WO2016009649A1 - Matériau à base d'aluminium traité en surface et son procédé de fabrication ainsi que ledit matériau à base d'aluminium traité en surface/matériau collé à une couche de résine - Google Patents

Matériau à base d'aluminium traité en surface et son procédé de fabrication ainsi que ledit matériau à base d'aluminium traité en surface/matériau collé à une couche de résine Download PDF

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WO2016009649A1
WO2016009649A1 PCT/JP2015/003580 JP2015003580W WO2016009649A1 WO 2016009649 A1 WO2016009649 A1 WO 2016009649A1 JP 2015003580 W JP2015003580 W JP 2015003580W WO 2016009649 A1 WO2016009649 A1 WO 2016009649A1
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oxide film
aluminum material
film layer
aluminum oxide
treated
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PCT/JP2015/003580
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English (en)
Japanese (ja)
Inventor
長谷川　真一
達矢 三村
小山　高弘
佑樹 村岡
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株式会社Uacj
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Priority to CN201580024989.2A priority Critical patent/CN106460221B/zh
Priority to JP2016534285A priority patent/JP6575968B2/ja
Priority to KR1020167025106A priority patent/KR20170032215A/ko
Publication of WO2016009649A1 publication Critical patent/WO2016009649A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • 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
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing

Definitions

  • the present invention relates to a surface-treated aluminum material, a method for producing the same, and the surface-treated aluminum material / resin layer assembly, and more particularly, has excellent long-term adhesion and adhesion over the entire surface of the aluminum material.
  • the present invention relates to a surface-treated aluminum material, a stable production method of such a surface-treated aluminum material, and the surface-treated aluminum material / resin layer assembly excellent in adhesion and adhesion.
  • Aluminum materials or aluminum alloy materials are lightweight, have appropriate mechanical properties, and have excellent characteristics such as aesthetics, moldability, and corrosion resistance. Widely used in various containers, structural materials, machine parts, etc. While these aluminum materials may be used as they are, by applying various surface treatments, corrosion resistance, abrasion resistance, resin adhesion, hydrophilicity, water repellency, antibacterial properties, design properties, infrared radiation, high reflectivity In many cases, functions such as sex are added and improved.
  • anodizing treatment for improving corrosion resistance and wear resistance
  • anodizing treatment is widely used.
  • an aluminum material is immersed in an acidic electrolytic solution and subjected to electrolytic treatment with a direct current, whereby a thickness of several to several tens of ⁇ m is formed on the surface of the aluminum material.
  • Various processing methods have been proposed depending on the application.
  • an alkaline alternating current electrolysis method as in Patent Document 1 comprises a porous aluminum oxide film layer having a thickness of 20 to 500 nm on the aluminum material surface and a barrier type aluminum oxide film layer having a thickness of 3 to 30 nm formed on the substrate side. Small holes having a diameter of 5 to 30 nm are formed, and the fluctuation range of the total thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer on the entire surface of the aluminum material is an arithmetic average of the total thickness. An oxide film that is within ⁇ 50% of the value is formed.
  • an alkaline aqueous solution having an aluminum material electrode and a counter electrode, a pH of 9 to 13, a liquid temperature of 35 to 80 ° C., and a dissolved aluminum concentration of 5 ppm to 1000 ppm is used as an electrolytic solution, and a frequency of 20 to
  • the above oxide film can be obtained by AC electrolytic treatment under the conditions of 100 Hz, current density of 4 to 50 A / dm 2 and electrolysis time of 5 to 60 seconds.
  • the present invention provides a surface-treated aluminum material excellent in long-term adhesion and adhesion over the entire surface of the aluminum material, a stable production method of such a surface-treated aluminum material, and the surface excellent in adhesion and adhesion.
  • the object is to provide a treated aluminum material / resin layer assembly.
  • the present invention according to claim 1 includes an aluminum material and an oxide film formed on at least one of the surfaces thereof, and the oxide film is formed on the surface side of porous aluminum having a thickness of 20 to 500 nm. It comprises an oxide film layer and a barrier type aluminum oxide film layer having a thickness of 3 to 30 nm formed on the substrate side. Small pores having a diameter of 5 to 30 nm are formed in the porous aluminum oxide film layer.
  • the surface-treated aluminum material was characterized in that the moisture contained in the film was 10 ⁇ g / cm 2 or less.
  • the present invention provides that in claim 1, the fluctuation range of the total thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer is ⁇ 50% of the arithmetic average value of the total thickness. It was assumed to be within. It was.
