Copper component, laminate, method for manufacturing a copper component, method for manufacturing a resin substrate with a seed layer, method for manufacturing a resin substrate with a plating layer

Abstract

The object of the present invention is to provide a copper member with excellent peelability and etching properties. [Solution] A copper member comprising a copper material and protrusions formed on part or all of the surface of the copper material, A metal layer other than copper is formed so as to cover part or all of the aforementioned protrusions. The metal layer other than copper is composed of two or more types of metal atoms. The 90° peel strength is 40 gf / cm or less. The Rz of the surface of the metal layer other than copper is 1 μm or less. Copper component.

Description

[Technical Field]

[0001] This invention relates to copper members, laminates, methods for manufacturing copper members, methods for manufacturing resin substrates with a seed layer, and methods for manufacturing resin substrates with a plating layer. [Background technology]

[0002] In recent years, there has been a growing demand for miniaturization of wiring in printed circuit boards, such as printed wiring boards and semiconductor package substrates. Known circuit formation methods for these substrates include subtractive methods, semi-additive methods such as SAP (Semi-Additive Process) and M-SAP (Modified Semi-Additive Process) (Patent Document 1), and fully additive methods.

[0003] The subtractive method involves preparing a laminate of a resin substrate and copper foil, covering the necessary areas on the copper foil (the areas where wiring is to be formed) with a resist, and then etching the copper foil. After etching, when the resist is removed from the copper foil, the copper foil in the areas covered by the resist remains unetched, forming the copper wiring. The subtractive method had a problem in that the copper in the wiring area was also affected during the etching of the copper foil, resulting in thinner wiring (so-called over-etching). Possible solutions to this problem include thinning the copper foil or shortening the etching time. However, thinning the copper foil can cause breakage, bending, and wrinkling during the laminate formation process and preparation stage, making it difficult to handle the copper foil on its own. For this reason, even when thinning the copper foil, the limit is approximately 9 μm.

[0004] As a construction method for solving the drawbacks of such subtractive methods, a semi-additive method can be cited. In the semi-additive method, a resist is formed on a resin substrate having a metal seed layer on its surface in a portion where wiring is not formed, and a metal plating layer is formed on the seed layer by performing plating treatment. Thereafter, the resist is removed, and a fine circuit can be formed by etching the remaining seed layer. As semi-additive methods, the SAP method and the M-SAP method are known. In the SAP method, a seed layer is formed by performing electroless plating treatment on the surface of a resin substrate. In the M-SAP method, a seed layer is formed using an ultra-thin copper foil on the surface of a resin substrate.

[0005] In the semi-additive method (particularly the M-SAP method), an ultra-thin copper foil with a thickness of 6 μm or less, which is adhered to a carrier layer via a release layer (ultra-thin copper foil with carrier), is used. The ultra-thin copper foil with carrier and the resin substrate are laminated, and the carrier is peeled off to transfer the ultra-thin copper foil to the resin substrate to form a seed layer. Therefore, the ultra-thin copper foil with carrier is required to have peelability from the resin substrate. That is, a property is required such that the carrier can be easily peeled off and the ultra-thin copper foil serving as the seed layer can be easily transferred to the resin substrate side. By adopting such a method, problems such as breakage, folding, and generation of wrinkles of the ultra-thin copper foil are solved. Although it is necessary to dissolve and remove the portion of the ultra-thin copper foil that becomes unnecessary for circuit formation by etching, since its thickness is thin, the influence of over-etching is small, and it has higher wiring accuracy than the subtractive method. As a material used in such a construction method, for example, an ultra-thin copper foil with carrier as described in Patent Document 1 can be cited.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, even when using the carrier-attached ultrathin copper foil described in Patent Document 1, if the thickness of the ultrathin copper foil was not sufficiently thin and etching was insufficient after transfer to the resin substrate, the ultrathin copper foil tended to remain incompletely, resulting in residue. Furthermore, excessive etching caused the wiring to become too thin. In addition, because the surface of the carrier-attached ultrathin copper foil was rough, when it was transferred to the resin substrate, the ultrathin copper foil would penetrate the surface of the resin substrate, preventing sufficient etching.

[0008] Therefore, the object of the present invention is to provide a copper member with excellent peelability and etching properties. [Means for solving the problem]

[0009] The inventors of this invention, after diligent research to achieve the above objectives, have found that the above problems can be solved by a copper member having a specific configuration. This invention was completed based on these findings.

[0010] In other words, the present invention provides a copper member comprising a copper material and protrusions formed on a part or all of the surface of the copper material, A metal layer other than copper is formed so as to cover part or all of the above-mentioned protrusions. The above-mentioned metal layer other than copper is composed of two or more metals other than copper. The 90° peel strength is 40 gf / cm or less. The present invention provides a copper member in which the surface Rz of the metal layer other than copper is 1 μm or less.

[0011] Furthermore, the present invention provides a copper member comprising a copper material and protrusions formed on a part or all of the surface of the copper material, A metal layer other than copper is formed so as to cover part or all of the above-mentioned protrusions. The above-mentioned metal layer other than copper is composed of two or more metals other than copper. Transcriptional loss is 80 μm 2 The following: The present invention provides a copper member in which the surface Rz of the metal layer other than copper is 1 μm or less.

[0012] In the above copper component, it is preferable that the metals other than copper are nickel and zinc.

[0013] The above copper component preferably contains copper oxide in its protrusions.

[0014] The copper component described above preferably has a metal layer other than copper with a thickness of 17 to 50 nm.

[0015] In a resin substrate with a seed layer obtained by heat-pressing a resin substrate onto the surface of the copper member on which the protrusions are formed to form a laminate, and then peeling the copper member from the resin substrate in the laminate, the thickness of the seed layer is preferably 150 to 410 nm. The thickness of the seed layer can be measured by the method described in the embodiments below.

[0016] Furthermore, the present invention provides a laminate in which the copper member and the resin substrate are laminated such that the resin substrate and the protrusions formed on the surface of the copper member come into contact with each other.

[0017] Furthermore, the present invention includes the step of obtaining a copper member by forming protrusions on part or all of the surface of a copper material, The process involves treating the above copper component with a release agent, The above copper component is subjected to a plating treatment using a plating solution to form a metal layer other than copper on its surface. A step of performing an alkali treatment on the metal layer other than copper of the above copper member, The present invention also provides a method for manufacturing the above-mentioned copper component, including the above-mentioned method.

[0018] The step of forming protrusions on part or all of the surface of the above copper material is: Preferably, the process involves an oxidation treatment to form protrusions containing copper oxide on part or all of the surface of the copper material.

[0019] Furthermore, the present invention provides a method for manufacturing a resin substrate with a seed layer, comprising a resin substrate and a seed layer formed on the surface of the resin substrate, A step of forming a laminate by laminating a resin substrate and the copper member such that the protrusions formed on the surface of the resin substrate and the copper member come into contact with each other, The process involves separating the resin substrate and the copper member, and transferring the protrusions formed on the surface of the copper member to the resin substrate, thereby forming a seed layer on the surface of the resin substrate. The present invention also provides a method for manufacturing a resin substrate with a seed layer, including the method described above.

[0020] Furthermore, the present invention provides a method for manufacturing a plated resin substrate comprising a resin substrate, a seed layer, and a plating layer in this order, A step of forming a laminate by laminating a resin substrate and the copper member such that the protrusions formed on the surface of the resin substrate and the copper member come into contact with each other, The process involves separating the resin substrate and the copper member, and transferring the protrusions formed on the surface of the copper member to the resin substrate, thereby forming a seed layer on the surface of the resin substrate. The process involves plating the surface of the above-mentioned resin substrate using a plating solution, The present invention also provides a method for manufacturing a resin substrate with a plated layer, including the above. [Effects of the Invention]

[0021] The copper component of the present invention exhibits excellent peelability and etching properties. [Brief explanation of the drawing]

[0022] [Figure 1] This is a schematic cross-sectional view showing one embodiment of the copper member of the present invention. [Figure 2] This is a schematic cross-sectional view showing one embodiment of the laminate of the present invention. [Figure 3] This is a schematic cross-sectional view showing one embodiment of the resin substrate with a seed layer of the present invention. [Figure 4] This is a schematic cross-sectional view showing one embodiment of the copper-plated resin substrate of the present invention. [Figure 5] This is a schematic cross-sectional view of the laminate to explain the "measurement range of the number of voids" in the evaluation of the laminate and seed layer-attached resin substrate in Example (3) of the example. [Figure 6] These are the copper components before and after testing in the alkali resistance evaluation of the example. [Figure 7] These are the copper components before and after the test in the etching performance evaluation of the example. [Modes for carrying out the invention]

[0023] One embodiment of the present invention (hereinafter referred to as Embodiment 1) is a copper member. The above copper member includes a copper material and protrusions formed on part or all of the surface of the copper material. A metal layer other than copper is formed so as to cover part or all of the above-mentioned protrusions. The above-mentioned metal layer other than copper is composed of two or more metals other than copper. The 90° peel strength is 40 gf / cm or less. The above-mentioned metal layer other than copper is characterized by having a surface Rz of 1 μm or less.

