Metal component, metal-resin composite, and method for manufacturing a metal component

Abstract

The present invention provides a metal member with excellent bonding strength with resin members, a metal-resin composite using this metal member, and a method for manufacturing this metal member. [Solution] A metal component having a surface containing metal and having an average length AR of roughness motifs of 25 μm or more.

Description

Technical Field

[0001] The present disclosure relates to a metal member, a metal resin composite, and a method for manufacturing a metal member.

Background Art

[0002] A metal resin composite formed by joining a metal member containing a metal and a resin member containing a resin has properties derived from the metal member (such as conductivity and heat conductivity) and properties derived from the resin member (such as insulation), and is used in many applications such as vehicle structural parts. In the production of a metal resin composite, in order to increase the bonding strength with the resin member, a metal member having a roughened surface may be used. Such a metal member is described in, for example, Patent Document 1.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] There is room for improvement in the bonding strength between the metal member and the resin member in existing metal resin composites. The problem to be solved by one embodiment of the present disclosure is to provide a metal member having excellent bonding strength with a resin member, a metal resin composite using this metal member, and a method for manufacturing this metal member.

Means for Solving the Problems

[0005] The present disclosure includes the following aspects. <1> A metal member containing a metal and having a surface with an average length AR of a roughness motif of 25 μm or more. <2> The metal member according to <1>, wherein the metal contains copper. <3> The aforementioned metals include copper and metal M, which has a greater ionization tendency than copper. <1> The metal components described above. <4> The content of metal M in the aforementioned metal is 10% by mass to 45% by mass. <3> The metal components described above. <5> The aforementioned metals include copper and zinc. <1> ~ <4> A metal member as described in any one of the items. <6> The zinc content in the aforementioned metal is 10% to 45% by mass. <5> The metal components described above. <7> <1> ~ <6> A metal member as described in any one of the items, A metal-resin composite comprising a resin member containing resin and bonded to the surface thereof. <8> The intrinsic viscosity [η] of the resin is 0.4 dL / g or more. <7> The metal-resin composite described above. <9> The process includes a step of roughening the surface of a substrate containing metal, and the roughening process is: A first roughening treatment is performed by bringing a first etching solution containing an inorganic acid and free of nitrogen-containing heteroaromatic compounds into contact with the surface, A method for manufacturing a metal member, comprising: a second roughening treatment in which a second etching solution containing an inorganic acid and a nitrogen-containing heteroaromatic compound is brought into contact with the surface; and performing these steps in this order. <10> The concentrations of the inorganic acid D1 in the first etching solution and D2 in the second etching solution satisfy the equation: 0.7 ≤ D1 / D2 ≤ 1.5. <9> A method for manufacturing metal components as described above. <11> The process includes a step of pre-treating the surface by bringing a nitrogen-containing heteroaromatic compound into contact with it before the roughening treatment. <9> or <10> A method for manufacturing metal components as described above. <12> The second etching solution further contains an amine compound. <9> ~ <11> A method for manufacturing a metal member as described in any one of the items. <13> The aforementioned metal includes copper. <9> ~ <12> A method for manufacturing a metal member as described in any one of the items. <14> The aforementioned metals include copper and metal M, which has a greater ionization tendency than copper. <9> ~ <13> A method for manufacturing a metal member as described in any one of the items. <15> The aforementioned metals include copper and zinc. <9> ~ <14> A method for manufacturing a metal member as described in any one of the items. [Effects of the Invention]

[0006] According to one embodiment of the present disclosure, a metal member having excellent bonding strength with a resin member, a metal-resin composite using this metal member, and a method for manufacturing this metal member are provided. [Modes for carrying out the invention]

[0007] In this disclosure, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this disclosure, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages, or with the values ​​shown in the examples. In this disclosure, the amount of each component in the material means the total amount of multiple substances present in the material, unless otherwise specified, if there are multiple substances corresponding to each component in the material. In this disclosure, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as their intended purpose is achieved.

[0008] <Metal components> One embodiment of this disclosure is, This is a metal component having a surface containing metal and having an average roughness motif length AR of 25 μm or more.

[0009] As shown in the examples described later, the metal member of this embodiment exhibits excellent bonding strength to the resin member. In particular, when forming a resin member by bringing a molten or softened resin into contact with a metal member, the metal member of this embodiment exhibits excellent bonding strength to the resin member even if the fluidity of the molten or softened resin is low.

[0010] The metal member of the present embodiment has a surface with an average length AR of the roughness motif of 25 μm or more. Hereinafter, a surface with an average length AR of the roughness motif of 25 μm or more is also referred to as a "roughened surface".

[0011] In the present disclosure, the average length AR of the roughness motif is a concept defined by JIS B 0631:2000 (ISO 12085:1996). The average length AR of the roughness motif of the metal member is measured by observing the cross-sectional curve (surface profile) of the metal member. The roughness motif means a curved portion sandwiched between two local peaks in the cross-sectional curve of the metal member. The local peak of profile means a solid portion between adjacent minimum points of the cross-sectional curve. The average length AR of the roughness motif means the average value of the lengths of the roughness motifs measured in the lateral direction of the cross-sectional curve of the metal member.

