WO2024116659A1 - アルミニウム合金箔、アルミニウム合金箔を用いた積層体およびそれらの製造方法 - Google Patents

アルミニウム合金箔、アルミニウム合金箔を用いた積層体およびそれらの製造方法 Download PDF

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WO2024116659A1
WO2024116659A1 PCT/JP2023/038351 JP2023038351W WO2024116659A1 WO 2024116659 A1 WO2024116659 A1 WO 2024116659A1 JP 2023038351 W JP2023038351 W JP 2023038351W WO 2024116659 A1 WO2024116659 A1 WO 2024116659A1
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aluminum alloy
alloy foil
mass
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aluminum
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English (en)
French (fr)
Japanese (ja)
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翔 合志
享 新宮
真輝 松本
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Toyo Aluminum KK
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Toyo Aluminum KK
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Priority to KR1020257008678A priority Critical patent/KR20250115976A/ko
Priority to JP2024561254A priority patent/JPWO2024116659A1/ja
Priority to CN202380065981.5A priority patent/CN119816611A/zh
Publication of WO2024116659A1 publication Critical patent/WO2024116659A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/10—Alloys based on aluminium with zinc as the next major constituent
    • 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
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/053—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to aluminum alloy foil, a laminate using aluminum alloy foil, and a method for manufacturing the same.
  • Aluminum foil and aluminum alloy foil are laminated with a resin film layer and/or coating layer on one or both sides and are widely used in fields such as building materials, food packaging, pharmaceutical packaging, and aluminum etched circuits.
  • etching As the etching treatment liquid, solutions such as hydrochloric acid (HCl), nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ), ferric chloride (FeCl 3 ), sodium hydroxide (NaOH), or hydrofluoric acid (HF), or a mixture containing two or more of these solutions, are used.
  • HCl hydrochloric acid
  • HNO 3 nitric acid
  • sulfuric acid H 2 SO 4
  • FeCl 3 ferric chloride
  • NaOH sodium hydroxide
  • HF hydrofluoric acid
  • Patent Document 1 discloses an aluminum alloy foil for printed circuits that contains Si, Fe, Cu, and Ni as an aluminum alloy foil with excellent chemical solubility during etching.
  • the aluminum alloy foil described in Patent Document 1 requires the use of hydrochloric acid (HCl) for the etching process, and has insufficient chemical solubility in weak acids, so there is a problem that it is not necessarily an effective solution to the issue of ceasing the use of harmful substances that have a large environmental impact or reducing their usage.
  • HCl hydrochloric acid
  • the etching process for aluminum foil or aluminum alloy foil must enable the formation of fine shapes such as circuits, but the occurrence of undissolved areas on the material surface after etching and the formation of locally deep dissolved pits must be suppressed as much as possible, as these can impair product characteristics such as circuits. Therefore, the chemical solubility of aluminum foil, etc., poses the challenge of ensuring uniform solubility in the etching process, which suppresses the formation of undissolved areas and pits.
  • the present invention aims to provide an aluminum alloy foil that has excellent chemical solubility in a weak acid environment and excellent uniform solubility in an acid environment, a laminate using the aluminum alloy foil, and a method for producing the same.
  • an aluminum alloy foil containing Fe, Ni, and Zn, with the remainder being Al and unavoidable impurities characterized in that, when the contents of Fe, Ni, and Zn in the aluminum alloy foil are [Fe], [Ni], and [Zn], respectively, in mass%, [Zn] is 0.4 to 5.1, [Fe] + [Ni] is 0.4 to 4.8, and [Fe] + [Ni] + 2 ⁇ [Zn] is 2.5 or more.
  • [Fe] in the aluminum alloy foil is 0.0001 or more and 3.1 or less, and [Ni] is 0.0001 or more and 3.0 or less, and the amount of Zn dissolved in the aluminum parent phase in the aluminum alloy foil is 0.3 mass% or more and 4.1 mass% or less.
  • [Fe] + [Ni] + 2 x [Zn] is controlled because adding Zn to form a solid solution makes the potential of the aluminum parent phase less noble, which has a synergistic effect with the effect of adding Fe or Ni described above, thereby further improving the chemical solubility of the aluminum alloy foil in a weak acid environment.
  • the reason for controlling [Zn], and preferably the amount of Zn in solid solution, is that most of the Zn dissolves in the aluminum parent phase, making the potential of the aluminum parent phase more base. Therefore, the aluminum parent phase in which Zn is dissolved increases the potential difference with the above-mentioned Al-Fe, Al-Ni and/or Al-Fe-Ni second phase particles, contributing to improving the chemical solubility of the aluminum alloy foil in a weak acid environment. Furthermore, the aluminum parent phase in which Zn is dissolved can improve the uniform solubility of the aluminum alloy foil in an acid environment.
  • the inevitable impurities are one or more elements selected from the group consisting of Si, Mn, Mg, Cu, In, Sn, Na, V, Ti, Zr, Cr, B, Ga, Bi, Pb, Sb, As, etc., and the total content of the one or more elements is preferably 0.6 mass% or less.
  • the content of Mn in the aluminum alloy foil is 0.4 mass% or less
  • the content of Mg is 0.4 mass% or less
  • the content of each of the above elements other than Mn and Mg contained as inevitable impurities in the aluminum alloy foil is preferably 0.2 mass% or less.