[0024] One embodiment of the present invention (hereinafter referred to as Embodiment 2) is a copper member. The above copper member includes a copper material and protrusions formed on part or all of the surface of the copper material. A metal layer other than copper is formed so as to cover part or all of the above-mentioned protrusions. The above-mentioned metal layer other than copper is composed of two or more metals other than copper. Transcriptional loss is 80 μm 2 The following: The above-mentioned metal layer other than copper is characterized by having a surface Rz of 1 μm or less.

[0025] Another embodiment of the present invention (hereinafter referred to as Embodiment 3) is a laminate. The above-described laminate is a laminate in which a copper member according to Embodiment 1 and / or 2 and a resin substrate are laminated such that the resin substrate and protrusions formed on the surface of the copper member come into contact with each other.

[0026] Yet another embodiment of the present invention (hereinafter referred to as Embodiment 4) is a method for manufacturing the copper members of Embodiments 1 and 2. The above method includes a protrusion formation step, a peelability improvement step, a copper component plating step, and an alkali treatment step, which will be described later.

[0027] Another embodiment of the present invention (hereinafter referred to as Embodiment 5) is a method for manufacturing a resin substrate with a seed layer, comprising a resin substrate and a seed layer formed on the surface of the resin substrate. The above method includes a laminate formation step and a laminate separation step, which will be described later.

[0028] Yet another embodiment of the present invention (hereinafter referred to as Embodiment 6) is a method for manufacturing a resin substrate with a plated layer. The above-mentioned resin substrate with a plated layer comprises a resin substrate, a seed layer, and a plating layer in this order. The above method includes a laminate formation step, a laminate separation step, and a seed layer plating step, which will be described later.

[0029] [Copper component] The copper members according to Embodiments 1 and 2 will be described below. In this specification, the copper members according to Embodiments 1 and 2 may be referred to as "the copper members of the present invention."

[0030] The copper member of the present invention comprises a copper material and protrusions formed on a part or all of the surface of the copper material, wherein a metal layer other than copper is formed to cover a part or all of the protrusions, the metal layer other than copper is composed of two or more metals other than copper, and the surface Rz of the metal layer other than copper is 1 μm or less.

[0031] In the copper member described above, protrusions are formed on the surface of the copper member. By treating the copper member on which copper oxide-containing protrusions are formed with a release agent, the protrusions become detachable from the copper member. This means that the protrusions are connected to the copper member via a surface that allows for separation (sometimes described as a "release surface" in this specification). In other words, by treating the copper member with a release agent, a surface is formed that allows for separation of the copper member and the protrusions. Because the copper member has this configuration, when the laminate formed through the "laminated body formation process" described later is separated from the resin substrate, the protrusions formed on the surface of the copper member are transferred to the resin substrate.

[0032] The copper component may include a copper oxide layer. More specifically, the copper material may have a copper oxide layer formed on its surface. When a copper oxide layer is formed on the surface of the copper material, the protrusions are formed on the surface of the copper material as part of the copper oxide layer. That is, the protrusions contain copper oxide and are formed on the surface of the copper oxide layer. When a copper oxide layer is formed on the surface of the copper material, the protrusions may be formed on part or all of the surface of the copper oxide layer. Such embodiments can be realized, for example, by an oxidation treatment step in the protrusion formation step.

[0033] The copper member described above includes a metal layer other than copper. More specifically, the copper member has a metal layer other than copper formed so as to cover part or all of the surface of the protrusion. If a copper oxide layer is formed on the surface of the copper material, the metal layer other than copper may be formed so as to cover part or all of the surface of the copper oxide layer. Such embodiments can be realized, for example, by a "copper member plating process".

[0034] The copper component described above may further have a silicon compound layer formed on part or all of the surface of the copper material, the copper oxide layer, and the metal layer. Such an embodiment can be realized, for example, by a "silane coupling treatment process".

[0035] The 90° peel strength of the copper member described above is preferably 40 gf / cm or less, more preferably 36 gf / cm or less, even more preferably 33 gf / cm or less, even more preferably 30 gf / cm or less, even more preferably 25 gf / cm or less, even more preferably 20 gf / cm or less, and particularly preferably 15 gf / cm or less.

[0036] The 90° peel strength of the above copper component can be measured by the following method. More specifically, it can be measured by the method described in the examples below. (Method for measuring 90° peel strength) A copper component and a resin substrate, GHPL-830NS (bismaleimide triazine resin, thickness: 100 μm, manufactured by Mitsubishi Gas Chemical Company, Inc.), were laminated so that the protrusions formed on the surface of the copper component abutted against the resin substrate, and then heat-pressed together. The resulting sample (laminated body of copper component and resin substrate) was subjected to a 90° peel test (Japanese Industrial Standard (JIS) C5016), and the peel strength (gf / cm) was measured when the copper component was peeled off the resin substrate at a speed of 50 mm / min in a 90° direction. The measurement width of the sample used for measurement was 10 mm.

[0037] The 90° peel strength of the copper component described above is the peel strength when the copper component is peeled from the resin substrate, as stated above. However, it can also be described as the peel strength when the protrusions peel off from the copper component. That is, when the copper component is peeled from the resin substrate, the protrusions that were formed on the surface of the copper component are transferred to the surface of the resin substrate as a seed layer, and at the same time, the protrusions peel off from the surface of the copper material. The 90° peel strength of the copper component can be described as the peel strength in this event.

[0038] The transfer defect in the above copper component is, for example, 80 μm. 2 The following is preferable, and more preferably 70 μm 2 More preferably 60 μm 2 More preferably 50 μm 2 The following is particularly preferred: 40 μm 2It is as follows. Note that the transfer defect can be explained as the area where the protrusions formed on the surface of the copper member did not transfer to the resin substrate when the copper member and the resin substrate were laminated and then separated. In the resin substrate, in the range where the transfer of the protrusions did not proceed sufficiently, the seed layer is not formed, and the resin of the resin substrate is exposed. The range (area) corresponding to this exposed portion was measured according to the method described later and regarded as a transfer defect. Since the exposed portion of the resin cannot deposit plating (for example, copper plating) in the subsequent plating process, a defect occurs in the wiring formed by plating. Therefore, it is preferable that the transfer defect of the copper member is small.

[0039] The transfer defect of the copper member can be measured by the following method. More specifically, it can be measured by the method described in the examples below. (Method for measuring transfer defect) A copper member and GHPL-830NS (bismaleimide triazine resin, thickness: 100 μm, manufactured by Mitsubishi Gas Chemical Company, Inc.), which is a resin substrate, were laminated and thermocompression bonded so that the protrusions formed on the surface of the copper member abutted against the resin substrate. After thermocompression bonding, the copper member was peeled off, and the surface of the seed layer-formed side of the resin substrate with a seed layer was observed. The obtained sample was observed under the following measurement conditions using a confocal scanning electron microscope OPTELICS H1200 (manufactured by Lasertec Corporation) to acquire an image. As the measurement conditions, the scan width was 100 μm, the scan type was area, the light source was Blue, and the cut-off value was 1 / 5. The objective lens was set to ×20, the contact lens was set to ×14, the digital zoom was set to ×1, and the Z pitch was set to 50 nm. The measurement range was 785000 μm 2 After adjusting the contrast of the image, a light and dark inversion process was performed. The "bright part" after the inversion process is the defective part, and the "dark part" is the seed layer. Automatic binarization of the image after the inversion process was performed. The threshold determination method used the "discriminant analysis method" to measure the area (μm 2 ) of the bright part, and this area was used as the value of the transfer defect. Note that the minimum value of the detection sensitivity in binarization is 4 μm 2 is.

[0040] The number of defects in the copper member described above is preferably 20 or less, more preferably 10 or less, even more preferably 8 or less, and particularly preferably 6 or less. The maximum defect size diameter of the copper member described above is preferably 30 μm or less, more preferably 20 μm or less, even more preferably 15 μm or less, even more preferably 10 μm or less, and particularly preferably 8 μm or less. The number of defects and the maximum defect size diameter can be measured by the method described in the examples below.

[0041] In the copper component described above, the surface Rz (maximum height roughness) of the metal layer other than copper is not particularly limited as long as it is 1 μm or less, but is preferably 0.9 μm or less, more preferably 0.8 μm or less, and particularly preferably 0.7 μm or less. For example, it may be 0.1 μm or more, 0.2 μm or more, 0.25 μm or more, or 0.3 μm or more. Here, "surface of the metal layer other than copper" refers to the surface of the metal layer other than copper after surface treatment, such as alkali treatment and silane coupling treatment, if such surface treatment is performed during the manufacturing stage of the copper component. Rz represents the sum of the maximum value of the peak height Zp and the maximum value of the valley depth Zv of the contour curve (y=Z(x)) at a reference length l. Rz can be calculated, for example, by the method specified in JIS B 0601:2013. Specifically, Rz can be calculated by the method described in the examples below.

[0042] In the copper component described above, the Ra (arithmetic mean roughness) of the surface of the metal layer other than copper is not particularly limited, but is preferably 0.1 μm or less, more preferably 0.095 μm or less, even more preferably 0.09 μm or less, even more preferably 0.085 μm or less, and particularly preferably 0.08 μm or less. Alternatively, it may be 0.01 μm or more, 0.02 μm or more, 0.03 μm or more, or 0.04 μm or more. Here, "surface of the metal layer other than copper" refers to the surface of the metal layer other than copper after surface treatment, such as alkali treatment and silane coupling treatment, if such surface treatment is performed during the manufacturing stage of the copper component. Ra represents the average of the absolute values ​​of the peak height Zp and valley depth Zv of the contour curve (y=Z(x)) at a reference length l. Ra can be calculated, for example, by the method specified in JIS B 0601:2013. Specifically, Ra can be calculated by the method described in the examples below.

