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WO2009144973A1 - Film plaqué de sn ou d'alliage de sn, matériau composite comportant celui-ci et procédé de fabrication de matériau composite - Google Patents

Film plaqué de sn ou d'alliage de sn, matériau composite comportant celui-ci et procédé de fabrication de matériau composite Download PDF

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Publication number
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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Prior art keywords
plating
alloy
plating film
foil
copper
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PCT/JP2009/052140
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English (en)
Japanese (ja)
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国芳 前澤
正輝 村田
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日鉱金属株式会社
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Application filed by 日鉱金属株式会社 filed Critical 日鉱金属株式会社
Priority to KR1020107025597A priority Critical patent/KR101245911B1/ko
Priority to CN2009801200337A priority patent/CN102046854B/zh
Priority to JP2009525834A priority patent/JP4484962B2/ja
Publication of WO2009144973A1 publication Critical patent/WO2009144973A1/fr

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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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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  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electromagnetism (AREA)
  • Physics & Mathematics (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Laminated Bodies (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)

Abstract

Le problème à résoudre dans le cadre de la présente invention est l’élaboration d’un film plaqué de Sn ou d'alliage de Sn et d’un matériau composite comportant celui-ci qui permettent un excellent maintien de rouleau et améliorent la productivité en empêchant le frottement et la perte du film plaqué de Sn ou d'alliage de Sn. À cet effet, un film plaqué de Sn ou d'alliage de Sn (2), dont la dureté est inférieure ou égale à 500 Mpa, est formé dans un bain d'électroplacage de Sn ou d'alliage de Sn ne contenant pas de méthanol sur l'autre côté d'une feuille de cuivre ou d'une feuille d'alliage de cuivre (1) stratifiée avec une couche ou un film de résine (4). La feuille de cuivre ou la feuille d'alliage de cuivre n'est pas exposée lorsque la surface du film plaqué de Sn ou d'alliage de Sn est observée avec un microscope électronique à balayage (cependant, si l'épaisseur du film plaqué de Sn ou d'alliage de Sn est supérieure à 1,5 µm, l'épaisseur du film plaqué de Sn ou d'alliage de Sn est réduite à 1,5 µm).
PCT/JP2009/052140 2008-05-30 2009-02-09 Film plaqué de sn ou d'alliage de sn, matériau composite comportant celui-ci et procédé de fabrication de matériau composite WO2009144973A1 (fr)

Priority Applications (3)

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KR1020107025597A KR101245911B1 (ko) 2008-05-30 2009-02-09 Ｓｎ 또는 Ｓｎ 합금 도금 피막, 그것을 갖는 복합 재료, 및 복합 재료의 제조 방법
CN2009801200337A CN102046854B (zh) 2008-05-30 2009-02-09 Sn或Sn合金镀敷被膜、具有该被膜的复合材料、以及复合材料的制备方法
JP2009525834A JP4484962B2 (ja) 2008-05-30 2009-02-09 Ｓｎ又はＳｎ合金めっき被膜、それを有する複合材料、及び複合材料の製造方法

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JP2008-142064 2008-05-30
JP2008142064 2008-05-30

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WO2009144973A1 true WO2009144973A1 (fr) 2009-12-03

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JP (1) JP4484962B2 (fr)
KR (1) KR101245911B1 (fr)
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JP2010236041A (ja) * 2009-03-31 2010-10-21 Nippon Mining & Metals Co Ltd Ｓｎ又はＳｎ合金めっき被膜、及びそれを有する複合材料
WO2011040280A1 (fr) * 2009-09-30 2011-04-07 Jx日鉱日石金属株式会社 Film de revêtement en étain ou en alliage d'étain formé par placage et matériau composite le comprenant
WO2013105265A1 (fr) * 2012-01-13 2013-07-18 Jx日鉱日石金属株式会社 Composite de feuille de cuivre, corps moulé, et procédé de production associé
JP5497949B1 (ja) * 2013-07-03 2014-05-21 Ｊｘ日鉱日石金属株式会社 電磁波シールド用金属箔、電磁波シールド材及びシールドケーブル
WO2015002130A1 (fr) 2013-07-04 2015-01-08 Jx日鉱日石金属株式会社 Feuille métallique pour blindage électromagnétique, composant de blindage électromagnétique, et câble blindé
RU2574461C1 (ru) * 2012-01-13 2016-02-10 ДжейЭкс НИППОН МАЙНИНГ ЭНД МЕТАЛЗ КОРПОРЕЙШН Композит с медной фольгой, формованный продукт и способ их получения
US9549471B2 (en) 2010-07-15 2017-01-17 Jx Nippon Mining & Metals Corporation Copper foil composite
KR20170009885A (ko) 2014-05-30 2017-01-25 제이엑스금속주식회사 전자파 실드용 금속박, 전자파 실드재 및 실드 케이블
JP2018053274A (ja) * 2016-09-26 2018-04-05 千住金属工業株式会社 金属体および金属体の製造方法
US9955574B2 (en) 2012-01-13 2018-04-24 Jx Nippon Mining & Metals Corporation Copper foil composite, formed product and method of producing the same
US10178816B2 (en) 2011-05-13 2019-01-08 Jx Nippon Mining & Metals Corporation Copper foil composite, copper foil used for the same, formed product and method of producing the same

