WO2017006804A1 - Procédé de fabrication d'un alliage d'aluminium, alliage d'aluminium et conjugué - Google Patents

Procédé de fabrication d'un alliage d'aluminium, alliage d'aluminium et conjugué Download PDF

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Publication number
WO2017006804A1
WO2017006804A1 PCT/JP2016/069090 JP2016069090W WO2017006804A1 WO 2017006804 A1 WO2017006804 A1 WO 2017006804A1 JP 2016069090 W JP2016069090 W JP 2016069090W WO 2017006804 A1 WO2017006804 A1 WO 2017006804A1
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aluminum alloy
alloy material
surface treatment
oxide film
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PCT/JP2016/069090
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English (en)
Japanese (ja)
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悟 高田
佑輔 高橋
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株式会社神戸製鋼所
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Priority claimed from JP2016113753A external-priority patent/JP2017203209A/ja
Application filed by 株式会社神戸製鋼所 filed Critical 株式会社神戸製鋼所
Priority to CN201680040156.XA priority Critical patent/CN107835869A/zh
Priority to US15/741,594 priority patent/US20180216236A1/en
Publication of WO2017006804A1 publication Critical patent/WO2017006804A1/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
    • 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
    • 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

Definitions

  • the present invention relates to a method for producing an aluminum alloy material, an aluminum alloy material, and a joined body using the aluminum alloy material.
  • JIS5000-based Al—Mg-based alloy materials, JIS6000-based Al—Mg—Si-based alloy plates, and JIS7000-based Al—Zn—Mg-based alloy materials are used for automobile members. It has been.
  • As a joining method of these aluminum alloy materials there are welding and adhesion by an adhesive, and these methods may be used in combination. Whereas welding joins an aluminum alloy material with dots or lines, bonding with an adhesive bonds the aluminum alloy material over the entire surface, which is advantageous in terms of high joint strength and impact safety. For this reason, in recent years, adhesion by an adhesive tends to increase in automobile members.
  • a composite of an aluminum alloy material and a resin is used to reduce the weight of an automobile.
  • Patent Document 1 proposes a method of removing the Mg concentrated layer on the surface of the aluminum alloy plate by pickling and simultaneously concentrating Cu on the surface of the aluminum alloy plate.
  • Patent Document 2 proposes a method in which the amount of Mg concentrated on the surface of an aluminum alloy plate and the OH absorption rate have a specific relationship.
  • Patent Document 3 proposes a method in which the Mg concentration, Si concentration, and OH concentration in the oxide film surface layer of the aluminum material are set to specific ranges by continuously performing solution treatment and hot water treatment. .
  • Japanese Unexamined Patent Publication No. 6-256881 Japanese Unexamined Patent Publication No. 2006-200007 Japanese Unexamined Patent Publication No. 2007-217750 Japanese Patent Laid-Open No. 8-144064 Japanese Laid-Open Patent Publication No. 7-188956
  • Patent Documents 1 to 3 described above are exposed to a high-temperature and humid environment in which moisture, oxygen, chloride ions, and the like permeate, the deterioration of the interface proceeds, and the interface peels off. There is a problem that the strength is lowered or the corrosion of Al is promoted.
  • the technique described in Patent Document 1 describes that the bonding with an adhesive is strengthened by concentration of Cu and the adhesiveness is improved.
  • an aluminum alloy plate to which this technique is applied is a resin in a wet environment. Decomposition may be accelerated, and high durability cannot be expected.
  • the present invention provides an aluminum alloy material production method, an aluminum alloy material, which can produce an aluminum alloy material that is less likely to have a reduced adhesive strength even when exposed to a high-temperature and humid environment, has excellent adhesion durability, and excellent productivity. And a joined body using an aluminum alloy material.
  • the present inventor has conducted extensive experiments to solve the above-described problems, and as a result, has obtained the following knowledge.
  • the interface is hydrated and bonding strength (hydrogen bonding) decreases when exposed to a high temperature and wet environment. To do.
  • the base of the aluminum alloy plate and the adhesive layer are basically bonded by hydrogen bonding, and when exposed to a high temperature and humidity environment where moisture, oxygen, chloride ions, etc. penetrate. , The interface is hydrated and the bond strength decreases.
  • the method of performing anodization complicates the apparatus and costs equipment, and further requires a long time for film formation, resulting in a reduction in production efficiency.
  • the interface deteriorates due to the hydration of the interface, and the interface peels off. Occurs and the adhesive strength decreases.
  • the present inventors examined the bonding state between the substrate surface and the adhesive resin layer, and after forming a film made of an oxide film on the surface of the aluminum alloy substrate, at least a part of this oxide film, It has been found that by applying a specific aqueous solution containing a silicate and an organosilane compound to form a surface treatment film, it is possible to suppress a decrease in adhesive strength when exposed to a high-temperature and humid environment, and the present invention has been achieved.
  • At least a part of the surface of the aluminum alloy substrate contains Mg at 0.1 atomic% or more and less than 30 atomic%, and Cu is less than 0.6 atomic%.
  • a surface treatment film forming step including applying an aqueous solution having an organic silane compound of less than mass% and a pH of 7 or more and 14 or less.
  • the amount of Mg and the amount of Cu in the film are values measured by a high-frequency glow discharge emission spectroscopic analysis (GD-OES: Glow Discharge-Optical Emission Spectroscopy).
  • the organosilane compound may include a silane compound having a plurality of hydrolyzable trialkoxysilyl groups in the molecule, a hydrolyzate thereof, or a polymer thereof. .
  • the silicate is a silicate represented by mM 2 O ⁇ nSiO 2 , wherein M is a monovalent cation, and M 2 O
  • the ratio n / m of m which is the number of moles of n and n which is the number of moles of SiO 2 may be 1.5 or more.
  • M may be sodium ion.
  • the said oxide film formation process may include an etching process step, and the etching amount in the said etching process step may be 1.9 g / m ⁇ 2 > or less.
  • the aluminum alloy substrate can be formed of, for example, an Al—Mg alloy, an Al—Cu—Mg alloy, an Al—Mg—Si alloy, or an Al—Zn—Mg alloy.
  • the present invention also includes an aluminum alloy material obtained by the method for producing an aluminum alloy material.
  • the joined body of the present invention is obtained by joining the aluminum alloy material and another member via an adhesive resin.
  • an aluminum alloy substrate on which an oxide film is formed can be simplified by simultaneously performing silicate treatment and organosilane treatment using an aqueous solution containing a silicate and an organosilane compound. With this process, an aluminum alloy material (also referred to as a surface-treated aluminum alloy material) can be manufactured, and capital investment costs and manufacturing costs can be reduced.
  • FIG. 1 is a flowchart showing a method for producing an aluminum alloy material according to the first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing the configuration of the aluminum alloy material before the surface treatment process in a state where an oxide film is formed on the surface of the aluminum alloy substrate.
  • FIG. 3 is a cross-sectional view schematically showing the configuration of the aluminum alloy material with an adhesive resin layer according to the first embodiment of the present invention.
  • FIG. 4 is a cross-sectional view schematically showing a configuration of an aluminum alloy material with an adhesive resin layer according to a modification of the first embodiment of the present invention.
