WO2022085464A1 - Film conducteur ayant une couche d'or - Google Patents

Film conducteur ayant une couche d'or Download PDF

Info

Publication number
WO2022085464A1
WO2022085464A1 PCT/JP2021/037072 JP2021037072W WO2022085464A1 WO 2022085464 A1 WO2022085464 A1 WO 2022085464A1 JP 2021037072 W JP2021037072 W JP 2021037072W WO 2022085464 A1 WO2022085464 A1 WO 2022085464A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
copper
conductive film
thickness
gold
Prior art date
Application number
PCT/JP2021/037072
Other languages
English (en)
Japanese (ja)
Inventor
敬之 野坂
昌利 後藤
英希 薩摩
Original Assignee
セーレン株式会社
敬之 野坂
昌利 後藤
英希 薩摩
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by セーレン株式会社, 敬之 野坂, 昌利 後藤, 英希 薩摩 filed Critical セーレン株式会社
Priority to KR1020237013500A priority Critical patent/KR20230091902A/ko
Priority to CN202180053408.3A priority patent/CN116096942A/zh
Priority to JP2022557418A priority patent/JPWO2022085464A1/ja
Publication of WO2022085464A1 publication Critical patent/WO2022085464A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • 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
    • 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
    • C25D3/48—Electroplating: Baths therefor from solutions of gold
    • 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
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • 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
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a conductive film. More specifically, the present invention relates to a conductive film in which a gold layer is laminated on the surface and the bending resistance and corrosion resistance of the gold layer are improved while suppressing the migration of copper to the gold layer.
  • an intermediate layer made of nickel, tin, etc. is provided.
  • new problems such as cracks on the surface of the layer made of gold due to bending and pinholes, which reduce corrosion resistance, have been presented. Is required to be resolved.
  • Patent Document 1 Japanese Patent Laid-Open No. 2009-176646
  • the average crystal grain size of a metal constituting a surface side region under a surface layer made of gold or the like is 0.001 to 0.3 ⁇ m.
  • a foil-like conductor provided with an intermediate (nickel) layer is proposed. It is said that this makes the area directly under the surface layer smooth and makes it difficult for pinholes to be formed in the surface layer, but the thickness of the intermediate layer cannot be made sufficiently thin, so that the bending resistance is inferior.
  • An object of the present invention is to solve the above-mentioned problems and to provide a conductive film having improved bending resistance and corrosion resistance of the gold layer while suppressing the migration of copper to the gold layer. ..
  • the conductive film of the present invention is a conductive film in which a metal layer composed of a copper layer, a nickel layer, and a gold layer is laminated in this order on one surface of an insulating film base material, and the thickness of the nickel layer is high. It is a conductive film characterized by having a thickness of 0.05 to 0.2 ⁇ m.
  • the arithmetic mean roughness Ra of the surface of the copper layer on the side where the nickel layer is laminated is 0.02 ⁇ m or less. According to this, the corrosion resistance of the conductive film can be enhanced.
  • the arithmetic mean roughness Ra of the surface of the gold layer is 0.03 ⁇ m or less. According to this, the corrosion resistance of the conductive film can be further improved.
  • the thickness of the copper layer is preferably 1 to 5 ⁇ m. It is preferable to provide a resin layer having an elongation rate of 200 to 2000% on the surface of the insulating film opposite to the surface on which the metal layer is provided.
  • a film made of at least one organic pore-treating agent selected from the group consisting of heterocyclic compounds, thiol compounds, and amine compounds is formed on the surface of the gold layer. It is desirable to seal a pinhole that is so small that it cannot be visually recognized.
  • the insulating film base material is made of a polyimide resin. According to this, it is possible to obtain a conductive film having excellent heat resistance.
  • the thickness of the insulating film substrate is preferably 4 to 25 ⁇ m.
  • the present invention it is possible to obtain a conductive film in which the gold layer is not cracked due to bending while suppressing discoloration with time. Further, a conductive film having excellent corrosion resistance can be obtained.
  • the conductive film of the present invention has a metal layer consisting of a copper layer, a nickel layer, and a gold layer on one surface of an insulating film base material, and a copper layer, a nickel layer, and gold on the insulating film base material. It is laminated in the order of layers. That is, the conductive film of the present invention has a layer structure of "insulating film base material / copper layer / nickel layer / gold layer", and one outermost layer is a gold layer.
  • the conductive film of the present invention is based on an insulating film base material.
  • a film made of a synthetic resin is preferably used as the insulating film base material.
  • the synthetic resin is not particularly limited, and examples thereof include a polyimide resin, a polyester resin, a polypropylene resin, a polyvinyl chloride resin, and a polycarbonate resin.
  • an insulating film base material made of a polyimide resin is preferable because a conductive film having excellent heat resistance can be obtained.
  • the thickness of the insulating film base material is not particularly limited, but the lower limit is preferably 2 ⁇ m, more preferably 3 ⁇ m, and particularly preferably 4 ⁇ m.
  • the upper limit of the thickness is preferably 100 ⁇ m, more preferably 50 ⁇ m, still more preferably 25 ⁇ m, and particularly preferably 13 ⁇ m.
  • the thickness of the insulating film substrate is 4 to 25 ⁇ m.
  • the insulating property of the insulating film base material is not particularly limited, but a preferable resistance value is 1 ⁇ 10 14 ⁇ / ⁇ or more.