[0043] The height (average height) of the protrusions in the copper member of the present invention is not particularly limited, but is preferably 30 nm or more, more preferably 50 nm or more, even more preferably 80 nm or more, and particularly preferably 120 nm or more. Alternatively, it is preferably 500 nm or less, more preferably 400 nm or less, even more preferably 300 nm or less, particularly preferably 250 nm or less, and most preferably 200 nm or less. The height of the protrusions can be measured, for example, by calculating the average value of the distance between the maximum point of the protrusion and the maximum point of the protrusion between the concave parts in a cross-sectional image obtained with a scanning electron microscope (SEM), where the distance between the minimum points of adjacent concave parts separated by a predetermined interval is defined as the height of the protrusion.

[0044] The average height of the protrusions can be determined, for example, by using a FIB-SEM (Carl Zeiss AURIGA) to expose a cross-section perpendicular to the copper member, taking a cross-sectional image at an acceleration voltage of 2kV and a magnification of 30,000x, and then measuring the length of the resulting cross-sectional image, specifically the distance between the midpoint of the line segment connecting the minimum points of adjacent concave parts on either side of the convex part and the maximum point of the convex part between the concave parts. The height of the protrusions can then be calculated by measuring the heights of five protrusions in the same way and calculating the average value. The five protrusions mentioned above can be obtained by dividing the obtained cross-sectional image into six equal parts horizontally and selecting the protrusion closest to each of these dividing lines.

[0045] The copper component of the present invention differs in structure from conventional carrier-attached ultrathin copper foil used in the semi-additive process. Specifically, the conventional carrier-attached ultrathin copper foil described above has a three-layer structure in which a carrier foil, a release layer, and an ultrathin copper foil are laminated in that order. On the other hand, the copper component described above differs in structure from conventional carrier-attached ultrathin copper foil in that it does not have a release layer. In other words, the copper component has a structure that differs from conventional carrier-attached ultrathin copper foil in that protrusions are formed on the surface of the copper component, and these protrusions are formed to be removable from the copper component.

[0046] (copper material) In the copper component of the present invention, the copper material refers to a material whose surface is partially or entirely composed of copper. The material inside the copper material (inside the copper present on the surface) may be copper or a substance other than copper (for example, a metal other than copper, a resin substrate, etc.), but it is preferably copper. In other words, it is preferable that the copper material is entirely made of copper.

[0047] When the interior of the copper material described above consists of a substance other than copper, the thickness of the copper on the surface is not particularly limited, but is preferably 1 nm or more, more preferably 10 nm or more, and even more preferably 100 nm or more. In this case, the copper on the surface of the copper material may be formed by a plating treatment using a copper plating solution.

[0048] The surface purity of the copper material described above is preferably, for example, 95% by mass or more, 99% by mass or more, or 99.9% by mass or more of pure copper. Furthermore, even if the copper material is entirely composed 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 these, oxygen-free copper with an oxygen content of 0.001 to 0.0005% by mass is preferred.

[0049] Examples of the copper materials mentioned above include copper foils such as electrolytic copper foil, rolled copper foil, and ultrathin copper foil with a carrier, as well as copper plates. Here, copper foil refers to a material with a thickness of 100 μm or less, and copper plates refer to a material with a thickness of more than 100 μm. The thickness of copper foil is preferably 0.1 μm or more, more preferably 0.5 μm or more, and even more preferably 1 μm or more. It is also preferably 80 μm or less, and even more preferably 50 μm or less. The thickness of copper plates is preferably 0.3 mm or more, more preferably 0.5 mm or more, even more preferably 1 mm or more, and especially preferably 5 mm or more. It is also preferably 5 cm or less, more preferably 3 cm or less, and even more preferably 1 cm or less.

[0050] The protrusions formed on the surface of the copper material described above preferably contain copper and / or copper oxide, and more preferably copper oxide. A method for forming copper-containing protrusions on the surface of the copper material is plating with a copper plating solution. A method for forming copper oxide-containing protrusions on the surface of the copper material is oxidation treatment. When copper oxide-containing protrusions are formed by oxidation treatment, the copper oxide layer described later is formed on the surface of the copper material.

[0051] (copper oxide layer) The copper component of the present invention may have a copper oxide layer formed on the surface of the copper material. That is, the copper component may include a copper material and a copper oxide layer formed on the surface of the copper material. The copper oxide layer is a portion that is transferred from the surface of the copper component to the resin substrate during the laminate separation process, and by this process constitutes a "seed layer containing copper and / or copper oxide" on the surface of the resin substrate.

[0052] Examples of copper oxides in the copper oxide layer include copper oxide (CuO) and cuprous oxide (Cu2O), and either or both may be included in the copper oxide layer. The copper oxide layer may also contain copper. The copper oxide content in the copper oxide layer is not particularly limited, but for example, it may be 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 1% by mass or more, 3% by mass or more, 5% by mass or more, or 10% by mass or more. The copper oxide layer may also contain copper hydroxide (Cu(OH)2), and its content may be, for example, 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 3% by mass or more, or 5% by mass or more.

[0053] The thickness of the copper oxide layer 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. Furthermore, the thickness of the copper oxide layer is preferably 20 nm or more, more preferably 30 nm or more, and even more preferably 40 nm or more. Note that the thickness of the copper oxide layer refers to the thickness when converted to a state of uniform thickness, for example, by SERA measurement. More specifically, the test methods used in the examples described later can be cited.

[0054] The method for forming the copper oxide layer is not particularly limited, but one example is to apply an oxidation treatment to the copper material using an oxidizing agent. Alternatively, the copper material after the above oxidation treatment may be subjected to a reduction treatment using a reducing agent.

[0055] (Metal layers other than copper) In the copper component of the present invention, a metal layer other than copper is formed on a part or all of the surface of the copper material so as to cover protrusions formed on the surface of the copper material. The metal layer other than copper is composed of two or more metals other than copper. If a copper oxide layer is formed on the surface of the copper material, the metal layer other than copper may be formed so as to cover a part or all of the surface of the copper oxide layer. The metal other than copper can be identified, for example, by energy-dispersive X-ray analysis (EDX) using a transmission electron microscope (TEM) on the surface and / or cross-section of the metal layer.

[0056] The term "metal layer other than copper" refers to a layer containing metals other than copper. Examples of metals other than copper include nickel (Ni), cobalt (Co), iron (Fe), gadolinium (Gd), zinc (Zn), chromium (Cr), molybdenum (Mo), titanium (Ti), aluminum (Al), and manganese (Mn). Among these, nickel and zinc are preferred from the viewpoint of improving peelability and etching properties. In other words, it is more preferable that the metal layer other than copper is a metal layer composed of nickel and zinc, with two or more metals other than copper being the other metals. The state in which the two or more metals other than copper exist is not particularly limited; they may be in layered form or as alloys. For example, in a metal layer composed of nickel and zinc, there may be a layer made of nickel and a layer made of zinc, or the nickel and zinc may constitute a layer as an alloy.

[0057] The non-copper metal layer is formed, for example, by plating the surface of the copper material or copper oxide layer using a plating solution. The plating solution is not particularly limited as long as it contains two or more metals other than copper. The plating method is not particularly limited, and can be electroplated, electroless, vacuum deposition, chemical conversion treatment, etc., but electroplating is preferred because it is preferable to form a uniform plating layer (non-copper metal layer).

[0058] In metal layers other than copper, the ratio of nickel per unit area to the total amount of nickel and zinc deposited per unit area (referred to as the "Ni ratio" herein) is not particularly limited, but is preferably 30% or more, more preferably 40% or more, even more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and particularly preferably 75% or more. Also, is preferably less than 100%, more preferably 98% or less, even more preferably 96% or less, and particularly preferably 95% or less. The amount of nickel and zinc deposited per unit area can be calculated, for example, by dissolving the copper member in an acidic solution, measuring the amount of metal by ICP (Inductively Coupled Plasma) analysis, and dividing it by the planar field of view area of ​​the structure. Specifically, it can be calculated by the method described in the examples below.