  • FIG. 5 is a flowchart showing a method of manufacturing the aluminum alloy material with an adhesive resin layer shown in FIG. FIG.
  • FIG. 6 is a cross-sectional view schematically showing a configuration example of a joined body according to the second embodiment of the present invention.
  • FIG. 7A is a cross-sectional view schematically showing another configuration example of the joined body according to the second embodiment of the present invention.
  • FIG. 7B is a cross-sectional view schematically showing another configuration example of the joined body according to the second embodiment of the present invention.
  • FIG. 8 is a cross-sectional view schematically showing another configuration example of the joined body according to the second embodiment of the present invention.
  • FIG. 9A is a cross-sectional view schematically showing another configuration example of the joined body according to the second embodiment of the present invention.
  • FIG. 9B is a cross-sectional view schematically showing another configuration example of the joined body according to the second embodiment of the present invention.
  • FIG. 10A is a side view schematically showing a method for measuring the cohesive failure rate.
  • FIG. 10B is a plan view schematically showing a method for measuring the cohesive failure rate.
  • the manufacturing method of the aluminum alloy material of this embodiment and the aluminum alloy material obtained by the manufacturing method will be described.
  • the percentage based on mass (% by mass) is the same as the percentage based on weight (% by weight).
  • Mg is contained in at least a part of the surface of the aluminum alloy base material in an amount of 0.1 atomic percent or more and less than 30 atomic percent, and Cu is restricted to less than 0.6 atomic percent
  • a surface treatment film forming step including applying an aqueous solution having a pH of 7 or more and 14 or less.
  • FIG. 1 is a flowchart showing a method for manufacturing an aluminum alloy material 10 of this embodiment. As shown in FIG. 1, when manufacturing the aluminum alloy material 10 of this embodiment, base material preparation process S1, oxide film formation process S2, and surface treatment film formation process S3 are performed. Hereinafter, each step will be described.
  • the shape of the substrate is not particularly limited, and depending on the shape of a member produced using an aluminum alloy material, in addition to a plate shape, a cast material, a forged material, an extruded material (for example, a hollow bar shape), etc. Any shape that can be taken as In the base material manufacturing step S1, when a plate-shaped base material (substrate) is manufactured as an example, the substrate is manufactured by the following procedure, for example. First, an aluminum alloy having a predetermined composition is melted by continuous casting and cast to produce an ingot (melting casting process). Next, the produced ingot is subjected to homogenization heat treatment (homogenization heat treatment step).
  • the ingot subjected to homogenization heat treatment is hot-rolled to produce a hot-rolled sheet (hot-rolling step).
  • the hot-rolled sheet is subjected to rough annealing or intermediate annealing at 300 to 580 ° C., and cold rolling with a final cold rolling rate of 5% or more is performed at least once, so that a cold-rolled sheet (substrate) having a predetermined thickness is obtained. (Cold rolling process).
  • the temperature of rough annealing or intermediate annealing it is preferable to set the temperature of rough annealing or intermediate annealing to 300 ° C. or higher, and thereby the effect of improving formability is more exhibited.
  • the temperature of rough annealing or intermediate annealing shall be 580 degrees C or less, and this becomes easy to suppress the fall of the moldability by generation
  • the final cold rolling rate is preferably 5% or more, and thereby, the effect of improving the formability is more exhibited.
  • the conditions of homogenization heat processing and hot rolling are not specifically limited, It can carry out on the conditions in the case of obtaining a hot rolled sheet normally. Further, intermediate annealing may not be performed.
  • the base material is made of an aluminum alloy.
  • the type of aluminum alloy that forms the base material is not particularly limited, and various non-heat treatment type or heat treatment type aluminum alloys that are prescribed in JIS or approximate to JIS, depending on the application of the member to be processed. Can be appropriately selected and used.
  • the non-heat treatment type aluminum alloy there are pure aluminum (1000 series), Al—Mn series alloy (3000 series), Al—Si series alloy (4000 series), and Al—Mg series alloy (5000 series).
  • the heat-treatable aluminum alloy there are an Al—Cu—Mg alloy (2000 series), an Al—Mg—Si alloy (6000 series), and an Al—Zn—Mg alloy (7000 series).
  • the base material when used for an automobile member, the base material preferably has a 0.2% proof stress of 100 MPa or more from the viewpoint of strength.
  • Aluminum alloys that can form a base material that satisfies such characteristics include those containing relatively large amounts of magnesium, such as 2000 series, 5000 series, 6000 series, and 7000 series, and these alloys are necessary. Depending on the condition, it may be tempered. Among various aluminum alloys, it is preferable to use a 6000 series aluminum alloy because it has excellent age-hardening ability, has a relatively small amount of alloy elements, and is excellent in scrap recyclability and formability.
  • Step S2 oxide film forming step>
  • Mg is 0.1 atomic% or more and 30 atomic% in at least a part (that is, part or all) of the surface of the base material manufactured in the base material manufacturing step in step S1. It forms less than, and forms the oxide film by which Cu was controlled to less than 0.6 atomic%.
  • the oxide film forming step (step S2) specifically includes, for example, a heat treatment stage in which the base material 3 is heat-treated to form the oxide film 1, and an etching treatment stage after the heat treatment stage. With.
  • FIG. 2 shows the aluminum alloy material before the surface treatment film forming step in which the oxide film 1 is formed on the surface of the base material 3.
  • the oxide film 1 is formed on the entire one surface of the base material 3, but this embodiment is not limited to this. Absent.
  • the oxide film 1 may be formed only on a part of the surface of the substrate 3.
  • the oxide film 1 may be formed on both surfaces of the base material 3.
  • the base material 3 is heated to a temperature of, for example, 400 to 580 ° C. to form the oxide film 1 on the surface of the base material 3. Further, the heat treatment also has an effect of adjusting the strength of the aluminum alloy material 10.
  • the heat treatment performed here is a solution treatment when the substrate 3 is formed of a heat-treatable aluminum alloy, and is annealed when the substrate 3 is formed of a non-heat-treatable aluminum alloy. It is heat processing in (final annealing).
  • This heat treatment is preferably rapid heating at a heating rate of 100 ° C./min or more from the viewpoint of improving the strength.
  • the strength of the aluminum alloy material 10 and the strength after heating (baking) of the aluminum alloy material 10 can be further increased by setting the heating temperature to 400 ° C. or higher and performing rapid heating.
  • the heating temperature is set to 580 ° C. or less and performing rapid heating, it is possible to suppress a decrease in formability due to the occurrence of burning.
  • the holding time in the heat treatment is preferably 3 to 30 seconds.
  • the etching treatment stage after the heat treatment at least one of treatment with an acidic solution (pickling) and treatment with an alkaline solution (alkali washing, alkaline degreasing) is performed on part or all of the surface of the substrate 3.
  • the chemical solution (acid detergent) used in the pickling is not particularly limited, for example, a solution containing one or more selected from the group selected from sulfuric acid, nitric acid and hydrofluoric acid can be used.
  • the acid detergent may contain a surfactant in order to improve the degreasing property.
  • the pickling conditions can be appropriately set in consideration of the alloy composition of the base material 3, the thickness of the oxide film 1 and the like, and are not particularly limited.