  • the thickness of the copper layer is not particularly limited, but the lower limit is preferably 0.5 ⁇ m, more preferably 1 ⁇ m, and particularly preferably 1.5 ⁇ m.
  • the upper limit of the thickness is preferably 8 ⁇ m, more preferably 6 ⁇ m, and particularly preferably 5 ⁇ m. When the thickness of the copper layer is within this range, sufficient conductivity can be ensured and a conductive film having excellent flexibility can be obtained. Desirably, the thickness of the copper layer is 1 to 5 ⁇ m.
  • the method for forming the copper layer is not particularly limited, but is preferably formed on an insulating film substrate by a known vapor deposition method such as a vacuum vapor deposition method, formed by a sputtering method, or a known electrolytic copper plating method. And the like.
  • the copper layer may be composed of a plurality of layers formed by two or more different methods.
  • the first copper layer has a copper vapor deposition layer formed on an insulating film base material by a vapor deposition method
  • the second copper layer is a copper plating layer formed on the first copper layer by an electrolytic copper plating method.
  • a copper layer having a desired thickness can be efficiently obtained.
  • the thickness of the first copper layer is preferably 0.1 to 2.0 ⁇ m, and the thickness of the second copper layer is preferably 0.5 to 5.0 ⁇ m. It is better to have a layer thickness. Further, the arithmetic mean roughness Ra of the copper layer surface is the roughness of the surface of the second copper layer in contact with the nickel layer when the first copper layer and the second copper layer are provided.
  • Ra arithmetic mean roughness
  • the arithmetic mean roughness Ra shall be measured by a method compliant with JIS B 0601: 2001 using a device such as a scanning confocal laser scanning microscope (for example, manufactured by Olympus Corporation, trade name "LEXT OLS30-SU"). Can be done.
  • a scanning confocal laser scanning microscope for example, manufactured by Olympus Corporation, trade name "LEXT OLS30-SU”
  • Nickel layer A nickel layer is laminated on the surface of the copper layer (on the opposite side of the insulating film base material, between the copper layer and the gold layer). It is important that the thickness of the nickel layer is 0.05 to 0.2 ⁇ m. That is, the lower limit of the thickness is 0.05 ⁇ m, preferably 0.07 ⁇ m or more. The upper limit of the thickness is 0.2 ⁇ m, preferably 0.15 ⁇ m or less, and more preferably 0.12 ⁇ m or less. When the thickness of the nickel layer is within this range, it is possible to suppress the occurrence of cracks in the gold layer described later when the conductive film is bent while suppressing the migration of copper.
  • the thickness of the nickel layer is extremely thin, the effect of suppressing the arithmetic mean roughness of the copper layer surface to a small value makes it possible to form not only the nickel layer but also the gold layer uniformly and thinly. There is.
  • Gold layer A gold layer is laminated on the surface of the nickel layer (opposite to the copper layer, the outermost layer).
  • the thickness of the gold layer is preferably 0.05 ⁇ m or less, more preferably 0.04 ⁇ m or less. When the thickness of the gold layer is not more than the above range, the cost can be suppressed and a low contact resistance value can be realized.
  • the lower limit of the thickness of the gold layer is not particularly limited, but is preferably 0.02 ⁇ m or more, and more preferably 0.03 ⁇ m or more.
  • the arithmetic mean roughness Ra of the surface of the gold layer is preferably 0.03 ⁇ m or less.
  • the arithmetic mean roughness Ra of the surface of the gold layer is the average roughness of the surface of the surface (outermost surface of the conductive film) that is not in contact with the nickel layer.
  • the arithmetic average roughness Ra of the surface of the copper layer is set within the above range (0.) by setting the arithmetic average roughness of the copper layer surface to 0.02 ⁇ m or less. It can be stored in (03 ⁇ m or less).
  • the gold layer can be formed by adopting a vacuum vapor deposition method, a sputtering method, a gold film forming method by electroplating containing a brightener, etc., so that the arithmetic mean roughness Ra of the surface of the gold layer can be easily kept within the above range. It is preferable because it can be stored.
  • the surface of the gold layer obtained by the electrogold plating method may have minute pinholes that cannot be visually recognized, and it is desirable to perform a treatment for sealing these.
  • the organic sealing treatment agent is preferably one or a combination of a plurality of types selected from the group consisting of heterocyclic compounds, thiol compounds, and amine compounds.
  • thiol compounds are preferable. Specific examples thereof include triazinethiol and mercaptobenzothiazole.
  • the thickness of the film formed by the organic sealing treatment agent is not particularly limited, but is preferably 0.01 ⁇ m or less.
  • a resin layer having excellent flexibility and high elongation can be provided on the other surface of the insulating film base material (the surface opposite to the surface on which the metal layer is provided).
  • the layer structure of the conductive film of the present invention is "resin layer / insulating film base material / copper layer / nickel layer / gold layer”.
  • the resin layer is preferably made of a resin film having a high elongation rate, and the lower limit is preferably 200%, more preferably 500%, and particularly preferably 1000%.
  • the upper limit of the elongation rate is not particularly limited, but is preferably 2000%, more preferably 1500%, and particularly preferably 1300%.
  • the bending resistance of the conductive film of the present invention is further improved, and metal cracks are generated even in a bending test under stricter conditions (the curvature of the bent portion is small). It can be suppressed.
