Aluminum material or aluminum alloy material having coating film, method for producing same, and aqueous surface treatment agent

Abstract

The present invention addresses the problem of providing an aluminum material or an aluminum alloy material with a surface treatment film, which has excellent heat resistance and corrosion resistance. The technical problem is solved by an aluminum material or an aluminum alloy material having a coating film containing chromium, zirconium, zinc, and carbon on the surface of the aluminum material or the aluminum alloy material, in the infrared spectrum of the coating film measured by a specular reflection method of Fourier transform infrared spectroscopy (FT-IR), peaks appear in the range of 3600 cm <-1 > to 3000 cm <-1 > and in the range of 1750 cm <-1 > to 1700 cm <-1 >.

Description

Technical Field

[0001] The present invention relates to an aluminum material or an aluminum alloy material having a surface treatment film excellent in heat and corrosion resistance, and a method for manufacturing the same. Further, the present invention relates to an aqueous surface treatment agent capable of forming a surface treatment film excellent in heat and corrosion resistance on the surface or on the surface of an aluminum material or an aluminum alloy material. Background Art

[0002] In a wide range of fields such as aircraft materials, building materials, and automotive parts, in order to impart corrosion resistance, an aluminum material or an aluminum alloy material having a film is used, and the film is a film obtained by surface treatment using a surface treatment agent containing chromium ions.

[0003] For example, Patent Document 1 discloses a chemical conversion treatment liquid for a metal material, which contains: a component (A) composed of a water-soluble trivalent chromium compound, a component (B) composed of at least one selected from a water-soluble titanium compound and a water-soluble zirconium compound, a component (C) composed of a water-soluble nitrate compound, a component (D) composed of a water-soluble aluminum compound, and a component (E) composed of a fluorine compound, and the pH is controlled in the range of 2.3 to 5.0.

[0004] Patent Document 2 discloses a chemical conversion treatment liquid that contains a specific trivalent chromium compound, a specific zirconium compound, and a specific dicarboxylic acid compound in a specified amount.

[0005] Further, Patent Document 3 discloses a surface treatment agent for aluminum or an aluminum alloy, which contains: an ion (A) containing trivalent chromium, an ion (B) selected from at least one of an ion containing titanium and an ion containing zirconium, an ion (C) containing zinc, a free fluoride ion (D), and a nitrate ion (E).

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 2006-328501;

[0009] Patent Document 2: Japanese Patent Application Laid-Open No. 2006-316334;

[0010] Patent Document 3: Japanese Patent No. 6910543. Summary of the Invention

[0011] Problems to be Solved by the Invention

[0012] Aluminum materials or aluminum alloy materials may be exposed to high-temperature environments depending on their uses. However, the films formed on aluminum materials or aluminum alloy materials using the surface treatment agents of Patent Documents 1 to 2 still have room for improvement in terms of corrosion resistance reduction due to exposure to high-temperature environments (heat-resistant corrosion resistance). In addition, even when using the surface treatment agent of Patent Document 3, although the heat-resistant corrosion resistance is also improved, it cannot be said to be sufficient.

[0013] An object of the present invention is to provide an aluminum material or an aluminum alloy material having a surface treatment film with excellent heat-resistant corrosion resistance. In addition, an object of the present invention is to provide a surface treatment agent capable of forming the surface treatment film.

[0014] Means for Solving the Problems

[0015] The inventors of the present invention conducted in-depth research to solve the above problems and found that an aluminum material or an aluminum alloy material having a film containing chromium, zirconium, zinc, and carbon and having characteristic infrared reflection peaks on the surface or on the surface of the aluminum material or aluminum alloy material has excellent corrosion resistance and excellent heat-resistant corrosion resistance, thus completing the present invention.

