Metal member

Abstract

To provide a metal member that combines high adhesion to a resin substrate and fine wiring processability.SOLUTION: The metal member comprises a surface with a root-mean-square height Sq of 0.01 μm or more and 0.095 μm or less, and an arithmetic average height Sa of 0.01 μm or more and 0.06 μm or less.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a metal component. [Background technology]

[0002] Metallic members such as copper foils used in printed wiring boards are required to have adhesion to a resin substrate as a support from the viewpoint of quality and reliability. A method of roughening the surface of a metallic member is known as a means for improving this adhesion. That is, from the viewpoint of high adhesion to a resin substrate, the surface of the metallic member is required to be rough. On the other hand, if the surface of a metallic member is roughened, root residues (a state in which the tip of the roughened shape remains unmelted) are generated when etching is performed, and excessive etching is required, making it difficult to form a fine wiring shape. Therefore, from the viewpoint of the performance of enabling fine wiring processing by etching (hereinafter referred to as "fine wiring processability"), the surface of the metallic member is required to be flat.

[0003] In order to satisfy these conflicting demands, a method for treating the surface of copper foil by oxidizing and reducing it has been disclosed (Patent Document 1). Furthermore, as a method for improving adhesion in copper foil treatment using oxidation and reduction, a method for adding surface active molecules in the oxidation step (Patent Document 2) and a method for forming a protective film on the surface of copper foil using an aminothiazole-based compound or the like after the reduction step (Patent Document 3) have been developed. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2014 / 126193 [Patent Document 2] Special Publication No. 2013-534054 [Patent Document 3] Japanese Patent Application Publication No. 8-97559 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the metal members of Patent Documents 1 to 3 are not sufficient in terms of providing a good balance between high adhesion to a resin substrate and high workability for fine wiring.

[0006] SUMMARY OF THE PRESENT EMBODIMENTS Accordingly, an object of the present invention is to provide a metal member that combines high adhesion to a resin substrate with high workability for forming fine wiring. [Means for solving the problem]

[0007] As a result of intensive research into achieving the above object, the present inventors have found that a metal member having a specific configuration can solve the above problems. The present invention was completed based on these findings.

[0008] That is, the present invention provides a metal member having a surface with a root mean square height Sq of 0.01 μm or more and 0.095 μm or less, and an arithmetic mean height Sa of 0.01 μm or more and 0.06 μm or less.

[0009] The product of the root mean square height Sq [μm] and the arithmetic mean height Sa [μm] is 1.0 × 10 -4 More than 5.5 x 10 -3 It is preferable that:

[0010] The surface area ratio of the above surface, calculated by the following formula, is preferably 4.5 or more. Surface area ratio = (BET measurement surface area (dm 2 )-Plane view area of ​​metal part (dm 2 )) / plan view area of ​​metal part (dm 2 )

[0011] The minimum autocorrelation length Sal of the surface is preferably 1.0 μm or more and 4.0 μm or less.

[0012] The metal member includes a metal material and a surface treatment layer formed on the surface of the metal material, and the surface treatment layer is preferably a layer containing Ni and Zn. Effect of the Invention

[0013] The metal member of the present invention has both high adhesion to resin substrates and high processability for forming fine wiring. [Brief description of the drawings]

[0014] [Figure 1] 1 is a schematic cross-sectional view showing one embodiment of a metal member of the present invention. [Diagram 2] 1 is a schematic cross-sectional view showing one embodiment of a laminate of a metal member and a resin substrate according to the present invention. [Diagram 3] FIG. 1 is an explanatory diagram regarding calculation of an etching factor (Ef). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] [Metal parts] The metal member of the present invention is characterized in that it has a surface having a root mean square height Sq of 0.01 μm or more and 0.095 μm or less and an arithmetic mean height Sa of 0.01 μm or more and 0.06 μm or less. In this specification, the surface having the above Sq and Sa may be referred to as "surface X".

[0016] The metal member of the present invention may be configured to have the above-mentioned surface X on the surface of a metal material, or may be configured to include a metal material and a surface treatment layer formed on the surface of the metal material. In the latter case, the surface of the surface treatment layer has the above-mentioned surface X.

[0017] In the metal member of the present invention, the surface X may be formed on at least a part of the surface of the metal member. For example, when the metal member is in the form of a sheet such as a metal foil or a plate such as a metal plate, the surface X may be formed on at least one surface of the metal member, or may be formed on both surfaces. When the surface X is formed on both surfaces of the metal member, at least one of the surfaces may have the surface X.

[0018] The Sq (root mean square height) of the surface X is not particularly limited as long as it is 0.01 μm or more and 0.095 μm or less, but is preferably 0.012 μm or more, and more preferably 0.014 μm or more. Also, for example, it is preferably 0.080 μm or less, more preferably 0.060 μm or less, even more preferably 0.050 μm or less, particularly preferably 0.040 μm or less, and most preferably 0.030 μm or less. Here, the root mean square height Sq represents a parameter (standard deviation of height) equivalent to the standard deviation of the distance from the mean plane, and is measured in accordance with ISO 25178. Sq is an index representing the variation in the height of the convex portion on the surface X. If Sq is large, the variation in the height of the convex portion on the surface X becomes large, and if Sq is small, the variation in the height of the convex portion on the surface X becomes small. When the Sq of the surface X is within the above range, the adhesion between the metal member of the present invention and the resin substrate tends to be improved. In addition, since the height of the fine irregularities of the surface X is uniform, the metal on the surface tends to dissolve stably during wiring formation by etching, a pattern with a high etching factor is obtained, and good fine wiring processability tends to be exhibited.

[0019] The Sa (arithmetic mean height) of the surface X is not particularly limited as long as it is 0.01 μm or more and 0.06 μm or less, but is preferably 0.011 μm or more, more preferably 0.012 μm or more, and even more preferably 0.013 μm or more. Also, for example, it is preferably 0.06 μm or less, more preferably 0.055 μm or less, even more preferably 0.05 μm or less, particularly preferably 0.045 μm or less, and most preferably 0.04 μm or less. Here, the arithmetic mean height Sa is an index representing the average roughness of the surface X, and is measured in accordance with ISO 25178. When Sa is large, the surface X becomes rough, and generally, while the adhesion between the metal member and the resin substrate is improved, the fine wiring processability tends to deteriorate. When Sa of the surface X is within the above range, the adhesion between the metal member of the present invention and the resin substrate is improved, and the root residue (the tip of the roughened shape is left unmelted) is suppressed during wiring formation by etching, so that good fine wiring processability tends to be exhibited. Furthermore, due to the skin effect, the transmission loss of the metal members tends to be further reduced. The root residue can be confirmed from cross-sectional images taken with a scanning electron microscope (SEM).