  • the type of the resin film examples include polyester, polyurethane, polyolefin, polyamide and the like.
  • the thickness of the resin is preferably about 10 to 100 ⁇ m, more preferably 20 to 50 ⁇ m.
  • the metal layer composed of the copper layer, the nickel layer, and the gold layer adheres to the insulating film base material.
  • the peel strength is preferably 0.6 kgf / 15 mm 2 or more. That is, in the present invention, the adhesiveness between the conductive film base material and the copper layer in contact with the base material is good.
  • the peel strength test follows the following procedure. First, the conductive film is cut into a length of 50 mm and a width of 5 mm to prepare a sample. Masking is performed so as to expose a length of 3 mm at the center of the sample in the length direction. Copper nail (Showa Electric Wire Cable System Co., Ltd.) is used on the exposed 3 mm x 5 mm sample surface (gold layer surface) using solder paste (manufactured by Senju Metal Industry Co., Ltd .; trade name "ECO SOLDER PASSE L20-BLT5-T7F"). With the head of a copper thin flat rivet M3 ⁇ 20) manufactured by the company attached, heat treatment is performed at 250 ° C. for 2 minutes.
  • a constant temperature dryer manufactured by Advantech Toyo Co., Ltd .; trade name "DRA630DA"
  • DVA630DA trade name "DRA630DA”
  • the sample is cooled to room temperature, folded in half at the position where the copper nail is connected, and the sample and the copper nail are pulled in the opposite directions with a tensile strength tester to measure the peel strength.
  • a tensile strength tester for example, a digital load meter SV-55 manufactured by Imada Seisakusho Co., Ltd. is used.
  • the tensile speed is 25 mm / min.
  • the conductive film of the present invention is less likely to cause cracks in the gold layer in the bending resistance test.
  • a schematic diagram showing the method of the bending resistance test is shown in FIG.
  • the conductive film 1 is cut into a sample having a length of 100 mm and a width of 30 mm, bent so that the conductive layer (metal layer 3) of the conductive film 1 is on the outside, and a PET film 4 (Toray Industries, Inc.) having a thickness of 163 ⁇ m is bent between them.
  • the bent portion 8 has a curvature of 82 ⁇ m by sandwiching the mirror 38S10 and 125S10).
  • evaluation method 1 The sample (conductive film 1) bent with the PET film 4 sandwiched between them is placed on a horizontal workbench 7 as shown in FIG. A 2.0 kg weight 5 is placed on the sample at the position shown in FIG. 1 via a slide glass 6 and allowed to stand for 1 second so that a predetermined load is applied to the bent portion 8. After removing the weight 5, the bent portion 8 is observed with a microscope or the like to confirm the occurrence of cracks. This method is referred to as evaluation method 1.
  • evaluation method 2 After changing the thickness of the PET film to 100 ⁇ m so that the bent portion of the sample has a curvature of a radius of 50 ⁇ m, the same method as described above is performed, and then the occurrence of cracks is confirmed by the same method. This method is referred to as evaluation method 2.
  • evaluation method 3 the same method as above was performed except that the bent portion of the sample had a curvature of 0 ⁇ m without sandwiching the PET film, and then the occurrence of cracks was confirmed by the same method. This method is referred to as evaluation method 3.
  • the corrosion resistance of the conductive film of the present invention can be evaluated in accordance with JIS standard 2371: 2015 neutral salt spray test method. That is, using an ISO type salt spray tester (for example, STP-90VR manufactured by Suga Test Instruments Co., Ltd.), a 5% sodium chloride aqueous solution (pH 6.8) was used as a spray liquid, and the spray liquid temperature was 35 ° C. and the air saturation temperature was 47. The treatment is carried out at ° C for a test time of 48 hours.
  • ISO type salt spray tester for example, STP-90VR manufactured by Suga Test Instruments Co., Ltd.
  • a 5% sodium chloride aqueous solution pH 6.8
  • the surface of the gold layer of the treated sample is visually observed, and the degree of corrosion is evaluated according to the following criteria. ⁇ : No change in metallic luster on the surface of the gold layer ⁇ : Metallic luster on the surface of the gold layer decreased, but no pinholes occurred ⁇ : Pinholes occurred on the surface of the gold layer.
  • the conductive film of the present invention suppresses the migration of copper to the gold layer.
  • the method for evaluating this characteristic include discoloration before and after the accelerated test by heat treatment and measurement of contact resistance value. As an accelerated test, heat treatment is performed at 260 ° C. for 15 minutes. Each sample before and after the accelerated test is color-measured by the SCI method with a colorimeter (for example, a spectrocolorimeter CM-2600d manufactured by Konica Minolta Japan Co., Ltd.), and a color difference ( ⁇ E) is calculated and evaluated. When the color difference ( ⁇ E) is 3.0 or less, it can be evaluated that the migration of copper is effectively suppressed.
  • a colorimeter for example, a spectrocolorimeter CM-2600d manufactured by Konica Minolta Japan Co., Ltd.
  • the migration suppressing effect of copper can be evaluated by measuring the contact resistance value of the samples before and after the accelerated test.
  • the contact resistance value (m ⁇ ) For the contact resistance value (m ⁇ ), prepare two gold-plated jigs with a contact resistance value (m ⁇ ) of 30 mm ⁇ 30 mm ⁇ 10 mm and a mass of 50 g, and place them side by side on the sample surface so that the surface with an area of 900 mm 2 is facing down and an interval of 1 mm is opened. ..
  • the resistance value (m ⁇ ) between the two jigs can be measured with a milliohm high tester (such as 3540 manufactured by Hioki Electric Co., Ltd.).
  • the contact resistance value is preferably 3.0 m ⁇ or less both before and after the accelerated test.