  • the area occupancy of second phase particles having an equivalent circle diameter of 0.1 ⁇ m or more distributed on the aluminum alloy foil surface is 1.7% or more, as determined by field emission scanning electron microscope (FE-SEM) analysis. It is also preferable that the area occupancy of second phase particles having an equivalent circle diameter of 3.0 ⁇ m or more distributed on the aluminum alloy foil surface is 2.0% or less.
  • the second phase particles are formed from Al-Fe, Al-Ni and/or Al-Fe-Ni particles, but in the case of particles with a circle-equivalent diameter of 0.1 ⁇ m or more, the potential difference with the aluminum parent phase becomes large, so unless the area occupancy rate on the aluminum alloy foil surface is controlled, the desired chemical solubility of the aluminum alloy foil in a weak acid environment cannot be obtained. On the other hand, in the case of coarse particles with a circle-equivalent diameter of 3.0 ⁇ m or more, they can cause defects such as cracks and pinholes, so unless the area occupancy rate on the aluminum alloy foil surface is controlled, rolling workability decreases.
  • the thickness is preferably 5 ⁇ m or more and 300 ⁇ m or less.
  • the aluminum alloy foil of the present invention may also be configured as a laminate by forming a resin film layer and/or a coating layer on one or both sides depending on the application.
  • the aluminum alloy foil having high chemical solubility in a weak acid environment and high uniform solubility in an acid environment as described above can be produced by a production method including the steps of: preparing a molten aluminum alloy containing Fe, Ni, and Zn with the remainder being Al and unavoidable impurities, in which the contents of Fe, Ni, and Zn in the molten aluminum alloy are, in mass %, [Fe], [Ni], and [Zn], respectively, such that [Zn] is 0.4 to 5.1, [Fe] + [Ni] is 0.4 to 4.8, and [Fe] + [Ni] + 2 ⁇ [Zn] is 2.5 or more; casting the molten aluminum alloy to obtain a casting; and cold rolling the casting to obtain an aluminum alloy foil.
  • the laminate using the aluminum alloy foil of the present invention can be produced by a production method including a step of preparing the aluminum alloy foil obtained by the above-mentioned production method, and a lamination step of laminating a resin film layer and/or a coating layer on one or both sides of the aluminum alloy foil.
  • the aluminum alloy foil of the present invention and the laminate using the aluminum alloy foil have high chemical solubility in a weak acid environment and high uniform solubility in an acid environment. Furthermore, the manufacturing method of the present invention makes it possible to manufacture the aluminum alloy foil and the laminate using the aluminum alloy foil having the above-mentioned characteristics.
  • 1 is a SEM photograph ( ⁇ 1000) of the surface of the aluminum alloy foil of Example 4, in which the area occupancy rate of second-phase particles having an equivalent circle diameter of 0.1 ⁇ m or more is 6.38%.
  • 1 is a SEM photograph ( ⁇ 1000) of the surface of the aluminum alloy foil of Example 12, in which the area occupancy rate of second-phase particles having an equivalent circle diameter of 3.0 ⁇ m or more is 1.69%.
  • 1 is a SEM photograph ( ⁇ 1000) of the surface of the aluminum alloy foil of Comparative Example 6, in which the area occupancy rate of second phase particles having an equivalent circle diameter of 0.1 ⁇ m or more is 3.85%.
  • FIG. 1 is a SEM photograph ( ⁇ 1000 magnification) of the surface of the aluminum alloy foil of Comparative Example 9, in which the area occupancy rate of second phase particles having an equivalent circle diameter of 3.0 ⁇ m or more is 7.55%.
  • FIG. 1 is a scatter plot showing the relationship between ([Fe]+[Ni]+2 ⁇ [Zn]) and chemical solubility in a weak acid environment (labeled “weak acid solubility” in the figure).
  • FIG. 1 is a scatter diagram showing the relationship between [Zn] and uniform solubility in an acidic environment (denoted as "uniform solubility" in the figure).
  • Aluminum alloy foil (1)
  • Aluminum alloy foil of the present invention contains iron (Fe), nickel (Ni), and zinc (Zn), with the balance being aluminum (Al) and inevitable impurities.
  • the aluminum alloy foil may contain inevitable impurities to the extent that they do not impair the chemical solubility in a weak acid environment, the uniform solubility in an acid environment, the rolling processability, the etching property, and the manufacturing suitability of the aluminum alloy foil.
  • the inevitable impurities consist of one or more elements selected from the group consisting of silicon (Si), manganese (Mn), magnesium (Mg), copper (Cu), indium (In), tin (Sn), sodium (Na), vanadium (V), titanium (Ti), zirconium (Zr), chromium (Cr), boron (B), gallium (Ga), bismuth (Bi), lead (Pb), antimony (Sb), and arsenic (As).
  • the content of aluminum (Al) contained in the aluminum alloy foil is preferably 89.0 mass% or more.
  • the Fe content exceeds 3.1% by mass, the material strength increases due to precipitation strengthening, and defects such as cracks occur, hindering rolling workability. Furthermore, coarse second phase particles are likely to be formed during casting, which not only hinders rolling workability and hinders uniform surface formation in etching treatment, but also causes defects such as pinholes in the process of manufacturing aluminum alloy foil with a thickness of 10 ⁇ m or less.