[0016] That is, the present invention includes the following:

[0017] (1) An aluminum material or an aluminum alloy material, which is an aluminum material or an aluminum alloy material having a film containing chromium, zirconium, zinc, and carbon on the surface or on the surface of the aluminum material or aluminum alloy material. In the infrared spectrum of the film measured by the specular reflection method of Fourier transform infrared spectroscopy (FT-IR), peaks appear at 3600 cm -1 ~3000 cm -1 and 1750 cm -1 ~1700 cm -1 ;

[0018] (2) The aluminum material or aluminum alloy material according to the above (1), wherein the content of chromium in the film is in the range of 5 mg / m 2 ~100 mg / m 2 , the content of zirconium is in the range of 2 mg / m 2 ~150 mg / m 2 , the content of carbon is in the range of 2 mg / m 2 ~20 mg / m 2 , and the total content of chromium, zirconium, and zinc measured by X-ray photoelectron spectroscopy (XPS) is 100 atomic%, and the content of zinc is 2 atomic% to 60 atomic%;

[0019] (3) An aqueous surface treatment agent, which is an aqueous surface treatment agent for surface treatment of aluminum or aluminum alloy materials. The above aqueous surface treatment agent contains: chromium-containing ions (A), zirconium-containing ions (B), zinc-containing ions (C), and an organic compound (D) having hydroxyl and carboxyl groups;

[0020] (4) A method for manufacturing an aluminum material or an aluminum alloy material having a film, the above manufacturing method includes a contacting step of bringing the surface treatment agent described in (3) into contact with the surface of the aluminum material or the aluminum alloy material or on the surface; etc.

[0021] Advantages of the Invention

[0022] According to the present invention, it is possible to provide an aluminum material or an aluminum alloy material having a surface treatment film with excellent heat and corrosion resistance. In addition, it is possible to provide a surface treatment agent capable of forming the surface treatment film. Detailed Embodiments

[0023] Hereinafter, the aluminum material or aluminum alloy material having a surface treatment film, the surface treatment agent capable of forming the surface treatment film, and their manufacturing methods according to the present embodiment will be described in the following order.

[0024] (1) Aluminum material or aluminum alloy material

[0025] (2) Surface treatment film

[0026] (3) Surface treatment agent

[0027] (4) Manufacturing method

[0028] (1) Aluminum material or aluminum alloy material

[0029] The aluminum material or aluminum alloy material is not particularly limited as long as it is a metal material containing aluminum. In particular, an aluminum die-cast material that is difficult to impart corrosion resistance due to the thickness of the surface oxide film and segregation of alloy components is effective as the material for forming the surface treatment film in the present embodiment. The use of the aluminum material or aluminum alloy material having a surface treatment film is not particularly limited, and it is preferably used as components such as engine peripheral components and ECU housings that are exposed to high-temperature environments according to the usage situation, because the heat and corrosion resistance is not easily reduced. The aluminum material or aluminum alloy material having the surface treatment film can be made to have a long service life by improving the heat and corrosion resistance, thereby enabling effective utilization of resources.

[0030] (2) Surface treatment film

[0031] The surface treatment film of the present embodiment is formed on the surface or on the surface of the aluminum material or aluminum alloy material, and it contains chromium, zirconium, zinc, and carbon. It can be formed only by these elements or can contain other components. Hereinafter, each film component and composition (content) will be described in detail.

[0032] (2-1) Chromium

[0033] The form of chromium contained in the surface treatment film may be metallic chromium, or chromium oxides such as hexavalent chromium oxide and trivalent chromium oxide, or chromium compounds combined with the components contained in the surface treatment agent, without particular limitation. One of these may be included, or two or more may be included. The chromium content in the surface treatment film is usually in the range of 5 mg / m 2 to 100 mg / m 2 in terms of metallic chromium conversion, preferably in the range of 10 mg / m 2 to 50 mg / m 2 in terms of metallic chromium conversion, more preferably in the range of 10 mg / m 2 to 30 mg / m 2 in terms of metallic chromium conversion. The chromium content in the surface treatment film is measured using a fluorescent X-ray analyzer.