  • the present invention provides the method for producing a surface-treated aluminum material according to claim 1 according to claim 3, wherein the surface-treated aluminum material electrode and the counter electrode are used, the pH is 9 to 13, and the liquid temperature is 35 to 85 ° C.
  • An electrolytic solution is applied to the surface of the aluminum material facing the counter electrode by subjecting it to an alternating current electrolytic treatment under the 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 300 seconds. And the aluminum material on which the oxide film is formed is exposed to an atmosphere exceeding 150 ° C.
  • the electrolytic solution of the alkaline aqueous solution contains 5 ppm or more and 1000 ppm or less of dissolved aluminum.
  • the time t (second) for exposure to the atmosphere exceeding 150 ° C. is the porous aluminum oxide film layer thickness L (nm) and the atmospheric temperature is T (° C.). ) To satisfy the relationship of t ⁇ 20 ⁇ L / T.
  • the surface temperature of the aluminum material in which the oxide film is formed by exposure to an atmosphere exceeding 150 ° C. after the end of the alternating current electrolysis treatment is 150 ° C. according to any one of claims 3 to 5. It was assumed that the time to reach was within 24 hours.
  • the relative humidity of the atmosphere is 50% or less.
  • the present invention provides a bonded body of surface-treated aluminum material / resin layer characterized in that, in claim 8, a resin layer is joined to the surface-treated surface of the surface-treated aluminum material according to claim 1 or 2. .
  • the resin used for the resin layer has at least one polar functional group selected from an amino group, an amide group, an ester group, a carboxyl group, an epoxy group, and a hydroxyl group. It was.
  • the value of the following formula 1 is 0.01 or more and 3 0.0 or less.
  • a surface-treated aluminum material excellent in adhesiveness and adhesiveness can be formed on the entire surface of the aluminum material by uniformly forming a highly adhesive and highly adhesive oxide film that is stable over a long period of time against a resin or the like.
  • the oxide film on the surface of the aluminum material has a two-layer structure of a porous aluminum oxide film layer and a barrier type aluminum oxide film layer.
  • the porous aluminum oxide film layer having a thickness of 20 to 500 nm formed on the surface side of the aluminum material and having a small hole with a diameter of 5 to 30 nm suppresses its own cohesive failure. By increasing the surface area, the adhesiveness and adhesion to a bonded product such as a resin are improved.
  • the barrier type aluminum oxide film layer having a thickness of 3 to 30 nm formed on the substrate side of the aluminum material is used to bond the aluminum substrate and the porous aluminum oxide film layer to improve the adhesion and adhesion.
  • the moisture contained in the oxide film is 10 ⁇ g / cm 2 or less, the area where the bonded product such as resin comes into contact with the porous aluminum oxide film layer is increased, and the porous film is porous during a long period of time.
  • the amount of water vapor generated inside the aluminum oxide film can be reduced, and as a result, high adhesion and adhesion can be maintained over a long period of time.
  • the surface-treated aluminum material thus obtained can be applied to various applications by coating the treated surface with a joined material such as a resin due to its excellent adhesiveness.
  • a resin when used as the bonded product, both a thermosetting resin and a thermoplastic resin are applicable, and various effects are imparted in combination with the oxide film formed on the specific treated surface of the present invention.
  • the joined body of an aluminum material and a resin has a higher coefficient of thermal expansion than the aluminum material, the interface is easily peeled off or cut.
  • the joined body of the surface-treated aluminum material and the resin according to the present invention since the adhesion is high, the stress generated at the joint interface due to the difference in the coefficient of thermal expansion is caused by the inside of the surface-treated aluminum material and / or the resin. Accumulated as stress. As a result, peeling and cutting at the interface are suppressed.
  • the joined body of the surface-treated aluminum material and the thermoplastic resin according to the present invention can be suitably used as a lightweight and highly rigid composite material.
  • the joined body of the surface-treated aluminum material and the thermosetting resin according to the present invention can be suitably used for printed wiring board applications and the like.
  • the surface-treated aluminum material is stabilized by performing heat treatment under suitable conditions after the electrolytic treatment, in addition to appropriately setting the AC electrolytic treatment conditions. Can be manufactured.
  • FIG. 6 is a chart of an infrared absorption spectrum for schematically explaining a region representing an integral value of a denominator of Equation 1.
