Anodized aluminum oxide member, method for producing same, method for producing surface-treated aluminum member, and printed wiring board

Abstract

An anodized aluminum oxide member (1) comprises a base material (2) that is formed of aluminum or an aluminum alloy, and an anodized oxide film (3) that covers the base material (2). The anodized oxide film (3) includes: a barrier layer (31) that is provided on the base material (2); and a porous layer (32) that is provided on the barrier layer (31) and has a plurality of pores (321). When element concentrations on the surface of the anodized oxide film (3) are calculated on the basis of the photoelectron spectrum obtained by X-ray photoelectron spectroscopy, the ratio of the P atom concentration to the Al atom concentration is 0.03 to 0.11 inclusive.

Description

Anodized aluminum component, method for manufacturing the same, method for manufacturing surface-treated aluminum component, and printed circuit board 【0001】 The present invention relates to anodized aluminum members, methods for manufacturing the same, methods for manufacturing surface-treated aluminum members, and printed circuit boards. 【0002】 An anodized coating may be formed on the surface of aluminum components for various purposes, such as improving scratch resistance, corrosion resistance, adhesion, and decorative properties. The anodized coating consists of a barrier layer formed on the base material that does not have pores, and a porous layer formed on the barrier layer that has pores. Depending on the application of the anodized aluminum component, a sealing treatment may be performed to close the pores in the porous layer. The sealing treatment is performed by bringing a sealing agent such as hot water, steam, or a metal salt into contact with the anodized coating and forming a hydrated oxide on the surface of the anodized coating (for example, Patent Document 1). 【0003】 Japanese Patent Publication No. 2023-141525 【0004】 However, the aluminum oxides that make up the anodic oxide film also hydrate with moisture in the atmosphere to form hydrated oxides. Therefore, if aluminum components that have undergone anodic oxidation are stored in the atmosphere, the surface properties may change due to the unintended formation of hydrated oxides, potentially leading to a deterioration of properties such as adhesion. Furthermore, if hydrated oxides are formed in the pores, it may become difficult for colorants such as dyes and pigments to penetrate the pores, potentially making it difficult to dye the aluminum components. 【0005】 This invention has been made in view of the above background, and aims to provide an anodized aluminum member that can suppress the formation of unintended hydrated oxides and form hydrated oxides at a desired timing, a method for manufacturing the same, a method for manufacturing a surface-treated aluminum member, and a printed circuit board. 【0006】A first aspect of the present invention is an anodized aluminum member comprising: a base material made of aluminum or an aluminum alloy; and an anodic oxide film covering the base material, wherein the anodic oxide film comprises: a barrier layer provided on the base material; and a porous layer provided on the barrier layer and having a plurality of pores, and the ratio of the concentration of P atoms to the concentration of Al atoms, when the photoelectron spectrum of the surface of the anodic oxide film is measured by X-ray photoelectron spectroscopy and the elemental concentrations are calculated based on the photoelectron spectrum, is 0.03 or more and 0.11 or less. 【0007】 A second aspect of the present invention is a method for producing an anodized aluminum member according to the above aspect, comprising: one or more primary electrolytes selected from the group consisting of phosphoric acid, diphosphate, triphosphate, polyphosphate and salts thereof; and one or more secondary electrolytes selected from the group consisting of inorganic acids other than acids contained in the primary electrolyte, carboxylic acids and salts thereof, wherein the concentration of the primary electrolyte is 0.1% by mass or more and 3% by mass or less, and the concentration of the secondary electrolyte is 1% by mass or more and 30% by mass or less, in an electrolyte solution with a current density of 2 mA / cm². 2 150mA / cm or more 2 The following describes a method for manufacturing an anodized aluminum member, which involves performing an anodizing treatment on the base material under the conditions of a temperature between 0°C and 80°C. 【0008】 A third aspect of the present invention is a method for manufacturing a surface-treated aluminum member using the anodized aluminum member of the above aspect, comprising: activating the surface of the anodized film by washing the anodized aluminum member with an acid that does not contain phosphorus atoms; and then sealing the pores of the porous layer by bringing the anodized film into contact with a sealing agent. 【0009】 A fourth aspect of the present invention is a printed circuit board including the anodized aluminum member of the above aspect. 【0010】In the anodized aluminum member (hereinafter referred to as the "anodicized member"), the ratio of the concentration of P atoms to the concentration of Al atoms on the surface of the anodized film is 0.03 or more and 0.11 or less. The P atoms present on the surface of the anodized film can suppress the progress of the hydration reaction of the aluminum oxide constituting the anodized film. Therefore, by keeping the ratio of the concentration of P atoms to the concentration of Al atoms on the surface of the anodized film within the specified range, the formation of unintended hydrated oxides due to reactions with moisture in the atmosphere can be suppressed. 