WO2014192895A1 - Copper foil, copper foil with carrier, copper-clad laminate, printed circuit board, circuit forming substrate for semiconductor package, semiconductor package, electronic device, resin substrate, circuit forming method, semiadditive method, and printed circuit board manufacturing method - Google Patents
Copper foil, copper foil with carrier, copper-clad laminate, printed circuit board, circuit forming substrate for semiconductor package, semiconductor package, electronic device, resin substrate, circuit forming method, semiadditive method, and printed circuit board manufacturing method Download PDFInfo
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- WO2014192895A1 WO2014192895A1 PCT/JP2014/064343 JP2014064343W WO2014192895A1 WO 2014192895 A1 WO2014192895 A1 WO 2014192895A1 JP 2014064343 W JP2014064343 W JP 2014064343W WO 2014192895 A1 WO2014192895 A1 WO 2014192895A1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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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
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
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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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
Definitions
- the present invention relates to a copper foil, a copper foil with a carrier, a copper clad laminate, a printed wiring board, a circuit forming substrate for a semiconductor package, a semiconductor package, an electronic device, a resin substrate, a circuit forming method, a semi-additive method, and a printed wiring board. It relates to the manufacturing method.
- Subtractive methods are the mainstream for circuit formation methods for printed circuit boards and semiconductor package substrates, but with the recent finer wiring, m-SAP (Modified Semi-Additive Process) and copper foil surface profiles were used. New methods such as the semi-additive method are emerging.
- the following can be cited as an example of the semi-additive method using the surface profile of the latter copper foil. That is, first, the entire surface of the copper foil laminated on the resin base material is etched, the etching base material surface to which the copper foil surface profile is transferred is drilled with a laser or the like, and an electroless copper plating layer for conducting the drilled portion is formed. The electroless copper plating surface is coated with a dry film, the dry film of the circuit forming part is removed by UV exposure and development, and the electroless copper plating surface not coated with the dry film is electroplated with copper.
- the surface profile of the transferred copper foil is small. However, if the profile is too small, the adhesion of the electroless copper plating film is weakened, which is required for a printed wiring board or a semiconductor package board. Reliability may be impaired. Therefore, the present invention uses a copper foil that provides good adhesion between the etched surface of the resin base material to which the copper foil surface profile has been transferred and the plating film when the entire surface is laminated and etched on the resin base material. It aims at providing the copper clad laminated body for semiconductor packages, a resin base material, and a semi-additive construction method.
- the present inventor can obtain a copper foil suitable for the present construction method by applying an appropriate rust prevention treatment to the base copper foil on which the roughened layer having an appropriate roughness is formed. I found.
- a copper foil comprising a copper foil bulk layer, a roughening treatment layer, and a rust prevention treatment layer containing chromium in this order
- the copper foil is laminated on the resin base material from the side having the roughening treatment layer and the copper foil is etched on the entire surface using an etching solution, the etched surface of the resin base material after the entire surface etching is performed.
- the weight concentrations (wt%) of Cr, Zn, C, O, and Si in surface analysis by XPS are A, B, C, D, and E, respectively
- the present invention is a copper foil comprising a copper foil bulk layer, a roughening treatment layer, a rust prevention treatment layer containing chromium, and a resin layer in this order,
- a copper foil comprising a copper foil bulk layer, a roughening treatment layer, a rust prevention treatment layer containing chromium, and a resin layer in this order,
- the weight concentrations (wt%) of Cr, Zn, C, O, and Si when the surface of the etched surface of the resin layer on the resin base material was analyzed by XPS were A, B, C, D, and E, respectively.
- a copper foil comprising a copper foil bulk layer, a rust-preventing treatment layer containing chromium, and a resin layer in this order
- the entire surface of the copper foil from the copper foil bulk layer to the anticorrosive treatment layer is etched using an etching solution, the entire surface is etched.
- the weight concentrations (wt%) of Cr, Zn, C, O, and Si when the surface of the etched surface of the resin layer on the resin base material was analyzed by XPS were A, B, C, D, and E, respectively.
- the resin layer is an adhesive resin.
- the resin layer is a primer.
- the resin layer is a semi-cured resin.
- the resin layer is a block copolymerized polyimide resin layer or a resin layer containing a block copolymerized polyimide resin and a polymaleimide compound.
- the roughening treatment layer formed between the copper foil bulk layer and the antirust treatment layer is composed of spherical particles or fine particles, and has a surface roughness Rz. Is 0.3 to 4.0 ⁇ m.
- a barrier layer is formed between the roughening treatment layer and the rust prevention treatment layer.
- a barrier layer is formed between the copper foil bulk layer and the antirust treatment layer.
- the barrier layer is composed of a brass plating layer or a zinc / nickel alloy plating layer.
- a silane coupling agent layer is provided on the surface of the resin base material laminated side.
- a silane coupling agent layer is provided between the antirust treatment layer and the resin layer.
- the thickness of the copper foil bulk layer is 12 ⁇ m or less.
- the etching solution is a sulfuric acid-hydrogen peroxide solution, a cupric chloride solution, a ferric chloride solution, or a persulfate solution.
- the copper foil of the present invention is used in a semi-additive construction method.
- FIG. 1 Another aspect of the present invention is a copper foil with a carrier in which the copper foil of the present invention is provided on one or both surfaces of the carrier via an intermediate layer from the copper foil bulk layer side.
- the copper foil of the present invention is provided on one surface of the carrier via an intermediate layer from the copper foil bulk layer side, and the other surface of the carrier is roughened. It is a copper foil with a carrier provided with a treatment layer.
- the present invention is a copper clad laminate using the copper foil of the present invention.
- the present invention is a copper clad laminate for a semiconductor package using the copper foil of the present invention.
- the present invention is a printed wiring board using the copper foil of the present invention.
- the weight concentrations (wt%) of Cr, Zn, C, O, and Si when the surface of the substrate surface is analyzed by XPS are A, B, C, D, and E, respectively.
- the resin base material of the present invention has a surface roughness Rz of 0.3 to 4.0 ⁇ m.
- the resin base material of the present invention is used in a semi-additive construction method in another embodiment.
- the present invention provides a circuit forming method including a step of forming a circuit by a semi-additive method using the copper foil of the present invention.
- the present invention is a semi-additive method for forming a circuit using the copper-clad laminate of the present invention.
- the present invention is a semi-additive method for forming a circuit using the resin base material of the present invention.
- FIG. 1 Another aspect of the present invention is a circuit forming substrate for a semiconductor package in which a circuit having a line / space of 30/30 ⁇ m or less is formed on the surface of the resin base material of the present invention by a semi-additive method.
- the present invention is a semiconductor package provided with the circuit forming substrate for a semiconductor package of the present invention.
- FIG. 1 Another aspect of the present invention is a printed wiring board manufacturing method including a step of forming a circuit by a semi-additive method using the copper foil of the present invention.
- the present invention is a printed wiring board using the resin base material of the present invention.
- the present invention is an electronic device using the printed wiring board of the present invention.
- a step of forming a circuit on the ultrathin copper layer side surface of the copper foil with a carrier of the present invention Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried; Forming a circuit on the resin layer; Forming the circuit on the resin layer, and then peeling the carrier; and After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Is the method.
- the present invention it is possible to provide a copper foil that provides good adhesion between the etched surface of the resin base material to which the copper foil surface profile has been transferred and the plating film when laminated on the resin base material and etched entirely. it can.
- a schematic example of a semi-additive construction method using a copper foil profile is shown.
- the sample preparation flow for obtaining the data of an Example and a comparative example is shown.
- the SEM photograph of the copper foil surface of Example 1 is shown.
- the SEM photograph of the copper foil surface of Example 2 is shown.
- the SEM photograph of the copper foil surface of Example 3 is shown.
- the SEM photograph of the copper foil surface of Example 4 is shown.
- the SEM photograph of the copper foil surface of Example 5 is shown.
- the SEM photograph of the copper foil surface of Example 6 is shown.
- the SEM photograph of the copper foil surface of the comparative example 2 is shown.
- the SEM photograph of the copper foil surface of the comparative example 6 is shown.
- the SEM photograph of the copper foil surface of the comparative example 9 is shown.
- the copper foil used in the present invention includes a copper foil bulk layer, a roughening treatment layer formed on the copper foil bulk layer, and a rust prevention treatment layer containing chromium formed on the roughening treatment layer. ing. In addition, you may provide another layer between a copper foil bulk layer and a roughening process layer. Moreover, you may provide another layer between a roughening process layer and the antirust process layer containing chromium.
- the copper foil bulk layer may be formed of either electrolytic copper foil or rolled copper foil.
- the “copper foil bulk layer” refers to a copper foil body (raw copper foil) portion excluding a surface treatment layer such as a roughening treatment layer, a barrier layer, a rust prevention layer, and a silane coupling layer. Further, from the viewpoint of reducing the amount of copper foil etching in the printed wiring board or semiconductor package substrate manufacturing process, an ultrathin copper foil (including an ultrathin copper foil with a carrier) having a copper thickness of 12 ⁇ m or less may be used. .
- the roughening treatment layer can be formed by using an electrolytic bath made of sulfuric acid / copper sulfate containing at least one substance selected from alkyl sulfate salts, tungsten ions, and arsenic ions, and appropriately adjusting the electrolytic treatment conditions.
- the roughening layer is preferably composed of spherical particles or fine particles, and the surface roughness Rz is preferably 0.3 to 4.0 ⁇ m.
- the surface roughness Rz is less than 0.3 ⁇ m, the fine wiring forming ability works advantageously, but the adhesion between the electroless plated copper and the base material is lowered, and the reliability required for the printed wiring board or the semiconductor package board There is a risk of damage.
- the surface roughness Rz is more than 4.0 ⁇ m, the anchor effect on the substrate side to which the copper foil profile is transferred improves the adhesion between the electroless copper plating and the substrate, but the above flash in the semi-additive method is used. In the etching process, there is a possibility that a problem that the ability to form fine wiring deteriorates occurs.
- the surface roughness Rz is preferably 0.3 to 3.0 ⁇ m, more preferably 0.5 to 2.0 ⁇ m.
- the roughening treatment can be performed by appropriately adjusting a known method. As an example, conditions for the roughening treatment are shown below.
- the rust prevention treatment layer can be formed by subjecting the copper foil roughening treatment layer to chromate treatment under predetermined conditions.
- chromate treatment containing high-concentration chromium is applied to the vicinity of the outermost layer of the anticorrosive film on the adhesion side surface (M surface) of the copper foil with the resin base material, even after the entire surface of the copper foil is etched, a small amount of chromium is etched. It remains on the surface of the material and improves the adhesion of the electroless copper plating film.
- a rust preventive film is formed by a chromate bath of pure chromium or a chromate bath whose Zn concentration is lowered to 0.1 g / L or less.
- the rust prevention treatment conditions for leaving Cr in the electrolytic chromate, after the chromate treatment, the entire surface of the roughened surface is showered by using the same chromate bath as the electrolytic chromate using the liquid shower piping. As a result, the chromate layer on the surface of the rust preventive layer is made denser, and Cr remains on the etching base surface.
- a barrier layer may be formed between the roughening treatment layer and the rust prevention treatment layer.
- the barrier layer can be composed of a brass plating layer or a zinc / nickel alloy plating layer.
- coating a silane coupling agent on the antirust process layer may be provided. A well-known thing can be used for a silane coupling agent, and it is not specifically limited.
- a copper-clad laminate can be formed by laminating the copper foil of the present invention on the resin base material from the roughening treatment side by a press method or a laminating method.
- the copper foil of the copper clad laminate is removed by etching the entire surface using an etching solution such as a sulfuric acid-hydrogen peroxide solution, a cupric chloride solution, a ferric chloride solution, or a persulfate solution.
- the unevenness of the roughened surface of the copper foil is transferred to the surface of the resin base material from which the copper foil has been removed.
- the unevenness on the surface of the resin substrate is controlled by the surface roughness Rz of the copper foil of the present invention described above, and affects the adhesion (peel strength) between the resin substrate and the copper plating formed on the substrate. give.
- Cr remains on the surface of the resin base material (full-surface etching base material) after the copper foil has been removed by full-surface etching, such as when a rust-proofing layer by chromate treatment is formed on the copper foil.
- the Cr content ratio is 0.1 to 10% with respect to the total weight concentration (wt%) of Cr, Zn, C, O, and Si when the surface analysis is performed by XPS, the resin base material (entire surface etching) Good adhesion (peel strength) between the base material and the copper plating formed on the base material is obtained.
- the Cr content ratio (%) is an extremely high value, there is a possibility that many etching residues of the copper foil are present on the surface of the resin base material. Therefore, when the Cr content ratio (%) is an extremely high value, the migration resistance may be deteriorated. Therefore, the Cr content ratio (%) is preferably 0.5 to 5.0%, more preferably 1.0 to 3.0%.
- the region of the resin base material (entire etching base material) analyzed by the XPS surface analysis is a region from the resin base material surface to a depth of about 10 nm.
- “entire etching” means that etching is performed until the copper foil is completely removed by the thickness and the resin is exposed on the entire surface.
- FIG. 1 shows a schematic example of a semi-additive construction method using a copper foil profile.
- a surface profile of copper foil is used. Specifically, first, the copper foil of the present invention is laminated on a resin base material to produce a copper clad laminate. Next, the entire surface of the copper foil of the copper clad laminate is etched. Next, electroless copper plating is applied to the surface of the resin substrate (entire etching substrate) to which the copper foil surface profile has been transferred.
- the semi-additive method refers to a method in which a thin electroless plating is performed on an insulating substrate or a copper foil seed layer, a pattern is formed, and then a conductive pattern is formed using electroplating and etching.