  • the surface-treated aluminum material according to the present invention has an oxide film formed on the surface thereof, and the oxide film has a porous aluminum oxide film layer formed on the surface side and a barrier type aluminum oxide film layer formed on the substrate side. It consists of. Small pores are formed in the porous aluminum oxide film layer.
  • Aluminum material As the aluminum material used in the present invention, pure aluminum or an aluminum alloy is used. There is no restriction
  • the plate thickness can be appropriately selected depending on the application, but is preferably 0.05 to 2.0 mm, more preferably 0.1 to 1.0 mm from the viewpoint of weight reduction and formability.
  • a porous aluminum oxide film layer formed on the surface side and a barrier type aluminum oxide film layer formed on the substrate side are formed on the surface of the aluminum material. That is, an oxide film composed of two layers of a porous aluminum oxide film layer and a barrier type aluminum oxide film layer is provided on the surface of the aluminum material. While the porous aluminum oxide film layer exhibits strong adhesion and adhesion for a long period of time, the entire aluminum oxide film layer and the aluminum substrate are firmly bonded by the barrier type aluminum oxide film layer.
  • Porous aluminum oxide film layer The thickness of the porous aluminum oxide film layer 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 adhesion is reduced.
  • the thickness of the porous aluminum oxide film layer is preferably 50 to 400 nm.
  • the porous aluminum oxide film layer has small holes extending from the surface in the depth direction.
  • the diameter of the small holes 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 pore area of the small pores to the surface area of the porous aluminum oxide film layer is not particularly limited.
  • the ratio of the total pore area of the small pores 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 entire porous aluminum oxide film layer becomes brittle and may cause cohesive failure, resulting in a decrease in adhesion and adhesion.
  • the thickness of the barrier type aluminum oxide film layer is 3 to 30 nm. If the thickness is less than 3 nm, a sufficient bonding force cannot be imparted to the bonding between the porous aluminum oxide film layer and the aluminum substrate as the intervening layer, and the bonding force particularly in a severe environment such as high temperature and high humidity becomes insufficient. On the other hand, if the thickness exceeds 30 nm, the barrier type aluminum oxide film layer 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 is preferably 5 to 25 nm.
  • the moisture content contained in the oxide film must be 10 ⁇ g / cm 2 or less. Specifically, the moisture detected from 1 cm 2 of the apparent surface area portion (length ⁇ width) of the surface-treated aluminum material needs to be 10 ⁇ g / cm 2 or less. Considering the structure of the oxide film, it is considered that most of the contained moisture is adsorbed inside the porous aluminum oxide film layer. When the amount of water contained in the oxide film exceeds 10 ⁇ g / cm 2 , water vapor corresponding to the amount of water is generated particularly during a long period of time, and the oxide film undergoes volume expansion due to this water vapor.
  • the volume expansion generates a peeling stress between the oxide film and a bonded material such as a resin, and dissociates hydrogen bonds generated at the bonding interface between the oxide film and the bonded material. As a result, the adhesive strength and adhesion after a long period of time are reduced.
  • the lower limit of the amount of water is not particularly specified, but according to the measurement method described later, since the lower limit of detection is around 0.1 ⁇ g / cm 2 , the industrial lower limit is also 0.1 ⁇ g / cm2. It can be said to be about cm 2 .
  • the amount of water contained in the oxide film is preferably 6 ⁇ g / cm 2 or less.
  • the total thickness of the oxide film that is, the total thickness of the porous aluminum oxide film layer described in B-1 and the barrier type aluminum oxide film layer described in B-2 is Even if it is measured at any location of the aluminum material, the fluctuation range is preferably within ⁇ 50%, and more preferably within ⁇ 20%.
  • the average value of the total thickness of the oxide film measured at a plurality of arbitrary locations on the surface of the aluminum material (10 or more are desirable, and it is desirable to have 10 or more measurement points in each location) is T (nm). In this case, it is desirable that the total thickness of the oxide film at all of the plurality of measurement points is in the range of (0.5 ⁇ T) to (1.5 ⁇ T).
  • 10 sample pieces prepared under the same conditions are prepared, and the thickness of the entire oxide film is measured at 10 points for each sample, thereby obtaining a total of 100 measurement values for the samples prepared under the same conditions.
  • the oxide film at that location becomes thinner than the surrounding area. Then, in this thin area, a gap is likely to occur between the adhesive, the resin layer to be bonded, etc., and the oxide film, and the sufficient contact area cannot be ensured and the adhesive force and adhesion force are reduced. There is.