【0011】 Furthermore, an anodized member whose concentration ratio is within the specified range can have its surface activated by cleaning the anodized film with acid. After activating the anodized film, contacting the anodized film with a sealing agent allows for the easy formation of hydrated aluminum oxide, thereby sealing the pores in the porous layer. Therefore, the anodized member can form hydrated oxide on the surface of the anodized film at a desired timing. 【0012】 In the method for manufacturing the anodic oxide member, an anodic oxide film can be easily formed in which the ratio of the concentration of P atoms to the concentration of Al atoms on the surface is within the specified range by performing an anodic oxidation treatment on the base material in the specified electrolyte under the specified conditions. 【0013】 In the method for manufacturing the surface-treated aluminum member (hereinafter referred to as the "surface-treated member"), the surface of the anodic oxide film can be activated by washing the anodic oxide member with acid. Then, by bringing the anodic oxide film into contact with a sealing agent after activating the anodic oxide film, the hydration reaction of aluminum oxide can be easily facilitated, and the pores can be sealed. 【0014】 Accordingly, according to the above embodiment, it is possible to provide an anodized aluminum member that can suppress the formation of unintended hydrated oxides and form hydrated oxides at a desired timing, a method for manufacturing the same, a method for manufacturing a surface-treated aluminum member, and a printed circuit board. 【0015】Figure 1 is a partial cross-sectional view of the anodized aluminum member in the embodiment. 【0016】 (Anodized Aluminum Member) The base material of the anodized member is made of aluminum or an aluminum alloy. The shape of the base material is not particularly limited and can take various shapes depending on the application of the aluminum member. For example, the base material may be a wrought material such as a rolled plate or an extruded material, or it may be a cast material or a forged material. 【0017】 Furthermore, the material of the base material can be appropriately selected from the group consisting of aluminum and aluminum alloys, depending on the application of the aluminum component. More specifically, for example, 1000 series aluminum can be used as the aluminum constituting the base material. For example, 2000 series aluminum alloy, 3000 series aluminum alloy, 4000 series aluminum alloy, 5000 series aluminum alloy, 6000 series aluminum alloy, 7000 series aluminum alloy, and 8000 series aluminum alloy can be used as the aluminum alloy constituting the base material. In addition, the base material may be a clad material in which two or more layers having different chemical compositions are laminated. 【0018】 The anodized component has an anodic oxide film covering the base material. The anodic oxide film is composed of aluminum oxide. The anodic oxide film may cover the entire surface of the base material or only a portion of its surface. The thickness of the anodic oxide film is not particularly limited, but can be appropriately set within a range of, for example, 50 nm to 50 μm. 【0019】 The anodic oxide film comprises a barrier layer provided on the base material and a porous layer provided on the barrier layer and having a plurality of pores. Preferably, the thickness of the barrier layer is 10 nm to 150 nm, and the thickness of the porous layer is 100 nm or more. In this case, the formation of unintended hydrated oxides can be suppressed more reliably, and hydrated oxides can be formed at the desired timing. 【0020】The photoelectron spectrum of the surface of the anodic oxide film is measured by X-ray photoelectron spectroscopy, and when the elemental concentrations are calculated based on this photoelectron spectrum, the ratio of the concentration of P atoms to the concentration of Al atoms is 0.03 or more and 0.11 or less. An anodized member equipped with such an anodized film can suppress the formation of unintended hydrated oxides due to the hydration reaction between moisture in the atmosphere and aluminum oxide. Furthermore, the surface of the anodized member can be activated by cleaning the surface of the anodized film with acid. Then, by contacting the anodized film after the surface has been activated with a sealing agent, the pores of the porous layer can be easily sealed at a desired timing. From the viewpoint of obtaining such effects more reliably, the ratio of the concentration of P atoms to the concentration of Al atoms is preferably 0.03 or more and 0.10 or less, and more preferably 0.03 or more and 0.09 or less. 【0021】 When the ratio of P atom concentration to Al atom concentration is less than 0.03, hydration reactions between moisture in the atmosphere and aluminum oxide are likely to occur. Therefore, in this case, it is difficult to suppress the formation of unintended hydrated oxides. On the other hand, when the ratio of P atom concentration to Al atom concentration exceeds 0.11, it is difficult to activate the surface of the anodic oxide film after cleaning with acid. Therefore, in this case, it is difficult to form aluminum hydrated oxides on the surface of the anodic oxide film. 