WO2015015768A1 - Matériau en aluminium à surface traitée et son procédé de fabrication - Google Patents

Matériau en aluminium à surface traitée et son procédé de fabrication Download PDF

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WO2015015768A1
WO2015015768A1 PCT/JP2014/003880 JP2014003880W WO2015015768A1 WO 2015015768 A1 WO2015015768 A1 WO 2015015768A1 JP 2014003880 W JP2014003880 W JP 2014003880W WO 2015015768 A1 WO2015015768 A1 WO 2015015768A1
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oxide film
aluminum material
aluminum
corrosion
porous
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PCT/JP2014/003880
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English (en)
Japanese (ja)
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達矢 三村
長谷川　真一
幸翁 本川
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株式会社Uacj
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Priority to JP2015529376A priority Critical patent/JP6563336B2/ja
Priority to CN201480041347.9A priority patent/CN105408527B/zh
Priority to KR1020157035097A priority patent/KR102155398B1/ko
Publication of WO2015015768A1 publication Critical patent/WO2015015768A1/fr

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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
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/005—Apparatus specially adapted for electrolytic conversion coating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/024—Anodisation under pulsed or modulated current or potential
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/007—Current directing devices
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
    • H05K1/053—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an inorganic insulating layer

Definitions

  • the present invention relates to a surface-treated pure aluminum material or aluminum alloy material (hereinafter referred to as “aluminum material”) and a method for producing the same, and more specifically, a corrosion-resistant oxide film layer having excellent corrosion resistance on a part of the surface.
  • aluminum material a surface-treated pure aluminum material or aluminum alloy material
  • the present invention relates to a surface-treated aluminum material in which a porous oxide film layer having excellent adhesion and adhesion is formed at a portion of the surface where the corrosion-resistant oxide film layer is not formed and a method for producing the same.
  • Aluminum materials are lightweight, have appropriate mechanical properties, and have excellent characteristics such as aesthetics, moldability, and corrosion resistance, so they can be used in various containers, structural materials, mechanical parts, electronic parts, etc. Widely used.
  • functions such as corrosion resistance, abrasion resistance, resin adhesion, adhesion, hydrophilicity, water repellency, antibacterial properties, design properties, infrared radiation, high reflectivity, etc. Often added and improved.
  • anodizing treatment for improving corrosion resistance and wear resistance
  • anodizing treatment is widely used.
  • an anodized film is formed by immersing an aluminum material in an acidic electrolytic bath and performing electrolytic treatment with a direct current. Accordingly, various processing methods have been proposed.
  • Patent Document 1 proposes an alkaline alternating current electrolysis method. That is, using an alkaline solution of a bath temperature 35 ⁇ 85 ° C., the time that the quantity of electricity exceeds 80C / dm 2 at a current density of 4 ⁇ 50A / dm 2, and performs an AC electrolysis process. As a result, a printed wiring board on which an oxide film having a thickness of 500 to 5000 mm is formed is obtained.
  • the electrolytic treatment is performed by directly connecting to the aluminum material, the aluminum material itself becomes the electrode.
  • the surface treatment is applied to the entire area where the aluminum material is in contact with the electrolytic solution.
  • the surface portion not subjected to the treatment is covered with a masking tape or the like. Since the surface treatment is performed on the uncoated portion, the resin adhesion is improved. However, since the portion where the coating is removed after the surface treatment is not subjected to the surface treatment, it is desirable that the resin adhesion is not given, but there is a disadvantage that the corrosion resistance cannot be obtained.
  • the present inventors have formed a corrosion-resistant oxide film only on a specific portion, and a portion having no corrosion-resistant oxide film has a porous property having adhesion.
  • the present invention has been completed by finding a surface-treated aluminum material on which a porous oxide film is formed, and a method for producing the surface-treated aluminum material that simultaneously forms the corrosion-resistant oxide film and the porous oxide film.
  • the present invention according to claim 1 is formed at a site where the aluminum material, the corrosion-resistant oxide film having a single-layer structure formed on a part of the surface thereof, and the corrosion-resistant oxide film on the surface of the aluminum material are not formed.
  • the corrosion-resistant oxide film has a thickness of 10 to 100 nm, the peak absorption wave number by FT-IR analysis is b (cm ⁇ 1 ), and the peak absorption rate at the peak absorption wave number b Is a porous aluminum oxide film layer having a thickness of 20 to 500 nm, which satisfies the relationship of 1 ⁇ a ⁇ 95 and b ⁇ 3a + 710, and is formed on the surface side.