  • Method for manufacturing a conductive film includes a first step of forming a copper layer on one surface of an insulating film substrate by a vapor deposition method and a nickel layer on the surface of the copper layer by an electroplating method.
  • the second step of forming a gold layer on the surface of the nickel layer by an electroplating method is included in this order.
  • a copper layer is formed on one surface of the insulating film base material.
  • the method for forming the copper layer include a vapor deposition method and a copper film forming method by electroless copper plating. Of these, the vapor deposition method is preferable. As the vapor deposition method, a known vapor deposition apparatus and method can be adopted.
  • the surface of the insulating film base material may be pretreated and modified by plasma treatment, ion irradiation treatment, or the like.
  • the surface of the copper layer formed by the first step is preferably smooth, and its arithmetic mean roughness Ra is preferably 0.02 ⁇ m or less. If a thin-film deposition method is used to form the copper layer, a copper layer having high surface smoothness can be formed.
  • a copper layer may be further formed by using an electrolytic copper plating method following the vapor deposition method. According to this, the thickness of the copper layer can be formed thicker more efficiently.
  • the second copper layer by the electrolytic copper plating method is laminated on the surface of the copper layer formed by the vapor deposition method. Therefore, it is preferable that the arithmetic mean roughness Ra of the surface of the second copper layer is 0.02 ⁇ m or less.
  • bis (3-sulfopropyl) disulfide disodium, 2,5-dimercapto-1,3,4-thiadiazole, 3-mercapto-1-propanesulfonic acid, N, N-dimethyldithiocarbamic acid examples include organic sulfur compounds such as 3-sulfopropyl) esters.
  • examples of the treatment agent for plating include organic nitrogen compounds such as phenazine compounds, safranin compounds, polyalkyleneimines, thiourea derivatives, and polyacrylic acid amides.
  • the organic nitrogen compound is considered to have an effect as a leveling agent for forming a uniform copper layer.
  • organic sulfur compounds and organic nitrogen compounds may be used alone or in combination of both.
  • nonionic polyether-based polymer surfactants such as polyethylene glycol and polyoxyethylene polyoxypropylene copolymer
  • water-soluble polymer compounds such as dextrin and glycerin
  • More preferable ones include a combination of an organic nitrogen compound and a surfactant, and a combination of an organic sulfur compound, an organic nitrogen compound and a surfactant.
  • additives for plating treatment can also be used.
  • organic sulfur compounds and / or organic nitrogen compounds mixed with a polymer surfactant or the like as appropriate are commercially available, and they can also be used.
  • All of the above-mentioned commercial products can be used in combination of 2 to 3 products.
  • the above-mentioned "Top Lucina SF Base WR”, “Top Lucina SF-QB” and “Top Lucina SF-Leveler-Z” are combinations that can be mixed and used.
  • the above-mentioned “DAINCOPPER LS004R” and “DAINCOPPER LS004S” are combinations that can be mixed and used.
  • KOTAC MU” and “KOTAC 1" are combinations that can be mixed and used.
  • a second step of forming a nickel layer on the surface of the copper layer is carried out.
  • the nickel layer is formed by a known electroplating method. As described above, it is important that the thickness of the nickel layer is 0.05 to 0.2 ⁇ m.
  • Each condition of the electrolytic nickel plating method in the second step is not particularly limited and may be set within a range in which a nickel layer having a desired thickness can be formed.
  • the temperature of the plating solution can be 20 to 60 ° C.
  • the current density can be 0.5 to 5.0 A / dm 2
  • the processing time can be 5 to 300 sec.
  • a third step of forming a gold layer on the surface of the nickel layer is carried out.
  • a known electroplating method is also adopted for forming the gold layer.
  • the arithmetic mean roughness Ra of the surface of the gold layer is preferably 0.03 ⁇ m or less. According to this, the corrosion resistance can be improved.
  • Each condition of the electrogold plating method in the third step is not particularly limited and may be set within a range in which a gold layer having a desired thickness can be formed.
  • the temperature of the plating solution can be 40 to 60 ° C.
  • the current density can be 0.1 to 3.0 A / dm 2
  • the processing time can be 5 to 300 sec.
  • a step of contacting the surface of the gold layer with a treatment liquid in which an organic sealing treatment agent is dissolved may be carried out.
  • a film made of the organic sealing treatment agent is formed on the surface of the gold layer, and fine pinholes can be sealed.
  • the organic sealing treatment agent is preferably one or a combination of a plurality of types selected from the group consisting of heterocyclic compounds, thiol compounds, and amine compounds.
  • thiol compounds are preferable. Specific examples thereof include alkylthiols, alkyldisulfides, triazinethiols, and mercaptobenzothiazoles.
  • Examples of the solvent for dissolving the organic sealing treatment agent include water, alcohols and the like.
  • a surfactant or the like may be added to disperse the organic sealing treatment agent.
  • Examples of such surfactants include polyoxyethylene nonylphenyl ether and the like.
  • a commercially available product can also be used as the organic sealing treatment agent dispersed with a surfactant or the like.
  • Examples of such commercially available products include EL-8000B (manufactured by Nikkei Seisei Co., Ltd.), CT-3 (manufactured by JX Nippon Mining & Metals Co., Ltd.), KG-230 (manufactured by JX Nippon Mining & Metals Co., Ltd.) and the like.
  • the commercially available product When the commercially available product is used, it is preferably used by diluting it to a concentration of 20 to 100 mL / L and bringing it into contact with the surface of the gold layer.