  • the oxide film at that location becomes thicker than its surroundings. Then, in this thick part, the stress from the resin layer etc. which should be joined concentrates, and the adhesive force and the adhesive force may fall relatively.
  • the optical characteristics are different in the portion where the total thickness of the oxide film as described above is thin or thick, it may be visible as a change in color tone such as brownish brown or cloudy color.
  • 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 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 alkaline component contained in such an alkaline aqueous solution is 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 ⁇ 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 alkaline etching power of the electrolytic solution is insufficient, so that the porous structure of the porous aluminum oxide film layer is incomplete.
  • the pH exceeds 13 the alkaline etching power becomes excessive, so that the porous aluminum oxide film layer is difficult to grow, and the formation of the barrier type aluminum oxide film layer is further inhibited.
  • the electrolytic solution temperature needs to be 35 to 85 ° C, preferably 40 to 70 ° C.
  • the electrolytic solution temperature is less than 35 ° C.
  • the alkaline etching ability is insufficient, and the porous structure of the porous aluminum oxide film layer becomes incomplete.
  • the temperature exceeds 85 ° C., the alkaline etching force becomes excessive, and thus growth is inhibited in both the porous aluminum oxide film layer and the barrier type aluminum oxide film layer.
  • the thickness of the entire oxide film including the porous aluminum oxide film layer and the barrier type aluminum oxide film layer is controlled by the quantity of electricity, that is, the product of the current density and the electrolysis time, and basically the quantity of electricity. As the amount increases, the thickness of the entire oxide film increases. From such a viewpoint, the AC electrolysis conditions of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer are as follows.
  • the frequency used for AC electrolysis is 10 to 100 Hz, preferably 20 to 90 Hz. If the frequency is less than 10 Hz, a direct current element increases as electrolysis. As a result, the formation of the porous structure of the porous aluminum oxide film layer does not proceed, resulting in a dense structure. 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 both the porous aluminum oxide film layer and the barrier type aluminum oxide film layer have a predetermined thickness. Takes an extremely long time.
  • the electrolysis waveform in alternating current electrolysis is not specifically limited, Waveforms, such as a sine wave, a rectangular wave, a trapezoid wave, a triangular wave, can be used.
  • the current density is 4 to 50 A / dm 2 , preferably 5 to 45 A / dm 2 .
  • the current density is less than 4 A / dm 2 , since only the barrier type aluminum oxide film layer is formed preferentially, a porous aluminum oxide film layer cannot be obtained.
  • the current becomes excessive, so that it is difficult to control the thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer, and processing unevenness is likely to occur.
  • Electrolysis time is 5 to 300 seconds, preferably 10 to 240 seconds.
  • the treatment time is less than 5 seconds, the formation of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer is too rapid, so that neither oxide film layer is sufficiently formed, and it is composed of amorphous aluminum oxide. This is because it becomes an oxide film.
  • it exceeds 300 seconds the porous aluminum oxide film layer and the barrier-type aluminum oxide film layer become too thick, and there is a risk of re-dissolution, and the productivity is further reduced.
  • the concentration of dissolved aluminum contained in the electrolytic solution is preferably 5 ppm or more and 1000 ppm or less for the purpose of reducing the thickness variation of the oxide film. More preferably, it is 10 ppm or more and 800 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 takes place abruptly. Therefore, the thickness of the oxide film to be formed varies depending on the treatment process. It becomes easy to be affected by the mounting state of the aluminum material. As a result, a locally thick oxide film is formed.
  • the concentration of dissolved aluminum exceeds 1000 ppm, the viscosity of the electrolytic solution increases and the uniform convection near the surface of the aluminum material is hindered in the electrolysis process, and at the same time, the dissolved aluminum acts to suppress film formation. . As a result, a thin oxide film is locally formed. If the dissolved aluminum concentration deviates from the above range, the fluctuation range of the total thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer on the entire aluminum material surface is within ⁇ 50% of the arithmetic average value of the total thickness. As a result, the adhesion strength and adhesion strength of the resulting oxide film may be reduced.
  • One electrode of the pair of electrodes used for the alternating current electrolytic treatment is an aluminum material to be electrolytically treated.
  • the other counter electrode for example, a known electrode such as a graphite, aluminum, or titanium electrode can be used.
  • 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 aluminum oxide film layer and the barrier type aluminum oxide film layer tend to be more uniform.