  • a barrier type aluminum oxide film layer having a thickness of 3 to 30 nm formed on the substrate side.
  • the porous aluminum oxide film layer has small holes with a diameter of 5 to 30 nm.
  • the fluctuation width of the total thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer is an arithmetic average of the total thickness.
  • the surface-treated aluminum material was characterized by being within ⁇ 50% of the value.
  • the peak absorption wave number b (cm ⁇ 1 ) is a peak wave number resulting from the strongest stretching vibration of Al—O, and appears in a range of 720 ⁇ b ⁇ 995. It was supposed to be.
  • the ratio of the total hole area of the small holes to the apparent surface area of the porous aluminum oxide film layer in the first or second aspect is 25 to 75%.
  • the present invention according to claim 4 uses an aluminum material electrode to be surface-treated, a counter electrode, and a conductive material connected to the aluminum material electrode, has a pH of 9 to 13 and a liquid temperature of 35 to 85 ° C., and By using an aqueous alkaline solution having a dissolved aluminum concentration of 5 ppm or more and 1000 ppm or less as an electrolytic solution and subjecting it to an alternating current electrolytic treatment under conditions of a frequency of 10 to 100 Hz, a current density of 4 to 50 A / dm 2 and an electrolysis time of 5 to 60 seconds, A surface-treated aluminum material characterized by forming a porous oxide film on the surface of the facing aluminum material and simultaneously forming a corrosion-resistant oxide film on the surface of the aluminum material facing the conductive material connected to the aluminum material electrode. It was set as the manufacturing method.
  • the surface of the aluminum material to be surface-treated and the counter electrode are both flat, and the area of the conductive material connected to the aluminum material electrode in the electrolytic solution is as follows.
  • the area where the corrosion-resistant oxide film is to be formed is 80 to 150%, and the distance between the conductive material and the aluminum material is 1 to 50 mm.
  • the conductive material connected to the aluminum material electrode in claim 4 or 5 is made of a stainless steel material or a copper material.
  • a conductive material is disposed on one surface side of the aluminum material electrode so as to face this surface, and the other surface side of the aluminum material electrode By arranging the counter electrode so as to face this surface, a corrosion-resistant oxide film is formed on the one surface of the aluminum electrode, and a porous oxide film is formed on the other surface.
  • the counter electrode is disposed on the other surface side of the aluminum material electrode so as to face the surface, and the other surface and the counter electrode are arranged.
  • the conductive material is disposed so as to face a part of the other surface of the aluminum material electrode, and the pair of the conductive material is opposed to another part complementary to the part of the other surface of the aluminum material electrode.
  • a surface treatment is characterized in that a corrosion-resistant oxide film is formed on a part of the surface, and a porous oxide film having adhesion is formed in a portion where the corrosion-resistant oxide film is not formed.
  • a corrosion-resistant oxide film 3 is formed on a part of the surface of the surface-treated aluminum material 1 according to the present invention.
  • the porous oxide film 4 is formed in the site
  • A. About aluminum material As an aluminum material used for this invention, pure aluminum or an aluminum alloy is used. There is no restriction
  • Corrosion-resistant oxide film structure on aluminum material surface As shown in FIG. 1, an amorphous corrosion-resistant oxide film having a thickness of 10 to 100 nm, preferably 20 to 80 nm, is formed on a part of the surface of the aluminum material 2 used in the present invention. 3 is formed.
  • This corrosion-resistant oxide film 3 is a film having a single layer structure. In the case of a multi-layer structure that is not a single-layer structure, crevice corrosion occurs between the surface layer and the intermediate layer, so that sufficient corrosion resistance is not exhibited. Further, the corrosion-resistant oxide film 3 can be formed on the entire surface of the aluminum material 2. When the thickness of the corrosion resistant oxide film 3 is less than 10 nm, sufficient corrosion resistance cannot be obtained. On the other hand, when the thickness exceeds 100 nm, it is difficult to control the thickness of the corrosion-resistant oxide film, and processing unevenness occurs.
  • the film quality of the corrosion-resistant oxide film 3 is analyzed by FT-IR (Fourier transform infrared spectrophotometer), and the peak absorption wave number b (cm ⁇ 1 ) of the infrared absorption spectrum and the baseline at the peak absorption wave number Characterized by the peak absorption from (a%).
  • the peak absorption wave number b (cm ⁇ 1 ) refers to the peak absorption wave number resulting from the strongest stretching vibration of Al—O.
  • the peak absorption wave number b (cm ⁇ 1 ) usually appears in the range of 720 ⁇ b ⁇ 995.