[0012] When the average length AR of the roughness motif of the metal member is 25 μm or more, the size in the lateral direction (the direction perpendicular to the depth direction of the recess) of the entrance of the recess in the concavo-convex structure formed on the roughened surface of the metal member is sufficiently large, and it is considered that the resin that has entered the recess exhibits an anchor effect and the resin member and the metal member are firmly joined.

[0013] The average length AR of the roughness motif on the roughened surface of the metal member is not particularly limited as long as it is 25 μm or more, and can be selected according to the use of the metal member, the type of the resin member joined to the metal member, and the like. For example, the average length AR of the roughness motif on the roughened surface of the metal member may be 30 μm or more, 35 μm or more, or 40 μm or more. For example, the average length AR of the roughness motif on the roughened surface of the metal member may be 100 μm or less, 80 μm or less, or 60 μm or less.

[0014] From the perspective of the bonding strength to the resin member, the roughened surface of the metal member may satisfy the following conditions for the line roughness parameter selected from the arithmetic mean roughness Ra, the maximum height Rz, and the average length RSm of the roughness curve elements.

[0015] In the present disclosure, the arithmetic mean roughness Ra, the maximum height Rz, and the average length RSm of the roughness curve elements are concepts defined by JIS B 0601:2001 (ISO 4287-1997).

[0016] For example, the arithmetic mean roughness Ra on the roughened surface of the metal member may be 0.2 μm or more, 0.4 μm or more, or 0.​​​​​​​​​​​​​​​​​​​​​The types of metals included in metal components are not particularly limited. Specific examples of metals include aluminum, iron, copper, nickel, gold, silver, platinum, cobalt, zinc, lead, tin, zirconium, titanium, niobium, chromium, magnesium, manganese, and alloys containing these metals. Specific examples of alloys include brass, phosphor bronze, and steel (e.g., stainless steel). The metal component may contain non-metallic elements such as phosphorus.

[0021] The metal component may consist of a single component or a combination of multiple components. In a metal component that is a combination of multiple components, if at least one component corresponding to the roughened surface satisfies any of the above-mentioned conditions (for example, including copper), then the metal component is deemed to satisfy the above-mentioned conditions. For example, if a metal component has a plating layer formed on the surface of a base material, and at least the plating layer corresponding to the roughened surface satisfies any of the above-mentioned conditions (for example, including copper), then the metal component is deemed to satisfy the above-mentioned conditions. Specific examples of materials used for the plating layer include zinc, nickel, and chromium. The base material may be metal, or it may be a non-metal such as resin, ceramic, glass, or carbon.

[0022] The metal component in this embodiment may contain copper. Previously reported metal components had room for improvement in their bonding strength to resin components when they contained copper. The metal component of this embodiment exhibits excellent bonding strength to resin components even when it contains copper.

[0023] When a metal component contains copper, the metal component may consist solely of copper, or it may be a combination of copper and other metals. When a metal component contains copper, the copper content relative to the total metal is not particularly limited and can be selected according to the intended use of the metal component. For example, the copper content in the total metal may be 55% to 100% by mass, or 60% to 80% by mass.

[0024] In one embodiment, the metal contained in the metal member includes copper and a metal M that has a higher ionization tendency than copper. When a metal component contains copper and metal M, the content of metal M in relation to the total metal is not particularly limited and can be selected according to the application of the metal component. For example, the content of metal M in the total metal may be 10% to 45% by mass. If the metal component contains copper and metal M, the copper and metal M may be in an alloy state.

[0025] The type of metal M, which has a greater ionization tendency than copper, is not particularly limited and can be selected according to the application of the metal component. Specific examples of metal M include zinc, lead, tin, iron, aluminum, nickel, and manganese. The metal component may contain only one type of metal M, or two or more types. The metal component may contain copper and zinc, or it may contain an alloy containing copper and zinc (such as brass). When a metal component contains both copper and zinc, the zinc content relative to the total metal is not particularly limited and can be selected according to the intended use of the metal component. For example, the zinc content may be 10% to 45% by mass, or 20% to 40% by mass.

[0026] When a metal component contains copper and zinc, the total content of copper and zinc in the entire metal is not particularly limited and can be selected according to the intended use of the metal component. For example, the total content of copper and zinc in the entire metal may be 90% to 100% by mass.

[0027] Metal components containing copper and zinc may also contain metals other than copper and zinc as needed. Examples of metals other than copper and zinc include lead, tin, iron, aluminum, nickel, and manganese. Metal components containing copper and zinc may also contain nonmetallic elements such as phosphorus. When a metal component contains copper and zinc, the content of metals other than copper and zinc in the total metal is not particularly limited and can be selected according to the intended use of the metal component. For example, the content of metals other than copper and zinc in the total metal may be 0% to 10% by mass.