- a step of preparing the copper foil and the insulating substrate according to the present invention Laminating the copper foil and the insulating substrate; After laminating the copper foil and the insulating substrate, if the copper foil has a carrier, the step of peeling the carrier, A step of removing all of the copper foil (if the copper foil has a carrier, the copper foil exposed by peeling off the carrier) by a method such as etching or plasma using a corrosive solution such as an acid, Providing a through hole or / and a blind via in the resin exposed by removing the copper foil by etching; Performing a desmear process on the region including the through hole or / and the blind via, Providing an electroless plating layer for the region including the resin and the through hole or / and the blind via; Providing a plating resist on the electroless plating layer; Exposing the plating resist, and then
- a step of preparing a copper foil and an insulating substrate according to the present invention Laminating the copper foil and the insulating substrate; After laminating the copper foil and the insulating substrate, if the copper foil has a carrier, the step of peeling the carrier, A step of removing all of the copper foil (if the copper foil has a carrier, the copper foil exposed by peeling the carrier) by a method such as etching or plasma using a corrosive solution such as an acid, Providing an electroless plating layer on the surface of the resin exposed by removing the copper foil by etching; Providing a plating resist on the electroless plating layer; Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed; Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed; Removing the plating resist; Removing the plating resist; Removing
- the line / space is 30/30 ⁇ m or less, preferably 20/20 ⁇ m or less on the etching surface of the whole surface etching base material (resin base material) after removing the copper foil of the copper clad laminate by whole surface etching.
- a circuit formation substrate for a semiconductor package can be manufactured by forming a fine circuit. Further, a semiconductor package can be manufactured using the circuit formation substrate.
- the copper foil and resin substrate of the present invention are suitable for a method for producing a printed wiring board including a step of forming a circuit by a semi-additive construction method.
- the copper foil of this invention can also be used for the manufacturing method of a printed wiring board including the process of forming a circuit by a subtractive construction method, a partly additive construction method, or a modified semiadditive construction method.
- the subtractive method, the partly additive method or the modified semi-additive method is not particularly limited, and a known method can be used.
- the subtractive method refers to a method of forming a conductor pattern by selectively removing unnecessary portions of a copper foil on a copper clad laminate by etching or the like.
- the partial additive method means that a catalyst circuit is formed on a substrate provided with a conductor layer, and if necessary, a substrate provided with holes for through holes or via holes, and etched to form a conductor circuit. Then, after providing a solder resist or a plating resist as necessary, it refers to a method of manufacturing a printed wiring board by thickening through holes, via holes, etc. on the conductor circuit by electroless plating.
- the modified semi-additive method is a method in which a metal foil is laminated on an insulating layer, a non-circuit forming portion is protected by a plating resist, and the copper is thickened in the circuit forming portion by electrolytic plating, and then the resist is removed. Then, a method of forming a circuit on the insulating layer by removing the metal foil other than the circuit forming portion by (flash) etching is indicated.
- the copper foil with a carrier of the present invention is constituted by providing the copper foil for a semi-additive method of the present invention from the copper foil bulk layer side via an intermediate layer on one surface or both surfaces of a carrier.
- the copper foil for the semi-additive method of the present invention includes an ultrathin copper layer as a copper foil bulk layer, a roughening treatment layer formed on the ultrathin copper layer (copper foil bulk layer), and a roughening And an anti-rust treatment layer containing chromium formed on the treatment layer, and an intermediate layer and a carrier are formed in this order on the surface of the ultrathin copper layer (copper foil bulk layer) opposite to the roughening treatment layer.
- the intermediate layer, the ultrathin copper layer (copper foil bulk layer), the roughened layer, and the rust preventive layer containing chromium are arranged in this order on the surface of the carrier opposite to the copper foil bulk layer. May be provided. Moreover, you may provide a roughening process layer in the opposite side surface of the said copper foil bulk layer of the said carrier.
- the roughening treatment layer may be provided using a known method, or may be provided by the above-described roughening treatment.
- Providing a roughened layer on the surface opposite to the copper foil bulk layer of the carrier means that the carrier and the resin substrate are peeled off when the carrier is laminated on a support such as a resin substrate from the surface side having the roughened layer. It has the advantage that it becomes difficult.
- the carrier is typically a metal foil or a resin film, such as a copper foil, a copper alloy foil, a nickel foil, a nickel alloy foil, an iron foil, an iron alloy foil, a stainless steel foil, an aluminum foil, an aluminum alloy foil, or an insulating resin film. , Polyimide films, LCP (liquid crystal polymer) films, and fluororesin films.
- Carriers that can be used in the present invention are typically provided in the form of rolled copper foil or electrolytic copper foil.
- the electrolytic copper foil is produced by electrolytic deposition of copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll.
- copper foil materials include high-purity copper such as tough pitch copper (JIS H3100 alloy number C1100) and oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), for example, Sn-containing copper, Ag-containing copper, Cr A copper alloy such as a copper alloy added with Zr or Mg, or a Corson copper alloy added with Ni, Si or the like can also be used.
- high-purity copper such as tough pitch copper (JIS H3100 alloy number C1100) and oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011)
- Sn-containing copper Ag-containing copper
- Cr A copper alloy such as a copper alloy added with Zr or Mg, or a Corson copper alloy added with Ni, Si or the like can also be used.
- the thickness of the carrier is not particularly limited, but may be appropriately adjusted to a thickness suitable for serving as a carrier, for example, 5 ⁇ m or more. However, if it is too thick, the production cost becomes high, so generally it is preferably 35 ⁇ m or less. Accordingly, the thickness of the carrier is typically 8 to 70 ⁇ m, more typically 12 to 70 ⁇ m, and more typically 18 to 35 ⁇ m. Moreover, it is preferable that the thickness of a carrier is small from a viewpoint of reducing raw material cost.
- the thickness of the carrier is typically 5 ⁇ m or more and 35 ⁇ m or less, preferably 5 ⁇ m or more and 18 ⁇ m or less, preferably 5 ⁇ m or more and 12 ⁇ m or less, preferably 5 ⁇ m or more and 11 ⁇ m or less, preferably 5 ⁇ m or more and 10 ⁇ m or less. It is as follows.
- the thickness of a carrier is small, it is easy to generate
- the intermediate layer has a copper foil with a carrier that is hardly peeled off from the carrier before the lamination process on the insulating substrate, while the ultra-thin copper layer can be peeled off from the carrier after the lamination process on the insulating substrate. If it is the structure which becomes, it will not specifically limit.
- the intermediate layer of the copper foil with a carrier of the present invention is Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, oxides thereof, One or two or more selected from the group consisting of organic substances may be included.
- the intermediate layer may be a plurality of layers.
- the intermediate layer is a single metal layer composed of one kind of element selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side.
- an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, From one or two or more elements hydrates or oxides or organic substances selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn
- a rust prevention layer such as a Ni plating layer on the opposite surface of the carrier on which the intermediate layer is formed.
- the intermediate layer is provided by chromate treatment, zinc chromate treatment, or plating treatment, it is considered that some of the attached metal such as chromium and zinc may be hydrates or oxides.
- strike plating with a copper-phosphorus alloy may be performed in order to reduce pinholes in the ultrathin copper layer.
- the strike plating include a copper pyrophosphate plating solution.
- the ultra-thin copper layer (copper foil bulk layer) can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc.
- a copper sulfate bath is preferable because copper foil can be formed at a high current density.
- the thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 ⁇ m or less. It is typically 0.5-12 ⁇ m, more typically 1-5 ⁇ m, more typically 2-5 ⁇ m.
- the copper foil of this invention contains the chromium formed on the said copper foil bulk layer, the said roughening process layer formed on the said copper foil bulk layer, and the said roughening process layer in another one side surface.
- the etched surface of the resin layer on the resin base material after the entire surface etching is subjected to surface analysis by XPS, Cr, Zn, C
- the weight concentration (wt%) of O, O, and Si is A, B, C, D, and E, respectively
- a silane coupling agent layer may be provided between the rust prevention treatment layer and the resin layer.
- the Cr content ratio (%) is preferably 0.5 to 5.0%, more preferably 1.0 to 3.0%.
- the region of the resin base material (entire etching base material) analyzed by the XPS surface analysis is a region from the resin base material surface to a depth of about 10 nm.
- “entire etching” means that etching is performed until the entire thickness from the copper foil bulk layer to the rust-proofing layer of the copper foil is removed and the resin is exposed on the entire surface.
- the copper foil of the present invention is the copper foil bulk layer, the rust prevention treatment layer containing chromium formed on the copper foil bulk layer, and the rust prevention treatment layer.
- the weight concentration (wt%) of Cr, Zn, C, O, and Si when the surface analysis is performed by XPS on the etched surface of the resin layer on the resin substrate after the entire surface etching is A, respectively.
- a barrier layer may be provided between the copper foil bulk layer and the antirust treatment layer.
- a silane coupling agent layer may be provided between the rust prevention treatment layer and the resin layer.
- the Cr content is 0.1 to 10% with respect to the total weight concentration (wt%) of Cr, Zn, C, O, and Si when the surface analysis is performed by XPS, Good adhesion (peel strength) with the copper plating formed on the material is obtained.
- the Cr content ratio (%) is preferably 0.5 to 5.0%, more preferably 1.0 to 3.0%.
- the region of the resin base material (entire etching base material) analyzed by the XPS surface analysis is a region from the resin base material surface to a depth of about 10 nm.
- the resin layer may be an adhesive or an insulating resin layer in a semi-cured state (B stage state) for bonding.
- the semi-cured state (B stage state) is a state in which there is no sticky feeling even if the surface is touched with a finger, the insulating resin layer can be stacked and stored, and a curing reaction occurs when subjected to heat treatment. Including that.
- the resin layer may be a primer.
- the “primer” refers to a resin layer that can bond the electroless copper plating layer and the resin base material particularly firmly.
- a known primer can be used as the primer.
- the resin layer may contain a thermosetting resin or may be a thermoplastic resin.
- the resin layer may include a thermoplastic resin.
- the type is not particularly limited, for example, a resin including an epoxy resin, a polyimide resin, a polyfunctional cyanate ester compound, a maleimide compound, a polyvinyl acetal resin, a urethane resin, or the like can be given as a preferable one.
- the resin layer may be a block copolymerized polyimide resin layer or a resin layer containing a block copolymerized polyimide resin and a polymaleimide compound.
- the resin layer may be made of any known dielectric such as a known resin, resin curing agent, compound, curing accelerator, dielectric (dielectric including an inorganic compound and / or organic compound, dielectric including a metal oxide). May be included), a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like.
- the resin layer may be, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent 3184485, International Publication. No. WO 97/02728, Japanese Patent No.
- WO 2008/114858 International Publication Number WO 2009/008471, JP 2011-14727, International Publication Number WO 2009/001850, International Publication Number WO 2009/145179, International Publication Number Nos. WO2011 / 068157 and JP2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeletal materials, etc.) and / or You may form using the formation method and formation apparatus of a resin layer.
- a solvent such as methyl ethyl ketone (MEK) or toluene to obtain a resin liquid, which is applied to the ultrathin copper layer, the heat-resistant layer, the rust-preventing layer, the chromate-treated layer, or the silane cup.
- MEK methyl ethyl ketone
- On the ring agent layer for example, it is applied by a roll coater method or the like, and then heat-dried as necessary to remove the solvent to obtain a B stage state.
- a hot air drying furnace may be used for drying, and the drying temperature may be 100 to 250 ° C., preferably 130 to 200 ° C.
- the copper foil (resin-coated copper foil) provided with the resin layer, after superposing the resin layer on a base material, thermocompressing the entire resin layer to thermally cure the resin layer, and then etching the entire copper foil, It is used in the form of forming a circuit on the resin. Moreover, you may use in the aspect of forming a predetermined wiring pattern, without etching a copper foil whole surface.
- the copper-clad laminate can be manufactured even if the resin layer is made thick enough to ensure interlayer insulation or no prepreg material is used. At this time, the surface smoothness can be further improved by undercoating the surface of the substrate with an insulating resin.
- the material cost of the prepreg material is saved and the laminating process is simplified, which is economically advantageous.
- the multilayer printed wiring board manufactured by the thickness of the prepreg material is used. The thickness is reduced, and there is an advantage that an extremely thin multilayer printed wiring board in which the thickness of one layer is 100 ⁇ m or less can be manufactured.
- the thickness of this resin layer is preferably 0.1 to 80 ⁇ m.
- the thickness of the resin layer is less than 0.1 ⁇ m, the adhesive strength is reduced, and when the resin-coated copper foil is laminated on the base material provided with the inner layer material without interposing the prepreg material, It may be difficult to ensure interlayer insulation therebetween.
- the thickness of the resin layer is made thicker than 80 ⁇ m, it becomes difficult to form a resin layer having a desired thickness in a single coating process, which is economically disadvantageous because of extra material costs and man-hours. Furthermore, since the formed resin layer is inferior in flexibility, cracks are likely to occur during handling, and excessive resin flow occurs during thermocompression bonding with the inner layer material, making smooth lamination difficult. There is.
- the copper foil bulk layer of the copper foil has a carrier, and the rust preventive treatment layer is coated with the resin layer, and after being in a semi-cured state, Then, the carrier can be peeled off to produce a resin-coated copper foil bulk layer in which no carrier is present.
- Step 1 First, a copper foil with a carrier (first layer) having an ultrathin copper layer with a roughened layer formed on the surface is prepared.
- Step 2 Next, a resist is applied on the roughened layer of the ultrathin copper layer, exposed and developed, and the resist is etched into a predetermined shape.
- Step 3 Next, after circuit plating is formed, the resist is removed to form circuit plating having a predetermined shape.
- Step 4 Next, an embedding resin is provided on the ultrathin copper layer so as to cover the circuit plating (so that the circuit plating is buried), and then a resin layer is laminated, followed by another copper foil with a carrier (second layer) ) Is bonded from the ultrathin copper layer side.
- Process 5 Next, a carrier is peeled off from the copper foil with a carrier of the 2nd layer. Note that a copper foil having no carrier may be used for the second layer.
- Step 6 Next, laser drilling is performed at predetermined positions of the second ultrathin copper layer or copper foil and resin layer to expose the circuit plating and form blind vias.
- Step 7 Next, copper is embedded in the blind via to form a via fill.
- Step 8 Next, circuit plating is formed on the via fill as in steps 2 and 3 above.
- Process 9 Next, a carrier is peeled off from the copper foil with a carrier of the 1st layer.
- Step 10 Next, ultra-thin copper layers (copper foil when a copper foil is provided as the second layer) on both surfaces are removed by flash etching, and the surface of the circuit plating in the resin layer is exposed.
- Step 11 Next, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder.
- the printed wiring board using the copper foil with a carrier of this invention is produced.
- the other carrier-attached copper foil may be the carrier-attached copper foil of the present invention, a conventional carrier-attached copper foil, or a normal copper foil.