[0059] In metal layers other than copper, the amount of nickel and zinc deposited per unit area (total amount) is not particularly limited, but for example, 0.8 mg / dm 2 More preferably 1.2 mg / dm 2 More preferably 1.4 mg / dm 2 More preferably 1.6 mg / dm 2 In particular, 1.8 mg / dm 2 That's all. Also, for example, 12 mg / dm 2 The following is preferable, and more preferably 10 mg / dm 2 More preferably 8 mg / dm 2 More preferably 6 mg / dm 2 The following is particularly preferred: 5.5 mg / dm 2 The following applies:

[0060] In metal layers other than copper, the amount of nickel deposited per unit area is not particularly limited, but for example, 0.3 mg / dm 2 Preferably, it is 0.6 mg / dm 2 More preferably 0.8 mg / dm 2 More preferably 1 mg / dm2 The above is particularly preferably 1.2 mg / dm 2 That's all. Also, for example, 10 mg / dm 2 The following is preferable, and more preferably 8 mg / dm 2 More preferably 6 mg / dm 2 More preferably 5 mg / dm 2 The following is particularly preferred: 4 mg / dm 2 The following applies:

[0061] In metal layers other than copper, the amount of zinc deposited per unit area is not particularly limited, but for example, 0.01 mg / dm 2 Preferably, the concentration is greater than or equal to 0.05 mg / dm 2 More preferably 0.1 mg / dm 2 In particular, 0.15 mg / dm 2 That's all. Also, for example, 5 mg / dm 2 The following is preferable, and more preferably 4 mg / dm 2 More preferably, 3 mg / dm 2 The following is particularly preferred: 2 mg / dm 2 The following applies:

[0062] The thickness of the metal layer other than copper (in planar terms) is not particularly limited, but is preferably 5 nm or more, more preferably 10 nm or more, even more preferably 15 nm or more, even more preferably 17 nm or more, even more preferably 18 nm or more, even more preferably 20 nm or more, and particularly preferably 25 nm or more. Also, is preferably 200 nm or less, more preferably 100 nm or less, even more preferably 80 nm or less, even more preferably 60 nm or less, and particularly preferably 50 nm or less. Because the thickness of the metal layer is within the above range, the metal layer is uniformly distributed, resulting in excellent adhesion to the resin substrate and a tendency for improved peelability. The thickness of the metal layer other than copper (in planar terms) can be calculated using the method described in "Plating Thickness (Planar Terms)" in the examples below.

[0063] (Silicon compound layer) In the copper component of the present invention, a silicon compound layer may be formed on part or all of the surface of the copper material, copper oxide layer, and metal layer other than copper. In particular, it is preferable that a silicon compound layer is formed on part or all of the surface of the above metal layer. The copper component of the present invention tends to have improved heat resistance reliability by including a silicon compound layer.

[0064] The silicon compound layer is a layer containing a silicon compound. In the context of the silicon compound layer, "containing a silicon compound" includes not only the silicon compound itself, but also a portion of the silicon compound that is chemically bonded to a material in contact with the silicon compound layer. Examples of such materials include copper materials, copper oxides contained in a copper oxide layer, and metals contained in a metal layer other than copper. A specific example is the silane coupling treatment described later, in which a portion of the silane coupling agent is chemically bonded to the above material. In other words, the silicon compound layer may be formed by a coupling treatment such as silane coupling.

[0065] Examples of the silicon compounds mentioned above include Si such as SiO, SiO2, and SiO4. x O y Silicon oxide represented by SiO4H4, Si2O7H6, SiO3H2, Si2O5H2, etc. x O y H zExamples include silicon hydroxide represented by ; inorganic silicon compounds such as water glass (Na2SiO3); organosilicon compounds such as alkoxysilanes, silane coupling agents, polyether-modified silicones, silicon carbides, silicon sulfides, and silicon nitrides; and silicon halides. As for the silane coupling agent, for example, those having 2 or 3 hydrolyzable groups are preferred, and those with methoxy or ethoxy groups as hydrolyzable groups are preferred. Examples of the silane coupling agents mentioned above include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, 3-ureidopropyltrialkoxysilane, and 3-acryloxypropyltrimethoxysilane. An example of a form in which a portion of the silicon compound is chemically bonded to the above material is a form in which the SiO group derived from the silane coupling agent is chemically bonded to the above material. In the silicon compound layer, one of the silicon compounds may be used alone, or two or more may be used in combination.

[0066] Methods for confirming the silicon compound layer, that is, methods for determining whether or not silicon compounds are present in the silicon compound layer, include, for example, elemental analysis by time-of-flight secondary ion mass spectrometry (TOF-SIMS) or X-ray photoelectron spectroscopy (XPS).

[0067] [Laminated structure] The laminate of the present invention is characterized by having the above-mentioned copper member and resin substrate laminated together. Examples of the above-mentioned 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, bismaleimide triazine resin, low dielectric constant polyimide, and cyanate resin.

[0068] The thickness of the resin substrate is not particularly limited, but is preferably 0.1 to 1000 μm, more preferably 1 to 800 μm, even more preferably 1 to 600 μm, even more preferably 10 to 500 μm, even more preferably 20 to 400 μm, even more preferably 30 to 300 μm, and particularly preferably 50 to 200 μm. The resin substrate may further contain inorganic fillers or glass fibers. The 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.

[0069] [Manufacturing method for copper components, etc.] The following describes the method for manufacturing a copper member according to Embodiment 4 of the present invention, the method for manufacturing a resin substrate with a seed layer according to Embodiment 5, and the method for manufacturing a resin substrate with a plating layer according to Embodiment 6.

[0070] The method for manufacturing a copper member according to Embodiment 4 includes a protrusion formation step, a peelability improvement step, a copper member plating step, and an alkali treatment step.

[0071] The method for manufacturing a resin substrate with a seed layer according to Embodiment 5 includes a laminate formation step and a laminate separation step using the copper members of Embodiments 1 and 2. In other words, the method for manufacturing a resin substrate with a seed layer according to Embodiment 5 includes a protrusion formation step, a peelability improvement step, a copper member plating step, an alkali treatment step, a laminate formation step, and a laminate separation step.

[0072] The method for manufacturing a copper-plated resin substrate according to Embodiment 6 includes a laminate formation step, a laminate separation step, and a seed layer plating step using the copper members of Embodiments 1 and 2. In other words, the method for manufacturing a copper-plated resin substrate according to Embodiment 6 includes a protrusion formation step, a peelability improvement step, a copper member plating step, an alkali treatment step, a laminate formation step, a laminate separation step, and a seed layer plating step.

[0073] (Protrusion formation process) The protrusion formation process is a process of obtaining a copper member by forming protrusions on part or all of the surface of a copper material. The protrusions may contain copper and / or copper oxide. One method for forming copper-containing protrusions (particularly protrusions made of copper) on the surface of a copper material is plating with a copper plating solution. In other words, this process may be a process (copper plating process) in which copper-containing protrusions are formed by performing a plating process with a copper plating solution on the surface of a copper material. One method for forming copper oxide-containing protrusions (particularly protrusions made of copper oxide) on the surface of a copper material is oxidation treatment. When copper oxide-containing protrusions are formed by oxidation treatment, a copper oxide layer is formed on the surface of the copper material. In other words, this step may be a step (oxidation treatment step) in which copper oxide-containing protrusions are formed by performing oxidation treatment on the surface of the copper material. The oxidation treatment step is a step in which copper oxide-containing protrusions are formed on the surface of the copper material by oxidation treatment. As a result of the above step, a copper oxide layer is formed on the surface of the copper material. The formation of protrusions by copper plating or oxidation treatment tends to improve the adhesion of the copper component to the resin substrate. In addition, the peelability of the copper component is improved in that it peels off appropriately when peeling is required.

[0074] In this process, before copper plating or oxidation, surface roughening treatments such as soft etching or etching, degreasing, acid cleaning to remove the native oxide film of the copper material, and alkaline treatment after the acid cleaning may be performed. The alkaline treatment is not particularly limited, but for example, it may be a method of treatment with an alkaline aqueous solution (e.g., sodium hydroxide aqueous solution) of 0.1 to 10 g / L or 1 to 2 g / L at 30 to 50°C for about 0.5 to 2 minutes.

[0075] The oxidation treatment method is not particularly limited and can include methods using an oxidizing agent, thermal oxidation, or electrolytic oxidation. Among these, the method using an oxidizing agent is preferred from the viewpoint of improving adhesion to the resin substrate.

[0076] The oxidizing agent is not particularly limited, but aqueous solutions of chlorates such as sodium chlorite, sodium hypochlorite, potassium chlorate, and potassium perchlorate are preferably used. The oxidizing agent may also contain additives such as phosphates such as trisodium phosphate dodecahydrate and surface-active molecules. The surface-active molecules are used to adjust the size of the protrusions formed, and examples include porphyrin, macro-ring porphyrin, expanded porphyrin, ring-contracted porphyrin, linear porphyrin polymer, porphyrin sandwich coordination complex, porphyrin sequence, silane, tetraorgano-silane, aminoethyl-aminopropyltrimethoxysilane, (3-aminopropyl)trimethoxysilane, (1-[3-(trimethoxysilyl)propyl]urea), (3-aminopropyl)triethoxysilane, ((3-glycidyloxypropyl)trimethoxysilane Examples include (3-chloropropyl)trimethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, dimethyldichlorosilane, 3-(trimethoxysilyl)propyl methacrylate, ethyltriacetoxysilane, triethoxy(isobutyl)silane, triethoxy(octyl)silane, tris(2-methoxyethoxy)(vinyl)silane, chlorotrimethylsilane, methyltrichlorosilane, silicon tetrachloride, tetraethoxysilane, phenyltrimethoxysilane, chlorotriethoxysilane, ethylene-trimethoxysilane, amines, and sugars. One or more of the above oxidizing agents may be used.

[0077] When oxidation treatment is performed using an oxidizing agent, the treatment temperature is not particularly limited, but is preferably 30 to 95°C, more preferably 35 to 80°C, and even more preferably 45 to 60°C. The treatment time is not particularly limited, but is preferably 0.2 to 20 minutes, and more preferably 0.4 to 10 minutes. The concentration of the components contained in the oxidizing agent (for example, the concentration of the chlorate) is not particularly limited, but is preferably 5 to 400 g / L, more preferably 10 to 350 g / L, and even more preferably 20 to 300 g / L. When the treatment temperature, treatment time, and concentration of the oxidizing agent are within the above ranges, the crystallinity of the resulting copper oxide layer tends to improve, and the peelability tends to be better.