  • the first step, the second step, and the third step may be continuously carried out.
  • the step of contacting the treatment liquid in which the organic sealing treatment agent is dissolved may also be continuously carried out following the third step. Further, a washing step and a drying step may be appropriately carried out between each of these steps.
  • the step of forming the resin layer is the insulating film base material.
  • a resin film can be attached to or laminated with an insulating film base material in advance.
  • the resin film is attached or laminated on the surface opposite to the surface on which the metal layer of the insulating film base material is provided. Can be done.
  • Peeling strength test (adhesion evaluation) The conductive film was cut into a length of 50 mm and a width of 5 mm to prepare a sample. Masking is performed so that the length of 3 mm is exposed at the center of the sample in the length direction, and solder paste (manufactured by Senju Metal Industry Co., Ltd .; trade name " ECO solder paste L20-BLT5-T7F ”) with the head of a copper nail (copper thin flat rivet M3 x 20 manufactured by Showa Densen Cable System Co., Ltd.) attached, heat treatment at 250 ° C for 2 minutes. Was carried out. A constant temperature dryer (manufactured by Advantech Toyo Co., Ltd .; trade name "DRA630DA”) was used for the heat treatment.
  • the sample was cooled to room temperature, folded in half at the position where the copper nail was connected, and the sample and the copper nail were pulled in the opposite directions with a tensile strength tester to measure the peel strength.
  • a tensile strength tester a digital load meter (manufactured by Imada Seisakusho Co., Ltd., trade name "SV-55") was used.
  • the tensile speed was 25 mm / min.
  • FIG. 1 shows a schematic diagram showing the method of the bending resistance test carried out in this example.
  • the conductive film 1 is cut into a sample having a length of 100 mm and a width of 30 mm, bent so that the conductive layer (metal layer 3) of the conductive film 1 is on the outside, and a PET film 4 (Toray Industries, Inc.) having a thickness of 163 ⁇ m is bent between them.
  • the bent portion 8 has a curvature with a radius of 82 ⁇ m by sandwiching the mirror 38S10 and 125S10).
  • the sample (conductive film 1) bent with the PET film 4 sandwiched between them was placed on a horizontal workbench 7 as shown in FIG.
  • a 2.0 kg weight 5 was placed on the sample at the position shown in FIG. 1 via a slide glass 6 and allowed to stand for 1 second so that a predetermined load was applied to the bent portion 8.
  • the bent portion 8 was observed with a microscope (trade name "Digital Microscope VHX-5000"; manufactured by KEYENCE CORPORATION), and the occurrence of cracks was confirmed. This method was used as evaluation method 1.
  • the same method as above was performed except that the thickness of the PET film was changed to 100 ⁇ m so that the bent portion of the sample had a curvature with a radius of 50 ⁇ m, and then the occurrence of cracks was confirmed by the same method (.
  • This method was used as evaluation method 2).
  • the surface of the gold layer of the treated sample is visually observed, and the degree of corrosion is evaluated according to the following criteria. ⁇ : No change in metallic luster on the surface of the gold layer ⁇ : Metallic luster on the surface of the gold layer decreased, but no pinholes occurred ⁇ : Pinholes occurred on the surface of the gold layer.
  • Copper migration suppression effect (change in contact resistance value) The effect of suppressing copper migration was evaluated by measuring the contact resistance values of the samples before and after the accelerated test by the heat treatment described above.
  • the contact resistance value (m ⁇ ) For the contact resistance value (m ⁇ ), prepare two gold plating jigs with a contact resistance value (m ⁇ ) of 30 mm ⁇ 30 mm ⁇ 10 mm and a mass of 50 g, and place them side by side on the sample surface so that the surface with an area of 900 mm 2 is facing down and an interval of 1 mm is opened.
  • the resistance value (m ⁇ ) between the two jigs was measured with a milliohm high tester (manufactured by Hioki Electric Co., Ltd., trade name "3540").
  • Arithmetic Mean Roughness Ra is measured by a method based on JIS B 0601: 2001 using a scanning confocal laser scanning microscope (manufactured by Olympus Co., Ltd., trade name "LEXT OLS30-SU"). bottom.
  • Elongation rate measurement method The elongation rate of the resin layer was calculated by the following formula from the elongation length until the resin layer broke by a tensile strength tester. Lo was the sample length before the test (mm), and L was the sample length at break (mm).
  • a single resin film for a resin layer of 20 mm x 5 mm was masked with tape (trade name "No. 642", manufactured by Teraoka Seisakusho) so that the center of 5 mm x 5 mm remained, and the two masked locations were masked with a tensile strength tester.
  • tape trade name "No. 642", manufactured by Teraoka Seisakusho
  • L was calculated from the numerical value of the tensile speed.
  • the Lo value is 5.
  • a digital load meter manufactured by Imada Seisakusho Co., Ltd., trade name "SV-55" was used, and the tensile speed was set to 30 mm / min.
  • Example 1 A copper vapor-deposited film manufactured by Toray KP Film Co., Ltd. (manufactured by Toray DuPont Co., Ltd.) in which a copper layer having a thickness of 1.5 ⁇ m is formed on one surface of a polyimide resin film having a thickness of 25 ⁇ m as an insulating film base material. Copper 100 V with a thick film vapor-deposited) was acid-washed with an aqueous solution of sulfuric acid 50 mL / L at 20 ° C. for 30 seconds. The arithmetic mean roughness Ra of the copper layer surface was measured and found to be 0.014 ⁇ m.
  • nickel plating was performed to form a nickel layer on the surface of the copper layer.
  • nickel sulfate hexahydrate was 200 g / L
  • trisodium citrate dihydrate was 60 g / L
  • the pH was 5.5