[0028] The shape of the metal component is not particularly limited and can be selected according to its intended use. Specific examples of metal component shapes include plate-shaped, rod-shaped, cylindrical, and block-shaped components. When a metal component is in the form of a plate, its thickness is not particularly limited and can be selected according to the intended use of the metal component. For example, the thickness of a plate-shaped metal component may range from 1 mm to 20 mm.

[0029] The method for manufacturing the metal component is not particularly limited. For example, the metal component may be manufactured by the metal component manufacturing method described later.

[0030] <Metal resin composite> One embodiment of this disclosure is, The metal member described above, This is a metal-resin composite comprising a resin member containing resin and bonded to the roughened surface of the metal member.

[0031] In the metal-resin composite of this embodiment, the resin included in the resin member is not particularly limited and can be selected according to the application of the metal-resin composite. Specific examples of resins included in resin components include thermoplastic resins (including elastomers) such as polyolefin resins, polyvinyl chloride, polyvinylidene chloride, polystyrene resins, AS resins, ABS resins, polyester resins (e.g., polybutylene terephthalate), poly(meth)acrylic resins, polyvinyl alcohol, polycarbonate resins, polyamide resins, polyimide resins, polyether resins, polyacetal resins, fluorine resins, polysulfone resins, polyphenylene sulfide resins, and polyketone resins, as well as thermosetting resins such as phenolic resins, melamine resins, urea resins, polyurethane resins, epoxy resins, and unsaturated polyester resins. These resins may be used individually or in combination of two or more types.

[0032] In one embodiment, the resin member may include a polyolefin containing structural units derived from a cyclic olefin. Polyolefins containing structural units derived from cyclic olefins may be either cyclic olefin copolymers (COCs) or cyclic olefin polymers (COPs). Specific examples of cyclic olefin copolymers include copolymers obtained by addition polymerization of cyclic olefins and ethylene. Specific examples of cyclic olefins that serve as raw materials for polyolefins containing structural units derived from cyclic olefins include norbornene and tetracyclododecene.

[0033] In one embodiment, the resin contained in the resin member may have high viscosity and low fluidity when melted or softened. For example, the intrinsic viscosity [η] of the resin contained in the resin component may be 0.4 dL / g or higher. The metal-resin composite of this embodiment exhibits excellent bonding strength even when using a resin with low fluidity when melted or softened as the raw material for the resin component to be bonded to the metal component. Examples of resins having an intrinsic viscosity of 0.4 dL / g or higher include polyolefins containing structural units derived from cyclic olefins, aromatic polyamides, and the like.

[0034] In this disclosure, if a resin component contains two or more types of resin, the intrinsic viscosity of the resins contained in the resin component means the intrinsic viscosity of the mixture of those two or more resins.

[0035] The resin contained in the resin component may contain various compounding agents. Examples of compounding agents include fillers, heat stabilizers, antioxidants, pigments, weathering agents, flame retardants, plasticizers, dispersants, lubricants, mold release agents, and antistatic agents.

[0036] The resin component may contain fillers. Examples of fillers include glass fibers, carbon fibers, carbon particles, clay, talc, silica, minerals, and cellulose fibers. These fillers may be used individually or in combination of two or more types.

[0037] The number of metal components included in the metal-resin composite may be one or more. If multiple metal components are included, the compositions of the multiple metal components may be the same or different. The number of resin components included in the metal-resin composite may be one or more. If multiple resin components are included, the compositions of the multiple resin components may be the same or different.

[0038] The method for manufacturing the metal-resin composite is not particularly limited and can be selected from known methods. A preferred example of a method for manufacturing metal-resin composites is: The process of placing metal components into a mold, The process includes supplying molten or softened resin to a mold in which metal components are placed.

[0039] In the above method, when molten or softened resin is supplied to the mold, the resin solidifies while in contact with at least a portion of the roughened surface of the metal member placed in the mold, forming a resin member. The resin member formed by this method exhibits an excellent anchoring effect against the roughened surface of the metal member.

[0040] Metal-resin composites can be used in a variety of applications. Examples of applications for metal-resin composites include cooling units, busbars, vehicle cooling components, vehicle structural components, vehicle-mounted accessories, electronic equipment housings, home appliance housings, building materials, structural components, machine parts, various automotive parts, electronic equipment components, furniture, kitchenware and other household goods, medical equipment, building material components, other structural components, and exterior components.

[0041] In one embodiment, the metal-resin composite is used as an article equipped with a camera function, such as a smartphone. In this case, the resin component may include a polyolefin containing structural units derived from a cyclic olefin. Polyolefins containing structural units derived from a cyclic olefin are suitable as a material for camera lenses because they have excellent transparency and strength.

[0042] <Method for manufacturing metal components> One embodiment of this disclosure is, The process includes a step of roughening the surface of a substrate containing metal, and the roughening process is: A first roughening treatment is performed by bringing a first etching solution containing an inorganic acid and free of nitrogen-containing heteroaromatic compounds into contact with the surface, A method for manufacturing a metal member, comprising performing, in this order, a second roughening treatment in which a second etching solution containing an inorganic acid and a nitrogen-containing heteroaromatic compound is brought into contact with the surface, and

[0043] According to the method of this embodiment, a metal member with excellent bonding strength to a resin member can be manufactured. For example, the method of this embodiment is suitable as a method for manufacturing the metal member of the above-described embodiment (i.e., a surface having an average length AR of roughness motifs of 25 μm or more).

