Metal components and methods for manufacturing metal components using metal materials

Abstract

The object of this invention is to provide a novel metal component. According to this invention, a metal component comprising a first metal is provided. Elemental analysis of the surface of this metal component using X-ray photoelectron spectroscopy (XPS) detects nitrogen and silicon, wherein the atomic ratio (N / Si) of nitrogen and silicon is 0.04 or higher and 0.8 or lower, and the color difference ΔE*ab before and after alkali metal leaching testing of the surface is 15 or lower.

Description

Technical Field

[0001] This invention relates to a metal component. Prior Technology

[0002] When dielectrics and conductors are pressed together, high temperatures and pressures are applied. Therefore, if the conductor's heat resistance is insufficient, surface degradation will occur, preventing proper adhesion to the dielectric. Furthermore, the soldering process in substrate manufacturing generates high temperatures, which can cause conductor surface peeling. Additionally, automotive electronic components and other applications operate at high temperatures and require long-term heat-resistant adhesion. In such cases where conductors require heat resistance, various surface treatments are applied to the metal parts used as conductors.

[0003] For example, Japanese Patent Application Publication No. 2021-147701 discloses a technique for forming a coating as a heat-resistant treatment layer on the surface of a conductor. This coating is formed from quaternary metal oxides of chromium, molybdenum, zinc, and nickel, and their compounds, which can suppress blister formation even under heat loads such as high-temperature pressing. International Patent Application Publication No. WO2019 / 093494 discloses a technique for obtaining low roughness, high adhesion, and high heat resistance by forming a metal layer on copper oxide. Furthermore, Japanese Patent Application Publication No. 2004-259937 discloses a surface treatment of the inner layer conductor by contacting the metal foil surface of the inner layer circuit with an acidic treatment solution containing noble metal ions and copper ions, thereby improving the conductor's heat resistance. International Patent Application Publication No. WO2017 / 138338 discloses that forming an appropriate amount of coupling layer on the surface of a conductor can effectively improve the conductor's heat resistance.

[0004] However, in recent years, the desire to reduce transmission losses has led to a demand for dielectrics with excellent electrical properties. Thermoplastic resins are among the dielectrics with excellent electrical properties. While thermoplastic resins offer excellent electrical properties, they require high-temperature pressing. For example, in the case of lamination with PTFE, pressing is carried out at temperatures above 300°C. Furthermore, the development of energy-saving technologies such as SiC devices is accelerating. These devices are required to operate at temperatures above 200°C, and the adhesion between the dielectric and conductor must withstand such high temperatures. Summary of the Invention

[0005] This invention provides a novel metal component.

[0006] One embodiment of the present invention is a metal component comprising a first metal. Elemental analysis of the surface of the metal component using X-ray photoelectron spectroscopy (XPS) detects nitrogen and silicon. The atomic ratio (N / Si) of nitrogen and silicon is 0.04 or higher and 0.8 or lower, or 0.05 or higher and 0.8 or lower, and satisfies any one of the following conditions:

[0007] [1] The color difference ΔE*ab before and after the alkali metal leaching test on the surface is less than 15. [2] The surface has a second metal layer, and in the waveform separation of the surface pattern using XPS, the area percentage of the peak area of ​​the second metal hydroxide relative to the sum of the peak areas from the second metal is 70 Area% or less or 63 Area% or less. Here, the second metal may be nickel.

[0008] Another embodiment of the present invention is a metal component comprising a first metal. Elemental analysis of the surface of the metal component using Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) detected hydroxides and SiOx of the first metal, with the peak value of SiOx being greater than that of the hydroxides of the first metal. Elemental analysis of the surface using TOF-SIMS also detected silicon and alkali metals, with the peak value of silicon potentially being greater than that of the alkali metals. Elemental analysis of the surface using X-ray Photoelectron Spectroscopy (XPS) detected nitrogen and silicon, with the nitrogen / silicon atomic ratio (N / Si) being either 0.04 or higher and 0.8 or lower, or 0.05 or higher and 0.8 or lower.

[0009] Another embodiment of the present invention is a metal component comprising a first metal and having a second metal layer on its surface. Elemental analysis of the surface of this metal component using TOF-SIMS detects SiO₂. In the waveform separation of the surface spectrum obtained using X-ray photoelectron spectroscopy (XPS), the area percentage of the peak area of ​​the second metal hydroxide relative to the sum of the peak areas from the second metal is 70% or less or 63% or less. The second metal may be nickel. The amount of alkali metal leached from the surface may be 0.2 ppm or less.

[0010] Another embodiment of the present invention is a method for manufacturing a metal component using a metallic material, comprising: a first step of treating the metallic material with a coupling agent; and a second step of treating the metallic material with water glass. The first step may be performed before, after, or both before and after the second step.

[0011] Another embodiment of the present invention is a method for manufacturing a metal component using a metallic material, comprising a third step of treating the metallic material with water glass containing a coupling agent. It may include a fourth step of treating the metallic material with a coupling agent. The third step may be performed before, after, or both before and after the fourth step. The coupling agent may be one or more selected from the group consisting of 3-epoxypropyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-cyanopropyltriethoxysilane, 3-ureopropyltrialkoxysilane, and 3-acryloxypropyltrimethoxysilane. Prior to the first and second steps, a fifth and / or a sixth step may be included, wherein the fifth step involves oxidizing the metal material, and the sixth step involves plating the metal material. Before the third and fourth steps, a fifth and / or a sixth step may be included, wherein the fifth step is to oxidize the metal material and the sixth step is to plate the metal material.

[0012] Cross-reference to related documents: This application claims priority based on Japanese Patent Application No. 2022-008216 filed on January 21, 2022, and is included in this specification by reference to that basic application. Simple Explanation of the Diagram

[0013] [Figure 1A] shows the analysis results of each test piece using TOF-SIMS according to an embodiment of the present invention. [Figure 1B] shows the analysis results of each test piece using TOF-SIMS for the comparative examples of the present invention. Implementation

[0014] The preferred embodiments of the present invention are described in detail below using accompanying drawings, but the present invention is not limited thereto. Furthermore, based on the description in this specification, those skilled in the art will understand the purpose, features, advantages, and concept of the present invention, and those skilled in the art can easily reproduce the present invention based on the description in this specification.

[0015] The embodiments and specific examples of the invention described below are preferred embodiments of the invention and are used for illustration and explanation, and are not intended to limit the invention. Those skilled in the art will understand that various changes and modifications can be made based on the description in this specification within the intent and scope of the invention disclosed herein.

[0016] Metal components: The characteristics of the metal components disclosed in this specification are described in detail below. Furthermore, the surfaces of metal components having the characteristics described below refer to the same surfaces.

[0017] The metal components disclosed in this specification are partially or entirely covered by metal. Metallic materials only require the presence of metal on their surface; the portion of the metal surface inwards can be non-metallic, or the inner portion can also be metallic and the entire metallic material can be formed of metal. The surface and inner portions of a metallic component can be made of the same metal or different metals. When the metal inside and on the surface of a metallic material are made of the same metal, the entire component can be a single metal block. When the metal inside and on the surface of a metallic material are made of different substances, the thickness of the surface metal can exceed 1 nm, or can be 10 nm or more, or 100 nm or more.

[0018] Elemental analysis of the surface of metal components using Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) can better detect hydroxides (referred to as metal hydroxides in this specification) and SiO₂x of the same metal as the surface metal. The presence of SiO₂x enhances the heat and water resistance of the metal bonded to the resin. This is presumably because SiO₂x acts as a protective film against heat and water. Metal hydroxides and SiO₂x can also be detected and analyzed by elemental analysis of the metal surface using X-ray Photoelectron Spectroscopy (XPS). Generally, in TOF-SIMS, molecules within 1 nm of the surface are analyzed, while in XPS, molecules within several nm to tens of nm (e.g., within 2 nm, 10 nm, or 20 nm) of the surface are analyzed. Under this limitation, the analytical conditions are not particularly restricted, and can be appropriately determined by those skilled in the art to which the invention pertains.