  • the temperature was 40 ° C.
  • the conditions for electrolytic nickel plating were a current density of 3.0 A / dm 2 , a processing time of 15 seconds, and an Anodec 100 (manufactured by Nikkei Seisei Co., Ltd.) as the anode.
  • the thickness of the obtained nickel layer was 0.12 ⁇ m.
  • electrogold plating was carried out to form a gold layer on the surface of the nickel layer, and a conductive film was obtained.
  • Eco Gold 24 manufactured by Nikkei Seisei Co., Ltd., gold concentration 8.0 g / L
  • Anodec 100 manufactured by Nikkei Seisei Co., Ltd. was used as the anode at a plating bath temperature of 40 ° C. and a current density of 0.32 A / dm 2 for 15 seconds.
  • the thickness of the obtained gold layer was 0.031 ⁇ m, and the arithmetic mean roughness Ra of the surface of the gold layer was 0.025 ⁇ m.
  • a conductive film having a gold layer formed in a 50 mL / L aqueous solution of the trade name "EL-8000B" manufactured by Nikkei Seisei Co., Ltd .; thiol compounds was placed at a treatment temperature of 40 ° C. Soaked for 16 seconds.
  • Example 2 In electrogold plating, a conductive film was obtained in the same manner as in Example 1 except that the treatment time was 22.5 seconds and the thickness of the gold layer was 0.046 ⁇ m. The arithmetic mean roughness Ra on the surface of the gold layer was 0.026 ⁇ m. Table 1 shows the results of each evaluation / measurement.
  • Example 3 A copper vapor-deposited film manufactured by Toray KP Film Co., Ltd. (Toray DuPont Co., Ltd.) in which a copper layer with a thickness of 0.3 ⁇ m is formed on one surface of a polyimide resin film having a thickness of 12.5 ⁇ m as an insulating film base material. A thick film of copper vapor-deposited on 100 V of DuPont manufactured by the company) was acid-washed with an aqueous solution of 50 mL / L of sulfuric acid at 20 ° C. for 30 seconds.
  • the copper plating bath 200 g / L of copper sulfate pentahydrate, 55 mL / L of sulfuric acid, 20 mL / L of soft copper film forming agent (trade name "CU-SOFT", manufactured by JCU Co., Ltd.), and sodium chloride.
  • the plating bath temperature was set to 40 ° C. using one containing 85 mg / L.
  • the conditions for electrolytic copper plating were 150 seconds at a current density of 3.0 A / dm 2 .
  • the arithmetic mean roughness Ra of the copper layer surface was measured and found to be 0.085 ⁇ m.
  • electrolytic nickel plating was performed to form a nickel layer on the surface of the copper layer.
  • the electrolytic nickel plating bath was the same as in Example 1, and the current density was 0.6 A / dm 2 and the processing time was 69.4 seconds.
  • the thickness of the obtained nickel layer was 0.11 ⁇ m.
  • Example 2 film formation by electrogold plating and an organic sealing treatment agent was carried out under the same conditions as in Example 1 to form a gold layer having a thickness of 0.033 ⁇ m and a surface arithmetic mean roughness Ra of 0.118 ⁇ m. bottom.
  • Table 1 shows the results of each evaluation / measurement.
  • Example 4 A copper vapor-deposited film manufactured by Toray KP Film Co., Ltd. (manufactured by Toray DuPont Co., Ltd.) in which a copper layer having a thickness of 0.3 ⁇ m is formed on one surface of a polyimide resin film having a thickness of 4 ⁇ m as an insulating film base material. A thick film of copper vapor-deposited on 100 V of Capton) was acid-washed with an aqueous solution of 50 ml / L of sulfuric acid at 20 ° C. for 30 seconds.
  • electrolytic nickel plating was performed to form a nickel layer on the surface of the copper layer.
  • the electrolytic nickel plating bath was the same as in Example 1, and the current density was 0.38 A / dm 2 and the processing time was 56 seconds.
  • the thickness of the obtained nickel layer was 0.07 ⁇ m.
  • Example 2 film formation by electrogold plating and an organic sealing treatment agent was carried out under the same conditions as in Example 1 to form a gold layer having a thickness of 0.046 ⁇ m and a surface arithmetic mean roughness Ra of 0.025 ⁇ m. bottom.
  • Table 1 shows the results of each evaluation / measurement.
  • Example 5 Regarding the conductive film obtained under the same conditions as in Example 4, a polyurethane resin film having a thickness of 30 ⁇ m (trade name “UH-203”, Japan) was placed on the surface opposite to the surface on which the metal layer of the insulating film substrate was provided. (Mattai Co., Ltd.) was bonded, and a 5 kg weight was placed on a hot plate (trade name "HT-1000", manufactured by AS ONE Co., Ltd.) at 100 ° C. for 10 seconds to bond the two. The elongation rate of the polyurethane resin film used in this experiment was 1300%. Table 1 shows the evaluation / measurement results of the obtained conductive film.
  • Example 1 A conductive film was obtained in the same manner as in Example 1 except that the treatment time for electrolytic nickel plating was 69.4 seconds and the thickness of the nickel layer was 0.61 ⁇ m. The arithmetic mean roughness Ra on the surface of the gold layer was 0.026. Table 1 shows the results of each evaluation / measurement.
  • Example 2 A conductive film was obtained in the same manner as in Example 1 except that the treatment time for electrolytic nickel plating was 1.0 second and the thickness of the nickel layer was 0.012 ⁇ m. The arithmetic mean roughness Ra on the surface of the gold layer was 0.017. Table 1 shows the results of each evaluation / measurement.
  • the conductive film of the present invention can be used as a conductive film for grounding. It can be wound around an elastic material to form a gasket, which can be sandwiched inside an electronic device housing and used as a countermeasure against electromagnetic interference. It is possible to shield noise generated from the electronic device itself, noise affecting the electronic device from the outside, and the like. Since it has a film shape, it can also be used as an electrical connection member to an electric circuit formed on a flexible base material such as a wearable device.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)

