WO2017195802A1 - 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 - Google Patents

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 Download PDF

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Publication number
WO2017195802A1
WO2017195802A1 PCT/JP2017/017615 JP2017017615W WO2017195802A1 WO 2017195802 A1 WO2017195802 A1 WO 2017195802A1 JP 2017017615 W JP2017017615 W JP 2017017615W WO 2017195802 A1 WO2017195802 A1 WO 2017195802A1
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Prior art keywords
aluminum alloy
film
alloy material
adhesive resin
coating
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PCT/JP2017/017615
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English (en)
Japanese (ja)
Inventor
佑輔 高橋
悟 高田
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株式会社神戸製鋼所
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Publication of WO2017195802A1 publication Critical patent/WO2017195802A1/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
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • 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 an aluminum alloy material, an aluminum alloy material with an adhesive resin layer, a method for producing an aluminum alloy material, and a method for producing an aluminum alloy material with an adhesive resin layer.
  • a surface treatment for improving the corrosion resistance and paint adhesion of a metal surface is known from the viewpoint of corrosion prevention.
  • Patent Document 1 discloses an adhesive formed on a metal such as aluminum by treating it with an aqueous composition containing a tetraalkylsilicate such as tetraethylorthosilicate and a hydrated oxide sol such as silica sol. A method for improving the initial adhesion of the coating film and the long-term stability of the adhesion is described.
  • Patent Document 2 discloses that after treating a metal substrate with a first treatment solution consisting essentially of at least one polyfunctional silane having at least two trisubstituted silyl groups, at least one kind of organo A technique for improving the corrosion resistance of a metal by applying a second coating containing a second treatment solution containing a functional silane is described.
  • Patent Document 3 describes a technique for improving the corrosion resistance of a metal by treating the metal substrate with a solution containing aminosilane and polysilyl functional silane.
  • Patent Document 4 describes a method of improving corrosion resistance by rinsing the surface of a galvanized steel sheet with an aqueous solution containing a silicate compound and then treating it with a silane coupling agent.
  • Patent Document 5 discloses that a solution containing a silicate ester, an aluminum inorganic salt and polyethylene glycol and further containing a silane coupling agent is applied onto a galvanized steel sheet and dried to form a film. Thus, a technique for improving paint adhesion and white rust resistance is described.
  • Patent Document 6 discloses a technique for improving paint adhesion by treating the surface of a metal material such as aluminum or aluminum alloy with an aqueous solution containing water glass such as sodium water glass and silane such as aminosilane. Are listed.
  • Patent Document 7 improves corrosion resistance and paint adhesion by treating a metal sheet with an alkaline solution containing an inorganic silicate, an organofunctional silane, and a crosslinking agent containing two or more trialkoxysilyl groups. The method is described.
  • Patent Documents 4 to 7 are intended only for the purpose of preventing corrosion of metal surfaces and improving the adhesion of paints. Therefore, although the formed film is thick, the mechanical film itself has low mechanical strength and becomes brittle with respect to tension and stress, and high adhesive strength cannot be obtained.
  • the surface-treated aluminum alloy material is coated with oil after the surface treatment to improve workability, and then molded and bonded.
  • oil such as lubricating oil, press oil, or processing oil
  • the adhesiveness of the adhesive is greatly reduced, and high adhesive strength cannot be obtained.
  • the present invention provides an aluminum alloy material, an aluminum alloy material with an adhesive resin layer, and an aluminum alloy that have excellent adhesion durability, even when exposed to a high-temperature and humid environment.
  • the main object is to provide a method for producing a material and a method for producing an aluminum alloy material with an adhesive resin layer.
  • the present inventor found that the amount of Mg, Si and Cu are within a specific range on the surface of the aluminum substrate, and in the FT-IR spectrum. It has been found that excellent adhesion durability can be obtained by forming a film made of an oxide of aluminum containing silicon and having a specific absorption, and further forming a film containing a polymer of a specific silane compound. Invented.
  • the present invention provides an aluminum alloy base material, a first film made of an aluminum oxide containing silicon, formed on at least a part of the surface of the aluminum alloy base material, and at least a part of the first film.
  • An aluminum alloy material provided with a second film containing a silane compound having two or more hydrolyzable trialkoxysilyl groups in the molecule, a hydrolyzate thereof, or a polymer thereof Has two absorption bands in the wave number range of 1000 to 1300 cm ⁇ 1 in the difference spectrum before and after the film treatment obtained by applying parallel polarized light with an incident angle of 75 ° by Fourier transform infrared spectroscopy.
  • One of the absorption band is in the range of wave numbers 1080 ⁇ 1140 cm -1 and a wavenumber of 1180 ⁇ 1240 cm -1, and the first coating, the Si 15 atomic% Over 70 atomic% and less than Mg with containing less than 0.1 atomic% to 30 atomic%, Cu is regulated to less than 0.6 atomic%, to provide an aluminum alloy material.
  • the amounts of Si, Mg, and Cu in the first film are values measured by a high-frequency glow discharge emission spectroscopy (GD-OES: Glow Discharge-Optical Emission Spectroscopy).
  • the coating does not substantially contain a particulate inorganic compound having a diameter of 1 nm or more.
  • the amount of Si in the first coating is preferably 20 atomic percent or more and less than 65 atomic percent, and more preferably 30 atomic percent or more and less than 60 atomic percent.
  • the second coating may further contain a silane coupling agent having a reactive functional group capable of chemically bonding with the organic resin component, a hydrolyzate thereof, or a polymer thereof.
  • the coating amount of the second coating is preferably 0.01 to 30 mg / m 2 , more preferably 0.2 to 20 mg / m 2 , and 0.5 to 10 mg. further preferably / m 2.
  • the aluminum alloy base material is made of an Al—Mg alloy, an Al—Cu—Mg alloy, an Al—Mg—Si alloy, or an Al—Zn—Mg alloy. Also good.
  • the present invention also provides an aluminum alloy material with an adhesive resin layer in which an adhesive resin layer is formed on the second film of the aluminum alloy material described above.
  • the adhesive resin layer may contain at least one selected from an epoxy resin, a urethane resin, a nitrile resin, a nylon resin, and an acrylic resin.