[0019] In the elemental analysis spectra recorded using TOF-SIMS, the peak value of SiOx is preferably greater than that of metal hydroxide. This suggests that SiOx acts as a protective film, improving the heat and water resistance of the metal bonded to the resin and reducing transmission loss. It is speculated that the metal hydroxide and SiOx form a stronger bond through dehydration condensation. If there is more metal hydroxide than SiOx, more unbonded metal hydroxide remains on the surface, weakening the adhesion when bonding the metal to the resin. Alternatively, it may create tiny spaces between SiOx and the surface of the metal component, worsening transmission loss when used as a conductor. However, this explanation is not strictly confined to the above theories.

[0020] Elemental analysis using TOF-SIMS further detected silicon and alkali metals, with silicon showing a higher peak value than the aforementioned alkali metals. This reduces transmission loss when the metal component is used as a conductor.

[0021] The amount of silicon adhering to the surface of the metal component is preferably 30 μg / dm² or more, and more preferably 35 μg / dm² or more. If the amount of silicon adhering is low, SiO₂ will not form, or if it does form, the amount will be small, failing to achieve the effect of a protective film. To determine the amount of silicon adhering, the silicon-containing portion of the metal component surface or the entire metal component is dissolved in an acidic solution. The mass of silicon is then determined by high-frequency inductively coupled plasma emission spectroscopy (ICP emission spectroscopy), and the volume is calculated from the density. The obtained volume and mass are then divided by the area of ​​the silicon-bearing metal component to calculate the average thickness and the amount of silicon adhering per unit area. The total mass of silicon can also be determined by dissolving the metal with the silicon layer itself and detecting only the amount of silicon forming the silicon layer.

[0022] Furthermore, the leaching amount of alkali metal ions on the side of the metal component containing the SiO x layer is preferably 0.2 ppm or less, more preferably 0.18 ppm or less, and even more preferably 0.10 ppm or less. Here, the leaching amount of alkali metal is determined by measuring the mass of sodium ions, potassium ions, and lithium ions in the leaching solution using ICP emission spectroscopy, and the total amount is obtained. Specifically, when the metal component is a thin sheet such as a metal foil, a metal component cut into a size of 40 mm × 18 mm can be used as a test piece. Only the treated surface is immersed in 20 mL of pure water and treated at 121°C, 85% humidity, and 2 atm for 60 hours. The resulting solution is then subjected to ICP emission spectroscopy to determine the mass of alkali metal, thereby obtaining the leaching amount of alkali metal ions. Furthermore, if the alkali metal ions originate from the reagent used to prepare the SiO x layer, it is presumed that they are present in the SiO x layer, therefore, it is presumed that the leaching amount and content are highly correlated.

[0023] The more SiO2 there is, the smaller the loss tangent. On the other hand, alkali metals have high permittivity, so from the perspective of transmission loss, the less alkali metal, the better. Also, alkali metals can corrode metal components, so the lower the content, the better. However, this is not a strict rule.

[0024] Furthermore, in X-ray photoelectron spectroscopy (XPS), the types of metals and the compounds containing them (monomers, oxides, hydroxides, etc.) have unique waveforms. Therefore, by separating the peaks of each metal and each compound from the waveform peaks, the amount and composition of each metal and compound can be determined. For example, in the case of copper, the peaks of Cu2p3 are used for separation, and in the case of nickel, the peaks of Ni2p are used for separation, thus determining the amount and composition of each metal and the compounds containing it.

[0025] Furthermore, in the elemental analysis of the surface of the metal component using XPS, the nitrogen and silicon composition detected is preferably such that the atomic ratio of nitrogen to silicon (N / Si) is 0.04 or higher, more preferably 0.05 or higher, even more preferably 0.24 or higher, even more preferably 0.33 or higher, still more preferably 0.39 or higher, and preferably 0.80 or lower, even more preferably 0.54 or lower. If the atomic ratio of nitrogen to silicon (N / Si) is less than 0.04, an adequate coupling agent layer is not formed in the SiO₂x layer, thus reducing adhesion, and insufficient removal of alkali metals worsens transport losses. If the atomic ratio of nitrogen to silicon (N / Si) is greater than 0.80, the SiO₂x layer is not formed, or the SiO₂x layer is insufficient, resulting in poor heat resistance and moisture resistance. However, this is not strictly adhered to.

[0026] Furthermore, when measuring the surface L*, a*, and b* of metal components before and after treatment under high temperature, high humidity, and long duration conditions, and calculating the color difference ΔE*ab before and after treatment, ΔE*ab is preferably below 15, 14, 13, 12, or 11. When ΔE*ab is the average of several test results, its standard deviation is preferably below 4, more preferably below 2, and even more preferably below 1.95. Furthermore, treatment conditions can be, for example, treatment in pure water at 121°C, 85% humidity, and 2 atmospheres for 60 hours. If SiO₂x is not bonded to the surface, it is presumed that the surface is oxidized during high temperature and high humidity treatment, leading to a greater color difference.

[0027] ΔE *ab=[(ΔL *) 2+(Δa *) 2+(Δb *) 2] 1 / 2

[0028] The metal components disclosed in this specification may have a layer on their surface comprising or formed of a second metal (referred to herein as a second metal layer or second metal layer). The second metal is not particularly limited as long as it differs from the metal of the metal component, but is preferably selected from at least one metal or alloy thereof from the group consisting of tin, silver, zinc, aluminum, titanium, bismuth, chromium, iron, cobalt, nickel, palladium, gold, and platinum. Particularly when the metal component is copper, for heat resistance, it is preferable to include a metal with higher heat resistance than copper, such as nickel, palladium, gold, and platinum or their alloys. For example, in the case of nickel and nickel alloys, examples include pure nickel, nickel-copper alloys, nickel-chromium alloys, nickel-cobalt alloys, nickel-zinc alloys, nickel-manganese alloys, nickel-lead alloys, and nickel-phosphorus alloys.

[0029] The average thickness of the second metal layer in the vertical direction is not particularly limited, but it is preferably 10 nm or more, more preferably 15 nm or more, and even more preferably 20 nm or more. Furthermore, it is preferably 100 nm or less, more preferably 70 nm or less, and even more preferably 50 nm or less.

[0030] Alternatively, the amount of metal in the second metal layer, expressed as the weight of metal per unit area, is preferably 0.5 mg / cm² or more, more preferably 1.0 mg / cm² or more, and even more preferably 1.8 mg / cm² or more. Furthermore, it is preferably 100 mg / cm² or less, more preferably 80 mg / cm² or less, even more preferably 50 mg / cm² or less, even more preferably 10 mg / cm² or less, and still most preferably 5 mg / cm² or less.

[0031] The average thickness of the second metal layer in the vertical direction can be calculated by dissolving the metal forming the second metal layer in an acidic solution, measuring the amount of metal by ICP analysis, and then dividing the measured amount by the area of ​​the second metal layer. Alternatively, it can be calculated by dissolving the metal component with the second metal layer itself and only detecting and measuring the amount of metal forming the second metal layer.

[0032] When the metal component disclosed in this specification has a second metal layer, in the elemental analysis of the surface using XPS, the area percentage of the peak area of ​​the second metal hydroxide, relative to the sum of the peak areas obtained by waveform separation of the spectrum (e.g., the sum of the peak areas from metal hydroxide, metal oxide, and metal monomer), is preferably 70 area% or less, more preferably 67.8 area% or less, even more preferably 65.0 area% or less, even more preferably 63.0 area% or less, even more preferably 62.1 area% or less, and preferably greater than 0 area%, more preferably 20 area% or more, even more preferably 56.4 area% or more, and even more preferably 57.2 area% or more. The area percentage of the peak area of ​​the second metal oxide, relative to the sum of the peak areas from the second metal, is preferably 25 area% or less, more preferably 23.7 area% or less, and even more preferably 22.8 area% or less.

[0033] Regarding the characteristics of the aforementioned metal components, it is particularly desirable to have any of the following combinations. In any combination, the most important factor is that SiO₂ and metal hydroxides are bonded to the surface of the metal component in an appropriate amount, with less metal hydroxides being better, and furthermore, less alkali metals on the surface being better.

[0034] [1] By using TOF-SIMS elemental analysis, metal hydroxides and SiO x were detected, and the peak value of SiO x was greater than that of metal hydroxides.