[0020] In the above metal member, the product of Sq [μm] and Sa [μm] (Sq [μm] × Sa [μm]) is not particularly limited, but is, for example, 1.0 × 10 -4 It is preferable that the ratio is 1.2×10 or more. -4 More preferably, 1.5×10 -4 More preferably, 1.8×10 -4 That's all. For example, 5.5×10 -3 It is preferable that the ratio is 4.5×10 or less, and more preferable that the ratio is 4.5×10 -3 Less than 4.0×10, more preferably -3 Less than 3.3×10 is particularly preferable. -3 When the product of Sq and Sa is within the above range, the adhesion between the metal member of the present invention and the resin base material is improved, and good fine wiring processability tends to be exhibited.

[0021] The Sal (minimum autocorrelation length) of the surface X is not particularly limited, but is preferably 1.0 μm or more, more preferably 1.1 μm or more, even more preferably 1.2 μm or more, and particularly preferably 1.3 μm or more. Also, for example, it is preferably 4.0 μm or less, more preferably 3.5 μm or less, even more preferably 3.0 μm or less, and particularly preferably 2.5 μm or less. Here, the minimum autocorrelation length Sal represents the closest lateral distance at which the autocorrelation of the surface decays to a correlation value s (0≦s<1), and is measured in accordance with ISO 25178. Sal is an index representing the presence or absence of a location on the surface where the height of the convex portion changes suddenly. The flatter the surface X is, the larger Sal is, and the more convex portions there are, the smaller Sal is. When the Sal of the surface X is within the above range, the adhesion between the metal member of the present invention and the resin substrate is improved, and good fine wiring processability tends to be exhibited.

[0022] The surface area ratio of the surface X is not particularly limited, but is preferably 4.5 or more, more preferably 4.8 or more, even more preferably 5.2 or more, and particularly preferably 5.5 or more. Also, for example, it is preferably 15 or less, more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. When the surface area ratio of the surface X is within the above range, the metal member of the present invention and the resin substrate tend to exhibit good adhesion. Here, the surface area ratio is the two-dimensional area 1 m calculated from the specific surface area measured by the krypton gas adsorption BET method. 2 This refers to the surface area ratio per unit area. More specific details will be described in the Examples below. The more convex parts there are on the surface X, the larger the surface area ratio becomes.

[0023] (metallic material) The metal material refers to a material whose surface is partly or entirely made of metal. The surface of the metal material has a different structure from that of the surface treatment layer described later (particularly, the metal oxide layer or other metal layer described later). The material inside the metal material (the inside of the metal present on the surface) may be a metal or a material other than a metal (e.g., a resin substrate, etc.), but is preferably a metal. That is, the metal material is preferably a material made entirely of a metal. Examples of metals as the metal material include titanium, niobium, tantalum, nickel, zinc, aluminum, copper, silver, gold, platinum, and alloys thereof (e.g., stainless steel). Among these, copper is preferable. That is, the metal material is preferably a copper material, and is preferably a material made entirely of copper.

[0024] When the metal material is a copper material, the purity of the copper on the surface of the copper material is preferably, for example, 95% by mass or more, 99% by mass or more, or 99.9% by mass or more of pure copper. Even when the copper material is a material made entirely of copper, the purity of the copper is preferably within the above range. Examples of such copper include tough pitch copper, deoxidized copper, and oxygen-free copper. Among them, oxygen-free copper having an oxygen content of 0.001 to 0.0005% by mass is preferable.

[0025] The shape of the metal material is not particularly limited, but is preferably a sheet such as a metal foil or a plate such as a metal plate. Examples of the metal foil include electrolytic metal foil and rolled metal foil. Examples of the metal foil include copper foil such as electrolytic copper foil, rolled copper foil, and copper foil with carrier. Examples of the metal plate include copper plates. Here, the metal foil refers to a metal foil having a thickness of 100 μm or less, and the metal plate refers to a metal foil having a thickness of more than 100 μm. The thickness of the metal foil is preferably 0.1 μm or more, more preferably 0.5 μm or more, and even more preferably 1 μm or more. Also, it is preferably 80 μm or less, and more preferably 50 μm or less. The thickness of the metal plate is preferably 0.3 mm or more, more preferably 0.5 mm or more, even more preferably 1 mm or more, and particularly preferably 5 mm or more. Also, it is preferably 5 cm or less, more preferably 3 cm or less, and even more preferably 1 cm or less.

[0026] (Surface treatment layer) The surface treatment layer may be either a metal layer or a non-metal layer, but is preferably a metal layer from the viewpoint of improving adhesion to the resin substrate and fine wiring processability. Here, the metal layer means a layer containing a metal, for example, other metal layers. In addition, for example, when the metal oxide layer contains a metal, the metal oxide layer corresponds to the metal layer. In addition, the non-metal layer means a layer that does not contain a metal, and is a concept that includes a layer that does not substantially contain a metal, such as a silicon compound layer described later. Examples of the surface treatment layer include a metal oxide layer, a layer of other metals other than the metal that is the main component of the metal material (other metal layers), a silicon compound layer, and the like. The metal oxide layer may be an oxide layer of the metal that constitutes the metal material, or an oxide layer of the other metal. In addition, the surface treatment layer may be a metal layer composed of the same composition as the metal that constitutes the metal material, but when the surface treatment layer has such a metal layer, the metal layer is present at a position that does not form an interface with the metal material. For example, when the metal constituting the metal member is copper, the metal oxide is preferably a copper oxide layer, and the other metal layer is preferably a layer containing a metal other than copper (a metal layer other than copper).

[0027] The surface treatment layer may be a single layer or a multilayer. When the surface treatment layer includes a metal oxide layer and another metal layer, the metal member of the present invention preferably includes, from the surface, another metal layer, a metal oxide layer, and a metal material. When the surface treatment layer includes a metal oxide layer, another metal layer, and a silicon compound layer, the metal member of the present invention preferably includes, from the surface, a silicon compound layer, another metal layer, a metal oxide layer, and a metal material.