[0078] After oxidation treatment, the surface of the copper material may be reduced with a reducing agent. As a result of the reduction treatment, cuprous oxide (copper(I) oxide) may be formed on the surface of the copper material. The reducing agent is not particularly limited, but examples include aqueous solutions of boron compounds such as dimethylamine borane (DMAB), diborane, sodium borohydride, and hydrazine.

[0079] Furthermore, the size, thickness, height, and length of the copper oxide-containing protrusions may be adjusted by chelation treatment using a chelating agent (especially a biodegradable chelating agent) on the surface of the copper material. The chelating agent is not particularly limited, but examples include solutions of ethylenediaminetetraacetic acid, diethanolglycine, L-glutamic acid diacetate tetrasodium, ethylenediamine-N,N'-disuccinic acid, 3-hydroxy-2,2'-iminodisuccinate sodium, methylglycine diacetate trisodium, aspartate diacetate tetrasodium, N-(2-hydroxyethyl)iminodiacetate disodium, and sodium gluconate. The pH of the chelating agent is not particularly limited, but it 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. Only one type of chelating agent may be used, or two or more types may be used.

[0080] (Process to improve peelability) The peelability improvement process is a step in which the copper member is treated with a peelability improver after the protrusion formation process. The purpose of this process is to make it easier to peel off the surface layer of the copper member on which the protrusions have been formed. In other words, the peelability improver can be said to be an agent that has properties that make it easier to peel off the surface layer of the copper member on which the protrusions have been formed. The "surface layer" of the copper member can be described as the oxide layer.

[0081] The above-mentioned peeling agent is not particularly limited, but examples include chlorides (nickel chloride, zinc chloride, iron chloride, chromium chloride, tin(II) chloride, etc.), ammonium salts (ammonium citrate, ammonium chloride, ammonium sulfate, nickelammonium sulfate, etc.), chelating agents (ethylenediaminetetraacetic acid, diethanolglycine, L-glutamic acid diacetate tetrasodium, ethylenediamine-N,N'-disuccinic acid, 3-hydroxy-2,2'-iminodisuccinate sodium, methylglycine diacetate trisodium, aspartate diacetate tetrasodium, N-(2-hydroxyethyl)iminodiacetate disodium, sodium gluconate, etc.), and aqueous solutions of citric acid, etc.

[0082] The processing temperature in this process is not particularly limited, but is preferably 20 to 90°C, more preferably 30 to 80°C, and even more preferably 40 to 55°C. The processing time is not particularly limited, but is preferably 0.2 to 20 minutes, more preferably 0.4 to 10 minutes, and even more preferably 1 to 8 minutes. The concentration of the peelability improver is not particularly limited, but is preferably 3 to 100 g / L, more preferably 5 to 80 g / L, even more preferably 12 to 60 g / L, and particularly preferably 15 to 50 g / L. When the processing temperature, processing time, and concentration of the peelability improver are within the above ranges, the peelability of the copper member tends to be better.

[0083] (Copper component plating process) The copper component plating process involves plating the copper component after the peelability improvement process using a plating solution to form a layer of metal other than copper. In this process, a layer of metal other than copper can be formed on the surface of the copper component by the plating process. The plating method is not particularly limited and can include electroplating, electroless plating, vacuum deposition, chemical conversion treatment, etc., but electroplating is preferred from the viewpoint of uniformly forming a layer of metal other than copper. This process may be carried out simultaneously with the peelability improvement process or as a separate process. For example, by plating the copper component using a mixture of a plating solution and a peelability improver, this process and the peelability improvement process can be carried out simultaneously.

[0084] Preferred electroplating methods include nickel plating, nickel alloy plating, zinc plating, and zinc alloy plating. Examples of metals included in the metal layer other than copper formed by nickel plating, nickel alloy plating, zinc plating, and zinc alloy plating include pure nickel, pure zinc, nickel-copper alloy, nickel-chromium alloy, nickel-cobalt alloy, nickel-zinc alloy, nickel-manganese alloy, nickel-lead alloy, nickel-phosphorus alloy, and aluminum-zinc alloy. One type of electroplating may be used, or two or more types may be used.

[0085] In the plating process, the composition of the plating solution is not particularly limited. Examples include nickel plating solutions containing nickel salts such as nickel sulfate, nickel sulfamate, nickel chloride, and nickel bromide; zinc plating solutions containing zinc salts such as zinc oxide, zinc chloride, zinc diphosphate, and zinc pyrophosphate; chromium plating solutions containing chromium salts such as chromic anhydride, chromium chloride, and sodium chromium sulfate; cobalt plating solutions containing cobalt salts such as cobalt sulfate; and manganese plating solutions containing manganese salts such as manganese sulfate. The plating solution may also contain additives such as pH buffers and brighteners.

[0086] The processing temperature in this process is not particularly limited, but is preferably 20 to 80°C, more preferably 25 to 60°C, and even more preferably 30 to 50°C. The processing time is not particularly limited, but is preferably 10 to 300 seconds, more preferably 20 to 200 seconds, even more preferably 30 to 150 seconds, and especially preferably 40 to 100 seconds. The concentration of metal ions in the plating solution is not particularly limited, but is preferably 0.1 to 30 g / L, more preferably 0.3 to 20 g / L, and even more preferably 0.5 to 15 g / L.

[0087] When electroplating is applied to the surface of an oxidized copper component, the charge is first used to reduce some of the copper oxide present on the surface to cuprous oxide or pure copper. Subsequently, the metal corresponding to the electroplating used begins to deposit, forming a metal layer. The amount of charge required varies depending on the type of plating solution and the amount of copper oxide. For example, when applying nickel plating or zinc plating to a copper component, the area dm of the copper component to be electroplated is... 2 It is preferable to apply a charge of 5C to 90C per unit area, and more preferably a charge of 10C to 65C per unit area. Also, for example, when nickel-zinc plating is applied to a copper member, the area dm of the copper member to be electroplated is 2 It is preferable to apply a charge of 5C to 90C per unit, and more preferably a charge of 10C to 65C per unit.

[0088] The current density in electroplating is not particularly limited, but is typically 0.2 to 10 A / dm 2 This is preferable. Furthermore, different current densities may be used for the time required to partially reduce the oxides contained in the protrusions on the copper member surface and for the time required to coat the plating.

[0089] (Alkali treatment process) The alkali treatment process involves applying an alkali treatment to the non-copper metal layer on the surface of the copper component obtained in the copper component plating process. The alkali treatment process tends to improve the peelability of the copper component. While the reason for this is unclear, it is thought that the alkali treatment removes metals in the non-copper metal layer that negatively affect the peelability of the copper component.

[0090] The conditions for the alkaline treatment described above are not particularly limited, but examples include using an alkaline aqueous solution (e.g., sodium hydroxide aqueous solution or potassium hydroxide aqueous solution) with a concentration of 1-200 g / L, 10-100 g / L, or 20-60 g / L, a treatment temperature of, for example, 25-100°C, 30-90°C, or 40-80°C, and a treatment time of, for example, 0.1-100 minutes, 0.3-80 minutes, 0.6-60 minutes, or 0.8-50 minutes.

[0091] The specific method of alkaline treatment is not limited, but one example is immersing the copper component in an alkaline aqueous solution.

[0092] (Silane coupling treatment process) The silane coupling treatment step is a step in which, after the alkali treatment step, a silane coupling treatment is performed on the metal layer other than copper on the surface of the copper member. The silane coupling agent used in the silane coupling treatment preferably has two or three hydrolyzable groups. Furthermore, the hydrolyzable groups are preferably methoxy groups or ethoxy groups.

[0093] The silane coupling agent described above is not particularly limited, and examples include those described in the section on the silicon compound layer. That is, the silicon compound layer described above can be formed by using the silane coupling agent.

[0094] The specific method of silane coupling treatment is not particularly limited, but examples include applying the silane coupling agent solution to the surface of a copper member using a roller or bar coater, spraying it, or immersing the copper member in the coupling agent solution. Examples of solvents used in the silane coupling agent solution include water, organic solvents, or mixtures thereof. The concentration of the silane coupling agent in the solution (100% by mass) obtained by dispersing the silane coupling agent in water or an organic solvent is not particularly limited, but for example, 0.5% by mass or more, 1% by mass or more, 2% by mass or more, 3% by mass or more, 4% by mass or more, 5% by mass or more, 6% by mass or more, 7% by mass or more, 8% by mass or more, or 9% by mass or more is preferred. Also, for example, 20% by mass or less, 15% by mass or less, or 10% by mass or less is preferred.

[0095] The copper component may be treated with a silane coupling agent solution and then baked. The baking temperature and time are not particularly limited as long as the conditions allow the solvent, water or organic solvent, to completely evaporate, but for example, 70°C for 1 minute or more is preferred, 100°C for 1 minute or more is more preferred, and 110°C for 1 minute or more is even more preferred.