[0035] [2] By using TOF-SIMS elemental analysis, metal hydroxides and SiO x were detected, and the peak value of SiO x was greater than that of metal hydroxides. Silicon and alkali metals were then detected on the surface, and the peak value of silicon was greater than that of the aforementioned alkali metals.

[0036] [3] Metal hydroxides and SiO x were detected by using TOF-SIMS elemental analysis, and nitrogen and silicon were detected by using XPS surface elemental analysis. The atomic ratio (N / Si) of nitrogen to silicon was 0.04 or more and 0.8 or less, or 0.05 or more and 0.8 or less.

[0037] [4] Having a second metal layer, SiO x was detected by elemental analysis using TOF-SIMS, and in the waveform separation of the surface spectrum using XPS, the area percentage of the peak area of ​​the second metal hydroxide relative to the sum of the peak areas from the second metal was 70 Area% or less or 63 Area% or less.

[0038] [5] It has a second metal layer. By using TOF-SIMS elemental analysis, SiO x was detected. In the waveform separation of the surface spectrum using XPS, the area percentage of the peak area of ​​the second metal hydroxide relative to the sum of the peak areas from the second metal is less than 70 Area%, and the amount of alkali metal leached from the surface is less than 0.2 ppm.

[0039] [6] By using XPS to analyze the surface, nitrogen and silicon were detected. The atomic ratio of nitrogen to silicon (N / Si) was 0.04 or more and 0.8 or less, or 0.05 or more and 0.8 or less. The color difference ΔE*ab before and after the alkali metal leaching test on the surface was 15 or less.

[0040] [7] By using the elemental analysis of the surface using XPS, nitrogen and silicon were detected, the atomic ratio of nitrogen to silicon (N / Si) was 0.04 or more and 0.8 or less, or 0.05 or more and 0.8 or less, and in the waveform separation of the surface spectrum using XPS, the area percentage of the peak area of ​​the second metal hydroxide relative to the sum of the peak areas from the second metal was 70 area% or less or 63 area% or less.

[0041] The arithmetic mean roughness (Ra) of the surface containing the SiO x layer of the metal component is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.03 μm or more, and more preferably 5.00 μm or less, more preferably 3 μm or less, and even more preferably 0.12 μm or less. Furthermore, the arithmetic mean roughness (Ra) represents the average absolute value of Z(x) (i.e., peak height and valley depth) in the profile curve (y=Z(x)) expressed by the following formula within the reference length l. Formula 1:

[0042] The maximum height roughness (Rz) of the surface containing the SiO x layer of the metal component is not particularly limited, but is preferably 0.1 μm or more, more preferably 0.28 μm or more, and more preferably 20.00 μm or less, more preferably 10.00 μm or less, and even more preferably 0.83 μm or less. Furthermore, the maximum height roughness (Rz) represents the sum of the maximum value of the height Zp of the convex portion and the maximum value of the depth Zv of the concave portion of the profile curve (y=Z(x)) within the reference length l.

[0043] Furthermore, Ra and Rz can be calculated according to the method specified in JIS B 0601:2001 (based on the international standard ISO4287-1997).

[0044] Manufacturing methods for metallic materials: The following describes the implementation of the manufacturing methods for the aforementioned metallic components.

[0045] (1) Metallic materials Materials for preparing metal components are metallic materials whose surfaces are partially or completely covered by metal. The metallic material only requires the presence of metal on its surface; the portion inwards from the surface (i.e., the interior of the metallic material) can be non-metallic, or the interior portion can also be metallic, and the entire metallic material can be formed of metal. If the metal on the surface and interior of the metallic material are formed of different substances, the thickness of the surface metal can exceed 1 nm, or even 10 nm or more, or 100 nm or more. The surface metal can be formed by plating. The type of metal is not particularly limited; for example, it can be copper, nickel, zinc, aluminum, iron, magnesium, etc., or alloys such as copper alloys, nickel alloys, zinc alloys, aluminum alloys, iron alloys, magnesium alloys, etc., or binary alloys, ternary alloys, quaternary alloys, etc. The types of metal on the surface and the metal inside the metallic material can be the same or different.

[0046] (2) Oxidation treatment First, an oxide layer is formed on the surface of the metal material by oxidizing it. This oxidation process roughens the surface of the metal material, increasing the adhesion of the metal component to the resin.

[0047] Before this oxidation step, roughening treatments such as soft etching or etching can be performed. Furthermore, degreasing, acid washing to remove the natural oxide film to homogenize the surface, and alkaline treatment to prevent acid from being carried into the oxidation step can also be performed before oxidation. The method of alkaline treatment is not particularly limited, but a 0.1~10 g / L alkaline aqueous solution is preferred, and a 1~2 g / L alkaline aqueous solution is even more preferred. An alkaline aqueous solution, such as sodium hydroxide solution, can be used, and treatment at 30~50 °C for 0.5~2 minutes is sufficient.

[0048] The oxidation treatment method is not particularly limited; it can be formed using an oxidizing agent, or by heat treatment or anodizing.

[0049] The oxidizing agent is not particularly limited; for example, aqueous solutions of sodium chlorite, sodium hypochlorite, potassium chlorate, and potassium perchlorate can be used. Various additives (such as phosphates like trisodium phosphate dodecahydrate) or surface-active molecules can be added to the oxidizing agent. Examples of surface-active molecules include oszoin, oszoin macrocycles, expanded oszoin, condensed oszoin, oszoin linear polymers, oszoin sandwich coordination complexes, oszoin arrays, silanes, tetraorgano-silanes, aminoethyl-aminopropyl-trimethoxysilane, (3-aminopropyl)trimethoxysilane, (1-[3-(trimethoxysilyl)propyl]urea)(l-[3-(Trimethoxysilyl)propyl]urea), (3-aminopropyl)triethoxysilane, and (3-epoxypropyloxypropyl) Trimethoxysilane, (3-chloropropyl)trimethoxysilane, (3-epoxypropyloxypropyl)trimethoxysilane, dimethyldichlorosilane, 3-(trimethoxysilyl)propyl methacrylate, ethyltriethoxysilane, triethoxy(isobutyl)silane, triethoxy(octyl)silane, tris(2-methoxyethoxy)(vinyl)silane, trichlorotrimethylsilane, methyltrichlorosilane, silica tetrachloride, tetraethoxysilane, phenyltrimethoxysilane, trichlorotriethoxysilane, vinyl-trimethoxysilane, amines, sugars, etc.

[0050] Various additives (such as phosphates like trisodium phosphate dodecahydrate) or surfactants can be added to the oxidant to adjust the precipitation of copper oxides. Examples of surfactants include violetin, violetin macrocycles, expanded violetin, condensed violetin, violetin linear polymers, violetin sandwich coordination complexes, violetin arrays, silanes, tetraorgano-silanes, aminoethyl-aminopropyl-trimethoxysilanes, (3-aminopropyl)trimethoxysilanes, (1-[3-(trimethoxysilyl)propyl]urea), (3-aminopropyl)triethoxysilanes, (3-epoxypropyloxypropyl)trimethoxysilanes, and (3-chloropropyl)trimethoxysilanes. Silanes, (3-epoxypropyloxypropyl)trimethoxysilane, dimethyl dichlorosilane, 3-(trimethoxysilyl)propyl methacrylate, ethyltriethoxysilane, triethoxy(isobutyl)silane, triethoxy(octyl)silane, tris(2-methoxyethoxy)(vinyl)silane, trichlorotrimethylsilane, methyltrichlorosilane, silica tetrachloride, tetraethoxysilane, phenyltrimethoxysilane, trichlorotriethoxysilane, vinyl-trimethoxysilane, amines, sugars, etc.

[0051] The oxidation reaction conditions are not particularly limited, but the preferred temperature of the oxidizing solution is 40~95 ℃, more preferably 45~80 ℃. The preferred reaction time is 0.5~30 minutes, more preferably 1~10 minutes.

[0052] For metal oxide layers, a solvent can be used to adjust the protrusions on the surface of the oxidized metal material. The solvent used in this dissolution step is not particularly limited, but a chelating agent is preferred, especially a biodegradable chelating agent, such as ethylenediaminetetraacetic acid, dihydroxyethylglycine, tetrasodium L-glutamyl diacetate, ethylenediamine-N,N'-disuccinic acid, sodium 3-hydroxy-2,2'-iminodisuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, disodium N-(2-hydroxyethyl)iminodiacetate, sodium gluconate, etc. The pH value of the dissolving solution is not particularly limited, but it is preferably alkaline, more preferably pH 8-10.5, even more preferably pH 9.0-10.5, and even more preferably pH 9.8-10.2.