[0028] Metal oxide layer The metal member of the present invention may have a metal oxide layer (metal oxide layer) of the metal constituting the metal material formed on the surface of the metal material. That is, the metal member may include a metal material and a metal oxide layer formed on the surface of the metal material. When the metal member of the present invention includes a metal oxide layer, the adhesion and heat resistance reliability between the metal member and the resin substrate tend to be improved. In particular, when a copper oxide layer is included as the metal oxide layer, the adhesion and heat resistance reliability of the metal member tend to be further improved. Examples of copper oxide in the copper oxide layer include copper oxide (CuO), cuprous oxide (CuO), and copper oxide (CuO). 2 O), either one or both of which may be contained in the copper oxide layer. The content of the metal oxide in the metal oxide layer is not particularly limited, and is, for example, 0.1 mass% or more, 0.3 mass% or more, 0.5 mass% or more, 1 mass% or more, 3 mass% or more, 5 mass% or more, or 10 mass% or more. When the metal oxide layer is a copper oxide layer, the copper oxide layer is copper hydroxide (Cu(OH) 2 ), and the content thereof is, for example, 0.01 mass% or more, 0.03 mass% or more, 0.05 mass% or more, 0.1 mass% or more, 0.5 mass% or more, 1 mass% or more, 3 mass% or more, or 5 mass% or more.

[0029] The thickness of the metal oxide layer is not particularly limited, but is preferably 500 nm or less, more preferably 300 nm or less, even more preferably 200 nm or less, particularly preferably 160 nm or less, and most preferably 90 nm or less. Also, for example, it is preferably 20 nm or more, more preferably 30 nm or more, and even more preferably 40 nm or more. The thickness of the metal oxide layer refers to the thickness measured, for example, by SERA measurement, when the thickness is converted into a uniform state.

[0030] The method for forming the metal oxide layer is not particularly limited, but examples thereof include a method of subjecting a metal material to an oxidation treatment using an oxidizing agent. Alternatively, the metal material after the oxidation treatment may be subjected to a reduction treatment using a reducing agent to form the metal oxide layer. In the case where a metal oxide layer is formed by subjecting a metal material to an oxidation treatment in the metal member of the present invention, the formed metal oxide layer is not a part of the metal material but is defined as a surface treatment layer.

[0031] Other metal layers In the metal member of the present invention, a metal layer (another metal layer) other than the metal that is the main component of the metal member may be formed on a part or all of the surface of the metal member. When a metal oxide layer is formed on the surface of the metal member, the other metal layer may be formed so as to cover a part or all of the surface of the metal oxide layer. When the other metal layer is a layer containing a metal other than copper, the adhesion and heat resistance reliability of the metal member tend to be further improved.

[0032] The metal in the other metal layer is not particularly limited, but is preferably a metal other than copper, and more preferably a magnetic metal or a non-magnetic metal other than copper. Examples of magnetic metals include Ni, Co, Fe, Gd, etc. Examples of non-magnetic metals other than copper include Zn, Cr, Mo, Ti, Al, Mn, etc. When the metal layer simultaneously contains a magnetic metal and a non-magnetic metal other than copper, the metal member tends to have excellent adhesion to the resin substrate and fine wiring processability. When the metal layer is a layer simultaneously containing a magnetic metal and a non-magnetic metal other than copper, the combination includes Ni-Cr, Ni-Zn, Ni-Mn, Co-Cr, Co-Zn, Co-Mn, Al-Ni-Co, etc. Among these, Ni has high corrosion resistance, and improves acid resistance, moisture resistance, and heat resistance, improving adhesion to the resin substrate, but has high resistance to the etching solution, so that it may remain undissolved after etching. On the other hand, Zn has a property of being more easily dissolved by etching than Ni, so it tends to be less likely to remain undissolved. However, Zn is not sufficiently resistant to corrosion compared to Ni, and adhesion to the resin substrate is difficult to maintain. When the metal layer is a layer containing Ni and Zn (Ni-Zn), the metal layer tends to be able to achieve both etching properties and adhesion to the resin substrate by containing both Ni, which has high corrosion resistance, and Zn, which is easily etched. In addition, if the metal layer has magnetism, it is greatly affected by the skin effect, which is not preferable from the viewpoint of transmission loss. When the metal layer is a layer containing Ni and Zn (Ni-Zn), although it contains ferromagnetic Ni, the presence of Zn causes magnetic transformation, which changes the ferromagnetic material to a paramagnetic material, so that it can exhibit excellent transmission loss without being affected by the skin effect due to magnetism. Note that the magnetic transformation of Ni by Zn tends to occur when the ratio of the amount of Zn attached per unit area to the total amount of Ni and Zn attached per unit area is around 20% (for example, 10% or more, 16% or more, 19% or more, or 25% or more).

[0033] In a layer containing a magnetic metal and a non-magnetic metal other than copper, the ratio of the amount of the non-magnetic metal other than copper attached per unit area to the total amount of the magnetic metal and the non-magnetic metal other than copper attached per unit area is not particularly limited, and is, for example, 10% or more, 16% or more, 19% or more, 25% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 73% or more, 75% or more, or 78% or more. Also, for example, it is less than 100%, 95% or less, 92% or less, 90% or less, or 87% or less. The amount of the magnetic metal or the non-magnetic metal other than copper attached per unit area can be calculated, for example, by dissolving it in an acidic solution, measuring the amount of metal by ICP analysis, and dividing it by the planar field area of ​​the structure.

[0034] In the layer containing a magnetic metal and a non-magnetic metal other than copper, the deposition amount (total amount) of the magnetic metal and the non-magnetic metal other than copper per unit area is not particularly limited, but is, for example, 1.1 mg / dm 2 More preferably, it is 1.4 mg / dm or more. 2 More preferably, 1.8 mg / dm 2 More preferably, 2.0 mg / dm 2 For example, 6.0 mg / dm 2 It is preferable that the concentration is less than 4.0 mg / dm 2 Less than 3.1 mg / dm 2 Less than 3.0 mg / dm 2 The following is the result.

[0035] In the layer containing a magnetic metal and a non-magnetic metal other than copper, the amount of the non-magnetic metal other than copper deposited per unit area is not particularly limited, but is, for example, 0.25 mg / dm 2 More preferably, it is 1.0 mg / dm or more. 2 More preferably, 1.3 mg / dm 2 More preferably, 1.6 mg / dm 2 or more, most preferably 1.7 mg / dm 2 For example, 6.0 mg / dm 2 It is preferable that the concentration is less than 4.0 mg / dm2 Less than 3.0 mg / dm 2 Less than 2.9 mg / dm 2 Less than 2.75 mg / dm 2 The following is the result.

[0036] In the layer containing a magnetic metal and a non-magnetic metal other than copper, the amount of the magnetic metal deposited per unit area is not particularly limited, but is, for example, 0.05 mg / dm 2 It is preferable that the concentration is 0.1 mg / dm or more, and more preferable that the concentration is 0.1 mg / dm 2 More preferably, 0.2 mg / dm 2 More preferably, 0.3 mg / dm 2 or more, most preferably 0.35 mg / dm 2 For example, 3.5 mg / dm 2 It is preferable that the concentration is less than 3.0 mg / dm 2 Less than 1.5 mg / dm 2 Less than 1.0 mg / dm 2 Less than 0.8 mg / dm 2 Less than 0.6 mg / dm 2 The following is the result.