  • the pH is 4 or less (preferably pH 2 or less), Conditions of a processing temperature of 10 to 80 ° C. and a processing time of 1 to 120 seconds can be applied.
  • the chemical solution used for alkali cleaning is not particularly limited, and for example, a solution containing at least one selected from the group selected from sodium hydroxide and potassium hydroxide can be used.
  • the conditions for the treatment with the alkaline solution can be appropriately set in consideration of the alloy composition of the base material 3, the thickness of the oxide film 1, etc., and are not particularly limited. Conditions of 80 ° C. and processing time of 1 to 120 seconds can be applied.
  • the pickling when performing alkali cleaning, it is preferable to perform pickling after alkali cleaning. Further, only the pickling may be performed without alkali cleaning. That is, in the etching treatment stage, it is preferable that the last stage is pickling.
  • the reason for this is as follows. That is, with alkali cleaning, it is difficult to remove Mg on the substrate surface, and the amount of etching needs to be increased due to the presence of Mg on the substrate surface. However, increasing the etching amount causes the concentration of Cu, so it is necessary to remove Mg by pickling.
  • the rinsing method is not particularly limited, and examples thereof include spraying and dipping.
  • Examples of the cleaning liquid used for rinsing include industrial water, pure water, and ion exchange water.
  • the Mg content in the oxide film 1 is adjusted to 0.1 atomic% or more and less than 30 atomic%, and the Cu content is regulated to less than 0.6 atomic%.
  • the amount of Mg and the amount of Cu in the oxide film can be adjusted or regulated by appropriately controlling various conditions (treatment time, treatment temperature, concentration of chemical solution, pH, etc.) in pickling and alkali washing. it can.
  • the etching amount in an etching process step is 1.9 g / m ⁇ 2 > or less.
  • the etching amount exceeds 1.9 g / m 2 , copper concentration occurs on the surface of the base material 3, which may cause deterioration of the adhesive resin in a high temperature wet environment which is a deterioration environment.
  • the etching amount is more preferably 1.5 g / m 2 or less, and further preferably 1.3 g / m 2 or less.
  • the lower limit of the etching amount is not particularly limited, but is preferably 0.005 g / m 2 .
  • the amount of etching (unit: g / m 2 ) in the present specification is the amount of decrease in the weight of the base material before and after the oxide film forming step (unit: g), and this is the surface area (unit) of the base material. : A value calculated by dividing by m 2 ).
  • At least a part of the surface of the base material 3 contains Mg in an amount of 0.1 atomic% to less than 30 atomic%, and Cu is regulated to less than 0.6 atomic%. Is formed.
  • the suitable range of each component amount contained in the oxide film 1 will be described.
  • the aluminum alloy constituting the base material of the aluminum alloy material usually contains magnesium as an alloy component.
  • the oxide film 1 which is a composite oxide of aluminum and magnesium is formed on the surface of the base material 3.
  • the magnesium oxide film is present on the surface in a concentrated state. Therefore, in this state, since the magnesium oxide film layer is too thick even if it passes through the surface treatment film forming step that is the next step S3 described later, the surface treatment film 2 described later contains a large amount of magnesium, In the surface treatment film 2 thus formed, the strength of the film itself cannot be obtained, and the initial adhesiveness is lowered.
  • the Mg content in the oxide film 1 before the surface treatment film formation described later is 30 atomic% or more, the initial adhesiveness and adhesion durability of the aluminum alloy material after the surface treatment film formation is lowered. Tend. Therefore, in the manufacturing method of the aluminum alloy material 10 of the present embodiment, the Mg content in the oxide film 1 before the formation of the surface treatment film is restricted to less than 30 atomic%. Thereby, initial adhesiveness and adhesion durability can be improved.
  • the Mg content of the oxide film 1 before forming the surface treatment film is preferably less than 25 atomic%, more preferably less than 20 atomic%, and even more preferably 10 atomic% from the viewpoint of improving the initial adhesiveness and adhesion durability. Is less than.
  • the lower limit value of the Mg content of the oxide film 1 before the formation of the surface treatment film is 0.1 atomic% or more from the viewpoint of economy.
  • the Mg content in the oxide film 1 before the formation of the surface treatment film can be measured by high-frequency glow discharge emission spectroscopy (GD-OES).
  • ⁇ Cu content> When excessive etching is performed on the base material 3 by a degreasing process or a pickling process when forming the oxide film 1, Cu contained in the base material 3 is concentrated on the surface, and the Cu content of the oxide film 1 is increased. To increase. If Cu is present on the surface of the oxide film 1, Cu is excessively contained in the surface treatment film 2 formed in the surface treatment film formation step, which is the next step S3 described later, which causes a decrease in adhesion durability. .
  • the Cu content in the oxide film 1 before the formation of the surface treatment film is restricted to less than 0.6 atomic%.
  • Cu content in the oxide film 1 before surface treatment film formation it is more preferable that it is less than 0.5 atomic%.
  • the thickness of the oxide film 1 before the formation of the surface treatment film is preferably 1 to 30 nm.
  • the film thickness of the oxide film 1 before forming the surface treatment film is less than 1 nm, the oxide film 1 to which the surface treatment liquid used in the surface treatment film formation process reacts is thin, the surface treatment liquid becomes excessive, and the unreacted surface The treatment liquid remains on the substrate, which may cause a decrease in adhesion durability.
  • the etching amount is 1.9 g / m 2 or less. It is preferable.
  • the film thickness of the oxide film 1 before the surface treatment film formation exceeds 30 nm
  • the surface treatment liquid used in the surface treatment film formation step is insufficient with respect to the oxide film 1 that reacts and reacts with the oxide film 1. Becomes insufficient, and this may cause a decrease in adhesion durability.
  • the oxide film 1 having a film thickness exceeding 30 nm contains a large amount of magnesium, so that the strength of the film itself is lowered and the initial adhesiveness may be deteriorated.
  • the film thickness of the oxide film 1 before surface treatment film formation it is more preferable that they are 2 nm or more and less than 20 nm from viewpoints, such as a chemical conversion property and productivity.
  • Step S3 Surface treatment film forming step>
  • the oxide film 1 formed in step 2 has a silicate of 0.001 mass% or more and less than 0.5 mass%, and 0.001 mass% or more.
  • the oxide film 1 reacts with the surface treatment liquid, and at least aluminum (Al), silicon ( A surface treatment film 2 containing Si), oxygen (O), and an organosilane compound is formed on the surface of the substrate 3.
  • the oxide film 1 does not become a uniform surface-treated film 2, and the oxide film 1 is modified to a film containing mainly Al and O and containing Si (including Al—O—Si bond).
  • a film mainly containing Si and O (siloxane bond) and containing Al (including Al—O—Si bond) is formed, and the Si concentration decreases from the outermost surface side to the substrate side, Moreover, it becomes a film
  • the Al—Si ratio of the Al—O—Si bond is different in the cross-sectional direction, and the bond between the surface treatment film 2 and the substrate 3 is an Al-rich Al—O—Si bond, and the aluminum alloy substrate And the surface of the surface treatment material (aluminum alloy material after the surface treatment) have Si-rich Al—O—Si bonds.
  • corrosion resistance can be improved.