- one or more circuits may be formed on the second-layer circuit in Step 8, and the circuit formation may be performed by any of the semi-additive method, subtractive method, partly additive method, or modified semi-additive method. It may be performed by any method.
- the circuit plating is embedded in the resin layer, for example, when the ultrathin copper layer is removed by flash etching as in Step 10, the circuit is formed.
- the plating is protected by the resin layer, and its shape is maintained, thereby facilitating the formation of a fine circuit.
- the circuit plating is protected by the resin layer, the migration resistance is improved, and the continuity of the circuit wiring is satisfactorily suppressed. For this reason, formation of a fine circuit becomes easy.
- the ultrathin copper layer is removed by flash etching as shown in Step 10 and Step 11
- the exposed surface of the circuit plating has a shape recessed from the resin layer, so that bumps are further formed on the circuit plating.
- the production efficiency is improved.
- a known resin or prepreg can be used as the embedding resin (resin).
- a prepreg that is a glass cloth impregnated with BT (bismaleimide triazine) resin or BT resin, an ABF film or ABF manufactured by Ajinomoto Fine Techno Co., Ltd. can be used.
- the resin layer and / or resin and / or prepreg as described in this specification can be used for the embedding resin (resin).
- the carrier-attached copper foil used in the first layer may have a substrate or a resin layer on the surface of the carrier-attached copper foil.
- substrate or resin layer By having the said board
- any substrate or resin layer can be used as long as it has an effect of supporting the copper foil with carrier used in the first layer.
- a printed circuit board is completed by mounting electronic components on the printed wiring board.
- the “printed wiring board” includes a printed wiring board, a printed circuit board, and a printed board on which electronic parts are mounted as described above.
- an electronic device may be manufactured using the printed wiring board, an electronic device may be manufactured using a printed circuit board on which the electronic components are mounted, and a printed circuit on which the electronic components are mounted.
- An electronic device may be manufactured using a substrate.
- FIG. 2 shows a sample production flow for obtaining data of the example and the comparative example.
- Double-sided flat electrolytic green foil Electrolytic copper sulfate electrolyte with copper concentration of 80-120 g / L, sulfuric acid concentration of 80-120 g / L, chloride ion concentration of 30-100 ppm, glue concentration of 1-5 ppm, and electrolyte temperature of 57-62 ° C
- the electrolytic solution flowing between the anode and cathode has a linear velocity of 1.5 to 2.5 m / sec, a current density of 70 A / dm 2 and a thickness of 12 ⁇ m (weight thickness).
- 95 g / m 2 general electrolytic green foil was prepared.
- a double-sided flat electrolytic raw foil having a thickness of 18 ⁇ m was produced under the above-mentioned double-sided flat electrolytic raw foil manufacturing conditions.
- a peeling layer and an ultrathin copper layer were formed by the following method to obtain an ultrathin copper foil with a carrier having a thickness of 3 ⁇ m.
- Ni layer peeling layer: base plating 1
- An Ni layer having an adhesion amount of 1000 ⁇ g / dm 2 was formed on the S surface of the copper foil carrier by electroplating with a roll-to-roll type continuous plating line under the following conditions. Specific plating conditions are described below.
- Nickel sulfate 270 to 280 g / L Nickel chloride: 35 to 45 g / L Nickel acetate: 10-20g / L Boric acid: 30-40g / L Brightener: Saccharin, butynediol, etc.
- Sodium dodecyl sulfate 55-75 ppm pH: 4-6
- Bath temperature 55-65 ° C
- Current density 10 A / dm 2
- Cr layer peeleling layer: base plating 2
- a Cr layer having an adhesion amount of 11 ⁇ g / dm 2 is continuously formed on the Ni layer on a roll-to-roll-type continuous plating line.
- Rolled copper foil Tough pitch copper (JIS H3100 C1100R) manufactured by JX Nippon Mining & Metals Co., Ltd. and a thickness of 12 ⁇ m were prepared.
- each surface treatment of roughening treatment, barrier treatment, rust prevention treatment, and silane coupling agent coating is applied to the M surface (the rolled copper foil is not defined) which is the surface of the raw foil bonded to the resin substrate. Were applied in this order.
- Each processing condition is shown below.
- Co-Ni plating was performed on the M surface of the double-sided flat copper foil subjected to the roughening treatment under the above conditions and the surface of the ultrathin copper foil with carrier.
- the covering plating conditions are described below.
- the barrier treatment was performed under the following conditions to form a brass plating layer or a zinc / nickel alloy plating layer.
- Barrier layer (brass plating) formation conditions of Example 23 Current density using brass plating bath with copper concentration 50-80g / L, zinc concentration 2-10g / L, sodium hydroxide concentration 50-80g / L, sodium cyanide concentration 5-30g / L, temperature 60-90 ° C A plating electric quantity of 30 As / dm 2 was applied to the M surface on which the roughening treatment layer was formed at 5 to 10 A / dm 2 (multistage treatment).
- Barrier layer (zinc / nickel plating) formation conditions of Example 24 Ni: 10 g / L to 30 g / L, Zn: 1 g / L to 15 g / L, sulfuric acid (H 2 SO 4 ): 1 g / L to 12 g / L, chloride ion: 0 g / L to 5 g / L
- a plating electric quantity of 5.5 As / dm 2 was applied to the M surface on which the roughening treatment layer was formed at a current density of 1.3 A / dm 2 .
- Rust prevention treatment (chromate treatment) was performed under the following conditions to form a rust prevention treatment layer.
- Chromate condition 1 CrO 3 : 2.5 g / L, Zn: 0.4 g / L, Na 2 SO 4 : 10 g / L, pH 4.8, electric quantity of 0.7 As / dm 2 in chromate bath at 54 ° C Added.
- the entire roughened surface was showered using the same chromate bath using a liquid shower pipe.
- silane coupling agent application For Example 25, a silane coupling agent coating treatment was performed by spraying a solution having a pH of 7 to 8 containing 0.2 to 2% by weight of alkoxysilane onto the roughened surface of the copper foil.
- a resin layer was further formed under the following conditions after the antirust treatment.
- Resin synthesis example To a 2-liter three-necked flask equipped with a stainless steel vertical stirring bar, a trap equipped with a nitrogen inlet tube and a stopcock, and a reflux condenser equipped with a ball cooling tube, 3,4, 3 ', 117.68 g (400 mmol) of 4′-biphenyltetracarboxylic dianhydride, 87.7 g (300 mmol) of 1,3-bis (3-aminophenoxy) benzene, 4.0 g (40 mmol) of ⁇ -valerolactone, 4.
- NMP N-methyl-2-pyrrolidone
- toluene 20 g were added, heated at 180 ° C. for 1 hour, cooled to near room temperature, then 3, 4, 3 ′, 4′- Add 29.42 g (100 mmol) of biphenyltetracarboxylic dianhydride, 82.12 g (200 mmol) of 2,2-bis ⁇ 4- (4-aminophenoxy) phenyl ⁇ propane, 200 g of NMP, and 40 g of toluene.
- NMP N-methyl-2-pyrrolidone
- the block copolymerized polyimide solution obtained in the synthesis example was further diluted with NMP to obtain a block copolymerized polyimide solution having a solid content of 10%.
- bis (4-maleimidophenyl) methane BMI-H, Silica Chemical
- a resin solution was prepared by dissolving and mixing at 60 ° C. for 20 minutes.
- the resin solution was applied to the M surface (high gloss surface) of the copper foil in Examples 28 and 30, and the ultrathin copper surface of the copper foil in Examples 29 and 31 using a reverse roll coating machine.
- heat treatment was performed at 300 ° C. for 2 minutes to produce a copper foil provided with a resin layer.
- the thickness of the resin layer was 2 ⁇ m in Examples 28 and 30, and 1.3 ⁇ m in Examples 29 and 31.
- each copper foil of the Example produced as mentioned above and a comparative example the following resin base material of a 20 cm square size is prepared, and the surface which has a roughening process layer of a copper foil with a resin base material and copper foil was laminated and pressed in contact with the resin substrate.
- the recommended conditions of each substrate manufacturer were used for the temperature, pressure, and time of the lamination press.
- Resin (1) Mitsubishi Gas Chemical Company, Inc. GHPL-830MBT
- Resin (2) 679-FG manufactured by Hitachi Chemical Co., Ltd.
- Resin (3) EI-6785TS-F manufactured by Sumitomo Bakelite Co., Ltd.
- Etching condition 1 Etching solution: sulfuric acid-hydrogen peroxide solution, H 2 O 2 concentration: 2.5%, H 2 SO 4 concentration: 4.0%, liquid temperature: 30 ° C.
- Etching solution Cupric chloride solution, HCl concentration: 3.5 mol / L, Temperature: 50 ° C., CuCl 2 concentration adjusted so as to have a specific gravity of 1.26 (Etching condition 3)
- Etching solution Chloride chloride FeCl 3 concentration adjustment so that the ferric solution, HCl concentration: 3.5 mol / L, temperature: 25 ° C., specific gravity 1.28 (etching condition 4)
- Etching solution sodium persulfate solution, Na 2 S 2 O 8 concentration : 36 g / L, HgCl 2 concentration: 15 ppm, H 3 PO 4 concentration: 15 mL / L
- a catalyst for depositing electroless copper on the etching surface of the resin base material (entire etching base material) (the etching surface of the resin layer for Examples 28 to 31), and KAP- manufactured by Kanto Kasei Electroless copper plating was carried out under the following conditions using 8 baths.
- the thickness of the obtained electroless copper plating was 0.5 ⁇ m.
- the copper thickness (total thickness of electroless plating and electrolytic plating) was 12 ⁇ m.
- Simple copper sulfate electrolyte Cu concentration: 100 g / L, H 2 SO 4 concentration: 80 g / L
- Comparative Examples 8 to 11 and 15 the formation conditions of the rust-proofing layer containing chromium were inappropriate, the Cr content ratio (%) could not be detected, and the peel strength was poor.
- 3 to 8 show Examples 1 to 6, and FIGS. 9 to 11 show SEM photographs of treated copper foil surfaces of Comparative Example 2, Comparative Example 6, and Comparative Example 9, respectively.
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Abstract
Description
そこで、本発明は、樹脂基材に積層して全面エッチングしたときに、銅箔表面プロファイルが転写した樹脂基材のエッチング面とメッキ皮膜との密着力が良好となる銅箔、それを用いた半導体パッケージ用銅張積層体、樹脂基材及びセミアディティブ工法を提供することを目的とする。 For the formation of fine wiring, it is preferable that the surface profile of the transferred copper foil is small. However, if the profile is too small, the adhesion of the electroless copper plating film is weakened, which is required for a printed wiring board or a semiconductor package board. Reliability may be impaired.
Therefore, the present invention uses a copper foil that provides good adhesion between the etched surface of the resin base material to which the copper foil surface profile has been transferred and the plating film when the entire surface is laminated and etched on the resin base material. It aims at providing the copper clad laminated body for semiconductor packages, a resin base material, and a semi-additive construction method.
樹脂基材上に前記銅箔を前記粗化処理層を有する面側から積層し、エッチング液を用いて前記銅箔を全面エッチングした場合に、前記全面エッチング後の前記樹脂基材のエッチング面をXPSにより表面分析した際のCr、Zn、C、O、Siの重量濃度(wt%)をそれぞれA、B、C、D、Eとしたとき、Cr含有比率(%)[=A/(A+B+C+D+E)×100]が0.1~10%である銅箔である。 The present invention completed on the basis of the above knowledge is, in one aspect, a copper foil comprising a copper foil bulk layer, a roughening treatment layer, and a rust prevention treatment layer containing chromium in this order,
When the copper foil is laminated on the resin base material from the side having the roughening treatment layer and the copper foil is etched on the entire surface using an etching solution, the etched surface of the resin base material after the entire surface etching is performed. When the weight concentrations (wt%) of Cr, Zn, C, O, and Si in surface analysis by XPS are A, B, C, D, and E, respectively, Cr content ratio (%) [= A / (A + B + C + D + E ) × 100] is 0.1 to 10% copper foil.
樹脂基材上に前記銅箔を前記樹脂層を有する面側から積層し、エッチング液を用いて前記銅箔の銅箔バルク層から防錆処理層までを全面エッチングした場合に、前記全面エッチング後の前記樹脂基材上の前記樹脂層のエッチング面をXPSにより表面分析した際のCr、Zn、C、O、Siの重量濃度(wt%)をそれぞれA、B、C、D、Eとしたとき、Cr含有比率(%)[=A/(A+B+C+D+E)×100]が0.1~10%である銅箔である。 In another aspect, the present invention is a copper foil comprising a copper foil bulk layer, a roughening treatment layer, a rust prevention treatment layer containing chromium, and a resin layer in this order,
When the copper foil is laminated on the resin base material from the side having the resin layer, and the entire surface of the copper foil from the copper foil bulk layer to the anticorrosive treatment layer is etched using an etching solution, the entire surface is etched. The weight concentrations (wt%) of Cr, Zn, C, O, and Si when the surface of the etched surface of the resin layer on the resin base material was analyzed by XPS were A, B, C, D, and E, respectively. In this case, the copper foil has a Cr content ratio (%) [= A / (A + B + C + D + E) × 100] of 0.1 to 10%.
樹脂基材上に前記銅箔を前記樹脂層を有する面側から積層し、エッチング液を用いて前記銅箔の銅箔バルク層から防錆処理層までを全面エッチングした場合に、前記全面エッチング後の前記樹脂基材上の前記樹脂層のエッチング面をXPSにより表面分析した際のCr、Zn、C、O、Siの重量濃度(wt%)をそれぞれA、B、C、D、Eとしたとき、Cr含有比率(%)[=A/(A+B+C+D+E)×100]が0.1~10%である銅箔である。 In another aspect of the present invention, a copper foil comprising a copper foil bulk layer, a rust-preventing treatment layer containing chromium, and a resin layer in this order,
When the copper foil is laminated on the resin base material from the side having the resin layer, and the entire surface of the copper foil from the copper foil bulk layer to the anticorrosive treatment layer is etched using an etching solution, the entire surface is etched. The weight concentrations (wt%) of Cr, Zn, C, O, and Si when the surface of the etched surface of the resin layer on the resin base material was analyzed by XPS were A, B, C, D, and E, respectively. In this case, the copper foil has a Cr content ratio (%) [= A / (A + B + C + D + E) × 100] of 0.1 to 10%.