【0022】The reason why the aforementioned anodic oxide material has such effects is not yet clear, but it is thought that the effects described above can be obtained for the following reasons, for example. Anions of electrolytes containing phosphorus atoms, such as phosphoric acid and diphosphate, used in the manufacturing process of the anodic oxide material, are adsorbed on the surface of the anodic oxide film of the anodic oxide material. These anions are thought to have the effect of inhibiting the hydration reaction between aluminum oxide and water. Therefore, it is thought that by setting the ratio of the concentration of P atoms to the concentration of Al atoms to 0.03 or higher, the amount of phosphorus-containing anions adsorbed on the surface of the anodic oxide film can be sufficiently increased. And it is thought that the formation of unintended hydrated oxides can be suppressed by the anions adsorbed on the surface of the anodic oxide film. 【0023】 Furthermore, anions adsorbed on the surface of the anodic oxide film are detached from the surface of the anodic oxide film when the film is washed with acid. It is believed that the detachment of phosphorus-containing anions from the surface of the anodic oxide film facilitates the hydration reaction between aluminum oxide and water. Therefore, by setting the ratio of the concentration of P atoms to the concentration of Al atoms to 0.11 or less, preferably 0.10 or less, and more preferably 0.09 or less, it is believed that the amount of anions adsorbed on the surface of the anodic oxide film can be reduced to an amount that can be easily removed by washing with acid. By controlling the amount of anions adsorbed on the surface of the anodic oxide film in this way, it is believed that the anodic oxide film can be activated at a desired timing by washing with acid, thereby sealing the pores of the porous layer. 【0024】 From the viewpoint of more reliably obtaining the aforementioned effects, it is preferable that the ratio of the sum of the concentrations of Al atoms and P atoms to the sum of the concentrations of Al atoms, P atoms and O atoms, when the photoelectron spectrum of the surface of the anodic oxide film is measured by X-ray photoelectron spectroscopy and the elemental concentrations are calculated based on this photoelectron spectrum, be 0.280 or more and 0.315 or less, more preferably 0.281 or more and 0.314 or less, and even more preferably 0.282 or more and 0.313 or less. 【0025】Furthermore, the specific surface area of ​​the anodic oxide film measured by the BET method is 0.1 m². 2 / g or more 10.0m 2 It is preferable that the amount be less than or equal to / g. In this case, the effects described above can be obtained more reliably. 【0026】 The applications of the anodized material are not particularly limited, but it is preferable, for example, to use it as a component of a printed circuit board where a highly reliable bond between the resin and the substrate is required. 【0027】 (Method for manufacturing anodized aluminum member) The anodized member comprises one or more primary electrolytes selected from the group consisting of phosphoric acid, diphosphate, triphosphate, polyphosphate and salts thereof, and one or more secondary electrolytes selected from the group consisting of inorganic acids other than acids contained in the primary electrolyte, carboxylic acids and salts thereof, wherein the concentration of the primary electrolyte is 0.1% by mass or more and 3% by mass or less, and the concentration of the secondary electrolyte is 1% by mass or more and 30% by mass or less, in an electrolyte solution with a current density of 2 mA / cm². 2 150mA / cm or more 2 The following is obtained by performing an anodic oxidation treatment on the base material under the conditions of a temperature between 0°C and 80°C. 【0028】 In the above manufacturing method, when anodizing is performed under the specific conditions, the dissolution of aluminum and the growth of aluminum oxide proceed in parallel at the interface between the base material and the electrolyte. As a result, an anodic oxide film having a barrier layer and a porous layer is formed on the base material. Furthermore, during the growth process of the anodic oxide film, some anions derived from the first electrolyte and some anions derived from the second electrolyte are incorporated into the anodic oxide film. Therefore, the anodic oxide film formed on the base material may contain anions derived from the first electrolyte and anions derived from the second electrolyte, in addition to aluminum oxide. After the anodizing process is completed, anions containing phosphorus atoms derived from the first electrolyte are adsorbed onto the surface of the anodic oxide film. As a result, the anodic oxide member can be obtained. 【0029】From the viewpoint of more easily obtaining the anodic oxidation member, the first electrolyte is preferably one or more salts selected from the group consisting of phosphates, diphosphates, triphosphates, and polyphosphates, more preferably diphosphates, and even more preferably sodium diphosphate. 【0030】 When the concentration of the primary electrolyte in the electrolyte solution is less than 0.1% by mass, the amount of phosphorus-containing anions adsorbed onto the surface of the anodic oxide film decreases, making the aluminum oxide constituting the anodic oxide film more susceptible to hydration reactions. Therefore, it is difficult to suppress the formation of unintended hydrated oxides in anodic oxide components manufactured under such conditions. 