  • the surface treatment film 2 itself is very thin, and the distribution state in the film thickness direction of the silicate and the organosilane compound is different, but at least a mixed structure is formed, and the surface treatment film 2 is extremely thin. Its strength is also high.
  • the surface treatment film 2 is formed by performing the surface treatment using the surface treatment liquid containing both the silicate and the organosilane compound, and the surface treatment is performed using only the organosilane compound.
  • an alloy material with improved adhesion durability can be obtained.
  • FIG. 3 shows the aluminum alloy material of the present embodiment in which the surface treatment film 2 is formed on the surface of the substrate 3.
  • the surface treatment film 2 is formed on the entire one surface of the substrate 3, but the present embodiment is not limited to this.
  • the surface treatment film 2 may be formed on only a part of the surface of the substrate 3. Further, the surface treatment film 2 may be formed on both surfaces of the substrate 3.
  • the surface treatment solution has a pH of 7 or more and 14 or less.
  • the pH of the surface treatment liquid is higher than 14, most of the organosilane compound is polymerized and precipitated, so that the solution itself becomes an unstable solution.
  • the polymerized organic silane compound is bonded to the oxide film on the surface of the aluminum alloy substrate, the resulting organic silane treatment layer becomes thick, and therefore, when stress is applied, the organic silane treatment layer is destroyed inside.
  • the pH of the surface treatment solution is lower than 7, silicate precipitates, so that aluminum and silicon cannot react. Therefore, the pH of the surface treatment liquid needs to be in the range of 7 or more and 14 or less.
  • the pH of the surface treatment solution is preferably 8 or more, more preferably 9 or more.
  • the pH of the surface treatment solution can be appropriately adjusted by adding a base such as sodium hydroxide, sodium carbonate, or ammonia, or an acid such as acetic acid.
  • the concentration of silicate in the surface treatment liquid is 0.001% by mass or more and less than 0.5% by mass. When the concentration of the silicate in the surface treatment liquid is 0.5% by mass or more, the formed film becomes thick and the strength decreases. On the other hand, if the concentration of silicate in the surface treatment liquid is less than 0.001% by mass, the concentration of silicate is too low, so that aluminum and silicon cannot sufficiently react, and sufficient adhesion durability is achieved. Sex cannot be obtained.
  • the concentration of the silicate in the surface treatment liquid is preferably 0.01% by mass or more, and more preferably 0.015% by mass or more. Further, the concentration of silicate in the surface treatment liquid is preferably less than 0.3% by mass, and more preferably less than 0.2% by mass.
  • the concentration of the organosilane compound in the surface treatment liquid is 0.001% by mass or more and less than 0.5% by mass.
  • concentration of the organosilane compound in the surface treatment liquid is 0.5% by mass or more, the generated surface treatment film becomes thick and the strength is lowered.
  • concentration of the organic silane compound in the surface treatment liquid is less than 0.001% by mass, the concentration of the organic silane compound is too low, so that a surface treatment film containing the organic silane compound cannot be sufficiently formed. Thus, sufficient adhesion durability cannot be obtained.
  • the concentration of the organosilane compound in the surface treatment liquid is preferably 0.005% by mass or more, and more preferably 0.01% by mass or more.
  • concentration of the organosilane compound in the surface treatment liquid is preferably less than 0.4% by mass, more preferably less than 0.3% by mass.
  • the type of silicate contained in the surface treatment liquid is not particularly limited, but from the viewpoint of water solubility, for example, basic silicates include silicates of alkali metals such as lithium, sodium, and potassium. Silicates containing monovalent cations (M), such as salts and ammonium silicates (mM 2 O ⁇ nSiO 2, and in the following, the number of moles of M 2 O and the moles of SiO 2 And a ratio n / m to n which is a number) is preferable.
  • M monovalent cations
  • alkali metal ions such as lithium ion, sodium ion and potassium ion are preferable, and sodium ion is particularly preferable from the viewpoint of economy.
  • n / m range of about 1.5 to 4
  • a silicate having an n / m of 1.5 or more is preferable because good adhesion durability is obtained. If the n / m ratio is less than 1.5, the corrosion resistance of the film formed by the reaction between the aqueous solution containing the silicate and the organosilane compound and the aluminum oxide film tends to be slightly lowered, and the adhesion durability may be lowered. There is.
  • the upper limit of n / m ratio is not defined, 4 or less is preferable from the problem on the production of silicate. Specific examples include layered crystal sodium silicate and water glass.
  • a layered crystal silicate is particularly preferable from the viewpoint of stabilization of operation because a high amount of reaction products with minerals is reduced due to high ion exchange capacity and adhesion to an apparatus or a container is reduced.
  • a silicate only 1 type may be used independently and may be used in combination of 2 or more type.
  • the type of the organic silane compound contained in the surface treatment liquid is not particularly limited, but the organic silane compound is a silane compound having a plurality of hydrolyzable trialkoxysilyl groups in the molecule, a hydrolyzate thereof, or a polymer thereof. May be included.
  • a silane compound having a plurality of hydrolyzable trialkoxysilyl groups in the molecule not only forms a dense siloxane bond, but also has a high reactivity with a metal oxide and forms a chemically stable film. The wet durability of the film can be further increased.
  • organosilane-treated films have high mutual solubility with machine oils such as processing oil and press oil and organic compounds such as adhesives, and even if machine oil such as process oil and press oil adheres to the film Since the influence can be mitigated, it also plays a role in preventing a decrease in adhesion durability due to oiling.
  • the kind of the silane compound is not particularly limited, from the viewpoint of economy, a silane compound (bissilane compound) having two hydrolyzable trialkoxysilyl groups in the molecule is preferable, and examples thereof include bistrialkoxysilylethane and bistrimethyl.
  • bistrialkoxysilylbenzene bistrialkoxysilylpropylamine, bistrialkoxysilylpropylamine, bistrialkoxysilylpropyltetrasulfide, and the like can be used.
  • bistriethoxysilylethane BTSE
  • an organosilane compound only 1 type may be used independently and it may be used in combination of 2 or more type.
  • the organic silane compound may include a silane coupling agent having a reactive functional group that can chemically bond with the organic resin component, a hydrolyzate thereof, or a polymer thereof.
  • a silane coupling agent having a reactive functional group such as amino group, epoxy group, methacryl group, vinyl group and mercapto group alone or in combination with the above silane compound, between the film and the resin A chemical bond can be formed to further enhance the adhesion durability.
  • the functional group of a silane coupling agent is not limited to what was mentioned above, The silane coupling agent which has various functional groups can be selected suitably according to the adhesive resin to be used.
  • silane coupling agents include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-aminoethyl) -aminopropyltrimethoxysilane, 3- (N— Aminoethyl) -aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxy Examples thereof include propyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane.
  • silane coupling agent only 1 type may be used independently and it may be used in combination of 2 or more type.
  • the surface treatment liquid may further contain one or more of a stabilizer, an auxiliary agent and the like, if desired, in addition to the silicate and the organosilane compound.
  • the stabilizer may include organic compounds such as carboxylic acids having 1 to 4 carbon atoms such as formic acid and acetic acid, and alcohols having 1 to 4 carbon atoms such as methanol and ethanol.