  • the peak absorption rate a (%) when analyzed by FT-IR is defined as 1 ⁇ a ⁇ 95, preferably 2 ⁇ a ⁇ 75. If this peak absorption rate is less than 1%, the thickness of the corrosion-resistant oxide film is less than 10 nm, resulting in insufficient corrosion resistance. When the peak absorption rate exceeds 95%, the thickness of the corrosion-resistant oxide film exceeds 100 nm, and it becomes difficult to control the thickness of the corrosion-resistant oxide film, and processing unevenness is likely to occur.
  • the peak absorption rate a (%) and the peak absorption wave number b (cm ⁇ 1 ) satisfy the relationship of b ⁇ 3a + 710, preferably b ⁇ 3a + 720.
  • this relationship is not satisfied, the corrosion resistance is deteriorated because the film shape of the corrosion-resistant oxide film becomes a porous shape.
  • Porous oxide film structure on aluminum material surface As shown in FIG. 2, a porous oxide film 4 is formed on the surface of the aluminum material where the corrosion-resistant oxide film is not formed.
  • the porous oxide film 4 includes a barrier-type aluminum oxide film layer 41 on the base side of the aluminum material 2 and a porous aluminum oxide film layer 42 on the surface layer side.
  • the thickness of the porous aluminum oxide film layer 42 is 20 to 500 nm. If the thickness is less than 20 nm, the thickness is not sufficient, so that the formation of a small pore structure, which will be described later, is likely to be insufficient, and the adhesive force and adhesion force are reduced. On the other hand, when the thickness exceeds 500 nm, the porous aluminum oxide film layer itself tends to cohesively break down, and the adhesive force and adhesion force are reduced.
  • the thickness of the porous aluminum oxide film layer 42 is preferably 30 to 400 nm.
  • the porous aluminum oxide film layer 42 includes small holes 420 that extend from the surface in the depth direction.
  • the diameter of the small holes 420 is 5 to 30 nm, preferably 10 to 20 nm. This small hole increases the contact area between the resin layer, the adhesive, and the like and the aluminum oxide film, and exhibits the effect of increasing the adhesive force and the adhesive force. If the diameter of the small hole is less than 5 nm, the contact area is insufficient, and sufficient adhesive force and adhesion force cannot be obtained. On the other hand, if the diameter of the small holes exceeds 30 nm, the entire porous aluminum oxide film layer becomes brittle and causes cohesive failure, resulting in a decrease in adhesion and adhesion.
  • the ratio of the total hole area of the small holes to the surface area of the porous aluminum oxide film layer is not particularly limited.
  • the ratio of the total hole area of the small holes to the apparent surface area of the porous aluminum oxide film layer is 25 to 75%. preferable. If it is less than 25%, the contact area may be insufficient and sufficient adhesive force or adhesion may not be obtained. On the other hand, if it exceeds 75%, the porous aluminum oxide film layer as a whole becomes brittle, causing cohesive failure and reducing the adhesive strength and adhesion.
  • the barrier type aluminum oxide film layer 41 is a dense oxide film having a thickness of 3 to 30 nm. If the thickness is less than 3 nm, sufficient bonding force cannot be imparted to the bonding between the porous aluminum oxide film layer 4 and the aluminum substrate 2 as an intervening layer. It becomes insufficient. On the other hand, if the thickness exceeds 30 nm, the barrier type aluminum oxide film layer 3 tends to cohesively break due to its denseness, and on the contrary, the adhesive strength and the adhesive strength are lowered.
  • the thickness of the barrier type aluminum oxide film layer 41 is preferably 5 to 25 nm.
  • the fluctuation range must be within ⁇ 50%, preferably within ⁇ 20%, regardless of where the porous oxide film 4 is formed. That is, the arithmetic average value of the total thickness of the porous oxide film measured at any plurality of locations on the aluminum material surface (preferably 10 locations or more and preferably 10 or more measurement points in each location) is T In the case of (nm), the total thickness of the porous oxide film in all of the plurality of measurement locations needs to be in the range of (0.5 ⁇ T) to (1.5 ⁇ T).
  • the porous oxide film at that location becomes thinner than its surroundings. Then, in this thin area, a gap is likely to be generated between the porous oxide film and the adhesive to be adhered or the resin layer to be adhered, and the sufficient contact area cannot be secured and the adhesion and adhesion are reduced. To do.
  • the optical characteristics are different in the portion where the total thickness of the porous oxide film as described above is thin or thick, it may be visible as a change in color tone such as brown or cloudy color.
  • Corrosion-resistant oxide film is formed on this part, and the part on the surface of the aluminum material facing the counter electrode is porous And a method in which reduction film is formed.
  • only the corrosion-resistant oxide film can be formed on the surface by making the entire surface of the aluminum material face the conductive material.
  • the surface-treated aluminum material according to the present invention performs an alternating current electrolytic treatment using an aluminum material electrode to be surface treated, a conductive material connected to the aluminum material electrode, and a counter electrode.