  • both the aluminum material to be electrolytically processed and the counter electrode are flat, and the vertical and horizontal dimensions of the surfaces of the opposing aluminum material and the counter electrode are substantially the same, and both electrodes are stationary. It is preferable to perform the electrolysis operation in the state. In this case, an oxide film is formed on one surface of the aluminum material facing the counter electrode.
  • an AC film is temporarily formed by forming an oxide film on one surface, and then the other surface is formed. The AC electrolysis treatment may be performed in the same manner by rearranging the electrodes so as to face the counter electrode.
  • the surface of the aluminum material that has not been opposed to the counter electrode in the electrolysis process is repositioned so as to face the counter electrode, and the electrolysis process is repeated, An oxide film can be formed on a desired surface.
  • the aluminum material obtained as described above is exposed to an atmosphere exceeding 150 ° C., moisture contained in the oxide film is effectively removed.
  • moisture contained in the oxide film In a temperature environment of 150 ° C. or lower, water vapor cannot escape from the inside of the porous aluminum oxide film layer, and moisture contained in the oxide film cannot be removed.
  • the atmosphere air, an inert gas such as nitrogen or argon, a mixed gas of these inert gases, a mixed gas of air and an inert gas, or the like can be used, but air is preferable from the viewpoint of economy.
  • the relative humidity of the exposed atmosphere is preferably 50% or less, and more preferably 30% or less. If the relative humidity exceeds 50%, the moisture contained in the oxide film may not be removed effectively.
  • the exposure time is t (seconds)
  • the thickness of the porous aluminum oxide film layer is L (nm)
  • the ambient temperature is T (° C.).
  • x (L / T) This is a calculation formula based on the assumption that most of the water contained in the oxide film is adsorbed inside the porous aluminum oxide film layer, and the exposure time is proportional to the thickness of the porous aluminum oxide film layer. In many cases, it becomes shorter in inverse proportion to the ambient temperature.
  • the coefficient 20 is a constant determined experimentally.
  • about the upper limit of atmospheric temperature Preferably it is 500 degreeC, More preferably, it is 300 degreeC.
  • the time until the surface temperature of the aluminum material that has been exposed to the atmosphere exceeding 150 ° C. to form an oxide film reaches 150 ° C. is less than 24 hours after the end of the AC electrolytic treatment. Preferably, it is within 12 hours.
  • Moisture taken into the oxide film generated by the alternating current electrolysis process is fixed to aluminum hydroxide as Al 2 O 3 .nH 2 O (n is an integer of 1 to 3), although the amount is very small with time. There is a case.
  • the moisture fixed to the aluminum hydroxide may be difficult to be removed by subsequent atmospheric exposure exceeding 150 ° C.
  • the AC electrolytic treatment is performed through the steps of electrolytic treatment, washing with water, and drying.
  • the starting time within 24 hours is the time when voltage application in the electrolytic treatment is stopped.
  • a thermometer such as a thermocouple is in contact with the surface of the aluminum material that has been subjected to AC electrolytic treatment, and this is exposed to an atmosphere exceeding 150 ° C., and the thermometer shows 150 ° C. And when Normally, the thermometer shows 150 ° C. in about 60 seconds after starting exposure to an atmosphere exceeding 150 ° C.
  • TEM transmission electron microscope
  • the thickness of the porous aluminum oxide film layer and the barrier-type aluminum oxide film layer, and the diameter of the small holes in the porous aluminum oxide film layer should be prepared by TEM observation using a micro-microtome. Can be measured by.
  • a method for measuring surface trace moisture using a temperature-programmed desorption gas analyzer can be used. Specifically, a surface-treated aluminum material is put in a closed cell and heated at a temperature rising rate of 10 to 60 ° C./min to a temperature 5 to 10 ° C. lower than the solidus temperature of the aluminum material. And it can measure by analyzing the gas component which generate
  • an oxide film is formed on at least one of the surfaces of the aluminum material by the AC electrolytic treatment step, and then the moisture of the at least one oxide film is reduced by exposure to an atmosphere exceeding 150 ° C.
  • a plate material is used as the aluminum material, only one surface may be a surface-treated surface, or both surfaces may be surface-treated surfaces.
  • the surface can be used as a surface-treated surface by subjecting a desired surface to electrolytic treatment and exposure to an atmosphere exceeding 150 ° C.
  • a surface-treated aluminum material / resin layer bonded body is obtained by bonding the resin layer to the surface-treated surface of the surface-treated aluminum material according to the present invention.