  • Examples of the method for applying the surface treatment liquid include immersion treatment, spraying, roll coating, bar coating, electrostatic coating, and the like. Moreover, it is better that there is no rinsing after the surface treatment, but in some cases, it may be performed with pure water or the like.
  • the surface treatment liquid is dried by heating as necessary.
  • the heating temperature is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and still more preferably 90 ° C. or higher. Further, if the heating temperature is too high, the characteristics of the aluminum alloy are affected. Therefore, the heating temperature is preferably 220 ° C. or lower, more preferably 200 ° C. or lower, and further preferably 190 ° C. or lower.
  • the drying time is preferably 2 seconds or more, more preferably 5 seconds or more, and further preferably 10 seconds or more, although it depends on the heating temperature. Moreover, the said drying time becomes like this. Preferably it is 20 minutes or less, More preferably, it is 5 minutes or less, More preferably, it is 2 minutes or less.
  • the coating amount of the surface treatment liquid is preferably adjusted so that the coating amount after drying is 0.001 mg / m 2 or more and 30 mg / m 2 or less from the viewpoint of obtaining a sufficient effect of improving the adhesion durability. More preferably, the coating amount after drying is adjusted to be 0.01 mg / m 2 or more and 20 mg / m 2 or less. If the coating amount of the surface treatment solution is too small, the amount of silicate or organosilane compound may be too small to obtain good adhesion durability. Moreover, when the coating amount of the surface treatment liquid is too large, the surface treatment film to be formed becomes too thick, peeling may occur in the surface treatment film, and adhesion durability may be impaired. In addition, for example, the surface treatment film is not removed in a degreasing etching process for painting after an automobile assembly process, which may adversely affect paint adhesion or may give a difference in paint paste.
  • ⁇ Other processes> In the manufacturing method of the aluminum alloy material 10 of the present embodiment, other steps may be included between or before and after each step within a range that does not adversely affect each step described above.
  • a preliminary aging treatment step for performing a preliminary aging treatment may be provided after the surface treatment film forming step S3.
  • This preliminary aging treatment is preferably performed by heating at 40 to 120 ° C. within 72 hours at a low temperature of 8 to 36 hours.
  • pre-aging treatment By performing pre-aging treatment under these conditions, it is possible to improve moldability and strength after baking.
  • a foreign matter removing step for removing foreign matter on the surface of the aluminum alloy material 10 or a defective product removing step for removing defective products generated in each step may be performed.
  • the manufactured aluminum alloy material 10 is coated with machine oil such as press oil on the surface thereof before manufacturing the joined body or before processing into a member for an automobile.
  • machine oil such as press oil
  • one containing an ester component is mainly used.
  • the method and conditions for applying the press oil to the aluminum alloy material 10 are not particularly limited, and methods and conditions for applying the normal press oil can be widely applied.
  • a press containing ethyl oleate as an ester component What is necessary is just to immerse the aluminum alloy material 10 in oil.
  • the ester component is not limited to ethyl oleate, and various materials such as butyl stearate and sorbitan monostearate can be used.
  • the aluminum alloy material 10 of this embodiment is provided with the surface treatment film 2 rich in the solubility of machine oil on the outermost surface, the adhesive resin is satisfactorily formed thereon even after the machine oil is applied. Can be joined.
  • an aqueous solution containing a silicate and an organosilane compound is used for an aluminum alloy base material on which an oxide film is formed.
  • the amount of Cu in the oxide film 1 before the surface treatment film forming step is regulated to be less than a specific amount, the adhesion durability between the surface treatment film 2 formed by subjecting the oxide film 1 to the surface treatment and the adhesive resin. Improves. As a result, even when the aluminum alloy material 10 of the present embodiment is exposed to a high-temperature and humid environment, the interfacial peeling is suppressed, and a decrease in adhesive strength can be suppressed over a long period of time. Further, the adhesion durability can be improved as compared with the surface treatment using only the organosilane compound.
  • FIG. 4 is a cross-sectional view schematically showing a configuration of an aluminum alloy material with an adhesive resin layer according to this modification.
  • the same components as those of the aluminum alloy material 10 shown in FIG. 3 are denoted by the same reference numerals, and detailed description thereof is omitted.
  • the aluminum alloy material 11 with an adhesive resin layer of the present modification is an adhesive resin layer 4 made of an adhesive resin so as to cover the surface treatment film 2 in the aluminum alloy material of the first embodiment described above. Is formed.
  • the adhesive resin layer 4 is made of an adhesive resin or the like, and the aluminum alloy material 11 with the adhesive resin layer of this modification is joined to another member via the adhesive resin layer 4.
  • the other members as with the aluminum alloy material 11 with the adhesive resin layer, another aluminum alloy material on which a surface treatment film is formed, an aluminum alloy material on which an oxide film and a surface treatment film are not formed, resin molding Body and the like are included.
  • the adhesive resin that constitutes the adhesive resin layer 4 is not particularly limited. When an aluminum alloy material such as an epoxy resin, a urethane resin, a nitrile resin, a nylon resin, or an acrylic resin is conventionally joined. The adhesive resin that has been used can be used.
  • the thickness of the adhesive resin layer 4 is not particularly limited, but is preferably 10 to 500 ⁇ m, and more preferably 50 to 400 ⁇ m. When the thickness of the adhesive resin layer 4 is less than 10 ⁇ m, the aluminum alloy material 11 with the adhesive resin layer and the aluminum alloy material not provided with another adhesive resin layer are joined via the adhesive resin layer 4. , High adhesion durability may not be obtained. On the other hand, when the thickness of the adhesive resin layer 4 exceeds 500 ⁇ m, the adhesive strength may be reduced.
  • FIG. 5 is a flowchart showing a method for manufacturing the aluminum alloy material 11 with an adhesive resin layer according to this modification. As shown in FIG. 5, when manufacturing the aluminum alloy material 11 with the adhesive resin layer of this modification, an adhesive resin layer forming step S4 is performed in addition to the above-described steps S1 to S3.
  • Step S4 Adhesive resin layer forming step
  • the adhesive resin layer 4 made of an adhesive or the like is formed so as to cover the surface treatment film 2.
  • the method for forming the adhesive resin layer 4 is not particularly limited. For example, when the adhesive resin is a solid, it is heated and pressure-bonded, or dissolved in a solvent to obtain a solution. Further, when the adhesive resin is in a liquid state, a method of spraying or coating the surface of the surface treatment film 2 as it is can be mentioned.
  • the oxide film forming step S2, the surface treatment film forming step S3, and / or the adhesive resin layer forming step S4 are performed as in the first embodiment.
  • a preliminary aging treatment step for performing preliminary aging treatment may be provided later.
  • the adhesive resin layer is provided in advance, the work such as applying the adhesive resin to the surface of the aluminum alloy material is omitted when producing a joined body or an automobile member. can do.
  • the configuration and effects other than those described above in the aluminum alloy material with an adhesive resin layer of the present modification are the same as those in the first embodiment described above.
  • the joined body of this embodiment uses the aluminum alloy material of the first embodiment described above or an aluminum alloy material with an adhesive resin layer of a modification thereof.
  • 6 to 9B are cross-sectional views schematically showing a configuration example of the joined body of this embodiment. 6 to 9B, the same components as those of the aluminum alloy material 10 and the aluminum alloy material 11 with the adhesive resin layer 11 shown in FIGS. 3 and 4 are denoted by the same reference numerals, and detailed description thereof is omitted.