  • the present invention also provides a first film forming step of forming a first film made of an oxide of aluminum containing silicon on at least a part of the surface of the aluminum alloy substrate, and a molecule on at least a part of the first film.
  • tetraalkylsilicate or oligomer thereof is used.
  • the oxide film is treated with a first aqueous solution containing 0.005% by mass to 2% by mass, and in the second film forming step, a silane compound having two or more hydrolyzable trialkoxysilyl groups in the molecule, and its hydrolysis
  • a method for producing an aluminum alloy material wherein the first film is treated with a second aqueous solution containing a product or a polymer thereof.
  • the etching amount in the etching treatment stage it is preferable to control the etching amount in the etching treatment stage to less than 700 nm.
  • the silicate treatment stage is after the etching treatment stage, and at least one of acid treatment and alkaline solution treatment is performed as the etching treatment stage. May be.
  • the silicate treatment stage in the first film formation step, may be simultaneous with the etching treatment stage.
  • the present invention includes an adhesive resin layer forming step of forming an adhesive resin layer on the second film of the aluminum alloy material manufactured by the above-described method for manufacturing an aluminum alloy material.
  • a manufacturing method is also provided.
  • the present invention it is possible to realize an aluminum alloy material that is hardly deteriorated in adhesive strength and is excellent in adhesion durability even when exposed to a high-temperature and humid environment.
  • FIG. 1 is a cross-sectional view schematically showing a configuration of an aluminum alloy material according to the first embodiment of the present invention.
  • FIG. 2 is a flowchart showing a method for manufacturing the aluminum alloy material shown in FIG.
  • FIG. 3 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. 4 is a flowchart showing a method of manufacturing the aluminum alloy material with an adhesive resin layer shown in FIG.
  • FIG. 5 is a cross-sectional view schematically showing a configuration example of a joined body according to the second embodiment of the present invention.
  • FIG. 6A is a cross-sectional view schematically showing another configuration example of the joined body according to the second embodiment of the present invention.
  • FIG. 1 is a cross-sectional view schematically showing a configuration of an aluminum alloy material according to the first embodiment of the present invention.
  • FIG. 2 is a flowchart showing a method for manufacturing the aluminum alloy material
  • FIG. 6B is a cross-sectional view schematically showing another configuration example of the joined body according to the second embodiment of the present invention.
  • FIG. 7 is a cross-sectional view schematically showing another configuration example of the joined body according to the second embodiment of the present invention.
  • FIG. 8A is a cross-sectional view schematically showing another configuration example of the joined body according to the second embodiment of the present invention.
  • FIG. 8B 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 side view schematically showing a method for measuring the cohesive failure rate.
  • FIG. 9B is a plan view schematically showing a method for measuring the cohesive failure rate.
  • the aluminum alloy material according to the first embodiment of the present invention includes an aluminum alloy base material, a first film made of an oxide of aluminum containing silicon, formed on at least a part of the surface of the aluminum alloy base material, and the first film.
  • One of the absorption band is in the range of wave numbers 1080 ⁇ 1140 cm -1 and a wavenumber of 1180 ⁇ 1240 cm -1, and the first coating, the Si 1 Less atomic% to 70 atomic% and Mg with containing less than 0.1 atomic% to 30 atomic%, Cu is regulated to less than 0.6 atomic%, an aluminum alloy material.
  • FIG. 1 is a cross-sectional view schematically showing the configuration of the aluminum alloy material of the present embodiment.
  • an aluminum alloy material 10 of the present embodiment is a first film made of an oxide of aluminum containing silicon on at least a part of the surface of an aluminum alloy substrate 3 (hereinafter also referred to as a substrate 3). 1 (hereinafter also referred to as film 1) is formed, and at least part of the first film 1 includes a silane compound having two or more trialkoxysilyl groups in the molecule, a hydrolyzate thereof, or a polymer thereof.
  • a second film 2 (hereinafter also referred to as film 2) is formed.
  • the substrate 3 is made of an aluminum alloy.
  • the type of aluminum alloy that forms the base material 3 is not particularly limited, and various non-heat-treatable or heat-treated aluminums that are defined in JIS or approximate to JIS, depending on the use of the processed member. It can be used by appropriately selecting from alloys.
  • 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 3 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.
  • the first film 1 (hereinafter also referred to as film 1) is a film made of an oxide of aluminum containing silicon and formed on at least a part of the surface of the substrate 3.
  • the film 1 has a wave number of 1000 in the difference spectrum before and after the film treatment obtained by entering parallel polarized light with an incident angle of 75 ° by Fourier transform infrared spectroscopy (FT-IR).
  • FT-IR Fourier transform infrared spectroscopy
  • the two absorption bands are in the range of wave numbers 1080 to 1140 cm ⁇ 1 and wave numbers of 1180 to 1240 cm ⁇ 1
  • the coating 1 contains Si at 15 atomic% While containing less than 70 atomic% and Mg in the range of 0.1 atomic% to less than 30 atomic%, Cu is restricted to less than 0.6 atomic%.
  • the coating 1 is a dense and corrosion-resistant coating as compared with a normal aluminum oxide coating, and is provided to increase the bonding strength with the adhesive and to improve the adhesion durability.
  • the suitable range of each component amount contained in the film 1 will be described.
  • the coating 1 is formed on the entire surface of one side of the substrate 3, but the present embodiment is not limited to this.
  • the film 1 may be formed on only a part of the surface of the substrate 3. Further, the coating 1 may be formed on both surfaces of the substrate 3.
  • a thin film derived from tetraalkylsilicate or an oligomer thereof has two different absorption bands derived from asymmetric stretching vibration of Si—O—Si bond in the wave number range of 1000 to 1300 cm ⁇ 1 , and these two absorption bands are , respectively present in the wave number range of 1080 ⁇ 1140 cm -1 and a wavenumber of 1180 ⁇ 1240 cm -1.
  • the peaks of the two absorption bands are averaged as the film becomes thicker, and become a single broad peak.
  • the film becomes thick it becomes a fragile film with low mechanical strength, and high adhesion durability cannot be obtained.
