layer was formed on the conductor layer, and a through-hole was embedded to form a through-hole wiring.
- Example 2 Ground treatment of circuit board Glass cloth base material epoxy resin double-sided copper clad laminate on which an electronic circuit (wiring layer) is formed (copper layer (wiring layer) thickness 18 ⁇ m, base material thickness 0.3 mm, The copper layer was removed by etching 1 ⁇ m of the thickness of the copper layer with a micro-etching agent (“CZ8100” manufactured by Mec Co., Ltd.) on both sides of the “R1515A” (circuit board) manufactured by Panasonic Corporation. The surface was subjected to desmear treatment.
- a micro-etching agent (“CZ8100” manufactured by Mec Co., Ltd.)
- epoxy silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyl
- Metal layer forming step In order to form a metal layer on the surface of the circuit board (structure) on which the molecular bonding layer is formed, the first electroless plating step similar to Example 1 already described (Atotech Japan) (Electroless copper plating step using a pharmaceutical solution). The thickness of the metal layer (first electroless plating layer) formed by the first electroless plating process was 0.5 ⁇ m.
- Desmear treatment The structure in which the via hole is formed is immersed in “Swelling Dip Securigans P” containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd., which is a swelling liquid, at 60 ° C. for 5 minutes. Next, as a roughening solution, it was immersed in “Concentrate Compact P” (KMnO 4 : 60 g / L, NaOH: 40 g / L aqueous solution) of Atotech Japan for 15 minutes at 80 ° C. As a Japanese liquid, a via hole desmear treatment was performed by dipping in “Reduction Solution Securigans P” manufactured by Atotech Japan Co., Ltd. for 5 minutes at 40 ° C. and then drying at 130 ° C. for 15 minutes.
- “Swelling Dip Securigans P” containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd., which is a swelling liquid, at 60 ° C. for 5 minutes.
- Conductive layer forming step In order to form a conductive layer on the molecular bonding layer exposed by removing the metal layer, a second electroless plating step (electroless copper plating using Atotech Japan Co., Ltd. pharmaceutical solution) Step).
- the thickness of the formed conductor layer was 0.8 ⁇ m.
- L (line: line width of the dry film) / S (space: spacing between the linear dry films) 8 ⁇ m / 8 ⁇ m, that is, 16 ⁇ m pitch comb-tooth pattern (wiring length 15 mm, 16 lines)
- L / S 10 ⁇ m / 10 ⁇ m, that is, 20 ⁇ m pitch comb-teeth pattern (wiring length 15 mm, 16 lines),
- L / S 15 ⁇ m / 15 ⁇ m, ie, 30 ⁇ m pitch comb-teeth pattern (wiring length 15 mm, 16 lines)
- a mask photomask is placed on the PET film side, which is a protective layer of a dry film laminated on the top diameter side of the via hole, and an exposure process of irradiating UV light of 150 mJ / cm 2 using a UV lamp is performed. A mask pattern was formed. Note that the entire surface of the dry film laminated on the bottom diameter side of the via hole was exposed to form a mask pattern covering the entire
- a spray treatment was performed in which a 1% sodium carbonate aqueous solution at a temperature of 30 ° C. was sprayed onto the structure at a pressure of 0.15 MPa for 30 seconds.
- the mask pattern was peeled from both surfaces of the structure by spraying the structure with a 3% NaOH solution at a temperature of 50 ° C. at a pressure of 0.2 MPa.
- an etchant for SAC process flash etching process manufactured by Sakakibara Denshi Co., Ltd.
- only the exposed conductor layer is removed by removing the mask pattern, and a wiring layer including a plurality of fine wirings is obtained. Formed.
- the wiring board concerning Example 2 was manufactured according to the above process.
- Comparative Example 1 By performing the roughening treatment process that also serves as the desmear treatment process after forming the through hole, and then performing the formation process of the molecular bonding layer, by performing the process up to forming the wiring layer in the same manner as in Example 1, A wiring board according to Comparative Example 1 was manufactured.
- Example 2 except that a via hole is formed after the molecular bonding layer is formed, then a roughening treatment step that also serves as a desmear treatment step is performed, and then a step of forming a conductor layer without forming a metal layer is performed. Similarly, the wiring board concerning the comparative example 2 was manufactured by performing even the process of forming a wiring layer.
- Example 1 Each wiring formed in Example 1, Example 2, Comparative Example 1 and Comparative Example 2 was checked for the presence or absence of peeling with an optical microscope, and further checked for the presence or absence of a conductor layer (and metal layer) residue to be removed. Confirmed and evaluated.
- the evaluation criteria are as follows. The results are shown in Table 2 below. Evaluation criteria ⁇ : No problem with 9 or more of the 10 linear portions of the comb pattern ⁇ : No problem with 2 or more of the 10 linear portions of the comb pattern
- Example 1 and Example 2 As is clear from Table 2, in the wiring boards manufactured in Example 1 and Example 2, the minimum wiring pitch could be 20 ⁇ m or less, and fine wiring could be realized. Moreover, in Example 1 and Example 2, it became clear that it has the peel strength which is not inferior compared with the comparative example 1 and the comparative example 2 which performed the roughening process as usual. On the other hand, in Comparative Example 1 and Comparative Example 2, since the roughening process is carried out, the surface roughness (Ra and Rq) is large, and due to this surface roughness, the minimum wiring pitch is 20 ⁇ m or less. I could't.