[0044] In the method of this embodiment, the details and preferred embodiments of the metal contained in the substrate to be subjected to the roughening treatment are the same as the details and preferred embodiments of the metal contained in the metal member described above. The base material may contain copper as a metal, or it may contain copper and a metal M that has a higher ionization tendency than copper, or it may contain copper and zinc as metals.

[0045] In the method of this embodiment, if the substrate to be roughened contains copper and a metal M with a higher ionization tendency than copper, a metal member with excellent bonding strength to the resin member is easily obtained. More specifically, a metal member having a surface with a rough structure where the size of the recess openings is relatively large is easily obtained. The reason for this can be considered as follows, for example.

[0046] In the first roughening treatment, when the first etching solution is brought into contact with a substrate containing copper and metal M, metal M dissolves on the surface of the substrate, while copper remains on the surface of the substrate without dissolving. In the first roughening treatment, a first etching solution that does not contain nitrogen-containing heteroaromatic compounds is used. Therefore, the selective elution of metal M proceeds without inhibition by nitrogen-containing heteroaromatic compounds.

[0047] In the second roughening treatment, the first etching solution is brought into contact with the substrate, and then the second etching solution is brought into contact with the surface of the substrate. In the second roughening treatment, a second etching solution containing nitrogen-containing heteroaromatic compounds is used. As a result, the nitrogen-containing heteroaromatic compounds adsorbed on the substrate surface partially inhibit the dissolution of copper remaining on the substrate surface. Consequently, an uneven structure with relatively large recess openings is formed by etching.

[0048] The concentrations of the inorganic acids in the first and second etching solutions used in the roughening process are not particularly limited and can be set considering the material of the substrate, etc. From the viewpoint of workability and ease of controlling conditions during the roughening process, it is preferable that the difference between the concentration D1 of the inorganic acid in the first etching solution and the concentration D2 of the inorganic acid in the second etching solution is small. Specifically, it is preferable that D1 and D2 satisfy the formula: 0.7 ≤ D1 / D2 ≤ 1.5, more preferably 0.8 ≤ D1 / D2 ≤ 1.3, even more preferably 0.9 ≤ D1 / D2 ≤ 1.1, and particularly preferable that D1 = D2.

[0049] The duration of the first and second roughening treatments in the roughening process is not particularly limited and can be set considering the material of the substrate, etc.

[0050] (First roughening treatment) In the first roughening treatment, a first etching solution containing an inorganic acid and free of nitrogen-containing heteroaromatic compounds is brought into contact with the surface of the substrate. The method for bringing the substrate into contact with the first etching solution is not particularly limited. Examples include a dipping method in which the substrate is immersed in the first etching solution, a spray method in which the first etching solution is sprayed onto the substrate, and a spin method in which the first etching solution is discharged onto a rotating substrate.

[0051] The temperature of the first etching solution may be appropriately adjusted considering the material of the substrate, the composition of the first etching solution, etc. For example, it is preferably 30°C to 60°C, and more preferably 35°C to 45°C.

[0052] From the viewpoint of etching properties, the pH of the first etching solution at 25°C is preferably 3.0 or less, and more preferably 1.0 or less.

[0053] The duration of the first roughening treatment (i.e., the time during which the substrate and the first etching solution are in contact) can be set considering the material of the substrate, the composition of the first etching solution, and so on. The duration of the first roughening treatment is preferably, for example, 1 to 15 minutes, and more preferably 5 to 12 minutes.

[0054] The first etching solution may contain water. Preferably, the water is one from which impurities such as metal ions and organic matter, as well as particle particles, have been removed by distillation, ion exchange treatment, filtration treatment, or various adsorption treatments, and pure water and ultrapure water are more preferred.

[0055] The first etching solution may contain components other than inorganic acid and water. For example, the first etching solution may contain hydrogen peroxide.

[0056] [Inorganic acid] The inorganic acid contained in the first etching solution dissolves the oxidized metal. The type of inorganic acid contained in the first etching solution is not particularly limited. Specific examples of inorganic acids include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, hypophosphorous acid, carbonic acid, sulfamic acid, boric acid, and hydrofluoric acid. Considering the environmental impact, inorganic acids other than hydrochloric acid, phosphoric acid, and hydrofluoric acid are preferred. From the viewpoint of the dissolution rate of metals (especially copper) contained in the base material and economic efficiency, sulfuric acid is preferred as the inorganic acid. The first etching solution may contain only one type of acid or two or more types.

[0057] From the viewpoint of etching properties, the inorganic acid content in the first etching solution is preferably 5% to 20% by mass, more preferably 5% to 15% by mass, even more preferably 6% to 13% by mass, and particularly preferably 8% to 12% by mass, based on the total mass of the first etching solution.

