Metallic member and manufacturing method thereof, etching solution, and metal-resin composite and manufacturing method thereof

Abstract

CIE1976(L * a * b * The present invention relates to a metal member and a manufacturing method thereof, an etching solution, and a metal-resin composite and a manufacturing method thereof, the metal member and the etching solution having a surface in which the L value, a value, and b value in the 1) color space satisfy at least one of formula (1) (b≧16) and formula (2) (L≧2.336×a-2.0536).

Description

[Technical field]

[0001] The present disclosure relates to a metal member and a manufacturing method thereof, an etching solution, and a metal-resin composite and a manufacturing method thereof. [Background technology]

[0002] Metal-resin composites have both properties derived from metal members (electrical conductivity, heat conductivity, etc.) and properties derived from resin members (insulation, etc.), and are used in many applications, such as vehicle structural parts. In the production of metal-resin composites, metal members having a roughened surface may be used to increase the bonding strength with the resin member. Such metal members are described in, for example, Patent Document 1. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 6387543 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of one embodiment of the present disclosure is to provide a metal member having excellent bonding strength with a resin member. A problem to be solved by another embodiment of the present disclosure is to provide a method for manufacturing the above-mentioned metal member. A problem to be solved by another embodiment of the present disclosure is to provide an etching solution used in manufacturing the above-mentioned metal member. A problem to be solved by another embodiment of the present disclosure is to provide a metal-resin composite body in which a resin member is joined to the above-mentioned metal member. The problem to be solved by another embodiment of the present disclosure is to provide a method for producing the above-mentioned metal-resin composite body. [Means for solving the problem]

[0005] The present disclosure includes the following aspects. <1> CIE1976(L * a * b * 2. A metal member having a surface in which the L value, a value, and b value in a color space satisfy at least one of the following formulas (1) and (2): b≧16 (1) L≧2.336×a-2.0536 (2) <2> CIE1976(L * a * b * ) the L value and a value in color space satisfy the above formula (2), and the surface satisfies the following formula (3): <1> The metal member according to claim 1. L≦2.336×a+14.649 (3) <3> CIE1976(L * a * b * ) The surface has an a value in color space that satisfies the following formula (4): <2> The metal member according to claim 1. 25≧a≧10 (4) <4> Contains at least one of copper and a copper alloy; <1> ~ <3> The metal member according to any one of claims 1 to 7. <5> A nitrogen-containing heteroaromatic compound is present on at least a portion of the surface. <1> ~ <4> The metal member according to any one of claims 1 to 7. <6> An etching solution comprising an amine compound, a nitrogen-containing heteroaromatic compound, hydrogen peroxide, and an inorganic acid. <7> The content of the amine compound is 0.0001% by mass to 5% by mass based on the total mass of the etching solution. <6> The etching solution according to claim 1. <8> The content of the nitrogen-containing heteroaromatic compound is 0.01% by mass to 2.0% by mass based on the total mass of the etching solution. <6> The etching solution according to claim 1. <9> The content of the hydrogen peroxide is 0.5% by mass to 7% by mass based on the total mass of the etching solution. <6> The etching solution according to claim 1. <10> The content of the inorganic acid is 5% by mass to 20% by mass based on the total mass of the etching solution. <6> The etching solution according to claim 1. <11> The amine compound is an amino acid compound. <6> The etching solution according to claim 1. <12> The amino acid compound is an aliphatic amino acid or a salt thereof. <11> The etching solution according to claim 1. <13> The amino acid compound is an α-amino acid or a salt thereof. <11> The etching solution according to claim 1. <14> The nitrogen-containing heteroaromatic compound is an azole compound. <6> ~ <13> 13. The etching solution according to claim 12. <15> The azole compound is a triazole compound. <14> The etching solution according to claim 1. <16> <1> ~ <5> A method for producing a metal member according to any one of the above claims, A step of roughening at least a portion of the surface of a metal material. A method for manufacturing a metal member comprising the steps of: <17> The roughening step comprises: <6> ~ <15> A step of etching with the etching solution according to any one of the above. <16> The method for producing the metal member according to claim 1 . <18> <1> ~ <5> 13. A metal resin composite comprising: the metal member according to claim 12; and a resin member joined to at least a portion of the surface of the metal member. <19> The resin member includes a thermoplastic resin. <18> The metal-resin composite according to claim 1. <20> The thermoplastic resin includes at least one selected from the group consisting of polyolefin-based resins, polyvinyl chloride, polyvinylidene chloride, polystyrene-based resins, AS resins, ABS resins, polyester-based resins, poly(meth)acrylic-based resins, polyvinyl alcohol, polycarbonate-based resins, polyamide-based resins, polyimide-based resins, polyether-based resins, polyacetal-based resins, fluorine-based resins, polysulfone-based resins, polyphenylene sulfide resins, and ketone-based resins. <19> The metal-resin composite according to claim 1. <21> <1> ~ <5> A step of placing the metal member according to any one of claims 1 to 4 in a mold, and a step of supplying a molten or softened resin to the mold. A method for producing a metal-resin composite comprising the steps of: Effect of the Invention