[0034] (2-2) Zirconium

[0035] The form of zirconium contained in the surface treatment film may be metallic zirconium, or zirconium oxide, or zirconium compounds combined with the components contained in the surface treatment agent, without particular limitation. One of these may be included, or two or more may be included. The zirconium content in the surface treatment film is usually in the range of 2 mg / m 2 to 150 mg / m 2 in terms of metallic zirconium conversion, preferably in the range of 5 mg / m 2 to 100 mg / m 2 in terms of metallic zirconium conversion, more preferably in the range of 5 mg / m 2 to 50 mg / m 2 in terms of metallic zirconium conversion. The zirconium content in the surface treatment film is measured using a fluorescent X-ray analyzer.

[0036] (2-3) Zinc

[0037] The form of zinc contained in the surface treatment film may be metallic zinc, or zinc oxide, or zinc compounds combined with the components contained in the surface treatment agent, without particular limitation. One of these may be included, or two or more may be included.

[0038] (2-4) Ratio of the content of zinc to the total content of chromium, zirconium and zinc

[0039] Taking the total content of chromium, zirconium and zinc contained in the surface treatment film as 100 atomic%, the ratio of the content of zinc (Zn / (Cr + Zr + Zn)) is usually preferably in the range of 2 atomic% to 60 atomic%, more preferably in the range of 10 atomic% to 40 atomic%, and further preferably in the range of 10 atomic% to 30 atomic%.

[0040] The determination of the content of each component in the surface treatment film for obtaining the ratio of the content of zinc to the total content of chromium, zirconium, and zinc (Zn / (Cr+Zr+Zn)) is carried out by using an X-ray photoelectron spectrometer through repeated sputtering and elemental amount determination based on X-ray photoelectron spectroscopy (XPS) multiple times. In addition, the depth position in XPS is managed by the distance of Ar ion sputtering of SiO2. Specifically, sputtering is carried out for 0.25 minutes (sputtering rate: 11.0 nm / min in terms of SiO2 conversion), monochromatic Al-Kα rays are irradiated onto the surface of the sample with an analysis diameter of 100 μm, and the photoelectrons thus obtained are measured. This operation is repeated to measure the contents of chromium, zirconium, and zinc obtained at each depth in the thickness direction of the surface treatment film. Taking their total as 100 atomic%, the ratio of the content of zinc (Zn / (Cr+Zr+Zn)) is calculated.

[0041] (2-5) Carbon

[0042] All or part of the carbon contained in the surface treatment film comes from the organic compound having a hydroxyl group and a carboxyl group compounded in the surface treatment agent. The content of carbon in the surface treatment film is usually in the range of 2 mg / m 2 ~20 mg / m 2 Preferably in the range of 3 mg / m 2 ~15 mg / m 2 More preferably in the range of 4 mg / m 2 ~12 mg / m 2 The content of carbon in the surface treatment film is measured by a total organic carbon analyzer.

[0043] (2-6) Peaks in infrared spectrum

[0044] By measuring the surface treatment film by the specular reflection method of Fourier transform infrared spectroscopy (FT-IR), the infrared spectrum of the film is obtained. The infrared spectrum obtained by measuring the surface treatment film of this embodiment has peaks in a specific wavelength range. The peak from the hydroxyl group appears at 3600 cm -1 ~3000 cm -1 , and the peak from the carboxyl group appears at 1750 cm -1 ~1700 cm -1 .

[0045] The infrared spectrum is obtained by using a Fourier transform infrared spectrophotometer under the conditions of measurement wavenumber = 4000 cm -1 ~400 cm -1 , resolution = 4 cm -1 , and scanning 128 times. The background uses an aluminum or aluminum alloy material without a surface treatment film.

[0046] As described above, the aluminum material or aluminum alloy material having the surface treatment film of the present embodiment has been described. Among them, by having the content of zinc in the surface treatment film within the above range and having a peak in the above wavelength range in the infrared spectrum of the surface treatment film, the heat and corrosion resistance can be improved.