【0031】 When the concentration of the primary electrolyte in the electrolyte exceeds 3% by mass, the amount of anions containing phosphorus atoms adsorbed onto the surface of the anodic oxide film increases, and a large amount of anions tend to remain on the surface of the anodic oxide film after acid washing. Therefore, it is difficult to activate the anodic oxide film and seal the pores of the porous layer at the desired timing in anodic oxide members manufactured under such conditions. From the viewpoint of more easily avoiding these problems and more reliably obtaining the effects described above, the concentration of the primary electrolyte in the electrolyte is preferably 0.1% by mass or more and 2.5% by mass or less, more preferably 0.1% by mass or more and 2.0% by mass or less, even more preferably 0.1% by mass or more and 1.5% by mass or less, and particularly preferably 0.1% by mass or more and 1.0% by mass or less. 【0032】 If the concentration of the secondary electrolyte in the electrolyte is less than 1% by mass, the anodic oxidation reaction is less likely to occur at the interface between the base material and the electrolyte, making it difficult to form an anodic oxide film on the base material. If the concentration of the secondary electrolyte in the electrolyte exceeds 30% by mass, the dissolving power of the electrolyte becomes excessively high, making it difficult to form an anodic oxide film on the base material. From the viewpoint of more easily avoiding these problems and more reliably obtaining the aforementioned effects, the concentration of the secondary electrolyte in the electrolyte is preferably 2% by mass or more and 25% by mass or less, and more preferably 3% by mass or more and 20% by mass or less. 【0033】 The current density in the anodizing process is 2 mA / cm².2 If it is less than this value, the anodic oxidation reaction hardly occurs at the interface between the base material and the electrolytic solution, making it difficult to form an anodic oxide film on the base material. When the current density in the anodic oxidation treatment is 150 mA / cm 2 exceeds this value, it is likely to form parts where the anodic oxidation reaction progresses easily and parts where it progresses hardly at the interface between the base material and the electrolytic solution, making it difficult to form a uniform anodic oxide film on the base material. 【0034】 In the anodic oxidation treatment, the anodic oxide film may be formed by any of the methods of direct current electrolysis, alternating current electrolysis, and pulse electrolysis. From the perspective of more easily obtaining the anodic oxidation member, in the anodic oxidation treatment, it is preferable to form an anodic oxide film on the base material by direct current electrolysis or alternating current electrolysis, and it is more preferable to form an anodic oxide film on the base material by direct current electrolysis. 【0035】 If the temperature of the electrolytic solution in the anodic oxidation treatment is less than 0 °C, the anodic oxidation reaction hardly occurs, making it difficult to form an anodic oxide film on the base material. If the temperature of the electrolytic solution in the anodic oxidation treatment exceeds 80 °C, the porous layer is likely to dissolve during the anodic oxidation treatment, making it difficult to form a porous layer on the base material. From the perspective of more easily avoiding these problems and more surely obtaining the above-described effects, the temperature of the electrolytic solution in the anodic oxidation treatment is preferably 0 °C or higher and 60 °C or lower, more preferably 0 °C or higher and 40 °C or lower, and even more preferably 0 °C or higher and 30 °C or lower. 【0036】 The treatment time in the anodic oxidation treatment is not particularly limited and may be appropriately set according to the current density, applied voltage, desired thickness of the anodic oxide film, etc. in the anodic oxidation treatment. More specifically, the treatment time of the anodic oxidation treatment can be appropriately set, for example, within the range of 1 minute or more and 6 hours or less. 【0037】 In the above manufacturing method, before performing the anodic oxidation treatment on the base material, pretreatment such as degreasing, etching, desmating, polishing, and grinding can also be performed as necessary. 【0038】(Method for manufacturing surface-treated aluminum member) A surface-treated aluminum member can be obtained by sealing the pores in the porous layer of the anodized member. More specifically, in manufacturing the surface-treated member, the surface of the anodized aluminum member is activated by washing it with an acid that does not contain phosphorus atoms, and then the pores in the porous layer are sealed by bringing the anodized aluminum member into contact with a sealing agent. 【0039】 In the method for manufacturing the surface-treated member, an acid that does not contain phosphorus atoms can be used as the acid used to activate the surface of the anodic oxide film. Examples of such acids include inorganic acids that do not contain phosphorus atoms, such as sulfuric acid, nitric acid, and hydrochloric acid, and carboxylic acids such as oxalic acid. 