[0058] [hydrogen peroxide] The first etching solution may further contain hydrogen peroxide. The hydrogen peroxide contained in the first etching solution functions as an oxidizing agent for oxidizing the metal.

[0059] If the first etching solution contains hydrogen peroxide, the hydrogen peroxide content is preferably 0.5% to 7% by mass, and more preferably 1.3% to 3.0% by mass, relative to the total mass of the first etching solution, from the viewpoint of etching properties.

[0060] (Second roughening treatment) In the second roughening treatment, a second etching solution containing an inorganic acid and a nitrogen-containing heteroaromatic compound is brought into contact with the surface of the substrate. The method for bringing the substrate into contact with the second etching solution is not particularly limited. Examples include a dipping method in which the substrate is immersed in the second etching solution, a spray method in which the second etching solution is sprayed onto the substrate, and a spin method in which the second etching solution is discharged onto a rotating substrate.

[0061] The temperature of the second etching solution may be appropriately adjusted considering the material of the substrate, the composition of the second etching solution, etc. For example, it is preferably 30°C to 60°C, and more preferably 35°C to 45°C.

[0062] From the viewpoint of etching properties, the pH of the second etching solution at 25°C is preferably 3.0 or less, and more preferably 1.0 or less.

[0063] The duration of the second roughening treatment (i.e., the time the substrate is in contact with the second etching solution) can be set considering the material of the substrate, the composition of the second etching solution, etc. The duration of the second roughening treatment is preferably, for example, 1 to 15 minutes, and more preferably 3 to 8 minutes.

[0064] The second etching solution may contain water. Specific and preferred examples of water contained in the second etching solution are the same as those for the specific and preferred examples of water contained in the first etching solution.

[0065] The second etching solution may contain components other than inorganic acids, nitrogen-containing heteroaromatic compounds, and water. For example, the second etching solution may further contain hydrogen peroxide and amine compounds.

[0066] Specific examples and preferred examples of inorganic acids and hydrogen peroxide contained in the second etching solution are the same as the specific examples and preferred examples of inorganic acids contained in the first etching solution.

[0067] From the viewpoint of etching properties, the inorganic acid content in the second etching solution is preferably 5% to 20% by mass, more preferably 5% to 15% by mass, even more preferably 6% to 13% by mass, and particularly preferably 8% to 12% by mass, based on the total mass of the second etching solution.

[0068] If the second etching solution contains hydrogen peroxide, the hydrogen peroxide content is preferably 0.5% to 7% by mass, and more preferably 1.3% to 3.0% by mass, relative to the total mass of the second etching solution, from the viewpoint of etching properties.

[0069] [Nitrogen-containing heteroaromatic compounds] The nitrogen-containing aromatic heterocyclic compounds in the second etching solution contribute to controlling the roughening of the metal surface by suppressing rapid metal etching.

[0070] In this disclosure, "nitrogen-containing aromatic heterocyclic compound" means a compound having a heterocyclic ring containing nitrogen.

[0071] Nitrogen-containing aromatic heterocyclic compounds are not particularly limited and include five-membered ring compounds such as pyrrole compounds, pyrazole compounds, imidazole compounds, triazole compounds, and their derivatives; six-membered ring compounds such as pyridine compounds, pyridazine compounds, pyrazine compounds, pyrimidine compounds, triazine compounds, and their derivatives; and heterocyclic compounds such as indole, purine, quinoline, isoquinoline, quinoxaline, sinnoline, quinazoline, phthalazine, naphthyridine, pteridine, acridine, naftazine, phenazine, henanthroline, and their derivatives.

[0072] From the viewpoint of etching properties, the nitrogen-containing heteroaromatic compound is preferably an azole compound. Examples of azole compounds include triazole compounds such as 1,2,3-triazole, 1,2,4-triazole, 5-phenyl-1,2,4-triazole, 5-amino-1,2,4-triazole, 1H-benzotriazole, 1-methyl-benzotriazole, 5-methyl-1H-benzotriazole, and 3-amino-1H-triazole; tetrazoles such as 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, and 5-amino-1H-tetrazole; imidazoles such as 1H-imidazole and 1H-benzimidazole; and thiazoles such as 1,3-thiazole and 4-methylthiazole. From the viewpoint of etching properties, triazole compounds are preferred as azole compounds.

[0073] The nitrogen-containing heteroaromatic compounds contained in the second etching solution may be one type or two or more types.

[0074] From the viewpoint of effectively controlling the progress of etching, the content of nitrogen-containing heteroaromatic compounds is preferably 0.01% to 2.0% by mass, and more preferably 0.8% to 1.5% by mass, relative to the total mass of the etching solution.

[0075] [Amine compounds] The second etching solution may further contain an amine compound. The amine compounds contained in the second etching solution function as complexing agents to dissolve the metal as a metal complex. The amine compounds are not particularly limited and include alkanolamine compounds, hydroxyamine compounds, amino acid compounds, and the like.