  • the film 1 is in the difference spectrum before and after coating treatment with FT-IR, tetraalkyl silicate or a range of wave numbers 1080 ⁇ 1140 cm -1 and a wavenumber of 1180 ⁇ 1240 cm -1 derived from an oligomer thereof Have two absorption bands, and the film is sufficiently thin, so that it has high adhesion durability.
  • “having an absorption band in a certain wavenumber range” means having a maximum absorption wavelength in the wavenumber range.
  • the shape of the absorption band may be an inflection point, may be a peak, or may be a shoulder.
  • the film having the two absorption bands described above in the difference spectrum before and after the film treatment by FT-IR is formed, for example, by subjecting an oxide film formed on the aluminum alloy base material to a silicate treatment described later. Can do.
  • a silicate process represents the process using tetraalkyl silicate or its oligomer.
  • an oxide film on an aluminum alloy substrate is silicate-treated using a tetraalkyl silicate or an oligomer thereof, if the film after the treatment is thin, there are two absorption bands in the difference spectrum before and after the film treatment by FT-IR. It has absorption bands in the range of wave numbers 1080 to 1140 cm ⁇ 1 and wave numbers 1180 to 1240 cm ⁇ 1 .
  • the difference spectrum before and after the coating treatment refers to the absorption spectrum of the surface of the aluminum alloy material on which the first coating is formed and the aluminum alloy base material on which the first coating is not formed. The difference between the absorption spectrum of
  • the coating 1 when the coating 1 contains a particulate inorganic compound having a diameter of 1 nm or more (hereinafter, also simply referred to as “particulate inorganic compound”), the coating becomes thick and the adhesive strength and the durability of adhesion may be reduced. There is. Therefore, it is preferable that the film 1 contains substantially no particulate inorganic compound.
  • the phrase “the film does not substantially contain a particulate inorganic compound” is not limited to an embodiment that does not contain any particulate inorganic compound, and it is allowed to contain the particulate inorganic compound at an impurity level. The Specifically, the particulate inorganic compound is allowed to be contained in an amount of 5% by mass or less with respect to the entire coating 1.
  • the particulate inorganic compound examples include sols of inorganic oxides such as silica and alumina.
  • the diameter of a particulate inorganic compound represents the diameter measured by the transmission electron microscope (TEM) of the solid content after processing liquid drying, or the diluted processing liquid from the particle counter in liquid.
  • the aluminum alloy constituting the base material of the aluminum alloy material usually contains magnesium (Mg) as an alloy component, and an oxide film that is a composite oxide of aluminum and magnesium is formed on the surface of the base material 3.
  • Mg magnesium
  • an adhesive resin is formed on the oxide film, the surface magnesium becomes a weak boundary layer of the adhesive interface, and the initial bonding strength is lowered.
  • the Mg content in the film is 30 atomic% or more, the bonding strength of the aluminum alloy material tends to decrease. Therefore, in the aluminum alloy material 10 of the present embodiment, the Mg content in the coating 1 is restricted to less than 30 atomic%. Thereby, adhesion durability can be improved.
  • the Mg content of the film 1 is preferably less than 25 atomic%, more preferably less than 20 atomic%, and still more preferably less than 10 atomic%, from the viewpoint of improving adhesion durability.
  • the lower limit of the Mg content of the film 1 is set to 0.1 atomic% or more from the viewpoint of economy.
  • the Mg content in the film 1 can be measured by a high-frequency glow discharge optical emission spectrometry (GD-OES).
  • the method for adjusting the Mg content of the film 1 is not particularly limited.
  • an acid solution such as nitric acid, sulfuric acid and hydrofluoric acid, or an acidic solution such as mixed acid, or potassium hydroxide, sodium hydroxide, silicic acid.
  • a method of performing a surface treatment with an alkaline solution containing a salt and a carbonate can be applied. This method adjusts the Mg content of the film 1 by dissolving magnesium in an acid or alkali solution, and adjusts the treatment time, temperature, concentration and pH of the surface treatment liquid, and thereby in the film 1.
  • the amount of Mg can be in the range described above.
  • Mg Even if Mg is contained to the extent of an impurity element, Mg may be concentrated in the film 1 when heat treatment is performed at a high temperature, and adjustment by surface treatment with acid or alkali is possible. Is necessary as appropriate. It is also possible to adjust the surface treatment chemical solution by containing Mg ions.
  • Silicon has the effect of improving the corrosion resistance of the coating 1 and stabilizing it in a wet environment, and also has the effect of improving the adhesion to the second coating (coating 2) described later. For this reason, it becomes possible to improve adhesion durability by making the film 1 contain silicon.
  • the Si content in the coating 1 is 15 atomic% or more and less than 70 atomic%.
  • the Si content in the film 1 is preferably 20 atomic% or more, and more preferably 30 atomic% or more. Moreover, from the viewpoint of spot weldability and chemical conversion treatment uniformity, the Si content in the coating 1 is preferably less than 65 atomic%, and more preferably less than 60 atomic%.
  • the Si content in the film 1 is adjusted, for example, by performing a surface treatment with an acid or an alkali in the same manner as described as a method for adjusting the amount of Mg. Moreover, it adjusts with the conditions of the process by the silicate aqueous solution mentioned later.
  • the Cu content in the coating 1 is restricted to less than 0.6 atomic%.
  • membrane 1 is less than 0.5 atomic% from a viewpoint of the adhesive improvement with the film
  • the etching method is not limited.
  • the same processing method as described in the numerical value limitation of Mg Can be applied. That is, for example, etching can be performed by treatment with an acid or alkali solution.
  • the element concentration such as Mg amount, Si amount, and Cu amount in the film 1 can be measured by, for example, high-frequency glow discharge emission spectroscopy (GD-OES).
  • GD-OES high-frequency glow discharge emission spectroscopy
  • Mg, copper (Cu), iron (Fe), titanium (Ti) and other metal elements and silicon (Si) and other elements were measured, and the content of Mg, Si, Cu, etc. was calculated as a percentage. The value is the amount of each element.
  • the film 1 preferably has a thickness of 1 to 30 nm.