  • the resin for the resin layer to be used various thermoplastic and thermosetting resins can be used.
  • the resin layer is formed by contacting and infiltrating the porous aluminum oxide film layer with the resin that has been heated to flow, and then cooling and solidifying.
  • an adhesive may be brought into contact with and permeated into the porous aluminum oxide film layer, and the resin layer may be bonded to the surface-treated aluminum material via this adhesive.
  • a liquid type or a hot melt type can be used.
  • the resin used for the resin layer bonded to the surface-treated surface of the surface-treated aluminum material according to the present invention is at least one polar functional group selected from an amino group, an amide group, an ester group, a carboxyl group, an epoxy group, and a hydroxyl group. It is preferable to have a seed.
  • the resin has the above-mentioned polar functional group, not only the anchor effect caused by impregnation of the porous aluminum oxide film with the resin, but also the polar functional group and the oxide film are attracted by Coulomb force and / or hydrogen bonding force. By meeting, excellent primary adhesion. Furthermore, since the moisture contained in the oxide film formed on the surface-treated surface of the surface-treated aluminum material according to the present invention is 10 ⁇ g / cm 2 or less, the Coulomb force as the bonding force at the bonding interface between the oxide film and the resin. And / or water does not inhibit the hydrogen bonding force, and is excellent in secondary adhesion.
  • the numerical value represented by the formula 1, that is, the abundance ratio of the polar functional group in the resin is 0.01 or more and 3.0. It is preferable that
  • the molecule of Formula 1 is an infrared absorption spectrum derived from an amino group, an amide group, an ester group, a carboxyl group, an epoxy group, and a hydroxyl group, a wave number range where the spectrum appears, and an integral value of a region surrounded by a horizontal axis. That is, it defines the amount of polar functional groups present in the resin.
  • the denominator of Formula 1 is an integral value of an infrared absorption spectrum derived from an aliphatic hydrocarbon and a benzene ring, a wave number range in which the spectrum appears, and a region surrounded by a horizontal axis. As shown schematically in FIG.
  • the abundance other than the polar functional group present in the resin is defined. That is, Formula 1 defines the abundance ratio of the polar functional group in the resin with respect to the skeleton structure, and it can be said that the higher the value, the richer the polar component.
  • thermoplastic resin examples include polyolefin (polyethylene, polypropylene, etc.), polyvinyl chloride, polyester (polyethylene terephthalate, polybutylene terephthalate, etc.), polyamide, polyphenylene sulfide, aromatic polyether ketone (polyether ether ketone, polyether).
  • Ketone, etc. polystyrene, various fluororesins (polytetrafluoroethylene, polychlorotrifluoroethylene, etc.), ethylene- (meth) acrylic acid copolymer, propylene- (meth) acrylic acid copolymer, acrylic resin (polymethacrylic) Acid methyl, etc.), ABS resin, polycarbonate, thermoplastic polyimide and the like can be used.
  • Polyester, polyamide, ethylene- (meth) acrylic acid copolymer, propylene- (meth) acrylic acid copolymer, and thermoplastic polyimide are preferable.
  • thermosetting resin when used, the resin in a fluid state before curing may be brought into contact / penetration with the porous aluminum oxide film layer and then cured. Also, instead of such a curing method, a liquid type or hot melt type adhesive is contacted and infiltrated into the porous aluminum oxide film layer in the same manner as a thermoplastic resin, and the resin layer is surfaced through this adhesive. You may join to a process aluminum material.
  • thermosetting resin for example, phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane, thermosetting polyimide and the like can be used.
  • thermoplastic resin or thermosetting resin may be used alone, or may be used as a polymer alloy in which a plurality of types of thermoplastic resins or a plurality of types of thermosetting resins are mixed. Moreover, you may improve physical properties, such as the intensity
  • Examples 1 to 33 and Comparative Examples 1 to 12 As the aluminum material, a JIS5052-H34 alloy flat plate having a length of 200 mm, a width of 400 mm, and a thickness of 1.0 mm was used. This aluminum alloy plate was used as one electrode, and a graphite plate having a flat plate shape of 300 mm long ⁇ 500 mm wide ⁇ 2.0 mm thick was used as the counter electrode. One surface of the aluminum alloy plate is opposed to the counter electrode, and on the surface layer of the one surface facing this, a porous aluminum oxide film layer on the surface side and a barrier type aluminum oxide film layer on the substrate side are formed. Both electrodes were placed. An alkaline aqueous solution mainly composed of sodium pyrophosphate was used as the electrolytic solution.