[0053] The surface of this metal oxide layer can be reduced using a reducing agent, in which case cuprous oxide can be formed on the surface of the metal oxide layer. Examples of reducing agents used in this reduction step include dimethylamine borane (DMAB), diborane, sodium borohydride, and hydrazine.

[0054] When copper is used as a metal to form circuits on printed wiring substrates or semiconductor packaging substrates, the resistivity of pure copper is 1.7 × 10⁻⁸ (Ωm). In comparison, the resistivity of copper oxide is 1~10 (Ωm), and the resistivity of cuprous oxide is 1 × 10⁶~1 × 10⁷ (Ωm). Therefore, the conductivity of the copper oxide layer is low. Even if a large amount of copper oxide layer is transferred to the resin substrate, transmission loss due to the skin effect is not likely to occur.

[0055] (3) Second metal layer formation process The second metal layer can be formed, for example, by plating on the surface of a metal material or a metal oxide layer, as a plating film. The plating method is not particularly limited, and can include, for example, electroplating, electroless plating, chemical formation treatment, sputtering, vacuum evaporation, etc. However, to form a uniform thin plating film, electroplating is preferred.

[0056] In electroplating, a charge is also required to reduce a portion of the oxide in the metal oxide layer. Therefore, in order to form a thickness within a better range, it is preferable to apply a charge of 15 C / dm² or more to 90 C / dm² or less.

[0057] Furthermore, the current density is preferably below 5 A / dm². If the current density is too high, the plating may concentrate on the protrusions, making it difficult to form a uniform plating. In addition, the current intensity can be varied between the period of partial reduction of the oxide in the metal oxide layer and the period of plating.

[0058] For example, in nickel plating, the bath composition preferably includes, for example, nickel sulfate (100 g / L~350 g / L), nickel aminosulfonate (100 g / L~600 g / L), nickel chloride (0 g / L~300 g / L) and mixtures thereof, and may also include sodium citrate (0 g / L~100 g / L) or boric acid (0 g / L~60 g / L) as additives.

[0059] Furthermore, these plating conditions can be easily adjusted according to the metal being coated or the required thickness.

[0060] (4) Water glass treatment The manufacturing method of the metal component includes a step of forming SiOx in the metal material. The method for forming SiOx is not particularly limited, but in the case of liquid treatment, water glass treatment is preferred. Through this treatment, the hydroxyl groups of the hydroxide contained in the metal material bond with the water glass, enhancing the acid resistance when bonded to resin.

[0061] Before water glass treatment, various treatments can be performed, such as degreasing, acid washing to remove the natural oxide film to homogenize the surface, alkaline treatment to prevent acid from being carried into subsequent steps after acid washing, soft etching or etching, and roughening treatment such as oxidation.

[0062] The water glass used for treating metallic materials is an aqueous solution of alkali metal silicates. Alkali metal silicates are represented by M₂O‧nSiO₂ (where M is any one of sodium, lithium, or potassium), but in the water glass, M₂O and SiO₂ are mixed in various proportions. The type of water glass used for treating metallic materials is not particularly limited, but n of 2 to 4 is preferred.

[0063] The specific method for water glass treatment is not particularly limited. Water glass can be applied to the metal surface using a roller or bar coater, sprayed onto the metal surface using a sprayer, or the metal material can be immersed in water glass. The concentration of M₂O‧nSiO₂ in the water glass is not particularly limited, and can be 0.1%~20%, 0.5%~10%, or 2%~5%. The reaction conditions are not particularly limited, but the treatment temperature is preferably 10℃~95℃, more preferably 20℃~85℃. When treating metal surfaces, since it reacts with hydroxides, the treatment temperature is preferably above 50℃. The treatment time is preferably 1 second to 10 minutes. Water glass treatment can be performed several times.

[0064] The metallic material is treated with water glass and then dried. Drying can be achieved by blowing away moisture with air or by heating. When heating, the preferred temperature is 30°C to 250°C, and more preferably above 50°C to form the SiO₂ layer. The preferred heating time is 10 seconds to 60 minutes.

[0065] A soluble coupling agent (hereinafter referred to as the mixture) is used in water glass for treating metallic materials. The concentration of the coupling agent is not particularly limited, but is preferably 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or more by weight, and more preferably 20%, 15% or less by weight.

[0066] (5) Coupling agent treatment Coupling agents have two or more different functional groups. By dehydrating and condensing the functional groups with hydroxyl groups on the metal surface or forming chemical bonds with organic materials, substances with different functional groups can be combined with each other.

[0067] The coupling agent used for processing metallic materials is not particularly limited, but silane coupling agents are preferred, especially those having 2 or 3 hydrolyzable groups, which are preferably methoxy or ethoxy groups. Specifically, 3-epoxypropyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-cyanopropyltriethoxysilane, 3-ureidopropyltrialkoxysilane, 3-acryloxypropyltrimethoxysilane, etc.

[0068] The specific method of coupling agent treatment is not particularly limited. The coupling agent can be applied to the metal surface using a roller or bar coater, sprayed onto the metal surface using a sprayer, or the metal material can be immersed in the coupling agent. The solvent used in the coupling agent solution can be water, organic solvents, or mixtures thereof. The concentration of the coupling agent is not particularly limited, but is preferably 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9% or more by weight percentage, and more preferably 20%, 15%, or less than 10%.

[0069] Furthermore, the coupling agent can be dissolved in water glass used for treating metallic materials (hereinafter, this solution is referred to as the mixture). The concentration of the coupling agent is not particularly limited, but is preferably 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9% or more by weight percentage, and even more preferably 20%, 15%, or 10% or less.

[0070] The metallic material is treated with a coupling agent solution and then dried. The drying temperature and time are not particularly limited as long as the solvent can be completely evaporated. It is preferred to dry at 70°C for more than 1 minute, more preferably at 100°C for more than 1 minute, and even more preferably at 110°C for more than 1 minute.

[0071] This coupling process provides the metal component with nitrogen compounds detected in the elemental analysis of the metal component surface using XPS, as described above. Examples of nitrogen compounds include coupling agents or silicones containing amine, mercapto, isocyanurate, urea, or isocyanate groups.

[0072] (6) Specific manufacturing methods for metal components The method for manufacturing metal components using metallic materials includes a first step and a second step, wherein the first step involves treating the metallic material with a coupling agent, and the second step involves treating the metallic material with water glass. The order of the first and second steps is not particularly limited if each step is performed at least once; for example, it can be any of the following.

[0073] (A) Step 1 is followed by Step 2. (B) Step 2 is followed by Step 1. (C) Step 1 is followed by Step 2, then Step 1 again. Within each step, each process can be performed several times consecutively.

[0074] Furthermore, as shown in the examples, if the first step is performed after the second step, the enhancement effect on moisture resistance when bonded to the resin is high, and the reduction effect on transport loss is also high. This is presumably because the removal of alkali metals is effectively carried out, but this is not a strict limitation. In addition, the SiOx formed in the first step has better reactivity with the reactive groups of the coupling agent compared to metal components, so various coupling agents can be used, easily achieving the effect of enhancing adhesion through the coupling agent. Also, if the first step is performed before the second step, the enhancement effect on heat resistance when bonded to the resin is high. This is presumably because the metal hydroxide reacts with the coupling agent, effectively reducing the metal hydroxide, and the coupling agent undergoes dehydration condensation with water glass to form a stable bond, but this is not a strict limitation. Furthermore, if the first step is performed before or after the second step, both moisture resistance and heat resistance are enhanced, thereby effectively reducing transport loss.

[0075] When using a mixture, the coupling agent treatment and water glass treatment can be performed simultaneously in one treatment (hereinafter referred to as the mixture treatment). However, more than one coupling agent treatment may be performed before and / or after the mixture treatment.

[0076] Before the first step, the metal material may undergo the above-mentioned oxidation treatment and / or second metal layer formation treatment.