[0037] In a layer containing a magnetic metal and a non-magnetic metal other than copper, the ratio of the amount of Mo deposited per unit area to the total amount of the magnetic metal and the non-magnetic metal other than copper deposited per unit area is not particularly limited, but is preferably, for example, 1.0% or less, more preferably 0.7% or less, even more preferably 0.4% or less, and particularly preferably 0.0%, i.e., essentially none.

[0038] The other metal layer is formed, for example, by plating the surface of the metal material or the metal oxide layer using a plating solution. In other words, the other metal layer can be said to be a plating layer containing other metals. The plating solution is not particularly limited as long as it contains a metal other than the metal that is the main component of the metal material, but it is preferable that it contains a metal other than copper, and more preferable that it contains a magnetic metal or a non-magnetic metal other than copper. The plating method is not particularly limited, and plating can be performed by electrolytic plating, electroless plating, vacuum deposition, chemical conversion treatment, etc., but electrolytic plating is preferable because it is preferable to form a uniform plating layer.

[0039] The thickness (equivalent to a planar surface) of the other metal layer is not particularly limited, but is preferably 1 to 190 nm, more preferably 5 to 150 μm, even more preferably 10 to 120 μm, particularly preferably 20 to 100 μm, and most preferably 30 to 80 μm. When the thickness of the metal layer is within the above range, the metal layer tends to be uniformly distributed, and therefore the adhesion to the resin substrate and the heat resistance reliability tend to be excellent. When the thickness of the metal layer is thin, the metal layer is not uniformly distributed and exists discretely, and therefore the adhesion and the heat resistance reliability tend to be poor. The thickness of the metal layer (equivalent to a planar surface) can be calculated, for example, by dividing the amount of adhesion of the metal per unit area by the density of the metal.

[0040] Silicon compound layer In the metal member of the present invention, the metal material, the metal oxide layer, and the other metal layer may have a silicon compound layer formed on a part or all of the surface thereof. In particular, it is preferable that the silicon compound layer is formed on a part or all of the surface of the metal layer. By including the silicon compound layer, the heat resistance reliability of the metal member of the present invention tends to be further improved.

[0041] The silicon compound layer is a layer containing a silicon compound. In the silicon compound layer, "containing a silicon compound" includes not only the silicon compound itself but also a part of the silicon compound chemically bonded to a material in contact with the silicon compound layer. Examples of the above material include metal materials, metal oxides contained in metal oxide layers, and metals contained in other metal layers. Specific examples include a part of a silane coupling agent chemically bonded to the above material by a silane coupling treatment described later. That is, the silicon compound layer may be formed by a coupling treatment such as silane coupling.

[0042] Examples of the silicon compound include SiO, SiO 2 , SiO 4 etc. x O y Silicon oxide represented by SiO 4 H 4 , Si 2 O 7 H 6 , SiO 3 H 2 , Si 2 O 5 H 2 etc. x O y H z Silicon hydroxide represented by the formula; water glass (Na 2 SiO 3) and other inorganic silicon compounds; alkoxysilanes, silane coupling agents, polyether modified silicones, silicon carbides, silicon sulfides, silicon nitrides and other organic silicon compounds; silicon halides. As the silane coupling agent, for example, those having 2 or 3 hydrolyzable groups are preferred, and those having a methoxy group or an ethoxy group as the hydrolyzable group are preferred. As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-ureidopropyltrialkoxysilane, 3-acryloxypropyltrimethoxysilane and the like can be mentioned. As an example of the embodiment in which a part of the silicon compound is chemically bonded to the above-mentioned material, for example, the SiO group derived from the silane coupling agent is chemically bonded to the above-mentioned material. In the silicon compound layer, the above-mentioned silicon compounds can be used alone or in combination of two or more.

[0043] Methods for confirming the silicon compound layer, i.e., methods for confirming whether or not the silicon compound layer contains a silicon compound, include, for example, elemental analysis by time-of-flight secondary ion mass spectrometry (TOF-SIMS) or X-ray photoelectron spectroscopy (XPS).

[0044] The metal member of the present invention may have protrusions. The protrusions may be formed as at least a part of the metal member, or may be formed as at least a part of the surface treatment layer. The protrusions may be formed on a part or the whole of the surface of the metal material. In addition, when the metal oxide layer is formed on the surface of the metal material, the protrusions may be formed on a part or the whole of the surface of the metal oxide layer.

[0045] The protrusions may contain a metal constituting the metal material and / or an oxide of the metal. A method for forming protrusions containing a metal on the surface of a metal material includes plating using a metal plating solution. A method for forming protrusions containing a metal oxide on the surface of a metal material includes oxidation of the surface of a metal material. When protrusions are formed by oxidation, the metal oxide layer is formed on the surface of the metal material. That is, when the metal member of the present invention includes a metal oxide layer as the surface treatment layer, the protrusions are formed on the surface of the metal material as part of the metal oxide layer.

[0046] In terms of adhesion to the resin substrate and fine wiring processability, the metal material is preferably a copper material. The protrusions preferably contain the above-mentioned copper and / or an oxide other than copper, more preferably an oxide other than copper. A method for forming the protrusions containing copper oxide on the surface of a copper material includes a method of subjecting the surface of the copper material to an oxidation treatment.

[0047] When the metal material has protrusions, the surface of the surface treatment layer is appropriately roughened, and the above Sq and Sa, the product of Sq [μm] and Sa [μm], and Sal are in an appropriate range, which tends to further improve the adhesion to the resin substrate and the fine wiring processability of the metal component of the present invention.

[0048] The height of the protrusions is not particularly limited, but is preferably larger than the Sq of the surface of the surface treatment layer, for example, preferably 100 nm or more, more preferably 120 nm or more, even more preferably 150 nm or more, and particularly preferably 158 nm or more. Also, it is preferably 600 nm or less, more preferably 500 nm or less, even more preferably 400 nm or less, particularly preferably 350 nm or less, and most preferably 301 nm or less. The height of the protrusions can be measured, for example, by calculating the average value of the distance between the midpoint of the line segment connecting the minimum points of adjacent recesses with a certain interval between the protrusions sandwiched between the recesses as the height of the protrusions in a cross-sectional image of a scanning electron microscope (SEM).

[0049] The metal member of the present invention can be suitably used in applications requiring high adhesion to a resin substrate. For example, in the form of a laminate in which a metal member and a resin substrate are laminated, it can be suitably used as a material for printed wiring boards and lithium ion batteries. Examples of printed wiring boards include flexible copper clad laminates (FCCL) for flexible printed circuit boards (FPC), copper clad laminates (CCL) for rigid substrates, and build-up materials. It can also be used as a peelable copper foil.