[0096] Figure 1 is a schematic cross-sectional view showing one embodiment of the copper member of the present invention. 1 is the copper member, 2 is the copper material, 3 is the copper oxide layer, 4 is the protrusion, and 5 is the non-copper metal layer. 6 is the surface (peel surface) that allows the copper material 2 and the protrusion 4 to be peeled apart. The copper material 2 and the protrusion 4 are connected via the peel surface 6. The protrusion 4 is part of the copper oxide layer 3 and contains copper oxide. The non-copper metal layer 5 is formed to cover the surface of the copper oxide layer 3 (protrusion 4). Although not shown, a silicon compound layer may be formed to cover the non-copper metal layer 5.

[0097] (Laminate formation process) The laminate formation step is a step in which, after the alkali treatment step or the silane coupling treatment step, a resin substrate and a copper member are laminated so that the protrusions formed on the surface of the resin substrate and the copper member come into contact with each other, thereby forming a laminate. By this step, the laminate of Embodiment 3 can be obtained. In this step, the laminate may be formed by applying pressure while heating the laminate as needed. That is, this step may be a step in which a resin substrate and a copper member are laminated so that the protrusions formed on the surface of the resin substrate and the copper member come into contact with each other, and a laminate is formed by applying pressure while heating as needed. This step is performed after the peelability improvement step. If the present invention includes a copper member plating treatment step, this step may be performed afterward.

[0098] When a resin substrate and a copper component are laminated, the surface profile of the copper component, including protrusions, is transferred to the resin substrate. Methods for laminating the resin substrate and copper component include, for example, a method in which the resin substrate is bonded to the surface of the copper component while heating part or all of the copper component as needed, and pressure is applied from the copper component side, the resin substrate side, or both, under predetermined conditions. The above predetermined conditions (e.g., temperature, pressure, time, etc.) can be set as appropriate, and conditions recommended by each substrate manufacturer may also be used. The above predetermined conditions will be described below.

[0099] (A) If the resin substrate contains epoxy resin or is made of epoxy resin, it is preferable to heat-press the copper member onto the resin substrate by applying a pressure of 0 to 20 MPa at a temperature of 50°C to 300°C for 1 minute to 5 hours.

[0100] (A-1) If the resin substrate is R-1551 (manufactured by Panasonic Industries, Ltd.), heat it under a pressure of 1.2 MPa until it reaches 130°C, then hold it at that temperature for 10 minutes. After that, heat it further under a pressure of 2.3 MPa until it reaches 190°C, then hold it at that temperature for 50 minutes to perform heat bonding. (A-2) If the resin substrate is R-1410A (manufactured by Panasonic Industries, Ltd.), heat it under a pressure of 1 MPa until it reaches 130°C, then hold it at that temperature for 10 minutes. After that, heat it further under a pressure of 2.9 MPa until it reaches 200°C, then hold it at that temperature for 70 minutes to perform heat bonding. (A-3) If the resin substrate is EM-285 (manufactured by Elite Material Co., Ltd.), it can be heat-pressed by heating under a pressure of 0.4 MPa until it reaches 100°C, then increasing the pressure to 2.4-2.9 MPa and heating further until it reaches 195°C, and then holding it at that temperature for 50 minutes. (A-4) If the resin substrate is GX13 (manufactured by Ajinomoto Fine Techno Co., Ltd.), it can be heat-pressed by heating it under pressure of 1.0 MPa and holding it at 180°C for 60 minutes.

[0101] (B) If the resin substrate contains or is made of PPE resin, it is preferable to heat-press the copper member onto the resin substrate by applying a pressure of 0 to 20 MPa at a temperature of 50°C to 350°C for 1 minute to 5 hours.

[0102] (B-1) If the resin substrate is R-5620 (manufactured by Panasonic Industries, Ltd.), after heat-pressing under a pressure of 0.5 MPa until it reaches 100°C, the temperature and pressure can be increased to 2.0-3.0 MPa and 200-210°C, and held for 120 minutes for further heat-pressing. (B-2) If the resin substrate is R-5670 (manufactured by Panasonic Industries, Ltd.), the heat-sealing can be performed by heating it to 110°C under a pressure of 0.49 MPa, then increasing the temperature and pressure to 2.94 MPa and holding it at 210°C for 120 minutes. (B-3) If the resin substrate is R-5680 (manufactured by Panasonic Industries, Ltd.), the heat-sealing can be performed by heating it to 110°C under a pressure of 0.5 MPa, then increasing the temperature and pressure to 3.0-4.0 MPa and 195°C, and holding it for 75 minutes. (B-4) If the resin substrate is N-22 (manufactured by Nelco Corporation), it can be heat-pressed by heating under pressure of 1.6 to 2.3 MPa, holding at 177°C for 30 minutes, then heating again and holding at 216°C for 60 minutes.

[0103] (C) If the resin substrate contains or is made of PTFE resin, it is preferable to heat-press the copper member onto the resin substrate by applying a pressure of 0 to 20 MPa at a temperature of 50°C to 400°C for 1 minute to 5 hours.

[0104] (C-1) If the resin substrate is NX9255 (manufactured by Park Electrochemical Co., Ltd.), the bond can be heat-pressed by heating it to 260°C while pressurizing it at 0.69 MPa, then increasing the pressure to 1.03~1.72 MPa and heating it to 385°C, and holding it at 385°C for 10 minutes. (C-2) If the resin substrate is RO3003 (manufactured by Rogers Co., Ltd.), heat bonding can be achieved by applying pressure to 2.4 MPa after 50 minutes of pressing (approximately 220°C) and holding at 371°C for 30 to 60 minutes.

[0105] (D) If the resin substrate contains or is made of liquid crystal polymer (LCP), it is preferable to heat-press the copper member onto the resin substrate by applying a pressure of 0 to 20 MPa at a temperature of 50°C to 400°C for 1 minute to 5 hours. For example, if the resin substrate is CT-Z (manufactured by Kuraray Co., Ltd.), it can be heat-pressed by heating under a pressure of 0 MPa, holding at 260°C for 15 minutes, then heating further while applying pressure of 4 MPa, and holding at 300°C for 10 minutes.

[0106] (E) When the resin substrate contains or consists of bismaleimide triazine resin, it is preferable to heat-press the copper member onto the resin substrate by applying a pressure of 0 to 20 MPa at a temperature of 50°C to 350°C for 1 minute to 5 hours. For example, when the resin substrate is GHPL-830NS (manufactured by Mitsubishi Gas Chemical Company, Inc.), the copper member can be heat-pressed by heating at 110°C for 30 minutes under a pressure of 0.5 MPa, then increasing the temperature and pressure and holding at 3.0 MPa and 220°C for 105 minutes.

[0107] Figure 2 is a schematic cross-sectional view showing one embodiment of the laminate of the present invention. 10 is the laminate, 11 is the copper member, and 12 is the resin substrate. The laminate 10 is formed by laminating the resin substrate 12 and the copper member 11 such that the resin substrate 12 and the protrusions formed on the surface of the copper member 11 are in contact with each other.

[0108] (Laminate separation process) The laminate separation step, performed after the laminate formation step, involves separating the resin substrate and the copper component from the laminate and transferring the protrusions formed on the surface of the copper component to the resin substrate, thereby forming a seed layer on at least a portion of the surface of the resin substrate. Methods for confirming that the transfer is complete include a change in the color of the resin substrate surface, observation of the cross-section of the resin substrate, and component analysis of the resin substrate surface (for example, detection of copper component by EDS analysis or XPS analysis).

[0109] The method for separating the resin substrate and the copper component is not particularly limited, but one example is peeling the copper component off the resin substrate. The method for peeling the copper component off the resin substrate is not particularly limited, but it may be performed based on the 90° peel test (Japanese Industrial Standard (JIS) C5016 "Test Method for Flexible Printed Wiring Boards"; corresponding international standards IEC249-1:1982, IEC326-2:1990). In that case, the angle in the direction of peeling the copper component is maintained at 90±5° with respect to the surface on which pressure was applied for adhesion. Alternatively, the copper component may be peeled off manually, in which case it is preferable to peel it off at an angle of 80 to 180° with respect to the surface on which pressure was applied.

[0110] (Pre-plating treatment process) The pre-plating treatment process is performed to clean and roughen the surface of the seed layer formed on the resin substrate before the process of plating the seed layer using a plating solution (i.e., the seed layer plating process). Examples of pre-plating treatment processes include a degreasing process, an acid cleaning process, and an etching process. The pre-plating treatment process may be performed, for example, by following the laminate separation process, followed by the degreasing process, the acid cleaning process, and the etching process in that order. In addition, in the above pre-plating treatment process, plasma treatment may be performed before the degreasing process, as long as it does not impair the performance in the present invention.

[0111] • Degreasing process The degreasing process is a process of removing oil and dirt adhering to the surface of the seed layer of a resin substrate with a seed layer, and can be carried out, for example, using an aqueous solution of a strong base such as potassium hydroxide.

[0112] The processing temperature in this step is not particularly limited, but is preferably 20 to 50°C, more preferably 25 to 40°C. The processing time is not particularly limited, but is preferably 0.2 to 20 minutes, more preferably 0.4 to 10 minutes, and even more preferably 1 to 8 minutes. The concentration of the strong base is not particularly limited, but is preferably 1 to 200 g / L, more preferably 2 to 100 g / L.