[0047] (3) Surface treatment agent

[0048] The surface treatment agent of the present embodiment is a surface treatment agent for surface-treating an aluminum or aluminum alloy material. This surface treatment agent can be used as a chemical conversion treatment agent.

[0049] The surface treatment agent contains: ions (A) containing chromium, ions (B) containing zirconium, ions (C) containing zinc, and an organic compound (D) having hydroxyl and carboxyl groups. The surface treatment agent may be a surface treatment agent prepared by simply mixing the supply sources of these ions (A) to (C) and the organic compound (D) into an aqueous medium, or may be a surface treatment agent prepared by further mixing other components in addition thereto. Hereinafter, each component, composition (content), and acidity and alkalinity will be described in detail.

[0050] (3-1) Aqueous medium

[0051] The aqueous medium is not particularly limited as long as it is water or a mixture of water and a water-miscible organic solvent (containing 50% by volume or more of water based on the volume of the aqueous medium). As the water-miscible organic solvent, there is no particular limitation as long as it is an organic solvent miscible with water, and examples thereof include: ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as N,N'-dimethylformamide and dimethylacetamide; alcohol solvents such as methanol, ethanol, and isopropyl alcohol; ether solvents such as ethylene glycol monobutyl ether and ethylene glycol monohexyl ether; pyrrolidone solvents such as 1-methyl-2-pyrrolidone and 1-ethyl-2-pyrrolidone, etc. These water-miscible organic solvents can be mixed with water alone or in combination of two or more.

[0052] (3-2) Ions (A) containing chromium

[0053] The supply source of the ions (A) containing chromium in the surface treatment agent is not particularly limited as long as it can provide ions (A) by mixing in an aqueous medium. Examples thereof include chromium fluoride, chromium nitrate, chromium sulfate, chromium phosphate, etc. These can be used alone or in combination of two or more. The content of ions (A) in the surface treatment agent is not particularly limited, and is usually in the range of 5 to 1000 mg / L in terms of chromium conversion mass concentration, preferably in the range of 50 to 500 mg / L, and more preferably in the range of 100 to 200 mg / L. Ions (A) may be ions containing trivalent chromium.

[0054] (3-3) Ions (B) containing zirconium

[0055] The supply source of the ions (B) containing zirconium in the surface treatment agent is not particularly limited as long as it can provide the ions (B) by mixing in an aqueous medium. Examples include zirconium sulfate, zirconyl sulfate, ammonium zirconium sulfate, zirconium nitrate, zirconyl nitrate, ammonium zirconium nitrate, hexafluorozirconic acid, hexafluorozirconium complex salt, zirconium acetate, zirconium lactate, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, tetra-n-butoxy zirconium, tetra-n-propoxy zirconium, etc. These can be used alone or in combination of two or more. The content of the ions (B) in the surface treatment agent is not particularly limited, and is usually in the range of 5 to 1000 mg / L in terms of zirconium-converted mass concentration, preferably in the range of 30 to 300 mg / L, and more preferably in the range of 70 to 200 mg / L.

[0056] (3-4) Ions (C) containing zinc

[0057] The supply source of the ions (C) containing zinc in the surface treatment agent is not particularly limited as long as it can provide the ions (C) by mixing in an aqueous medium. Examples include metallic zinc, zinc oxide, zinc carbonate, zinc nitrate, zinc chloride, zinc sulfate, zinc fluoride, zinc iodide, zinc dihydrogen phosphate, zinc acetylacetonate, etc. These can be used alone or in combination of two or more. The content of the ions (C) in the surface treatment agent is not particularly limited, and is usually in the range of 500 to 10000 mg / L in terms of zinc-converted mass concentration, preferably in the range of 1000 to 5000 mg / L, and more preferably in the range of 1500 to 2000 mg / L.