[0006] According to one embodiment of the present disclosure, there is provided a metal member having excellent bonding strength with a resin member. According to another embodiment of the present disclosure, there is provided a method for manufacturing the metal member. According to another embodiment of the present disclosure, there is provided an etching solution for use in manufacturing the above-mentioned metal member. According to another embodiment of the present disclosure, there is provided a metal-resin composite body in which a resin member is joined to the above-mentioned metal member. According to another embodiment of the present disclosure, there is provided a method for producing the above metal-resin composite. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a cross-sectional view that illustrates an example of a metal-resin composite. [Diagram 2] FIG. 2 is a schematic diagram of a test piece for evaluating airtightness. [Diagram 3] FIG. 3 is a cross-sectional view that illustrates a cross section in a diagonal direction of a test piece for evaluating airtightness. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] In the present disclosure, a numerical range indicated using "~" indicates a range that includes the numerical values ​​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 value described in a certain numerical range may be replaced by the upper or lower limit value of another numerical range described in stages, or may be replaced by a value shown in the examples. In this disclosure, when a material contains multiple substances corresponding to each component, the amount of each component in the material means the total amount of the multiple substances present in the material, unless otherwise specified. In the present disclosure, the term "process" refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

[0009] <Metal parts> The metal member according to the present disclosure is compliant with CIE1976(L * a * b * ) The L value, a value, and b value in the color space satisfy at least one of the following formula (1) and the following formula (2), and the bonding strength with a resin member is excellent. b≧16 (1) L≧2.336×a-2.0536 (2)

[0010] The mechanism by which the metal member according to the present disclosure can improve the bonding strength with the resin member is presumed to be as follows. The L value, a value, and b value of the surface of a metal component are related to the reflected light of the surface, and reflect the degree of surface roughness. The surface of a metal component whose L value, a value, and b value satisfy at least one of formulas (1) and (2) has a microstructure with appropriately controlled roughness, and it is considered that such a microstructure is suitable for increasing the bonding strength with a resin component. Although the speculated mechanism has been described above, the scope of the present disclosure is in no way limited by the above speculation.

[0011] The upper limit of the b value is not particularly limited, and may be 28, for example.

[0012] It is preferable that the metal member has the above surface in which the L value and the a value satisfy the formula (2) and also satisfy the following formula (3), which makes it easier to suppress leakage of fluid from the joint between the metal member and the resin member. L≦2.336×a+14.649 (3)

[0013] A metal member that satisfies formula (3) in addition to formula (2) has a more appropriately controlled surface roughness, and is therefore considered to be suitable for preventing fluid leakage in addition to improving the bonding strength. Although the speculated mechanism has been described above, the scope of the present disclosure is in no way limited by the above speculation.

[0014] Metallic parts are CIE1976(L *a * b * It is preferable that the a value in the color space of the surface satisfies the following formula (4). This makes it easier to suppress leakage of the fluid. 25≧a≧10 (4)

[0015] The L value, a value, and b value are measured using a spectrophotometer. For example, the spectrophotometer "NF333" manufactured by Nippon Denshoku Industries Co., Ltd. can be used as the spectrophotometer.

[0016] The type of metal contained in the metal member is not particularly limited. Examples of metals include aluminum, iron, copper, nickel, gold, silver, platinum, cobalt, zinc, lead, tin, zirconium, titanium, niobium, chromium, aluminum, magnesium, manganese, alloys containing the above metals, and plated materials obtained by plating base materials of the above metals and alloys.