[0050] Examples of the resin substrate include at least one insulating resin selected from the group consisting of polyphenylene ether (PPE), epoxy, polyphenylene oxide (PPO), polybenzoxazole (PBO), polytetrafluoroethylene (PTFE), liquid crystal polymer (LCP), thermoplastic polyimide (TPI), fluororesin, polyetherimide, polyetheretherketone, polycycloolefin, bismaleimide resin, low dielectric constant polyimide, and cyanate resin.

[0051] FIG. 1 is a schematic cross-sectional view showing one embodiment of the metal member of the present invention. 1 is a metal member (particularly a copper member), 2 is a metal material (particularly a copper material), 3 is a surface treatment layer, 4 is a protrusion, and 5 is another metal layer (particularly a metal layer other than copper). Although a silicon compound layer is not shown, it may be formed on the surface of the other metal layer 5. The protrusion 4 is a part of the surface treatment layer 3 and contains a metal oxide (particularly a copper oxide). The other metal layer 5 is formed on the surface of the protrusion 4 so as to form the surface of the surface treatment layer 3. FIG. 2 is a schematic cross-sectional view showing one embodiment of the laminate of the metal member and the resin substrate of the present invention. 10 is a laminate, 11 is a metal member, and 12 is a resin substrate.

[0052] [Metal component manufacturing method] An example of the method for producing a metal member of the present invention will be described below, but the method is not limited thereto. The method for producing a metal member of the present invention includes, for example, the following steps. A process for forming protrusions containing metal and / or metal oxide on the surface of a metal material (protrusion forming process) After the protrusion forming process, the surface of the obtained metal material is plated with a plating solution (plating process). After the plating process, the surface of the resulting metal material is treated with a coupling agent (coupling process).

[0053] In addition, when a laminate is produced using the metal member of the present invention and a resin substrate, the method for producing the laminate may further include the following steps. After the coupling treatment step, the metal material obtained and the resin substrate are laminated together so that the projections formed on the surface of the metal material come into contact with the resin substrate to form a laminate (laminate formation step).

[0054] (Protrusion formation process) The protrusion forming step is a step of forming protrusions containing a metal and / or a metal oxide on the surface of a metal material. A method of forming protrusions containing a metal on the surface of a metal material includes, for example, plating with a metal plating solution such as a copper plating solution. That is, this step may be a step of forming protrusions containing a metal by plating the surface of a metal material with a metal plating solution (metal plating step). An example of a method for forming protrusions containing a metal oxide on the surface of a metal material is a method for performing an oxidation treatment on the metal material. In the above method, when the protrusions containing a metal oxide are formed by the oxidation treatment, a metal oxide layer is formed on the surface of the metal material. That is, this process may be a process for forming protrusions containing a metal oxide by performing an oxidation treatment on the surface of the metal material (oxidation treatment process).

[0055] The oxidation treatment step is a step of forming protrusions containing a metal oxide on the surface of a metal material by oxidation treatment, and also forms a metal oxide layer on the surface of the metal material.

[0056] In the oxidation treatment step, before the oxidation treatment, a roughening treatment such as soft etching or etching, a degreasing treatment, an acid cleaning treatment for removing a natural oxide film of the metal material, an alkali treatment after the acid cleaning treatment, etc. may be performed. The alkali treatment is not particularly limited, but an example thereof is a method of treating with a 0.1 to 100 g / L alkali aqueous solution (e.g., a sodium hydroxide aqueous solution) at 30 to 60° C. for about 0.5 to 2 minutes.

[0057] The method of the oxidation treatment is not particularly limited, and examples thereof include a method using an oxidizing agent, a method using thermal oxidation, a method using electrolytic oxidation, and the like. Among these, the method using an oxidizing agent is preferred from the viewpoint of improving adhesion to a resin substrate.

[0058] The oxidizing agent is not particularly limited, but for example, an aqueous solution of a chlorate such as sodium chlorite, sodium hypochlorite, potassium chlorate, or potassium perchlorate is preferably used. The oxidizing agent may contain additives such as an alkali salt such as potassium hydroxide, a phosphate such as trisodium phosphate dodecahydrate, an alkali such as potassium hydroxide, or a surface active molecule (for example, a silane coupling agent such as 3-glycidoxypropyltrimethoxysilane). The oxidizing agent may be used alone or in combination of two or more kinds.

[0059] When the oxidation treatment is performed using an oxidizing agent, the treatment temperature is not particularly limited, but is preferably, for example, 30 to 95° C., and more preferably, 40 to 80° C. The treatment time is not particularly limited, but is preferably, for example, 0.2 to 30 minutes, and more preferably, 0.4 to 10 minutes. The concentration of the chlorate in the oxidizing agent is not particularly limited, but is preferably, for example, 5 to 400 g / L, and more preferably, 10 to 300 g / L.

[0060] After the oxidation treatment step, the surface of the metal material may be reduced with a reducing agent. When a copper material is used as the metal material, cuprous oxide (copper (I) oxide) may be formed on the surface of the metal material by the reduction treatment. The reducing agent is not particularly limited, but examples thereof include solutions of boron compounds such as dimethylamine borane (DMAB), diborane, sodium borohydride, and hydrazine.

[0061] The size, thickness, height, length, etc. of the protrusions containing metal oxide may be adjusted by a chelating treatment using a chelating agent (particularly a biodegradable chelating agent) on the surface of the metal material. The chelating agent is not particularly limited, but examples thereof include solutions of ethylenediaminetetraacetic acid, diethanolglycine, tetrasodium L-glutamic acid diacetate, ethylenediamine-N,N'-disuccinic acid, sodium 3-hydroxy-2,2'-iminodisuccinate, trisodium methylglycine diacetate, tetrasodium aspartic acid diacetate, disodium N-(2-hydroxyethyl)iminodiacetate, sodium gluconate, nickel chloride, etc. The pH of the chelating agent is not particularly limited, but is preferably alkaline, more preferably pH 8 to 10.5, even more preferably pH 9.0 to 10.5, and even more preferably pH 9.8 to 10.2. The chelating agents may be used alone or in combination of two or more.

[0062] In the metal material of the present invention, parameters relating to the surface roughness of the surface of the surface treatment layer (e.g., root mean square height (Sq), arithmetic mean height (Sa), minimum autocorrelation length (Sal), etc.) can be adjusted, for example, by the oxidation treatment method in the oxidation treatment step. Specifically, they can be adjusted by the type of oxidizing agent used, the contents of components contained in the oxidizing agent, and the temperature and time in the oxidation treatment. However, the above parameters can also be adjusted by means other than the oxidation treatment method. In addition, protrusions may be formed by a plating treatment step described later.