Abstract

Le problème décrit par la présente invention est d'obtenir un film conducteur dans lequel la migration de cuivre dans une couche d'or est inhibée, la décoloration de la couche d'or dans le temps est inhibée et la couche d'or ne se fissure pas en cas de pliage. En outre, un film conducteur présentant une excellente résistance à la corrosion peut être obtenu. La solution selon l'invention porte sur un film conducteur qui est formé par stratification, dans cet ordre, d'une couche de cuivre, d'une couche de nickel et d'une couche d'or sur une surface d'un substrat de film isolant, le film conducteur étant caractérisé en ce que l'épaisseur de la couche de nickel va de 0,05 à 0,2 µm. La rugosité moyenne arithmétique (Ra) de la surface de la couche de cuivre sur le côté où est stratifiée la couche de nickel est de préférence inférieure ou égale à 0,02 µm.
PCT/JP2021/037072 2020-10-20 2021-10-06 Film conducteur ayant une couche d'or WO2022085464A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020237013500A KR20230091902A (ko) 2020-10-20 2021-10-06 금층을 갖는 도전 필름
CN202180053408.3A CN116096942A (zh) 2020-10-20 2021-10-06 具有金层的导电膜
JP2022557418A JPWO2022085464A1 (fr) 2020-10-20 2021-10-06

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020176079 2020-10-20
JP2020-176079 2020-10-20

Publications (1)

Publication Number Publication Date
WO2022085464A1 true WO2022085464A1 (fr) 2022-04-28

Family

ID=81290331

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/037072 WO2022085464A1 (fr) 2020-10-20 2021-10-06 Film conducteur ayant une couche d'or

Country Status (4)

