WO2009144973A1 - Sn or sn alloy plated film, composite material having same and composite material production method - Google Patents
Sn or sn alloy plated film, composite material having same and composite material production method Download PDFInfo
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- WO2009144973A1 WO2009144973A1 PCT/JP2009/052140 JP2009052140W WO2009144973A1 WO 2009144973 A1 WO2009144973 A1 WO 2009144973A1 JP 2009052140 W JP2009052140 W JP 2009052140W WO 2009144973 A1 WO2009144973 A1 WO 2009144973A1
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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
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0084—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a single continuous metallic layer on an electrically insulating supporting structure, e.g. metal foil, film, plating coating, electro-deposition, vapour-deposition
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- 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- C25D3/30—Electroplating: Baths therefor from solutions of tin
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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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- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
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- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
- B32B2255/205—Metallic coating
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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- 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
- B32B2605/00—Vehicles
Definitions
- the present invention relates to an Sn or Sn alloy plating film formed on the other surface of a copper foil or a copper alloy foil laminated with a resin or the like, used for an electromagnetic wave shielding material or the like, a composite material having the same, and a method for producing the composite material About.
- the Sn plating film is characterized by excellent corrosion resistance, good solderability and low contact resistance. For this reason, for example, Sn plating is used for metal foils, such as copper, as a composite material of a vehicle-mounted electromagnetic wave shielding material.
- metal foils such as copper
- a composite material of a vehicle-mounted electromagnetic wave shielding material As the above composite material, as a composite material such as an electromagnetic shielding material based on copper or copper alloy foil, a resin layer or a film is laminated on one surface of copper foil or copper alloy foil, and Sn is formed on the other surface. A structure in which a plating film is formed is used.
- Sn plating on copper or copper alloy foil is usually performed by wet plating, but in order to improve the stability of the plating film (the color must be uniform and free of color spots and patterns) and the wear resistance of the Sn plating film
- bright Sn plating is performed by adding an additive to the plating solution.
- a technique is disclosed in which a brightening agent is added to a plating solution to perform bright Sn plating to make Sn particles as small as possible (see Patent Document 2).
- whisker-like crystals called whiskers are generated in Sn plating due to internal stress and external stress. In order to prevent this, it is known that the internal stress is reduced by extremely reducing the brightening agent during plating.
- JP 2002-298963 A Japanese Patent No. 3007207 JP 2007-254860 JP
- the composite material when a composite material obtained by Sn plating on a copper foil is used as an electromagnetic shielding material for a cable or the like, the composite material is wound around the outer periphery of the cable and further coated with resin on the outside.
- resin coating process if a composite material in which Sn plating easily adheres to the line as described above is used, when the composite material passes through a die (die), the Sn plating film tends to fall off, and the Sn residue is removed from the die. The possibility of adhering increases. And if Sn residue adheres to the die, time is required for maintenance, and productivity is lowered.
- Patent Document 3 describes that the hardness of the Sn plating film is 400 MPa or less in order to make it less susceptible to external stress.
- the technique described in Patent Document 3 is a plating film with many voids because it contains a high concentration of methanol in the plating bath, and if the electrolysis is continued for a long time, a large defect (exposure of the ground) occurs in the Sn plating film. It has been clarified by the inventors' investigation. This is presumably because methanol in the plating bath is converted into formaldehyde by electrolysis, which inhibits normal Sn deposition and causes defects in the plating film. And if the foundation
- the present invention has been made to solve the above-described problems, and prevents Sn or Sn alloy plating film from being slid or dropped during plating or use, thereby improving productivity and being excellent in corrosion resistance.
- an object is to provide a Sn alloy plating film and a composite material having the same.
- the present inventors reduced the sliding or falling off of the Sn or Sn alloy plating film by setting the hardness of the Sn or Sn alloy plating film on the surface of the copper or copper alloy foil to a predetermined hardness or less. Succeeded in doing.
- electroplating using a plating bath not containing methanol the exposure of the substrate due to defects in the plating film was suppressed, and the corrosion resistance was also successfully improved.
- the Sn or Sn alloy plating film of the present invention is a Sn or Sn alloy electroplating bath not containing methanol on the other surface of the copper foil or copper alloy foil in which the resin layer or film is laminated.
- the surface of the Sn or Sn alloy plating film is observed with a scanning electron microscope (however, the thickness of the Sn or Sn alloy plating film is When the thickness exceeds 1.5 ⁇ m, when the thickness of the Sn or Sn alloy plating film is reduced to 1.5 ⁇ m), the copper foil or copper alloy foil is not exposed.
- the carbon content in the Sn or Sn alloy plating film is 0.01% by mass or less.
- the thickness of the Sn or Sn alloy plating film is preferably 0.5 ⁇ m or more. Moreover, it is preferable that the thickness of Sn or Sn alloy plating film is less than 2.0 micrometers.
- the Sn or Sn alloy plating film is preferably formed by continuous plating.
- the composite material of the present invention is formed on a copper foil or copper alloy foil, a resin layer or film laminated on one surface of the copper foil or copper alloy foil, and the other surface of the copper foil or copper alloy foil. And the Sn or Sn alloy plating film.
- the thickness of the composite material is preferably 0.1 mm or less, and is preferably used for an electromagnetic wave shield.
- the Sn plating hardness is an indentation hardness with a maximum load of 1 mN in an ultra-micro hardness test measured in accordance with ISO 14577-1 2002-10-01 Part 1. Details of the measurement method will be described later.
- the copper foil or copper alloy foil is not exposed means that the reflected electron image of the Sn or Sn alloy plating film has a luminance different from that of the reflected electron image. It means that an electron image is not observed at a normal magnification (for example, about 1000 times), and a reflected electron image having a uniform luminance is obtained.
- the thickness of the Sn or Sn alloy plating film is an average macro thickness of the Sn or Sn alloy plating film, and is obtained from the amount of electricity when the plating film is electrolyzed and completely dissolved.
- the carbon content analysis method in Sn plating film can be performed using the high frequency induction heating infrared absorption method. In this method, a Sn-plated sample is heated and dissolved in an oxygen atmosphere, carbon in the sample is reacted with oxygen in the atmosphere, and the amount of carbon dioxide in the atmosphere is measured to calculate the amount of carbon.
- the amount of carbon in the Sn plating film is determined by the difference from the sample with the Sn plating film, with the sample (plating base material) from which the plating film has been removed beforehand being used as a blank.
- the present invention by preventing the Sn plating film from sliding or falling off, it is possible to obtain an Sn plating film that is excellent in roll maintenance and can improve productivity, and a composite material having the Sn plating film.
- % means “% by mass” unless otherwise specified.
- the composite material which concerns on embodiment of this invention is the copper foil (or copper alloy foil) 1, the resin layer (or film) 4 laminated
- the copper foil tough pitch copper having a purity of 99.9% or more, oxygen-free copper
- a known copper alloy can be used depending on required strength and conductivity.
- Known copper alloys include, for example, 0.01 to 0.3% tin-containing copper alloys and 0.01 to 0.05% silver-containing copper alloys. -0.12% Sn and Cu-0.02% Ag are often used.
- the thickness of the copper foil (or copper alloy foil) is not particularly limited, but when used as a shielding material, for example, a thickness of 5 to 50 ⁇ m can be suitably used.
- copper foil (or copper alloy foil) it is preferable to use a rolled foil having higher strength than electrolytic foil.
- the center line average roughness is preferably 0.3 ⁇ m or less, more preferably 0.2 ⁇ m or less.
- the resin layer for example, a resin such as polyimide can be used, and as the film, for example, a film of PET (polyethylene terephthalate) or PEN (polyethylene naphthalate) can be used.
- the resin layer or film may be bonded to the copper foil (or copper alloy foil) with an adhesive, but the molten resin is cast on the copper foil (copper alloy foil) without using the adhesive, or the film is made of copper. You may make it thermocompression-bond to foil (copper alloy foil).
- the thickness of the resin layer or film is not particularly limited, but for example, a thickness of 5 to 50 ⁇ m can be suitably used. When an adhesive is used, the thickness of the adhesive layer can be set to 10 ⁇ m or less, for example.
- Sn alloy plating film for example, Sn—Cu, Sn—Ag, Sn—Pb or the like can be used.
- the Sn or Sn alloy plating film is formed from an Sn or Sn alloy electroplating bath not containing methanol.
- defects exposure of the base
- the plating film is converted into formaldehyde by electrolysis, which inhibits normal Sn deposition and causes defects in the plating film.
- substrate is exposed, the malfunction which the corrosion resistance of a foundation
- the electrolysis time for giving defects to the plating film varies depending on the plating conditions, but as the total electrolysis time increases, the formaldehyde in which methanol has changed accumulates in the plating bath, and plating defects that expose the substrate are more likely to occur. .
- “not containing methanol” in the plating bath means that the methanol concentration in the plating bath is at an impurity level (usually several ppm (several mg / L) or less, for example, 5 mg / L or less).
- the thickness of the Sn or Sn alloy plating film exceeds 1.5 ⁇ m, coarse plating grains may cover the exposed part of the base (plating defect part) (however, the base is completely covered).