[0076] Examples of alkanolamine compounds include monoalkanolamine compounds, dialkanolamine compounds, and trialkanolamine compounds. Specific examples of monoalkanolamine compounds include monoethanolamine, 2-methylaminoethanol, 2-ethylaminoethanol, 2-(2-aminoethoxy)ethanol, 1-amino-2-propanol, monopropanolamine, dimethylaminoethanol, and their salts. Specific examples of dialkanolamine compounds include diethanolamine, N-methyldiethanolamine, dibutanolamine, and their salts. Specific examples of trialkanolamine compounds include triisopropanolamine, triethanolamine, and their salts.

[0077] Examples of hydroxylamines include hydroxylamine, N-methylhydroxylamine, N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine, hydroxylamine sulfate, and hydroxylamine hydrochloride.

[0078] The amine compound contained in the second etching solution may be one type or two or more types.

[0079] If the second etching solution contains an amine compound, the content of the amine compound is preferably 0.0001% to 5% by mass, more preferably 0.01% to 0.5% by mass, even more preferably 0.01% to 0.3% by mass, and particularly preferably 0.01% to 0.1% by mass, based on the total mass of the second etching solution, from the viewpoint of etching properties.

[0080] From the viewpoint of ensuring good bonding strength, amino acid compounds are preferred as amine compounds. Because amino acid compounds have high adsorption capacity to metals, they can suitably function as complexing agents for dissolving metals as metal complexes. Furthermore, amino acid compounds can reduce the influence of hydrogen peroxide concentration, which is an oxidizing agent, on the etching rate. Specifically, since hydrogen peroxide can decompose over time, the concentration of hydrogen peroxide in the etching solution decreases, which can lead to a decrease in the etching rate. In contrast, using amino acid compounds can reduce the impact of the decrease in etching rate due to the decomposition of hydrogen peroxide. Furthermore, amino acid compounds have a pH buffering effect, which can suppress fluctuations in the pH of the etching solution and stabilize the pH.

[0081] In this disclosure, “amino acid compound” means amino acids and their salts. Amino acids are organic compounds that have both an amino group and a carboxyl group as functional groups.

[0082] The amino acids are not particularly limited and include, for example, alanine, glutamic acid, glycine, leucine, isoleucine, proline, serine, threonine, valine, β-alanine, γ-alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, histidine, lysine, methionine, tryptophan, tyrosine, ornithine, phenylalanine, 4-chlorophenylalanine, 4-bromophenylalanine, 4-nitrophenylalanine, 3-(3,4-dihydrophenyl)alanine, α-methylphenylalanine, etc. Examples of amino acid salts include alkali metal salts and ammonium salts. From the viewpoint of etching properties, the amino acid compound is preferably an aliphatic amino acid or a salt thereof. From the viewpoint of etching properties, the amino acid compound is preferably an α-amino acid or a salt thereof.

[0083] The amino acid compound contained in the second etching solution may be one type or two or more types.

[0084] From the viewpoint of etching properties, the content of the amino acid compound is preferably 0.0001% to 5% by mass, more preferably 0.01% to 0.5% by mass, even more preferably 0.01% to 0.3% by mass, and particularly preferably 0.01% to 0.1% by mass, relative to the total mass of the second etching solution.

[0085] [Other ingredients] The second etching solution may further contain components other than those described above. For example, the second etching solution may contain a halide ion source that produces fluoride ions, chloride ions, bromide ions, etc., in order to create deeper irregularities. Chloride ions are generally preferred as the halide ions. Examples of halide ion sources include alkali metal salts such as sodium chloride, ammonium chloride, and potassium chloride, oxohalides such as sodium chlorate and potassium chlorate, and copper chloride. The halide ion source contained in the second etching solution may be one type or two or more types. If the second etching solution contains a halide ion source, the amount of the halide ion source may be approximately 0.0001% to 0.05% by mass relative to the total mass of the etching solution, from the viewpoint of etching properties.

[0086] The second etching solution may further contain water-soluble organic solvents such as alcohol, glycol, or ether as a solvent other than water to adjust its etching properties. A single water-soluble organic solvent may be used alone, or two or more may be used in combination. If the second etching solution contains a water-soluble organic solvent, the amount of the water-soluble organic solvent may be approximately 0.1% to 20% by mass relative to the total mass of the second etching solution, from the viewpoint of etching properties.

[0087] The second etching solution may contain organic acids other than amino acid compounds to adjust its etching properties. Examples of organic acids other than amino acid compounds include aliphatic carboxylic acids and aromatic carboxylic acids. Organic acids may be used individually or in combination of two or more types. If the second etching solution contains an organic acid, the amount of the organic acid may be approximately 1% to 15% by mass relative to the total mass of the second etching solution, from the viewpoint of etching properties.

[0088] The second etching solution may contain, in addition to the above components, various additives commonly used in etching solutions. Examples of additives include stabilizers, solubilizers, defoamers, pH adjusters, specific gravity adjusters, viscosity adjusters, wettability improvers, chelating agents, oxidizing agents, reducing agents, and surfactants. Additives may be used individually or in combination of two or more. If the second etching solution contains an additive, the amount of the additive may be 0.001% to 10% by mass relative to the total mass of the second etching solution.