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Abstract
Description
〔1〕工程(A)第1主表面及び該第1主表面と対向する第2主表面を有している絶縁層と、前記第1主表面のみ又は該第1主表面及び前記第2主表面の両方に設けられている分子接合層とを備える構造体を用意する工程と、
工程(B)前記分子接合層に接合する金属層を形成する工程と、
工程(C)レーザー照射を行って、前記金属層、前記分子接合層及び前記絶縁層を貫通する孔部を形成する工程と、
工程(D)前記孔部に対してデスミア処理を行う工程と、
工程(E)導体層を形成する工程と、
工程(F)配線層を形成する工程と
を含む、配線板の製造方法。
[2]前記工程(A)が、前記絶縁層が硬化プリプレグであり、前記分子接合層が前記絶縁層の前記第1主表面及び前記第2主表面の両方に設けられている構造体を用意する工程である、[1]に記載の配線板の製造方法。
[3]前記工程(A)が、前記絶縁層が回路基板に設けられ、前記分子接合層が該回路基板が接合されている前記第2主表面とは反対側の前記第1主表面のみに設けられている構造体を用意する工程である、[1]に記載の配線板の製造方法。
[4]前記工程(A)が、前記分子接合層に接合する保護フィルムをさらに備える構造体を用意する工程であり、
前記工程(B)が、前記保護フィルムを剥離して、前記分子接合層に接合する金属層を形成する工程である、[1]~[3]のいずれか1つに記載の配線板の製造方法。
[5]前記工程(A)が、前記分子接合層に接合する保護フィルムを設ける工程をさらに含み、
前記工程(B)が、前記構造体から前記保護フィルムを剥離して、前記分子接合層に接合する金属層を形成する工程である、[1]~[3]のいずれか1つに記載の配線板の製造方法。
[6]前記工程(D)の後であって前記工程(E)の前に、工程(G)前記金属層を除去する工程をさらに含み、
前記工程(E)が、露出した前記分子接合層及び前記孔部に、導体層を形成する工程である、[1]~[5]のいずれか1つに記載の配線板の製造方法。
[7]前記工程(B)が、無電解めっき工程により金属層を形成する工程である、[1]~[6]のいずれか1つに記載の配線板の製造方法。
〔配線板〕
まず、本発明の第1の実施形態にかかる配線板の製造方法により製造される配線板の構成例について、図1を参照して説明する。図1は、孔部を通る切断線で切断した配線板の模式的な図である。
以下、絶縁層20、分子接合層30などを含む、配線板10の製造中途の構造体を単に「構造体」という場合がある。
以下、本発明の第1の実施形態にかかる配線板の製造方法について説明する。
図2を参照して、第1の実施形態にかかる工程(A)で用意される構造体について説明する。図2は、配線板の製造に用いられる構造体の模式的な図である。
硬化プリプレグ22は、シート状繊維基材に樹脂組成物を含浸させたシート状のプリプレグを硬化した構造体である。硬化プリプレグ22としては、配線板10の用途に応じた任意好適なプリプレグを用いて形成することができる。
プリプレグの形成に用いられ得る樹脂組成物の成分及びその含有量は、硬化プリプレグとされたときに十分な硬度と絶縁性とを有していることを条件として特に限定されない。
樹脂組成物は、硬化されたときの熱膨張率を低下させて熱膨張率の差によるクラック、回路歪みなどの不具合の発生を抑制し、溶融粘度の過度の低下を抑制する観点から無機充填材を含むことが好ましい。
樹脂組成物は、めっき工程により形成される層との密着性を向上させる観点から有機充填材を含むことが好ましい。有機充填材の例としては、ゴム粒子が挙げられる。有機充填材であるゴム粒子としては、例えば、後述する有機溶剤に溶解せず、後述するエポキシ樹脂、硬化剤、及び熱可塑性樹脂などとも相溶しないゴム粒子が使用される。このようなゴム粒子は、一般には、ゴム粒子の成分の分子量を有機溶剤、樹脂に溶解しない程度まで大きくし、粒子状とすることで調製される。
エポキシ樹脂としては、例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、ビスフェノールAF型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、トリスフェノールエポキシ樹脂、ナフトールノボラックエポキシ樹脂、フェノールノボラック型エポキシ樹脂、tert-ブチル-カテコール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ナフトール型エポキシ樹脂、アントラセン型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、線状脂肪族エポキシ樹脂、ブタジエン構造を有するエポキシ樹脂、脂環式エポキシ樹脂、複素環式エポキシ樹脂、スピロ環含有エポキシ樹脂、シクロヘキサンジメタノール型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂及びトリメチロール型エポキシ樹脂等が挙げられる。エポキシ樹脂は1種単独で用いてもよく、又は2種以上を併用してもよい。