前記キャリア付銅箔と絶縁基板とを積層する工程、
前記キャリア付銅箔と絶縁基板とを積層した後に、前記キャリア付銅箔のキャリアを剥がす工程を経て銅張積層板を形成し、
その後、セミアディティブ法、サブトラクティブ法、パートリーアディティブ法又はモディファイドセミアディティブ法のいずれかの方法によって、回路を形成する工程を含むプリント配線板の製造方法である。 In another aspect of the present invention, a step of preparing the carrier-attached copper foil of the present invention and an insulating substrate,
Laminating the copper foil with carrier and an insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the carrier-attached copper foil,
Thereafter, the printed wiring board manufacturing method includes a step of forming a circuit by any one of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method.
前記回路が埋没するように前記キャリア付銅箔の前記極薄銅層側表面に樹脂層を形成する工程、
前記樹脂層上に回路を形成する工程、
前記樹脂層上に回路を形成した後に、前記キャリアを剥離させる工程、及び、
前記キャリアを剥離させた後に、前記極薄銅層を除去することで、前記極薄銅層側表面に形成した、前記樹脂層に埋没している回路を露出させる工程
を含むプリント配線板の製造方法である。 In yet another aspect of the present invention, a step of forming a circuit on the ultrathin copper layer side surface of the copper foil with a carrier of the present invention,
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
Forming the circuit on the resin layer, and then peeling the carrier; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Is the method.
本発明において、「銅箔バルク層」とは、粗化処理層、バリヤー層、防錆層、シランカップリング層等の表面処理層を除く銅箔本体(生銅箔)部分を示す。
また、プリント配線基板、または、半導体パッケージ基板製造プロセスでの銅箔エッチング量を少なくするという観点から、銅厚12μm以下の極薄銅箔(キャリア付き極薄銅箔を含む)を用いてもよい。 The copper foil used in the present invention includes a copper foil bulk layer, a roughening treatment layer formed on the copper foil bulk layer, and a rust prevention treatment layer containing chromium formed on the roughening treatment layer. ing. In addition, you may provide another layer between a copper foil bulk layer and a roughening process layer. Moreover, you may provide another layer between a roughening process layer and the antirust process layer containing chromium. The copper foil bulk layer may be formed of either electrolytic copper foil or rolled copper foil.
In the present invention, the “copper foil bulk layer” refers to a copper foil body (raw copper foil) portion excluding a surface treatment layer such as a roughening treatment layer, a barrier layer, a rust prevention layer, and a silane coupling layer.
Further, from the viewpoint of reducing the amount of copper foil etching in the printed wiring board or semiconductor package substrate manufacturing process, an ultrathin copper foil (including an ultrathin copper foil with a carrier) having a copper thickness of 12 μm or less may be used. .
CuSO4・5H2O:39.3~118g/L
Cu:10~30g/L
H2SO4:10~150g/L
Na2WO4・2H2O:0~90mg/L
W:0~50mg/L
ドデシル硫酸ナトリウム:0~50mg/L
H3AsO3(60%水溶液):0~6315mg/L
As:0~2000mg/L (Processing liquid composition)
CuSO 4 .5H 2 O: 39.3 to 118 g / L
Cu: 10-30 g / L
H 2 SO 4 : 10 to 150 g / L
Na 2 WO 4 · 2H 2 O: 0 to 90 mg / L
W: 0-50mg / L
Sodium dodecyl sulfate: 0 to 50 mg / L
H 3 AsO 3 (60% aqueous solution): 0-6315 mg / L
As: 0 to 2000 mg / L
温度:30~70℃
(電流条件1)
電流密度:25~110A/dm2
粗化クーロン量:50~500A/dm2
めっき時間:0.5~20秒
(液組成2)
CuSO4・5H2O:78~314g/L
Cu:20~80g/L
H2SO4:50~200g/L (Electroplating condition 1)
Temperature: 30-70 ° C
(Current condition 1)
Current density: 25 to 110 A / dm 2
Roughening coulomb amount: 50 to 500 A / dm 2
Plating time: 0.5 to 20 seconds (Liquid composition 2)
CuSO 4 .5H 2 O: 78 to 314 g / L
Cu: 20-80 g / L
H 2 SO 4 : 50 to 200 g / L
温度:30~70℃
(電流条件2)
電流密度:5~50A/dm2
粗化クーロン量:50~300A/dm2
めっき時間:1~60秒 (Electroplating condition 2)
Temperature: 30-70 ° C
(Current condition 2)
Current density: 5 to 50 A / dm 2
Roughening coulomb amount: 50 to 300 A / dm 2
Plating time: 1-60 seconds
また、「全面エッチング」とは、銅箔が厚み分、全て除去されて、全面に樹脂が露出するまでエッチングすることをいう。 Moreover, the copper foil of this invention is the weight concentration (Cr, Zn, C, O, Si when the surface of the etched surface of the resin base material after the copper foil of the copper clad laminate is etched by XPS ( wt%) is A, B, C, D and E, respectively, the Cr content ratio (%) [= A / (A + B + C + D + E) × 100] is 0.1 to 10%. As described above, Cr remains on the surface of the resin base material (full-surface etching base material) after the copper foil has been removed by full-surface etching, such as when a rust-proofing layer by chromate treatment is formed on the copper foil. Since the Cr content ratio is 0.1 to 10% with respect to the total weight concentration (wt%) of Cr, Zn, C, O, and Si when the surface analysis is performed by XPS, the resin base material (entire surface etching) Good adhesion (peel strength) between the base material and the copper plating formed on the base material is obtained. When the Cr content ratio (%) is an extremely high value, there is a possibility that many etching residues of the copper foil are present on the surface of the resin base material. Therefore, when the Cr content ratio (%) is an extremely high value, the migration resistance may be deteriorated. Therefore, the Cr content ratio (%) is preferably 0.5 to 5.0%, more preferably 1.0 to 3.0%. Here, generally, the region of the resin base material (entire etching base material) analyzed by the XPS surface analysis is a region from the resin base material surface to a depth of about 10 nm.
Further, “entire etching” means that etching is performed until the copper foil is completely removed by the thickness and the resin is exposed on the entire surface.
また、セミアディティブ工法の別の一実施形態は以下の通りである。 A fine circuit can be formed by a semi-additive method using the copper foil of the present invention. FIG. 1 shows a schematic example of a semi-additive construction method using a copper foil profile. In this construction method, a surface profile of copper foil is used. Specifically, first, the copper foil of the present invention is laminated on a resin base material to produce a copper clad laminate. Next, the entire surface of the copper foil of the copper clad laminate is etched. Next, electroless copper plating is applied to the surface of the resin substrate (entire etching substrate) to which the copper foil surface profile has been transferred. Then, a portion of the resin base material (entire etching base material) where the circuit is not formed is covered with a dry film or the like, and electroless (electrolytic) copper plating is applied to the surface of the electroless copper plating layer not covered with the dry film. Then, after removing the dry film, a fine circuit is formed by removing the electroless copper plating layer formed in the portion where the circuit is not formed. Since the fine circuit formed in the present invention is in close contact with the etching surface of the resin base material (entire etching base material) to which the copper foil surface profile of the present invention is transferred, the adhesion force (peel strength) is good. It has become.
Another embodiment of the semi-additive construction method is as follows.
前記銅箔と絶縁基板とを積層する工程、
前記銅箔と絶縁基板とを積層した後に、前記銅箔がキャリアを有する場合には当該キャリアを剥がす工程、
前記銅箔(前記銅箔がキャリアを有する場合にはキャリアを剥がして露出した銅箔)を酸などの腐食溶液を用いたエッチングやプラズマなどの方法によりすべて除去する工程、
前記銅箔をエッチングにより除去することにより露出した前記樹脂にスルーホールまたは/およびブラインドビアを設ける工程、
前記スルーホールまたは/およびブラインドビアを含む領域についてデスミア処理を行う工程、
前記樹脂および前記スルーホールまたは/およびブラインドビアを含む領域について無電解めっき層を設ける工程、
前記無電解めっき層の上にめっきレジストを設ける工程、
前記めっきレジストに対して露光し、その後、回路が形成される領域のめっきレジストを除去する工程、
前記めっきレジストが除去された前記回路が形成される領域に、電解めっき層を設ける工程、
前記めっきレジストを除去する工程、
前記回路が形成される領域以外の領域にある無電解めっき層をフラッシュエッチングなどにより除去する工程、
を含む。 Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing the copper foil and the insulating substrate according to the present invention,
Laminating the copper foil and the insulating substrate;
After laminating the copper foil and the insulating substrate, if the copper foil has a carrier, the step of peeling the carrier,
A step of removing all of the copper foil (if the copper foil has a carrier, the copper foil exposed by peeling off the carrier) by a method such as etching or plasma using a corrosive solution such as an acid,
Providing a through hole or / and a blind via in the resin exposed by removing the copper foil by etching;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the resin and the through hole or / and the blind via;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.
前記銅箔と絶縁基板とを積層する工程、
前記銅箔と絶縁基板とを積層した後に、前記銅箔がキャリアを有する場合には当該キャリアを剥がす工程、
前記銅箔(前記銅箔がキャリアを有する場合には、前記キャリアを剥がして露出した銅箔)を酸などの腐食溶液を用いたエッチングやプラズマなどの方法によりすべて除去する工程、
前記銅箔をエッチングにより除去することにより露出した前記樹脂の表面について無電解めっき層を設ける工程、
前記無電解めっき層の上にめっきレジストを設ける工程、
前記めっきレジストに対して露光し、その後、回路が形成される領域のめっきレジストを除去する工程、
前記めっきレジストが除去された前記回路が形成される領域に、電解めっき層を設ける工程、
前記めっきレジストを除去する工程、
前記回路が形成される領域以外の領域にある無電解めっき層及び極薄銅層をフラッシュエッチングなどにより除去する工程、
を含む。 In another embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing a copper foil and an insulating substrate according to the present invention,
Laminating the copper foil and the insulating substrate;
After laminating the copper foil and the insulating substrate, if the copper foil has a carrier, the step of peeling the carrier,
A step of removing all of the copper foil (if the copper foil has a carrier, the copper foil exposed by peeling the carrier) by a method such as etching or plasma using a corrosive solution such as an acid,
Providing an electroless plating layer on the surface of the resin exposed by removing the copper foil by etching;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer and the ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like;
including.
なお、本発明の銅箔は、サブトラクティブ工法、パートリーアディティブ工法又はモディファイドセミアディティブ工法によって回路を形成する工程を含むプリント配線板の製造方法にも用いることもできる。サブトラクティブ工法、パートリーアディティブ工法又はモディファイドセミアディティブ工法は特に限定はされず、公知の工法を用いることができる。
本発明において、サブトラクティブ法とは、銅張積層板上の銅箔の不要部分を、エッチングなどによって、選択的に除去して、導体パターンを形成する方法を指す。
本発明において、パートリーアディティブ法とは、導体層を設けてなる基板、必要に応じてスルーホールやバイアホール用の孔を穿けてなる基板上に触媒核を付与し、エッチングして導体回路を形成し、必要に応じてソルダレジストまたはメッキレジストを設けた後に、前記導体回路上、スルーホールやバイアホールなどに無電解めっき処理によって厚付けを行うことにより、プリント配線板を製造する方法を指す。
本発明において、モディファイドセミアディティブ法とは、絶縁層上に金属箔を積層し、めっきレジストにより非回路形成部を保護し、電解めっきにより回路形成部の銅厚付けを行った後、レジストを除去し、前記回路形成部以外の金属箔を(フラッシュ)エッチングで除去することにより、絶縁層上に回路を形成する方法を指す。 The copper foil and resin substrate of the present invention are suitable for a method for producing a printed wiring board including a step of forming a circuit by a semi-additive construction method.
In addition, the copper foil of this invention can also be used for the manufacturing method of a printed wiring board including the process of forming a circuit by a subtractive construction method, a partly additive construction method, or a modified semiadditive construction method. The subtractive method, the partly additive method or the modified semi-additive method is not particularly limited, and a known method can be used.
In the present invention, the subtractive method refers to a method of forming a conductor pattern by selectively removing unnecessary portions of a copper foil on a copper clad laminate by etching or the like.
In the present invention, the partial additive method means that a catalyst circuit is formed on a substrate provided with a conductor layer, and if necessary, a substrate provided with holes for through holes or via holes, and etched to form a conductor circuit. Then, after providing a solder resist or a plating resist as necessary, it refers to a method of manufacturing a printed wiring board by thickening through holes, via holes, etc. on the conductor circuit by electroless plating.
In the present invention, the modified semi-additive method is a method in which a metal foil is laminated on an insulating layer, a non-circuit forming portion is protected by a plating resist, and the copper is thickened in the circuit forming portion by electrolytic plating, and then the resist is removed. Then, a method of forming a circuit on the insulating layer by removing the metal foil other than the circuit forming portion by (flash) etching is indicated.