[0063] (Plating process) The plating process is a process of plating the surface of a metal material using a plating solution. This process may be performed after the protrusion forming process. This process may also be a process of performing plating for the purpose of forming metal-containing protrusions on the surface of a metal material. In other words, this process may also serve as a protrusion forming process. The plating method is not particularly limited, and examples thereof include electrolytic plating, electroless plating, vacuum deposition, and chemical conversion treatment, but electrolytic plating is preferred from the viewpoint of forming a uniform plating layer. By performing plating on a metal material, the above-mentioned other metal layers can be formed.

[0064] When forming a layer containing a magnetic metal and a non-magnetic metal other than copper as the other metal layer, the plating solution may be used for plating with a plating solution containing either magnetic metal ions or non-magnetic metal ions other than copper, followed by plating with a plating solution containing the other ions, or may be used for plating with a plating solution containing both magnetic metal ions and non-magnetic metal ions other than copper. For example, when the magnetic metal and non-magnetic metal other than copper are Ni and Zn, the plating solution containing nickel ions may contain nickel sulfate, nickel pyrophosphate, nickel chloride, nickel oxide, nickel carbonate, nickel hydroxide, nickel nitrate, nickel sulfamate, etc., and the plating solution containing zinc ions may contain zinc sulfate, zinc pyrophosphate, zinc chloride, zinc oxide, zinc carbonate, zinc hydroxide, zinc nitrate, zinc sulfide, zinc sulfamate, etc. The plating solution may contain additives such as a pH buffer and a brightener. Other additives including pH buffers and gloss agents include, for example, boric acid, nickel acetate, citric acid, sodium citrate, ammonium citrate, potassium formate, malic acid, sodium malate, sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium chloride, sodium cyanide, potassium sodium tartrate, potassium thiocyanate, sulfuric acid, hydrochloric acid, potassium chloride, ammonium sulfate, ammonium chloride, potassium sulfate, sodium sulfate, sodium thiocyanate, sodium thiosulfate, potassium bromate, potassium pyrophosphate, potassium chloride, ethylenediamine, nickel ammonium sulfate, sodium thiosulfate, sodium chloride, hydrofluoric acid, sodium silicofluoride, strontium sulfate, cresol sulfonic acid, β-naphthol, saccharin, 1,3,6-naphthalene trisulfonic acid, naphthalene (di, tri), sodium sulfonate, sulfonamide, sulfinic acid, and ammonia.

[0065] For example, when applying Ni plating to a metal material, the area of ​​the metal material to be electrolytically plated is dm 2 It is preferable to apply a charge of 5 C to 90 C, and more preferably 10 C to 65 C, per unit area dm of the metal material to be electrolytically plated. 2It is preferable to apply a charge of 5C to 90C, and more preferably 10C to 65C, per unit time. When electrolytic plating is performed on the surface of an oxidized copper material, an electric charge is first used to reduce the copper oxide on the surface to cuprous oxide or pure copper. Then, the metal corresponding to the electrolytic plating used starts to precipitate, forming a metal layer. The amount of electric charge required varies depending on the type of plating solution and the amount of copper oxide.

[0066] When plating is performed, the treatment temperature is not particularly limited, but is preferably, for example, 20 to 100° C., and more preferably, 25 to 90° C. The treatment time is not particularly limited, but is preferably, for example, 0.2 to 30 minutes, and more preferably, 0.4 to 10 minutes. The concentration of the magnetic metal salt and the non-magnetic metal salt other than copper in the plating solution used for plating is not particularly limited, but is, for example, preferably 0.01 to 100 g / L, and more preferably 0.1 to 30 g / L.

[0067] The current density in electrolytic plating is not particularly limited, but is preferably 0.2 A / dm 2 ~10A / dm 2 is preferred.

[0068] In the metal material of the present invention, parameters relating to the surface roughness of the surface of the surface treatment layer (e.g., root mean square height (Sq), arithmetic mean height (Sa), minimum autocorrelation length (Sal), etc.) can be adjusted, for example, by the plating method in the plating process. Specifically, they can be adjusted by the contents of the components contained in the plating solution, and the temperature and time in the plating process. However, the above parameters can also be adjusted by means other than the plating method.

[0069] (Coupling treatment process) The coupling treatment step is a step of performing a coupling treatment on a metal material. This step may be performed after the oxidation treatment step.

[0070] The coupling agent for treating metal material is not particularly limited, but silane coupling agent is preferred.As the silane coupling agent, the one described in the above-mentioned silicon compound layer can be mentioned.When using silane coupling agent as the coupling agent for treating metal material, the above-mentioned silicon compound layer can be formed.

[0071] The specific method of the coupling treatment is not particularly limited, and examples thereof include a method of applying the coupling agent solution to the surface of the metal material with a roller or a bar coater, a method of spraying the solution, or a method of immersing the metal material in the coupling agent solution. After the metal material is treated with the coupling agent solution, it is dried. The temperature and time for drying are not particularly limited as long as the solvent is completely evaporated, but it is preferable to dry at 70°C for 1 minute or more. Examples of the solvent used in the coupling agent solution include water, an organic solvent, or a mixed solvent thereof. The concentration of the coupling agent is not particularly limited, but it is preferably 0.5 to 20 mass% or less.

[0072] (Laminate formation process) The laminate formation step is a step of laminating a resin substrate and a metal material to form a laminate. More specifically, the resin substrate and the metal material are laminated so that the resin substrate and the protrusions formed on the surface of the metal material are in contact with each other to form a laminate. In this step, the laminate may be formed by applying pressure to the laminate while heating it as necessary. That is, this step may be a step of laminating a resin substrate and a metal material so that the resin substrate and the protrusions formed on the surface of the metal material are in contact with each other, and forming a laminate by applying pressure while heating it as necessary.

[0073] The resin substrate is not particularly limited, but preferably contains at least one insulating resin selected from the group consisting of polyphenylene ether (PPE), epoxy, polyphenylene oxide (PPO), polybenzoxazole (PBO), polytetrafluoroethylene (PTFE), liquid crystal polymer (LCP), thermoplastic polyimide (TPI), fluororesin, polyetherimide, polyetheretherketone, polycycloolefin, bismaleimide resin, low dielectric constant polyimide, and cyanate resin. That is, the resin substrate is preferably an insulating substrate.