硬化剤としては、前記エポキシ樹脂を硬化する機能を有する限り特に限定されないが、例えば、フェノール系硬化剤、ナフトール系硬化剤、活性エステル系硬化剤、ベンゾオキサジン系硬化剤、シアネートエステル系硬化剤、カルボジイミド系硬化剤が挙げられる。硬化剤は1種単独で用いてもよく、又は2種以上を併用してもよい。
熱可塑性樹脂としては、例えば、フェノキシ樹脂、アクリル樹脂、ポリビニルアセタール樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリエーテルスルホン樹脂、及びポリスルホン樹脂等が挙げられる。熱可塑性樹脂は1種単独で用いてもよく、又は2種以上を併用してもよい。
硬化促進剤としては、例えば、リン系硬化促進剤、アミン系硬化促進剤、イミダゾール系硬化促進剤、グアニジン系硬化促進剤等が挙げられる。
難燃剤としては、例えば、有機リン系難燃剤、有機系窒素含有リン化合物、窒素化合物、シリコーン系難燃剤、金属水酸化物等が挙げられる。用い得る難燃剤の例としては三光(株)製「HCA-HQ-HST」が挙げられる。難燃剤は1種単独で用いてもよく、又は2種以上を併用してもよい。樹脂組成物層中の難燃剤の含有量は特に限定されないが、0.5質量%~10質量%の範囲であることが好ましく、1質量%~9質量%の範囲であることがより好ましく、1.5質量%~8質量%の範囲であることがさらに好ましい。
樹脂組成物は、必要に応じて、樹脂組成物又はその硬化体の特性を調整することを目的とする他の添加剤を含んでいてもよく、かかる他の添加剤としては、例えば、有機銅化合物、有機亜鉛化合物及び有機コバルト化合物等の有機金属化合物、並びに増粘剤、消泡剤、レベリング剤、密着性付与剤、及び着色剤等の樹脂添加剤等が挙げられる。
先ずプリプレグの形成工程について説明する。プリプレグは、ホットメルト法、ソルベント法等の公知の方法により製造することができる。ホットメルト法では、樹脂組成物を有機溶剤に溶解することなく、樹脂組成物と剥離性のよい離型紙に一旦コーティングし、それをシート状繊維基材にラミネートするか、あるいはダイコーターによりシート状繊維基材に直接的に塗工するなどして、プリプレグを製造している。またソルベント法では、樹脂組成物を有機溶剤に溶解した樹脂ワニスにシート状繊維基材を浸漬することにより、樹脂組成物をシート状繊維基材に含浸させ、その後乾燥させて、プリプレグを形成している。さらにはプリプレグは、樹脂組成物からなる2枚の樹脂シートでシート状繊維基材をその両面側から挟み込んで加圧条件下で加熱することにより、連続的に熱ラミネートすることで形成することもできる。
硬化プリプレグ22の第1主表面20a及び第2主表面20bの両方に設けられている分子接合層30は、分子接合層30を形成するための材料として選択された分子接合剤に好適な方法により形成することができる。
図2に示されるように、工程(A)は、分子接合層30に接合する保護フィルム110をさらに備える構造体60を用意する工程とすることが好ましい。
図2及び3を参照して、工程(B)について説明する。図3は、配線板の製造工程を説明するための模式的な図である。
図2及び図3に示されるように、第1の実施形態にかかる工程(B)は、保護フィルム110が設けられている場合には構造体60から保護フィルム110を剥離して、露出した分子接合層30に接合する金属層42を形成すればよい。
(2)次いでパラジウム(Pd)を分子接合層30の表面に付与するために電荷を調整するプレディップ工程を行う。
(3)次に分子接合層30にアクティヴェーターであるパラジウムを付与する。
(4)次いで分子接合層30の表面に付与されたパラジウムを還元する。
(5)次に、銅を分子接合層30に析出させることにより金属層42を形成する。
図3を参照して、引き続き工程(C)について説明する。
工程(C)は、レーザー照射を行って、金属層、分子接合層、及び絶縁層を貫通する、孔部を形成する工程である。
図3を参照して、引き続き工程(D)について説明する。
工程(D)は、孔部に対してデスミア処理を行う工程である。
デスミア処理は、孔部26内のスミア除去のために行われる。このデスミア処理は、湿式のデスミア処理であっても、乾式のデスミア処理であってもよい。
図4を参照して、工程(E)について説明する。図4は、配線板の製造工程を説明するための模式的な図である。
工程(E)は、導体層を形成する工程である。
図5及び図6を参照して、工程(F)について説明する。図5及び図6は、配線板の製造工程を説明するための模式的な図である。
ここでは、配線層40である第1配線層46及び第2配線層48は、同時に単一の工程を実施することにより形成してもよいし、それぞれ別の工程として形成してもよい。第1配線層46及び第2配線層48それぞれを異なるタイミングで別の工程として実施する場合には、後のタイミングで形成される側の表面を保護するためにレジスト層などの保護層で覆っておいて、先のタイミングで形成される側の処理を行った後に、保護層を除去して後のタイミングで形成される側の処理を行えばよい。
以下、第1配線層46及び第2配線層48の形成をセミアディティブ法により単一の工程として行う例について説明する。
以下、かかる工程(G)について説明する。