[0017] Examples of the alloy include brass, phosphor bronze, steel (e.g., stainless steel), brass, etc. Examples of the plated material (i.e., a base material of the metal or alloy that is plated) include plated steel, etc., and examples of the material of the plated layer include zinc, nickel, chromium, etc.

[0018] Among the metals listed above, it is preferable that the metal member contains at least one of copper and a copper alloy.

[0019] The shape of the metal member is not particularly limited, and examples thereof include a flat plate, a disk, a curved plate, a rod, a cylinder, a block, etc. The shape of the surface of the metal member is not particularly limited, and examples thereof include a flat surface, a curved surface, etc.

[0020] The thickness of the metal member is not particularly limited and may be, for example, 1 mm to 20 mm. For example, when used for cooling units, bus bars, etc., the thickness may be 1 mm to 5 mm, and when used for vehicle cooling parts, etc., the thickness may be 1 mm to 5 mm.

[0021] <Metal resin composite> The metal resin composite according to the present disclosure includes a metal member according to the present disclosure and a resin member joined to at least a portion of a surface of the metal member.

[0022] [Resin material] The resin contained in the resin member is not particularly limited and can be selected according to the application of the metal member. Examples of the resin include thermoplastic resins (including elastomers) such as polyolefin resins (e.g., polypropylene), 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, and thermosetting resins such as phenol resins, melamine resins, urea resins, polyurethane resins, epoxy resins, and unsaturated polyester resins. These resins may be used alone or in combination of two or more. From the viewpoint of moldability, the resin contained in the resin member is preferably a thermoplastic resin.

[0023] The resin contained in the resin member may contain various compounding agents, such as fillers, heat stabilizers, antioxidants, pigments, weather resistance agents, flame retardants, plasticizers, dispersants, lubricants, release agents, and antistatic agents.

[0024] The resin member may contain a filler. Examples of the filler include glass fiber, carbon fiber, carbon particles, clay, talc, silica, minerals, cellulose fiber, etc. These fillers may be used alone or in combination of two or more.

[0025] [composition] The configuration of the metal resin composite is not particularly limited as long as it includes a metal member and a resin member bonded to at least a portion of the surface of the metal member, and may be designed appropriately taking into account the use of the metal resin composite, etc.

[0026] The metal-resin composite may, for example, include a plurality of metal members, and may include one type of metal or two or more types of metal members including different metals. Furthermore, the metal resin composite may, for example, include a plurality of resin members, and may include one type of resin or two or more types of resin members including different resins.

[0027] For example, as shown in FIG. 2, a metal resin composite 100 may include a metal member 10 and a resin member 30 provided on the metal member 10.

[0028] The metal-resin composite can be used in various applications, such as cooling units, bus bars, vehicle cooling parts, vehicle structural parts, vehicle mounted items, electronic device housings, home appliance housings, building materials, structural parts, machine parts, various automobile parts, electronic device parts, furniture, kitchenware and other household goods applications, medical equipment, building material parts, other structural parts, exterior parts, and the like.

[0029] <Etching solution> In order to obtain the metal member according to the present disclosure, for example, the etching solution according to the present disclosure described below can be suitably used.

[0030] The etching solution according to the present disclosure comprises an amine compound, a nitrogen-containing heteroaromatic compound, hydrogen peroxide, and an inorganic acid.

[0031] [Amine compounds] The amine compound functions as a complexing agent for dissolving a metal as a metal complex. The amine compound is not particularly limited, and examples thereof include alkanolamine compounds, hydroxyamine compounds, and amino acid compounds.

[0032] Examples of the alkanolamine compound include monoalkanolamine compounds, dialkanolamine compounds, and trialkanolamine compounds. Examples of the monoalkanolamine compound include monoethanolamine, 2-methylaminoethanol, 2-ethylaminoethanol, 2-(2-aminoethoxy)ethanol, 1-amino-2-propanol, monopropanolamine, dimethylaminoethanol, and salts thereof. Examples of the dialkanolamine compound include diethanolamine, N-methyldiethanolamine, dibutanolamine, and salts thereof. Examples of the trialkanolamine compound include triisopropanolamine, triethanolamine, and salts thereof.

[0033] Examples of hydroxylamines include hydroxylamine, N-methylhydroxylamine, N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine, hydroxylamine sulfate, and hydroxylamine hydrochloride.

[0034] The amine compounds may be used alone or in combination of two or more kinds.