  • the conductive material connected to the electrode of the aluminum material to be surface-treated is arranged in the electrolytic solution in the vicinity of the surface portion of the aluminum material on which the corrosion-resistant oxide film is to be formed so as to face the surface portion.
  • a porous oxide film is formed on the surface portion of the aluminum material that is not opposed to the conductive material.
  • the area of the conductive material facing the aluminum material is 80 to 150%, preferably 90 to 130%, of the area of the aluminum material on which the corrosion-resistant oxide film is to be formed.
  • the distance between the conductive material facing the aluminum material is 1 to 50 mm. If the area of the conductive material is less than 80% of the area of the aluminum material for which the corrosion-resistant oxide film is to be formed, a porous oxide film may be formed in a portion where the corrosion-resistant oxide film is to be formed. In some cases, the corrosion-resistant oxide film may be formed on the portion where the porous oxide film is to be formed.
  • the distance between the conductive material facing the aluminum material is less than 1 mm, convection of the electrolytic solution hardly occurs between the conductive material and the facing aluminum material, and uneven treatment of the corrosion-resistant oxide film is likely to occur.
  • the distance exceeds 50 mm the distance between the conductive material and the facing aluminum material is too wide, so that a porous oxide film is formed on the entire surface of the aluminum material.
  • the alkaline aqueous solution used as the electrolytic solution in the AC electrolytic treatment step is a phosphate such as sodium phosphate, potassium hydrogen phosphate, sodium pyrophosphate, potassium pyrophosphate and sodium metaphosphate; sodium hydroxide and potassium hydroxide.
  • An alkali metal hydroxide such as sodium carbonate, a carbonate such as sodium carbonate, sodium hydrogen carbonate, or potassium carbonate; an ammonium hydroxide; or an aqueous solution of a mixture thereof can be used. Since it is necessary to keep the pH of the electrolytic solution in a specific range as will be described later, it is preferable to use an alkaline aqueous solution containing a phosphate-based substance that can be expected to have a buffer effect.
  • the concentration of the alkali component contained in such an alkaline aqueous solution is appropriately adjusted so that the pH of the electrolytic solution becomes a desired value, but is usually 1 ⁇ 10 ⁇ 4 to 1 mol / liter, preferably 1 ⁇ 10 6. -3 to 0.8 mol / liter.
  • the pH of the electrolytic solution needs to be 9 to 13, and preferably 9.5 to 12.
  • the pH is less than 9, the alkaline etching power of the electrolytic solution is insufficient, so that the porous oxide film becomes an amorphous film and the formation of the predetermined porous aluminum oxide film layer and the barrier type aluminum oxide film layer becomes incomplete.
  • the pH is less than 9, it is difficult to control the thickness of the corrosion-resistant oxide film, and uneven processing tends to occur.
  • the pH exceeds 13 the alkaline etching force becomes excessive, and the oxide film layer is difficult to grow, and the formation of a desired porous oxide film is hindered.
  • the electrolytic solution temperature needs to be 35 to 85 ° C, preferably 40 to 70 ° C.
  • the electrolytic bath temperature is less than 35 ° C.
  • the formation of the porous oxide film becomes incomplete because the alkaline etching power is insufficient.
  • the temperature exceeds 85 ° C. the alkali etching force becomes excessive, and thus the formation of the porous oxide film and the corrosion-resistant oxide film is hindered.
  • the concentration of dissolved aluminum contained in the electrolytic solution needs to be 5 ppm or more and 1000 ppm or less, and preferably 10 ppm or more and 500 ppm or less.
  • the dissolved aluminum concentration is less than 5 ppm, the formation reaction of the oxide film at the initial stage of the electrolytic reaction occurs abruptly, resulting in the formation of a locally thick porous oxide film and unevenness in the corrosion-resistant oxide film.
  • the dissolved aluminum concentration exceeds 1000 ppm, the viscosity of the electrolytic solution is increased, and uniform convection near the surface of the aluminum material is prevented in the electrolysis process, and at the same time, the dissolved aluminum suppresses the formation of a porous oxide film. Act on.
  • the concentration of dissolved aluminum deviates from the above range, the fluctuation width of the total thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer in the entire porous oxide film formed on the surface of the aluminum material is determined as follows. It becomes difficult to make it within ⁇ 50% of the arithmetic average value of the total thickness. As a result, the resulting porous oxide film is deteriorated in adhesion and adhesion.
  • the frequency used is 10 to 100 Hz. If the frequency is less than 10 Hz, a direct current element increases as electrolysis, and as a result, the formation of the porous aluminum oxide film layer does not proceed and a dense structure is obtained. On the other hand, when the frequency exceeds 100 Hz, the reversal of the anode and the cathode is too fast, so that the formation of the entire oxide film becomes extremely slow, and it takes an extremely long time to obtain a predetermined thickness for both the porous oxide film and the corrosion-resistant oxide film. It will take.