  • the alkaline component concentration of the electrolytic solution was 0.5 mol / liter, and the pH was adjusted with hydrochloric acid and a sodium hydroxide aqueous solution (both concentrations were 0.1 mol / liter).
  • AC electrolytic treatment is performed under the electrolysis conditions shown in Tables 1 and 2 to form a porous aluminum oxide film layer and a barrier type aluminum oxide film layer, and an air atmosphere exceeding 150 ° C. under the conditions shown in Tables 1 and 2 Exposure in was performed.
  • the atmospheric air temperature was less than 150 ° C.
  • Comparative Example 12 no atmospheric exposure was performed.
  • “elapsed time until reaching 150 ° C. after the AC electrolysis step” is the time until the surface of the aluminum material reaches 150 ° C. starting from the time when the voltage application of the electrolytic treatment is stopped.
  • a test material was prepared in which an oxide film composed of a porous aluminum oxide film layer and a barrier type aluminum oxide film layer was formed on one surface of the aluminum material.
  • the specimen prepared as described above was subjected to cross-sectional observation by TEM and measurement of water content by TDS-MS.
  • TEM cross-sectional observation an ultramicrotome was used to measure the thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer, and the diameter of the small holes in the porous aluminum oxide film layer. From this, a slice sample for cross-sectional observation was prepared.
  • the thin piece sample was cross-sectionally observed with a TEM, and the thicknesses of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer at any 10 points in the observation field (1 ⁇ m ⁇ 1 ⁇ m), and the porous aluminum oxide
  • the diameter of the small holes in the coating layer was measured at each point, and the arithmetic average value of each was taken as the measurement result.
  • the temperature rising rate was set to 30 ° C./min, the temperature was raised to 620 ° C., and the abundance per unit area of water molecules was measured.
  • the total thickness was obtained by adding the thicknesses of the coating layers to obtain the oxide coating thickness at each point.
  • the maximum value, the minimum value, and the arithmetic mean value of the 100 oxide film thicknesses obtained in this way are shown in the column of “total oxide film thickness” in Tables 3 and 4. Furthermore, it was examined whether or not the fluctuation range of the oxide film thickness at these 100 points 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). The case where it existed was set as (circle) and the case where it was not in the range was set as x.
  • the presence rate of the polar functional group in resin was evaluated. That is, the infrared absorption spectrum of the resin was measured using a Fourier transform type spectral hardness meter having a measurement wave number range of 4000 cm ⁇ 1 to 650 cm ⁇ 1 and a resolution of 1 cm ⁇ 1 . Next, the measured infrared absorption spectrum, the wave number range in which the spectrum appears, and the region surrounded by the horizontal axis were numerically integrated using the trapezoidal method at intervals of 1 cm ⁇ 1 to obtain the area. By substituting the obtained integral value into Equation 1 and calculating the value, the abundance of polar functional groups in the resin was evaluated. The results are shown in Tables 5-7.
  • Each end in the length direction of the two specimens is pulled in the opposite direction along the length direction at a speed of 100 mm / min with a tensile tester, and is closely adhered by the load (converted to shear stress) and the peeled state. Sex was evaluated according to the following criteria.
  • the shear test piece produced 10 sets of test pieces from the same test material, and evaluated each.
  • ⁇ 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 Tables 5 and 6. The table shows the number of pairs of the above-mentioned ⁇ , ⁇ , and ⁇ of 10 sets of test pieces, respectively.
  • Comparative Example 7 since the current density in the alternating current electrolysis treatment was too low, the barrier type aluminum oxide film layer was preferentially formed. Therefore, the thickness of the porous aluminum oxide film layer was insufficient, and the primary adhesion and long-term stability were unacceptable.
  • Comparative Examples 11 and 12 since the shapes of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer satisfied the provisions of the present invention, the primary adhesion was excellent. However, in Comparative Example 11, the temperature of the atmospheric exposure after the electrolytic treatment was too low, and in Comparative Example 12, since the atmospheric exposure was not performed, the moisture contained in the oxide film could not be removed, and long-term stability was improved. It was a failure.