  • the two aluminum alloy materials 10 shown in FIG. 3 are arranged so that the surfaces on which the surface treatment film 2 is formed face each other. It can be set as the structure arrange
  • the same adhesive resin as the adhesive resin layer 4 described above can be used as the adhesive resin 5.
  • an epoxy resin, a urethane resin, a nitrile resin, a nylon resin, an acrylic resin, or the like can be used as the adhesive resin 5.
  • the thickness of the adhesive resin 5 is not particularly limited, but is preferably 10 to 500 ⁇ m, more preferably 50 to 400 ⁇ m from the viewpoint of improving the adhesive strength.
  • both surfaces of the adhesive resin 5 are the surface treatment film 2 of the aluminum alloy material 10 of the first embodiment.
  • the adhesive strength at the interface between the adhesive resin 5 and the surface treatment film 2 is hardly lowered, and the adhesion durability is improved.
  • the adhesive durability at the interface is improved in all adhesive resins conventionally used for joining aluminum alloy materials without being affected by the type of the adhesive resin 5.
  • the surface where the surface treatment film 2 of the aluminum alloy material 10 shown in FIG. It can also be set as the structure which joined the other aluminum alloy material 6 or the resin molding 7 in which the membrane
  • the other aluminum alloy material 6 on which the oxide film and the surface treatment film are not formed the same material as the base material 3 described above can be used, and specifically, as defined in JIS or Those made of various non-heat treatment type or heat treatment type aluminum alloys similar to JIS can be used.
  • Examples of the resin molded body 7 include glass fiber reinforced plastic (GFRP), carbon fiber reinforced plastic (CFRP), boron fiber reinforced plastic (BFRP), aramid fiber reinforced plastic (AFRP, KFRP), polyethylene fiber reinforced plastic (A fiber reinforced plastic molded body formed of various fiber reinforced plastics such as DFRP) and Zylon reinforced plastic (ZFRP) can be used. By using these fiber-reinforced plastic molded bodies, it is possible to reduce the weight of the joined body while maintaining a certain strength.
  • GFRP glass fiber reinforced plastic
  • CFRP carbon fiber reinforced plastic
  • BFRP boron fiber reinforced plastic
  • AFRP aramid fiber reinforced plastic
  • KFRP polyethylene fiber reinforced plastic
  • a fiber reinforced plastic molded body formed of various fiber reinforced plastics such as DFRP
  • ZFRP Zylon reinforced plastic
  • the resin molded body 7 is made of polypropylene (PP), acrylic-butadiene-styrene copolymer (ABS) resin, polyurethane (PU), polyethylene (PE), polyvinyl chloride (PVC). , Nylon 6, nylon 6,6, polystyrene (PS), polyethylene terephthalate (PET), polyamide (PA), polyphenylene sulfide (PPS), polybutylene terephthalate (PBT), polyphthalamide (PPA), etc. No resin can be used.
  • PP polypropylene
  • ABS acrylic-butadiene-styrene copolymer
  • PU polyurethane
  • PE polyethylene
  • PVC polyvinyl chloride
  • the joined bodies 21a and 21b shown in FIGS. 7A and 7B since one surface of the adhesive resin 5 is joined to the surface treatment film 2 side, when used for a member for an automobile as in the above-described joined body 20, the temperature is high. Even when exposed to a wet environment, the adhesion durability at the interface is improved without being affected by the type of the adhesive resin. Moreover, since the joined body 21b shown to FIG. 7B has joined the aluminum alloy material 10 and the resin molding 7, it is lightweight compared with the joined body of aluminum alloy materials, By using this joined body 21b, Further weight reduction of the automobile can be realized. The other configurations and effects of the joined bodies 21a and 21b shown in FIGS. 7A and 7B are the same as those of the joined body 20 shown in FIG.
  • the aluminum alloy material 11 with the adhesive resin layer provided with the adhesive resin layer 4 shown in FIG. 4 and the aluminum alloy material 10 not provided with the adhesive resin layer 4 shown in FIG. It can also be set as the structure which joined. Specifically, the surface treatment film 2 of the aluminum alloy material 10 is bonded to the adhesive resin layer 4 side of the aluminum alloy material 11 with the adhesive resin layer. As a result, the film 2 of the aluminum alloy material 10 and the film 2 of the aluminum alloy material 11 with the adhesive resin layer were arranged to face each other via the adhesive resin layer 4 of the aluminum alloy material 11 with the adhesive resin layer. It has a configuration.
  • the surface treatment is performed on the adhesive resin layer 4 side of the aluminum alloy material 11 with the adhesive resin layer provided with the adhesive resin layer 4 shown in FIG.
  • Another aluminum alloy material 6 on which a film is not formed or a resin molded body 7 such as a fiber reinforced plastic molded body may be joined.
  • a high-temperature wet environment is used. Even if it is exposed to, the durability of adhesion at the interface is improved without being affected by the type of adhesive resin.
  • the joined body 23b shown to FIG. 9B has joined the aluminum alloy material 11 with an adhesive resin layer, and the resin molding 7, it is lightweight compared with the joined body of aluminum alloy materials, and weight reduction is calculated
  • the structure and effect other than the above in the joined bodies 23a and 23b shown in FIGS. 9A and 9B are the same as those of the joined body 20 shown in FIG.
  • a manufacturing method of the joined bodies 20 to 23 As a manufacturing method of the joined bodies 20 to 23, particularly a joining method, a conventionally known joining method can be used.
  • the method for forming the adhesive resin 5 on the aluminum alloy material is not particularly limited.
  • an adhesive sheet prepared in advance using the adhesive resin 5 may be used, or the adhesive resin 5 may be used as the surface treatment film 2. You may form by spraying or apply
  • the joined bodies 20 to 23 may be coated with a machine oil such as press oil on the surface thereof before being processed into a member for an automobile, like the aluminum alloy material 10 and the aluminum alloy material 11 with an adhesive resin layer. .
  • the member for motor vehicles of this embodiment uses the joined object of a 2nd embodiment mentioned above, for example, is a panel for motor vehicles.
  • the manufacturing method of the automobile member of the present embodiment is not particularly limited, but a conventionally known manufacturing method can be applied.
  • the joined members 20 to 23b shown in FIGS. 6 to 9B are cut or pressed to produce a predetermined-shaped automobile member.
  • the automobile member according to the present embodiment is manufactured from the joined body according to the second embodiment described above, even if it is exposed to a high temperature and wet environment, the influence of the hydration of the adhesive resin or the adhesive resin layer and the oxide film is affected. Almost no elution of the aluminum alloy base material can be suppressed with little. As a result, in the automotive member of this embodiment, it is possible to suppress interfacial peeling when exposed to a high-temperature and humid environment, and to suppress a decrease in adhesive strength.
  • an aluminum alloy material was produced by the following method and conditions, and its adhesion durability and the like were evaluated.