  • the frequency used is preferably 20 to 80 Hz.
  • the current density needs to be 4 to 50 A / dm 2 .
  • the current density is less than 4 A / dm 2 , only the barrier type aluminum oxide film layer is preferentially formed in the porous oxide film, so that the porous type aluminum oxide film layer cannot be obtained.
  • the current density is preferably 5 to 30 A / dm 2 .
  • Electrolysis time should be 5-60 seconds. When the treatment time is less than 5 seconds, the porous oxide film is formed too rapidly, so that the porous aluminum oxide film layer is not sufficiently formed, resulting in an oxide film composed of amorphous aluminum oxide. On the other hand, if it exceeds 60 seconds, the oxide film is re-dissolved, so that the corrosion-resistant oxide film layer is not sufficiently formed, and the productivity is also lowered.
  • the electrolysis time is preferably 10 to 50 seconds.
  • One electrode of the pair of electrodes used for the alternating current electrolytic treatment is an aluminum material to be surface-treated by electrolytic treatment.
  • the other counter electrode for example, a known electrode such as a graphite, aluminum, or titanium electrode can be used.
  • the electrode does not deteriorate with respect to the alkaline component or temperature of the electrolytic solution, and has excellent conductivity. Must be made of a material that does not cause an electrochemical reaction. From such points, a graphite electrode is preferably used as the counter electrode. This is because the graphite electrode is chemically stable, inexpensive and easily available, and due to the action of many pores existing in the graphite electrode, the electric lines of force diffuse moderately in the AC electrolysis process. This is because the porous oxide film and the corrosion-resistant oxide film tend to be more uniform.
  • the conductive material connected to the portion where the corrosion-resistant oxide film is formed on the aluminum material by the electrolytic treatment needs to have a higher electrode potential than the aluminum material.
  • a conductive material having a higher electrode potential than the aluminum material is connected to the aluminum material, and is placed in the vicinity of the aluminum material to perform electrolysis, thereby causing the cathode reaction in the alternating current electrolysis to occur on the surface of the conductive material, and the anode reaction to the aluminum material and conductive It can occur on the surface of the material. Therefore, a corrosion-resistant oxide film is formed on the aluminum material surface by the anodic reaction.
  • the conductive material having a higher electrode potential than the aluminum material is, for example, gold, platinum, copper, iron, stainless steel, nickel or the like. In the present invention, stainless steel or copper is preferably used. This is because it is excellent in corrosion resistance in an alkaline solution, inexpensive and easy to process.
  • both the aluminum material to be electrolytically treated and the counter electrode are flat, and the opposing aluminum material and the opposing surface of the counter electrode have substantially the same dimensions, and both electrodes are electrolyzed in a stationary state. It is preferable to perform the operation. As shown in FIG. 3, it is preferable to prepare the counter electrode 5 and install the surface of the aluminum material 2 to be surface-treated so as to face the counter electrode plate 5 so as to be parallel to the surface of the counter electrode 5. .
  • 7 is an AC power source
  • 8 is an electrolytic solution.
  • the shape of the conductive material 6 connected to the flat plate-shaped aluminum material 2 to be subjected to electrolytic treatment does not have to be a flat plate shape, and may be a net shape or a multi-hole shape.
  • a conductive material 6 is disposed on one surface (the left surface in the drawing) side of the surface-treated aluminum material 2 so as to face this surface, and the other surface of the aluminum material 2 is disposed.
  • the counter electrode 5 is disposed so as to face this surface, and alternating current electrolysis is performed, whereby a corrosion-resistant oxide film is formed on the one surface of the aluminum material 2, and the other A porous oxide film can be formed on the surface.
  • a conductive material 6 is provided between the other surface (the right surface in the drawing) of the aluminum material 2 to be surface-treated and the counter electrode 5 corresponding to this surface. It can also be arranged.
  • a part (the upper half in the figure) of the other surface of the aluminum material 2 is opposed to the conductive material 6, and the other part (the lower half in the figure) of the other surface of the aluminum material 2 is The conductive material 6 is opposed to the counter electrode 5.
  • a corrosion-resistant oxide film is formed on a part of the other surface of the aluminum material facing the conductive material 6, and the other of the aluminum materials facing the counter electrode 5 instead of the conductive material 6 is formed.
  • a porous oxide film is formed on another part of the surface, and a corrosion-resistant oxide film and a porous oxide film can be formed on the same surface of the aluminum material 2.