工程(G)は、工程(D)の後であって工程(E)の前に、金属層を除去する工程である。
工程(G)を実施する場合には、工程(E)は、露出した分子接合層30及び孔部26に、導体層44を形成する工程とされる。
〔配線板〕
まず、本発明の第2の実施形態にかかる配線板の製造方法により製造される配線板の構成例について、図7を参照して説明する。図7は、孔部を通る切断線で切断した配線板の端面を示す模式的な図である。
図8~図13を参照して、前記構成を備える第2の実施形態にかかる配線板の製造方法について説明する。
図8を参照して、先ず第2の実施形態にかかる工程(A)で用意される構造体について説明する。図8は、配線板の製造に用いられる構造体の模式的な図である。
先ず工程(A)にかかる構造体60を形成するため用いられる接着フィルム及びその製造工程について説明する。
接着フィルムは、有機支持体と、この有機支持体の一方の主面に設けられた樹脂組成物層とを含んでいる。
有機支持体の材料としては、第1の実施形態で説明した保護フィルム110と同様の材料が挙げられる。
樹脂組成物層の厚さは、めっき工程により配線が形成できることを条件として特に限定されない。樹脂組成物層は、厚さが0.5μm~10μmであることが好ましく、1μm~5μmであることがより好ましい。
樹脂組成物層の形成に用いられ得る樹脂組成物の成分及びその含有量は、硬化されて絶縁層20とされたときに十分な硬度と絶縁性とを有していることを条件として特に限定されない。
樹脂組成物層に用いられる樹脂組成物は、上記の成分を適宜混合し、また、必要に応じて混練手段(3本ロール、ボールミル、ビーズミル、サンドミル等)あるいは撹拌手段(スーパーミキサー、プラネタリーミキサー等)により混練又は混合することにより調製することができる。
次に、絶縁層20の形成工程について説明する。
まず前記回路基板24の電子回路24aに接触するように、用意された接着フィルムの樹脂組成物層をラミネートするラミネート工程を行う。
絶縁層20の第1主表面20aに設けられている分子接合層30は、選択された分子接合剤に好適な方法により形成することができる。
図9を参照して、工程(B)について説明する。図9は、配線板の製造工程を説明するための模式的な図である。
図10を参照して、引き続き工程(C)について説明する。図10は、配線板の製造工程を説明するための模式的な図である。
図10を参照して、引き続き工程(D)について説明する。
工程(D)は、孔部に対してデスミア処理を行う工程である。このデスミア処理は、湿式のデスミア処理であっても、乾式のデスミア処理であってもよい。
図11を参照して、工程(E)について説明する。図11は、配線板の製造工程を説明するための模式的な図である。
工程(E)は、導体層を形成する工程である。
図12及び図13を参照して、工程(F)について説明する。図12及び図13は、配線板の製造工程を説明するための模式的な図である。
配線層40は、導体層44をシード層とするセミアディティブ法により形成することが好ましい。以下、セミアディティブ法により配線層40を形成する例について説明する。
本発明の製造方法により製造される配線板は、半導体チップ等の電子部品を搭載するための配線板として用いることができる。またかかる配線板を用いて、種々の態様の半導体装置を製造することができる。かかる配線板を備える半導体装置は、電気製品(例えば、コンピューター、携帯電話、デジタルカメラ及びテレビ等)及び乗物(例えば、自動二輪車、自動車、電車、船舶及び航空機等)等に好適に用いることができる。
ナフタレン型エポキシ樹脂(DIC(株)製「HP4032SS」、エポキシ当量約144)5部、ナフタレン型エポキシ樹脂(DIC(株)製「HP-4710」、エポキシ当量約171)5部、ナフタレン型エポキシ樹脂(DIC(株)製「HP-6000」、エポキシ当量約248)5部、ビフェニル型エポキシ樹脂(三菱化学(株)製「YX4000HK」、エポキシ当量約185)5部、ビフェニル型エポキシ樹脂(日本化薬(株)製「NC3000H」、エポキシ当量約288)10部、フェノキシ樹脂(三菱化学(株)製「YL7553BH30」、不揮発成分30質量%のMEK:シクロヘキサノン=1:1溶液)5部を、ソルベントナフサ50部に撹拌しながら加熱して溶解させた。室温にまで冷却した後、そこへ、トリアジン骨格含有フェノールノボラック系硬化剤(DIC(株)製「LA-7054」、水酸基当量125、不揮発成分60%のMEK溶液)6部、活性エステル系硬化剤(DIC(株)製「HPC8000-65T」、活性基当量約223、不揮発成分65質量%のトルエン溶液)20部、硬化促進剤(4-ジメチルアミノピリジン、不揮発成分5質量%のMEK溶液)4部、フェニルアミノシラン系カップリング剤(信越化学工業(株)製「KBM573」)で表面処理された球形シリカ(平均粒径0.5μm、(株)アドマテックス製「SOC2」、単位面積当たりのカーボン量0.39mg/m2)160部、難燃剤(三光(株)製「HCA-HQ-HST」、10-(2,5-ジヒドロキシフェニル)-10-ヒドロ-9-オキサ-10-フォスファフェナンスレン-10-オキサイド、平均粒径2μm)4部を混合し、高速回転ミキサーで均一に分散して、樹脂ワニス1を調製した。組成を下記表1に示す。