  • the lower limit of the Fe content is not particularly limited, but is usually about 0.0001% by mass. In order to reduce the Fe content to less than 0.0001% by mass, it is necessary to repeat the three-layer electrolysis method, which significantly increases the manufacturing cost.
  • the Fe content in the aluminum alloy foil is preferably 0.0001% by mass or more and 3.1% by mass or less, more preferably 0.0001% by mass or more and 1.8% by mass or less, and even more preferably 0.0001% by mass or more and 1.5% by mass or less.
  • Ni Nickel (Ni)>
  • Ni Ni-containing second phase particles and/or Al-Fe-Ni second phase particles together with Fe.
  • the Ni-containing second phase particles have a large potential difference with the aluminum matrix, and increase the effect as a cathode site. Therefore, adding Ni to an aluminum alloy improves the chemical solubility of the aluminum alloy foil in a weak acid environment.
  • the Ni content exceeds 3.0% by mass, the material strength increases due to precipitation strengthening, and defects such as cracked edges occur, hindering rolling workability. Furthermore, coarse second phase particles are likely to be formed during casting, which not only hinders rolling workability and hinders uniform surface formation in etching treatment, but also causes defects such as pinholes in the process of manufacturing aluminum alloy foil with a thickness of 10 ⁇ m or less.
  • the lower limit of the Ni content is not particularly limited, but is usually about 0.0001% by mass. In order to reduce the Ni content to less than 0.0001% by mass, it is necessary to repeat the three-layer electrolysis method, which significantly increases the manufacturing cost.
  • the Ni content in the aluminum alloy foil is preferably 0.0001% by mass or more and 3.0% by mass or less, more preferably 0.0001% by mass or more and 2.6% by mass or less, and even more preferably 0.0001% by mass or more and 1.8% by mass or less.
  • ⁇ Zinc (Zn)> When a certain amount of Zn is added to an aluminum alloy, most of it dissolves in the aluminum matrix, making the potential of the aluminum matrix less noble, thereby increasing the potential difference between the Al-Fe, Al-Ni and/or Al-Fe-Ni second phase particles and the aluminum matrix, improving the chemical solubility of the aluminum alloy foil in a weak acid environment, and improving the uniform solubility of the aluminum alloy foil in an acid environment.
  • the Zn content falls below 0.4 mass%, the amount of Zn dissolved in the aluminum parent phase decreases, the effect of making the potential of the aluminum parent phase less base becomes insufficient, and the chemical solubility of the aluminum alloy foil in a weak acid environment and the uniform solubility of the aluminum alloy foil in an acidic environment are impaired.
  • the Zn content exceeds 2.1 mass%, the uniform solubility of the aluminum alloy foil remains unchanged, but the chemical solubility is impaired.
  • the Zn content exceeds 5.1 mass%, the material strength increases due to solid solution strengthening, hindering rolling workability.
  • the Zn content in the aluminum alloy foil is preferably 0.4 mass% or more and 5.1 mass% or less, more preferably 0.5 mass% or more and 2.9 mass% or less, and even more preferably 0.75 mass% or more and 2.1 mass% or less.
  • [Fe] + [Ni] is preferably 0.4 to 4.8, more preferably 0.9 to 4.0, and even more preferably 1.4 to 2.9.
  • [Fe] + [Ni] + 2 x [Zn] is preferably 2.5 or more, more preferably 2.85 or more, and even more preferably 2.95 or more.
  • the amount of Zn in solid solution in the aluminum parent phase is preferably 0.3 mass% or more and 4.1 mass% or less, more preferably 0.4 mass% or more and 2.7 mass% or less, and even more preferably 0.5 mass% or more and 1.5 mass% or less.
  • the aluminum alloy foil may contain one or more elements selected from the group consisting of Si, Mn, Mg, Cu, In, Sn, Na, V, Ti, Zr, Cr, B, Ga, Bi, Pb, Sb, and As as inevitable impurities.
  • the total content of the one or more elements is preferably 0.6 mass% or less.
  • the content of Mn in the aluminum alloy foil is preferably 0.4 mass% or less
  • the content of Mg is preferably 0.4 mass% or less
  • the content of each of the above elements other than Mn and Mg contained as inevitable impurities in the aluminum alloy foil is preferably 0.2 mass% or less.
  • Si ⁇ Impurity components> (Si) Adding a certain amount of Si to an aluminum alloy improves the chemical solubility of the aluminum alloy foil in a weak acid environment, but if the Si content exceeds 0.2 mass %, it promotes coarsening of Al-Fe, Al-Ni and/or Al-Fe-Ni second phase particles, impairing the rolling workability and the uniform solubility of the aluminum alloy foil in an acid environment.
  • the lower limit of the Si content is not particularly limited, but is usually around 0.0001% by mass. In order to reduce the Si content to less than 0.0001% by mass, it becomes necessary to repeat the three-layer electrolysis method, which significantly increases the manufacturing cost. Therefore, the Si content in the aluminum alloy foil is preferably 0.0001% by mass or more and 0.2% by mass or less, more preferably 0.0001% by mass or more and 0.15% by mass or less, and even more preferably 0.0001% by mass or more and 0.1% by mass or less.