  • a part of the other surface of the aluminum material 2 (the lower half in the drawing) is made to face the conductive material 6, and the other portion of the other surface of the aluminum material 2 (the upper half in the drawing). Is arranged so as to face the counter electrode 5 instead of the conductive material 6, thereby forming a corrosion-resistant oxide film on a part of the other surface and forming a porous oxide film on the other part of the other surface. May be.
  • the part facing the conductive material 6 as a part of the other surface of the aluminum material 2 can have any shape, size and position.
  • part of the other surface of the aluminum material 2 can be made into a part complementary to the said part in the other surface.
  • TEM transmission electron microscope
  • a JIS 5052 flat plate having a length of 500 mm, a width of 500 mm, and a thickness of 1.0 mm was used.
  • This aluminum plate was used as one electrode, and a graphite plate or a titanium plate having a length of 500 mm, a width of 550 mm, and a thickness of 2.0 mm was used as the counter electrode.
  • the counter electrode 5 and the aluminum material 2 were disposed so as to be parallel to each other.
  • a conductive material 6 is disposed in the vicinity of the surface of the aluminum alloy plate 2 opposite to the counter electrode 5, and a corrosion-resistant oxide film is provided on the entire surface of the aluminum alloy plate 2 on the conductive material 6 side, and the entire surface of the counter electrode side is porous. An oxide film was formed.
  • Example 24 as shown in FIG. 4, a part (the upper half in the drawing) of the other surface (the right-hand surface in the drawing) of the aluminum material 2 is opposed to the conductive material, The other part of the other surface (the lower half in the figure) is disposed so as to face the counter electrode 5 instead of the conductive material 6, and a corrosion-resistant oxide film and a porous oxide film are formed on the same surface of the aluminum material 2. Formed.
  • Example 1 a SUS304 stainless steel plate having a length of 500 mm, a width of 500 mm, and a thickness of 0.5 mm was used as the conductive material.
  • Example 15 a copper plate having a length of 500 mm, a width of 500 mm, and a thickness of 0.5 mm was used.
  • Example 16 a SUS304 stainless steel wire mesh having a length of 500 mm ⁇ width of 500 mm, a line diameter of 0.5 mm, a space ratio of 64.5%, and 10 mesh was used.
  • Example 17 SUS304 stainless steel punching metal having a length of 500 mm ⁇ width of 500 mm, a hole diameter of 6 mm, and a distance between holes (pitch) of 8 mm was used.
  • Example 22 a SUS304 stainless steel plate having a length of 480 mm, a width of 480 mm, and a thickness of 0.5 mm was used.
  • Example 23 a SUS304 stainless steel plate having a length of 570 mm, a width of 570 mm, and a thickness of 0.5 mm was used.
  • Example 24 a SUS304 stainless steel plate having a length of 250 mm, a width of 500 mm, and a thickness of 0.5 mm was used.
  • the distance between the conductive material and the aluminum alloy plate was 5 mm in Examples 1 to 17, 22 to 24, and Comparative Examples 1 to 13. In Example 18, it was 2 mm, in Example 19, 45 mm, in Example 20, 0.5 mm, and in Example 21, 55 mm. In addition, in the area ratio of the electrically conductive material with respect to the area of the aluminum material shown in Table 1, the area of the electrically conductive material was calculated
  • an alkaline aqueous solution mainly composed of sodium pyrophosphate having the pH, temperature, and dissolved aluminum concentration shown in Table 1 was used as the electrolytic solution.
  • the pH of the electrolytic solution was adjusted with a 0.1 mol / liter NaOH aqueous solution.
  • the alkaline component concentration of the alkaline aqueous solution was 0.1 mol / liter.
  • the test material of the surface treatment aluminum material which implemented the electrolysis process on the alternating current electrolysis process conditions shown in Table 1 formed the corrosion-resistant oxide film in one surface of the aluminum plate, and formed the porous oxide film in the other surface was made.
  • the cross section of the corrosion-resistant oxide film was observed by TEM for the test material produced as described above. Specifically, the thickness of the corrosion-resistant oxide film was measured, and the structure of the corrosion-resistant oxide film (whether the film layer has a single layer structure) was observed. In order to measure the thickness of the corrosion-resistant oxide film and observe the structure of the corrosion-resistant oxide film, a slice sample for cross-sectional observation was prepared from the test material using an ultramicrotome.
  • any 100 points in the observation field (1 ⁇ m ⁇ 1 ⁇ m) are selected, and the thickness of the corrosion-resistant oxide film is measured by TEM cross-sectional observation, and whether or not the corrosion-resistant oxide film has a single-layer structure.
  • the case of a single layer structure was marked with ⁇ , and the case of no single layer structure was marked with x).
  • the evaluation is acceptable ( ⁇ ), and the thickness of the corrosion-resistant oxide film is not in the range of 10 to 100 nm and The evaluation in at least one of the cases where the corrosion-resistant oxide film is not a single layer structure was determined to be rejected (x).
  • Table 2 The results are shown in Table 2.