[0113] • Acid washing process The acid cleaning process is a process of removing impurities (e.g., native oxide film, etc.) from the surface of the seed layer of a resin substrate with a seed layer, and can be carried out using, for example, an aqueous solution of a strong acid such as sulfuric acid.

[0114] The processing temperature in this step is not particularly limited, but is preferably 20 to 50°C, more preferably 25 to 40°C. The processing time is not particularly limited, but is preferably 0.2 to 20 minutes, more preferably 0.4 to 10 minutes, and even more preferably 1 to 8 minutes. The concentration of the strong acid is not particularly limited, but is preferably 1 to 20 g / L, more preferably 2 to 10 g / L.

[0115] • Etching process The etching process is a process of roughening the surface of the seed layer of a resin substrate with a seed layer by treating it with an etching solution.

[0116] Examples of the etching solution include aqueous solutions containing an oxidizing agent and a corrosive agent. The oxidizing agent is not particularly limited, but examples include oxygen, ozone, hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, etc. The corrosive agent is not particularly limited, but examples include hydrogen fluoride, buffered hydrofluoric acid, ammonia, sulfuric acid, hydrochloric acid, citric acid, etc.

[0117] Figure 3 is a schematic cross-sectional view showing one embodiment of the resin substrate with a seed layer of the present invention. 21 is the resin substrate with a seed layer, 22 is the protrusion (the protruding portion transferred to the resin substrate), 23 is the resin substrate, and 24 is the seed layer. In the laminate 10 of Figure 2, when the copper member 11 and the resin substrate 12 are separated, the protrusion formed on the surface of the copper member 11 is transferred to the resin substrate in a shape that is embedded in the surface of the resin substrate 12, resulting in a form like the resin substrate with a seed layer 21 in Figure 3.

[0118] (Seed layer plating process) The seed layer plating process is a process performed after the laminate separation process in which the surface of the seed layer of the resin substrate with the seed layer is plated using a plating solution. This process yields a resin substrate with a plated layer. The above-mentioned resin substrate with a plated layer comprises a resin substrate, a seed layer, and a plating layer in that order. The plating layer formed on the seed layer (specifically a metal plating layer, more specifically a copper plating layer) can be used as wiring for printed circuit boards (especially printed wiring boards and semiconductor package substrates, etc.).

[0119] The plating method is not particularly limited and may be either electrolytic plating or electroless plating. The metal included in the plating is also not particularly limited and can be at least one metal selected from the group consisting of nickel, tin, aluminum, chromium, cobalt, and copper. From the viewpoint of obtaining a highly accurate wiring pattern, electrolytic plating using copper is preferred. That is, the resin substrate with the plated layer is preferably a resin substrate with a copper plating layer. The current density in electrolytic plating is not particularly limited, but is 1 to 10 A / dm². 2 It is preferable.

[0120] Figure 4 is a schematic cross-sectional view showing one embodiment of the copper-plated resin substrate of the present invention. 31 is the copper-plated resin substrate, 32 is the resin substrate, 33 is the copper plating layer, and 34 is the seed layer. In the copper-plated resin substrate 31, the copper plating layer 33 is formed on the seed layer 34. [Examples]

[0121] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0122] (1) Treatment of copper foil In Examples 1-18 and Comparative Examples 2-10, copper components were fabricated by performing the following treatment on the shiny side of copper foil (product name: DR-WS, thickness: 18 μm, manufactured by Furukawa Electric Co., Ltd.). The shiny side is also called the glossy side and refers to a surface that is flatter than the other side. The other side is called the matte side (non-glossy side).

[0123] (1-1) Acid treatment The copper foil was immersed in 8% by volume sulfuric acid at 25°C for 1 minute to remove surface contaminants. The copper foil was then rinsed with water.

[0124] (1-2) Pretreatment The copper foil after the treatment described in (1-1) was degreased by immersing it in a 5g / L potassium hydroxide aqueous solution at a liquid temperature of 25°C for 1 minute to remove dirt from the surface of the copper foil.

[0125] (1-3) Oxidation treatment The copper foil after treatment (1-2) was subjected to oxidation treatment according to the conditions described in Tables 1 and 2. For example, in Example 1, the copper foil was subjected to oxidation treatment by immersing it in an aqueous solution containing an oxidizing agent (sodium chlorite at a concentration of 227.5 g / L, potassium hydroxide at a concentration of 20 g / L, and 3-glycidoxypropyltrimethoxysilane (product name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) at a concentration of 0.5 g / L) at a liquid temperature of 50°C for 1 minute, thereby forming fine protrusions on the surface of the copper foil. The obtained copper foil was then washed with water.

[0126] (1-4) Treatment to improve peelability In Examples 1-18 and Comparative Examples 2, 3, and 5-10, the copper foil treated according to (1-3) was immersed in a 45 g / L nickel chloride hexahydrate aqueous solution at a liquid temperature of 45°C for 2 minutes to improve its release properties. After that, the obtained copper foil was washed with water. In Comparative Example 4, the following treatment was performed without the release property improvement treatment.

[0127] (1-5) Copper component plating treatment (electrolytic plating treatment) Electroplating was performed on the copper foil after the treatment related to (1-4) according to the conditions described in Tables 1 and 2. For example, in Example 1, the copper foil was immersed in a Ni electroplating solution (an aqueous solution with a concentration of nickel sulfate hexahydrate of 8.96 g / L, zinc diphosphate of 9.32 g / L, and nickel diphosphate of 100 g / L) at a liquid temperature of 40°C, and then subjected to a current density of 0.5 A / dm 2 Electroplating was performed under conditions of 60 seconds. After that, the treated copper foil was washed with water.

[0128] (1-6) Alkali treatment Alkaline treatment was performed on the copper foil after processing (1-5) according to the conditions described in Tables 1 and 2. For example, in Example 1, the copper foil was immersed in a 45 g / L sodium hydroxide aqueous solution at a liquid temperature of 50°C for 1 minute. After that, the obtained copper foil was washed with water. Note that no alkaline treatment was performed on Comparative Examples 4-9.

[0129] (1-7) Silane coupling treatment The copper foil after the treatment described in (1-6) was immersed for 1 minute in a 1 vol% aqueous solution of 3-aminopropyltriethoxysilane (product name: KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) at a liquid temperature of 25°C. Subsequently, it was baked by drying at 110°C for 1 minute.

[0130] (2) Evaluation of copper components The copper components prepared in Examples 1-18 and Comparative Examples 2-10 were evaluated as follows. In addition, a similar evaluation was performed using MT18FL, an ultrathin copper foil with a carrier (thickness of the ultrathin copper foil is 1.5 μm, manufactured by Mitsui Mining & Smelting Co., Ltd.), as Comparative Example 1.

[0131] (2-1) Measurement of the thickness of the plating layer The thickness of the plating layer was measured on the treated surface (the shiny side of the copper foil) of the copper components prepared in Examples 1-18 and Comparative Examples 2-10. In addition, for the ultrathin copper foil with carrier in Comparative Example 1, the thickness of the plating layer on the ultrathin copper foil side was measured.

[0132] • Amount of Ni and Zn deposited per unit area (mg / dm 2 ) measurement For the copper components of Examples 1-18 and Comparative Examples 2-10, and for Comparative Example 1, only the ultrathin copper foil was dissolved in 12% nitric acid. The concentrations of Ni and Zn in the resulting liquid were measured using an ICP emission spectrometer 5100 SVDV ICP-OES (manufactured by Agilent Technologies, Inc.), and the amount of Ni and Zn deposited per unit area of ​​the copper component used (mg / dm²) was determined. 2The following formula was used to calculate the Ni ratio in the plating layer (the layer containing Ni and Zn). "Ni ratio (%)" = Ni deposition amount (mg / dm 2 ) / [Ni adhesion amount (mg / dm 2 ) + Zn deposition amount (mg / dm 2 )] × 100 (%)

[0133] • Calculation of the thickness of the plating layer (planar equivalent) The plating thickness in planar terms was calculated using the following formula. "Plating thickness (planar equivalent) (nm)" = (Amount of metal deposited per unit area (mg / dm²) 2 ) / Density of metal (g / cm³) 3 )) × 100 The Zn density is 7.14 g / cm³. 3 The Ni density is 8.91 g / cm³. 3 The plating thickness was calculated assuming that the metals included were Zn and Ni. In other words, the total plating thickness is calculated as the sum of the calculated plating thickness when the metal is Zn and the calculated plating thickness when the metal is Ni.

[0134] In Tables 3 and 4, the "Plating Thickness (nm)" column should contain the Ni thickness (nm), Zn thickness (nm), total thickness (nm), and Ni ratio (%).

[0135] (2-2) Measurement of surface roughness (Ra and Rz) For the treated surfaces of the copper components fabricated in Examples 1-18 and Comparative Examples 2-10, and for the ultrathin copper foil side of the carrier-attached ultrathin copper foil of Comparative Example 1, the contour curve was measured from the surface shape observation results using a confocal scanning electron microscope OPTELICS H1200 (Lasertec Corporation), and the surface roughness (Ra and Rz) was calculated according to the method specified in JIS B 0601:2013 (in accordance with the international standard ISO 4287-1997). The measurement conditions were a scan width of 100 μm, an area scan type, a blue light source, and a cutoff value of 1 / 5. The object lens was set to ×100, the contact lens to ×14, the digital zoom to ×1, and the Z pitch to 10 nm. Data was acquired at three arbitrary locations, and Ra and Rz were the average values ​​of the three locations. The measurement results for Ra (μm) and Rz (μm) are shown in the "Ra" and "Rz" columns of "Surface Roughness (μm)" in Tables 3 and 4.