  • the ester in the press oil used when producing a joined body or an automobile member from the rust preventive oil or the aluminum alloy material 10 used when the base material 3 is produced. Adsorption of components is suppressed. For this reason, even if it does not provide the membrane
  • in order to control the film thickness of the film 1 to be less than 1 nm excessive acid cleaning or the like is required, so that productivity is inferior and practicality tends to be lowered.
  • excessive etching by alkali degreasing or acid causes the Cu contained in the base material 3 to be concentrated on the surface, and causes a decrease in adhesion durability.
  • the film thickness of the film 1 exceeds 30 nm, the amount of the film becomes excessive and irregularities are easily formed on the surface.
  • the film thickness of the film 1 is more preferably 2 nm or more and less than 20 nm from the viewpoints of chemical conversion and productivity.
  • the coating amount after drying is preferably adjusted to be 0.2 mg / m 2 or more and 20 mg / m 2 or less. Further, the coating amount after drying is more preferably adjusted to 1 mg / m 2 or more and 15 mg / m 2 or less, and further preferably 2 mg / m 2 or more and 10 mg / m 2 or less. If the coating amount of the silicate aqueous solution is too small, the amount of tetraalkyl silicate or its oligomer may be too small to obtain good adhesion durability. Moreover, when the application amount of the silicate aqueous solution is too large, the formed film becomes too thick and peeling occurs in the film, which may impair adhesion durability.
  • the second film 2 (hereinafter also referred to as film 2) contains, as a main component, a silane compound having a plurality of hydrolyzable trialkoxysilyl groups in the molecule, a hydrolyzate thereof, or a polymer thereof.
  • Silane compounds with multiple hydrolyzable trialkoxysilyl groups in the molecule not only form dense siloxane bonds by self-polymerization, but also form highly chemically reactive bonds with metal oxides. Therefore, the wet durability of the film 1 can be further improved.
  • the film containing the silane compound, its hydrolyzate or its polymer has high mutual solubility with organic compounds such as machine oils and adhesives, and even if machine oil adheres to the film, the influence can be mitigated. For this reason, 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 economical viewpoint, a silane compound (bissilane compound) having two hydrolyzable trialkoxysilyl groups in the molecule is preferable.
  • bistrialkoxysilylethane bistrialkoxysilylethane, bistrialkoxy Silylbenzene, bistrialkoxysilylpropylhexane, bistrialkoxysilylpropylamine, bistrialkoxysilylpropyltetrasulfide, and the like can be used.
  • bistriethoxysilylethane BTSE
  • BTSE bistriethoxysilylethane
  • silane compound its hydrolyzate, or its polymer, only 1 type may be used independently and it may be used in combination of 2 or more type.
  • the amount of the silane compound having a plurality of hydrolyzable trialkoxysilyl groups in the film, its hydrolyzate or its polymer in the film 2 is preferably 0.01% by mass or more, and 0.2% by mass. % Or more, more preferably 0.5% by mass or more. Moreover, although it does not specifically limit as an upper limit, For example, 100 mass% may be sufficient.
  • the film 2 further includes a silane coupling agent having a reactive functional group capable of chemically bonding to the organic resin component, a hydrolyzate thereof or a polymer thereof in addition to the silane compound, a hydrolyzate thereof or a polymer thereof.
  • a silane coupling agent having a reactive functional group capable of chemically bonding to the organic resin component, a hydrolyzate thereof or a polymer thereof in addition to the silane compound, a hydrolyzate thereof or a polymer thereof.
  • the silane coupling agent include silane coupling agents having a reactive functional group such as an amino group, an epoxy group, a methacryl group, a vinyl group, or a mercapto group.
  • silane coupling agent which has various functional groups can be selected suitably according to the adhesive resin to be used.
  • suitable 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.
  • the coating amount after drying of the coating 2 is preferably 0.01 mg / m 2 or more and less than 30 mg / m 2 . Further, the coating amount after drying of the coating 2 is more preferably 0.2 mg / m 2 or more and less than 20 mg / m 2 , and further preferably 0.5 mg / m 2 or more and less than 10 mg / m 2 .
  • FIG. 2 is a flowchart showing a method for manufacturing the aluminum alloy material 10 of the present embodiment shown in FIG. As shown in FIG. 2, when manufacturing the aluminum alloy material 10 of this embodiment, base material preparation process S1, 1st film formation process S2, and 2nd 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.
  • Step S2 First film formation step>
  • the film 1 is formed on at least a part (that is, a part or all) of the surface of the base material 3 produced in the base material production process of step S1.
  • the first film forming step (step S2) specifically includes, for example, a heat treatment stage in which the base material 3 is heat-treated to form an oxide film on the surface of the base material 3, and the heat treatment stage.
  • a subsequent etching process step and a silicate treatment step is performed with an aqueous solution containing tetraalkyl silicate or an oligomer thereof.
  • the film 1 is formed so that the Mg amount, the Si amount, and the Cu amount in the film are in a specific range and have a specific absorption in the FT-IR spectrum.
  • the base material 3 is heated to, for example, 400 to 580 ° C. to form an oxide film 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 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, etc., and are not particularly limited. For example, the pH is 2 or less, the treatment temperature is 10 to 80 ° C., Conditions with 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 substrate 3, the thickness of the oxide film, and the like, and are not particularly limited.
  • the pH is 10 or more
  • the treatment temperature is 10 to 80.
  • Conditions of ° C and a treatment time of 1 to 120 seconds can be applied.
  • 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 processing conditions are adjusted so that the etching amount of the oxide film is preferably less than 700 nm, more preferably less than 500 nm.
  • the etching amount in the etching treatment stage in the present specification is the dissolution amount of the oxide film or the base material including the oxide film, and the decrease in weight before and after the etching treatment is measured, and the thickness (film thickness) is measured. ).
  • the conversion from the weight reduction amount to the film thickness is performed by calculating the aluminum thickness using the aluminum density of 2.7 g / cm 3 for convenience.
  • the total etching amount of the oxide film and the base material is defined as the etching amount.
  • the substrate having an oxide film is treated with an aqueous solution containing tetraalkyl silicate or an oligomer thereof (hereinafter also referred to as a silicate aqueous solution or a first aqueous solution).
  • the treatment with the silicate aqueous solution includes not only the application of the silicate aqueous solution but also the immersion in the silicate aqueous solution.