  • the diameter of the small holes in the porous oxide film layer was measured at each point.
  • the maximum value, the minimum value, and the arithmetic average value of the total thickness of 100 porous aluminum oxide film layers and barrier aluminum oxide film layers thus measured were determined. Further, it was also examined whether or not the fluctuation range of the total thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer was within ⁇ 50% of the arithmetic average value. Specifically, when the arithmetic average value is T (nm), the total thickness including the maximum value and the minimum value is in the range of (0.5 ⁇ T) to (1.5 ⁇ T). A case where it was acceptable was determined to be acceptable (O), and a case where it was not in range was regarded as unacceptable (x). In Example 24, the surface on the side facing the counter electrode was used. The results are shown in Table 2.
  • the lengthwise ends of the two specimens are pulled in the opposite direction along the length direction at a speed of 10 mm / min with a tensile tester, and the adhesive is changed depending on the load (converted to shear stress) and the peeled state.
  • the adhesion was evaluated according to the following criteria.
  • the shear test piece produced 10 sets of test pieces, and evaluated each.
  • the surface on the side facing the counter electrode was used.
  • ⁇ The shear stress is 20 N / mm 2 or more and the adhesive layer itself is agglomerated and broken ⁇ : The shear stress is 20 N / mm 2 or more, but the adhesive layer and the test material are separated at the interface ⁇ : Shear stress is less than 20 N / mm 2 and the state where the adhesive layer and the specimen were peeled from each other The results are shown in Table 3. The table shows the number of pairs of the above-mentioned ⁇ , ⁇ , and ⁇ of 10 sets of test pieces, respectively.
  • the test piece was subjected to a peel test using a transparent pressure-sensitive adhesive tape.
  • the adhesion was evaluated according to the following criteria by the coating film residual ratio.
  • the adhesive test piece produced 10 test pieces from the same test material, and evaluated each.
  • the surface on the side facing the counter electrode was used.
  • ⁇ The film remaining rate is 100%.
  • ⁇ The film remaining rate is 75% or more and less than 100%.
  • X The film remaining rate is less than 75%.
  • the table shows the number of the above-mentioned ⁇ , ⁇ , and ⁇ among the 10 test pieces, respectively, and the case where all were ⁇ was determined to be acceptable, and the other was determined to be unacceptable.
  • Comparative Example 1 the pH of the electrolytic solution in AC electrolysis was too low, so that the alkaline etching power was insufficient. Therefore, the diameter of the small holes in the porous aluminum oxide film layer was insufficient, the thickness of the barrier type aluminum oxide film layer was increased, and the fluctuation range of the porous oxide film thickness was increased. As a result, the adhesive adhesion and coating film adhesion of the porous oxide film were rejected, and the overall evaluation was rejected.
  • Comparative Example 6 a large amount of dissolved aluminum was present in the electrolytic solution of AC electrolysis. Therefore, the formation of the barrier type aluminum oxide film layer became non-uniform, and a locally thick part was formed, and the diameter of the small hole of the porous type aluminum oxide film layer was reduced. Furthermore, the fluctuation range of the porous oxide film thickness was increased. As a result, the adhesive adhesion and coating film adhesion of the porous oxide film were rejected, and the overall evaluation was rejected.
  • Comparative Example 11 since the electrolysis time in AC electrolysis was too short, the thickness of the corrosion-resistant oxide film and the thickness of the porous aluminum oxide film layer were insufficient. Moreover, the fluctuation range of the porous oxide film thickness was increased. As a result, the corrosion resistance and film quality of the corrosion-resistant oxide film were rejected, and the adhesive adhesion and coating film adhesion of the porous oxide film were rejected, and the overall evaluation was rejected.
  • Comparative Example 13 the dissolved aluminum was less than 5 ppm in the electrolytic solution of AC electrolysis. Therefore, the formation reaction of the porous oxide film at the initial stage of the electrolytic reaction occurred rapidly, and the fluctuation range of the thickness of the porous oxide film became large. Moreover, the formation of the corrosion-resistant oxide film became non-uniform and the thickness was insufficient. As a result, the corrosion resistance of the corrosion resistant oxide film was rejected, and the adhesive adhesion and coating film adhesion of the porous oxide film were rejected, resulting in a failure of the overall evaluation.
  • the present invention it is possible to obtain a surface-treated aluminum material in which a part of the surface of the aluminum material is excellent in corrosion resistance and the other part of the surface of the aluminum material is excellent in adhesion and adhesion.
  • the surface-treated aluminum material according to the present invention is suitably used for an aluminum-resin bonding member, a printed wiring board, and the like that require adhesion and adhesion only to a part of the aluminum material.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Laminated Bodies (AREA)