  • Mn When a certain amount of Mn is added to an aluminum alloy, most of it dissolves in the aluminum matrix, but a part of it forms second-phase particles such as Al-Mn-based, Al-Mn-Ni-based, Al-Mn-Si-based, Al-Mn-Fe-Ni-based, Al-Mn-Fe-Ni-based, Al-Mn-Ni-Si-based, Al-Mn-Si-Fe-based, or Al-Mn-Fe-Ni-Si-based together with Al-Mn, Fe, Ni, and Si.
  • second-phase particles such as Al-Mn-based, Al-Mn-Ni-based, Al-Mn-Si-based, Al-Mn-Fe-Ni-based, Al-Mn-Ni-Si-Fe-based, or Al-Mn-Fe-Ni-Si-based together with Al-Mn, Fe, Ni, and Si.
  • the Mn content in the second-phase particles and the amount of Mn dissolved in the aluminum matrix increase, and the potential of the second-phase particles approaches that of the aluminum matrix, reducing the effect of the second-phase particles as cathode sites. This reduces the chemical solubility of the aluminum alloy foil in a weak acid environment.
  • the lower limit of the Mn content is not particularly limited, but is usually around 0.0001% by mass. In order to reduce the Mn content to less than 0.0001% by mass, it becomes necessary to repeat the three-layer electrolysis method, which significantly increases the manufacturing cost. Therefore, the Mn content in the aluminum alloy foil is preferably 0.0001% by mass or more and 0.4% by mass or less, more preferably 0.0001% by mass or more and 0.2% by mass or less, and even more preferably 0.0001% by mass or more and 0.1% by mass or less.
  • Mg When a certain amount of Mg is added to an aluminum alloy, a part of it dissolves in the aluminum parent phase. When the Mg content exceeds 0.4 mass%, Mg is concentrated in the oxide film formed on the surface of the aluminum alloy material, and the oxide film is likely to have defects. Such defects in the oxide film can cause delamination at the bonding interface of a laminate in which, for example, an aluminum alloy foil and a resin film are laminated. In addition, the addition of Mg has the effect of reducing the chemical solubility of the aluminum alloy foil and improving the corrosion resistance.
  • the lower limit of the Mg content is not particularly limited, but is usually around 0.0001% by mass. In order to reduce the Mg content to less than 0.0001% by mass, it becomes necessary to repeat the three-layer electrolysis method, which significantly increases the manufacturing cost. Therefore, the Mg content in the aluminum alloy foil is preferably 0.0001% to 0.4% by mass, more preferably 0.0001% to 0.2% by mass, and even more preferably 0.0001% to 0.1% by mass.
  • Cu When a certain amount of Cu is added to an aluminum alloy, a part of it dissolves in the aluminum matrix. If the Cu content exceeds 0.2 mass%, the amount of Cu dissolved in the aluminum matrix increases, and the material strength increases due to solid solution strengthening, which may impair rolling workability.
  • the lower limit of the Cu content is not particularly limited, but is usually around 0.0001% by mass.
  • the Cu content in the aluminum alloy foil is preferably 0.0001% by mass or more and 0.2% by mass or less, more preferably 0.0001% by mass or more and 0.15% by mass or less, and even more preferably 0.0001% by mass or more and 0.1% by mass or less.
  • the In content in the aluminum alloy foil is preferably 0.0001 mass% or more and 0.2 mass% or less, and the Sn content is preferably 0.0001 mass% or more and 0.2 mass% or less.
  • Second Phase Particles Having an Equivalent Circle Diameter of 0.1 ⁇ m or More Distributed on the Aluminum Alloy Foil Surface Adding the above-mentioned elements to aluminum produces second-phase particles in the aluminum matrix.
  • the second-phase particles are Al-Fe, Al-Ni, and/or Al-Fe-Ni, etc. These second-phase particles have a large potential difference with the aluminum matrix and act as cathode sites. This improves the chemical solubility of the aluminum alloy foil in a weak acid environment.
  • the area occupancy rate of second phase particles having a circular equivalent diameter of 0.1 ⁇ m or more distributed on the surface of the aluminum alloy foil falls below 1.7%, the effect as a cathode site will not be sufficient, and the chemical solubility of the aluminum alloy foil in a weak acid environment will be insufficient. Therefore, on the surface of the aluminum alloy foil, the area occupancy rate of second phase particles having a circular equivalent diameter of 0.1 ⁇ m or more is preferably 1.7% or more, more preferably 4.1% or more, and even more preferably 5.6% or more.
  • Second-phase particles are Al-Fe, Al-Ni and/or Al-Fe-Ni type second-phase particles, and coarse second-phase particles having an equivalent circle diameter of 3.0 ⁇ m or more impair the rolling workability.
  • the area occupancy rate of second-phase particles with an equivalent circle diameter of 3.0 ⁇ m or more distributed on the surface of an aluminum alloy foil exceeds 2.0%, defects such as edge cracks will occur, impairing rolling workability. Therefore, on the surface of the aluminum alloy foil, the area occupancy rate of second-phase particles with an equivalent circle diameter of 3.0 ⁇ m or more is preferably 2.0% or less, more preferably 0.8% or less, and even more preferably 0.5% or less.