- the surface of the plating film is observed with a scanning electron microscope, the reflected electron image of the ground which should be exposed may not be obtained.
- the thickness of the plating film is reduced to 1.5 ⁇ m and observed with a scanning electron microscope.
- a method of reducing the thickness of the plating film to 1.5 ⁇ m a method of producing a cross section of the plating film by FIB (focused ion beam), or a plating metal (or alloy) for reducing the thickness of the plating film to 1.5 ⁇ m.
- FIB focused ion beam
- a plating metal or alloy
- the thickness of the Sn or Sn alloy plating film is an average macro thickness of the Sn or Sn alloy plating film, and is determined from the amount of electricity when the plating film is electrolyzed and completely dissolved.
- the hardness of the Sn or Sn alloy plating film is 500 MPa or less.
- the hardness of the Sn or Sn alloy plating film is 500 MPa or less, slip between the Sn or Sn alloy plating surface and the roll is reduced during Sn or Sn alloy plating, and the adhesion of Sn or Sn alloy plating is lost.
- the obtained composite material is used for an electromagnetic shielding material such as a cable, the adhesion of Sn or Sn alloy to the roll or die during processing is not seen, and the productivity can be improved.
- the powder fall of Sn or Sn alloy plating film does not arise, and adhesiveness does not fall.
- the lower limit of the plating hardness of the Sn or Sn alloy plating film is 100 MPa.
- the carbon content in the Sn or Sn alloy plating film is preferably 0.01% by mass or less, and more preferably 0.006% by mass or less. If the amount of carbon in the Sn or Sn alloy plating film exceeds 0.01% by mass, even if the Sn plating film has a hardness of 500 MPa or less, the film is brittle and Sn tends to adhere to the roll. Moreover, the carbon content analysis method in Sn or Sn alloy plating film can be performed using the high frequency induction heating infrared absorption method.
- a sample plated with Sn or Sn alloy is heated and dissolved in an oxygen atmosphere, the carbon in the sample is reacted with oxygen in the atmosphere, and the amount of carbon dioxide in the atmosphere is measured to calculate the amount of carbon. .
- the amount of carbon in the Sn or Sn alloy plating film is determined by the difference from the sample with the Sn or Sn alloy plating film, with the sample (plating base material) from which the plating film has been removed beforehand being used as a blank.
- the thickness of the Sn or Sn alloy plating film is preferably 0.5 ⁇ m or more. When the thickness is less than 0.5 ⁇ m, the corrosion resistance and solderability may deteriorate.
- the upper limit of the thickness of the Sn or Sn alloy plating film is not particularly limited because it varies depending on the manufacturing conditions of the Sn or Sn alloy plating, etc. Even if the Sn or Sn alloy plating is thickened to 2 ⁇ m or more, the corrosion resistance and solderability are further improved. However, there are also problems such as increasing the Sn or Sn alloy plating allowance and reducing productivity. Therefore, it is preferable that the thickness of the Sn plating film is 0.5 ⁇ m or more and less than 2 ⁇ m.
- the hardness of the Sn or Sn alloy plating film is an indentation hardness with a maximum load of 1 mN in an ultra micro hardness test measured in accordance with ISO (International Organization for Standardization) 14477-1 2002-10-01 Part 1.
- ISO International Organization for Standardization
- the measuring instrument used for this measurement is not limited as long as it can be measured in accordance with ISO 14577-1 2002-10-01 Part1, but for example, ENT-2100 made by Elionix can be used, and Berkovich indenter ( Diamond triangular pyramid indenter) can be used.
- the measurement conditions of indentation hardness are as follows.
- Test mode Load-unloading test (unload after pushing to maximum load)
- Maximum load 1mN Measurement temperature: 32 ⁇ 1 °C
- the hardness value is an average value of five locations.
- the indentation hardness that can be measured by this method is affected by the film thickness. That is, the thicker the film, the harder the film itself, and the thinner the film, the influence of the hardness of the intermetallic compound of Cu or Cu—Sn, which is the base metal.
- the “apparent hardness” of the surface layer and when this is measured softly, it does not slip with the roll.
- the index the result of hardness measurement under the above conditions is effective.
- the thickness of the plating film is measured with a fluorescent X-ray film thickness meter, and the average value of the five points is defined as the thickness of the plating layer.
- the hardness of the Sn or Sn alloy plating film can be performed by controlling the electrodeposited grains (increasing the electrodeposited grains).
- the size of the electrodeposited grains depends on the plating conditions such as current density, Sn concentration and bath temperature, or in the Sn or Sn alloy plating bath, brighteners (for example, aldehyde, imidazole, benzalacetone, etc. are commercially available. Can be controlled by not adding to the plating bath.
- embrittlement of the Sn or Sn alloy plating film can be prevented by controlling the carbon amount in the Sn or Sn alloy plating film (reducing the carbon amount).
- the method for reducing the amount of carbon in the Sn or Sn alloy plating film can be controlled, for example, by reducing the addition of chemicals made of organic compounds (for example, brighteners) to the plating bath.
- a naphthol surfactant such as EN (ethoxylated naphthol) may be added to the Sn or Sn alloy plating bath.
- a nonionic surfactant such as ENSA (ethoxylated naphthol sulfonic acid), polyethylene glycol, or polyethylene glycol nonylphenol ether may be added to the Sn or Sn alloy plating bath.
- ENSA ethoxylated naphthol sulfonic acid
- polyethylene glycol polyethylene glycol nonylphenol ether
- an organic substance such as naphthol having a low gloss effect may be added.
- Examples of the base of the Sn or Sn alloy plating bath include phenolsulfonic acid, sulfuric acid, methanesulfonic acid and the like.
- the size of the electrodeposited grains can be adjusted by reducing the current density, increasing the Sn concentration in the bath, and increasing the bath temperature under plating conditions. For example, when the current density is 2 to 12 A / dm 2 , the Sn concentration is 30 to 60 g / L, and the bath temperature is 30 to 60 ° C., the granular electrodeposited Sn (or Sn alloy) can be uniformly electrodeposited on the copper foil surface. Yes, but it is not particularly limited because it varies depending on the device.
- the amount of carbon in the Sn or Sn alloy plating film varies depending on the type of brightener, the type of surfactant, and the plating conditions. Most brighteners increase the amount of carbon in the Sn or Sn alloy plating film and often exceed 0.01% by weight. However, in some cases, the amount of carbon in the coating can be reduced by adding very little brightener, reducing the current density under plating conditions, increasing the Sn concentration, and increasing the temperature. When only a surfactant is added to the plating solution, the amount of carbon in the coating is often 0.01% by mass or less. However, if the amount of the surfactant added to the plating solution is large, or if the surfactant has a structure that is easily adsorbed to Sn, the amount of carbon in the coating increases. Therefore, the surfactant is appropriately selected.
- a strip of a tough pitch copper foil (thickness 7.3 ⁇ m) of 99.9% or more copper bonded to a 12.5 ⁇ m thick PET film and a thermoplastic adhesive was used as a strip.
- This strip was electroplated in a continuous plating cell facing the tin anode.
- a phenolsulfonic acid bath was used as a plating bath, and 10 g / L of a surfactant (EN) and tin oxide were added to obtain a Sn concentration of 32 to 40 g / L.
- the plating conditions were a bath temperature of 45 to 55 ° C., a current density of 10 A / dm 2 , and a plating thickness of 1.5 ⁇ m.
- the obtained Sn plating film was obtained without using a brightener, and the size of the electrodeposited grains was 1.0 ⁇ m by JIS H0501 cutting method (2007 version).
- size of an electrodeposition grain is as follows. A scanning electron microscope image at a magnification of 5000 times was taken from the surface of the Sn plating film. Using the grain boundary of this image as the electrodeposition grain boundary, count the number of electrodeposition grain boundaries at a total of 6 locations, 3 in the horizontal direction and 3 in the vertical direction, using the JIS H0501 cutting method (2007 version). The size of was calculated. In order to reduce measurement errors, the measurement locations were measured by averaging the size of the electrodeposited grains in a sample of about 10 ⁇ 10 mm.
- the hardness of the Sn plating was 470 MPa.
- the hardness at the maximum load of 1 mN from the plated surface is measured, the measuring instrument is ENT-2100 made by Elionix, and Barcovich indenter (diamond triangular pyramid indenter) is used as the indenter.
- Test mode Load-unloading test (unloading after pushing to maximum load), measuring temperature: 32 ⁇ 1 ° C.
- the hardness value was an average value of five measurements. It was 0.005 mass% when the carbon content in Sn plating film was measured using the high frequency induction heating infrared absorption method.
- Continuous plating was performed in exactly the same manner as in Example 1 except that the plating thickness was 0.5 ⁇ m.
- the obtained Sn plating film was obtained without using a brightener, the size of the electrodeposited grains was 1.0 ⁇ m, and the hardness of the Sn plating was 480 MPa. It was 0.007 mass% when the carbon content in Sn plating film was measured using the high frequency induction heating infrared absorption method.
- Sn adhesion was not observed on the roll even when 4700 m was fed.
- corrosion resistance evaluation was also a favorable result.
- Continuous plating was performed in the same manner as in Example 1 except that the plating thickness was 1.9 ⁇ m and the current density was 7 A / dm 2 .