ビスフェノール型エポキシ樹脂(新日鐵化学(株)製「ZX1059」、ビスフェノールA型エポキシ樹脂とビスフェノールF型エポキシ樹脂との1:1混合品、エポキシ当量169)8部、ナフタレン型エポキシ樹脂(DIC(株)製「HP4032SS」、エポキシ当量約144)3部、ビフェニル型エポキシ樹脂(三菱化学(株)製「YX4000HK」、エポキシ当量約185)6部、ビフェニル型エポキシ樹脂(日本化薬(株)製「NC3000H」、エポキシ当量約288)15部、フェノキシ樹脂(三菱化学(株)製「YX6954BH30」、不揮発成分30質量%のMEK:シクロヘキサノン=1:1溶液)25部を、ソルベントナフサ10部に撹拌しながら加熱溶解させた。室温(常温)まで冷却した後、そこへ、トリアジン骨格含有フェノールノボラック系硬化剤(DIC(株)製「LA-7054」、水酸基当量125、不揮発成分60%のMEK溶液)12部、ナフトール系硬化剤(新日鐵化学(株)製「SN-485」、水酸基当量215、不揮発成分60%のMEK溶液)12部、ポリビニルアセタール樹脂溶液(積水化学工業(株)製「KS-1」)、不揮発成分15%のエタノールとトルエンとの1:1溶液との混合溶液)25部、硬化促進剤(4-ジメチルアミノピリジン、不揮発成分5質量%のMEK溶液)1部、フェニルアミノシラン系カップリング剤(信越化学工業(株)製「KBM573」)で表面処理された球形シリカ(平均粒径0.24μm、(株)アドマテックス製「SOC1」、単位面積当たりのカーボン量0.36mg/m2)60部、有機充填材であるゴム粒子(ガンツ化成(株)製「スタフィロイドAC3816N」)4部を混合し、高速回転ミキサーで均一に分散して、樹脂ワニス2を調製した。不揮発成分換算の組成を下記表1に示す。
(1)真空熱プレス工程
前記<プリプレグの形成>において形成されたプリプレグを、250mm角にカットし、クッション紙(阿波製紙(株)製「AACP-9N」、厚さ800μm)/ステンレス(SUS)板(厚さ1mm)/離型シート(旭硝子(株)製「アフレックス50N NT」、厚さ50μm)/プリプレグ/離型シート/SUS板/クッション紙の順に積層して真空熱プレス装置(北川精機(株)製「VH1-1603」)を使用して真空熱プレス工程を実施して硬化プリプレグを形成した。
温度:室温(常温)から200℃に至るまで昇温率5℃/分で昇温し、200℃で90分間ホールドし、その後降温率5℃/分で室温まで降温
押圧力:押圧せず(0kg/cm2)20分間ホールドし、温度が約125℃となった時点で押圧力を50kg/cm2としてこれを降温終了時までホールド
気圧:70mm/hg~74mm/hg(9.3×10-3MPa~9.9×10-3MPa)
形成された硬化プリプレグを、分子接合剤(信越化学工業(株)製トリアジンチオール官能性シリコーンアルコキシオリゴマー、フッ素化アルキル基タイプ「X-24-9453」)の0.5重量%溶液(混合溶媒;水:イソプロピルアルコール:酢酸=70:30:0.5)に23℃で3分間浸漬し、その後100℃で30分間乾燥させて硬化プリプレグの第1主表面及び第2主表面を含む表面に分子接合層を形成した。
分子接合層を形成した硬化プリプレグの表面に金属層を形成するため、第1の無電解めっき工程(アトテックジャパン(株)製薬液を使用する、下記の無電解銅めっき工程)を行った。第1無電解めっき工程により形成された金属層(第1無電解めっき層)の厚さは0.5μmであった。
1.アルカリクリーニング(分子結合層の表面の洗浄と電荷調整)
Cleaning Cleaner Securiganth 902(商品名)を用いて60℃で2分間洗浄した。
2.プレディップ(Pd付与のための分子結合層の表面の電荷の調整)
Pre. Dip Neoganth B(商品名)を用い、室温で1分間処理した。
3.アクティヴェーター(分子結合層の表面へのPdの付与)
Activator Neoganth 834(商品名)を用い、35℃で5分間処理した。
4.還元(分子結合層の表面に付与されたPdを還元)
Reducer Neoganth WA(商品名)及びReducer Acceralator 810 mod.の混合液を用い、30℃で5分間処理した。
5.無電解銅めっき(Cuを分子結合層の表面(Pd表面)に析出)
Basic Solution Printganth MSK-DK(商品名)、Copper solution Printganth MSK(商品名)、Stabilizer Printganth MSK-DK(商品名)及びReducer Cu(商品名)の混合液を用いて、35℃で10分間処理した。
日立ビアメカニクス(株)製CO2レーザー加工機「LC-2k212/2C」を使用して穴あけ加工することにより、金属層及び硬化プリプレグを貫通するスルーホールを形成した。硬化プリプレグの表面におけるスルーホールのトップ径(直径)は65μmであった。なお、穴あけ加工は、マスク径を3.5mmとし、パワーを1Wとし、周波数を2000Hzとし、パルス幅を4μsとし、ショット数を3とし、サイクルモードとして実施した。