[0035] From the viewpoint of etching properties, the content of the amine compound is preferably 0.0001 mass % to 5 mass %, more preferably 0.01 mass % to 0.5 mass %, further preferably 0.01 mass % to 0.3 mass %, and particularly preferably 0.01 mass % to 0.1 mass %, relative to the total mass of the etching solution.

[0036] From the viewpoint of more easily suppressing leakage of fluid, the amine compound is preferably an amino acid compound.

[0037] [Amino acid compounds] The amino acid compound functions as a complexing agent for dissolving metals as metal complexes, and also has a high ability to adsorb to metals, so that the above-mentioned function can be suitably exhibited. In addition, the amino acid compound can reduce the effect of the concentration of hydrogen peroxide, which is an oxidizing agent, on the etching rate. Specifically, hydrogen peroxide can decompose over time, so the concentration of hydrogen peroxide in the etching solution can decrease, and the etching rate can decrease. In contrast, the use of the amino acid compound can reduce the effect of the decrease in the etching rate caused by the decomposition of hydrogen peroxide. Furthermore, the amino acid compound has a pH buffering effect, and can suppress the pH fluctuation of the etching solution and stabilize the pH.

[0038] In the present disclosure, "amino acid compound" refers to amino acids and their salts. Amino acids are organic compounds that have both amino and carboxy functional groups.

[0039] The amino acid compound is not particularly limited, and examples thereof include 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, and salts thereof. Examples of the salts include alkali metal salts and ammonium salts.

[0040] From the viewpoint of etching properties, the amino acid compound is preferably an aliphatic amino acid or a salt thereof.

[0041] From the viewpoint of etching properties, the amino acid compound is preferably an α-amino acid or a salt thereof.

[0042] The amino acid compound may be used alone or in combination of two or more kinds.

[0043] From the viewpoint of etching properties, the content of the amino acid compound is preferably 0.0001 mass% to 5 mass%, more preferably 0.01 mass% to 0.5 mass%, further preferably 0.01 mass% to 0.3 mass%, and particularly preferably 0.01 mass% to 0.1 mass%, relative to the total mass of the etching solution.

[0044] [Nitrogen-containing heteroaromatic compounds] The nitrogen-containing aromatic heterocyclic compound suppresses rapid etching of the metal, and thereby favorably contributes to adjusting the roughness of the metal surface.

[0045] In the present disclosure, a "nitrogen-containing aromatic heterocyclic compound" refers to a compound having a nitrogen-containing heterocycle.

[0046] The nitrogen-containing aromatic heterocyclic compound is not particularly limited, and examples thereof include 5-membered ring compounds such as pyrrole compounds, pyrazole compounds, imidazole compounds, triazole compounds, and derivatives thereof; 6-membered ring compounds such as pyridine compounds, pyridazine compounds, pyrazine compounds, pyrimidine compounds, triazine compounds, and derivatives thereof; and heterocyclic compounds such as indole, purine, quinoline, isoquinoline, quinoxaline, cinnoline, quinazoline, phthalazine, naphthyridine, pteridine, acridine, naphthazine, phenazine, henanthroline, and derivatives thereof.

[0047] From the viewpoint of etching properties, the nitrogen-containing heteroaromatic compound is preferably an azole compound.

[0048] The azole compound is not particularly limited, and examples thereof 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.

[0049] From the viewpoint of etching properties, the azole compound is preferably a triazole compound.

[0050] The nitrogen-containing heteroaromatic compounds may be used alone or in combination of two or more kinds.

[0051] From the viewpoint of easily ensuring bonding strength and airtightness, the content of the nitrogen-containing heteroaromatic compound is preferably 0.01 mass % to 2.0 mass %, and more preferably 0.8 mass % to 1.5 mass %, relative to the total mass of the etching solution.

[0052] [hydrogen peroxide] The hydrogen peroxide functions as an oxidizing agent to oxidize the metal.

[0053] From the viewpoint of etching properties, the content of hydrogen peroxide is preferably 0.5 mass % to 7 mass %, and more preferably 1.3 mass % to 3.0 mass %, based on the total mass of the etching solution.

[0054] [Inorganic acid] The inorganic acid is used to dissolve the oxidized metal.

[0055] The inorganic acid is not particularly limited, and examples thereof include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, hypophosphorous acid, carbonic acid, sulfamic acid, boric acid, hydrofluoric acid, etc. Considering the environmental load, it is preferable to use an inorganic acid other than hydrochloric acid, phosphoric acid, and hydrofluoric acid. Moreover, it is preferable to use sulfuric acid from the viewpoint of high copper dissolution rate and economical advantage.