- the Sn plating film was obtained without using a brightener, the size of the electrodeposited grains was 2.0 ⁇ m, and the hardness of the Sn plating was 450 MPa. It was 0.004 mass% when the carbon content in Sn plating film was measured using the high frequency induction heating infrared absorption method.
- Sn adhesion was not observed on the roll even when 4700 m was fed.
- corrosion resistance evaluation was also a favorable result. The reason why the size of the electrodeposited grains is larger than the plating thickness is that the electrodeposited grains were observed from the plating surface, indicating that the electrodeposited grains are flat.
- a strip of a tough pitch copper foil (thickness 7.3 ⁇ m) of 99.9% or more copper bonded to a 12.5 ⁇ m thick PET film and a thermoplastic adhesive was used as a strip.
- This strip was electroplated in a continuous plating cell facing the tin anode.
- a phenolsulfonic acid bath was used as a plating bath, and 10 g / L of a surfactant (EN) and tin oxide were added to obtain a Sn concentration of 32 to 40 g / L.
- the plating conditions were such that the bath temperature was 55 to 65 ° C., the current density was 10 A / dm 2 , the bath temperature was high, and the plating thickness was 1.9 ⁇ m.
- the obtained Sn plating film was obtained without using a brightener, the size of the electrodeposited grains was 2.5 ⁇ m, and the hardness of the Sn plating was 475 MPa. It was 0.01 mass% when the carbon content in Sn plating film was measured using the high frequency induction heating infrared absorption method. In addition, when the roll on the plating outlet side was observed during continuous plating, Sn adhesion was not observed on the roll even when 4700 m was fed. Moreover, corrosion resistance evaluation was also a favorable result.
- a strip was obtained by bonding a PET film having a thickness of 12.5 ⁇ m to one surface of a tough pitch copper foil (thickness: 7.3 ⁇ m) of 99.9% or more copper using a thermoplastic adhesive.
- This strip was electroplated in a continuous plating cell facing the tin anode.
- a phenolsulfonic acid bath was used as a plating bath, and a surfactant EN10 g / L, a brightener (paraaldehyde 5 ml / L, naphthaldehyde 0.1 ml / L) and tin oxide were added to obtain a Sn concentration of 32 to 40 g / L. .
- the plating conditions were a bath temperature of 45 to 55 ° C., a current density of 10 A / dm 2 , and a plating thickness of 1.5 ⁇ m.
- the size of the electrodeposited grains of the obtained Sn plating film was 1.0 ⁇ m, and the hardness was 495 MPa. It was 0.02 mass% when the carbon content in Sn plating film was measured using the high frequency induction heating infrared absorption method.
- Sn adhesion was observed on the roll when the foil passed through 4000 m. Corrosion resistance was good.
- Example 1 Under the conditions of Example 1, after electroplating until 40000m was passed, the same evaluation as in Example 1 was performed (however, the presence or absence of Sn adhesion to the roll was not evaluated), but the corrosion resistance was good. Met. For the samples of Examples 1 to 7, when the surface of the plating film was observed with a scanning electron microscope at a magnification of 1000 times, only a reflected electron image of Sn was observed uniformly, and a reflected electron image having a luminance different from that of Sn was observed. Not detected. From this, it is considered that the composition different from the Sn plating film does not exist on the surface of the plating film, and the copper foil as the base is not exposed.
- Example 2 a 12.5 ⁇ m thick PET film was bonded to one side of a 99.9% or more copper tough pitch copper foil (thickness 7.3 ⁇ m) using a urethane adhesive and the plating thickness was 0.4 ⁇ m.
- Continuous plating was performed exactly as in Example 1.
- the obtained Sn plating was obtained without using a brightener, the size of the electrodeposited grains was 1.0 ⁇ m, and the hardness of the Sn plating was 495 MPa. It was 0.005 mass% when the carbon content in Sn plating film was measured using the high frequency induction heating infrared absorption method. Further, during the continuous plating, when the roll on the plating outlet side was observed, Sn adhesion was not observed even when the foil was fed through 4700 m, but corrosion was observed in the salt spray test (Z2371).
- ⁇ Comparative example 2> Exactly the same as Example 1 except that the plating thickness was 1.5 ⁇ m and a brightener (paraaldehyde 12 ml / L, naphthaldehyde 0.2 ml / L) was added to the Sn plating bath to obtain a current density of 13 A / dm 2. Then, continuous plating was performed. The size of the electrodeposited grains of the obtained Sn plating film was 0.8 ⁇ m, and the hardness of the Sn plating was 580 MPa. It was 0.10 mass% when the amount of carbon in Sn plating film was measured using the high frequency induction heating infrared absorption method. Further, when the roll on the plating outlet side was observed during continuous plating, Sn adhesion was noticeably observed on the roll when 3000 m was passed through. The corrosion resistance evaluation was a good result.
- a brightener paraaldehyde 12 ml / L, naphthaldehyde 0.2 ml /
- Example 3 Exactly the same as Example 1 except that the plating thickness was 1.5 ⁇ m, and a brightener (paraaldehyde 12 ml / L, naphthaldehyde 0.2 ml / L) was added to the Sn plating bath to obtain a current density of 7 A / dm 2. Then, continuous plating was performed. The size of the electrodeposited grains of the obtained Sn plating film was 1.0 ⁇ m, and the hardness of the Sn plating was 505 MPa. It was 0.10 mass% when the amount of carbon in Sn plating film was measured using the high frequency induction heating infrared absorption method. Further, when the roll on the plating outlet side was observed during continuous plating, Sn adhesion was noticeably observed on the roll when 3500 m was passed through. The corrosion resistance evaluation was a good result.
- a brightener paraaldehyde 12 ml / L, naphthaldehyde 0.2 ml / L
- Example 4 Except that methanol (100 mg / L) was added to the Sn plating bath, the same evaluation as in Example 7 was performed after electroplating until 40000 m was passed in the same manner as in Example 7. ( However, the presence or absence of Sn adhesion to the roll was not evaluated.) However, corrosion was observed in the salt spray test (Z2371), and the corrosion resistance deteriorated. Further, regarding the sample of Comparative Example 4, when the surface of the plating film was observed with a scanning electron microscope at a magnification of 1000 times, reflected electron images having brightness different from Sn were scattered in the reflected electron images of Sn. From this, it is considered that a composition different from that of the Sn plating film exists on the surface of the plating film, a defect of the plating film occurs, and the copper foil as the base is exposed.
- Example 7 which does not contain methanol in the plating bath, even if plating was performed for a longer period (40000 m), the plating film was not defective, and the corrosion resistance was good.
- Comparative Example 4 containing 100 mg / L of methanol in the plating bath, when plating was performed for a long time (40000 m), defects were generated in the plating film, and the corrosion resistance was deteriorated.
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Abstract
Description
上記の複合材料としては、銅又は銅合金箔を基材とする電磁波シールド材料等の複合材料として、銅箔又は銅合金箔の一方の面に樹脂層又はフィルムを積層し、他の面にSnめっき被膜を形成した構造が用いられている。
また、近年、コネクター等の用途において、耐摩耗性・挿抜性の観点からSnめっき被膜を硬くすることが望まれており、Snめっき表層のヌープ硬度Hkを規定した技術が開示されている(特許文献1参照)。 The Sn plating film is characterized by excellent corrosion resistance, good solderability and low contact resistance. For this reason, for example, Sn plating is used for metal foils, such as copper, as a composite material of a vehicle-mounted electromagnetic wave shielding material.
As the above composite material, as a composite material such as an electromagnetic shielding material based on copper or copper alloy foil, a resin layer or a film is laminated on one surface of copper foil or copper alloy foil, and Sn is formed on the other surface. A structure in which a plating film is formed is used.
In recent years, in applications such as connectors, it has been desired that the Sn plating film be hardened from the viewpoint of wear resistance and insertion / removability, and a technique for defining the Knoop hardness Hk of the Sn plating surface layer has been disclosed (patent). Reference 1).
例えば、めっき液に光沢剤を加えて光沢Snめっきを行い、Sn粒子をできるだけ小さくする技術が開示されている(特許文献2参照)。
一方、Snめっきには,その内部応力や外部応力によって,ウィスカとよばれるひげ状結晶が発生する。これを防止するために,めっき時に光沢剤を極端に減らして,内部応力を低下することが知られている。しかし,この方法によっても外部応力に伴うウィスカ発生を防止することは難しい。このため、電気めっき浴中の光沢剤を減らすと共にメタノールを添加し、Snめっき皮膜に空隙を持たせて,めっき後に曲げ加工や打ち抜き加工等で発生する外部応力を緩和する技術が開示されている。(特許文献3参照) Sn plating on copper or copper alloy foil is usually performed by wet plating, but in order to improve the stability of the plating film (the color must be uniform and free of color spots and patterns) and the wear resistance of the Sn plating film In many cases, bright Sn plating is performed by adding an additive to the plating solution.
For example, a technique is disclosed in which a brightening agent is added to a plating solution to perform bright Sn plating to make Sn particles as small as possible (see Patent Document 2).