スルーホールが形成された構造体を、膨潤液である、アトテックジャパン(株)のジエチレングリコールモノブチルエーテルを含有する「スウェリング・ディップ・セキュリガンスP」に60℃で5分間浸漬し、次に粗化液として、アトテックジャパン(株)の「コンセントレート・コンパクトP」(KMnO4:60g/L、NaOH:40g/Lの水溶液)に80℃で15分間浸漬し、水洗処理後、中和液として、アトテックジャパン(株)の「リダクションソリューション・セキュリガンスP」に40℃で5分間浸漬した。その後、130℃で15分間乾燥した。
金属層の表面及びスルーホール内に導体層を形成するため、再度、無電解めっき工程(アトテックジャパン(株)製の薬液を使用した下記の無電解銅めっき工程である第2無電解めっき工程)を行って導体層(第2無電解めっき層)を形成した。形成された導体層の厚さは0.8μmであった。硬化プリプレグの表面の金属層と導体層との厚さの総和は、約1.3μmであった。
1.アルカリクリーニング(金属層の表面及びスルーホール内の表面の洗浄と電荷調整)
「Cleaning Cleaner Securiganth 902」(商品名)を用いて60℃で2分間洗浄した。
2.プレディップ(Pd付与のための金属層の表面及びスルーホールの表面の電荷の調整)
「Pre. Dip Neoganth B」(商品名)を用い、室温で1分間処理した。
3.アクティヴェーター(金属層の表面及びスルーホールの表面へのPdの付与)
「Activator Neoganth 834」(商品名)を用い、35℃で5分間処理した。
4.還元(金属層の表面及びスルーホールの表面に付与されたPdを還元)
「Reducer Neoganth WA」(商品名)及び「Reducer Acceralator 810 mod.」の混合液を用い、30℃で5分間処理した。
5.無電解銅めっき(Cuを金属層の表面及びスルーホールの表面(Pd表面)に析出)
「Basic Solution Printganth MSK-DK」(商品名)、「Copper solution Printganth MSK」(商品名)、「Stabilizer Printganth MSK-DK」(商品名)及び「Reducer Cu」(商品名)の混合液を用いて、35℃で18分間処理した。
<マスクパターンの形成工程>
次いで、構造体の表面を5%硫酸水溶液で30秒間処理し、厚さ25μmのマスクパターン形成用のPETフィルム付きドライフィルムであるニチゴー・モートン(株)製「ALPHO NIT3025」(商品名)を構造体の両面に真空ラミネーターにて積層した。積層は、(株)名機製作所製バッチ式真空加圧ラミネーター「MVLP-500」(商品名)を用いて、圧力を0.1MPaとし、温度を70℃とし、30秒間減圧して気圧を13hPa以下にしてから、20秒間加圧して行った。
次に、構造体を水洗して、現像工程を行った。現像工程を行った構造体にアトテックジャパン(株)製の薬液を使用して、スルーホールに銅が充填される条件で電解めっき工程(電解銅めっき工程)を行って、マスクパターンから露出している導体層に電解めっき層(電解銅めっき層)を形成し、併せてスルーホールを埋め込んでスルーホール内配線を形成した。
次に、構造体に対して温度50℃の3%NaOH溶液を圧力0.2MPaで噴霧するスプレー処理を行い、構造体の両面からのマスクパターンの剥離を行った。次いで、(株)荏原電産製のSACプロセス(フラッシュエッチング工程)用エッチャントを用いて、マスクパターンを除去することにより露出した導体層及び露出した導体層の直下の領域の金属層を除去して、微細な複数の配線を含む配線層を構造体の両面に形成した。
以上の工程により実施例1にかかる配線板が製造された。
(1)回路基板の下地処理
電子回路(配線層)が形成されたガラス布基材エポキシ樹脂両面銅張積層板(銅層(配線層)の厚さ18μm、基材の厚さ0.3mm、パナソニック(株)製「R1515A」)(回路基板)の両面をマイクロエッチング剤(メック(株)製「CZ8100」)にて銅層の厚さのうちの1μmをエッチングすることにより除去して銅層の表面のデスミア処理を行った。
既に説明した<接着フィルムの製造>と同様の工程で作製された接着フィルムを用意し、接着フィルムを、バッチ式真空加圧ラミネーター(ニチゴー・モートン(株)製2ステージビルドアップラミネーター「CVP700」)を用いて、樹脂組成物層が回路基板と接合するように、回路基板の両面にラミネートした。ラミネートは、30秒間減圧して気圧を13hPa以下とした後、温度を110℃とし、押圧力を0.74MPaとして30秒間圧着させることにより実施した。次いで、ラミネートされた接着フィルムを、大気圧下、温度を100℃とし、押圧力を0.5MPaとして60秒間熱プレスすることにより平滑化した。
次に、接着フィルムがラミネートされた構造体を100℃にて30分間、次いで160℃にて30分間加熱処理することにより樹脂組成物層を硬化して、絶縁層を形成した。
絶縁層が形成された回路基板から、接着フィルムに由来する離型PETフィルムを剥離し、分子接合剤として、アミノトリアジンノボラック樹脂(DIC(株)製「LA-1356」、不揮発成分60重量%のMEK溶液、N含有量19重量%、固形分水酸基価146)0.5重量%、エポキシシランカップリング剤(信越化学工業(株)製、3-グリシドキシプロピルトリメトキシシラン、「KBM403」、分子量236.3)0.5重量%の混合溶液(エタノール:MEK:水=50:50:1の混合溶媒に溶解させた混合溶液)に23℃で3分間浸漬し、その後100℃で30分間乾燥した。