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KR101620449B1 (ko) * 2014-06-26 2016-05-12 삼성전자 주식회사 로봇 청소기 및 로봇 청소기의 제어방법
CN106757190A (zh) * 2016-11-21 2017-05-31 江苏梦得新材料科技有限公司 一种电镀锡用光亮剂溶液
CN114214600A (zh) * 2021-12-17 2022-03-22 东莞市光志光电有限公司 一种抗氧化pet银膜制备方法

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JP2006070340A (ja) * 2004-09-03 2006-03-16 Matsushita Electric Ind Co Ltd 錫めっき皮膜及びそれを備えた電子部品並びにその製造方法
JP2007254860A (ja) * 2006-03-24 2007-10-04 Fujitsu Ltd めっき膜及びその形成方法

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JP2010236041A (ja) * 2009-03-31 2010-10-21 Nippon Mining & Metals Co Ltd Ｓｎ又はＳｎ合金めっき被膜、及びそれを有する複合材料
WO2011040280A1 (fr) * 2009-09-30 2011-04-07 Jx日鉱日石金属株式会社 Film de revêtement en étain ou en alliage d'étain formé par placage et matériau composite le comprenant
JP2011074458A (ja) * 2009-09-30 2011-04-14 Jx Nippon Mining & Metals Corp Ｓｎ又はＳｎ合金めっき被膜、及びそれを有する複合材料
US9549471B2 (en) 2010-07-15 2017-01-17 Jx Nippon Mining & Metals Corporation Copper foil composite
US10178816B2 (en) 2011-05-13 2019-01-08 Jx Nippon Mining & Metals Corporation Copper foil composite, copper foil used for the same, formed product and method of producing the same
KR101628590B1 (ko) 2012-01-13 2016-06-08 제이엑스금속주식회사 동박 복합체, 그리고 성형체 및 그 제조 방법
US9955574B2 (en) 2012-01-13 2018-04-24 Jx Nippon Mining & Metals Corporation Copper foil composite, formed product and method of producing the same
WO2013105265A1 (fr) * 2012-01-13 2013-07-18 Jx日鉱日石金属株式会社 Composite de feuille de cuivre, corps moulé, et procédé de production associé
RU2570030C1 (ru) * 2012-01-13 2015-12-10 ДжейЭкс НИППОН МАЙНИНГ ЭНД МЕТАЛЗ КОРПОРЕЙШН Композит с медной фольгой, формованный продукт и способ их получения
RU2574461C1 (ru) * 2012-01-13 2016-02-10 ДжейЭкс НИППОН МАЙНИНГ ЭНД МЕТАЛЗ КОРПОРЕЙШН Композит с медной фольгой, формованный продукт и способ их получения
KR20140099530A (ko) * 2012-01-13 2014-08-12 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 동박 복합체, 그리고 성형체 및 그 제조 방법
US9981450B2 (en) 2012-01-13 2018-05-29 Jx Nippon Mining & Metals Corporation Copper foil composite, formed product and method of producing the same
JP5497949B1 (ja) * 2013-07-03 2014-05-21 Ｊｘ日鉱日石金属株式会社 電磁波シールド用金属箔、電磁波シールド材及びシールドケーブル
US9485894B2 (en) 2013-07-03 2016-11-01 Jx Nippon Mining & Metals Corporation Metal foil for electromagnetic shielding, electromagnetic shielding material, and shielding cable
WO2015001817A1 (fr) 2013-07-03 2015-01-08 Jx日鉱日石金属株式会社 Feuille métallique à usage de blindage contre les ondes électromagnétiques, matériau de blindage contre les ondes électromagnétiques et câble de blindage
WO2015002130A1 (fr) 2013-07-04 2015-01-08 Jx日鉱日石金属株式会社 Feuille métallique pour blindage électromagnétique, composant de blindage électromagnétique, et câble blindé
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 (ko) 2014-05-30 2017-01-25 제이엑스금속주식회사 전자파 실드용 금속박, 전자파 실드재 및 실드 케이블
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 (ja) * 2016-09-26 2018-04-05 千住金属工業株式会社 金属体および金属体の製造方法

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JPWO2009144973A1 (ja) 2011-10-06
KR20100135904A (ko) 2010-12-27
KR101245911B1 (ko) 2013-03-20
CN102046854A (zh) 2011-05-04
CN102046854B (zh) 2013-09-25

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