[0058] (3-5) Organic compound (D) having a hydroxyl group and a carboxyl group

[0059] The organic compound (D) having a hydroxyl group and a carboxyl group is not particularly limited as long as it can be mixed in an aqueous medium. Examples include organic acids such as gluconic acid, glucoheptonic acid, galactonic acid, mannonic acid, glucaric acid, galactaric acid, mannaric acid, arabic acid, fructoketonic acid, glucuronic acid, iduronic acid, galacturonic acid, mannuronic acid, guluronic acid and their salts (such as sodium salts, potassium salts), etc. These can be used alone or in combination of two or more. The compounding amount of the organic compound having a hydroxyl group and a carboxyl group in the surface treatment agent is not particularly limited, and is usually in the range of 2 to 2000 mg / L, preferably in the range of 10 to 1000 mg / L, and more preferably in the range of 100 to 300 mg / L.

[0060] (3-6) Free fluoride ions (E)

[0061] The surface treatment agent may contain free fluoride ions (E). The source of the free fluoride ions (E) in the surface treatment agent is not particularly limited as long as it can provide free fluoride ions (E) by mixing in an aqueous medium. Examples thereof include hydrofluoric acid, ammonium fluoride, chromium fluoride, hexafluorotitanic acid, hexafluorotitanium complex salt, hexafluorozirconic acid, hexafluorozirconium complex salt, magnesium fluoride, aluminum fluoride, hexafluorosilicic acid, sodium fluoride, potassium fluoride, zinc fluoride, fluoboric acid, sodium fluoborate, ammonium fluoborate, etc. These may be used alone or in combination of two or more. In addition, the free fluoride ions (E) may be provided by the same compound as the source of the above ions (A), (B) and / or (C), or may be provided by a compound different from the source of the above ions (A), (B) and / or (C). The mass concentration of the free fluoride ions (E) in terms of fluorine in the surface treatment agent is not particularly limited, preferably 70 to 200 mg / L, more preferably 80 to 150 mg / L.

[0062] The free fluoride ion concentration in this specification refers to the value at the temperature when the surface treatment agent contacts the surface of an aluminum material or an aluminum alloy material. The measurement of the free fluoride ion concentration is a value measured according to a known method and can be carried out using, for example, a commercially available ion meter.

[0063] In the surface treatment agent of the present embodiment, various metal components and additives may also be added as long as the effects of the present invention are not impaired. Examples of the metal components include vanadium, molybdenum, tungsten, manganese, cerium, magnesium, calcium, cobalt, nickel, strontium, lithium, niobium, yttrium, bismuth, etc. Examples of the additives include compounds having a formyl group, compounds having a benzoyl group, compounds having an amino group, compounds having an imino group, compounds having a cyano group, compounds having an azo group, compounds having a mercapto group, compounds having a sulfo group, compounds having a nitro group, compounds having an amidino group, compounds having a urethane bond, compounds having an aromatic ring. These metal components and additives may be used alone or in combination of two or more. Since these metal components and additives are added within the range not impairing the effects of the present invention, their content is at most a few mass% with respect to the total amount of the surface treatment agent.

[0064] (3-7) pH of the surface treatment agent

[0065] The pH of the surface treatment agent of the present embodiment is not particularly limited, preferably 3.0 to 6.0, more preferably 4.0 to 5.0. The pH in this specification refers to the value at the temperature when the surface treatment agent contacts the surface of an aluminum material or an aluminum alloy material. The measurement of the pH is a value measured according to a known method and can be carried out using, for example, a commercially available pH meter.

[0066] The composition of the surface treatment agent of the present embodiment has been described above. As another aspect of the present invention, a surface treatment agent for surface treatment of aluminum or aluminum alloy materials is formed by mixing a supply source of ions (A) containing chromium, a supply source of ions (B) containing zirconium, a supply source of ions (C) containing zinc, and an organic compound (D) having hydroxyl and carboxyl groups in an aqueous medium. As the compounds of the supply sources, one or more than two kinds can be used respectively.