On the other hand, whisker-like crystals called whiskers are generated in Sn plating due to internal stress and external stress. In order to prevent this, it is known that the internal stress is reduced by extremely reducing the brightening agent during plating. However, it is difficult to prevent whisker generation due to external stress even by this method. For this reason, a technique has been disclosed in which the brightener in the electroplating bath is reduced and methanol is added to create a void in the Sn plating film to relieve external stress generated by bending or punching after plating. . (See Patent Document 3)
このような不具合が発生する理由は不明であるが、端子やコネクター等の場合にはSnめっきが硬いほうが挿抜性がよいことから、Snめっきが硬いとSnの接する面同士のすべり性が良くなることが考えられる。すなわち、Snめっきが硬い場合には、ロールと金属箔上のSnめっき表面とのスリップが起こりやすく、仮にスリップが生じ始めると摩擦熱等によりSnめっきがロールに凝着しやすくなり、Snめっきの付着が見られるものと考えられる。
また、光沢剤の有機物がSn被膜に共析して、めっきが脆くなり、脱落し易くなることも考えられる。 However, when hard Sn plating (for example, normal bright Sn plating) is performed on a metal foil such as copper or copper alloy foil in a continuous line, there is a problem that the surface of the Sn plating is rubbed and transferred and adhered to the roll. When plating adheres to the roll surface, the productivity during plating is reduced by cleaning the roll, etc., and when the adhesion of plating is extremely severe, the Sn plating film becomes thin, leading to a reduction in the corrosion resistance of the resulting composite material. This is a problem that cannot be ignored because there is a fear.
The reason why such a defect occurs is unknown, but in the case of terminals, connectors, etc., the harder the Sn plating, the better the insertion / extraction, so the harder the Sn plating, the better the slipperiness between the Sn contact surfaces. It is possible. That is, when the Sn plating is hard, slippage between the roll and the Sn plating surface on the metal foil is likely to occur, and if slip begins to occur, the Sn plating tends to adhere to the roll due to frictional heat or the like. It is thought that adhesion is seen.
It is also conceivable that the organic material of the brightener co-deposits on the Sn coating, making the plating brittle and easy to fall off.
このようなSnめっきの付着は,めっき工程以降にロールを用いた連続工程がある場合にも同様である。たとえば,Snめっき後にストリップを所望の幅にスリットする工程がこれにあたる。 Furthermore, when passing a metal foil through a continuous line, it is considered that the above-described slip is more likely to occur. That is, since the copper foil is thin, its strength is low, and folding and wrinkling are likely to occur when passing through a continuous line such as Sn plating, laminator, and slitter. Therefore, when used as a shielding material, it is common to first paste a resin or film on a copper foil and then perform Sn plating, but even a copper foil with such a resin or film attached When the tension applied to the strip is increased during continuous line passing, folding and wrinkles are likely to occur. Therefore, in order to stably prevent the occurrence of folds and wrinkles, it is desirable to pass the plate with a low tension. On the other hand, when the tension applied to the strip decreases, the contact pressure between the roll and the strip decreases, and the roll And slip easily between strips. Therefore, the adhesion of Sn plating is more likely to occur.
Such adhesion of Sn plating is the same when there is a continuous process using a roll after the plating process. For example, this is the process of slitting the strip to the desired width after Sn plating.
これは、めっき浴中のメタノールが電解によってホルムアルデヒドに変化し、このホルムアルデヒドが正常なSnの析出を阻害し、めっき被膜の欠陥をもたらすためと考えられる。そして、下地が露出すると、下地(金属箔)の耐食性が低下する不具合が生じる。 On the other hand, Patent Document 3 describes that the hardness of the Sn plating film is 400 MPa or less in order to make it less susceptible to external stress. However, the technique described in Patent Document 3 is a plating film with many voids because it contains a high concentration of methanol in the plating bath, and if the electrolysis is continued for a long time, a large defect (exposure of the ground) occurs in the Sn plating film. It has been clarified by the inventors' investigation.
This is presumably because methanol in the plating bath is converted into formaldehyde by electrolysis, which inhibits normal Sn deposition and causes defects in the plating film. And if the foundation | substrate is exposed, the malfunction which the corrosion resistance of a foundation | substrate (metal foil) falls will arise.
Sn又はSn合金めっき被膜の厚みが0.5μm以上であることが好ましい。又、Sn又はSn合金めっき被膜の厚みが2.0μm未満であることが好ましい。
Sn又はSn合金めっき被膜が連続めっきによって形成されていることが好ましい。 Furthermore, it is preferable that the carbon content in the Sn or Sn alloy plating film is 0.01% by mass or less.
The thickness of the Sn or Sn alloy plating film is preferably 0.5 μm or more. Moreover, it is preferable that the thickness of Sn or Sn alloy plating film is less than 2.0 micrometers.
The Sn or Sn alloy plating film is preferably formed by continuous plating.
本発明において、Sn又はSn合金めっき被膜の表面を走査電子顕微鏡で観察したとき、「銅箔又は銅合金箔が露出しない」とは、Sn又はSn合金めっき被膜の反射電子像と異なる輝度の反射電子像が通常の倍率(例えば、1000倍程度)で観察されず、一様な輝度の反射電子像が得られることをいう。
又、Sn又はSn合金めっき被膜の厚みは、Sn又はSn合金めっき被膜の平均的なマクロな厚みであり、めっき被膜を電解して完全に溶解したときの電気量から求める。
また、Snめっき被膜内の炭素量分析方法は、高周波誘導加熱赤外線吸収法を用いて行うことができる。この方法は、Snめっきした試料を酸素雰囲気中で加熱溶解させ、試料中の炭素と雰囲気の酸素を反応させ、該雰囲気中の二酸化炭素量を測定することにより、炭素量を算出する。Snめっき被膜内の炭素量はめっき被膜をあらかじめ取り除いた試料(めっき基材)をブランクとし、Snめっき被膜付の試料との差で求める。 In the present invention, the Sn plating hardness is an indentation hardness with a maximum load of 1 mN in an ultra-micro hardness test measured in accordance with ISO 14577-1 2002-10-01
In the present invention, when the surface of the Sn or Sn alloy plating film is observed with a scanning electron microscope, “the copper foil or copper alloy foil is not exposed” means that the reflected electron image of the Sn or Sn alloy plating film has a luminance different from that of the reflected electron image. It means that an electron image is not observed at a normal magnification (for example, about 1000 times), and a reflected electron image having a uniform luminance is obtained.
The thickness of the Sn or Sn alloy plating film is an average macro thickness of the Sn or Sn alloy plating film, and is obtained from the amount of electricity when the plating film is electrolyzed and completely dissolved.
Moreover, the carbon content analysis method in Sn plating film can be performed using the high frequency induction heating infrared absorption method. In this method, a Sn-plated sample is heated and dissolved in an oxygen atmosphere, carbon in the sample is reacted with oxygen in the atmosphere, and the amount of carbon dioxide in the atmosphere is measured to calculate the amount of carbon. The amount of carbon in the Sn plating film is determined by the difference from the sample with the Sn plating film, with the sample (plating base material) from which the plating film has been removed beforehand being used as a blank.
材料の軽薄化の観点から、複合材料の厚みは0.1mm以下であることが好ましい。 The composite material which concerns on embodiment of this invention is the copper foil (or copper alloy foil) 1, the resin layer (or film) 4 laminated | stacked on one surface of the copper foil (or copper alloy foil) 1, and copper It consists of
From the viewpoint of reducing the material thickness, the thickness of the composite material is preferably 0.1 mm or less.
銅箔(又は銅合金箔)の厚みは特に制限されないが、シールド材として使用する場合、例えば5~50μmのものを好適に用いることができる。
なお、銅箔(又は銅合金箔)としては、電解箔よりも高強度の圧延箔を用いることが好ましい。
又、銅箔(又は銅合金箔)の表面粗さは、厚み5~50μmの場合、中心線平均粗さで0.3μm以下が好ましく、さらに0.2μm以下のものを用いることが好ましい。 As the copper foil, tough pitch copper having a purity of 99.9% or more, oxygen-free copper, and as the copper alloy foil, a known copper alloy can be used depending on required strength and conductivity. Known copper alloys include, for example, 0.01 to 0.3% tin-containing copper alloys and 0.01 to 0.05% silver-containing copper alloys. -0.12% Sn and Cu-0.02% Ag are often used.
The thickness of the copper foil (or copper alloy foil) is not particularly limited, but when used as a shielding material, for example, a thickness of 5 to 50 μm can be suitably used.
In addition, as copper foil (or copper alloy foil), it is preferable to use a rolled foil having higher strength than electrolytic foil.
Further, when the thickness of the copper foil (or copper alloy foil) is 5 to 50 μm, the center line average roughness is preferably 0.3 μm or less, more preferably 0.2 μm or less.
樹脂層やフィルムの厚みは特に制限されないが、例えば5~50μmのものを好適に用いることができる。又、接着剤を用いた場合、接着層の厚みは例えば10μm以下とすることができる。 As the resin layer, for example, a resin such as polyimide can be used, and as the film, for example, a film of PET (polyethylene terephthalate) or PEN (polyethylene naphthalate) can be used. The resin layer or film may be bonded to the copper foil (or copper alloy foil) with an adhesive, but the molten resin is cast on the copper foil (copper alloy foil) without using the adhesive, or the film is made of copper. You may make it thermocompression-bond to foil (copper alloy foil).