本発明のキャリア付銅箔は、キャリアの一方の表面又は両方の表面に、中間層を介して、本発明のセミアディティブ工法用銅箔が銅箔バルク層側から設けられて構成されている。この場合、本発明のセミアディティブ工法用銅箔は、銅箔バルク層としての極薄銅層と、極薄銅層(銅箔バルク層)上に形成された粗化処理層、及び、粗化処理層上に形成されたクロムを含む防錆処理層とを備え、さらに、極薄銅層(銅箔バルク層)の粗化処理層と反対側の表面に、中間層及びキャリアがこの順に形成されている。そして、キャリアの前記銅箔バルク層の反対側表面には、同様に、上記の中間層、極薄銅層(銅箔バルク層)、粗化処理層、クロムを含む防錆処理層がこの順で設けられていてもよい。また、当該キャリアの前記銅箔バルク層の反対側表面には、粗化処理層を設けてもよい。当該粗化処理層は公知の方法を用いて設けてもよく、上述の粗化処理により設けてもよい。キャリアの前記銅箔バルク層の反対側表面に粗化処理層を設けることは、キャリアを当該粗化処理層を有する表面側から樹脂基板などの支持体に積層する際、キャリアと樹脂基板が剥離し難くなるという利点を有する。なお、前記極薄銅層(銅箔バルク層)と前記粗化処理層との間には他の層を設けてもよい。また、前記粗化処理層と前記クロムを含む防錆処理層との間には他の層を設けてもよい。また、前記キャリアと前記中間層との間には他の層を設けてもよい。また、前記中間層と前記極薄銅層(銅箔バルク層)との間には他の層を設けてもよい。 (Copper foil with carrier)
The copper foil with a carrier of the present invention is constituted by providing the copper foil for a semi-additive method of the present invention from the copper foil bulk layer side via an intermediate layer on one surface or both surfaces of a carrier. In this case, the copper foil for the semi-additive method of the present invention includes an ultrathin copper layer as a copper foil bulk layer, a roughening treatment layer formed on the ultrathin copper layer (copper foil bulk layer), and a roughening And an anti-rust treatment layer containing chromium formed on the treatment layer, and an intermediate layer and a carrier are formed in this order on the surface of the ultrathin copper layer (copper foil bulk layer) opposite to the roughening treatment layer. Has been. Similarly, the intermediate layer, the ultrathin copper layer (copper foil bulk layer), the roughened layer, and the rust preventive layer containing chromium are arranged in this order on the surface of the carrier opposite to the copper foil bulk layer. May be provided. Moreover, you may provide a roughening process layer in the opposite side surface of the said copper foil bulk layer of the said carrier. The roughening treatment layer may be provided using a known method, or may be provided by the above-described roughening treatment. Providing a roughened layer on the surface opposite to the copper foil bulk layer of the carrier means that the carrier and the resin substrate are peeled off when the carrier is laminated on a support such as a resin substrate from the surface side having the roughened layer. It has the advantage that it becomes difficult. In addition, you may provide another layer between the said ultra-thin copper layer (copper foil bulk layer) and the said roughening process layer. Moreover, you may provide another layer between the said roughening process layer and the antirust process layer containing the said chromium. Further, another layer may be provided between the carrier and the intermediate layer. Moreover, you may provide another layer between the said intermediate | middle layer and the said ultra-thin copper layer (copper foil bulk layer).
上記キャリアは典型的には金属箔または樹脂フィルムであり、例えば銅箔、銅合金箔、ニッケル箔、ニッケル合金箔、鉄箔、鉄合金箔、ステンレス箔、アルミニウム箔、アルミニウム合金箔、絶縁樹脂フィルム、ポリイミドフィルム、LCP(液晶ポリマー)フィルム、フッ素樹脂フィルムの形態で提供される。
本発明に用いることのできるキャリアは典型的には圧延銅箔や電解銅箔の形態で提供される。一般的には、電解銅箔は硫酸銅めっき浴からチタンやステンレスのドラム上に銅を電解析出して製造され、圧延銅箔は圧延ロールによる塑性加工と熱処理を繰り返して製造される。銅箔の材料としてはタフピッチ銅(JIS H3100 合金番号C1100)や無酸素銅(JIS H3100 合金番号C1020またはJIS H3510 合金番号C1011)といった高純度の銅の他、例えばSn入り銅、Ag入り銅、Cr、Zr又はMg等を添加した銅合金、Ni及びSi等を添加したコルソン系銅合金のような銅合金も使用可能である。 <Career>
The carrier is typically a metal foil or a resin film, such as a copper foil, a copper alloy foil, a nickel foil, a nickel alloy foil, an iron foil, an iron alloy foil, a stainless steel foil, an aluminum foil, an aluminum alloy foil, or an insulating resin film. , Polyimide films, LCP (liquid crystal polymer) films, and fluororesin films.
Carriers that can be used in the present invention are typically provided in the form of rolled copper foil or electrolytic copper foil. In general, the electrolytic copper foil is produced by electrolytic deposition of copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll. Examples of copper foil materials include high-purity copper such as tough pitch copper (JIS H3100 alloy number C1100) and oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), for example, Sn-containing copper, Ag-containing copper, Cr A copper alloy such as a copper alloy added with Zr or Mg, or a Corson copper alloy added with Ni, Si or the like can also be used.
上記中間層は、キャリア付銅箔が絶縁基板への積層工程前にはキャリアから極薄銅層が剥離し難い一方で、絶縁基板への積層工程後にはキャリアから極薄銅層が剥離可能となるような構成であれば特に限定されない。例えば、本発明のキャリア付銅箔の中間層はCr、Ni、Co、Fe、Mo、Ti、W、P、Cu、Al、Zn、これらの合金、これらの水和物、これらの酸化物、有機物からなる群から選択される一種又は二種以上を含んでも良い。また、中間層は複数の層であっても良い。 <Intermediate layer>
The intermediate layer has a copper foil with a carrier that is hardly peeled off from the carrier before the lamination process on the insulating substrate, while the ultra-thin copper layer can be peeled off from the carrier after the lamination process on the insulating substrate. If it is the structure which becomes, it will not specifically limit. For example, the intermediate layer of the copper foil with a carrier of the present invention is Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, oxides thereof, One or two or more selected from the group consisting of organic substances may be included. The intermediate layer may be a plurality of layers.
中間層の上に極薄銅層を設ける前に、極薄銅層のピンホールを低減させるために銅-リン合金によるストライクめっきを行ってもよい。ストライクめっきにはピロリン酸銅めっき液などが挙げられる。 <Strike plating>
Before providing the ultrathin copper layer on the intermediate layer, strike plating with a copper-phosphorus alloy may be performed in order to reduce pinholes in the ultrathin copper layer. Examples of the strike plating include a copper pyrophosphate plating solution.
極薄銅層(銅箔バルク層)は、硫酸銅、ピロリン酸銅、スルファミン酸銅、シアン化銅等の電解浴を利用した電気めっきにより形成することができ、一般的な電解銅箔で使用され、高電流密度での銅箔形成が可能であることから硫酸銅浴が好ましい。極薄銅層の厚みは特に制限はないが、一般的にはキャリアよりも薄く、例えば12μm以下である。典型的には0.5~12μmであり、より典型的には1~5μm、より典型的には2~5μmである。 <Ultra-thin copper layer (copper foil bulk layer)>
The ultra-thin copper layer (copper foil bulk layer) can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc. A copper sulfate bath is preferable because copper foil can be formed at a high current density. The thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 μm or less. It is typically 0.5-12 μm, more typically 1-5 μm, more typically 2-5 μm.
また、「全面エッチング」とは、銅箔の銅箔バルク層から防錆処理層までが厚み分、全て除去されて、全面に樹脂が露出するまでエッチングすることをいう。 Moreover, the copper foil of this invention contains the chromium formed on the said copper foil bulk layer, the said roughening process layer formed on the said copper foil bulk layer, and the said roughening process layer in another one side surface. A copper foil provided with the rust-proofing layer and a resin layer formed on the rust-proofing layer, wherein the copper foil is laminated on the resin substrate from the side having the resin layer, and an etching solution is used. When the entire surface of the copper foil from the copper foil bulk layer to the anticorrosive treatment layer is etched, the etched surface of the resin layer on the resin base material after the entire surface etching is subjected to surface analysis by XPS, Cr, Zn, C When the weight concentration (wt%) of O, O, and Si is A, B, C, D, and E, respectively, the Cr content ratio (%) [= A / (A + B + C + D + E) × 100] is 0.1 to 10%. It is a certain copper foil. In addition, you may provide another layer between the said copper foil bulk layer and the said roughening process layer. Moreover, you may provide another layer between the said roughening process layer and the said rust prevention process layer containing chromium. Moreover, you may provide another layer between the said antirust process layer containing chromium, and the said resin layer. For example, a silane coupling agent layer may be provided between the rust prevention treatment layer and the resin layer. On the surface of the resin layer on the resin substrate after removing the entire surface from the copper foil bulk layer of the copper foil to the rust prevention treatment layer by etching, such as when a rust prevention treatment layer by chromate treatment is formed on the copper foil Cr remains. Since the Cr content is 0.1 to 10% with respect to the total weight concentration (wt%) of Cr, Zn, C, O, and Si when the surface analysis is performed by XPS, Good adhesion (peel strength) with the copper plating formed on the material is obtained. The Cr content ratio (%) is preferably 0.5 to 5.0%, more preferably 1.0 to 3.0%. Here, generally, the region of the resin base material (entire etching base material) analyzed by the XPS surface analysis is a region from the resin base material surface to a depth of about 10 nm.
Further, “entire etching” means that etching is performed until the entire thickness from the copper foil bulk layer to the rust-proofing layer of the copper foil is removed and the resin is exposed on the entire surface.
前記樹脂層は公知の樹脂、樹脂硬化剤、化合物、硬化促進剤、誘電体(無機化合物及び/または有機化合物を含む誘電体、金属酸化物を含む誘電体等どのような誘電体を用いてもよい)、反応触媒、架橋剤、ポリマー、プリプレグ、骨格材等を含んでよい。また、前記樹脂層は例えば国際公開番号WO2008/004399号、国際公開番号WO2008/053878、国際公開番号WO2009/084533、特開平11-5828号、特開平11-140281号、特許第3184485号、国際公開番号WO97/02728、特許第3676375号、特開2000-43188号、特許第3612594号、特開2002-179772号、特開2002-359444号、特開2003-304068号、特許第3992225、特開2003-249739号、特許第4136509号、特開2004-82687号、特許第4025177号、特開2004-349654号、特許第4286060号、特開2005-262506号、特許第4570070号、特開2005-53218号、特許第3949676号、特許第4178415号、国際公開番号WO2004/005588、特開2006-257153号、特開2007-326923号、特開2008-111169号、特許第5024930号、国際公開番号WO2006/028207、特許第4828427号、特開2009-67029号、国際公開番号WO2006/134868、特許第5046927号、特開2009-173017号、国際公開番号WO2007/105635、特許第5180815号、国際公開番号WO2008/114858、国際公開番号WO2009/008471、特開2011-14727号、国際公開番号WO2009/001850、国際公開番号WO2009/145179、国際公開番号WO2011/068157、特開2013-19056号に記載されている物質(樹脂、樹脂硬化剤、化合物、硬化促進剤、誘電体、反応触媒、架橋剤、ポリマー、プリプレグ、骨格材等)および/または樹脂層の形成方法、形成装置を用いて形成してもよい。 The resin layer may contain a thermosetting resin or may be a thermoplastic resin. The resin layer may include a thermoplastic resin. Although the type is not particularly limited, for example, a resin including an epoxy resin, a polyimide resin, a polyfunctional cyanate ester compound, a maleimide compound, a polyvinyl acetal resin, a urethane resin, or the like can be given as a preferable one. . The resin layer may be a block copolymerized polyimide resin layer or a resin layer containing a block copolymerized polyimide resin and a polymaleimide compound.
The resin layer may be made of any known dielectric such as a known resin, resin curing agent, compound, curing accelerator, dielectric (dielectric including an inorganic compound and / or organic compound, dielectric including a metal oxide). May be included), a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like. The resin layer may be, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent 3184485, International Publication. No. WO 97/02728, Japanese Patent No. 3676375, Japanese Patent Application Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Application Laid-Open No. 2002-179721, Japanese Patent Application Laid-Open No. 2002-309444, Japanese Patent Application Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Application Laid-Open No. -249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent No. 4570070, and Japanese Patent Application Laid-Open No. 4570070. No. 5-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004 / 005588, Japanese Patent Application Laid-Open No. 2006-257153, Japanese Patent Application Laid-Open No. 2007-326923, Japanese Patent Application Laid-Open No. 2008-11169, and Japanese Patent No. 5024930. No. WO 2006/028207, Japanese Patent No. 4828427, JP 2009-67029, International Publication No. WO 2006/134868, Japanese Patent No. 5046927, JP 2009-173017, International Publication No. WO 2007/105635, Patent No. 5180815, International Publication No. WO 2008/114858, International Publication Number WO 2009/008471, JP 2011-14727, International Publication Number WO 2009/001850, International Publication Number WO 2009/145179, International Publication Number Nos. WO2011 / 068157 and JP2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeletal materials, etc.) and / or You may form using the formation method and formation apparatus of a resin layer.
この樹脂層の厚みは0.1~80μmであることが好ましい。 In addition, when the prepreg material is not used, the material cost of the prepreg material is saved and the laminating process is simplified, which is economically advantageous. Moreover, the multilayer printed wiring board manufactured by the thickness of the prepreg material is used. The thickness is reduced, and there is an advantage that an extremely thin multilayer printed wiring board in which the thickness of one layer is 100 μm or less can be manufactured.
The thickness of this resin layer is preferably 0.1 to 80 μm.
工程1:まず、表面に粗化処理層が形成された極薄銅層を有するキャリア付銅箔(1層目)を準備する。
工程2:次に、極薄銅層の粗化処理層上にレジストを塗布し、露光・現像を行い、レジストを所定の形状にエッチングする。
工程3:次に、回路用のメッキを形成した後、レジストを除去することで、所定の形状の回路メッキを形成する。
工程4:次に、回路メッキを覆うように(回路メッキが埋没するように)極薄銅層上に埋め込み樹脂を設けて樹脂層を積層し、続いて別のキャリア付銅箔(2層目)を極薄銅層側から接着させる。
工程5:次に、2層目のキャリア付銅箔からキャリアを剥がす。なお、2層目にはキャリアを有さない銅箔を用いてもよい。
工程6:次に、2層目の極薄銅層または銅箔および樹脂層の所定位置にレーザー穴あけを行い、回路メッキを露出させてブラインドビアを形成する。
工程7:次に、ブラインドビアに銅を埋め込みビアフィルを形成する。
工程8:次に、ビアフィル上に、上記工程2及び3のようにして回路メッキを形成する。
工程9:次に、1層目のキャリア付銅箔からキャリアを剥がす。
工程10:次に、フラッシュエッチングにより両表面の極薄銅層(2層目に銅箔を設けた場合には銅箔)を除去し、樹脂層内の回路メッキの表面を露出させる。
工程11:次に、樹脂層内の回路メッキ上にバンプを形成し、当該はんだ上に銅ピラーを形成する。このようにして本発明のキャリア付銅箔を用いたプリント配線板を作製する。 Here, the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail.
Step 1: First, a copper foil with a carrier (first layer) having an ultrathin copper layer with a roughened layer formed on the surface is prepared.
Step 2: Next, a resist is applied on the roughened layer of the ultrathin copper layer, exposed and developed, and the resist is etched into a predetermined shape.