分子接合層が形成された回路基板(構造体)の表面に金属層を形成するため、既に説明した実施例1と同様の第1の無電解めっき工程(アトテックジャパン(株)製薬液を使用する、無電解銅めっき工程)を行った。第1の無電解めっき工程により形成された金属層(第1の無電解めっき層)の厚さは0.5μmであった。
CO2レーザー加工機(日立ビアメカニクス(株)製「LC-2E21B/1C」)を使用し、マスク径1.60mm、フォーカスオフセット値0.050、パルス幅25μs、パワー0.66W、アパーチャー13、ショット数2、バーストモードの条件で穴あけして、金属層、分子接合層、絶縁層を貫通して配線層の一部分を露出させるビアホールを形成した。絶縁層の表面におけるビアホールのトップ径(直径)は50μmであった。
ビアホールが形成された構造体に対し、膨潤液である、アトテックジャパン(株)のジエチレングリコールモノブチルエーテル含有の「スウェリング・ディップ・セキュリガンスP」に60℃で5分間浸漬し、次に粗化液として、アトテックジャパン(株)の「コンセントレート・コンパクトP」(KMnO4:60g/L、NaOH:40g/Lの水溶液)に80℃で15分間浸漬し、水洗処理後、中和液として、アトテックジャパン(株)の「リダクションソリューション・セキュリガンスP」に40℃で5分間浸漬し、その後、130℃で15分間乾燥する、ビアホールのデスミア処理を行った。
デスミア処理後、後述する配線層の形成工程におけるフラッシュエッチング工程により除去される層の厚さを薄くし、より微細な配線を形成するために、金属層を塩化第2鉄水溶液に25℃で1分間浸漬して除去した。
金属層を除去したことにより露出した分子接合層に導体層を形成するため、第2の無電解めっき工程(アトテックジャパン(株)製薬液を使用した無電解銅めっき工程)を行った。形成された導体層の厚さは0.8μmであった。
<マスクパターンの形成工程>
次いで、構造体の表面を5%硫酸水溶液で30秒間処理し、厚さ25μmのマスクパターン形成用のPETフィルム付きドライフィルムであるニチゴー・モートン(株)製「ALPHO NIT3025」(商品名)を構造体の両面に真空ラミネーターにて積層した。積層は、バッチ式真空加圧ラミネーター((株)名機製作所製「MVLP-500」(商品名))を用いて、圧力を0.1MPaとし、温度を70℃とし、30秒間減圧して気圧を13hPa以下にしてから、20秒間加圧して行った。
次に、構造体を水洗して、現像工程を行った。現像工程を行った構造体にアトテックジャパン(株)製の薬液を使用して、ビアホールに銅が充填される条件で電解めっき工程(電解銅めっき工程)を行って、マスクパターンから露出している導体層に電解めっき層(電解銅めっき層)を形成し、併せてビアホールを埋め込んでフィルドビアを形成した。
次に、構造体に対して温度50℃の3%NaOH溶液を圧力0.2MPaで噴霧するスプレー処理を行って、構造体の両面からのマスクパターンの剥離を行った。次いで、(株)荏原電産製のSACプロセス(フラッシュエッチング工程)用エッチャントを用いて、マスクパターンを除去することにより露出した導体層のみを除去して、微細な複数の配線を含む配線層を形成した。
以上の工程により実施例2にかかる配線板が製造された。
スルーホールを形成した後にデスミア処理工程を兼ねる粗化処理工程を行い、その後分子接合層の形成工程を実施した以外は、実施例1と同様にして配線層を形成する工程までを行うことにより、比較例1にかかる配線板を製造した。
分子接合層を形成した後にビアホールを形成し、次いでデスミア処理工程を兼ねる粗化処理工程を行い、その後、金属層を形成することなく導体層を形成する工程を実施した以外は、実施例2と同様にして配線層を形成する工程までを行うことにより、比較例2にかかる配線板を製造した。
実施例1、実施例2、比較例1及び比較例2で製造された配線板それぞれについて、非接触型表面粗さ計(ビーコインスツルメンツ社製「WYKO NT3300」)を用いて、VSIコンタクトモード、50倍レンズにより測定範囲を121μm×92μmとして得られる測定値に基づいて算術平均粗さRa及び二乗平均平方根粗さRq(表面粗さ)を求めた。それぞれ無作為に選んだ10点の測定値の平均値を求めることによりこれを算術平均粗さRaの値又は二乗平均平方根粗さRqの値とした。結果を下記表2に示す。
実施例1、実施例2、比較例1及び比較例2で形成された配線層それぞれに、幅10mm、長さ100mmの長方形状の切込みをいれ、その一端を剥がしてつかみ具(株式会社ティー・エス・イー、オートコム型試験機「AC-50C-SL」)で掴み、室温にて、50mm/分の速度で垂直方向に35mmを引き剥がした時の荷重(kgf/cm)を測定して評価した。評価基準は下記の通りである。結果を下記表2に示す。
評価基準:
○:ピール強度が0.4kgf/cm超
×:ピール強度が0.4kgf/cm未満