[0056] The inorganic acid may be used alone or in combination of two or more kinds.

[0057] From the viewpoint of etching properties, the content of the inorganic acid is preferably 5 mass % to 20 mass %, more preferably 5 mass % to 15 mass %, further preferably 6 mass % to 13 mass %, and particularly preferably 8 mass % to 12 mass %, relative to the total mass of the etching solution.

[0058] [Other ingredients] The etching solution may contain water in addition to the amino acid compound, the nitrogen-containing heteroaromatic compound, hydrogen peroxide, and the inorganic acid. The water is preferably one from which impurities such as metal ions and organic matter, and particle particles have been removed by distillation, ion exchange treatment, filter treatment, various adsorption treatments, etc. In particular, pure water and ultrapure water are preferred.

[0059] The etching solution may contain a halide ion source that generates fluoride ions, chloride ions, bromide ions, etc., to create deeper irregularities. Chloride ions are generally preferred as the halide ion. 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 may be used alone or in combination of two or more kinds. When a halide ion source is contained, the content of the halide ion source may be about 0.0001 mass % to 0.05 mass % with respect to the total mass of the etching liquid, from the viewpoint of etching properties.

[0060] The etching solution may contain a water-soluble organic solvent such as alcohol, glycol, or ether as a solvent other than water in order to adjust the etching properties. The water-soluble organic solvent may be used alone or in combination of two or more kinds. When the etching solution contains a water-soluble organic solvent, the content of the water-soluble organic solvent may be about 0.1% by mass to 20% by mass with respect to the total mass of the etching solution from the viewpoint of etching properties.

[0061] The etching solution may contain an organic acid other than the amino acid compound in order to adjust the etching property. Examples of the organic acid other than the amino acid compound include an aliphatic carboxylic acid and an aromatic carboxylic acid. The organic acids may be used alone or in combination of two or more. When the organic acid is contained, the content of the organic acid may be about 1% by mass to 15% by mass with respect to the total mass of the etching liquid, from the viewpoint of etching properties.

[0062] In addition to the above components, the etching solution may contain various additives that are commonly used in etching solutions, such as a stabilizer, a solubilizer, an antifoaming agent, a pH adjuster, a specific gravity adjuster, a viscosity adjuster, a wettability improver, a chelating agent, an oxidizing agent, a reducing agent, and a surfactant.

[0063] The additives may be used alone or in combination of two or more kinds.

[0064] When the additive is contained, the content of the additive may be about 0.001% by mass to 10% by mass with respect to the total mass of the etching liquid.

[0065] [pH] From the viewpoint of etching properties, the pH of the etching solution at 25° C. is preferably 3.0 or less, and more preferably 1.0 or less. The pH is measured using a pH meter.

[0066] The etching solution according to the present disclosure is not particularly limited in terms of the metal to be etched, and can be used, for example, to etch the above-mentioned metals in metal members.

[0067] There is no particular limitation on the method for producing the etching solution, and the etching solution can be produced by mixing the above-mentioned components and stirring them as necessary.

[0068] <Metal member manufacturing method> The manufacturing method of the metal component according to the present disclosure is not particularly limited, but it can be suitably manufactured by the manufacturing method of the metal component according to the present disclosure described below.

[0069] The method for producing a metal component according to the present disclosure includes a step of roughening at least a portion of the surface of a metal material (hereinafter sometimes referred to as a "roughening step").

[0070] The method for producing a metal member may include a pretreatment step before the roughening step, and may include a post-treatment step after the roughening step. Hereinafter, the method for producing a metal member will be described in detail, taking as an example an embodiment in which the pretreatment step, the roughening step, and the post-treatment step are carried out in this order.

[0071] [Pretreatment process] A pretreatment is carried out to remove films made of oxides and hydroxides present on the surfaces of metal materials. Mechanical polishing or chemical polishing is usually carried out. If the joining surface is significantly contaminated by machine oil or the like, a degreasing process using an alkaline aqueous solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution may be carried out before the pretreatment process.