Step 3: Next, after circuit plating is formed, the resist is removed to form circuit plating having a predetermined shape.
Step 4: Next, an embedding resin is provided on the ultrathin copper layer so as to cover the circuit plating (so that the circuit plating is buried), and then a resin layer is laminated, followed by another copper foil with a carrier (second layer) ) Is bonded from the ultrathin copper layer side.
Process 5: Next, a carrier is peeled off from the copper foil with a carrier of the 2nd layer. Note that a copper foil having no carrier may be used for the second layer.
Step 6: Next, laser drilling is performed at predetermined positions of the second ultrathin copper layer or copper foil and resin layer to expose the circuit plating and form blind vias.
Step 7: Next, copper is embedded in the blind via to form a via fill.
Step 8: Next, circuit plating is formed on the via fill as in steps 2 and 3 above.
Process 9: Next, a carrier is peeled off from the copper foil with a carrier of the 1st layer.
Step 10: Next, ultra-thin copper layers (copper foil when a copper foil is provided as the second layer) on both surfaces are removed by flash etching, and the surface of the circuit plating in the resin layer is exposed.
Step 11: Next, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. Thus, the printed wiring board using the copper foil with a carrier of this invention is produced.
また、当該プリント配線板を用いて電子機器を作製してもよく、当該電子部品類が搭載されたプリント回路板を用いて電子機器を作製してもよく、当該電子部品類が搭載されたプリント基板を用いて電子機器を作製してもよい。 Furthermore, a printed circuit board is completed by mounting electronic components on the printed wiring board. In the present invention, the “printed wiring board” includes a printed wiring board, a printed circuit board, and a printed board on which electronic parts are mounted as described above.
Moreover, an electronic device may be manufactured using the printed wiring board, an electronic device may be manufactured using a printed circuit board on which the electronic components are mounted, and a printed circuit on which the electronic components are mounted. An electronic device may be manufactured using a substrate.
図2に、実施例及び比較例のデータを得るためのサンプル作製フローを示す。 Examples of the present invention are shown below, but these examples are provided for better understanding of the present invention and its advantages, and are not intended to limit the invention.
FIG. 2 shows a sample production flow for obtaining data of the example and the comparative example.
銅濃度80~120g/L、硫酸濃度80~120g/L、塩化物イオン濃度30~100ppm、ニカワ濃度1~5ppm、電解液温度57~62℃の硫酸銅電解液を電解銅メッキ浴とし、アノードとカソード(銅箔用電着用金属製ドラム)の間を流れる電解液の線速度を1.5~2.5m/秒、電流密度70A/dm2で厚み12μm(重量厚み95g/m2)の一般電解生箔を作製した。 ・ General electrolytic raw foil Copper copper electrolyte with copper concentration 80-120 g / L, sulfuric acid concentration 80-120 g / L, chloride ion concentration 30-100 ppm, glue concentration 1-5 ppm, electrolyte temperature 57-62 ° C As a plating bath, the linear velocity of the electrolyte flowing between the anode and the cathode (electrodeposition metal drum for copper foil) is 1.5 to 2.5 m / sec, the current density is 70 A / dm 2 , and the thickness is 12 μm (weight thickness 95 g). / M 2 ) general electrolytic green foil was prepared.
銅濃度80~120g/L、硫酸濃度80~120g/L、塩化物イオン濃度30~100ppm、ニカワ濃度1~5ppm、電解液温度57~62℃の硫酸銅電解液を電解銅メッキ浴とし、アノードとカソード(銅箔用電着用金属製ドラム)の間を流れる電解液の線速度を1.5~2.5m/秒、電流密度70A/dm2で厚み12μm(重量厚み95g/m2)の一般電解生箔を作製した。 ・ Double-sided flat electrolytic green foil Electrolytic copper sulfate electrolyte with copper concentration of 80-120 g / L, sulfuric acid concentration of 80-120 g / L, chloride ion concentration of 30-100 ppm, glue concentration of 1-5 ppm, and electrolyte temperature of 57-62 ° C As a copper plating bath, the electrolytic solution flowing between the anode and cathode (a metal drum for copper foil electrodeposition) has a linear velocity of 1.5 to 2.5 m / sec, a current density of 70 A / dm 2 and a thickness of 12 μm (weight thickness). 95 g / m 2 ) general electrolytic green foil was prepared.
前述の両面フラット電解生箔製造条件で、厚み18μmの両面フラット電解生箔を作製した。これを銅箔キャリアとして、以下の方法により、剥離層、極薄銅層を形成し、厚み3μmのキャリア付き極薄銅箔を得た。
(1)Ni層(剥離層:下地メッキ1)
銅箔キャリアのS面に対して、以下の条件でロール・トウ・ロール型の連続メッキラインで電気メッキすることにより1000μg/dm2の付着量のNi層を形成した。具体的なメッキ条件を以下に記す。
硫酸ニッケル:270~280g/L
塩化ニッケル:35~45g/L
酢酸ニッケル:10~20g/L
ホウ酸:30~40g/L
光沢剤:サッカリン、ブチンジオール等
ドデシル硫酸ナトリウム:55~75ppm
pH:4~6
浴温:55~65℃
電流密度:10A/dm2
(2)Cr層(剥離層:下地メッキ2)
次に、(1)にて形成したNi層表面を水洗及び酸洗後、引き続き、ロール・トウ・ロール型の連続メッキライン上でNi層の上に11μg/dm2の付着量のCr層を以下の条件で電解クロメート処理することにより付着させた。
重クロム酸カリウム1~10g/L、亜鉛0g/L
pH:7~10
液温:40~60℃
電流密度:2A/dm2
(3)極薄銅層
次に、(2)にて形成したCr層表面を水洗及び酸洗後、引き続き、ロール・トウ・ロール型の連続メッキライン上で、Cr層の上に厚み2μmの極薄銅層を以下の条件で電気メッキすることにより形成し、キャリア付極薄銅箔を作製した。
銅濃度:80~120g/L
硫酸濃度:80~120g/L
電解液温度:50~80℃
電流密度:100A/dm2 -Ultra-thin raw copper foil with carrier A double-sided flat electrolytic raw foil having a thickness of 18 µm was produced under the above-mentioned double-sided flat electrolytic raw foil manufacturing conditions. Using this as a copper foil carrier, a peeling layer and an ultrathin copper layer were formed by the following method to obtain an ultrathin copper foil with a carrier having a thickness of 3 μm.
(1) Ni layer (peeling layer: base plating 1)
An Ni layer having an adhesion amount of 1000 μg / dm 2 was formed on the S surface of the copper foil carrier by electroplating with a roll-to-roll type continuous plating line under the following conditions. Specific plating conditions are described below.
Nickel sulfate: 270 to 280 g / L
Nickel chloride: 35 to 45 g / L
Nickel acetate: 10-20g / L
Boric acid: 30-40g / L
Brightener: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 55-75 ppm
pH: 4-6
Bath temperature: 55-65 ° C
Current density: 10 A / dm 2
(2) Cr layer (peeling layer: base plating 2)
Next, after the surface of the Ni layer formed in (1) is washed with water and pickled, a Cr layer having an adhesion amount of 11 μg / dm 2 is continuously formed on the Ni layer on a roll-to-roll-type continuous plating line. It was made to adhere by carrying out the electrolytic chromate process on the following conditions.
Potassium dichromate 1-10g / L, zinc 0g / L
pH: 7-10
Liquid temperature: 40-60 ° C
Current density: 2 A / dm 2
(3) Ultra-thin copper layer Next, the surface of the Cr layer formed in (2) was washed with water and pickled, and then continuously on a roll-to-roll-type continuous plating line with a thickness of 2 μm on the Cr layer. An ultrathin copper layer was formed by electroplating under the following conditions to produce an ultrathin copper foil with a carrier.
Copper concentration: 80-120 g / L
Sulfuric acid concentration: 80-120 g / L
Electrolyte temperature: 50-80 ° C
Current density: 100 A / dm 2
・球状粗化(通常):
先に記した各種生箔のM面、及び、キャリア付き極薄生銅箔の表面に、下記条件で粗化処理を行った。
(電解液組成)
Cu:20~30g/L(硫酸銅5水和物で添加、以下同様)
H2SO4:80~120g/L
砒素:1.0~2.0g/L
(電解液温)
35~40℃
(電流条件)
電流密度:70A/dm2 (浴の限界電流密度以上) [Roughening treatment]
・ Spherical roughening (normal):
The roughening process was performed on the M surface of various raw foils described previously, and the surface of the ultra-thin raw copper foil with a carrier on the following conditions.
(Electrolytic solution composition)
Cu: 20 to 30 g / L (added with copper sulfate pentahydrate, the same applies hereinafter)
H 2 SO 4 : 80-120g / L
Arsenic: 1.0-2.0 g / L
(Electrolyte temperature)
35-40 ° C
(Current condition)
Current density: 70 A / dm 2 (above the limiting current density of the bath)
Cu:40~50g/L
H2SO4:80~120g/L
(電解液温)
43~47℃
(電流条件)
電流密度:29A/dm2 (浴の限界電流密度未満) (Electrolytic solution composition)
Cu: 40-50 g / L
H 2 SO 4 : 80-120g / L
(Electrolyte temperature)
43-47 ° C
(Current condition)
Current density: 29 A / dm 2 (less than the limit current density of the bath)
先に記した各種生箔のM面、及び、キャリア付き極薄生銅箔の表面に、下記条件で粗化処理を行った。
(電解液組成)
Cu濃度:10~20g/L
H2SO4濃度:80~120g/L
タングステン濃度:1~10mg/L(タングステン酸ナトリウム2水和物で添加)
ドデシル硫酸ナトリウム濃度:1~10mg/L
(電解液温)
35~45℃
(電流条件)
電流密度:54A/dm2 -Fine roughening (1):
The roughening process was performed on the M surface of various raw foils described previously, and the surface of the ultra-thin raw copper foil with a carrier on the following conditions.
(Electrolytic solution composition)
Cu concentration: 10 to 20 g / L
H 2 SO 4 concentration: 80-120 g / L
Tungsten concentration: 1 to 10 mg / L (added with sodium tungstate dihydrate)
Sodium dodecyl sulfate concentration: 1 to 10 mg / L
(Electrolyte temperature)
35-45 ° C
(Current condition)
Current density: 54 A / dm 2
(電解液組成)
Cu:40~50g/L
H2SO4:80~120g/L
(電解液温)
43~47℃
(電流条件)
電流密度:41A/dm2 (浴の限界電流密度未満) Cover the M surface of various copper foils roughened under the above conditions and the surface of the ultrathin copper foil with carrier with a copper electrolytic bath made of sulfuric acid and copper sulfate to prevent the removal of the roughened particles and improve the peel strength. Plating was performed. The covering plating conditions are described below.
(Electrolytic solution composition)
Cu: 40-50 g / L
H 2 SO 4 : 80-120g / L
(Electrolyte temperature)
43-47 ° C
(Current condition)
Current density: 41 A / dm 2 (less than the limit current density of the bath)
先に記した両面フラット電解生箔のM面、及び、キャリア付き極薄生銅箔の表面に、下記条件で粗化処理を行った。
(電解液組成)
Cu:10~20g/L
Co:1~10g/L
Ni:1~10g/L
pH:1~4
(電解液温度)
40~50℃
(電流条件)
電流密度:25A/dm2 -Fine roughening (2):
The roughening process was performed on the M surface of the double-sided flat electrolytic raw foil described above and the surface of the ultrathin raw copper foil with a carrier under the following conditions.
(Electrolytic solution composition)
Cu: 10 to 20 g / L
Co: 1-10g / L
Ni: 1-10g / L
pH: 1 to 4
(Electrolyte temperature)
40-50 ℃
(Current condition)
Current density: 25 A / dm 2
(電解液組成)
Co:1~30g/L
Ni:1~30g/L
pH:1.0~3.5
(電解液温)
30~80℃
(電流条件)
電流密度5.0A/dm2 Co-Ni plating was performed on the M surface of the double-sided flat copper foil subjected to the roughening treatment under the above conditions and the surface of the ultrathin copper foil with carrier. The covering plating conditions are described below.
(Electrolytic solution composition)
Co: 1-30g / L
Ni: 1-30g / L
pH: 1.0 to 3.5
(Electrolyte temperature)
30-80 ℃
(Current condition)
Current density 5.0A / dm 2
バリヤー処理を下記の条件で行い、真鍮メッキ層又は亜鉛・ニッケル合金メッキ層を形成した。 [Barrier treatment]
The barrier treatment was performed under the following conditions to form a brass plating layer or a zinc / nickel alloy plating layer.
銅濃度50~80g/L、亜鉛濃度2~10g/L、水酸化ナトリウム濃度50~80g/L、シアン化ナトリウム濃度5~30g/L、温度60~90℃の真鍮メッキ浴を用い、電流密度5~10A/dm2(多段処理)でメッキ電気量30As/dm2を、粗化処理層を形成したM面に付与した。 Barrier layer (brass plating) formation conditions of Example 23:
Current density using brass plating bath with copper concentration 50-80g / L, zinc concentration 2-10g / L, sodium hydroxide concentration 50-80g / L, sodium cyanide concentration 5-30g / L, temperature 60-90 ° C A plating electric quantity of 30 As / dm 2 was applied to the M surface on which the roughening treatment layer was formed at 5 to 10 A / dm 2 (multistage treatment).
Ni:10g/L~30g/L、 Zn:1g/L~15g/L、 硫酸(H2SO4):1g/L~12g/L、塩化物イオン:0g/L~5g/Lを添加したメッキ浴を用い、電流密度1.3A/dm2でメッキ電気量5.5As/dm2を、粗化処理層を形成したM面に付与した。 Barrier layer (zinc / nickel plating) formation conditions of Example 24:
Ni: 10 g / L to 30 g / L, Zn: 1 g / L to 15 g / L, sulfuric acid (H 2 SO 4 ): 1 g / L to 12 g / L, chloride ion: 0 g / L to 5 g / L Using a plating bath, a plating electric quantity of 5.5 As / dm 2 was applied to the M surface on which the roughening treatment layer was formed at a current density of 1.3 A / dm 2 .