【0040】 The acid used to activate the surface of the anodic oxide film is preferably an acid capable of dissolving aluminum oxide. That is, in the above manufacturing method, it is preferable to activate the surface of the anodic oxide film by washing the anodic oxide member with an acid capable of dissolving aluminum oxide and dissolving the surface of the anodic oxide film. Examples of such acids include oxalic acid. By dissolving the surface of the anodic oxide film in this way, anions containing phosphorus atoms adsorbed on the surface of the anodic oxide film can be removed more easily. As a result, the anodic oxide film can be activated more reliably, and when the activated anodic oxide film is brought into contact with the sealing agent, hydrated oxides can be formed more reliably, sealing the pores of the porous layer. 【0041】The concentration of the acid used for activating the surface of the anodic oxide film and the time for bringing the anodic oxide film into contact with the acid are not particularly limited. The concentration of the acid used for activating the surface of the anodic oxide film can be appropriately set, for example, within the range of 1% by mass or more and 25% by mass or less. The concentration of the acid used for activating the surface of the anodic oxide film is preferably 2% by mass or more and 20% by mass or less, and more preferably 2.5% by mass or more and 15% by mass or less. Also, the time for bringing the anodic oxide film into contact with the acid may be, for example, 10 minutes or less. The temperature of the acid used for activating the surface of the anodic oxide film is preferably 10°C or more and 80°C or less, and more preferably 20°C or more and 60°C or less. 【0042】 By X-ray photoelectron spectroscopy, after performing the activation, the photoelectron spectrum of the surface of the anodic oxide film before bringing it into contact with the sealing agent is measured, and when the elemental concentration on the surface of the anodic oxide film is calculated based on this photoelectron spectrum, the ratio of the concentration of P atoms to the concentration of Al atoms is preferably less than 0.03, more preferably 0.029 or less, and even more preferably 0.028 or less. In this case, the hydration reactivity of the anodic oxide film can be further enhanced. Therefore, a hydrated oxide can be more easily formed on the surface of the anodic oxide film. 【0043】 As the sealing agent, for example, hot water or steam at a temperature of 80°C or higher, Ni (nickel), Cr (chromium), Zr (zirconium), Si (silicon), Ti (titanium), Au (gold), Ag (silver), Co (cobalt), Mo (molybdenum), Mn (manganese), Nb (niobium), Ta (tantalum), W (tungsten), Zn (zinc), Fe (iron), Ir (iridium), and Sc (scandium), an aqueous solution containing ions of one or more metal elements selected from the group consisting of, substances capable of reacting with the oxide of aluminum to form a hydrated oxide can be used. When performing sealing using hot water or steam, a hydrated oxide layer composed of hydrated oxide of aluminum can be formed on the surface of the anodic oxide film. 【0044】Also, when performing sealing using an aqueous solution containing ions of the metal element, a hydrated oxide layer containing aluminum hydrated oxide and a salt and / or oxide of the metal element can be formed on the surface of the anodic oxide film. The metal element may exist as metal ions or as complex ions in the aqueous solution. More specifically, as a sealing agent containing a metal element, an aqueous solution of a metal salt containing the metal element, such as an aqueous solution of nickel acetate, an aqueous solution of cobalt acetate, an aqueous chromate solution, and an aqueous silicate solution, can be used. 【0045】 An example of the anodic aluminum member and its manufacturing method will be described below. As shown in FIG. 1, the anodic member 1 of this example has a base material 2 made of aluminum or an aluminum alloy and an anodic oxide film 3 covering the base material 2. The anodic oxide film 3 has a barrier layer 31 provided on the base material 2 and a porous layer 32 provided on the barrier layer 31 and having a plurality of pores 321. When the photoelectron spectrum of the surface of the anodic oxide film 3 is measured by X-ray photoelectron spectroscopy and the element concentration is calculated based on this photoelectron spectrum, the ratio of the concentration of P atoms to the concentration of Al atoms is 0.03 or more and 0.11 or less. 【0046】 The anodic member 1 of this example contains one or more first electrolytes selected from the group consisting of phosphoric acid, diphosphoric acid, triphosphoric acid, polyphosphoric acid, and salts thereof, and one or more second electrolytes selected from the group consisting of inorganic acids other than the acids contained in the first electrolyte, carboxylic acids, and salts thereof. In an electrolytic solution where the concentration of the first electrolyte is 0.1% by mass or more and 3% by mass or less, and the concentration of the second electrolyte is 1% by mass or more and 30% by mass or less, at a current density of 2 mA / cm 2 or more and 150 mA / cm 2 or less, and is obtained by performing anodic oxidation treatment on the base material 2 under the conditions of a temperature of 0°C or more and 80°C or less. 【0047】Tables 1 to 3 show specific examples of the anodized members (test materials A1 to A9) used in this example. Test materials A1 to A9 can be obtained, for example, by the following method. First, an aluminum plate having the chemical composition represented by alloy number A5052 is prepared as the base material. This base material is subjected to a pretreatment for anodizing. In the pretreatment, the base material is first immersed in a 5% by mass sodium hydroxide aqueous solution at 55°C for 30 seconds to perform alkaline etching. Then, the base material is immersed in 30% by mass nitric acid at room temperature for 60 seconds to perform desmatt treatment. Note that sodium pyrophosphate shown in Table 1 is sometimes also called sodium diphosphate. 