  • the surface treatment aluminum material which is excellent in adhesiveness and adhesiveness over the whole surface of an aluminum material, and can maintain this characteristic for a long time, and a joined body with the resin layer using the same are obtained stably. be able to.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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Abstract

Le problème posé par la présente invention concerne un matériau à base d'aluminium traité en surface présentant une excellente adhésivité de la résine à long terme sur toute la surface du matériau à base d'aluminium et un procédé de fabrication stable d'un tel matériau à base d'aluminium traité en surface. La solution proposée par la présente invention concerne un matériau à base d'aluminium traité en surface et son procédé de fabrication, le matériau à base d'aluminium traité en surface comprenant un matériau à base d'aluminium et un film d'oxyde formé sur au moins une surface de celui-ci et étant caractérisé en ce que le film d'oxyde est obtenu à partir d'une couche de film d'oxyde d'aluminium poreuse de 20 à 500 nm d'épaisseur formée sur la surface avant et d'une couche de film d'oxyde d'aluminium barrière de 3 à 30 nm d'épaisseur formée sur la surface de la base, des pores de 5 à 30 nm de diamètre sont formés dans la couche de film d'oxyde d'aluminium poreuse et la teneur en humidité contenue dans le film d'oxyde n'excède pas 10 µg/cm 2.
PCT/JP2015/003580 2014-07-18 2015-07-15 Matériau à base d'aluminium traité en surface et son procédé de fabrication ainsi que ledit matériau à base d'aluminium traité en surface/matériau collé à une couche de résine WO2016009649A1 (fr)

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CN201580024989.2A CN106460221B (zh) 2014-07-18 2015-07-15 表面处理铝材及其制造方法和该表面处理铝材/树脂层的接合体
JP2016534285A JP6575968B2 (ja) 2014-07-18 2015-07-15 表面処理アルミニウム材及びその製造方法、ならびに、当該表面処理アルミニウム材／樹脂層の接合体
KR1020167025106A KR20170032215A (ko) 2014-07-18 2015-07-15 표면 처리 알루미늄재 및 그 제조 방법, 및, 당해 표면 처리 알루미늄재/수지층의 접합체

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WO2021176847A1 (fr) * 2020-03-06 2021-09-10 富士フイルム株式会社 Procédé de fabrication d'une microstructure remplie de métal

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KR20210093682A (ko) * 2020-01-20 2021-07-28 (주)포인트엔지니어링 양극산화막 구조체의 제조 방법 및 양극산화막 구조체

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JPS60500831A (ja) * 1983-02-22 1985-05-30 デルファックス・システムズ 陽極酸化された静電イメ−ジング表面
JP2002155397A (ja) * 2000-07-31 2002-05-31 Mitsubishi Plastics Ind Ltd 熱可塑性樹脂被覆アルミニウム板およびこの成形体
WO2013011637A1 (fr) * 2011-07-21 2013-01-24 国立大学法人東北大学 Stator destiné à une pompe d'évacuation de gaz, procédé de fabrication de ce stator, pompe munie dudit stator, et procédé de fabrication et procédé d'assemblage de cette pompe
WO2013118870A1 (fr) * 2012-02-12 2013-08-15 古河スカイ株式会社 Matière d'aluminium traitée en surface, son procédé de fabrication et matière d'aluminium traitée en surface revêtue de résine

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JPS60500831A (ja) * 1983-02-22 1985-05-30 デルファックス・システムズ 陽極酸化された静電イメ−ジング表面
JP2002155397A (ja) * 2000-07-31 2002-05-31 Mitsubishi Plastics Ind Ltd 熱可塑性樹脂被覆アルミニウム板およびこの成形体
WO2013011637A1 (fr) * 2011-07-21 2013-01-24 国立大学法人東北大学 Stator destiné à une pompe d'évacuation de gaz, procédé de fabrication de ce stator, pompe munie dudit stator, et procédé de fabrication et procédé d'assemblage de cette pompe
WO2013118870A1 (fr) * 2012-02-12 2013-08-15 古河スカイ株式会社 Matière d'aluminium traitée en surface, son procédé de fabrication et matière d'aluminium traitée en surface revêtue de résine

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021176847A1 (fr) * 2020-03-06 2021-09-10 富士フイルム株式会社 Procédé de fabrication d'une microstructure remplie de métal
JPWO2021176847A1 (fr) * 2020-03-06 2021-09-10
JP7336584B2 (ja) 2020-03-06 2023-08-31 富士フイルム株式会社 金属充填微細構造体の製造方法

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TWI647340B (zh) 2019-01-11
JPWO2016009649A1 (ja) 2017-04-27
CN106460221B (zh) 2021-05-11

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