The thickness of the resin layer or film is not particularly limited, but for example, a thickness of 5 to 50 μm can be suitably used. When an adhesive is used, the thickness of the adhesive layer can be set to 10 μm or less, for example.
これは、めっき浴中のメタノールが電解によってホルムアルデヒドに変化し、このホルムアルデヒドが正常なSnの析出を阻害し、めっき被膜の欠陥をもたらすためと考えられる。そして、下地が露出すると、下地(銅箔又は銅合金箔)の耐食性が低下する不具合が生じる。めっき被膜に欠陥を与えるための電解時間はめっき条件によって変化するが、電解時間の合計が多くなるほど、メタノールが変化したホルムアルデヒドがめっき浴中に蓄積し、下地が露出するめっき欠陥が発生し易くなる。
なお、めっき浴中に「メタノールを含有しない」とは、めっき浴中のメタノール濃度が不純物レベル(通常は、数ppm(数mg/L)以下、例えば5mg/L以下)であることをいう。 In the present invention, the Sn or Sn alloy plating film is formed from an Sn or Sn alloy electroplating bath not containing methanol. When methanol is contained in the plating bath, defects (exposure of the base) occur in the plating film when electrolysis is continued for a long time.
This is presumably because methanol in the plating bath is converted into formaldehyde by electrolysis, which inhibits normal Sn deposition and causes defects in the plating film. And when a foundation | substrate is exposed, the malfunction which the corrosion resistance of a foundation | substrate (copper foil or copper alloy foil) falls arises. The electrolysis time for giving defects to the plating film varies depending on the plating conditions, but as the total electrolysis time increases, the formaldehyde in which methanol has changed accumulates in the plating bath, and plating defects that expose the substrate are more likely to occur. .
Note that “not containing methanol” in the plating bath means that the methanol concentration in the plating bath is at an impurity level (usually several ppm (several mg / L) or less, for example, 5 mg / L or less).
なお、Sn又はSn合金めっき被膜の厚みが1.5μmを超える場合、粗雑なめっき粒が下地の露出部分(めっき欠陥部分)を覆う場合があるため(但し、下地を完全に被覆しているわけではない)、めっき被膜の表面を走査電子顕微鏡で観察すると、露出しているはずの下地の反射電子像が得られないことがある。この場合も実際には下地が露出して耐食性が劣ることから、下地の露出の有無を正確に判定するため、めっき被膜の厚みを1.5μmに減じて走査電子顕微鏡で観察することとする。
めっき被膜の厚みを1.5μmに減じる方法としては、FIB(集束イオンビーム)によりめっき被膜の断面を作製する方法や、めっき被膜の厚みを1.5μmにするための、めっき金属(又は合金)の減量を求めておき、めっき被膜を電解したときの溶解量がこの減量に一致するよう電解時の電気量を設定する方法がある。 By plating using a Sn or Sn alloy electroplating bath that does not contain methanol, when the surface of the plating film is observed with a scanning electron microscope, the base (copper foil or copper alloy foil) is not exposed, and there is no defect. A film is obtained. In this case, when the surface of the plating film is observed with a scanning electron microscope, a reflected electron image having a luminance different from that of the reflected electron image of the plating film is not observed at a normal magnification (for example, about 1000 times). An electronic image is obtained. That is, the composition different from the plating film is not detected from the surface of the plating film, and the base (copper foil or copper alloy foil) is not exposed.
If the thickness of the Sn or Sn alloy plating film exceeds 1.5 μm, coarse plating grains may cover the exposed part of the base (plating defect part) (however, the base is completely covered). However, when the surface of the plating film is observed with a scanning electron microscope, the reflected electron image of the ground which should be exposed may not be obtained. Also in this case, since the base is actually exposed and the corrosion resistance is inferior, in order to accurately determine whether the base is exposed or not, the thickness of the plating film is reduced to 1.5 μm and observed with a scanning electron microscope.
As a method of reducing the thickness of the plating film to 1.5 μm, a method of producing a cross section of the plating film by FIB (focused ion beam), or a plating metal (or alloy) for reducing the thickness of the plating film to 1.5 μm. There is a method in which the amount of electricity at the time of electrolysis is set so that the amount of dissolution when electrolyzing the plating film coincides with this amount of reduction.
Sn又はSn合金めっき被膜のめっきの硬さの下限を特に限定する理由はないが、溶融凝固したSn又はSn合金の硬さ以下にはなりえず、本発明では、100MPaを下限とする。 The hardness of the Sn or Sn alloy plating film is 500 MPa or less. When the hardness of the Sn or Sn alloy plating film is 500 MPa or less, slip between the Sn or Sn alloy plating surface and the roll is reduced during Sn or Sn alloy plating, and the adhesion of Sn or Sn alloy plating is lost. Further, when the obtained composite material is used for an electromagnetic shielding material such as a cable, the adhesion of Sn or Sn alloy to the roll or die during processing is not seen, and the productivity can be improved. And when processing the obtained composite material, the powder fall of Sn or Sn alloy plating film does not arise, and adhesiveness does not fall.
There is no reason to specifically limit the lower limit of the plating hardness of the Sn or Sn alloy plating film, but it cannot be less than the hardness of the melted and solidified Sn or Sn alloy. In the present invention, the lower limit is 100 MPa.
また、Sn又はSn合金めっき被膜内の炭素量分析方法は、高周波誘導加熱赤外線吸収法を用いて行うことができる。この方法は、Sn又はSn合金めっきした試料を酸素雰囲気中で加熱溶解させ、試料中の炭素と雰囲気の酸素を反応させ、該雰囲気中の二酸化炭素量を測定することにより、炭素量を算出する。Sn又はSn合金めっき被膜内の炭素量はめっき被膜をあらかじめ取り除いた試料(めっき基材)をブランクとし、Sn又はSn合金めっき被膜付の試料との差で求める。 Further, the carbon content in the Sn or Sn alloy plating film is preferably 0.01% by mass or less, and more preferably 0.006% by mass or less. If the amount of carbon in the Sn or Sn alloy plating film exceeds 0.01% by mass, even if the Sn plating film has a hardness of 500 MPa or less, the film is brittle and Sn tends to adhere to the roll.
Moreover, the carbon content analysis method in Sn or Sn alloy plating film can be performed using the high frequency induction heating infrared absorption method. In this method, a sample plated with Sn or Sn alloy is heated and dissolved in an oxygen atmosphere, the carbon in the sample is reacted with oxygen in the atmosphere, and the amount of carbon dioxide in the atmosphere is measured to calculate the amount of carbon. . The amount of carbon in the Sn or Sn alloy plating film is determined by the difference from the sample with the Sn or Sn alloy plating film, with the sample (plating base material) from which the plating film has been removed beforehand being used as a blank.
Sn又はSn合金めっき被膜の厚みの上限は、Sn又はSn合金めっきの製造条件等によって変化するので特に制限されないが、2μm以上にSn又はSn合金めっきを厚くしても耐食性、はんだ付け性の更なる向上はみられず、逆に、Sn又はSn合金めっき代を増加させる、生産性を低下させる等の不具合もある。従って、Snめっき被膜の厚みが0.5μm以上2μm未満であることが好ましい。 The thickness of the Sn or Sn alloy plating film is preferably 0.5 μm or more. When the thickness is less than 0.5 μm, the corrosion resistance and solderability may deteriorate.
The upper limit of the thickness of the Sn or Sn alloy plating film is not particularly limited because it varies depending on the manufacturing conditions of the Sn or Sn alloy plating, etc. Even if the Sn or Sn alloy plating is thickened to 2 μm or more, the corrosion resistance and solderability are further improved. However, there are also problems such as increasing the Sn or Sn alloy plating allowance and reducing productivity. Therefore, it is preferable that the thickness of the Sn plating film is 0.5 μm or more and less than 2 μm.
試験モード:負荷-除荷試験(最大荷重まで押し込んだ後、除荷する)
最大荷重:1mN
測定温度:32±1℃
硬さの値は5箇所の平均値とする。
本方法で測定できる押し込み硬さは被膜厚さの影響を受ける。すなわち、被膜が厚いほど被膜そのものの硬さとなり、被膜が薄いほど下地金属である、CuやCu-Snの金属間化合物の硬さの影響を受ける。しかし、本発明で問題にするのは表層の「みかけ硬さ」であり、これが柔らかく測定される場合にロールとのスリップを起こさない。その指標として、上記条件での硬さ測定結果が有効である。
めっき被膜の厚みは蛍光X線膜厚計で測定し、5箇所の平均値をめっき層の厚みとする The hardness of the Sn or Sn alloy plating film is an indentation hardness with a maximum load of 1 mN in an ultra micro hardness test measured in accordance with ISO (International Organization for Standardization) 14477-1 2002-10-01
Test mode: Load-unloading test (unload after pushing to maximum load)
Maximum load: 1mN
Measurement temperature: 32 ± 1 ℃
The hardness value is an average value of five locations.