  • the thickness of the aluminum alloy foil of the present invention is preferably 5 ⁇ m or more from the viewpoint of strength and ease of production. From the viewpoint of weight reduction of the aluminum alloy foil, the thickness of the aluminum alloy foil is preferably 300 ⁇ m or less. Furthermore, the thickness of the aluminum alloy foil is more preferably 5 ⁇ m or more and 200 ⁇ m or less. In order to control the thickness of the aluminum alloy foil within the above range, casting and rolling may be performed according to a conventional method. In addition, a heat treatment may be appropriately performed for the purpose of homogenizing the aluminum alloy foil.
  • the manufacturing method of the aluminum alloy foil of the present invention is characterized by comprising a step of rolling a casting (hereinafter also referred to as an "ingot") containing Fe, Ni and Zn with the balance being Al and inevitable impurities, in which, when the contents of Fe, Ni and Zn are [Fe], [Ni] and [Zn], respectively, in mass%, [Zn] is 0.4 to 5.1, [Fe] + [Ni] is 0.4 to 4.8, and [Fe] + [Ni] + 2 ⁇ [Zn] is 2.5 or more.
  • An ingot having the above composition can be obtained, for example, by melting aluminum ingot, and adding Fe or Al-Fe mother alloy, Ni or Al-Ni mother alloy, and Zn or Al-Zn mother alloy to adjust the composition of the molten metal, and then casting and solidifying the molten metal.
  • the casting method There are no particular limitations on the casting method, and known methods such as semi-continuous casting, continuous casting, and mold casting can be used.
  • the obtained ingot may be subjected to heat treatment for the purpose of homogenization.
  • the homogenization heat treatment is preferably performed under conditions of a heating temperature of 400°C or higher and 630°C or lower, and a heating time of 1 hour or higher and 20 hours or lower.
  • the rolling method can be any widely known rolling method and is not particularly limited. However, from the viewpoint of making it easier to adjust the thickness of the aluminum alloy foil, it is preferable to provide a cold rolling process after the hot rolling process. Furthermore, the number of hot rollings in the hot rolling process and the number of cold rollings in the cold rolling process may be appropriately set according to the target final thickness of the aluminum alloy foil.
  • intermediate annealing When cold rolling is performed multiple times in the cold rolling process, it is preferable to perform intermediate annealing. In this case, it is preferable to perform the cold rolling process in the following order: one or more cold rollings, intermediate annealing, and one or more cold rollings. It is preferable to perform intermediate annealing under conditions of an annealing temperature of 50°C or higher and 500°C or lower, and an annealing time of 1 second or higher and 20 hours or lower. By performing intermediate annealing, it becomes possible to easily adjust the thickness of the aluminum alloy foil.
  • a heat treatment process may be performed at a temperature of 50°C to 450°C for 1 second to 50 hours.
  • the aluminum alloy foil of the present invention may be formed into a laminate by laminating a resin film layer and/or a coating layer on all or a part of one or both sides of the aluminum alloy foil.
  • a resin film layer and a coating layer on all or a part of one or both sides of the aluminum alloy foil it is preferable to laminate the coating layer on the aluminum alloy foil and then laminate the resin film layer on the coating layer.
  • the aluminum alloy foil of the present invention has excellent chemical solubility in a weak acid environment, so even if a laminate is formed by laminating a resin film layer and/or a coating layer on both the front and back sides of an aluminum alloy foil, when immersed in a weak acid, the aluminum alloy foil layer dissolves from the end face of the laminate, making it possible to easily separate the resin film layer and/or the coating layer from the aluminum alloy foil layer.
  • the number of resin film layers and coating layers to be laminated on the aluminum alloy foil and the order of lamination can be appropriately set according to the intended use of the laminate, and there are no particular limitations.
  • the thickness of the entire laminate is preferably 6 ⁇ m or more from the viewpoint of strength, and preferably 301 ⁇ m or less from the viewpoint of weight reduction, and more preferably 10 ⁇ m or more and 201 ⁇ m or less when both viewpoints are taken into consideration.
  • the resin film used for the resin film layer laminated on the aluminum alloy foil can be a wide variety of films made of known resins, and is not particularly limited.Specifically, films made of one or more resins selected from polyethylene, polypropylene, polybutylene, polyethylene terephthalate, polyethylene naphthalate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl acetate copolymer, polyamide, polyimide, and vinyl chloride can be used.
  • the thickness of the resin film layer laminated to the aluminum alloy foil may be appropriately set, taking into consideration the thickness of the aluminum alloy foil and the thickness of the coating layer described below, so that the thickness of the entire laminate falls within the above-mentioned numerical range.
  • adhesion and lamination methods When laminating the resin film layer onto the aluminum alloy foil, a wide variety of known adhesion and lamination methods can be used as a method for adhering the two together, and there are no particular limitations. Specific examples include the dry lamination method using a two-component curing adhesive such as a polyester urethane or polyester adhesive, the co-extrusion method, the extrusion coating method, the extrusion lamination method, the heat sealing method, or the heat lamination method using an anchor coating agent.
  • a two-component curing adhesive such as a polyester urethane or polyester adhesive
  • the coating layer of the aluminum alloy foil may be an inorganic coating layer made of titanium oxide, silicon oxide, zirconium oxide, a chromium composition, or the like, or a resin coating layer made of acrylic, polycarbonate, silicone resin, fluororesin, or the like.
  • suitable coating layers for the aluminum alloy foil include surface modifications such as plasma treatment, fatty acids, and silane coupling agents, and modified products formed using acids and/or alkalis, and are not particularly limited.