防錆処理(クロメート処理)を下記の条件で行い、防錆処理層を形成した。
(クロメート条件1) CrO3:2.5g/L、Zn:0.4g/L、Na2SO4:10g/L、pH4.8、54℃のクロメート浴で0.7As/dm2の電気量を付加。更に、クロメート浴での防錆処理終了直後、液シャワー配管を用いて、同じクロメート浴を使って粗化処理面全面をシャワーリングした。 [Rust prevention treatment]
Rust prevention treatment (chromate treatment) was performed under the following conditions to form a rust prevention treatment layer.
(Chromate condition 1) CrO 3 : 2.5 g / L, Zn: 0.4 g / L, Na 2 SO 4 : 10 g / L, pH 4.8, electric quantity of 0.7 As / dm 2 in chromate bath at 54 ° C Added. Furthermore, immediately after completion of the rust prevention treatment in the chromate bath, the entire roughened surface was showered using the same chromate bath using a liquid shower pipe.
(アルカリ浴なので、Zn2+はZn(OH)2となって沈殿するため、フリーのZnは存在しない。) (Chromate condition 3) Electricity of 0.7 As / dm 2 in an alkaline pure chromate bath of copper foil K 2 Cr 2 O 7 : 4 g / L,
(Because it is an alkaline bath, Zn 2+ precipitates as Zn (OH) 2 , so there is no free Zn.)
実施例25について、銅箔の粗化処理面に、0.2~2重量%のアルコキシシランを含有するpH7~8の溶液を噴霧することで、シランカップリング剤塗布処理を行った。 [Silane coupling agent application]
For Example 25, a silane coupling agent coating treatment was performed by spraying a solution having a pH of 7 to 8 containing 0.2 to 2% by weight of alkoxysilane onto the roughened surface of the copper foil.
(樹脂合成例)
ステンレス製の碇型攪拌棒、窒素導入管とストップコックのついたトラップ上に、玉付冷却管を取り付けた還流冷却器を取り付けた2リットルの三つ口フラスコに、3,4、3',4'-ビフェニルテトラカルボン酸二無水物117.68g(400mmol)、1,3-ビス(3-アミノフェノキシ)ベンゼン87.7g(300mmol)、γ-バレロラクトン4.0g(40mmol)、ピリジン4.8g(60mmol)、N-メチル-2-ピロリドン(以下NMPと記す)300g、トルエン20gを加え、180℃で1時間加熱した後室温付近まで冷却した後、3,4、3',4'-ビフェニルテトラカルボン酸二無水物29.42g(100mmol)、2,2-ビス{4-(4-アミノフェノキシ)フェニル}プロパン82.12g(200mmol)、NMP200g、トルエン40gを加え、室温で1時間混合後、180℃で3時間加熱して、固形分38%のブロック共重合ポリイミドを得た。このブロック共重合ポリイミドは、下記に示す一般式(1):一般式(2)=3:2であり、数平均分子量:70000、重量平均分子量:150000であった。 For Examples 28 to 31, a resin layer was further formed under the following conditions after the antirust treatment.
(Resin synthesis example)
To a 2-liter three-necked flask equipped with a stainless steel vertical stirring bar, a trap equipped with a nitrogen inlet tube and a stopcock, and a reflux condenser equipped with a ball cooling tube, 3,4, 3 ', 117.68 g (400 mmol) of 4′-biphenyltetracarboxylic dianhydride, 87.7 g (300 mmol) of 1,3-bis (3-aminophenoxy) benzene, 4.0 g (40 mmol) of γ-valerolactone, 4. 8 g (60 mmol), N-methyl-2-pyrrolidone (hereinafter referred to as NMP) 300 g, and toluene 20 g were added, heated at 180 ° C. for 1 hour, cooled to near room temperature, then 3, 4, 3 ′, 4′- Add 29.42 g (100 mmol) of biphenyltetracarboxylic dianhydride, 82.12 g (200 mmol) of 2,2-bis {4- (4-aminophenoxy) phenyl} propane, 200 g of NMP, and 40 g of toluene. After 1 hour mixing at room temperature, and heated for 3 hours at 180 ° C., to obtain a 38% solids polyimide block copolymer. The block copolymerized polyimide had the following general formula (1): general formula (2) = 3: 2, number average molecular weight: 70000, and weight average molecular weight: 150,000.
樹脂(1):三菱ガス化学社GHPL-830MBT
樹脂(2):日立化成工業社製679-FG
樹脂(3):住友ベークライト社製EI-6785TS-F About each copper foil of the Example produced as mentioned above and a comparative example, the following resin base material of a 20 cm square size is prepared, and the surface which has a roughening process layer of a copper foil with a resin base material and copper foil Was laminated and pressed in contact with the resin substrate. The recommended conditions of each substrate manufacturer were used for the temperature, pressure, and time of the lamination press.
Resin (1): Mitsubishi Gas Chemical Company, Inc. GHPL-830MBT
Resin (2): 679-FG manufactured by Hitachi Chemical Co., Ltd.
Resin (3): EI-6785TS-F manufactured by Sumitomo Bakelite Co., Ltd.
(エッチング条件1)エッチング液:硫酸-過酸化水素溶液、H2O2濃度:2.5パーセント、H2SO4濃度:4.0パーセント、液温:30℃
(エッチング条件2)エッチング液:塩化第二銅溶液、HCl濃度:3.5mol/L、温度:50℃、比重1.26となるようにCuCl2濃度調節
(エッチング条件3)エッチング液:塩化第二鉄溶液、HCl濃度:3.5mol/L、温度:25℃、比重1.28となるようにFeCl3濃度調節
(エッチング条件4)エッチング液:過硫酸ナトリウム溶液、Na2S2O8濃度:36g/L、HgCl2濃度:15ppm、H3PO4濃度:15mL/L Next, the copper foil on the resin substrate (for Examples 28 to 31, from the copper foil bulk layer to the rust-proofing layer) was removed by whole surface etching under the following etching conditions.
(Etching condition 1) Etching solution: sulfuric acid-hydrogen peroxide solution, H 2 O 2 concentration: 2.5%, H 2 SO 4 concentration: 4.0%, liquid temperature: 30 ° C.
(Etching condition 2) Etching solution: Cupric chloride solution, HCl concentration: 3.5 mol / L, Temperature: 50 ° C., CuCl 2 concentration adjusted so as to have a specific gravity of 1.26 (Etching condition 3) Etching solution: Chloride chloride FeCl 3 concentration adjustment so that the ferric solution, HCl concentration: 3.5 mol / L, temperature: 25 ° C., specific gravity 1.28 (etching condition 4) Etching solution: sodium persulfate solution, Na 2 S 2 O 8 concentration : 36 g / L, HgCl 2 concentration: 15 ppm, H 3 PO 4 concentration: 15 mL / L
CuSO4濃度:0.06mol/L、HCHO濃度:0.5mol/L、EDTA濃度:0.12mol/L、pH12.5、添加剤:2,2’-ジピリジル、添加剤濃度:10mg/L、表面活性剤:REG-1000、表面活性剤濃度:500mg/L Next, a catalyst for depositing electroless copper on the etching surface of the resin base material (entire etching base material) (the etching surface of the resin layer for Examples 28 to 31), and KAP- manufactured by Kanto Kasei Electroless copper plating was carried out under the following conditions using 8 baths. The thickness of the obtained electroless copper plating was 0.5 μm.
CuSO 4 concentration: 0.06 mol / L, HCHO concentration: 0.5 mol / L, EDTA concentration: 0.12 mol / L, pH 12.5, additive: 2,2′-dipyridyl, additive concentration: 10 mg / L, Surfactant: REG-1000, Surfactant concentration: 500 mg / L
単純硫酸銅電解液:Cu濃度:100g/L、H2SO4濃度:80g/L Next, electrolytic plating was further performed on the electroless copper plating using the following electrolytic solution. The copper thickness (total thickness of electroless plating and electrolytic plating) was 12 μm.
Simple copper sulfate electrolyte: Cu concentration: 100 g / L, H 2 SO 4 concentration: 80 g / L
株式会社小坂研究所製接触式粗さ計SP-11を使用し、JIS B0601-1994に準拠して十点平均粗さを銅箔粗化面について測定した。なお、バリヤー層、防錆層、シランカップリング層は生箔や粗化粒子の厚みと比べ無視でき、銅箔粗化面の表面粗度は生箔と粗化粒子の組み合わせによって決まることから、生箔と粗化粒子が同一条件のものは表面粗度は同一とした(実際に測定したが同一であった)。また、測定は試作サンプルの幅方向10点について行い、その平均値を求め、表面粗度とした。 (1) Surface roughness Rz:
Using a contact roughness meter SP-11 manufactured by Kosaka Laboratory Ltd., the ten-point average roughness was measured on the roughened copper foil surface in accordance with JIS B0601-1994. The barrier layer, rust prevention layer, and silane coupling layer are negligible compared to the thickness of raw foil and roughened particles, and the surface roughness of the copper foil roughened surface is determined by the combination of raw foil and roughened particles, The surface roughness was the same for the raw foil and the roughened particles having the same conditions (actually measured but the same). Moreover, the measurement was performed about 10 points in the width direction of the prototype sample, and the average value was obtained as the surface roughness.
前記3種類の樹脂基材を用い、樹脂基材と各実施例、比較例で得られた銅箔とを、銅箔の粗化処理層を有する面を樹脂基材に接するようにして積層プレスした。積層プレスの温度、圧力、時間は、各基材メーカーの推奨条件を用いた。そして、銅箔を全面エッチング後、樹脂基材(全面エッチング基材)(実施例28~31については樹脂層のエッチング面)に無電解銅メッキ、電解銅メッキを施して銅層厚を12μmとしたメッキ銅付き積層板について、幅10mmの銅回路を湿式エッチングにより作製した。JIS-C-6481に準じ、この銅回路を90度で剥離したときの強度を測定し、ピール強度とした。 (2) Peel strength:
Using the three types of resin base materials, the resin base material and the copper foils obtained in the respective examples and comparative examples are laminated press so that the surface having the roughened layer of the copper foil is in contact with the resin base material. did. The recommended conditions of each substrate manufacturer were used for the temperature, pressure, and time of the lamination press. Then, after etching the entire surface of the copper foil, electroless copper plating and electrolytic copper plating are applied to the resin base material (full surface etching base material) (the etching surface of the resin layer in Examples 28 to 31) to obtain a copper layer thickness of 12 μm. About the laminated plate with plated copper, a copper circuit having a width of 10 mm was prepared by wet etching. In accordance with JIS-C-6481, the strength when the copper circuit was peeled at 90 degrees was measured to obtain the peel strength.
樹脂基材(全面エッチング基材)〔実施例28~31については樹脂層のエッチング面〕のエッチング面の任意の3箇所に対し、島津/KRATOS社製高性能光電子分光分析装置AXIS-HSを用いてXPS表面分析を行った。なお、XPS表面分析は「第19回 X線光電子分析(ESCA)講習会テキスト 1997.6.26~27 秦野 株式会社島津製作所 表面・半導体機器部カスタマーサポートセンター」の6-15ページ~6-19ページ 「2.3 定量分析」に準じて行った。前述の任意の3箇所について分析結果から得られたCr、Zn、C、O、Siの重量濃度(wt%)をそれぞれA、B、C、D、Eとし、Cr含有比率(%)[=A/(A+B+C+D+E)×100]を算出し、前述の任意の3箇所のCr含有比率(%)の平均値をCr含有比率(%)の値とした。 (3) Cr content ratio:
A high-performance photoelectron spectrometer AXIS-HS manufactured by Shimadzu / KRATOS was used for any three locations on the etched surface of the resin substrate (entirely etched substrate) (the etched surface of the resin layer for Examples 28 to 31). XPS surface analysis was performed. For XPS surface analysis, please refer to pages 6-15 to 6-19 of “19th X-ray Photoelectron Analysis (ESCA) Workshop Text 1997.26.26-27. The measurement was performed according to “2.3 Quantitative Analysis”. The weight concentrations (wt%) of Cr, Zn, C, O, and Si obtained from the analysis results for the above-mentioned arbitrary three locations are A, B, C, D, and E, respectively, and the Cr content ratio (%) [= A / (A + B + C + D + E) × 100] was calculated, and the average value of the Cr content ratio (%) at the above-mentioned arbitrary three locations was taken as the value of the Cr content ratio (%).
実施例1~31は、いずれも上記Cr含有比率(%)が0.1~10%であり、良好なピール強度が得られた。
また、図1に示すプロセスに則り、実施例2、実施例3、実施例5の銅箔を使用して微細配線基板を作製したところ、各々、ライン/スペースが20μm/20μm、15μm/15μm、10μm/10μmの超微細回路が形成できることを確認した。
比較例1~6、12~14は、クロムを含む防錆処理層を形成しておらず、上記Cr含有比率(%)が検出できず、ピール強度が不良であった。
比較例7は、粗化粒子層及び樹脂層のいずれも形成しておらず、ピールが不良であった。
比較例8~11、15は、クロムを含む防錆処理層の形成条件が不適当であり、上記Cr含有比率(%)が検出できず、ピール強度が不良であった。
図3~8に実施例1~6、図9~11に比較例2、比較例6、比較例9の銅箔処理面のSEM写真をそれぞれ示す。 (Evaluation results)
In each of Examples 1 to 31, the Cr content ratio (%) was 0.1 to 10%, and good peel strength was obtained.
Further, according to the process shown in FIG. 1, when the fine wiring board was produced using the copper foils of Example 2, Example 3, and Example 5, the lines / spaces were 20 μm / 20 μm, 15 μm / 15 μm, It was confirmed that an ultrafine circuit of 10 μm / 10 μm can be formed.
In Comparative Examples 1 to 6 and 12 to 14, the rust-proofing layer containing chromium was not formed, the Cr content ratio (%) could not be detected, and the peel strength was poor.
In Comparative Example 7, neither the roughened particle layer nor the resin layer was formed, and the peel was poor.
In Comparative Examples 8 to 11 and 15, the formation conditions of the rust-proofing layer containing chromium were inappropriate, the Cr content ratio (%) could not be detected, and the peel strength was poor.
3 to 8 show Examples 1 to 6, and FIGS. 9 to 11 show SEM photographs of treated copper foil surfaces of Comparative Example 2, Comparative Example 6, and Comparative Example 9, respectively.