【0048】 After pre-treating the base material as described above, an anodic oxidation treatment is performed by DC electrolysis to form an anodic oxidation film on the surface of the base material. The composition of the electrolyte used in the anodic oxidation treatment, the temperature, the voltage applied to the base material during the anodic oxidation treatment, the current density, and the treatment time for the anodic oxidation treatment are as shown in Table 1. Test materials A1 to A9 can be obtained by following these steps. 【0049】 The anodic oxide film formed in this manner is a so-called porous type anodized film, consisting of a barrier layer formed on the base material that has no pores, and a porous layer formed on the barrier layer that has multiple pores. The thickness of the anodic oxide film in test materials A1 to A9 is in the range of 200 nm to 10 μm. In addition, the thickness of the barrier layer in test materials A1 to A9 is in the range of 10 nm to 50 nm, and the thickness of the porous layer is in the range of 100 nm to 9.9 μm. 【0050】 Note that test materials B1 and B2 shown in Tables 1 to 3 are test materials for comparison with test materials A1 to A9. The manufacturing method of test material B1 is the same as that of test material A1, except that an electrolyte solution containing only the second electrolyte and not the first electrolyte was used. The manufacturing method of test material B2 is the same as that of test material A1, except that an electrolyte solution containing only the first electrolyte and not the second electrolyte was used. 【0051】Table 2 shows the concentrations of Al, P, and O atoms calculated based on the photoelectron spectrum of the surface of the anodic oxide film 3. An X-ray photoelectron spectrometer (ULVAC-PHI "PHI 5000 VersaProbe III") can be used to measure the photoelectron spectrum. The concentration of Al atoms is calculated based on the narrow spectrum of the 2p orbital of Al, the concentration of P atoms is calculated based on the narrow spectrum of the 2p orbital of P, and the concentration of O atoms is calculated based on the narrow spectrum of the 1s orbital of O. In Table 2, the "P / Al" column shows the ratio of P atoms to the concentration of Al atoms, and the "(P+Al) / (P+Al+O)" column shows the ratio of the sum of the concentrations of Al atoms and P atoms to the sum of the concentrations of Al atoms, P atoms and O atoms. 【0052】 Table 3 shows the moisture stability, surface composition after acid cleaning, and hydration reactivity after acid cleaning for each test material. The evaluation methods are as follows. 【0053】 [Stability against moisture] After immersing each test material in boiling water for 60 seconds, the test material is removed from the boiling water and dried. Then, the surface of the anodic oxide film is observed using an electron microscope to determine whether or not the pores of the porous layer are sealed by hydrated oxides. In the "Stability against moisture" column of Table 3, "Good" indicates that the pores of the porous layer are open and the hydration reaction is suppressed, while "Poor" indicates that the pores of the porous layer are sealed and the hydration reaction has occurred. 【0054】 [Surface composition after acid cleaning] The surface of the anodized film is cleaned with oxalic acid by immersing the test material in a 0.3 mol / L oxalic acid aqueous solution for 5 minutes. Next, the oxalic acid adhering to the surface of the anodized film is removed using cold water. After that, the test material is immersed in boiling water for 60 seconds. After drying the test material removed from the boiling water, the photoelectron spectrum of the surface of the anodized film is obtained by X-ray photoelectron spectroscopy. Then, based on the obtained photoelectron spectrum, the concentrations of Al atoms and P atoms on the surface of the anodized film are measured. 【0055】Table 3 shows the concentrations of Al atoms and P atoms on the surface of the anodic oxide film after acid cleaning. The photoelectron spectrum measurement method is the same as that described above for measuring the photoelectron spectrum of the anodic oxide film before acid cleaning. For test materials in which the surface composition of the anodic oxide film after acid cleaning was not measured, the symbol "-" is indicated in the "Surface composition after acid cleaning" column of Table 3. 【0056】 [Hydration Reactivity After Acid Washing] The surface of the anodic oxide film is washed with oxalic acid by immersing the test material in a 0.3 mol / L oxalic acid aqueous solution for 5 minutes. Next, the oxalic acid adhering to the surface of the anodic oxide film is removed using cold water. After that, the test material is immersed in boiling water for 60 seconds. After drying the test material removed from the boiling water, the surface of the anodic oxide film is observed using an electron microscope to determine whether or not the pores of the porous layer are sealed by hydrated oxides. In the "Hydration Reactivity After Acid Washing" column of Table 3, "Good" indicates that the pores of the porous layer are sealed by hydrated oxides and that a hydration reaction has occurred, while "Poor" indicates that the pores of the porous layer are open and the hydration reaction has been suppressed. For test materials in which the hydration reactivity after acid washing has not been evaluated, the symbol "-" is written in the "Hydration Reactivity After Acid Washing" column of Table 3. 