  • the thickness of the coating layer may be appropriately set, taking into consideration the thicknesses of the aluminum alloy foil and the resin film layer, so that the thickness of the entire laminate falls within the above-mentioned numerical range.
  • Any known method can be used to form a coating layer on the aluminum alloy foil, including, for example, a method of applying a coating agent such as spin coating, bar coating, flow coating, dip coating, or die coating, or a combination of two or more of the above coating methods. Furthermore, after application, a heat treatment for drying or reaction may be performed.
  • a coating agent such as spin coating, bar coating, flow coating, dip coating, or die coating, or a combination of two or more of the above coating methods.
  • a heat treatment for drying or reaction may be performed.
  • a coating layer examples include surface treatment methods such as ion plasma treatment, ion plating treatment, sputtering treatment, vapor deposition treatment, and plating treatment, or a surface treatment method that combines two or more of the above surface treatment methods. Furthermore, a lamination method of a coating layer that combines one or more of the above-mentioned coating methods and one or more of the above-mentioned surface treatment methods may be used.
  • Aluminum alloys having the compositions shown in Tables 1 and 2 were melted and cast using a metal mold casting method at a cooling rate of 1°C/sec or more and 15°C/sec or less to obtain ingots of the aluminum alloys of the Examples and Comparative Examples. The resulting ingots of the aluminum alloys were then heat treated at 530°C for 5 hours. Subsequently, cold rolling was performed multiple times to a thickness of 50 ⁇ m to produce the aluminum alloy foils of Examples 1 to 45 shown in Table 1 and the aluminum alloy foils of Comparative Examples 1 to 16 shown in Table 2.
  • the area occupancy rate of the second phase particles on each sample surface was measured using a backscattered electron image obtained by observing each sample surface with a field emission scanning electron microscope (FE-SEM). Specifically, 10 rectangular fields randomly selected from the backscattered electron images of each sample surface were observed. The range of each rectangular field was a rectangular field of 0.01069 mm2 (119.4 ⁇ m ⁇ 89.5 ⁇ m).
  • the backscattered electron images of each rectangular field were binarized under the condition of brightness of 100 to 255 using image processing software (Mitani Shoji Co., Ltd.: WinROOF2021) to extract second phase particles with a circle equivalent diameter of 0.1 ⁇ m or more and second phase particles with a circle equivalent diameter of 3.0 ⁇ m or more.
  • the area occupancy rate of the second phase particles in the measurement surface was calculated using the image processing software described above, and the average value of the above calculation results obtained from 10 rectangular fields of view was taken as the area occupancy rate of the second phase particles.
  • Tables 1 and 2 The results are shown in Tables 1 and 2.
  • Figure 1A shows an SEM photograph of the aluminum alloy foil surface of Example 4, in which the area occupancy of second phase particles with a circle-equivalent diameter of 0.1 ⁇ m or more is 6.38%, as an example of an SEM photograph before binarization processing
  • Figure 1B shows an SEM photograph of the aluminum alloy foil surface of Example 12, in which the area occupancy of second phase particles with a circle-equivalent diameter of 3.0 ⁇ m or more is 1.69%.
  • Figure 2A shows an SEM photograph of the aluminum alloy foil surface of Comparative Example 6, in which the area occupancy of second phase particles with a circle-equivalent diameter of 0.1 ⁇ m or more is 3.85%
  • Figure 2B shows an SEM photograph of the aluminum alloy foil surface of Comparative Example 9, in which the area occupancy of second phase particles with a circle-equivalent diameter of 3.0 ⁇ m or more is 7.55%.
  • the chemical solubility of the aluminum alloy foil surface in a weak acid environment was evaluated by the following method. That is, the aluminum alloy foil of each example and each comparative example was cut into a size of 40 mm x 40 mm, and as a pretreatment, it was immersed in a 1 mass% sodium hydroxide solution at 35 ° C for 60 seconds, and then immersed in a 30 mass% nitric acid solution at 25 ° C for 60 seconds to prepare a test piece for measurement.
  • test piece was immersed in an aqueous solution containing 3 mass% sodium chloride and 3 mass% acetic acid at 40 ° C for 2700 seconds, and the masses before and after immersion were measured to calculate the dissolution loss per unit surface area of each test piece.
  • a test piece with a dissolution loss per unit surface area of 2.8 ⁇ g / mm 2 or more was evaluated as having sufficient chemical solubility. The results are shown in Tables 1 and 2.
  • the evaluation of the uniform solubility of the aluminum alloy foil surface in an acidic environment was performed by the following method. That is, the aluminum alloy foil of each example and each comparative example was cut into a size of 10 mm x 40 mm, and was pretreated by immersing in a 1 mass% sodium hydroxide solution at 35 ° C for 60 seconds, and then immersing in a 30 mass% nitric acid solution at 25 ° C for 60 seconds to obtain a test piece for measurement.
  • Each test piece was immersed in an aqueous solution containing 8 mass% hydrochloric acid and 4 mass% aluminum chloride at 35 ° C for a predetermined time so that the dissolution loss of each test piece was 0.0025 g or more and 0.0029 g or less.
  • the maximum height roughness Sz of the surface of each test piece (aluminum alloy foil) after immersion was measured based on observation with a laser microscope.