実施例1、実施例2、比較例1及び比較例2で形成された配線それぞれについて、形成可能な櫛歯パターンの最小ピッチを視覚的に評価した。結果を下記表2に示す。
実施例1、実施例2、比較例1及び比較例2で形成された配線それぞれに剥離の有無を光学顕微鏡にて確認し、さらに除去されるべき導体層(及び金属層)の残滓の有無を確認して評価した。評価基準は下記の通りである。結果を下記表2に示す。
評価基準
○:櫛歯パターンのうちの線状部分10本中、9本以上で問題なし
×:櫛歯パターンのうちの線状部分10本中、2本以上で問題あり
20 絶縁層
20a 第1主表面
20b 第2主表面
22 硬化プリプレグ
24 回路基板
24a 電子回路
26 孔部(スルーホール、ビアホール)
30 分子接合層
40 配線層
42 金属層
44 導体層
44a、45a 第1領域
44b、45b 第2領域
44c 第3領域
45 電解めっき層
45c 埋込領域
46 第1配線層
48 第2配線層
50 スルーホール内配線、フィルドビア
60 構造体
100 マスクパターン
110 保護フィルム
Claims (7)
- 工程(A)第1主表面及び該第1主表面と対向する第2主表面を有している絶縁層と、前記第1主表面のみ又は該第1主表面及び前記第2主表面の両方に設けられている分子接合層とを備える構造体を用意する工程と、
工程(B)前記分子接合層に接合する金属層を形成する工程と、
工程(C)レーザー照射を行って、前記金属層、前記分子接合層及び前記絶縁層を貫通する孔部を形成する工程と、
工程(D)前記孔部に対してデスミア処理を行う工程と、
工程(E)導体層を形成する工程と、
工程(F)配線層を形成する工程と
を含む、配線板の製造方法。 - 前記工程(A)が、前記絶縁層が硬化プリプレグであり、前記分子接合層が前記絶縁層の前記第1主表面及び前記第2主表面の両方に設けられている構造体を用意する工程である、請求項1に記載の配線板の製造方法。
- 前記工程(A)が、前記絶縁層が回路基板に設けられ、前記分子接合層が該回路基板が接合されている前記第2主表面とは反対側の前記第1主表面のみに設けられている構造体を用意する工程である、請求項1に記載の配線板の製造方法。
- 前記工程(A)が、前記分子接合層に接合する保護フィルムをさらに備える構造体を用意する工程であり、
前記工程(B)が、前記保護フィルムを剥離して、前記分子接合層に接合する金属層を形成する工程である、請求項1~3のいずれか1項に記載の配線板の製造方法。 - 前記工程(A)が、前記分子接合層に接合する保護フィルムを設ける工程をさらに含み、
前記工程(B)が、前記構造体から前記保護フィルムを剥離して、前記分子接合層に接合する金属層を形成する工程である、請求項1~3のいずれか1項に記載の配線板の製造方法。 - 前記工程(D)の後であって前記工程(E)の前に、工程(G)前記金属層を除去する工程をさらに含み、
前記工程(E)が、露出した前記分子接合層及び前記孔部に、導体層を形成する工程である、請求項1~5のいずれか1項に記載の配線板の製造方法。 - 前記工程(B)が、無電解めっき工程により金属層を形成する工程である、請求項1~6のいずれか1項に記載の配線板の製造方法。
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JP2003234573A (ja) * | 2002-02-07 | 2003-08-22 | Fujitsu Ltd | 多層配線基板の製造方法およびこれにより製造される多層配線基板 |
JP2013004619A (ja) * | 2011-06-14 | 2013-01-07 | Daitech Inc | フレキシブル配線板及びその製造方法 |
WO2013143732A1 (en) * | 2012-03-29 | 2013-10-03 | Atotech Deutschland Gmbh | Method for manufacture of fine line circuitry |
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JP2003234573A (ja) * | 2002-02-07 | 2003-08-22 | Fujitsu Ltd | 多層配線基板の製造方法およびこれにより製造される多層配線基板 |
JP2013004619A (ja) * | 2011-06-14 | 2013-01-07 | Daitech Inc | フレキシブル配線板及びその製造方法 |
WO2013143732A1 (en) * | 2012-03-29 | 2013-10-03 | Atotech Deutschland Gmbh | Method for manufacture of fine line circuitry |
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CN111133847A (zh) * | 2017-09-29 | 2020-05-08 | 日东电工株式会社 | 布线电路基板、布线电路基板的制造方法以及拍摄装置 |
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