Claims (36)
- 銅箔バルク層、粗化処理層、及び、クロムを含む防錆処理層をこの順に備える銅箔であって、
樹脂基材上に前記銅箔を前記粗化処理層を有する面側から積層し、エッチング液を用いて前記銅箔を全面エッチングした場合に、前記全面エッチング後の前記樹脂基材のエッチング面をXPSにより表面分析した際のCr、Zn、C、O、Siの重量濃度(wt%)をそれぞれA、B、C、D、Eとしたとき、Cr含有比率(%)[=A/(A+B+C+D+E)×100]が0.1~10%である銅箔。 A copper foil comprising a copper foil bulk layer, a roughening treatment layer, and a rust prevention treatment layer containing chromium in this order,
When the copper foil is laminated on the resin base material from the side having the roughening treatment layer and the copper foil is etched on the entire surface using an etching solution, the etched surface of the resin base material after the entire surface etching is performed. When the weight concentrations (wt%) of Cr, Zn, C, O, and Si in surface analysis by XPS are A, B, C, D, and E, respectively, Cr content ratio (%) [= A / (A + B + C + D + E ) × 100] is 0.1 to 10% copper foil. - 銅箔バルク層、粗化処理層、クロムを含む防錆処理層、及び、樹脂層をこの順に備える銅箔であって、
樹脂基材上に前記銅箔を前記樹脂層を有する面側から積層し、エッチング液を用いて前記銅箔の銅箔バルク層から防錆処理層までを全面エッチングした場合に、前記全面エッチング後の前記樹脂基材上の前記樹脂層のエッチング面をXPSにより表面分析した際のCr、Zn、C、O、Siの重量濃度(wt%)をそれぞれA、B、C、D、Eとしたとき、Cr含有比率(%)[=A/(A+B+C+D+E)×100]が0.1~10%である銅箔。 A copper foil comprising a copper foil bulk layer, a roughening treatment layer, a rust prevention treatment layer containing chromium, and a resin layer in this order,
When the copper foil is laminated on the resin base material from the side having the resin layer, and the entire surface of the copper foil from the copper foil bulk layer to the anticorrosive treatment layer is etched using an etching solution, the entire surface is etched. The weight concentrations (wt%) of Cr, Zn, C, O, and Si when the surface of the etched surface of the resin layer on the resin base material was analyzed by XPS were A, B, C, D, and E, respectively. When the copper foil has a Cr content ratio (%) [= A / (A + B + C + D + E) × 100] of 0.1 to 10%. - 銅箔バルク層、クロムを含む防錆処理層、及び、樹脂層をこの順に備える銅箔であって、
樹脂基材上に前記銅箔を前記樹脂層を有する面側から積層し、エッチング液を用いて前記銅箔の銅箔バルク層から防錆処理層までを全面エッチングした場合に、前記全面エッチング後の前記樹脂基材上の前記樹脂層のエッチング面をXPSにより表面分析した際のCr、Zn、C、O、Siの重量濃度(wt%)をそれぞれA、B、C、D、Eとしたとき、Cr含有比率(%)[=A/(A+B+C+D+E)×100]が0.1~10%である銅箔。 A copper foil comprising a copper foil bulk layer, a rust-proofing layer containing chromium, and a resin layer in this order,
When the copper foil is laminated on the resin base material from the side having the resin layer, and the entire surface of the copper foil from the copper foil bulk layer to the anticorrosive treatment layer is etched using an etching solution, the entire surface is etched. The weight concentrations (wt%) of Cr, Zn, C, O, and Si when the surface of the etched surface of the resin layer on the resin base material was analyzed by XPS were A, B, C, D, and E, respectively. When the copper foil has a Cr content ratio (%) [= A / (A + B + C + D + E) × 100] of 0.1 to 10%. - 前記Cr含有比率(%)[=A/(A+B+C+D+E)×100]が0.5~5%である請求項1~3のいずれか一項に記載の銅箔。 The copper foil according to any one of claims 1 to 3, wherein the Cr content ratio (%) [= A / (A + B + C + D + E) × 100] is 0.5 to 5%.
- 前記Cr含有比率(%)[=A/(A+B+C+D+E)×100]が1~3%である請求項4に記載の銅箔。 The copper foil according to claim 4, wherein the Cr content ratio (%) [= A / (A + B + C + D + E) × 100] is 1 to 3%.
- 前記樹脂層が接着用樹脂である請求項2~5のいずれか一項に記載の銅箔。 The copper foil according to any one of claims 2 to 5, wherein the resin layer is an adhesive resin.
- 前記樹脂層がプライマーである請求項6に記載の銅箔。 The copper foil according to claim 6, wherein the resin layer is a primer.
- 前記樹脂層が半硬化状態の樹脂である請求項2~7のいずれか一項に記載の銅箔。 The copper foil according to any one of claims 2 to 7, wherein the resin layer is a semi-cured resin.
- 前記樹脂層がブロック共重合ポリイミド樹脂層またはブロック共重合ポリイミド樹脂とポリマレイミド化合物を含有する樹脂層である請求項2~8のいずれか一項に記載の銅箔。 The copper foil according to any one of claims 2 to 8, wherein the resin layer is a block copolymerized polyimide resin layer or a resin layer containing a block copolymerized polyimide resin and a polymaleimide compound.
- 前記銅箔バルク層と前記防錆処理層との間に形成された前記粗化処理層が球状粒子又は微細粒子から成り、表面粗度Rzが0.3~4.0μmである請求項1~2及び4~9のいずれか一項に記載の銅箔。 The roughening treatment layer formed between the copper foil bulk layer and the antirust treatment layer is composed of spherical particles or fine particles, and has a surface roughness Rz of 0.3 to 4.0 μm. The copper foil according to any one of 2 and 4 to 9.
- 前記粗化処理層と前記防錆処理層との間に、バリヤー層が形成された請求項1~10のいずれか一項に記載の銅箔。 The copper foil according to any one of claims 1 to 10, wherein a barrier layer is formed between the roughening treatment layer and the rust prevention treatment layer.
- 前記銅箔バルク層と前記防錆処理層との間に、バリヤー層が形成された請求項3~9のいずれか一項に記載の銅箔。 The copper foil according to any one of claims 3 to 9, wherein a barrier layer is formed between the copper foil bulk layer and the antirust treatment layer.
- 前記バリヤー層が、真鍮メッキ層又は亜鉛・ニッケル合金メッキ層で構成されている請求項11又は12に記載の銅箔。 The copper foil according to claim 11 or 12, wherein the barrier layer is composed of a brass plating layer or a zinc / nickel alloy plating layer.
- 樹脂基材積層側の表面にシランカップリング剤層が設けられた請求項1~13のいずれか一項に記載の銅箔。 The copper foil according to any one of claims 1 to 13, wherein a silane coupling agent layer is provided on the surface of the resin base material laminated side.
- 前記防錆処理層と前記樹脂層との間にシランカップリング剤層が設けられた請求項2~14のいずれか一項に記載の銅箔。 The copper foil according to any one of claims 2 to 14, wherein a silane coupling agent layer is provided between the antirust treatment layer and the resin layer.
- 前記銅箔バルク層の厚みが12μm以下である請求項1~15のいずれか一項に記載の銅箔。 The copper foil according to any one of claims 1 to 15, wherein the thickness of the copper foil bulk layer is 12 袖 m or less.
- 前記エッチング液が、硫酸-過酸化水素溶液、塩化第二銅溶液、塩化第二鉄溶液、又は、過硫酸塩系溶液である請求項1~16のいずれか一項に記載の銅箔。 The copper foil according to any one of claims 1 to 16, wherein the etching solution is a sulfuric acid-hydrogen peroxide solution, a cupric chloride solution, a ferric chloride solution, or a persulfate solution.
- セミアディティブ工法に用いられる請求項1~17のいずれか一項に記載の銅箔。 The copper foil according to any one of claims 1 to 17, which is used in a semi-additive construction method.
- キャリアの一方の表面又は両方の表面に、中間層を介して、請求項1~18のいずれか一項に記載の銅箔が前記銅箔バルク層側から設けられたキャリア付銅箔。 A copper foil with a carrier, wherein the copper foil according to any one of claims 1 to 18 is provided on one surface or both surfaces of a carrier via an intermediate layer from the copper foil bulk layer side.
- 前記キャリアの一方の表面に、中間層を介して、請求項1~18のいずれか一項に記載の銅箔が前記銅箔バルク層側から設けられ、前記キャリアの他方の表面に、粗化処理層が設けられたキャリア付銅箔。 The copper foil according to any one of claims 1 to 18 is provided on one surface of the carrier via an intermediate layer from the copper foil bulk layer side, and the other surface of the carrier is roughened. Copper foil with carrier provided with a treatment layer.
- 請求項1~20のいずれか一項に記載の銅箔を用いた銅張積層体。 A copper-clad laminate using the copper foil according to any one of claims 1 to 20.
- 請求項1~20のいずれか一項に記載の銅箔を用いた半導体パッケージ用銅張積層体。 A copper clad laminate for a semiconductor package using the copper foil according to any one of claims 1 to 20.
- 請求項1~20のいずれか一項に記載の銅箔を用いたプリント配線板。 A printed wiring board using the copper foil according to any one of claims 1 to 20.
- 基材表面をXPSにより表面分析した際のCr、Zn、C、O、Siの重量濃度(wt%)をそれぞれA、B、C、D、Eとしたとき、Cr含有比率(%)[=A/(A+B+C+D+E)×100]が0.1~10%である樹脂基材。 When the weight concentration (wt%) of Cr, Zn, C, O, and Si when the surface of the substrate surface is analyzed by XPS is A, B, C, D, and E, the Cr content ratio (%) [= A resin base material having A / (A + B + C + D + E) × 100] of 0.1 to 10%.
- 表面粗度Rzが0.3~4.0μmである請求項24に記載の樹脂基材。 The resin base material according to claim 24, wherein the surface roughness Rz is 0.3 to 4.0 μm.
- セミアディティブ工法に用いられる請求項24又は25に記載の樹脂基材。 The resin base material according to claim 24 or 25, which is used in a semi-additive construction method.
- 請求項1~20のいずれか一項に記載の銅箔を用いてセミアディティブ工法によって回路を形成する工程を含む回路の形成方法。 A circuit forming method including a step of forming a circuit by a semi-additive method using the copper foil according to any one of claims 1 to 20.
- 請求項21又は22に記載の銅張積層体を用いて回路を形成するセミアディティブ工法。 A semi-additive method for forming a circuit using the copper-clad laminate according to claim 21 or 22.
- 請求項24~26のいずれか一項に記載の樹脂基材を用いて回路を形成するセミアディティブ工法。 A semi-additive method of forming a circuit using the resin base material according to any one of claims 24 to 26.
- 請求項24~26のいずれか一項に記載の樹脂基材の表面に、セミアディティブ工法によってライン/スペースが30/30μm以下の回路を形成した半導体パッケージ用回路形成基板。 A circuit forming substrate for a semiconductor package, wherein a circuit having a line / space of 30/30 μm or less is formed on the surface of the resin base material according to any one of claims 24 to 26 by a semi-additive method.
- 請求項30に記載の半導体パッケージ用回路形成基板を備えた半導体パッケージ。 A semiconductor package comprising the circuit forming substrate for a semiconductor package according to claim 30.
- 請求項1~20のいずれか一項に記載の銅箔を用いてセミアディティブ工法によって回路を形成する工程を含むプリント配線板の製造方法。 A method for producing a printed wiring board, comprising a step of forming a circuit by a semi-additive construction method using the copper foil according to any one of claims 1 to 20.
- 請求項24~26のいずれか一項に記載の樹脂基材を用いたプリント配線板。 A printed wiring board using the resin base material according to any one of claims 24 to 26.
- 請求項23又は33に記載のプリント配線板を用いた電子機器。 Electronic equipment using the printed wiring board according to claim 23 or 33.
- 請求項19又は20に記載のキャリア付銅箔と絶縁基板とを準備する工程、
前記キャリア付銅箔と絶縁基板とを積層する工程、
前記キャリア付銅箔と絶縁基板とを積層した後に、前記キャリア付銅箔のキャリアを剥がす工程を経て銅張積層板を形成し、
その後、セミアディティブ法、サブトラクティブ法、パートリーアディティブ法又はモディファイドセミアディティブ法のいずれかの方法によって、回路を形成する工程を含むプリント配線板の製造方法。 A step of preparing the carrier-attached copper foil and the insulating substrate according to claim 19 or 20,
Laminating the copper foil with carrier and an insulating substrate;
After laminating the carrier-attached copper foil and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the carrier-attached copper foil,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method. - 請求項19又は20に記載のキャリア付銅箔の前記極薄銅層側表面に回路を形成する工程、
前記回路が埋没するように前記キャリア付銅箔の前記極薄銅層側表面に樹脂層を形成する工程、
前記樹脂層上に回路を形成する工程、
前記樹脂層上に回路を形成した後に、前記キャリアを剥離させる工程、及び、
前記キャリアを剥離させた後に、前記極薄銅層を除去することで、前記極薄銅層側表面に形成した、前記樹脂層に埋没している回路を露出させる工程
を含むプリント配線板の製造方法。 Forming a circuit on the ultrathin copper layer side surface of the copper foil with a carrier according to claim 19 or 20,
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
Forming the circuit on the resin layer, and then peeling the carrier; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Method.
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KR1020157036469A KR101822251B1 (en) | 2013-05-29 | 2014-05-29 | Copper foil, copper foil with carrier, copper-clad laminate, printed circuit board, circuit forming substrate for semiconductor package, semiconductor package, electronic device, resin substrate, circuit forming method, semiadditive method, and printed circuit board manufacturing method |
CN201480030858.0A CN105264123B (en) | 2013-05-29 | 2014-05-29 | Copper foil and forming method, semi-additive process, the manufacturing method of printing distributing board for using the component, circuit that have it |
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JP2013121955A JP5470487B1 (en) | 2013-05-29 | 2013-06-10 | Copper foil, copper clad laminate for semiconductor package using the same, printed wiring board, printed circuit board, resin substrate, circuit forming method, semi-additive method, circuit forming substrate for semiconductor package, and semiconductor package |
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JPWO2020071287A1 (en) * | 2018-10-05 | 2021-09-02 | パナソニックIpマネジメント株式会社 | Copper-clad laminates, wiring boards, and copper foil with resin |
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JP2015007261A (en) | 2015-01-15 |
CN105264123B (en) | 2019-04-05 |
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