[0072] [Roughening process] The method for roughening at least a part of the surface of the metal material is not particularly limited, and examples thereof include chemical treatment, mechanical cutting treatment, etc. Examples of mechanical polishing treatment include sandblasting, knurling, laser processing, etc. Examples of etching treatment include treatment using an alkaline etching agent, treatment using an acid etching agent, etc. These methods can be used alone or in appropriate combination. Among these, treatment using an acid etching agent is preferred.

[0073] As the acid-based etching agent, the etching solution according to the present disclosure can be suitably used. In this embodiment, the roughening step is a step of etching at least a part of the surface of the metal material with the etching solution according to the present disclosure.

[0074] Examples of methods for contacting the metal material with the etching solution include a dipping method in which the metal material is immersed in the etching solution, a spraying method in which the etching solution is sprayed onto the metal material, and a spinning method in which the etching solution is ejected onto a rotating metal material.

[0075] The temperature of the etching solution may be appropriately adjusted in consideration of the type of metal material, the composition of the etching solution, etc., and is preferably 30°C to 60°C, for example, and more preferably 35°C to 45°C.

[0076] The treatment time (i.e., the contact time between the metal material and the etching solution) may be appropriately adjusted taking into consideration the type of metal material, the composition of the etching solution, etc., and is, for example, preferably 60 to 480 seconds, and more preferably 150 to 300 seconds.

[0077] Etching may cause pH fluctuations, so the pH of the etching solution may be adjusted during etching, if necessary.

[0078] [Post-processing process] After the roughening treatment, the metal material is washed. The post-treatment step usually consists of a water washing and drying operation. The post-treatment step may also include an ultrasonic cleaning operation to remove smut.

[0079] When a metal member is produced by roughening the surface of a metal material using the etching solution according to the present disclosure, the nitrogen-containing heteroaromatic compound contained in the etching solution may remain on the surface of the metal member. That is, in the metal member according to the present disclosure, the nitrogen-containing heteroaromatic compound may be present on at least a part (or the whole) of the surface. When a metal resin composite material is produced using such a metal member, the nitrogen-containing heteroaromatic compound may be present on at least a part (or the whole) of the bonding interface between the metal material and the metal resin.

[0080] <Mechanism of manufacturing metal-resin composite> The method for producing the metal resin composite according to the present disclosure is not particularly limited, but it can be suitably produced by the method for producing the metal resin composite according to the present disclosure described below.

[0081] The method for producing a metal-resin composite according to the present disclosure includes: A step of placing the metal member according to the present disclosure in a mold (hereinafter sometimes referred to as a "mold placement step"); and A process of supplying molten or softened resin to the mold (hereinafter referred to as the "resin supply process") Includes.

[0082] In the die placement step, a metal member is placed in the die, and in the resin supply step, molten or softened resin is supplied to the die.

[0083] The molten resin supplied to the mold solidifies in a state of contact with at least a portion of the roughened surface of the metal member (that is, the surface that satisfies formula (1)), to form the resin member.

[0084] The details and preferred aspects of the resin are the same as those of the resin contained in the resin member contained in the metal-resin composite body described above.

[0085] Other production conditions may be appropriately selected in accordance with known conditions. EXAMPLES

[0086] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0087] <Example 1> A copper alloy plate (thickness: 2 mm) of alloy number C1100 specified in JIS H3100:2012 was cut to a length of 45 mm and a width of 18 mm to prepare a metal material for manufacturing a metal member.

[0088] [Pretreatment process] The metal material was immersed for 5 minutes in a 2.6% by mass aqueous solution of sodium hydroxide (55°C) containing 0.16% by mass of sodium gluconate while being subjected to ultrasonic cleaning, and then washed with water (20 seconds x 3 times) to carry out a degreasing process. Next, the metal material was immersed for 20 seconds in a 0.002 mass% aqueous sodium hydroxide solution (35°C) containing 0.1 mass% benzotriazole and 0.3 mass% 2-isopropoxyethanol, and then washed with water (20 seconds x 3 times) to remove the coating on the surface of the metal material.

[0089] [Roughening process] An etching solution was prepared by dissolving 9.5% by mass of sulfuric acid, 2% by mass of hydrogen peroxide, 1.1% by mass of benzotriazole, 0.024% by mass of glycine, and 0.00225% by mass of sodium chloride in water. A metal material was immersed in the etching solution (40°C) for 3 minutes, and then washed with water (20 seconds x 3 times) to form a microstructure on the surface of the metal material. The pH of the etching solution at 25°C was measured using a pH meter "D-71" manufactured by Horiba, Ltd., and was found to be 0.3.