  • the aluminum oxide film becomes dense and excellent in corrosion resistance, the strength of the film itself is improved, and the corrosion resistance is also improved.
  • the silicate treatment step is performed as a final final film formation step of the film formation step, and no pickling is performed after the treatment with the silicate aqueous solution.
  • the washing and / or drying is also included in the silicate treatment stage, and the order thereof is not limited.
  • the concentration of the tetraalkyl silicate or the oligomer thereof in the silicate aqueous solution applied to the oxide film is preferably 0.005% by mass or more and 2% by mass or less.
  • concentration of the tetraalkyl silicate or the oligomer thereof in the silicate aqueous solution is 0.005% by mass or more, the film becomes dense, and a film excellent in strength and corrosion resistance can be formed.
  • concentration of tetraalkyl silicate or oligomer in the silicate aqueous solution is more preferably 0.01% by mass or more, and further preferably 0.05% by mass or more.
  • the concentration of the silicate in the silicate aqueous solution is preferably 2% by mass or less, more preferably 1% by mass or less, and further preferably 0.8% by mass or less.
  • aqueous silicate solution it is preferable to first add a predetermined amount of tetraalkylsilicate to ethanol and then dilute to a predetermined concentration with water. By doing so, it becomes easy to adjust a uniform aqueous solution.
  • the amount of ethanol is preferably 5 to 20 vol% with respect to water.
  • the aqueous silicate solution needs to have a pH in the neutral to acidic region from the viewpoint of stability. Therefore, the pH of the aqueous silicate solution is 7 or less, preferably 6.5 or less, and more preferably 6 or less.
  • the lower limit of the pH of the silicate aqueous solution is not particularly limited, but is, for example, 1 or more.
  • the pH adjuster is not particularly limited, and carboxylic acid such as hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, and acetic acid can be used. desirable.
  • the tetraalkyl silicate or oligomer thereof contained in the aqueous silicate solution is preferably a tetraalkyl silicate or oligomer thereof that does not produce a by-product that causes corrosion of the film or deterioration of the adhesive resin after the reaction.
  • tetramethyl orthosilicate, tetraethyl orthosilicate, tetraisopropyl orthosilicate, and the like, or oligomers thereof are preferable, and among them, tetraethyl orthosilicate or the oligomer thereof is preferable from the viewpoint of economy and safety.
  • a tetraalkyl silicate or its oligomer only 1 type may be used independently and it may be used in combination of 2 or more type.
  • the aqueous silicate solution does not substantially contain a particulate inorganic compound (particulate inorganic compound) having a diameter of 1 nm or more.
  • the particulate inorganic compound include inorganic oxide sols such as silica and alumina.
  • Particulate inorganic compounds such as silica are generally used for densification and uniform film thickness of the tetraalkylsilicate film, but the resulting film becomes thick.
  • silica sol or the like that exerts such an effect.
  • the aqueous silicate solution does not substantially contain the particulate inorganic compound” is not limited to an embodiment that does not contain the particulate inorganic compound at all, and it is acceptable to contain the particulate inorganic compound at the impurity level. Is done. Specifically, it is allowed that the particulate inorganic compound is contained in an aqueous silicate solution up to 0.05% by mass or less.
  • the silicate aqueous solution may further contain one or more of a stabilizer, an auxiliary agent and the like, if desired, in addition to the tetraalkyl silicate or its oligomer.
  • 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 application method of the silicate aqueous solution include immersion treatment, spraying, roll coating, and bar coating.
  • the oxide film is treated with the silicate aqueous solution, it may be washed (rinsed) if necessary.
  • the aqueous silicate solution is dried.
  • the drying temperature is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and still more preferably 90 ° C. or higher.
  • the drying temperature is preferably 220 ° C. or lower, more preferably 200 ° C. or lower, and further preferably 190 ° C. or lower.
  • the drying time depends on the drying temperature, but is preferably 2 seconds or more, more preferably 5 seconds or more, and further preferably 10 seconds or more. 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 silicate solution is to form a film having a FT-IR spectrum as described above, from the viewpoint of obtaining a satisfactory improvement in adhesion durability, coating amount after drying 0.1 mg / m 2 or more 20 mg / m 2 It is preferable to adjust so that it may become the following. Further, the coating amount after drying is more preferably adjusted to 1 mg / m 2 or more and 15 mg / m 2 or less, and further preferably 2 mg / m 2 or more and 10 mg / m 2 or less. If the coating amount of the silicate aqueous solution is too small, the amount of tetraalkyl silicate or its oligomer may be too small to obtain good adhesion durability. Moreover, when the application amount of the silicate aqueous solution is too large, the formed film becomes too thick and peeling occurs in the film, which may impair adhesion durability.
  • the silicate treatment stage is performed after the etching treatment stage.
  • these may be performed in a single process.
  • the oxide film may be treated with a neutral or acidic aqueous solution containing tetraalkyl silicate or an oligomer thereof.
  • Step S3 Second film forming step>
  • a film 2 containing a silane compound having a plurality of hydrolyzable trialkoxysilyl groups in the molecule, a hydrolyzate thereof, or a polymer thereof is formed.
  • the film 2 is coated with an aqueous solution mainly containing a silane compound having a plurality of hydrolyzable trialkoxysilyl groups in the molecule, a hydrolyzate thereof or a polymer thereof (hereinafter also referred to as a silane compound aqueous solution or a second aqueous solution). 1 is formed by processing.
  • the aqueous silane compound solution may further contain a silane coupling agent, a hydrolyzate thereof, or a polymer thereof.
  • the silane compound aqueous solution may further contain one or more stabilizers, auxiliary agents, and the like as desired.
  • 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.
  • the coating amount of the second aqueous solution from the viewpoint of the adhesion durability, coating amount of the film 2 after drying, per side, it is preferable to be 0.01 mg / m 2 or more 30 mg / m of less than 2.
  • the coating amount of the coating 2 is, for example, diluting the silane compound with a solvent (water, organic solvent, or a mixture thereof) to reduce the solid content concentration or viscosity, or adjusting the wet coating amount by the coater count It can be easily controlled.