[0077] Method of using metal components: The metal components of the present invention are suitable for use as components requiring high heat resistance, moisture resistance, and adhesion to resin when bonding metal to resin. For example, if copper is used as the metal, it is suitable for copper wiring, copper pillars, and lead frames of printed circuit boards, which are laminates containing a resin substrate on a copper surface, or it can be used for positive or negative current collectors of lithium-ion batteries.

[0078] Example: (1) Manufacturing of metal components In this embodiment, copper foil is used as the metal material for manufacturing metal components, except for test piece 5. Aluminum foil is used for test piece 5. The processing of the metal materials is summarized in Table 1. Each processing method is described in detail below. Table 1 Test piece number 1 2 3 4 5 Oxidation Oxidizing agent potassium hydroxide g / L twenty one twenty one twenty one - - Sodium chlorite g / L 227.5 227.5 227.5 - - 3-Epoxypropyloxypropyltrimethoxysilane g / L 0.5 0.5 0.5 - - Processing conditions temperature ℃ 50 50 50 - - time Second 60 60 60 - - Metal layer Electroplating solution Nickel sulfate g / L 240 240 Refer to the main text of the instruction manual 240 - boric acid g / L 30 30 30 - Processing conditions temperature ℃ 45 45 20 45 - time Second 60 60 45 350 - Current density A / dm 2 0.5 0.5 0.5 0.5 - coupling Coupling agent KBE-903 vol% - 3 3 3 3 Processing conditions temperature ℃ - twenty three twenty three twenty three twenty three time minute - 1 1 1 1 Firing conditions temperature ℃ - 130 130 130 130 time minute - 1 1 1 1 Water glass Treatment solution Water glass (Types of salt) g / L 41 (Sodium) 41 (Sodium) 41 (Sodium) 41 (Sodium) 41 (Sodium) KBE-903 vol% - - - - - Processing conditions temperature ℃ 80 80 80 80 80 time minute 1 1 1 1 1 Drying conditions temperature ℃ 100 100 100 100 100 time minute 1 1 1 1 1 coupling Coupling agent KBE-903 vol% 3 3 3 3 3 Processing conditions temperature ℃ twenty three twenty three twenty three twenty three twenty three time minute 1 1 1 1 1 Firing conditions temperature ℃ 130 130 130 130 130 time minute 1 1 1 1 1 Test piece number 6 7 8 9 10 11 Oxidation Oxidizing agent potassium hydroxide g / L twenty one twenty one twenty one twenty one - twenty one Sodium chlorite g / L 227.5 227.5 227.5 227.5 - 227.5 3-Epoxypropyloxypropyltrimethoxysilane g / L 0.5 0.5 0.5 0.5 - 0.5 Processing conditions temperature ℃ 50 50 50 50 - 50 time Second 60 60 60 60 - 60 Metal layer Electroplating solution Nickel sulfate g / L 240 240 240 240 240 240 boric acid g / L 30 30 30 30 30 30 Processing conditions temperature ℃ 45 45 45 45 45 45 time Second 60 60 60 60 350 60 Current density A / dm 2 0.5 0.5 0.5 0.5 0.5 0.5 coupling Coupling agent KBE-903 vol% 3 3 - - - - Processing conditions temperature ℃ twenty three twenty three - - - - time minute 1 1 - - - - Firing conditions temperature ℃ 130 130 - - - - time minute 1 1 - - - - Water glass Treatment solution Water glass (Types of salt) g / L 41 (potassium) 41 (Sodium) 41 (Sodium) - - 41 (Sodium) KBE-903 vol% - 3 - - - - Processing conditions temperature ℃ 80 80 80 - - 25 time minute 1 1 1 - - 1 Drying conditions temperature ℃ 100 100 100 - - R / T time minute 1 1 1 - - 1 coupling Coupling agent KBE-903 vol% 3 - - 3 3 3 Processing conditions temperature ℃ twenty three - - twenty three twenty three twenty three time minute 1 - - 1 1 1 Firing conditions temperature ℃ 130 - - 130 130 130 time minute 1 - - 1 1 1

[0079] (1-1) Metallic Materials In addition to test piece 5, the bright side (glossy side, which is flat compared to the opposite side) of copper foil from DR-WS (thickness: 18 μm) (manufactured by Furukawa Electric Co., Ltd.) was used. Test piece 5 used the lower-roughness side of aluminum foil (thickness: 11 μm) (manufactured by Mitsubishi Aluminum).

[0080] (1-2) Pretreatment In addition to Example 5, degreasing was performed by immersing the metal surface in a 40 g / L sodium hydroxide aqueous solution at 50 °C for 1 minute to remove dirt. The surface was then rinsed with water.

[0081] Next, the degreased metal material is immersed in a 10% by weight sulfuric acid aqueous solution at 25°C for 2 minutes to perform acid pickling and remove the oxide film on the metal surface. The metal material is then rinsed with water.

[0082] In addition, for test pieces 1-3, 6-9, and 11, the acid-washed metal materials were immersed in an aqueous solution of 1.2 g / L sodium hydroxide (pH 10.5) at 40°C for 1 minute to prevent the acid from being carried into the next step, namely oxidation treatment.

[0083] (1-3) Oxidation treatment For test pieces 1-3, 6-9, and 11, the bright side of the copper foil was oxidized at 50°C for 60 seconds using the oxidizing agent listed in Table 1 (a mixed solution of 227.5 g / L sodium chlorite, 21.0 g / L potassium hydroxide, and 0.5 g / L 3-epoxypropyloxypropyltrimethoxysilane), forming fine protrusions on the surface of the copper foil. Afterwards, it was washed with water at room temperature for 1 minute.

[0084] (1-4) Electroplating treatment After oxidation treatment, for test pieces 1, 2, 6-9, and 11, nickel plating was performed on the bright side of the copper foil using the plating solution (240 g / L nickel sulfate; 30 g / L boric acid) as described in Table 1, under the conditions described in Table 1, to form a nickel layer on the surface. For test pieces 4 and 10, no oxidation treatment was performed, and nickel plating was performed on the bright side of the copper foil using the plating solution (240 g / L nickel sulfate; 30 g / L boric acid) as described in Table 1, under the conditions described in Table 1, to form a nickel layer on the surface. For test piece 3, zinc plating was performed using the plating solution (10 g / L zinc oxide; 115 g / L sodium hydroxide; 5 mL / L 9500A (Japan Surface Chemicals Co., Ltd.); 0.5 mL / L 9500B (Japan Surface Chemicals Co., Ltd.); 10 mL / L Hypersoft (Japan Surface Chemicals Co., Ltd.)) as described in Table 1, under the conditions described in Table 1, to form a zinc layer on the surface. Afterward, all test pieces were washed with water at room temperature for 1 minute and then dried.

[0085] (1-5) Coupling Process I For test pieces 2-4, 6, and 7, coupling treatment was performed after electroplating treatment (1-4). For test piece 5, no surface treatment such as oxidation or electroplating was performed; commercially available aluminum foil was used directly for coupling treatment. The coupling treatment involved immersing the metal foil of test pieces 2-7 in 3 vol% KBE-903 (3-aminopropyltriethoxysilane) (Shin-Etsu Chemical Co., Ltd.) under the conditions described in Table 1. Afterward, all test pieces were washed with water and dried at 130°C for 1 minute.

[0086] (1-6) Water Glass Treatment Regarding test pieces 2-7, after the coupling treatment in (1-5), and for test pieces 1, 8, and 11, after the electroplating treatment in (1-4), the metal foil was immersed in 41 g / L water glass and treated with water glass under the reaction conditions described in Table 1. However, regarding test piece 11, it is speculated that the water glass treatment was carried out under the inappropriate condition of 25°C, resulting in a high residual amount of metal hydroxide, and the test piece did not react with the water glass, or the reaction was insufficient. As for the water glass, potassium silicate aqueous solution (potassium silicate solution (Fujifilm and Wako Pure Chemical Industries Co., Ltd.), potassium silicate 48.5-52.5 wt%, SiO2 / K2O ratio 1.8-2.2) was used for test piece 6, and sodium silicate aqueous solution (sodium silicate 52-57 wt%, SiO2 / Na2O ratio 2.06-2.31) was used for the other test pieces. Furthermore, water glass containing 3 vol% KBE-903 was used for test piece 7. Afterward, all test pieces were washed with water and dried at 100°C for 1 minute.