【0057】 【0058】 【0059】 【0060】 As shown in Table 1, test materials A1 to A9 were prepared by anodic oxidation treatment of a base material under specific conditions in an electrolyte containing a first electrolyte and a second electrolyte at concentrations within the specified range. As a result, an anodic oxide film comprising a barrier layer and a porous layer is formed on the base material of these test materials. Furthermore, when the elemental concentrations on the surface of the anodic oxide film are calculated based on the photoelectron spectrum obtained by X-ray photoelectron spectroscopy, the ratio of the concentration of P atoms to the concentration of Al atoms is between 0.03 and 0.11. 【0061】As shown in Table 3, test materials A1 to A9, having the above configuration, exhibit excellent stability against moisture and can suppress the formation of hydrated oxides due to unintended hydration reactions with moisture in the atmosphere. Furthermore, the hydration reactivity of test materials A1 to A9 can be improved by activating the anodic oxide film by washing it with acid. Therefore, test materials A1 to A9 can seal the pores of the porous layer at a desired timing. 【0062】 In contrast, test material B1 is produced by anodic oxidation in an electrolyte solution that does not contain the primary electrolyte. Therefore, test material B1 has low stability against moisture and is prone to hydration reactions when it comes into contact with moisture in the air. 【0063】 Since test material B2 is manufactured by anodic oxidation in an electrolyte that does not contain a second electrolyte, a large amount of phosphorus-containing anions tend to remain on the surface of the anodic oxide film after washing the anodic oxide film with acid. Therefore, it is difficult to seal the pores of the porous layer of test material B2 at the desired timing. 【0064】 Although embodiments of the anodized aluminum member and its manufacturing method have been described above based on the examples, the anodized aluminum member, its manufacturing method, the manufacturing method of the surface-treated aluminum member, and the printed circuit board according to the present invention are not limited to the embodiments described in the examples, and the configuration can be appropriately modified without impairing the spirit of the present invention. 【0065】 For example, the anodized aluminum member may take the following forms [1] to [4]. 【0066】 [1] An anodized aluminum member comprising: a base material made of aluminum or an aluminum alloy; and an anodic oxide film covering the base material, wherein the anodic oxide film comprises: a barrier layer provided on the base material; and a porous layer provided on the barrier layer and having a plurality of pores, and the ratio of the concentration of P atoms to the concentration of Al atoms, when the photoelectron spectrum of the surface of the anodic oxide film is measured by X-ray photoelectron spectroscopy and the elemental concentrations are calculated based on the photoelectron spectrum, is 0.03 or more and 0.11 or less. 【0067】 [2] The anodized aluminum member according to [1], wherein the thickness of the barrier layer is 10 nm or more and 150 nm or less, and the thickness of the porous layer is 100 nm or more. [3] The anodized aluminum member according to [1] or [2], wherein the photoelectron spectrum of the surface of the anodized film is measured by X-ray photoelectron spectroscopy, and the elemental concentrations are calculated based on the photoelectron spectrum, and the ratio of the sum of the concentrations of Al atoms and P atoms to the sum of the concentrations of Al atoms, P atoms and O atoms is 0.280 or more and 0.315 or less. [4] The specific surface area of ​​the anodized film measured by the BET method is 0.1 m². 2 / g or more 10.0m 2 An anodized aluminum component according to any one of [1] to [3], wherein the amount is less than or equal to / g. 【0068】 Furthermore, the method for manufacturing the anodized aluminum member may take the following forms [5] to [7]. 【0069】 A method for producing an anodized aluminum member according to any one of [5], [1] to [4], comprising: a primary electrolyte comprising one or more types selected from the group consisting of phosphoric acid, diphosphate, triphosphate, polyphosphate and salts thereof; and a secondary electrolyte comprising one or more types selected from the group consisting of inorganic acids other than acids contained in the primary electrolyte, carboxylic acids and salts thereof, wherein the concentration of the primary electrolyte is 0.1% by mass or more and 3% by mass or less, and the concentration of the secondary electrolyte is 1% by mass or more and 30% by mass or less, in an electrolyte with a current density of 2 mA / cm². 2 150mA / cm or more 2 The following are methods for producing an anodized aluminum member, wherein the base material is subjected to an anodizing treatment under the conditions of a temperature of 0°C to 80°C. [6] The method for producing an anodized aluminum member according to [5], wherein the first electrolyte is one or more salts selected from the group consisting of phosphates, diphosphates, triphosphates and polyphosphates. [7] The method for producing an anodized aluminum member according to [6], wherein the first electrolyte is sodium diphosphate. 【0070】Furthermore, the method for manufacturing the surface-treated aluminum member may take the following forms [8] to