  • Examples 1 and 2> Using a 6000 series aluminum alloy of JIS 6016 (Mg: 0.54 mass%, Si: 1.11 mass%, Cu: 0.14 mass%), an aluminum alloy cold-rolled sheet having a thickness of 1 mm is produced by the method described above. did. And this cold-rolled board was cut
  • a solution containing potassium hydroxide adjusted to pH 13 at a temperature of 50 ° C. for a treatment time of 1 to 120 seconds, and then washed with water.
  • the nitric acid solution treatment was performed under the conditions of a temperature of 40 ° C. and a treatment time of 1 to 120 seconds, and then washed with water to obtain the etching amounts shown in Table 1. As described in 1, an oxide film in which the amount of Mg and the amount of Cu were controlled was formed.
  • Examples 3 to 5> Using a 6000 series aluminum alloy of JIS 6016 (Mg: 0.54 mass%, Si: 1.11 mass%, Cu: 0.14 mass%), an aluminum alloy cold-rolled sheet having a thickness of 1 mm is produced by the method described above. did. And this cold-rolled board was cut
  • a solution containing potassium hydroxide adjusted to pH 13 at a temperature of 50 ° C. for a treatment time of 1 to 120 seconds, and then washed with water.
  • the sulfuric acid / hydrofluoric acid solution treatment was performed under the conditions of a temperature of 50 ° C. and a treatment time of 1 to 120 seconds, and then washed with water.
  • An oxide film was formed in which the etching amount was as described and the Mg amount and Cu amount were controlled as shown in Table 1.
  • Examples 6 to 7> Using a 6000 series aluminum alloy of JIS 6016 (Mg: 0.54 mass%, Si: 1.11 mass%, Cu: 0.14 mass%), an aluminum alloy cold-rolled sheet having a thickness of 1 mm is produced by the method described above. did. And this cold-rolled board was cut
  • Examples 8 to 9> Using a 6000 series aluminum alloy of JIS 6016 (Mg: 0.54 mass%, Si: 1.11 mass%, Cu: 0.14 mass%), an aluminum alloy cold-rolled sheet having a thickness of 1 mm is produced by the method described above. did. And this cold-rolled board was cut
  • Ethanol and acetic acid were used for dissolution of BTSE and pH adjustment in the preparation process of the aqueous solution (surface treatment solution), but no fluorine-based drug was used.
  • the amount of ethanol in the entire solution was about 2%.
  • coating of a surface treatment liquid was performed for 1 minute at 105 degreeC. The coating amount after drying was confirmed to be about 4 mg / m 2 by measurement with before and after coating with fluorescent X-rays.
  • Example 10 To the oxide film on the surface of the aluminum alloy substrate on which the oxide film was formed, obtained in Example 1, 0.1% by mass of sodium metasilicate (a molar ratio of SiO 2 and Na 2 O of about 1), An aqueous solution (surface treatment solution) containing 0.09% by mass of bistriethoxysilylethane (BTSE) and having a pH adjusted to 11.2 was applied by a bar coater to form a surface treatment film. An aluminum alloy material was produced. Ethanol and acetic acid were used for dissolution of BTSE and pH adjustment in the preparation process of the aqueous solution (surface treatment solution), but no fluorine-based drug was used. The amount of ethanol in the entire solution was about 2%. In addition, drying after application
  • BTSE bistriethoxysilylethane
  • Example 11 0.1% by mass of water glass (SiO 2 to Na 2 O molar ratio of 3 to 3.4) was added to the oxide film on the surface of the aluminum alloy substrate on which the oxide film was formed, obtained in Example 1. And an aqueous solution (surface treatment liquid) containing 0.09% by mass of bistriethoxysilylethane (BTSE) and having a pH adjusted to 11.2 is applied by a bar coater to form a surface treatment film. 11 aluminum alloy materials were produced. Ethanol and acetic acid were used for dissolution of BTSE and pH adjustment in the preparation process of the aqueous solution (surface treatment solution), but no fluorine-based drug was used. The amount of ethanol in the entire solution was about 2%. In addition, drying after application
  • ⁇ Comparative Example 3> In the oxide film on the surface of the aluminum alloy substrate on which the oxide film was formed, obtained in Example 1, 0.55% by mass of crystalline layered sodium silicate (SiO 2: Na 2 O molar ratio is about 2) (Pre-feed made by Tokuyama Siltec) and 0.05% by mass of bistriethoxysilylethane (BTSE), and an aqueous solution (surface treatment liquid) adjusted to pH 12.1 was applied by a bar coater. A treatment film was formed, and an aluminum alloy material of Comparative Example 3 was produced. Ethanol and acetic acid were used for dissolution of BTSE and pH adjustment in the preparation process of the aqueous solution (surface treatment solution), but no fluorine-based drug was used.
  • crystalline layered sodium silicate SiO 2: Na 2 O molar ratio is about 2
  • BTSE bistriethoxysilylethane
  • the amount of ethanol in the entire solution was about 2%.
  • coating of a surface treatment liquid was performed for 1 minute at 105 degreeC.
  • the coating amount after drying was confirmed to be 35 mg / m 2 by fluorescence X-rays and measured before and after coating.
  • BTSE bistriethoxysilylethane
  • the amount of ethanol in the entire solution was about 2%.
  • coating of a surface treatment liquid was performed for 1 minute at 105 degreeC.
  • the coating amount after drying was confirmed to be 36 mg / m 2 by fluorescence X-rays and measured before and after coating.
  • the press oil diluted with toluene was applied to the surface of the aluminum alloy material according to each of Examples and Comparative Examples produced in this way so that the coating amount after drying was 1 g / m 2 .
  • the oxide film of the aluminum alloy base material according to each of Examples and Comparative Examples was subjected to high-frequency glow discharge emission spectroscopy (GD-OES: model manufactured by Horiba Joban Yvon) JY-5000RF) while sputtering in the film thickness direction, metal elements such as aluminum (Al), magnesium (Mg), copper (Cu), iron (Fe), and titanium (Ti), and oxygen (O), The amount of each component was measured for elements such as nitrogen (N), carbon (C), silicon (Si) and sulfur (S).
  • GD-OES high-frequency glow discharge emission spectroscopy
  • the maximum concentration of magnesium (Mg), copper (Cu) and silicon (Si) in the oxide film was defined as the film concentration in the film.
  • oxygen (O) and carbon (C) are particularly susceptible to contamination on the outermost surface and in the vicinity thereof. From the above, in the concentration calculation of each element, the concentration was calculated excluding oxygen (O) and carbon (C). Note that oxygen (O) is likely to be affected by contamination at the outermost surface and in the vicinity thereof, and it is difficult to measure the exact concentration. However, the oxide film of all samples contains oxygen (O). It was clear that
  • the etching amount (unit: g / cm 2 ) is obtained by measuring the amount of decrease in the weight of the base material before and after the oxide film formation step (unit: g) and dividing this by the surface area of the base material (unit: m 2 ). Calculated.
  • 10A and 10B are diagrams schematically showing a method for measuring the cohesive failure rate
  • FIG. 10A is a side view
  • FIG. 10B is a plan view.
  • the adhesive resin 35 used here is a thermosetting epoxy resin-based adhesive resin (bisphenol A type epoxy resin amount 40 to 50 mass%).
  • the prepared adhesion test specimen was held in a high temperature and humidity environment of 50 ° C. and a relative humidity of 95% for 30 days, and then pulled at a rate of 50 mm / min with a tensile tester to evaluate the cohesive failure rate of the adhesive resin at the adhesion portion.