[0074] The thickness of the resin substrate is not particularly limited, but is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm, and even more preferably 1 to 30 μm. The resin substrate may further contain an inorganic filler or glass fiber. The relative dielectric constant of the resin substrate is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.8 or less. EXAMPLES

[0075] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0076] [Manufacturing of metal parts] In Examples 1 to 8 and Comparative Examples 3 to 5, copper members were manufactured using copper foil (product name: DR-WS, thickness: 18 μm, manufactured by Furukawa Electric Co., Ltd.) as the copper material. Specifically, the shiny side of the copper foil was subjected to the following treatments to form a surface treatment layer on the copper foil. Each treatment is described in detail below. Conditions for some of the treatments are shown in Table 1. The shiny side is also called the glossy side, and refers to a side that is flatter than the other side. The other side is called the matte side (non-glossy side).

[0077] Alkaline degreasing treatment The copper foil was degreased by immersing it in a 40 g / L aqueous solution of sodium hydroxide at a liquid temperature of 50° C. for 1 minute to remove dirt from the copper surface. The copper foil was then washed with water. Acid cleaning treatment Next, the copper foil that had been subjected to the alkaline degreasing treatment was subjected to acid cleaning by immersing it in a 10% by mass aqueous sulfuric acid solution at a liquid temperature of 25° C. for 2 minutes to remove the oxide film on the copper surface. Thereafter, the copper foil was washed with water. Pre-dip processing Furthermore, the copper foil that had been subjected to the acid washing treatment was subjected to a pre-dip treatment by immersing it in a 5 g / L aqueous solution of sodium hydroxide at 25° C. for 60 seconds to prevent the inclusion of acid in the subsequent oxidation treatment process.

[0078] Oxidation treatment The copper foil that had been pre-dip treated was subjected to an oxidation treatment using an oxidizing agent and treatment conditions of the composition shown in Table 1 to form a copper oxide layer on the surface of the copper foil. For example, in Example 1, an oxidizing agent consisting of 230 g / L sodium chlorite, 18 g / L potassium hydroxide, and 0.5 g / L 3-glycidoxypropyltrimethoxysilane (product name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was used, and the copper foil was immersed in the oxidizing agent at 50° C. for 60 seconds to perform the oxidation treatment.

[0079] Plating process The copper foil after the pre-plating treatment was subjected to plating treatment using the plating solution and treatment conditions of the composition shown in Table 1 to form a plating layer on the surface of the copper foil. For example, in Example 1, the copper foil was immersed in a Ni-Zn electrolytic plating solution (a plating solution having a Ni ion concentration of 0.25 g / L (nickel sulfate hexahydrate was used as the Ni source), a Zn ion concentration of 4 g / L (zinc diphosphate was used as the Zn source), and 100 g / L potassium diphosphate) at 40° C., and then immersed in the plating solution for 50 seconds at a current density of 0.5 A / dm 2 The electrolytic plating treatment was carried out under the following conditions.

[0080] Coupling treatment The copper foil after plating was immersed in an aqueous solution of 3-aminopropyltriethoxysilane (product name: KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) at a liquid temperature of 25° C. for 60 seconds. Then, baking was performed by drying at 110° C. for 1 minute. In this manner, a surface treatment layer was formed on the copper foil.

[0081] [evaluation] The copper members obtained in Examples 1 to 8 and Comparative Examples 3 to 5, Comparative Example 1 / FV-WS (manufactured by Furukawa Electric Co., Ltd.), and Comparative Example 2 / SI-VSP (manufactured by Mitsui Mining and Smelting Co., Ltd.) were evaluated as follows.

[0082] (Evaluation 1: Ni and Zn adhesion amount per unit area) The amount of Ni and Zn attached per unit area was measured for the treated surface (shiny surface of copper foil) of the copper members of Examples 1 to 8 and Comparative Examples 3 to 5. First, the copper members were dissolved in 12% nitric acid, and the resulting liquid was analyzed using an ICP emission spectrometer 5100 SVDV ICP-OES (manufactured by Agilent Technologies, Inc.) to measure the concentration of Ni and Zn, and the amount of Ni and Zn attached per unit area of ​​the copper members used was calculated. In addition, the ratio of the amount of Zn attached to the layer containing Ni and Zn was calculated using the following formula. "Proportion of Zn coating weight in layer containing Ni and Zn" = [Zn coating weight / (Ni coating weight+Zn coating weight)] x 100(%)

[0083] The measurement results (calculated results) are shown in Table 1 under "Plating weight" as "Zn (mg / dm 2 )," "Ni(mg / dm 2 ) and "Zn deposition rate (%)".

[0084] (Evaluation 2: Measurement of surface roughness) The treated surfaces of the copper members of Examples 1 to 8 and Comparative Examples 1 to 5 were measured for their root mean square height (Sq), arithmetic mean height (Sa), and minimum autocorrelation length (Sal) using a laser microscope (Olympus Corporation / LEXT OLS5100), which is a confocal microscope conforming to ISO25178-607, with a wavelength of 405 nm, an objective lens magnification of 100x, an optical zoom of 1.0x, an evaluation area (image area) of 129μm×129μm, automatic tilt removal mode, no S filter, an L filter of 8μm, and a Gaussian filter. The measurement results are shown in the "Sq (μm)", "Sa (μm)", and "Sal (μm)" sections of "Surface roughness" in Table 1. The product of "Sa (μm)" and "Sq (μm)" was also calculated, and "Sa *The values ​​are shown in the "Sq" section.

[0085] (Rating 3: Surface area ratio) For the copper members of Examples 1 to 8 and Comparative Examples 1 to 5, the surface area ratio was calculated by the following formula, and the measurement results are shown in the "Surface Area Ratio" section of Table 1. The surface area ratio of the metal member was calculated from the following formula with "copper member" replaced with "metal member." Surface area ratio = (BET measurement surface area (dm 2 )-Plane area of ​​copper part (dm 2 )) / plan view area of ​​copper part (dm 2 )

[0086] BET measured surface area of ​​each copper component (dm 2 ) was measured by the multi-point krypton gas adsorption BET method using a multi-sample high-performance specific surface area analyzer 3FLEX manufactured by Micromeritics Co., Ltd. In addition, each copper component was pretreated by drying under reduced pressure at 100°C for 2 hours before the measurement. The test pieces used for the measurement were cut into 110 pieces of 30 mm x 7 mm per 3.83 g of original copper foil.

[0087] In addition, in the surface area measurement by the BET method, the surface area of ​​the entire surface of the test piece introduced into the device is measured, so it is not possible to measure the surface area of ​​only the treated surface of the copper member that has been treated on only one side. Therefore, the surface area ratio of the untreated surface (the surface opposite to the treated surface) is considered to be 1, that is, the same as the area of ​​the test piece (the "planar area of ​​the copper member" in the formula related to the surface area ratio), and the surface area ratio is calculated. In addition, in the surface area measurement by the BET method, surfaces other than the treated surface and its opposite surface (side surfaces) are also included in the measurement, but since their areas are negligible compared to the treated surface and its opposite surface, they are not taken into account in the calculation formula for the surface area ratio.