[0090] [Post-processing process] The metal material was immersed in water (at room temperature) for 3 minutes while being subjected to ultrasonic cleaning to remove smut, and then dried at 80°C for 20 minutes.

[0091] In this manner, the metal member of Example 1 was produced.

[0092] (Measurement of L value, a value and b value) The L value, a value, and b value of the surface of the metal member were measured using a spectrophotometer "NF333" manufactured by Nippon Denshoku Industries Co., Ltd.

[0093] [Preparation of metal-resin composite] The metal member was placed in a small dumbbell metal insert mold attached to a J55-AD injection molding machine manufactured by Japan Steel Works, Ltd. Next, polyphenylene sulfide (PPS, Tosoh Corporation, Sasteel BGX545) was injection molded into the mold at a mold temperature of 150°C to produce a metal resin composite in which a resin member was formed on the metal member. The area of ​​the joint interface between the metal member and the resin member at this time was 10 mm x 50 mm.

[0094] (Measuring the bonding strength) The shear bond strength (MPa) of the metal-resin composite was measured using a method in accordance with ISO19095. Specifically, a special jig was attached to a tensile testing machine "Model 1323 (manufactured by Aiko Engineering Co., Ltd.)" and the breaking load (N) was measured at room temperature (23°C), with a chuck distance of 60 mm and a tensile speed of 10 mm / min. The measured breaking load (N) was measured based on the area of ​​the joint between the metal and resin parts (50 mm 2 ) to obtain the shear joint strength (MPa). Metal composites with a shear joint strength of 15 MPa or more were judged to have excellent joint strength. The results are shown in Table 1.

[0095] (Helium leak evaluation) To evaluate the airtightness of the metal-resin composite, the helium leak rate was measured using a helium leak detector. A Canon Anelva Technics M-212LD helium leak detector was used. Figure 2 shows the shape of the test specimen for airtightness evaluation (Type D.2.2 specimen) specified in ISO19095-2, and Figure 3 shows its diagonal cross section. This test specimen was made by injecting a light-absorbing material into a rectangular metal plate (50 mm × 50 mm × 2 mm) with a hole of 20 mm in diameter, and bonding the resin material to the periphery of the hole (see Figure 3). In order to ensure the airtightness of the O-ring (packing) installed in the gap between the helium leak detector test jig (test port flange surface) and the test specimen, a non-etched area was provided on the periphery of the metal surface of the test specimen. To leave a part of the metal surface unetched, masking tape (masking tape product name 854 made by 3M Japan) was used.

[0096] A test piece in which no helium leakage was observed within 1 minute after helium gas was pressurized (0.1 MPa) (specifically, the amount of helium leakage from the blank sample within 1 minute after pressurization (5.5 × 10 -7 P a m 3 Test pieces in which the increase in helium leakage from the blank sample exceeded 10% within 1 minute after pressurization were rated as "P" (excellent helium leakage resistance), and test pieces in which helium leakage was observed (specifically, test pieces in which the increase in helium leakage from the blank sample exceeded 10% within 1 minute after pressurization) were rated as "F." The results are shown in Table 1.

[0097] <Example 2 to Example 23> Metal members and metal-resin composites were produced in the same manner as in Example 1, except that the composition of the etching solution, the bonding resin, the solution temperature, and the treatment time were changed as shown in Tables 1 to 4 below. In Table 4, PP represents polypropylene (Prime Polymer Co., Ltd., Prime Polypro V7100), PA6 represents polyamide 6 (Toray Industries, Inc., Amilan CM1011G-30), and PBT represents polybutylene terephthalate (Polyplastics Co., Ltd., Duranex 930HL).

[0098] For Examples 2 to 23, the L value, a value, and b value were measured, the bonding strength was measured, and the helium leakage property was evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 4.