The indentation hardness that can be measured by this method is affected by the film thickness. That is, the thicker the film, the harder the film itself, and the thinner the film, the influence of the hardness of the intermetallic compound of Cu or Cu—Sn, which is the base metal. However, what is a problem in the present invention is the “apparent hardness” of the surface layer, and when this is measured softly, it does not slip with the roll. As the index, the result of hardness measurement under the above conditions is effective.
The thickness of the plating film is measured with a fluorescent X-ray film thickness meter, and the average value of the five points is defined as the thickness of the plating layer.
Sn又はSn合金めっき浴の基剤としては、フェノールスルホン酸、硫酸、メタンスルホン酸等を挙げることができる。
電着粒の大きさは、めっき条件において、電流密度を低く、浴中のSn濃度を高く、浴温度を高くすることで調整できる。例えば電流密度2~12A/dm2、Sn濃度30~60g/L、浴温30~60℃とするで、粒状の電着Sn(又はSn合金)を銅箔面に均一に電着させることができるが、装置によって異なるので特に限定されない。
また、Sn又はSn合金めっき被膜中の炭素量は、光沢剤の種類や界面活性剤の種類や、めっき条件によって変化する。光沢剤の場合、ほとんどがSn又はSn合金めっき被膜中の炭素量を増加させ、0.01質量%を超えることが多い。しかし、光沢剤を極わずかしか添加しなかったり、めっき条件の電流密度を低く、Sn濃度を高く、温度を高くしたりして、被膜中の炭素量を低減できる場合もある。
めっき液に界面活性剤のみを添加した場合には被膜中の炭素量は、0.01質量%以下になることが多い。ただし、めっき液への界面活性剤の添加量が多かったり、Snに吸着しやすい構造の界面活性剤であったりすると、被膜中の炭素量は増加するので、適宜界面活性剤を選択する。 A more specific method will be described below.
Examples of the base of the Sn or Sn alloy plating bath include phenolsulfonic acid, sulfuric acid, methanesulfonic acid and the like.
The size of the electrodeposited grains can be adjusted by reducing the current density, increasing the Sn concentration in the bath, and increasing the bath temperature under plating conditions. For example, when the current density is 2 to 12 A / dm 2 , the Sn concentration is 30 to 60 g / L, and the bath temperature is 30 to 60 ° C., the granular electrodeposited Sn (or Sn alloy) can be uniformly electrodeposited on the copper foil surface. Yes, but it is not particularly limited because it varies depending on the device.
Further, the amount of carbon in the Sn or Sn alloy plating film varies depending on the type of brightener, the type of surfactant, and the plating conditions. Most brighteners increase the amount of carbon in the Sn or Sn alloy plating film and often exceed 0.01% by weight. However, in some cases, the amount of carbon in the coating can be reduced by adding very little brightener, reducing the current density under plating conditions, increasing the Sn concentration, and increasing the temperature.
When only a surfactant is added to the plating solution, the amount of carbon in the coating is often 0.01% by mass or less. However, if the amount of the surfactant added to the plating solution is large, or if the surfactant has a structure that is easily adsorbed to Sn, the amount of carbon in the coating increases. Therefore, the surfactant is appropriately selected.
得られたSnめっき被膜は、光沢剤を用いずに得られ、電着粒の大きさはJIS H0501切断法(2007年版)により1.0μmであった。
なお、電着粒の大きさの測定方法は以下のとおりである。Snめっき被膜表面から5000倍の倍率の走査型電子顕微鏡像を撮影した。この画像の粒子状の境界を電着粒界として、JIS H0501切断法(2007年版)により、画像の横3箇所、縦3箇所の計6箇所の電着粒界の数を数え、電着粒の大きさを求めた。又、測定箇所は,測定誤差を低減するため、10×10mm程度の試料内で電着粒の大きさを測定し、平均した。
Snめっきの硬さは、470MPaであった。なお、めっき表面からの超微小硬さ試験による最大荷重1mNでの硬さを測定し、測定機器はエリオニクス製ENT-2100とし、圧子にバーコビッチ圧子(ダイヤモンド三角錐圧子)を用い、測定条件は、試験モード:負荷-除荷試験(最大荷重まで押し込んだ後、除荷する)、測定温度:32±1℃とした。硬さの値は5回の測定の平均値とした。
Snめっき被膜中の炭素量を、高周波誘導加熱赤外線吸収法を用いて測定したところ、0.005質量%であった。
又、連続めっき中、めっき出側のロールを観察したところ、4700m通箔してもロールにSn付着が見られなかった。
さらに、耐食性評価として塩水噴霧試験(Z2371)(温度:35℃、塩水濃度:5%(塩化ナトリウム)、噴霧圧力:98±10kPa、噴霧時間:480h)を行い、良好な結果を得た。 A strip of a tough pitch copper foil (thickness 7.3 μm) of 99.9% or more copper bonded to a 12.5 μm thick PET film and a thermoplastic adhesive was used as a strip. This strip was electroplated in a continuous plating cell facing the tin anode. A phenolsulfonic acid bath was used as a plating bath, and 10 g / L of a surfactant (EN) and tin oxide were added to obtain a Sn concentration of 32 to 40 g / L. The plating conditions were a bath temperature of 45 to 55 ° C., a current density of 10 A / dm 2 , and a plating thickness of 1.5 μm.
The obtained Sn plating film was obtained without using a brightener, and the size of the electrodeposited grains was 1.0 μm by JIS H0501 cutting method (2007 version).
In addition, the measuring method of the magnitude | size of an electrodeposition grain is as follows. A scanning electron microscope image at a magnification of 5000 times was taken from the surface of the Sn plating film. Using the grain boundary of this image as the electrodeposition grain boundary, count the number of electrodeposition grain boundaries at a total of 6 locations, 3 in the horizontal direction and 3 in the vertical direction, using the JIS H0501 cutting method (2007 version). The size of was calculated. In order to reduce measurement errors, the measurement locations were measured by averaging the size of the electrodeposited grains in a sample of about 10 × 10 mm.
The hardness of the Sn plating was 470 MPa. In addition, the hardness at the maximum load of 1 mN from the plated surface is measured, the measuring instrument is ENT-2100 made by Elionix, and Barcovich indenter (diamond triangular pyramid indenter) is used as the indenter. , Test mode: Load-unloading test (unloading after pushing to maximum load), measuring temperature: 32 ± 1 ° C. The hardness value was an average value of five measurements.
It was 0.005 mass% when the carbon content in Sn plating film was measured using the high frequency induction heating infrared absorption method.
In addition, when the roll on the plating outlet side was observed during continuous plating, Sn adhesion was not observed on the roll even when 4700 m was fed.
Further, as a corrosion resistance evaluation, a salt spray test (Z2371) (temperature: 35 ° C., salt water concentration: 5% (sodium chloride), spray pressure: 98 ± 10 kPa, spray time: 480 h) was performed, and good results were obtained.
得られたSnめっき被膜は、光沢剤を用いずに得られ、電着粒の大きさは1.0μmであり、Snめっきの硬さは、480MPaであった。
Snめっき被膜中の炭素量を、高周波誘導加熱赤外線吸収法を用いて測定したところ、0.007質量%であった。
又、連続めっき中、めっき出側のロールを観察したところ、4700m通箔してもロールにSn付着が見られなかった。また、耐食性評価も良好な結果であった。 Continuous plating was performed in exactly the same manner as in Example 1 except that the plating thickness was 0.5 μm.
The obtained Sn plating film was obtained without using a brightener, the size of the electrodeposited grains was 1.0 μm, and the hardness of the Sn plating was 480 MPa.
It was 0.007 mass% when the carbon content in Sn plating film was measured using the high frequency induction heating infrared absorption method.
In addition, when the roll on the plating outlet side was observed during continuous plating, Sn adhesion was not observed on the roll even when 4700 m was fed. Moreover, corrosion resistance evaluation was also a favorable result.
Snめっき被膜は、光沢剤を用いずに得られ、電着粒の大きさは2.0μmであり、Snめっきの硬さは、450MPaであった。
Snめっき被膜中の炭素量を、高周波誘導加熱赤外線吸収法を用いて測定したところ、0.004質量%であった。
又、連続めっき中、めっき出側のロールを観察したところ、4700m通箔してもロールにSn付着が見られなかった。また、耐食性評価も良好な結果であった。
なお、電着粒の大きさがめっき厚より大きいのは、電着粒をめっき表面から観察したためであり、電着粒が扁平状であることを示す。 Continuous plating was performed in the same manner as in Example 1 except that the plating thickness was 1.9 μm and the current density was 7 A / dm 2 .
The Sn plating film was obtained without using a brightener, the size of the electrodeposited grains was 2.0 μm, and the hardness of the Sn plating was 450 MPa.
It was 0.004 mass% when the carbon content in Sn plating film was measured using the high frequency induction heating infrared absorption method.
In addition, when the roll on the plating outlet side was observed during continuous plating, Sn adhesion was not observed on the roll even when 4700 m was fed. Moreover, corrosion resistance evaluation was also a favorable result.
The reason why the size of the electrodeposited grains is larger than the plating thickness is that the electrodeposited grains were observed from the plating surface, indicating that the electrodeposited grains are flat.