  • the observation of the surface irregularities of the test piece with a laser microscope was performed using a laser microscope VK-X3000 manufactured by Keyence Corporation, with laser confocal shape measurement being performed in a rectangular field of view of 285.727 ⁇ m x 214.295 ⁇ m.
  • the maximum height roughness Sz of the test piece was measured using the obtained observation results with the multi-file analysis application of the VK-X3000 manufactured by Keyence Corporation. Specifically, first, surface shape correction was performed to remove waviness with a cutoff value of 0.5 mm for the obtained shape data, and then height cut level correction was performed with a cut level of 50 to remove noise components of laser light reflection.
  • the maximum height roughness Sz of each test specimen was measured using Keyence Corporation's VK-X3000 multi-file analysis application in accordance with the morphological parameters in the surface quality parameters of ISO 25178.
  • the maximum height roughness Sz of each test specimen used for evaluation was the average value of the calculation results obtained from five rectangular fields of view. Test specimens with a maximum height roughness Sz of 7.1 ⁇ m or less were evaluated as having sufficient uniform solubility. The results are shown in Tables 1 and 2.
  • the rolling workability of the aluminum alloy foil was evaluated by the following method. That is, in the cold rolling process, when the ingots (cast bodies) of each Example and each Comparative Example having the composition shown in Tables 1 and 2 were cold rolled to a predetermined thickness, the rolling workability of the sample (aluminum alloy foil) in which the reduction in material width due to edge cracking was less than 3% of the material width before the start of cold rolling was evaluated as "A”, the rolling workability of the sample in which the reduction in material width due to edge cracking was 3% or more but less than 10% was evaluated as "B”, the rolling workability of the sample in which the reduction in material width due to edge cracking was 10% or more but less than 25% was evaluated as "C”, and the rolling workability of the sample in which the reduction in material width due to edge cracking was 25% or more was evaluated as "F”. The results are shown in Tables 1 and 2.
  • the amount of Zn dissolved in the aluminum alloy foil was measured by the following method. That is, 0.1 g of a sample was taken from each aluminum alloy foil, and only the aluminum parent phase in the aluminum alloy foil was dissolved with phenol, and the second phase particles were collected by filtering with a membrane filter (H100A047A, manufactured by Toyo Roshi Kaisha, Ltd.) having a pore size of 0.1 ⁇ m. The second phase particles were dissolved with acid and alkali, and the amount of Zn precipitated was determined using an inductively coupled plasma emission spectrometer (ICPS-8100, manufactured by Shimadzu Corporation). The amount of Zn dissolved in the aluminum alloy foil was determined by subtracting the amount of Zn precipitated from the Zn content of the entire aluminum alloy foil. The results are shown in Table 3.
  • the above-mentioned potential measurements were carried out at a temperature of 25°C and in the open atmosphere using the following method.
  • the aluminum alloy foil of each Example and Comparative Example was cut into a size of 15 mm x 17 mm, and as a pretreatment, it was immersed in a 1% by mass sodium hydroxide solution at 35°C for 15 seconds, and then immersed in a 30% by mass nitric acid solution at 25°C for 30 seconds to prepare a test piece.
  • the potential was measured using a corrosion cell VM1 manufactured by EC Frontier Co., Ltd.
  • the electrode potential was measured by a three-electrode method using a 25°C, pH 5.5, 5 mass% NaCl aqueous solution as the test solution, a platinum-plated titanium rod (counter electrode VM1-5 manufactured by EC Frontier Co., Ltd.) as the counter electrode, an Ag/AgCl reference electrode RE-1A manufactured by EC Frontier Co., Ltd. as the reference electrode, and a sample holder VM1-3 manufactured by EC Frontier Co., Ltd. as the working electrode sample holder.
  • the sample holder has a circular sample window with an area of 1 cm2 , and the surface of the test piece exposed from this sample window acts as the working electrode.
  • the measurement of the natural potential and the potential when the absolute value of the cathodic current density reaches 1 mA/cm 2 was performed by first immersing the above working electrode, counter electrode, and reference electrode in the above test solution and leaving it for 600 seconds. During this time, the electrode potential was measured at a sampling interval of 10 seconds, and the average value of 60 points was taken as the "natural potential" of the aluminum alloy foil. Next, the natural potential of each test piece was swept in the negative direction to -1500 mV at a sweep rate of 0.5 mV/s using a potentiostat (Hokuto Denko Corporation: Electrochemical Measurement System HZ-7000 Series), and a cathodic polarization curve was measured.
  • a potentiostat Hokuto Denko Corporation: Electrochemical Measurement System HZ-7000 Series
  • the aluminum alloy foils of Examples 1 to 45 shown in Table 1 have a chemical solubility in a weak acid environment (dissolution loss per unit surface area) of 2.8 ⁇ g/ mm2 or more, a uniform solubility in an acid environment (maximum height roughness Sz after acid treatment) of 7.1 ⁇ m or less, and rolling workability when cold rolled is evaluated as "A", "B” or “C” (see Table 1). It was found that each aluminum alloy foil has excellent chemical solubility in a weak acid environment, excellent uniform solubility in an acid environment, and excellent rolling workability.