  • the cohesive failure rate was calculated based on Equation 1 below.
  • the test specimen a was used as one side after the tension of the adhesion test specimen, and the test specimen b was used as the other side.
  • the cohesive failure rate was the average value of the three samples. Further, the evaluation criteria are that the cohesive failure rate is less than 60% as bad (x), 60% or more and less than 70% is slightly good ( ⁇ ), 70% or more and less than 90% is good ( ⁇ ), and 90% or more is particularly good. ( ⁇ ) and 60% or more was accepted.
  • the aluminum alloy material of Comparative Example 1 in which the concentration of Cu in the oxide film is out of the range specified in the present invention has a poor cohesive failure rate of less than 60%, and is in a high temperature humid environment.
  • the adhesion durability was inferior.
  • the aluminum alloy material of Comparative Example 2 manufactured without pickling or alkali cleaning has a Mg concentration in the oxide film that is out of the scope of the present invention, and the cohesive failure rate is less than 60%. It was inferior in adhesion durability in a high-temperature and humid environment.
  • the aluminum alloy material of Comparative Example 3 in which the concentration of silicate in the surface treatment liquid is out of the range defined in the present invention has a poor cohesive failure rate of less than 60%, and the adhesion durability in a high-temperature and humid environment. It was inferior in nature.
  • the aluminum alloy material of Comparative Example 4 in which the concentration of the organosilane compound in the surface treatment liquid is out of the range defined in the present invention has a poor cohesive failure rate of less than 60%, and the adhesion durability in a high-temperature and humid environment. It was inferior in nature.
  • Examples 10 instead of the crystalline layered sodium silicate as used in Example 1 (molar ratio of SiO 2 and Na 2 O of about 2) (Tokuyama Siltech made pre feed), sodium metasilicate (SiO 2 And the Na 2 O molar ratio is about 1), and is an example produced under substantially the same conditions as in Example 1 except that the sodium silicate species was changed.
  • Example 10 the molar ratio of SiO 2 and Na 2 O was used sodium metasilicate less than 1.5 (about 1), although the cohesive failure rate was less than 90% to 70% pass level, SiO 2 The cohesive failure rate was slightly inferior to Example 1 using crystalline layered sodium silicate in which the molar ratio of Na 2 O was about 2. Further, in Example 11, instead of the crystalline layered sodium silicate (a molar ratio of SiO 2 and Na 2 O of about 2) used in Example 1 (pre-feed made by Tokuyama Siltec), water glass (SiO 2 and This is an example in which the molar ratio of Na 2 O is 3 to 3.4), and is an example prepared under substantially the same conditions as in Example 1 except that the sodium silicate species is changed.
  • crystalline layered sodium silicate a molar ratio of SiO 2 and Na 2 O of about 2
  • water glass SiO 2 and This is an example in which the molar ratio of Na 2 O is 3 to 3.4
  • Example 11 using a water glass having a molar ratio of SiO 2 to Na 2 O of 1.5 or more (about 3 to 3.4), a crystalline layered structure having a molar ratio of SiO 2 to Na 2 O of about 2 A cohesive failure rate equivalent to that in Example 1 using sodium silicate was obtained.

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Abstract

La présente invention concerne un procédé de fabrication d'un alliage d'aluminium comprenant : une étape de formation d'un revêtement d'oxyde consistant à former un revêtement d'oxyde, contenant de 0,1 % atomique à moins de 30 % atomique de Mg et moins de 0,6 % atomique de Cu, sur au moins une partie de la surface d'un matériau de base en un alliage d'aluminium ; et une étape de formation d'un revêtement de surface traitée consistant à recouvrir d'une solution aqueuse contenant de 0,001 % en masse à moins de 0,5 % en masse d'un sel d'acide silicique et de 0,001 % en masse à moins de 0,5 % en masse d'un composé de silane organique et dont le pH est compris entre 7 et 14, sur au moins une partie dudit revêtement d'oxyde. Le procédé de fabrication d'un alliage d'aluminium d'après la présente invention permet de fabriquer un alliage d'aluminium qui n'est pas susceptible de présenter une diminution de la résistance d'adhérence même lorsqu'il est exposé à un environnement chaud et humide, qui présente une excellente durabilité d'adhérence et qui peut être produit efficacement.
PCT/JP2016/069090 2015-07-09 2016-06-28 Procédé de fabrication d'un alliage d'aluminium, alliage d'aluminium et conjugué WO2017006804A1 (fr)

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WO2017195811A1 (fr) * 2016-05-10 2017-11-16 株式会社神戸製鋼所 Matériau en alliage d'aluminium, matériau en alliage d'aluminium ayant une couche de résine adhésive, procédé de production de matériau en alliage d'aluminium, et procédé de production de matériau en alliage d'aluminium ayant une couche de résine adhésive
WO2019017026A1 (fr) * 2017-07-19 2019-01-24 昭和電工株式会社 Procédé de traitement de surface d'article en aluminium
WO2021188610A1 (fr) * 2020-03-18 2021-09-23 Novelis Inc. Article en alliage d'aluminium présentant une durabilité de liaison améliorée et procédés de fabrication de celui-ci
WO2023153192A1 (fr) * 2022-02-08 2023-08-17 東洋アルミニウム株式会社 Feuille d'aluminium et procédé pour la production de celle-ci

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JP2006299356A (ja) * 2005-04-21 2006-11-02 Chubu Kiresuto Kk 防錆剤組成物および水性防錆潤滑剤、並びにこれを用いた加工法
JP2015003514A (ja) * 2013-05-23 2015-01-08 株式会社神戸製鋼所 アルミニウム合金板、接合体及び自動車用部材

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WO2017195802A1 (fr) * 2016-05-10 2017-11-16 株式会社神戸製鋼所 Matériau en alliage d'aluminium, matériau en alliage d'aluminium ayant une couche de résine adhésive, procédé de production de matériau en alliage d'aluminium, et procédé de production de matériau en alliage d'aluminium ayant une couche de résine adhésive
WO2017195811A1 (fr) * 2016-05-10 2017-11-16 株式会社神戸製鋼所 Matériau en alliage d'aluminium, matériau en alliage d'aluminium ayant une couche de résine adhésive, procédé de production de matériau en alliage d'aluminium, et procédé de production de matériau en alliage d'aluminium ayant une couche de résine adhésive
WO2019017026A1 (fr) * 2017-07-19 2019-01-24 昭和電工株式会社 Procédé de traitement de surface d'article en aluminium
JPWO2019017026A1 (ja) * 2017-07-19 2020-05-28 昭和電工株式会社 アルミニウム物品表面の処理方法
JP6994508B2 (ja) 2017-07-19 2022-01-14 昭和電工株式会社 アルミニウム物品表面の処理方法
WO2021188610A1 (fr) * 2020-03-18 2021-09-23 Novelis Inc. Article en alliage d'aluminium présentant une durabilité de liaison améliorée et procédés de fabrication de celui-ci
WO2023153192A1 (fr) * 2022-02-08 2023-08-17 東洋アルミニウム株式会社 Feuille d'aluminium et procédé pour la production de celle-ci

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