[0087] (1-7) Coupling Process II Test pieces 1-6 and 11 are metal foils treated with water glass as described in step (1-6). Test pieces 9 and 10 are metal foils that have undergone electroplating treatment as described in step (1-4). All test pieces were immersed in 3 vol% KBE-903 (3-aminopropyltriethoxysilane) (Shin-Etsu Chemical Co., Ltd.) and coupled under the conditions described in Table 1. Afterward, all test pieces were washed with water and dried at 130°C for 1 minute.

[0088] (2) Testing of metal components I (2-1) Surface roughness (Ra and Rz)

[0089] For the processed surfaces of metal components, the surface shape of copper foil was measured using an OPTELICS H1200 conjugate scanning electron microscope (Lasertec Corporation). Ra and Rz were calculated according to the method specified in JIS B 0601:2001 (based on international standard ISO 4287-1997). Measurement conditions: scan width 100 μm, scan type Area, blue light source, cut-off value 1 / 5. Objective lens x100, eyepiece x14, digital zoom x1, Z-spacing set to 10 nm. Data were obtained from three locations, and the average of the three locations was used as Ra and Rz. The results are shown in Table 2. Table 2 Test piece number 1 2 3 4 5 6 7 Ra μm 0.06 0.04 0.07 0.03 0.12 0.04 0.04 Rz μm 0.43 0.38 0.47 0.28 0.83 0.39 0.40 Test piece number 8 9 10 11 Ra μm 0.05 0.05 0.03 0.04 Rz μm 0.41 0.40 0.29 0.39

[0090] (2-2) Average thickness of the metal layer and Si content per unit area The average thickness of the nickel layer formed on the surface by electroplating and the amount of silicon per unit area bonded to the metal surface by water glass treatment and coupling treatment were measured.

[0091] First, the metal component was dissolved by treating it with 12% nitric acid. The mass of nickel and silicon in the dissolution solution was determined using an ICP-OES 5100 SVDV instrument (manufactured by Agilent Technologies). Then, the volume of nickel was calculated using its density. The average thickness of the nickel layer was calculated by dividing the obtained mass and volume by the area of ​​the metal component where the nickel layer was dissolved. Similarly, the mass of silicon per unit area was calculated. The results are shown in Table 3. Table 3 Test piece number 1 2 3 4 5 6 7 Metal layer type nickel nickel Zinc nickel aluminum nickel nickel Nickel layer thickness (nm) 35 35 - 400 - 35 35 Si amount μg / dm 2 59 62 71 50 45 58 32 Test piece number 8 9 10 11 Metal layer type nickel nickel nickel nickel Nickel layer thickness (nm) 35 35 400 35 Si amount μg / dm 2 56 27 twenty two 42

[0092] (2-3) Time-of-flight secondary ion mass spectrometry (TOF-SIMS) For the fabricated metal components, a TRIFT V nano-TOF device (manufactured by ULVAC-PHI Corporation) was used to detect metals and metal compounds under the conditions shown in Table 4. Representative results are shown in Figure 1. Table 4 condition settings Primary ions 30 kV, Bi3++ Measurement mode Bunching Quality range 0-1850u raster size 100 μm × 100 μm Measurement time 30 frames / 1 field of view Charge neutralization none Pixel count 512×512 pixels GCIB - spectrum Nitrogen compounds: positive spectrum SiOx: Negative spectrum

[0093] Furthermore, the results are summarized in Table 5 for the following points.

[0094] [1] Whether there is a peak of SiO x (if present, indicate with ○, if absent, indicate with ╳). [2] Whether the peak value of SiO x is larger than that of the metal hydroxide (if larger, indicate ○, if not larger, indicate ╳). [3] Whether the peak value of Si is larger than that of alkali metals (if larger, indicate with ○, if not larger, indicate with ╳). Table 5 condition [1] There is a peak of SiO x. [2] The peak value of SiO₂ is larger than that of metal hydroxides. [3] The peak value of Si is larger than that of alkali metals. Test piece number 1 2 3 4 5 6 7 [1] ○ ○ ○ ○ ○ ○ ○ [2] ○ ○ ○ ○ ○ ○ ○ [3] ○ ○ ○ ○ ○ ○ ○ Test piece number 8 9 10 11 [1] ○ ╳ ╳ ○ [2] ○ ╳ ╳ ╳ [3] ╳ ○ ○ ○

[0095] (2-4)XPS The processed surfaces of metal components were analyzed using narrow spectrum X-ray photoelectron spectroscopy (XPS). The apparatus used was a Quantera SXM (ULVAC-PHI).

[0096] [1] Survey spectrum First, detect elements using the following conditions. X-ray beam diameter: 100 μm (25W 15kV) Pass energy: 280eV, 1eV step Line analysis: φ100 μm × 700 μm Total number of times: 6

[0097] [2] Narrow spectrum For the elements detected in [1], a narrow spectrum was obtained under the following conditions. Regarding nitrogen and silicon in the detected components, the proportion (atomic percentage) of each component was determined when the total number of elements in the two components was taken as 100 atom%, and the ratio of (atomic percentage of nitrogen) / (atomic percentage of silicon) was calculated. The ratio of the number of nitrogen atoms to the number of silicon atoms was then obtained. The results are shown in Table 6. X-ray beam diameter: 100 μm (25W 15kV) Pass energy: 112eV, 0.1eV step Line analysis: φ100 μm × 700 μm

[0098] [3] Waveform separation For the Ni2p peak detected in [1], waveform separation was performed on Ni, NiO and Ni(OH)2, and the proportion (area percentage) of the individual peak area when the total peak area of ​​these three components was taken as 100 Area% was calculated. These results are shown in Table 6. As for Cu2p3 (940-945eV), which was presumed to contain peaks of CuO and Cu(OH)2, it was determined that no peak was detected because the waveform was so small as to be noise. Table 6 Test piece number 1 2 3 4 5 6 7 Narrow spectrum N1s atom% 19 33 35 28 31 33 25 Si2p atom% 81 67 65 72 69 67 75 N / Si - 0.24 0.50 0.54 0.39 0.45 0.49 0.33 Ni2p waveform separation Ni Area% 17.7 19.1 - 19.8 - 18.9 18.0 NiO Area% 17.3 23.7 - 22.8 - 20.1 19.9 Ni(OH)2 Area% 65.0 57.2 - 57.4 - 61.0 62.1 total Area% 100.0 100.0 - 100.0 - 100.0 100.0 Test piece number 8 9 10 11 Narrow spectrum N1s atom% 4 48 47 25 Si2p atom% 96 52 53 75 N / Si - 0.04 0.92 0.89 0.33 Ni2p waveform separation Ni Area% 11.7 17.2 17.9 11.1 NiO Area% 20.5 26.1 25.7 18.5 Ni(OH)2 Area% 67.8 56.7 56.4 70.4 total Area% 100.0 100.0 100.0 100.0

[0099] (2-5) Alkali metal leaching test Metal components were cut into 40 mm × 18 mm pieces to create metal sheets. The untreated surfaces were masked with masking tape (plating masking tape 851A:3M), and leaching tests were performed only on the treated surfaces. Ten metal sheets were immersed in 20 mL of pure water and treated at 121°C, 85% humidity, and 2 atm for 60 hours to obtain a metal treatment solution. Furthermore, to determine only alkali metals from the metal surface, metal foils with masking tape applied to one side of untreated metal components were immersed in pure water, and the immersion water was simultaneously treated under the same conditions. The resulting treatment solution was input into an ion chromatography system consisting of a 940 IC Vario Two ChS / PP and a 930 Compact IC Flex Oven / SeS / PP / Deg (Metrohm) to determine the leaching amounts of sodium and potassium. As shown in the following formula, the mass of sodium and potassium leached from the metal component is calculated by subtracting the mass of sodium and potassium detected from the leaching solution of the untreated metal component with masking tape applied to one side from the measured mass of sodium and potassium. The results are shown in Table 7.