Country Link
JP (1) JPWO2022085464A1 (fr)
KR (1) KR20230091902A (fr)
CN (1) CN116096942A (fr)
WO (1) WO2022085464A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4343039A1 (fr) * 2022-09-26 2024-03-27 Rohm and Haas Electronic Materials LLC Compositions d'électrodéposition de nickel pour nickel rugueux

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024085369A1 (fr) 2022-10-21 2024-04-25 (주) 엘지화학 Composition de résine thermoplastique, son procédé de production et article moulé la comprenant

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62102590A (ja) * 1985-10-29 1987-05-13 古河電気工業株式会社 フレキシブルプリント回路基板
JP2007103648A (ja) * 2005-10-04 2007-04-19 Hitachi Chem Co Ltd プリント配線板、半導体チップ搭載基板、半導体パッケージ、プリント配線板の製造方法、及び半導体チップ搭載基板の製造方法
JP2009176646A (ja) * 2008-01-28 2009-08-06 Sumitomo Electric Ind Ltd 箔状導体及び配線部材並びに配線部材の製造方法
JP2019007068A (ja) * 2017-06-28 2019-01-17 小島化学薬品株式会社 無電解ニッケルストライクめっき液及びニッケルめっき皮膜の成膜方法
JP2020167224A (ja) * 2019-03-28 2020-10-08 大日本印刷株式会社 配線基板及び配線基板の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62102590A (ja) * 1985-10-29 1987-05-13 古河電気工業株式会社 フレキシブルプリント回路基板
JP2007103648A (ja) * 2005-10-04 2007-04-19 Hitachi Chem Co Ltd プリント配線板、半導体チップ搭載基板、半導体パッケージ、プリント配線板の製造方法、及び半導体チップ搭載基板の製造方法
JP2009176646A (ja) * 2008-01-28 2009-08-06 Sumitomo Electric Ind Ltd 箔状導体及び配線部材並びに配線部材の製造方法
JP2019007068A (ja) * 2017-06-28 2019-01-17 小島化学薬品株式会社 無電解ニッケルストライクめっき液及びニッケルめっき皮膜の成膜方法
JP2020167224A (ja) * 2019-03-28 2020-10-08 大日本印刷株式会社 配線基板及び配線基板の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4343039A1 (fr) * 2022-09-26 2024-03-27 Rohm and Haas Electronic Materials LLC Compositions d'électrodéposition de nickel pour nickel rugueux

Also Published As

Publication number Publication date
CN116096942A (zh) 2023-05-09
KR20230091902A (ko) 2023-06-23
JPWO2022085464A1 (fr) 2022-04-28

Similar Documents

Publication Publication Date Title
WO2022085464A1 (fr) Film conducteur ayant une couche d'or
CN108728874B (zh) 具有低反弹力的电解铜箔、其制造方法及其应用
JP5598700B2 (ja) 電解銅箔及びその製造方法
KR102274906B1 (ko) 구리박 및 이것을 갖는 동장 적층판
EP2899298A1 (fr) Matériau plaqué à surface traitée et son procédé de production, et composant électronique
WO2007125994A1 (fr) Feuille de cuivre electrolytique et son procede de fabrication, feuille de cuivre a surface traitee utilisant la premiere et plaque laminee a revetement de cuivre utilisant la seconde
EP1802183A2 (fr) Feuille de cuivre ultra-mince avec support et circuit imprimé l'utilisant
JP5115527B2 (ja) プリント配線板用銅箔およびその製造方法
EP2873752A1 (fr) Procédé de dépôt d'or sans courant et matériau revêtu d'un placage d'or
US11622445B2 (en) Surface-treated copper foil, manufacturing method thereof, copper foil laminate including the same, and printed wiring board including the same
US20060016692A1 (en) Reduction of surface oxidation during electroplating
GB1558919A (en) Electrolytic surface treating process for copper foil for use in printed circuit
EP2620530A1 (fr) Feuille de cuivre pour carte de circuit imprimé, et procédé de fabrication de celle-ci
JP3944027B2 (ja) フレキシブルプリント配線板の製造方法及びその製造方法で得られたフレキシブルプリント配線板
WO2009157457A1 (fr) Matériau composite pour composant électrique/électronique et composant électrique/électronique l’utilisant
US20030096082A1 (en) Copper alloy foil
US11013124B2 (en) Printed circuit board and method of manufacturing printed circuit board
US20060240272A1 (en) Stabilized aluminum laminate having aluminum and stabilizing layer laminated thereon
US20110088932A1 (en) Wiring circuit board and method of manufacturing the same
JP2004319918A (ja) フレキシブルプリント配線板の製造方法及びその製造方法で得られたフレキシブルプリント配線板
JP7276025B2 (ja) 銅張積層板および銅張積層板の製造方法
EP1137331A2 (fr) Composant de cuivre-sur-polymère à adhésion améliorée
JPH07207490A (ja) 電気銅めっき液
KR101546458B1 (ko) 동박 적층시트의 제조방법
JP2014122414A (ja) キャリア付き銅箔

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21882605

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022557418

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21882605

Country of ref document: EP

Kind code of ref document: A1