[0089] [Pre-treatment process] The method for manufacturing a metal component may include a pretreatment step before the roughening step. In the pretreatment step, for example, a process is performed to prepare the surface of the substrate for roughening treatment. Specific examples of pretreatment include processes to remove coatings such as oxide films and hydroxides present on the surface of the substrate (e.g., mechanical polishing, chemical polishing), and processes to remove contaminants such as machine oil present on the surface of the substrate (e.g., degreasing process with an alkaline solution).

[0090] A method for manufacturing a metal component may include a step of bringing a nitrogen-containing heteroaromatic compound into contact with the surface of a substrate as a pretreatment step. When nitrogen-containing heteroaromatic compounds are brought into contact with the substrate surface before the roughening process, the nitrogen-containing heteroaromatic compounds adsorbed on the substrate surface partially inhibit the etching of the substrate during the roughening process. As a result, a surface texture with relatively large depressions is more effectively formed on the substrate surface.

[0091] The step of bringing a nitrogen-containing heteroaromatic compound into contact with the surface of a substrate can be carried out, for example, using a pretreatment solution containing the nitrogen-containing heteroaromatic compound. The pretreatment solution containing nitrogen-containing heteroaromatic compounds may also contain water. If the pretreatment solution contains water, from the viewpoint of improving the compatibility between nitrogen-containing heteroaromatic compounds and water, the pretreatment solution containing nitrogen-containing heteroaromatic compounds may also contain a substance capable of dissolving nitrogen-containing heteroaromatic compounds. Specific examples of substances capable of dissolving nitrogen-containing heteroaromatic compounds include ethylene glycol monoisopropyl ether. The pretreatment solution is preferably neutral (pH 6-8 at 25°C).

[0092] [Post-processing steps] The method for manufacturing a metal component may include a post-processing step after the roughening step. In the post-processing step, for example, the substrate after roughening treatment is washed. Specific examples of post-treatment include washing with water and ultrasonic cleaning to remove smut. [Examples]

[0093] The present disclosure will be described in more detail below with reference to examples. However, the present disclosure is not limited to these examples.

[0094] <Example 1> A copper alloy sheet (thickness: 2 mm) of alloy number C2680, as specified in JIS H3100:2012, was cut to a size of 45 mm in length and 18 mm in width to prepare test pieces for metal component fabrication. The composition of the copper alloy of alloy number C2680 is shown below. Copper (Cu): 64.0~68.0% by mass Lead (Pb): 0.05% by mass or less Iron (Fe): 0.05% by mass or less Zinc (Zn): Remainder

[0095] [Pre-treatment process] The test specimens were immersed for 5 minutes in a 2.6% by mass sodium hydroxide aqueous solution (55°C) containing 0.16% by mass sodium gluconate, while being ultrasonically cleaned. After that, the test specimens were rinsed with water (20 seconds x 3 times). Next, the test specimen was immersed for 20 seconds in a 0.002% by mass sodium hydroxide aqueous solution (35°C, pH: neutral) containing 0.1% by mass benzotriazole and 0.3% by mass ethylene glycol monoisopropyl ether. After that, the test specimen was washed with water (20 seconds x 3 times).

[0096] [First roughening step] A first etching solution was prepared by mixing 9.5% by mass of sulfuric acid and 2% by mass of hydrogen peroxide with water. The pH of the first etching solution at 25°C was 0.3. The test specimen was immersed in the first etching solution (40°C) for 8 minutes. After that, the test specimen was washed with water (20 seconds x 3 times).

[0097] [Second roughening process] A second etching solution was prepared by mixing 9.5% by mass sulfuric acid, 2% by mass hydrogen peroxide, 1.09% by mass benzotriazole, 0.024% by mass glycine, and 0.0023% by mass sodium chloride with water. The pH of the second etching solution at 25°C was 0.3. The test specimen was immersed in the second etching solution (40°C) for 5 minutes. After that, the test specimen was washed with water (20 seconds x 3 times).

[0098] [Post-processing steps] The test specimen was immersed in water (25°C) for 3 minutes while undergoing ultrasonic cleaning to remove smut. The test specimen was then dried at 80°C. The metal component of Example 1 was fabricated in this manner.

[0099] <Comparative Example 1> A metal component of Comparative Example 1 was manufactured in the same manner as in Example 1, except that the first roughening step was not performed.

[0100] <Comparative Example 2> The metal component of Comparative Example 2 was manufactured in the same manner as in Example 1, except that the first roughening step was omitted and the time of the second roughening step was changed to 15 minutes.

[0101] [Measurement of average AR of roughness motif] The average AR of the roughness motifs of the metal components prepared in Example 1 and Comparative Examples 1 and 2 was measured using a method compliant with JIS B 0631:2000 (ISO 12085:1996). The results are shown in Table 1.

[0102] [Measurement of line roughness parameters] The arithmetic mean roughness Ra, maximum height Rz, and average length RSm of the roughness curve elements of the metal components prepared in Example 1 and Comparative Examples 1 and 2 were measured according to a method conforming to JIS B 0601:2001 (ISO 4287-1997). The results are shown in Table 1.