[0100] The alkali metal leaching amount of test pieces 1-11 = (mass of alkali metal in test pieces 1-11) - (mass of metal leached from untreated metal components) Table 7 Test piece number 1 2 3 4 5 6 7 alkali metals Sodium (ppm) 0.00 0.00 0.01 0.00 0.00 0.04 0.06 Potassium (ppm) 0.01 0.01 0.02 0.01 0.01 0.01 0.05 Total (ppm) 0.01 0.01 0.03 0.01 0.01 0.05 0.11 Test piece number 8 9 10 11 alkali metals Sodium (ppm) 0.19 0.04 0.02 0.01 Potassium (ppm) 0.04 0.03 0.04 0.02 Total (ppm) 0.23 0.07 0.06 0.03

[0101] (2-6) Determination of color change before and after dissolution test The color difference ΔE*ab before and after the dissolution test was calculated from the (L*, a*, b*) on the surface of the metal sheet in (2-5). Furthermore, the dissolution test, except that it used only one metal sheet, was conducted under the same conditions as in (2-5). The (L*, a*, b*) were measured using an NF999 spectrophotometer manufactured by Nippon Denshoku Kogyo Co., Ltd. (illumination conditions: C; field of view angle: 2; measurement items: L*, a*, b*). Three positions were measured on each metal sheet, and the average value was calculated. The results are recorded in Table 8.

[0102] Formula 2: ΔE *ab=[(ΔL *) 2+(Δa *) 2+(Δb *) 2] 1 / 2 Table 8 Test piece number 1 2 3 4 5 6 7 average value 7 6 11 7 4 8 8 Test piece number 8 9 10 11 average value 9 37 18 20

[0103] (2-7) Heat resistance and water resistance For the treated surfaces of metal components, resin (TU-933P+) insulating material is laminated and heat-pressed using a vacuum high-pressure press.

[0104] (2-7-1) Reduction rate of peel strength after heat treatment After hot pressing, unwanted portions are removed to make the metal component 10 mm wide, and test pieces are fabricated. For the freshly fabricated test pieces, and for test pieces that have undergone three cycles of immersion in a welding bath at 288°C for 10 seconds followed by a 60-second pull-out, the peel strength (kgf / cm) is determined using a 90° peel test (Japanese Industrial Standard (JIS) C5016). The measured values ​​are referred to as the initial peel strength and the peel strength after heat treatment, respectively.

[0105] Calculate the ratio of (initial peel strength - peel strength after heat treatment) to the initial peel strength (recorded as the reduction rate of peel strength after heat treatment in Table 9).

[0106] (2-7-2) Next, heat resistance After hot pressing, the test pieces were cut to a size of 25 mm × 25 mm. For test pieces immersed in a welding bath at 300°C for 5 minutes, the metal component was peeled off from the resin, and the peeled surface of the metal component was observed. If more than 50% of the peeled surface had resin adhering to it, it was considered that the resin had been damaged internally and was rated as ○; if the amount of resin adhering was less than 50% of the peeled surface, it was considered that the peeling occurred at the interface between the metal component and the resin and was rated as ╳.

[0107] (2-7-3)Moisture resistance After hot pressing, unwanted portions are removed to ensure the metal component has a width of 10 mm, and test pieces are prepared. After being placed in a sealed space at 121°C, 85% humidity, and 2 atmospheres for 20 hours, the test pieces are immersed in a welding bath at 288°C for 10 seconds, and the peel strength (kgf / cm) is determined using a 90° peel test (Japanese Industrial Standard (JIS) C5016). The measured value is referred to as the wet-treated peel strength. The ratio of (initial peel strength - wet-treated peel strength) to the initial peel strength is calculated (reduced as the wet-treated peel strength reduction rate in Table 9).

[0108] (2-7-4) Result The results above are shown in Table 9. Table 9 Test piece number 1 2 3 4 5 6 7 Initial peel strength kgf / cm 0.54 0.57 0.49 0.42 0.38 0.56 0.57 Peel strength after heat treatment kgf / cm 0.45 0.52 0.45 0.40 0.33 0.50 0.52 Reduction in peel strength after heat treatment % 16.7 8.8 8.2 4.8 13.2 10.7 8.8 Next, heat resistance* ○ ○ ○ ○ ○ ○ ○ Peel strength after wet treatment kgf / cm 0.54 0.54 0.48 0.4 0.37 0.52 0.50 Reduction in peel strength after wet treatment % 0.0 5.6 2.1 5.0 2.7 7.7 14.0 Test piece number 1 2 3 4 Initial peel strength kgf / cm 0.41 0.50 0.14 0.51 Peel strength after heat treatment kgf / cm 0.36 0.39 0.10 0.40 Reduction in peel strength after heat treatment % 12.2 22.0 28.6 21.6 Next, heat resistance* ○ ╳ ╳ ╳ Peel strength after wet treatment kgf / cm 0.34 0.41 - 0.40 Reduction in peel strength after wet treatment % 20.6 22.0 - 27.5 *○: Damage inside; ╳: Damage at the interface

[0109] (2-8) Summary The peel strength reduction rate of test pieces 1-8 after heat treatment was less than 20%, and the metal remained bonded to the resin after heat treatment, exhibiting excellent heat resistance (see Table 9). Like this:

[0110] [A] In the elemental analysis of the surface using TOF-SIMS, the peak of SiO x was detected (see Table 5 [1]). The peak value of SiO x is greater than that of the metal hydroxide (see Table 5 [2]).

[0111] [B] In the elemental analysis of the surface using TOF-SIMS, a peak of SiO₂ was detected (see Table 5 [1]). In the elemental analysis of the surface using XPS, when the Ni₂p waveform was separated, the area percentage of the peak area of ​​nickel hydroxide relative to the sum of the peak areas of nickel compounds (including nickel, nickel oxides, and nickel hydroxides) was less than 70 Area% (see Table 6).

[0112] [C] In the elemental analysis of the surface using XPS, the atomic ratio of nitrogen to silicon (N / Si) is greater than or equal to 0.04 and less than or equal to 0.8 (refer to Table 6), and the maximum color difference ΔE*ab before and after the alkali metal leaching test is less than or equal to 15 (refer to Table 7);

[0113] [D] In the elemental analysis of the surface using XPS, the nitrogen to silicon atomic ratio (N / Si) is 0.04 or higher and 0.8 or lower, and the area percentage of the peak area of ​​nickel hydroxide relative to the sum of the peak areas of nickel compounds (including nickel, nickel oxides, and nickel hydroxides) is 70% or lower (see Table 6);

[0114] By manufacturing metal components that meet any of the above requirements, it is possible to produce heat-resistant metal components that can be bonded to resin. A specific manufacturing method could be, for example, by treating the surface of the metal material with water glass.

[0115] In particular, test pieces 2-7 showed a peel strength reduction rate of less than 15% after heat treatment, and exhibited high heat resistance when bonded to the resin. Like this:

[0116] [E] In the elemental analysis of the surface using XPS, the nitrogen to silicon atomic ratio (N / Si) is 0.04 or higher and 0.8 or lower, and the area percentage of the peak area of ​​nickel hydroxide relative to the sum of the peak areas of nickel compounds (including nickel, nickel oxides, and nickel hydroxides) is 63 Area% or lower (see Table 6);

[0117] [F] In the elemental analysis of the surface using TOF-SIMS, a peak of SiO₂ was detected (see Table 5 [1]). In the elemental analysis of the surface using XPS, when the Ni₂p waveform was separated, the area percentage of the peak area of ​​nickel hydroxide relative to the sum of the peak areas of nickel compounds (including nickel, nickel oxides, and nickel hydroxides) was less than 63 Area% (see Table 6).

[0118] By manufacturing metal components that meet any of the above requirements, it is possible to manufacture metal components with greater heat resistance that can be bonded to resin.

[0119] On the other hand, the peel strength reduction rate of test pieces 1-7 after wet treatment was less than 20%, demonstrating excellent moisture resistance. Like this:

[0120] [G] In the elemental analysis of the surface using XPS, the atomic ratio of nitrogen to silicon (N / Si) is greater than or equal to 0.05 and less than or equal to 0.8 (refer to Table 6), and the maximum color difference ΔE*ab before and after the alkali metal leaching test is less than or equal to 15 (refer to Table 7);

[0121] [H] In the elemental analysis of the surface using TOF-SIMS, peaks of metal hydroxides, SiO₂, silicon, and alkali metals were detected. The peak value of SiO₂ was greater than that of metal hydroxides, and the peak value of silicon was greater than that of alkali metals (refer to Table 5 [1], [2], [3]).