[0099] [Table 1]

[0100] [Table 2]

[0101] [Table 3]

[0102] [Table 4]

[0103] As shown in Tables 1 to 4, the metal-resin composites of Examples 1 to 23, which were produced using metal members satisfying formula (1), were excellent in bonding strength. Comparing Examples 1 to 17 and Examples 20 to 23 in which the etching solution contains an amino acid compound as the amine compound, the metal resin composites of Examples 1 to 7, 14 to 17, and 20 to 23, which were made using metal members satisfying formulas (2) and (3), had excellent helium leak resistance. Furthermore, a comparison of Example 14 and Examples 16 to 19, in which the etching solutions contain the same amount of an amine compound, shows that the metal resin composites of Examples 14, 16 and 17, in which the etching solutions contain an amino acid compound, were excellent in helium leak resistance. [Explanation of symbols]

[0104] 10 Metal materials 30 Resin parts 100 Metal resin composite

Claims

1. CIE1976(L ＊ a ＊ b ＊ 2. A metal member having a surface in which the L value, a value, and b value in a color space satisfy at least one of the following formulas (1) and (2): b≧16 (1) L≧2.336×a−2.0536 (2)

2. CIE1976(L ＊ a ＊ b ＊ 2. The metal member according to claim 1, having a surface in which the L value and a value in the .lambda.) color space satisfy the formula (2) and also satisfy the following formula (3): L≦2.336×a+14.649 (3)

3. CIE1976(L ＊ a ＊ b ＊ 3. The metal member according to claim 2, wherein the surface has an a value in a color space of 1:1, which satisfies the following formula (4): 25≧a≧10 (4)

4. The metal member according to any one of claims 1 to 3, comprising at least one of copper and a copper alloy.

5. The metal member according to any one of claims 1 to 4, wherein a nitrogen-containing heteroaromatic compound is present on at least a portion of the surface.

6. An etching solution comprising an amine compound, a nitrogen-containing heteroaromatic compound, hydrogen peroxide, and an inorganic acid.

7. The etching solution according to claim 6, wherein the content of the amine compound is 0.0001% by mass to 5% by mass with respect to the total mass of the etching solution.

8. 7. The etching solution according to claim 6, wherein the content of the nitrogen-containing heteroaromatic compound is 0.01% by mass to 2.0% by mass with respect to the total mass of the etching solution.

9. 7. The etching solution according to claim 6, wherein the content of the hydrogen peroxide is 0.5% by mass to 7% by mass based on the total mass of the etching solution.

10. 7. The etching solution according to claim 6, wherein the content of the inorganic acid is 5% by mass to 20% by mass based on the total mass of the etching solution.

11. The etching solution according to claim 6 , wherein the amine compound is an amino acid compound.

12. The etching solution according to claim 11 , wherein the amino acid compound is an aliphatic amino acid or a salt thereof.

13. The etching solution according to claim 11, wherein the amino acid compound is an α-amino acid or a salt thereof.

14. The etching solution according to any one of claims 6 to 13, wherein the nitrogen-containing heteroaromatic compound is an azole compound.

15. The etching solution according to claim 14 , wherein the azole compound is a triazole compound.

16. A method for producing a metal member according to any one of claims 1 to 5, A step of roughening at least a portion of the surface of a metal material. A method for manufacturing a metal member comprising the steps of:

17. The method for producing a metal member according to claim 16, wherein the roughening step is a step of etching the at least part of the surface with the etching solution according to any one of claims 6 to 15.

18. A metal resin composite comprising: the metal member according to any one of claims 1 to 5; and a resin member joined to at least a portion of the surface of the metal member.

19. The metal resin composite according to claim 18 , wherein the resin member comprises a thermoplastic resin.

20. The thermoplastic resin is selected from the group consisting of polyolefin-based resins, polyvinyl chloride, polyvinylidene chloride, polystyrene-based resins, AS resins, ABS resins, polyester-based resins, poly(meth)acrylic resins, polyvinyl alcohol, polycarbonate-based resins, polyamide-based resins, polyimide-based resins, polyether-based resins, polyacetal-based resins, fluorine-based resins, polysulfone-based resins, polyphenylene sulfide resins, and ketone-based resins. The metal resin composite according to claim 19, comprising at least one selected from the group consisting of polyolefin-based resins, polyvinyl chloride, polyvinylidene chloride, polystyrene-based resins, AS resins, ABS resins, polyester-based resins, poly(meth)acrylic resins, polyvinyl alcohol, polycarbonate-based resins, polyamide-based resins, polyimide-based resins, polyether-based resins, polyacetal-based resins, fluorine-based resins, polysulfone-based resins, polyphenylene sulfide resins, and ketone-based resins.

21. A step of placing the metal member according to any one of claims 1 to 5 in a mold, and a step of supplying a molten or softened resin to the mold. A method for producing a metal-resin composite comprising the steps of:

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