得られたSnめっき被膜は、光沢剤を用いずに得られ、電着粒の大きさは2.5μmであり、Snめっきの硬さは、425MPaであった。
Snめっき被膜中の炭素量を、高周波誘導加熱赤外線吸収法を用いて測定したところ、0.003質量%であった。
又、連続めっき中、めっき出側のロールを観察したところ、4700m通箔してもロールにSn付着が見られなかった。また、耐食性評価も良好な結果であった。 Continuous plating was performed in exactly the same manner as in Example 1 except that the plating thickness was 1.9 μm and the current density was 5 A / dm 2 .
The obtained Sn plating film was obtained without using a brightener, the size of the electrodeposited grains was 2.5 μm, and the hardness of the Sn plating was 425 MPa.
It was 0.003 mass% when the carbon content in Sn plating film was measured using the high frequency induction heating infrared absorption method.
In addition, when the roll on the plating outlet side was observed during continuous plating, Sn adhesion was not observed on the roll even when 4700 m was fed. Moreover, corrosion resistance evaluation was also a favorable result.
得られたSnめっき被膜は、光沢剤を用いずに得られ、電着粒の大きさは2.5μmであり、Snめっきの硬さは、475MPaであった。
Snめっき被膜中の炭素量を、高周波誘導加熱赤外線吸収法を用いて測定したところ、0.01質量%であった。
又、連続めっき中、めっき出側のロールを観察したところ、4700m通箔してもロールにSn付着が見られなかった。また、耐食性評価も良好な結果であった。 A strip of a tough pitch copper foil (thickness 7.3 μm) of 99.9% or more copper bonded to a 12.5 μm thick PET film and a thermoplastic adhesive was used as a strip. This strip was electroplated in a continuous plating cell facing the tin anode. A phenolsulfonic acid bath was used as a plating bath, and 10 g / L of a surfactant (EN) and tin oxide were added to obtain a Sn concentration of 32 to 40 g / L. The plating conditions were such that the bath temperature was 55 to 65 ° C., the current density was 10 A / dm 2 , the bath temperature was high, and the plating thickness was 1.9 μm.
The obtained Sn plating film was obtained without using a brightener, the size of the electrodeposited grains was 2.5 μm, and the hardness of the Sn plating was 475 MPa.
It was 0.01 mass% when the carbon content in Sn plating film was measured using the high frequency induction heating infrared absorption method.
In addition, when the roll on the plating outlet side was observed during continuous plating, Sn adhesion was not observed on the roll even when 4700 m was fed. Moreover, corrosion resistance evaluation was also a favorable result.
得られたSnめっき被膜の電着粒の大きさは1.0μmであり、硬さは495MPaであった。Snめっき被膜中の炭素量を、高周波誘導加熱赤外線吸収法を用いて測定したところ、0.02質量%であった。
連続めっき中、めっき出側のロールを観察したところ、4000m通箔したところでロールにSn付着が見られた。耐食性は良好であった。 A strip was obtained by bonding a PET film having a thickness of 12.5 μm to one surface of a tough pitch copper foil (thickness: 7.3 μm) of 99.9% or more copper using a thermoplastic adhesive. This strip was electroplated in a continuous plating cell facing the tin anode. A phenolsulfonic acid bath was used as a plating bath, and a surfactant EN10 g / L, a brightener (paraaldehyde 5 ml / L, naphthaldehyde 0.1 ml / L) and tin oxide were added to obtain a Sn concentration of 32 to 40 g / L. . The plating conditions were a bath temperature of 45 to 55 ° C., a current density of 10 A / dm 2 , and a plating thickness of 1.5 μm.
The size of the electrodeposited grains of the obtained Sn plating film was 1.0 μm, and the hardness was 495 MPa. It was 0.02 mass% when the carbon content in Sn plating film was measured using the high frequency induction heating infrared absorption method.
During continuous plating, when the roll on the plating outlet side was observed, Sn adhesion was observed on the roll when the foil passed through 4000 m. Corrosion resistance was good.
なお、実施例1~7の試料につき、めっき被膜の表面を走査電子顕微鏡で倍率1000倍で観察したところ、Snの反射電子像のみが一様に観察され、Snと異なる輝度の反射電子像が検出されなかった。このことより、Snめっき被膜と異なる組成がめっき被膜表面に存在せず、下地である銅箔が露出していないものと考えられる。 Under the conditions of Example 1, after electroplating until 40000m was passed, the same evaluation as in Example 1 was performed (however, the presence or absence of Sn adhesion to the roll was not evaluated), but the corrosion resistance was good. Met.
For the samples of Examples 1 to 7, when the surface of the plating film was observed with a scanning electron microscope at a magnification of 1000 times, only a reflected electron image of Sn was observed uniformly, and a reflected electron image having a luminance different from that of Sn was observed. Not detected. From this, it is considered that the composition different from the Sn plating film does not exist on the surface of the plating film, and the copper foil as the base is not exposed.
得られたSnめっきは、光沢剤を用いずに得られ、電着粒の大きさは1.0μmであり、Snめっきの硬さは、495MPaであった。
Snめっき被膜中の炭素量を、高周波誘導加熱赤外線吸収法を用いて測定したところ、0.005質量%であった。
又、連続めっき中、めっき出側のロールを観察したところ、4700m通箔してもロールにSn付着が見られなかったが、塩水噴霧試験(Z2371)で腐食が見られた。 Implemented except that a 12.5 μm thick PET film was bonded to one side of a 99.9% or more copper tough pitch copper foil (thickness 7.3 μm) using a urethane adhesive and the plating thickness was 0.4 μm. Continuous plating was performed exactly as in Example 1.
The obtained Sn plating was obtained without using a brightener, the size of the electrodeposited grains was 1.0 μm, and the hardness of the Sn plating was 495 MPa.
It was 0.005 mass% when the carbon content in Sn plating film was measured using the high frequency induction heating infrared absorption method.
Further, during the continuous plating, when the roll on the plating outlet side was observed, Sn adhesion was not observed even when the foil was fed through 4700 m, but corrosion was observed in the salt spray test (Z2371).
めっき厚を1.0μmとし、Snめっき浴中に光沢剤(パラアルデヒド12ml/L、ナフトアルデヒド0.2ml/L)を添加したこと以外は実施例1とまったく同様にして連続めっきを行った。
得られたSnめっき被膜の電着粒の大きさは、0.9μmであった。Snめっきの硬さは、550MPaであった。
Snめっき被膜中の炭素量を、高周波誘導加熱赤外線吸収法を用いて測定したところ、0.05質量%であった。
又、連続めっき中、めっき出側のロールを観察したところ3000m通箔した時点でロールにSn付着が顕著に見られた。耐食性評価は良好な結果であった。 <Comparative Example 1>
Continuous plating was performed in exactly the same manner as in Example 1 except that the plating thickness was 1.0 μm and a brightener (paraaldehyde 12 ml / L, naphthaldehyde 0.2 ml / L) was added to the Sn plating bath.
The size of the electrodeposited grains of the obtained Sn plating film was 0.9 μm. The hardness of the Sn plating was 550 MPa.
It was 0.05 mass% when the carbon amount in Sn plating film was measured using the high frequency induction heating infrared absorption method.
Further, when the roll on the plating outlet side was observed during continuous plating, Sn adhesion was noticeably observed on the roll when 3000 m was passed through. The corrosion resistance evaluation was a good result.
めっき厚を1.5μmとし、Snめっき浴中に光沢剤(パラアルデヒド12ml/L、ナフトアルデヒド0.2ml/L)を添加し、電流密度13A/dm2としたこと以外は実施例1とまったく同様にして連続めっきを行った。
得られたSnめっき被膜の電着粒の大きさは、0.8μmであり、Snめっきの硬さは、580MPaであった。
Snめっき被膜中の炭素量を、高周波誘導加熱赤外線吸収法を用いて測定したところ、0.10質量%であった。
又、連続めっき中、めっき出側のロールを観察したところ3000m通箔した時点でロールにSn付着が顕著に見られた。耐食性評価は良好な結果であった。 <Comparative example 2>
Exactly the same as Example 1 except that the plating thickness was 1.5 μm and a brightener (paraaldehyde 12 ml / L, naphthaldehyde 0.2 ml / L) was added to the Sn plating bath to obtain a current density of 13 A / dm 2. Then, continuous plating was performed.
The size of the electrodeposited grains of the obtained Sn plating film was 0.8 μm, and the hardness of the Sn plating was 580 MPa.
It was 0.10 mass% when the amount of carbon in Sn plating film was measured using the high frequency induction heating infrared absorption method.
Further, when the roll on the plating outlet side was observed during continuous plating, Sn adhesion was noticeably observed on the roll when 3000 m was passed through. The corrosion resistance evaluation was a good result.
めっき厚を1.5μmとし、Snめっき浴中に光沢剤(パラアルデヒド12ml/L、ナフトアルデヒド0.2ml/L)を添加し、電流密度7A/dm2としたこと以外は実施例1とまったく同様にして連続めっきを行った。
得られたSnめっき被膜の電着粒の大きさは、1.0μmであり、Snめっきの硬さは、505MPaであった。
Snめっき被膜中の炭素量を、高周波誘導加熱赤外線吸収法を用いて測定したところ、0.10質量%であった。
又、連続めっき中、めっき出側のロールを観察したところ3500m通箔した時点でロールにSn付着が顕著に見られた。耐食性評価は良好な結果であった。 <Comparative Example 3>
Exactly the same as Example 1 except that the plating thickness was 1.5 μm, and a brightener (paraaldehyde 12 ml / L, naphthaldehyde 0.2 ml / L) was added to the Sn plating bath to obtain a current density of 7 A / dm 2. Then, continuous plating was performed.