[0067] (4-1) Manufacturing method of surface treatment agent

[0068] The surface treatment agent of the present embodiment can be obtained by appropriately mixing a supply source of ions (A) containing chromium, a supply source of ions (B) containing zirconium, a supply source of ions (C) containing zinc, and an organic compound (D) having hydroxyl and carboxyl groups in an aqueous medium and stirring. In addition, during manufacturing, a solid supply source can be mixed in the aqueous medium, or the solid supply source can be dissolved in the aqueous medium in advance and then mixed as an aqueous medium solution. Furthermore, as described above, the pH range of the surface treatment agent is preferably adjusted using pH regulators such as nitric acid, sulfuric acid, hydrofluoric acid, ammonium bicarbonate, ammonia water, sodium bicarbonate, sodium hydroxide, etc., but is not limited to these components. In addition, one or more than two kinds of pH regulators can be used.

[0069] (4-2) Manufacturing method of aluminum or aluminum alloy material having surface treatment film

[0070] The manufacturing method of an aluminum or aluminum alloy material having a surface treatment film formed by the surface treatment agent of the present embodiment includes: a step of bringing the surface treatment agent of the present embodiment into contact with the surface or on the surface of the aluminum or aluminum alloy material. Thereby, a surface treatment film is formed on the surface or on the surface of the aluminum or aluminum alloy material. Pretreatment steps such as a cleaning step and a pickling step can be performed before the contact step. In addition, a water washing step can be performed after each step, and a drying step can also be performed after the water washing step.

[0071] (4-3) Aluminum or aluminum alloy material

[0072] The aluminum or aluminum alloy material as the object of the surface treatment agent is not particularly limited, and in particular, it is effective for aluminum die-cast materials with surface oxide film thickness and alloy composition segregation. The use of the aluminum or aluminum alloy material is not particularly limited, and examples include engine peripheral equipment, ECU housings, etc.

[0073] (4-4) Cleaning step

[0074] In the manufacturing method of the present embodiment, it is preferable to perform a cleaning process in which a known cleaning agent contacts the surface or the surface of an aluminum or aluminum alloy material before the contacting process. The cleaning method is not particularly limited, and examples thereof include solvent degreasing and alkaline degreasing.

[0075] (4-5) Pickling process

[0076] In the manufacturing method of the present embodiment, it is preferable to perform a pickling process in which a known pickling agent contacts the surface or the surface of an aluminum or aluminum alloy material before the contacting process. The pickling agent is not particularly limited, and examples thereof include nitric acid and hydrofluoric acid.

[0077] (4-6) Contacting process

[0078] In the contacting process of the manufacturing method of the present embodiment, the contacting temperature and the contacting time are not particularly limited. Generally, the surface treatment agent contacts the surface or the surface of the aluminum or aluminum alloy material at 30 to 80 °C, preferably at 40 to 60 °C for 10 to 1200 seconds. In addition, after this process, water washing and deionized water washing can be performed as needed, and then it can be dried. The drying temperature is not particularly limited, and preferably it is 15 to 100 °C. In addition, as a method of making the surface treatment agent contact the surface or the surface of the aluminum or aluminum alloy material, there is no particular limitation, and examples thereof include an immersion method, a spraying method, and a flow coating method.

[0079] (Post-treatment process)

[0080] Furthermore, the aluminum or aluminum alloy material having a surface treatment film manufactured by the above manufacturing method can be further post-treated with hot water, a rust inhibitor, a post-treatment agent, a pH regulator, a coupling agent, etc. After the above post-treatment, it can be washed with water and then dried, or it can be dried without washing with water.

[0081] In addition, the aluminum or aluminum alloy material having a surface treatment film has excellent corrosion resistance even without performing a coating process on the surface treatment film, and also has excellent corrosion resistance (heat-resistant corrosion resistance) even when the surface treatment film is exposed to high temperatures, but a coating process can also be performed.

[0082] The above coating process is not particularly limited. For example, a known coating composition can be used to perform coating methods such as aqueous coating, solvent coating, powder coating, anion electrodeposition coating, and cation electrodeposition coating.