  • the concentration of the silane compound having a plurality of hydrolyzable trialkoxysilyl groups in the molecule, the hydrolyzate thereof or the polymer thereof in the second aqueous solution is not particularly limited, but for example 0.005% by mass to 5% by mass, preferably 0.01% by mass to 2% by mass, more preferably 0.05% by mass to 1% by mass.
  • the application method of the second aqueous solution is not particularly limited, and an existing method can be applied. Specifically, application method by immersion, roll coater, bar coater, gravure coater, micro gravure coater, reverse gravure coater, dip coater, method using various coating machines such as electrostatic coating, spray coating method, etc. are applied. Can do.
  • the second aqueous solution is dried by heating after application.
  • the heating temperature is preferably 60 ° C. or higher, more preferably 75 ° C. or higher, and still more preferably 90 ° C. or higher.
  • the heating temperature is preferably 250 ° C. or less, more preferably 200 ° C. or less, and even more preferably 150 ° C. It is as follows.
  • 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.
  • ⁇ Other processes> In the manufacturing process of the aluminum alloy material 10 of the present embodiment, other processes may be included between or before and after each process as long as the processes described above are not adversely affected.
  • 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 may be coated with machine oil such as press oil on the surface before manufacturing the joined body or before processing into a member for an automobile.
  • 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 coating 2 rich in the solubility of machine oil on the outermost surface, even after the machine oil is applied, the adhesive resin is satisfactorily bonded thereon. be able to.
  • the oxide film formed on the surface of the aluminum alloy substrate 3 is silicate-treated to form a film 1 made of an oxide of aluminum containing silicon, and then an aqueous silane compound solution.
  • the aluminum alloy material 10 is manufactured by processing the film 1 to form the film 2.
  • the covalent bond of a silane compound and a metal oxide is formed in the interface of the membrane
  • the outstanding adhesive durability can be obtained.
  • the amount of Mg in the film 1 is adjusted to a specific range, the formation of an oxide film that is mechanically brittle and has low corrosion resistance can be suppressed, and deterioration of the adhesive resin interface can be suppressed.
  • the coating film 1 contains a specific amount of Si and the amount of Cu in the coating film 1 is restricted to less than a specific amount, the adhesion between the coating film 1 and the coating film 2 is improved. 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.
  • FIG. 3 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. 1 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 made of an adhesive resin so as to cover the film 1 and the film 2 of the aluminum alloy material of the first embodiment described above. 4 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 the present modification is joined to another member via the adhesive resin layer 4.
  • the other members include another aluminum alloy material in which a film is formed as in the case of the aluminum alloy material 11 with the adhesive resin layer, an aluminum alloy material in which no oxide film is formed, a resin molded body, and the like. .
  • 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. Of these, epoxy resins are preferable from the viewpoint of adhesive strength. Further, only one kind of adhesive resin may be used, or a plurality of adhesive resins may be used in combination.
  • 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. 4 is a flowchart showing a method for manufacturing the aluminum alloy material 11 with an adhesive resin layer of the present modification. As shown in FIG. 4, when manufacturing the aluminum alloy material 11 with an 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 is formed so as to cover the film 1 and the 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 film 2 as it is can be mentioned.
  • a preliminary aging treatment step for performing preliminary aging treatment may be provided.
  • 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.
  • 5 to 8B are cross-sectional views schematically showing a configuration example of the joined body of this embodiment. 5 to 8B, the same components as those of the aluminum alloy material 10 and the aluminum alloy material 11 with the adhesive resin layer shown in FIGS. 1 and 3 are denoted by the same reference numerals, and detailed description thereof is omitted.
  • the two aluminum alloy materials 10 shown in FIG. 1 are opposed to each other on the surfaces on which the film 1 and the film 2 are formed. It can be set as the structure which has 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 film 1 and the film 2 of the aluminum alloy material 10 of the first embodiment. Even if it does, the adhesive strength of the interface of the adhesive resin 5 and the membrane
  • the surface on which the coating 1 and the coating 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 1st membrane
  • the other aluminum alloy material 6 in which the first film and the second film are not formed the same material as the base material 3 described above can be used, and specifically, it is defined in JIS. Or what consists of various non-heat processing type
  • 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. Not engineering plastics can be used.
  • the joined bodies 21a and 21b shown in FIGS. 6A and 6B since one surface of the adhesive resin 5 is joined to the coating 1 and the coating 2 side of the aluminum alloy material 10, as in the joined body 20 described above, a member for an automobile. When used in the above, even when exposed to a high temperature and humidity 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. 6B 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. 6A and 6B 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. 3, 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 film 1 and the film 2 side of the aluminum alloy material 10 are joined to the adhesive resin layer 4 side of the aluminum alloy material 11 with the adhesive resin layer. As a result, the coating 1 and coating 2 side of the aluminum alloy material 10 and the coating 1 and coating 2 side of the aluminum alloy material 11 with the adhesive resin layer are respectively connected via the adhesive resin layer 4 of the aluminum alloy material 11 with the adhesive resin layer. It is the structure arrange
  • both surfaces of the adhesive resin layer 4 are joined to the film 1 and film 2 side of the aluminum alloy material 10 and the film 1 and film 2 side of the aluminum alloy material 11 with the adhesive resin layer, respectively.
  • the adhesion durability at the interface is improved without being affected by the type of the adhesive resin.
  • the structure and effect other than the above in the joined body 22 shown in FIG. 7 are the same as those of the joined body 20 shown in FIG.
  • Another aluminum alloy material 6 or a resin molded body 7 such as a fiber reinforced plastic molded body on which the film and the second film are not formed may be joined.
  • the joined body 23 since one surface of the adhesive resin layer 4 is joined to the coating 1 and the coating 2 side of the aluminum alloy material 11 with the adhesive resin layer, the joined body 23 is formed in the same manner as the joined body 20 described above.
  • the adhesion durability at the interface is improved without being affected by the type of adhesive resin.
  • the joined body 23b shown in FIG. 8B joins the aluminum alloy material 11 with the adhesive resin layer and the resin molded body 7, it is lighter than the joined body of the aluminum alloy materials, and weight reduction is required. It is suitable for the members of automobiles and vehicles.
  • the structures and effects of the joined bodies 23a and 23b shown in FIGS. 8A and 8B other than those described above are the same as those of the joined body 20 shown in FIG.