[0088] (Evaluation 4: Peel strength measurement and reliability test) MEGTRON7 (manufactured by Panasonic Corporation, thickness 100 μm) was pressed against the treated surface of the copper member of Examples 1 to 8 and Comparative Examples 1 to 5 at 0.49 MPa while heating to 110°C using a vacuum press, and then held at 210°C and 2.94 MPa for 120 minutes for thermocompression. Measurement samples were prepared by masking with a 6 mm wide tape and etching. Then, in accordance with the 90° peel test (Japanese Industrial Standards (JIS) C5016), the peel strength (kgf / cm) was measured when the copper member was peeled from the resin substrate at a speed of 50 mm / min in the 90° direction. The measurement results are shown in the "Initial (kgf / cm)" section of "Peel Strength" in Table 1. The measurement samples used in this measurement were those produced within one month.

[0089] As reliability tests, acid resistance, heat resistance, and moisture resistance tests were carried out by the following methods. Acid resistance test: The above measurement sample was immersed in 12N HCl at 25°C for 1 hour, thoroughly rinsed with water, and then dried at 105°C for 1 hour. The peel strength of the obtained sample was measured in the same manner as above. The measurement results are shown in the "Acid resistance (kgf / cm)" section of "Peel strength" in Table 1. The ratio (%) of the peel strength after the acid resistance test to the initial peel strength (= [Peel strength after acid resistance test] / [Initial peel strength] x 100) is shown in the "Acid resistance / initial" section of "Peel strength" in Table 1. Heat resistance test: The above measurement sample was placed in a dryer at 180°C for 48 hours, and then the peel strength of the obtained sample was measured in the same manner as above. The measurement results are shown in the "Heat resistance (kgf / cm)" section of "Peel strength" in Table 1. The ratio (%) of the peel strength after the heat resistance test to the initial peel strength (= [Peel strength after heat resistance test] / [Initial peel strength] x 100) is shown in the "Heat resistance / initial" section of "Peel strength" in Table 1. Moisture resistance test: The above measurement sample was placed in boiling water for 2 hours, after which the moisture was lightly wiped off, and the peel strength of the obtained sample was measured in the same manner as above within 30 minutes after the test. The measurement results are shown in the "Moisture resistance (kgf / cm)" section of "Peel strength" in Table 1. The ratio (%) of the peel strength after the moisture resistance test to the initial peel strength (= [Peel strength after moisture resistance test] / [Initial peel strength] x 100) is shown in the "Moisture resistance / initial" section of "Peel strength" in Table 1.

[0090] (Evaluation 5: Measurement of transmission loss) A resin substrate (product name: ADFLEMA, Dk: 2.3, Df: 0.0012, manufactured by Namics Corporation) having a thickness of 100 μm was thermocompressed to the treated surface of the copper member of Examples 1 to 8 and Comparative Examples 1 to 5 by holding it at 200° C. and 1 MPa for 120 minutes using a vacuum press machine to prepare a measurement sample. For the evaluation of transmission loss, a known stripline resonator method suitable for measurement in the 10 MHz to 95 GHz band was used to measure from 10 MHz to 95 GHz in 10 MHz steps. Specifically, the S21 parameter was measured under the following conditions without a coverlay film. The results of S21 at 95 GHz are shown in “Transmission loss (db / 100 mm)” in Table 1.

[0091] Measurement conditions: microstrip structure; Resin substrate: ADFLEMA (Dk: 2.3, Df: 0.0012, manufactured by Namics Corporation) Circuit length: 100mm Conductor width: 285μm Conductor thickness: 28μm Substrate thickness: 100μm Characteristic impedance: 50Ω

[0092] (Evaluation 6: Measurement of etching factor) A resist pattern with an L / S of 30 / 30 μm was formed on the treated surface of the copper members of Examples 1 to 8 and Comparative Examples 1 to 5. A dry resist film (product name: Sunfort ADV-408, manufactured by Asahi Kasei Corporation) was used as the resist. Then, an etching solution (CuCl 2Etching was performed using a 1000-mL aqueous solution of 1,000 mol / L HCl (pH 7.0, specific gravity 1.26, temperature 45°C) for a period of time until no residual roots could be detected by SEM, forming a wiring pattern. The etching factor (Ef) of the resulting wiring pattern was measured. The results are shown in the "Etching Factor" column of Table 1.

[0093] Ef will be described with reference to Fig. 3. In Fig. 3, 22 denotes the formed wiring pattern. Ef is a value expressed by the following formula, where H is the thickness of the copper member (copper foil) (height of wiring pattern 22), B is the bottom width of wiring pattern 22, and T is the top width of the formed wiring pattern 22. The thickness H of the copper member, the bottom width B, and the top width T were measured using a confocal microscope OPTELICS H1200 (manufactured by Lasertec Corporation). Ef=2H / (BT)

[0094] Here, a large Ef means that the sidewalls of the wiring pattern form an angle close to perpendicular to the bottom (closer to a rectangle). The larger Ef is, the less likely it is that unmelted copper foil will remain between adjacent wiring patterns, even when forming fine wiring patterns with narrow line widths (wiring widths), and the less mutual influence between wiring patterns will occur, making it less likely that wiring will break, which means that the product reliability of the copper component will be high.

[0095] [Table 1] [Explanation of symbols]

[0096] 1 Metallic parts 2 Metal materials 3 Surface treatment layer 4 protrusions 5 Other metal layers 10 Laminate 11 Metallic parts 12 Resin substrate 22 Wiring Pattern H Thickness of copper material B Bottom width T Top Width

Claims

1. A metal member having a surface having a root mean square height Sq of 0.01 μm or more and 0.095 μm or less and an arithmetic mean height Sa of 0.01 μm or more and 0.06 μm or less.

2. The product of the root mean square height Sq [μm] and the arithmetic mean height Sa [μm] is 1.0×10 -4 Above 5.5 x 10 -3 The metal member according to claim 1 , wherein:

3. The metal member according to claim 1 or 2, wherein the surface has a surface area ratio calculated by the following formula of 4.5 or more. Surface area ratio = (BET measurement surface area (dm 2 ) - Plan view area of ​​metal member (dm 2 ) / Plan view area of ​​metal member (dm 2 )

4. The metal member according to claim 1 or 2, wherein the minimum autocorrelation length Sal of the surface is 1.0 μm or more and 4.0 μm or less.

5. A metal material and a surface treatment layer formed on a surface of the metal material, The metal member according to claim 1 or 2, wherein the surface treatment layer comprises a layer containing Ni and Zn.

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