[0083] Examples

[0084] Hereinafter, examples and comparative examples of the present invention will be described. In addition, the present invention is not limited to this example.

[0085] <Aluminum material>

[0086] Aluminum die-casting material (JIS-ADC12)

[0087] <Surface treatment agent>

[0088] Using the raw materials shown in Table 1, and adding various raw materials to water in such a way as to achieve the concentrations shown in Table 1, and mixing them to obtain the surface treatment agents for the examples and comparative examples. In addition, ammonia water or nitric acid was used as the pH regulator. In addition, the pH and the free fluoride ion concentration (denoted as FF in Table 1) were measured using a portable ion pH meter [IM-32P (manufactured by Toa DKK Corporation), pH electrode: GST-2729C (manufactured by Toa DKK Corporation), ion electrode: fluoride ion composite electrode F-2021 (manufactured by Toa DKK Corporation)].

[0089] <Treatment method>

[0090] Specifically, the above aluminum die-casting material was immersed in an alkaline degreaser [20 g / L aqueous solution of Fine Cleaner 315E (manufactured by Nippon Parkerizing Co., Ltd.)] at 50 °C for 2 minutes, and then the surface was rinsed with tap water to make it clean. Then, the above surface treatment agent was immersed on or on the surface of the aluminum die-casting material at the contact temperature recorded in Table 1, thereby performing the contact process. Then, it was washed with running tap water (room temperature, 30 seconds), washed with running deionized water (room temperature, 30 seconds), and then dried with a blower (room temperature, 30 seconds) to obtain an aluminum die-casting material with a surface treatment film (test pieces 1 to 39).

[0091] <Measurement of surface treatment film>

[0092] The content of each component in the surface treatment film of the aluminum die-casting material with a surface treatment film obtained by the above surface treatment method and the infrared peak of the surface treatment film were measured by the following method. The measurement results are shown in Table 2.

[0093] <Metal content>

[0094] The metal content (chromium, zirconium) was measured using a fluorescent X-ray analyzer [ZSX PrimusIV (manufactured by Rigaku Corporation)].

[0095] <Ratio of the content of zinc to the total content of chromium, zirconium, and zinc>

[0096] The content of each component in the surface treatment film for obtaining the ratio of the zinc content to the total content of chromium, zirconium, and zinc (Zn / (Cr+Zr+Zn)) was measured using an X-ray photoelectron spectrometer [PHI 5000 Versaprobe III (manufactured by Ulvac-Phi)] by repeatedly sputtering and measuring the elemental amounts based on XPS multiple times. In addition, the depth position in XPS was controlled by the distance of Ar ion sputtering of SiO2. Specifically, sputtering was performed for 0.25 minutes (sputtering rate: 11.0 nm / min in terms of SiO2 conversion), monochromatic Al-Kα rays were irradiated onto the surface of the sample with an analysis diameter of 100 μm, and the photoelectrons thus obtained were measured. This operation was repeated to measure the contents of chromium, zirconium, and zinc obtained at each depth in the thickness direction of the surface treatment film. Taking their total as 100 atomic%, the ratio of the zinc content (Zn / (Cr+Zr+Zn)) was calculated.

[0097] <Carbon content>

[0098] The carbon content (total organic carbon adhesion amount) was measured using a total organic carbon analyzer [TOC-LCSH (manufactured by Shimadzu Corporation)].

[0099] <Infrared peak>

[0100] By measuring the surface treatment film using the specular reflection method of Fourier transform infrared spectroscopy (FT-IR), the infrared spectrum of the film was obtained. Specifically, using a Fourier transform infrared spectrophotometer [ALPHA (manufactured by Bruker)], the infrared spectrum was obtained under the conditions of measurement wave number = 4000 cm -1 ~400 cm -1 、resolution = 4 cm -1 、and scanning 128 times. Aluminum die-casting materials without a surface treatment film were used as the background. It was confirmed whether there were peaks in the obtained infrared spectrum in the wavelength ranges of 3600 cm -1 ~3000 cm -1 and 1750 cm -1 ~1700 cm -1 。

[0101] <Evaluation of test pieces>

[0102] Furthermore, each test was performed on the test pieces as follows to evaluate the corrosion resistance and post-heating corrosion resistance (heat-resistant corrosion resistance) of the aluminum die-casting materials with a surface treatment film. The results are shown in Table 3.