  • 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 formed on the surface of the film 2. You may form by spraying or apply
  • the bonded bodies 20 to 23 may be coated with press oil on their surfaces before being processed into automobile members, similarly to the aluminum alloy material 10 and the aluminum alloy material 11 with an adhesive 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. 5 to 8B are cut or pressed to produce a member for an automobile having a predetermined shape.
  • the adhesive resin or the adhesive resin layer and the oxide film (first film) can be formed even when exposed to a high temperature and wet environment.
  • the elution of the aluminum alloy base material can be suppressed with almost no influence of hydration.
  • an aluminum alloy material was produced by the following method and conditions, and adhesion durability and the like were evaluated.
  • Example 1 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 was produced. And this cold-rolled board was cut
  • a 6000 series aluminum alloy of JIS 6016 Mg: 0.54 mass%, Si: 1.11 mass%, Cu: 0.14 mass%
  • Example 1 The aluminum alloy material of Example 1 was produced.
  • TEOS aqueous solution containing 0.013% by mass of tetraethylorthosilicate (TEOS) was uniformly applied to the surface with a bar coater, and heated and dried at 100 ° C. for 1 minute to form a first film.
  • BTSE bistriethoxysilylethane
  • Example 2 An aluminum alloy material of Example 2 was obtained in the same manner as Example 1 except that the concentration of the TEOS aqueous solution was 0.325% by mass. Moreover, the press oil diluted with toluene was apply
  • Example 3 An aluminum alloy material of Example 3 was obtained in the same manner as Example 1 except that the concentration of the TEOS aqueous solution was 0.065% by mass and the concentration of the BTSE aqueous solution was 1% by mass. Moreover, the press oil diluted with toluene was apply
  • Example 4 An aluminum alloy material of Example 4 was obtained in the same manner as Example 1 except that the concentration of the TEOS aqueous solution was 0.065% by mass and the concentration of the BTSE aqueous solution was 0.01% by mass. Moreover, the press oil diluted with toluene was apply
  • Example 5 An aluminum alloy material of Example 5 was obtained in the same manner as Example 1 except that the concentration of the TEOS aqueous solution was 0.065% by mass and the concentration of the BTSE aqueous solution was 0.025% by mass. Moreover, the press oil diluted with toluene was apply
  • Example 6 An aluminum alloy material of Example 6 was obtained in the same manner as Example 1 except that the concentration of the TEOS aqueous solution was 0.13% by mass and the concentration of the BTSE aqueous solution was 0.1% by mass. Moreover, the press oil diluted with toluene was apply
  • Example 7 An aluminum alloy material of Example 7 was obtained in the same manner as Example 1 except that the concentration of the TEOS aqueous solution was 0.065% by mass and the concentration of the BTSE aqueous solution was 0.41% by mass. Moreover, the press oil diluted with toluene was apply
  • Example 8> The aluminum alloy material of Example 8 was obtained in the same manner as in Example 2 except that the base material was washed with water after applying the TEOS aqueous solution, dried by heating at 100 ° C. for 1 minute, and then applied with the BTSE aqueous solution. Moreover, the press oil diluted with toluene was apply
  • Example 9 An aluminum alloy material of Example 9 was obtained in the same manner as Example 1 except that the concentration of the TEOS aqueous solution was 0.013 mass% and the concentration of the BTSE aqueous solution was 0.025 mass%. Moreover, the press oil diluted with toluene was apply
  • Example 10 An aluminum alloy material of Example 10 was obtained in the same manner as Example 9 except that 0.1% by mass of 3-aminopropyltriethoxysilane (APS) was added to the BTSE aqueous solution. Moreover, the press oil diluted with toluene was apply
  • APS 3-aminopropyltriethoxysilane
  • Example 11 An aluminum alloy material of Example 11 was obtained in the same manner as Example 9, except that 0.1% by mass of 3-glycidoxypropyltriethoxysilane (GPS) was added to the BTSE aqueous solution. Moreover, the press oil diluted with toluene was apply
  • GPS 3-glycidoxypropyltriethoxysilane
  • Example 12 An aluminum alloy material of Example 12 was obtained in the same manner as in Example 4 except that an aqueous solution containing 0.1% by mass of bistriethoxysilylbenzene (BTSB) was used instead of the BTSE aqueous solution. Moreover, the press oil diluted with toluene was apply
  • BTSB bistriethoxysilylbenzene
  • Example 13 An aluminum alloy material of Example 13 was obtained in the same manner as Example 4 except that an aqueous solution containing 0.1% by mass of bistriethoxysilylpropylamine (BTSA) was used instead of the BTSE aqueous solution. Moreover, the press oil diluted with toluene was apply
  • BTSA bistriethoxysilylpropylamine
  • Example 14 An aluminum alloy material of Example 14 was obtained in the same manner as Example 4 except that an aqueous solution containing 0.1% by mass of bistriethoxysilylpropyltetrasulfide (BTSS) was used instead of the BTSE aqueous solution. Moreover, the press oil diluted with toluene was apply
  • BTSS bistriethoxysilylpropyltetrasulfide
  • Comparative Example 1 An aluminum alloy material of Comparative Example 1 was obtained in the same manner as Example 1 except that the concentration of the TEOS aqueous solution was 2.3% by mass. Moreover, the press oil diluted with toluene was apply
  • Comparative Example 2 An aluminum alloy material of Comparative Example 2 was obtained in the same manner as in Example 1 except that the concentration of the TEOS aqueous solution was 0.0061 mass% and the concentration of the BTSE aqueous solution was 0.025%. Moreover, the press oil diluted with toluene was apply
  • Comparative Example 3 An aluminum alloy material of Comparative Example 3 was obtained in the same manner as in Example 1 except that an TEOS aqueous solution containing 0.12% by mass of TEOS and further adding 0.1% by mass of silica sol having a particle diameter of 4 nm was used. Moreover, the press oil diluted with toluene was apply
  • Comparative Example 4 An aluminum alloy material of Comparative Example 4 was obtained in the same manner as in Example 1 except that the treatment with the BTSE aqueous solution was not performed. Moreover, the press oil diluted with toluene was apply
  • Comparative Example 5 The aluminum alloy material of Comparative Example 5 was obtained in the same manner as in Example 1 except that the concentration of the TEOS aqueous solution was 0.13% by mass and the degreasing and pickling treatment before the treatment with the TEOS aqueous solution was not performed. Moreover, the press oil diluted with toluene was apply
  • Comparative Example 6 An aluminum alloy material of Comparative Example 6 was obtained in the same manner as in Example 1 except that the concentration of the TEOS aqueous solution was 0.13% by mass and the pickling treatment before the treatment with the TEOS aqueous solution was performed for 300 seconds. Moreover, the press oil diluted with toluene was apply
  • FT-IR Fastier transform infrared spectrophotometer: Magna-750 spectrometer manufactured by Nicolet
  • Table 1 shows the maximum point of absorption in each absorption band.