[0122] [I] Elemental analysis of the surface using TOF-SIMS detected metallic hydroxides and SiO₂. Elemental analysis of the surface using XPS detected nitrogen and silicon, with a nitrogen / silicon atomic ratio (N / Si) of ≥0.05 and ≤0.8.

[0123] [J] In the elemental analysis of the surface using TOF-SIMS, a SiO x peak was detected (see Table 5 [1]). In the elemental analysis of the surface using XPS, when the Ni2p waveform was separated, the area percentage of the peak area of ​​nickel hydroxide relative to the sum of the peak areas of nickel compounds (including nickel, nickel oxide, and nickel hydroxide) was 70 Area% or less (see Table 6), and the amount of alkali metal leached from the surface was 0.2 ppm or less (see Table 7).

[0124] By manufacturing metal components that meet any of the above requirements, it is possible to produce metal components with high moisture resistance that can be bonded to resin. A specific manufacturing method could be, for example, by applying a coupling agent treatment to the surface of the metal material that is independent of the water glass treatment.

[0125] In particular, test pieces 2-6 showed a peel strength reduction rate of less than 10% after wet treatment, and exhibited excellent moisture resistance when bonded to resin. By performing coupling agent treatment before and after water glass treatment, metal components with greater moisture resistance when bonded to resin can be manufactured.

[0126] (3) Testing of Metal Components II (3-1) Methods for measuring transmission loss

[0127] Test pieces 1-3, 6-9, and 11 were laminated with a 100 μm thick TU-933P+ layer using a vacuum high-pressure press to fabricate a 100 mm long microstrip line. The circuit width was set to 230 μm, and the characteristic impedance was set to 50 Ω. A network analyzer N5227B (Keysight Technologies) (10MHz~67GHz) and a high-frequency extender WR12 (VDI) (55GHz~95GHz) were used to transmit a 90GHz signal along this transmission path. The S 21 (dB) per 100 mm was measured (=20×log(Vout / Vin)), and the S 21 per 1 mm was calculated.

[0128] (3-2) Results The results are shown in Table 10. Table 10 Test piece number 1 2 3 6 7 Transmission loss dB / mm -0.073 -0.072 -0.073 -0.073 -0.074 Test piece number 8 9 11 Transmission loss dB / mm -0.077 -0.078 -0.076

[0129] In test pieces 1-3, 6, and 7, the S 21 per 1 mm is greater than -0.075, and the transmission loss is less compared to test pieces 8, 9, and 11. In this way, by performing a coupling agent treatment on the surface of the metal material independently of the water glass treatment, metal components that meet the conditions of Table 5 [1], [2], and [3] can be produced, thereby producing metal components with less transmission loss.

[0130] Industrial applicability: According to the present invention, novel metal components can be provided.

[0131] none

Claims

1. A metal component comprising a first metal, wherein nitrogen and silicon are detected by elemental analysis of the surface of the metal component using X-ray photoelectron spectroscopy, wherein the atomic ratio (N / Si) of nitrogen and silicon is 0.04 or more and 0.8 or less, and the color difference ΔE*ab before and after alkali metal leaching test of the surface is 15 or less.

2. A metal component comprising a first metal and having a second metal layer on its surface, wherein nitrogen and silicon are detected by elemental analysis of the surface of the metal component using X-ray photoelectron spectroscopy, wherein the atomic ratio (N / Si) of nitrogen and silicon is 0.04 or more and 0.8 or less, and in waveform separation of the surface spectrum obtained by X-ray photoelectron spectroscopy, the area percentage of the peak area of ​​the hydroxide of the second metal relative to the sum of the peak areas from the second metal is 70% or less.

3. The metal component as claimed in claim 2, wherein, In waveform separation of surface spectra using X-ray photoelectron spectroscopy, the area percentage of the peak area of ​​the hydroxide of the second metal relative to the sum of the peak areas from the second metal is 63 Area% or less.

4. The metal component as claimed in item 2 or 3, wherein, The second metal is nickel.

5. The metal component as claimed in item 1 or 2, wherein, The atomic ratio (N / Si) of nitrogen and silicon is greater than 0.05 and less than 0.

8.

6. A metal component comprising a first metal, wherein elemental analysis of the surface of the metal component using time-of-flight secondary ion mass spectrometry detects hydroxides and SiOx of the first metal, and the peak value of SiOx is greater than the peak value of hydroxides of the first metal.

7. The metal component as claimed in claim 6, wherein, Elemental analysis of the surface using time-of-flight secondary ion mass spectrometry detected silicon and alkali metals, with the peak value of silicon being greater than that of the alkali metals.

8. The metal component as claimed in claim 6, wherein, Elemental analysis of the surface using X-ray photoelectron spectroscopy detected nitrogen and silicon, with a nitrogen / silicon atomic ratio (N / Si) of ≥0.05 and ≤0.

8.

9. A metal component comprising a first metal and having a second metal layer on its surface, wherein SiOx is detected by elemental analysis of the surface of the metal component using time-of-flight secondary ion mass spectrometry, and in waveform separation of the surface spectrum using X-ray photoelectron spectroscopy, the area percentage of the peak area of ​​the hydroxide of the second metal relative to the sum of the peak areas from the second metal is less than 70 Area%.

10. The metal component as claimed in claim 9, wherein, In waveform separation of surface spectra using X-ray photoelectron spectroscopy, the area percentage of the peak area of ​​the hydroxide of the second metal relative to the sum of the peak areas from the second metal is 63 Area% or less.

11. The metal component as claimed in item 9 or 10, wherein, The second metal is nickel.

12. The metal component as claimed in item 9 or 10, wherein, The amount of alkali metals leached from this surface is less than 0.2 ppm.

13. A method for manufacturing a metal component using a metallic material, comprising: a first step of treating the metallic material with a coupling agent; and a second step of treating the metallic material with water glass, wherein the metal component is a metal component comprising a first metal, and nitrogen and silicon are detected by elemental analysis of the surface of the metal component using X-ray photoelectron spectroscopy, wherein the atomic ratio (N / Si) of nitrogen and silicon is 0.04 or more and 0.8 or less, and the color difference ΔE*ab before and after alkali metal leaching test of the surface is 15 or less.

14. The method of manufacturing metal components using metallic materials as described in claim 13, wherein, The first step is performed before, after, or before and after the second step.

15. A method for manufacturing a metal component using a metallic material, comprising the step of treating the metallic material with water glass containing a coupling agent, the metallic component being a metal component comprising a first metal, wherein nitrogen and silicon are detected by elemental analysis of the surface of the metallic component using X-ray photoelectron spectroscopy, the atomic ratio (N / Si) of the nitrogen and silicon being 0.04 or more and 0.8 or less, and the color difference ΔE*ab of the surface before and after alkali metal leaching test being 15 or less.

16. The method of manufacturing metal components using metallic materials as described in claim 15, wherein, The process includes treating the metallic material with a coupling agent.

17. The method of manufacturing metal components using metallic materials as described in claim 16, wherein, The step of treating the metal material with water glass containing the coupling agent is performed before, after, or before and after the step of treating the metal material with the coupling agent.

18. A method for manufacturing metal components using metallic materials, as described in any of claims 13 to 17, wherein, The coupling agent is selected from one or more of the group consisting of 3-epoxypropyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-cyanopropyltriethoxysilane, 3-ureopropyltrialkoxysilane, and 3-acryloxypropyltrimethoxysilane.

19. A method for manufacturing metal components using metallic materials, as described in claims 13 or 14, wherein, Prior to the first step and the second step, there is a step of oxidizing the metal material and / or plating the metal material.

20. A method for manufacturing metal components using metallic materials, as described in claim 16 or 17, wherein, Prior to the steps of treating the metal material with water glass containing a coupling agent and the steps of treating the metal material with a coupling agent, the process includes an oxidation treatment of the metal material and / or a plating treatment of the metal material.

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