The size of the electrodeposited grains of the obtained Sn plating film was 1.0 μm, and the hardness of the Sn plating was 505 MPa.
It was 0.10 mass% when the amount of carbon in Sn plating film was measured using the high frequency induction heating infrared absorption method.
Further, when the roll on the plating outlet side was observed during continuous plating, Sn adhesion was noticeably observed on the roll when 3500 m was passed through. The corrosion resistance evaluation was a good result.
Snめっき浴中にメタノール(100mg/L)を添加したこと以外は、実施例7とまったく同様にして、40000m通箔するまで電気めっきを行った後、実施例7と同様な評価を行った(但し、ロールへのSnの付着の有無は評価せず)ところ、塩水噴霧試験(Z2371)で腐食が見られ、耐食性が劣化した。
又、比較例4の試料につき、めっき被膜の表面を走査電子顕微鏡で倍率1000倍で観察したところ、Snの反射電子像の中に、Snと異なる輝度の反射電子像が散見された。このことより、Snめっき被膜と異なる組成がめっき被膜表面に存在し、めっき被膜の欠陥が生じて下地である銅箔が露出したものと考えられる。 <Comparative Example 4>
Except that methanol (100 mg / L) was added to the Sn plating bath, the same evaluation as in Example 7 was performed after electroplating until 40000 m was passed in the same manner as in Example 7. ( However, the presence or absence of Sn adhesion to the roll was not evaluated.) However, corrosion was observed in the salt spray test (Z2371), and the corrosion resistance deteriorated.
Further, regarding the sample of Comparative Example 4, when the surface of the plating film was observed with a scanning electron microscope at a magnification of 1000 times, reflected electron images having brightness different from Sn were scattered in the reflected electron images of Sn. From this, it is considered that a composition different from that of the Sn plating film exists on the surface of the plating film, a defect of the plating film occurs, and the copper foil as the base is exposed.
但し、Snめっき被膜内の炭素量が0.01質量%を超えた実施例6の場合、他の実施例1~5に比べて、ロールにSnが付着するまでのめっき時間(4000m)が短かった。
一方、Snめっき被膜の硬さが500MPaを超える比較例1~3の場合、連続めっきを3000~3500m行った時点でロールにSnが付着した。なお、比較例1~3は光沢剤の含有量が実施例より多かった。 As is clear from Table 1, in each of Examples 1 to 8 where the Sn plating film had a hardness of 500 MPa or less, Sn did not adhere to the roll for a long time (4000 m or more) even by continuous plating.
However, in Example 6 in which the amount of carbon in the Sn plating film exceeded 0.01% by mass, the plating time (4000 m) until Sn adhered to the roll was shorter than in other Examples 1 to 5. It was.
On the other hand, in the case of Comparative Examples 1 to 3 in which the hardness of the Sn plating film exceeded 500 MPa, Sn adhered to the roll when continuous plating was performed 3000 to 3500 m. In Comparative Examples 1 to 3, the content of the brightener was higher than that in the Examples.
2 Snめっき被膜
4 樹脂層(又はフィルム) 1 Copper foil (or copper alloy foil)
2
Claims (9)
- 樹脂層又はフィルムを積層した銅箔又は銅合金箔の他の面に、メタノールを含有しないSn又はSn合金電気めっき浴から形成され、硬さが500MPa以下のSn又はSn合金めっき被膜であって、該Sn又はSn合金めっき被膜の表面を走査電子顕微鏡で観察したとき(但し、該Sn又はSn合金めっき被膜の厚みが1.5μmを超える場合、該Sn又はSn合金めっき被膜の厚みを1.5μmに減じたとき)、前記銅箔又は銅合金箔が露出しないSn又はSn合金めっき被膜。 The other surface of the copper foil or copper alloy foil laminated with a resin layer or film is formed from a Sn or Sn alloy electroplating bath not containing methanol, and is a Sn or Sn alloy plating film having a hardness of 500 MPa or less, When the surface of the Sn or Sn alloy plating film is observed with a scanning electron microscope (however, when the thickness of the Sn or Sn alloy plating film exceeds 1.5 μm, the thickness of the Sn or Sn alloy plating film is 1.5 μm). Sn or Sn alloy plating film in which the copper foil or copper alloy foil is not exposed.
- 前記Sn又はSn合金めっき被膜内の炭素量が0.01質量%以下である請求項1に記載のSn又はSn合金めっき被膜。 The Sn or Sn alloy plating film according to claim 1, wherein the amount of carbon in the Sn or Sn alloy plating film is 0.01 mass% or less.
- 前記Sn又はSn合金めっき被膜の厚みが0.5μm以上である請求項1または2に記載のSn又はSn合金めっき被膜。 The Sn or Sn alloy plating film according to claim 1 or 2, wherein the Sn or Sn alloy plating film has a thickness of 0.5 µm or more.
- 前記Sn又はSn合金めっき被膜の厚みが2.0μm未満である請求項1~3のいずれかに記載のSn又はSn合金めっき被膜。 The Sn or Sn alloy plating film according to any one of claims 1 to 3, wherein the Sn or Sn alloy plating film has a thickness of less than 2.0 µm.
- 前記Sn又はSn合金めっき被膜が連続めっきによって形成されている請求項1~4のいずれかに記載のSn又はSn合金めっき被膜。 The Sn or Sn alloy plating film according to any one of claims 1 to 4, wherein the Sn or Sn alloy plating film is formed by continuous plating.
- 銅箔又は銅合金箔と、前記銅箔又は銅合金箔の一方の面に積層された樹脂層又はフィルムと、前記銅箔又は銅合金箔の他の面に形成された請求項1~5のいずれかに記載のSn又はSn合金めっき被膜とからなる複合材料。 The copper foil or copper alloy foil, a resin layer or film laminated on one surface of the copper foil or copper alloy foil, and the other surface of the copper foil or copper alloy foil. A composite material comprising the Sn or Sn alloy plating film according to any one of the above.
- 厚みが0.1mm以下である請求項6に記載の複合材料。 The composite material according to claim 6, wherein the thickness is 0.1 mm or less.
- 電磁波シールドに用いられる請求項7に記載の複合材料。 The composite material according to claim 7, which is used for electromagnetic shielding.
- 銅箔又は銅合金箔の一方の面に樹脂層又はフィルムを積層した後、当該銅箔又は銅合金箔の他の面に、メタノールを含有しないSn又はSn合金電気めっき浴を用い、硬さが500MPa以下であるSn又はSn合金めっき被膜を形成する複合材料の製造方法。 After laminating the resin layer or film on one side of the copper foil or copper alloy foil, the other side of the copper foil or copper alloy foil is made of Sn or Sn alloy electroplating bath that does not contain methanol. The manufacturing method of the composite material which forms Sn or Sn alloy plating film which is 500 Mpa or less.
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2010236041A (en) * | 2009-03-31 | 2010-10-21 | Nippon Mining & Metals Co Ltd | Sn OR Sn ALLOY PLATING FILM AND COMPOSITE MATERIAL HAVING THE SAME |
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JP5497949B1 (en) * | 2013-07-03 | 2014-05-21 | Jx日鉱日石金属株式会社 | Metal foil for electromagnetic wave shielding, electromagnetic wave shielding material and shielded cable |
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US9955574B2 (en) | 2012-01-13 | 2018-04-24 | Jx Nippon Mining & Metals Corporation | Copper foil composite, formed product and method of producing the same |
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JP5497949B1 (en) * | 2013-07-03 | 2014-05-21 | Jx日鉱日石金属株式会社 | Metal foil for electromagnetic wave shielding, electromagnetic wave shielding material and shielded cable |
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US10842058B2 (en) | 2013-07-04 | 2020-11-17 | Jx Nippon Mining & Metals Corporation | Metal foil for electromagnetic shielding, electromagnetic shielding material, and shielding cable |
KR20170009885A (en) | 2014-05-30 | 2017-01-25 | 제이엑스금속주식회사 | Metal foil for electromagnetic wave shielding, electromagnetic wave shielding member, and shielded cable |
US10221487B2 (en) | 2014-05-30 | 2019-03-05 | Jx Nippon Mining & Metals Corporation | Metal foil for electromagnetic shielding, electromagnetic shielding material and shielded cable |
JP2018053274A (en) * | 2016-09-26 | 2018-04-05 | 千住金属工業株式会社 | Metal body and method for producing metal body |
Also Published As
Publication number | Publication date |
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JPWO2009144973A1 (en) | 2011-10-06 |
JP4484962B2 (en) | 2010-06-16 |
KR101245911B1 (en) | 2013-03-20 |
KR20100135904A (en) | 2010-12-27 |
CN102046854B (en) | 2013-09-25 |
CN102046854A (en) | 2011-05-04 |
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