  • the first film was measured while sputtering in the film thickness direction by high-frequency glow discharge optical emission spectrometry (GD-OES: model JY-5000RF manufactured by Horiba Joban Yvon), and aluminum (Al), magnesium (Mg), copper (Cu), iron (Fe), titanium (Ti) and other metal elements, and oxygen (O), nitrogen (N), carbon (C), silicon (Si), sulfur (S) and other elements
  • GD-OES high-frequency glow discharge optical emission spectrometry
  • the concentration of the outermost surface is defined as the film concentration of aluminum (Al).
  • 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, but the film 1 of all samples contains oxygen (O). It was clear that
  • the amount of etching is the amount of dissolution of the oxide film and the base material including the oxide film, and the amount of decrease in weight before and after the etching treatment was measured and estimated as the thickness (film thickness).
  • the conversion from the decrease in weight to the film thickness was performed by calculating the aluminum thickness using the aluminum density of 2.7 g / cm 3 for convenience.
  • the film amounts of the first and second films formed by the treatment with the silicate and the silane compound aqueous solution were measured by fluorescent X-rays. Specifically, the amount of silicon in the first film after the silicate treatment and the second film after the silane compound treatment are respectively measured by fluorescent X-rays, and the conversion of the intensity of the fluorescent X-rays and the amount of the film is performed using a calibration curve. Each was calculated by performing. The results are shown in Table 1.
  • 9A and 9B are diagrams schematically showing a method of measuring the cohesive failure rate
  • FIG. 9A is a side view
  • FIG. 9B 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 immersed in an aqueous sodium chloride solution having a concentration of 5% at 40 ° C. for 20 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 bonded 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 evaluation criteria are that the cohesive failure rate is less than 60% defective (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 excellent. ( ⁇ ).
  • the results are shown in Table 1.
  • the Si concentration in the first film was higher than the range specified in the present invention, and the adhesion durability was poor.
  • the aluminum alloy material of Comparative Example 2 has a Si concentration in the first film lower than the range specified in the present invention, and one of the absorption bands is outside the range of the wave number specified in the present invention. It was scarce.
  • one of the absorption bands of the first coating was outside the range of the wave number defined in the present invention, and the adhesion durability was poor.
  • the aluminum alloy material of Comparative Example 4 does not form the second film, but applies the press oil on the first film having poor solubility of the press oil.
  • the adhesion durability was poor.
  • the aluminum alloy material of Comparative Example 5 had a Mg concentration in the first film higher than the range specified in the present invention, and had poor adhesion durability.
  • the aluminum alloy material of Comparative Example 6 had a Cu concentration in the first film higher than the range specified in the present invention, and had poor adhesion durability.
  • the aluminum alloy materials of Examples 1 to 14 that satisfy the requirements specified in the present invention had good wet durability under a high temperature and high humidity environment.

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  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

La présente invention concerne un matériau en alliage d'aluminium qui comprend : un matériau de base en alliage d'aluminium ; un premier film de revêtement qui est formé sur au moins une partie de la surface du matériau de base en alliage d'aluminium et qui comprend un oxyde d'aluminium qui comprend du silicium ; et un second film de revêtement qui est formé sur au moins une partie du premier film de revêtement et qui comprend un composé de silane qui a au moins deux groupes trialkoxysilyl hydrolysables dans sa molécule, un hydrolysat du composé de silane ou un polymère du composé de silane. Sur un spectre de différence de pré-revêtement et de post-revêtement obtenu par spectroscopie infrarouge à transformée de Fourier à l'aide d'une lumière polarisée parallèle qui est incidente à un angle de 75°, le premier film de revêtement a deux bandes d'absorption dans la plage de nombres d'ondes de 1000 à 1300 cm-1, et les deux bandes d'absorption sont dans les plages de nombres d'ondes de 1080 à 1140 cm-1 et de 1180 à 1240 cm-1. La teneur en Si du premier film de revêtement est d'au moins 15 % atomique mais inférieure à 70 % atomique, la teneur en Mg du premier film de revêtement est d'au moins 0,1 % atomique mais inférieure à 30 % atomique, et la teneur en Cu du premier film de revêtement est limitée à moins de 0,6 % atomique.
PCT/JP2017/017615 2016-05-10 2017-05-10 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 WO2017195802A1 (fr)

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JP2016-094920 2016-05-10
JP2016094920A JP6721406B2 (ja) 2016-05-10 2016-05-10 アルミニウム合金材、接着樹脂層付きアルミニウム合金材、アルミニウム合金材の製造方法、及び接着樹脂層付きアルミニウム合金材の製造方法

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2014189090A1 (fr) * 2013-05-23 2014-11-27 株式会社神戸製鋼所 Feuille d'alliage d'aluminium, objet lié et élément pour véhicule automobile
WO2017006804A1 (fr) * 2015-07-09 2017-01-12 株式会社神戸製鋼所 Procédé de fabrication d'un alliage d'aluminium, alliage d'aluminium et conjugué

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2014189090A1 (fr) * 2013-05-23 2014-11-27 株式会社神戸製鋼所 Feuille d'alliage d'aluminium, objet lié et élément pour véhicule automobile
WO2017006804A1 (fr) * 2015-07-09 2017-01-12 株式会社神戸製鋼所 Procédé de fabrication d'un alliage d'aluminium, alliage d'aluminium et conjugué

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