[0103] [Measurement of shear joint strength] The metal components produced in Example 1 and Comparative Examples 1 and 2 were placed in a small dumbbell metal insert mold mounted on an injection molding machine (J100-ADS, manufactured by Japan Steel Works, Ltd.). Next, a high-speed heat cycle molding mold temperature control device (YHT-C2420, manufactured by Yamashita Electric Co., Ltd.) was connected to the mold, and the surface temperature of the mold was heated to 200°C using a sheath heater. A cyclic olefin copolymer (manufactured by Mitsui Chemicals, brand name: Apel 5514ML, intrinsic viscosity: 0.44 dL / g) was injected into a mold heated to 200°C. The injection conditions were: cylinder temperature 290°C, injection speed 20 mm / sec, holding pressure 120 MPa, and injection holding pressure time 10 seconds. After injection holding pressure was completed, the mold surface temperature was rapidly cooled to 120°C using water as a cooling medium to fabricate a metal-resin composite structure. The interface area between the metal component and the resin is 50 mm². 2 The dimensions were set to (10mm x 5mm). The shear joint strength (MPa) of this metal-resin composite was measured using a method compliant with ISO 19095-3. Specifically, a dedicated jig was attached to a tensile testing machine (Shimadzu Corporation, AGS-500-D), and the breaking load (N) was measured at room temperature (23°C) and a tensile speed of 10 mm / min. The measured breaking load (N) is calculated by multiplying the interface area (50 mm²) between the metal component and the resin layer. 2 The shear joint strength (MPa) was calculated by dividing by ). The results are shown in Table 1.

[0104] [Table 1]

[0105] As shown in Table 1, the metal member of Example 1, whose average roughness motif AR was 25 μm or higher, showed superior shear bonding strength to the resin member compared to the metal members of Comparative Examples 1 and 2, whose average roughness motif AR was less than 25 μm. This is thought to be because the size of the entrance to the recess formed on the surface of the metal member of Example 1 was large, allowing the resin that entered the recess to exert a sufficient anchoring effect.

[0106] Although some of the wire roughness parameters of the metal member obtained in Comparative Example 2 were equal to or better than those of Example 1, the shear bonding strength to the resin member was lower. This is thought to be because the size of the entrance to the recess formed on the surface of the metal member was small, preventing low-flow resins such as cyclic olefin copolymers from penetrating the recesses.

[0107] In Example 1, where both the first and second roughening treatments were performed, the average roughness motif AR on the roughened surface of the metal member was 25 μm or higher. In contrast, in Comparative Examples 1 and 2, where only the second roughening treatment was performed without the first roughening treatment, the average roughness motif AR on the roughened surface of the metal member was less than 25 μm. These results suggest that performing the first roughening treatment before the second roughening treatment is effective in controlling the average roughness motif AR of the metal member.

Claims

1. A metal component having a surface containing metal and having an average roughness motif length AR of 25 μm or more.

2. The metal member according to claim 1, wherein the metal includes copper.

3. The metal member according to claim 1, wherein the aforementioned metal includes copper and a metal M that has a greater ionization tendency than copper.

4. The metal member according to claim 3, wherein the content of metal M in the aforementioned metal is 10% by mass to 45% by mass.

5. The metal member according to claim 1, wherein the aforementioned metal includes copper and zinc.

6. The metal member according to claim 5, wherein the zinc content in the metal is 10% by mass to 45% by mass.

7. A metal member according to any one of claims 1 to 6, A metal-resin composite comprising a resin member containing resin and bonded to the surface thereof.

8. The metal-resin composite according to claim 7, wherein the intrinsic viscosity [η] of the resin is 0.4 dL / g or more.

9. The process includes a step of roughening the surface of a substrate containing metal, and the roughening process is: A first roughening treatment is performed by bringing a first etching solution containing an inorganic acid and free of nitrogen-containing heteroaromatic compounds into contact with the surface, A method for manufacturing a metal member, comprising: a second roughening treatment in which a second etching solution containing an inorganic acid and a nitrogen-containing heteroaromatic compound is brought into contact with the surface; and performing these steps in this order.

10. A method for manufacturing a metal member according to claim 9, wherein the concentration D1 of the inorganic acid in the first etching solution and the concentration D2 of the inorganic acid in the second etching solution satisfy the formula: 0.7 ≤ D1 / D2 ≤ 1.

5.

11. A method for manufacturing a metal member according to claim 9 or 10, comprising the step of performing a pretreatment in which a nitrogen-containing heteroaromatic compound is brought into contact with the surface before the roughening treatment.

12. The method for producing a metal member according to claim 9 or claim 10, wherein the second etching solution further comprises an amine compound.

13. The method for manufacturing a metal member according to claim 9 or claim 10, wherein the metal includes copper.

14. The method for manufacturing a metal member according to claim 9 or claim 10, wherein the metal includes copper and a metal M that has a greater ionization tendency than copper.

15. The method for manufacturing a metal member according to claim 9 or claim 10, wherein the metal comprises copper and zinc.

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