Abstract

Le problème à résoudre dans le cadre de la présente invention consiste à fournir un matériau en aluminium à surface traitée sur une partie de la surface duquel une couche de film d'oxyde résistant à la corrosion est formée, une couche de film d'oxyde poreux ayant d'excellentes adhésivité et qualité d'adhérence étant formée sur les autres zones de la surface. La présente invention concerne donc un matériau en aluminium à surface traitée et son procédé de fabrication. Le matériau en aluminium à surface traitée contient un matériau en aluminium, un film d'oxyde résistant à la corrosion et ayant une structure monocouche formé sur une partie de la surface du matériau en aluminium et un film d'oxyde poreux formé sur les autres zones de la surface. Le film d'oxyde résistant à la corrosion a une épaisseur comprise entre 10 et 100 nm et il possède des caractéristiques d'analyse FT-IR spécifiées. Le film d'oxyde poreux est obtenu à partir d'une couche de film d'oxyde d'aluminium poreux ayant une épaisseur comprise entre 20 et 500 nm et formée du côté de la surface, et d'une couche de film d'oxyde d'aluminium barrière ayant une épaisseur comprise entre 3 et 30 nm et formée du côté de la base. Des pores ayant un diamètre de 5 à 30 nm sont formés dans la couche de film d'oxyde d'aluminium poreux. La plage de fluctuation de l'épaisseur dans l'ensemble du film d'oxyde poreux formé sur la surface du matériau en aluminium est inférieure à ±50 % de sa moyenne arithmétique.
PCT/JP2014/003880 2013-08-01 2014-07-23 Matériau en aluminium à surface traitée et son procédé de fabrication WO2015015768A1 (fr)

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JP2015529376A JP6563336B2 (ja) 2013-08-01 2014-07-23 表面処理アルミニウム材及びその製造方法
CN201480041347.9A CN105408527B (zh) 2013-08-01 2014-07-23 表面处理铝材及其制造方法
KR1020157035097A KR102155398B1 (ko) 2013-08-01 2014-07-23 표면 처리 알루미늄재 및 그 제조 방법

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
WO2017026461A1 (fr) * 2015-08-13 2017-02-16 株式会社Uacj Matériau d'aluminium traité en surface offrant une excellente adhésion à la résine, procédé pour le fabriquer et corps assemblé en résine et matériau d'aluminium traité en surface
US11560641B2 (en) 2015-08-13 2023-01-24 Uacj Corporation Surface-treated aluminum material having excellent adhesiveness to resins, method for manufacturing the same, and surface-treated aluminum material-resin bonded body

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110312824B (zh) * 2017-02-22 2022-03-22 株式会社Uacj 表面处理铝材的制备方法
JP7026547B2 (ja) * 2018-03-22 2022-02-28 株式会社Uacj 表面処理アルミニウム合金材及びその製造方法

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JPH0413894A (ja) * 1990-05-03 1992-01-17 Sky Alum Co Ltd 自動車用アルミニウム合金塗装用材及びその製造方法
JP2001020082A (ja) * 1999-07-07 2001-01-23 Kobe Steel Ltd リン酸亜鉛処理用アルミニウム合金材
JP2011021260A (ja) * 2009-07-17 2011-02-03 Furukawa-Sky Aluminum Corp アルミニウム基板及びその製造方法

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JP2630858B2 (ja) 1991-02-26 1997-07-16 スカイアルミニウム株式会社 プリント配線用基板の製造方法

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Publication number Priority date Publication date Assignee Title
JPH0413894A (ja) * 1990-05-03 1992-01-17 Sky Alum Co Ltd 自動車用アルミニウム合金塗装用材及びその製造方法
JP2001020082A (ja) * 1999-07-07 2001-01-23 Kobe Steel Ltd リン酸亜鉛処理用アルミニウム合金材
JP2011021260A (ja) * 2009-07-17 2011-02-03 Furukawa-Sky Aluminum Corp アルミニウム基板及びその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017026461A1 (fr) * 2015-08-13 2017-02-16 株式会社Uacj Matériau d'aluminium traité en surface offrant une excellente adhésion à la résine, procédé pour le fabriquer et corps assemblé en résine et matériau d'aluminium traité en surface
US11560641B2 (en) 2015-08-13 2023-01-24 Uacj Corporation Surface-treated aluminum material having excellent adhesiveness to resins, method for manufacturing the same, and surface-treated aluminum material-resin bonded body

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CN105408527B (zh) 2018-07-13
TWI656223B (zh) 2019-04-11
JPWO2015015768A1 (ja) 2017-03-02
KR102155398B1 (ko) 2020-09-11
CN105408527A (zh) 2016-03-16
JP6563336B2 (ja) 2019-08-21
MY177082A (en) 2020-09-04
TW201510233A (zh) 2015-03-16

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