  • the aluminum alloy foils of Comparative Examples 1 to 16 shown in Table 2 have a chemical solubility in a weak acid environment (dissolution loss per unit surface area) of less than 2.8 ⁇ g/ mm2 , a uniform solubility in an acid environment (maximum height roughness Sz after acid treatment) of more than 7.1 ⁇ m, or the rolling workability when cold-rolled is evaluated as "F" (see Table 2). Therefore, it was found that good results were not obtained in at least one of the evaluations of chemical solubility in a weak acid environment, uniform solubility in an acid environment, and rolling workability.
  • Fig. 3 shows a scatter diagram illustrating the relationship between [Fe] + [Ni] + 2 ⁇ [Zn] and weak acid solubility ( ⁇ g/mm 2 ) when the contents of Fe, Ni and Zn in the aluminum alloy foils of Examples 1 to 45 and Comparative Examples 1 to 16 are [Fe], [Ni] and [Zn], respectively, in mass % .
  • Fig. 4 shows a scatter diagram illustrating the relationship of uniform solubility ( ⁇ m) to [Zn].
  • the Fe content is at least 0.0001% by mass to 3.1% by mass
  • the Ni content is at least 0.0001% by mass to 3.0% by mass
  • the Zn solid solution amount is at least 0.3% by mass to 4.1% by mass
  • the inevitable impurities are one or more elements selected from the group consisting of Si, Mn, Mg, Cu, In, Sn, Na, V, Ti, Zr, Cr, B, Ga, Bi, Pb, Sb, and As, the total content of the one or more elements is 0.6% by mass or less, the Mn content is preferably 0.4% by mass or less, the Mg content is preferably 0.4% by mass or less, and the content of each of the above elements other than Mn and Mg contained as inevitable impurities is preferably 0.2% by mass or less.
  • the area occupancy of second phase particles having an equivalent circle diameter of 0.1 ⁇ m or more distributed on the aluminum alloy foil surface is preferably 1.7% or more, and the area occupancy of second phase particles having an equivalent circle diameter of 3.0 ⁇ m or more distributed on the aluminum alloy foil surface is preferably 2.0% or less.
  • the aluminum alloy foil developed in the present invention has excellent chemical solubility in a weak acid environment and uniform solubility in an acid environment, so that it can be used effectively as a substrate for etching treatments aimed at forming special fine surfaces in fields where switching to etching treatment solutions with less environmental impact is required.
  • it has excellent chemical solubility in a strong acid environment, so that it can contribute to improving the efficiency of conventional etching treatments and reducing the amount of etching treatment solution used.
  • the aluminum alloy foil of the present invention may be configured as a laminate by laminating a resin film layer and/or a coating layer on one or both sides depending on the application.
  • the aluminum alloy foil in the laminate using the aluminum alloy foil of the present invention has the excellent properties described above, such as high chemical solubility, so that surface treatment for improving adhesive strength and etching treatment for processing into a desired shape can be performed using a weak acid. Therefore, the laminate using the aluminum alloy foil of the present invention can be manufactured by a manufacturing method with less environmental impact. Furthermore, the aluminum alloy foil (layer) in the laminate easily dissolves even when the laminate using the aluminum alloy foil of the present invention is disposed of, so that it is extremely easy to separate the resin film layer and recycle it.
  • 1a, 1b, 1c, 1d Aluminum alloy foil 2a, 2b, 2c, 2d: Aluminum parent phase 3a, 3c: Second phase particles having an equivalent circle diameter of 0.1 ⁇ m or more 4b, 4d: Second phase particles having an equivalent circle diameter of 3.0 ⁇ m or more

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PCT/JP2023/038351 2022-11-28 2023-10-24 アルミニウム合金箔、アルミニウム合金箔を用いた積層体およびそれらの製造方法 Ceased WO2024116659A1 (ja)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007070714A (ja) * 2005-09-09 2007-03-22 Mitsubishi Alum Co Ltd 抗菌性アルミニウム展伸材及びその製造方法
JP2008024992A (ja) * 2006-07-21 2008-02-07 Toyo Aluminium Kk 印刷回路用アルミニウム合金箔
JP2018537292A (ja) * 2015-11-13 2018-12-20 グランジェス・アーベー ろう付けシート及びその製造方法
JP2021532985A (ja) * 2018-06-21 2021-12-02 アーコニック テクノロジーズ エルエルシーArconic Technologies Llc 耐食性高強度ろう付けシート
WO2022196574A1 (ja) * 2021-03-17 2022-09-22 Ｍａアルミニウム株式会社 ろう付用アルミニウムブレージングシートおよびその製造方法

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JP2008121090A (ja) 2006-11-15 2008-05-29 Mitsubishi Alum Co Ltd 印刷回路用アルミニウム箔

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007070714A (ja) * 2005-09-09 2007-03-22 Mitsubishi Alum Co Ltd 抗菌性アルミニウム展伸材及びその製造方法
JP2008024992A (ja) * 2006-07-21 2008-02-07 Toyo Aluminium Kk 印刷回路用アルミニウム合金箔
JP2018537292A (ja) * 2015-11-13 2018-12-20 グランジェス・アーベー ろう付けシート及びその製造方法
JP2021532985A (ja) * 2018-06-21 2021-12-02 アーコニック テクノロジーズ エルエルシーArconic Technologies Llc 耐食性高強度ろう付けシート
WO2022196574A1 (ja) * 2021-03-17 2022-09-22 Ｍａアルミニウム株式会社 ろう付用アルミニウムブレージングシートおよびその製造方法

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