[0103] 《Evaluation method》

[0104] <Corrosion resistance>

[0105] The neutral salt spray test (JIS-Z2371:2015) was conducted on test pieces 1 to 39 for 360 hours. After drying, the proportion of white rust generated on the surface of the test pieces was visually measured. The proportion of white rust is the ratio of the area where white rust is generated to the area of the observation part. The evaluation criteria are as follows. The evaluation results are shown in Table 3.

[0106] <Evaluation Criteria>

[0107] 5 The proportion of white rust is 5% or less

[0108] 4 The proportion of white rust is greater than 5% to 10% or less

[0109] 3 The proportion of white rust is greater than 10% to 30% or less

[0110] 2 The proportion of white rust is greater than 30% to 50% or less

[0111] 1 The proportion of white rust is greater than 50%

[0112] <Heat and Corrosion Resistance>

[0113] After heating each test piece in an electric oven (150 °C, 6 hours), a neutral salt spray test (JIS-Z2371:2015) was conducted for 240 hours. After drying, the proportion of white rust generated on the surface of the test piece was visually measured. The proportion of white rust is the ratio of the area where white rust is generated to the area of the observation part. The evaluation criteria are as follows. The evaluation results are shown in Table 3.

[0114] <Evaluation Criteria>

[0115] 5 The proportion of white rust is 5% or less

[0116] 4 The proportion of white rust is greater than 5% to 10% or less

[0117] 3 The proportion of white rust is greater than 10% to 30% or less

[0118] 2 The proportion of white rust is greater than 30% to 50% or less

[0119] 1 The proportion of white rust is greater than 50%

[0120] [Table 1]

[0121]

[0122] [Table 2]

[0123] Table 2

[0124]

[0125] ※1 The total content of chromium, zirconium, and zinc is 100 atomic %

[0126] [Table 3]

[0127] Table 3

[0128]

[0129] Although the present invention has been described in detail with reference to specific embodiments, it is obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

Claims

1. An aluminum material or an aluminum alloy material, which is an aluminum material or an aluminum alloy material having a film containing chromium, zirconium, zinc, and carbon on the surface or on the surfaces of the aluminum material or the aluminum alloy material. In the infrared spectrum of the film measured by the specular reflection method of Fourier transform infrared spectroscopy (FT-IR), peaks appear at 3600 cm -1 ~3000 cm -1 and 1750 cm -1 ~1700 cm -1 .

2. The aluminum material or aluminum alloy material according to claim 1, wherein The chromium content of the film is in the range of 5 mg / m 2 to 100 mg / m 2 ; the zirconium content is in the range of 2 mg / m 2 to 150 mg / m 2 ; the carbon content is in the range of 2 mg / m 2 to 20 mg / m 2 ; and the total content of chromium, zirconium, and zinc measured by X-ray photoelectron spectroscopy (XPS) is 100 atomic %, and the zinc content is 2 atomic % to 60 atomic %.

3. An aqueous surface treatment agent, which is an aqueous surface treatment agent for surface treatment of an aluminum or aluminum alloy material, and the aqueous surface treatment agent contains: ions (A) containing chromium, ions (B) containing zirconium, ions (C) containing zinc, and an organic compound (D) having hydroxyl groups and carboxyl groups.

4. A method for manufacturing an aluminum material or an aluminum alloy material having a film, the manufacturing method including a contacting step of bringing the surface treatment agent according to claim 3 into contact with the surface or on the surfaces of the aluminum material or the aluminum alloy material.

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