[10] . A method for manufacturing a surface-treated aluminum member using the anodized aluminum member described in any one of [8], [1] to [4], wherein the surface of the anodized film is activated by washing the anodized aluminum member with an acid that does not contain phosphorus atoms, and then the pores of the porous layer are sealed by bringing the anodized film into contact with a sealing agent. 【0071】 [9] A method for manufacturing a surface-treated aluminum member according to [8], wherein, after the activation, the photoelectron spectrum of the surface of the anodic oxide film before contact with the sealing agent is measured by X-ray photoelectron spectroscopy, and when the elemental concentrations are calculated based on the photoelectron spectrum, the ratio of the concentration of P atoms to the concentration of Al atoms is less than 0.03.

[10] A method for manufacturing a surface-treated aluminum member according to [8] or [9], wherein, during the activation, the anodic oxide aluminum member is washed with an acid that does not contain phosphorus atoms to dissolve the surface of the anodic oxide film. 【0072】 Furthermore, the printed circuit board may take the form described in

[11] below: A printed circuit board containing an anodized aluminum member as described in any one of [1] to [4].

Claims

1. An anodized aluminum member comprising: a base material made of aluminum or an aluminum alloy; and an anodic oxide film covering the base material, wherein the anodic oxide film comprises: a barrier layer provided on the base material; and a porous layer provided on the barrier layer and having a plurality of pores, and the ratio of the concentration of P atoms to the concentration of Al atoms, when the photoelectron spectrum of the surface of the anodic oxide film is measured by X-ray photoelectron spectroscopy and the elemental concentrations are calculated based on the photoelectron spectrum, is 0.03 or more and 0.11 or less.

2. The anodized aluminum member according to claim 1, wherein the thickness of the barrier layer is 10 nm or more and 150 nm or less, and the thickness of the porous layer is 100 nm or more.

3. The anodized aluminum member according to claim 1, wherein the photoelectron spectrum of the surface of the anodized film is measured by X-ray photoelectron spectroscopy, and the elemental concentrations are calculated based on the photoelectron spectrum, and the ratio of the sum of the concentrations of Al atoms and P atoms to the sum of the concentrations of Al atoms, P atoms and O atoms is 0.280 or more and 0.315 or less.

4. The specific surface area of ​​the anodic oxide film measured by the BET method is 0.1 m². 2 / g or more 10.0m 2 The anodized aluminum member according to claim 1, wherein the amount is less than or equal to / g.

5. A method for producing an anodized aluminum member according to any one of claims 1 to 4, comprising: a first electrolyte selected from the group consisting of phosphoric acid, diphosphate, triphosphate, polyphosphate and salts thereof; and a second electrolyte selected from the group consisting of inorganic acids other than acids contained in the first electrolyte, carboxylic acids and salts thereof, wherein the concentration of the first electrolyte is 0.1% by mass or more and 3% by mass or less, and the concentration of the second electrolyte is 1% by mass or more and 30% by mass or less, in an electrolyte with a current density of 2 mA / cm². 2 150mA / cm or more 2 The following is a method for manufacturing an anodized aluminum member, comprising performing an anodizing treatment on the base material under the conditions of a temperature of 0°C to 80°C.

6. The method for producing an anodized aluminum member according to claim 5, wherein the first electrolyte is one or more salts selected from the group consisting of phosphates, diphosphates, triphosphates, and polyphosphates.

7. The method for producing an anodized aluminum member according to claim 6, wherein the first electrolyte is sodium diphosphate.

8. A method for manufacturing a surface-treated aluminum member using an anodized aluminum member according to any one of claims 1 to 4, comprising: activating the surface of the anodized film by washing the anodized aluminum member with an acid that does not contain phosphorus atoms; and then sealing the pores of the porous layer by bringing the anodized film into contact with a sealing agent.

9. A method for manufacturing a surface-treated aluminum member according to claim 8, wherein the photoelectron spectrum of the surface of the anodic oxide film is measured by X-ray photoelectron spectroscopy after the activation and before contact with the sealing agent, and the ratio of the concentration of P atoms to the concentration of Al atoms, when the elemental concentrations are calculated based on the photoelectron spectrum, is less than 0.

03.

10. The method for manufacturing a surface-treated aluminum member according to claim 8, wherein, during the activation, the anodized aluminum member is washed with an acid that does not contain phosphorus atoms to dissolve the surface of the anodized film.

11. A printed circuit board comprising an anodized aluminum member according to any one of claims 1 to 4.

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