[0136] (3) Evaluation of laminates and resin substrates with seed layers (3-1) Formation of the laminate The treated surfaces of the copper components prepared in Examples 1-18 and Comparative Examples 2-10, as well as the ultrathin copper foil side of the ultrathin copper foil with carrier in Comparative Example 1, were laminated in contact with a resin substrate (bismaleimide triazine resin, product name: GHPL-830NS, thickness: 100 μm, manufactured by Mitsubishi Gas Chemical Company, Inc.), and a laminate was obtained by heat-pressing under the following conditions.

[0137] • Heat sealing conditions The parts were heat-pressed under a pressure of 0.5 MPa until they reached 110°C, and held for 30 minutes. Then, they were heated to 220°C. After reaching 220°C, the pressure was changed to 3.0 MPa and held for 105 minutes.

[0138] (3-2) Measurement of the number of voids The voids in the copper members after the formation of the laminate were measured from SEM images of the laminate's cross-section using the following procedure. The cross-section of the laminate sample was obtained by FIB (focused ion beam) processing under conditions of an acceleration voltage of 30kV and a probe current of 4nA. The obtained cross-section was observed using a focused ion beam scanning electron microscope (Auriga, Carl Zeiss) at a magnification of 30,000x and a resolution of 1024×768, and an SEM cross-sectional image was obtained. The obtained SEM cross-sectional image of the laminate (positioned so that the needle-shaped protrusions face upwards in the image; image width = 3.78μm × 2.61μm; resolution 1024×768) was binarized using the image analysis software WinROOF2018 (Mitani Corporation, Ver4.5.5) using the following procedure. 1) Obtain a cross-sectional SEM image with the resin substrate at the top and the copper member at the bottom. The "measurement range of the number of voids" in the above SEM cross-sectional image will be explained below using Figure 5. Figure 5 is a schematic cross-sectional view of the laminate 50. The laminate 50 includes a copper member 51 and a resin substrate 52. 2) In Figure 5, the lower surface of the copper member 51 is referred to as the "outer surface." First, a straight line 53 is drawn along the outer surface of the copper member 51. Next, the void 54 located closest to the resin substrate 52 within the copper member 51 is identified. Furthermore, a straight line 55 is drawn passing through the upper end of the void 54 and parallel to the straight line 53. The region enclosed by the straight lines 53 and 54 is defined as the measurement range 56 for the number of voids. 3) After adjusting the contrast of the image within the measurement range, an inversion process is performed to reverse the bright and dark parts of the image. 4) Perform automatic binarization and select the measurement range. 5) Remove any 1-pixel square elements as noise. 6) The upper left corner of the image within the measurement range is taken as the origin, with the X-axis pointing downwards and the Y-axis pointing to the right. The region (1) selected by automatic binarization, where X=maximum and Y=minimum, is taken as the starting point, and the region closest in the Y-axis direction is designated as region (2). The region closest in the Y-axis direction to region (2) is designated as region (3), and then regions (4) to (N) are determined using the same procedure until Y=maximum within the measurement range. Each of the regions (1) to (N) determined here is a gap. Binarization is performed by cutting off the image's grayscale at a predetermined threshold, treating values ​​above the threshold as 1 and values ​​below the threshold as 0. Binarization can be performed using methods such as Otsu's method (discriminant analysis), Sauvola's method, and Goto's method. The measurement results are shown in the "Number of voids" column of Tables 3 and 4.

[0139] (3-3) Formation and measurement of the seed layer thickness The copper component was peeled off from the laminate obtained in (3-1) to form a resin substrate with a seed layer. The thickness of the seed layer in the resin substrate with a seed layer was measured using a scanning electron microscope (SEM) (magnification 30,000x, resolution 1024 × 768). In the cross-sectional image of the resin substrate with a seed layer taken using a scanning electron microscope (SEM), two parallel lines were drawn touching the upper edge corresponding to the upper surface of the seed layer and the lower edge corresponding to the lower surface of the seed layer, and the distance between these lines was taken as the thickness of the seed layer. The measurement results are shown in the "Thickness of Seed Layer (μm)" column of Tables 3 and 4.

[0140] (3-4) Measurement of 90° peel strength Using the laminate obtained in (3-1), the peel strength (gf / cm) was measured when the copper component was peeled off from the resin substrate at a speed of 50 mm / min in the 90° direction, in accordance with the 90° peel test (Japanese Industrial Standard (JIS) C5016). The measurement results are shown in the "90° Peel Strength (gf / cm)" column of Tables 3 and 4.

[0141] (3-5) Measurement of transcriptional defects The copper component was peeled off from the laminate obtained in (3-1) to form a resin substrate with a seed layer as a measurement sample. The measurement sample was observed and images were acquired using a confocal scanning electron microscope OPTELICS H1200 (Lasertec Corporation) under the following measurement conditions. The measurement conditions were: scan width 100 μm, scan type area, light source blue, cutoff value 1 / 5. The object lens was set to ×20, the contact lens to ×14, digital zoom to ×1, and Z pitch to 50 nm. The measurement range was 785000 μm. 2After adjusting the image contrast, the brightness is inverted, and the area of ​​the bright parts (μm²) is calculated from the binarized image analysis. 2 The area was measured. This bright area corresponds to the part where the seed layer was not formed, i.e., the part where the transfer of the copper oxide layer did not proceed properly. Therefore, a smaller area means fewer defects in the transfer. The minimum detection sensitivity is 4 μm 2 The measurement results are shown in Tables 3 and 4 under "Transcription Deficiency (μm)". 2 This is shown in the section ) . Also, in Tables 3 and 4, "Number of defects" shows the number of bright areas, and "Maximum defect size diameter (μm)" shows the length of the diameter of the bright area with the largest diameter.

[0142] (3-6) Evaluation of alkali resistance The copper component was peeled from the laminate obtained in (3-1) to form a resin substrate with a seed layer as an evaluation sample. The evaluation sample was immersed in a 100 g / L NaOH aqueous solution at a liquid temperature of 70°C for 15 minutes, then washed with water and dried. The surface of the seed layer side of the evaluation sample after alkali treatment was visually inspected to confirm the presence or absence of the seed layer according to the following evaluation criteria. The results are shown in the "Alkali Resistance Evaluation" section of Tables 3 and 4. In addition, the copper components of Example 1 and Comparative Examples 6 and 7 before and after the test in this evaluation, as well as the copper component for which the evaluation criterion was "×" for reference, are shown in Figure 6. • Evaluation criteria ○: Upon visual inspection, the seed layer was not completely dissolved, and no exposure of the resin substrate was observed. ×: Upon visual inspection, it was found that the seed layer had dissolved, exposing the resin substrate.

[0143] (3-7) Evaluation of etching properties The copper component was peeled off from the laminate obtained in (3-1) to form a resin substrate with a seed layer as a measurement sample. One drop of H-1000A (Sunhayato), diluted 20 times as an etching solution, was placed on the surface of the seed layer side of the measurement sample, left for 10 seconds, and then washed with water. The etching properties were evaluated according to the following evaluation criteria. The results are shown in the "Etching Properties Evaluation" section of Tables 3 and 4. In addition, the copper components of Example 1 and Comparative Example 4 before and after the test in this evaluation are shown in Figure 7. • Evaluation criteria 〇: Upon visual inspection, it was found that the seed layer had dissolved, completely exposing the resin substrate beneath the etching droplet. ×: Upon visual inspection, it was found that the seed layer did not completely dissolve, and residual seed layer was observed at the bottom of the etching droplet.

[0144] (3-8) Color tone of the treated foil Regarding the evaluation sample, the color tone (L * a * , b * The values ​​were measured using a spectrophotometer NR-12 (manufactured by Nippon Denshoku Industries Co., Ltd.).

[0145] [Table 1]

[0146] [Table 2]

[0147] [Table 3]

[0148] [Table 4] [Explanation of symbols]

[0149] 1 Copper member 2 Copper material 3 Copper oxide layer 4 protrusions 5. Metal layers other than copper 6. Peeling surface 10 Laminate 11 Copper component 12 Resin base material 21 Resin substrate with seed layer 22. Protrusions (protrusions transferred to the resin substrate) 23 Resin base material 24 Seed Layer 31 Copper-plated resin substrate 32 Resin base material 33 Copper plating layer 34 Seed Layer 50-layer structure 51 Copper component 52 Resin base material 53. Straight line (outer surface of copper member) 54 void 55 straight line 56 Measurement range

Claims

1. A copper member comprising a copper material and protrusions formed on part or all of the surface of the copper material, A metal layer other than copper is formed so as to cover part or all of the aforementioned protrusions. The aforementioned metal layer other than copper is composed of two or more metals other than copper. The 90° peel strength is 40 gf / cm or less. The Rz of the surface of the metal layer other than copper is 1 μm or less. Copper component.

2. A copper member comprising a copper material and protrusions formed on part or all of the surface of the copper material, A metal layer other than copper is formed so as to cover part or all of the aforementioned protrusions. The aforementioned metal layer other than copper is composed of two or more metals other than copper. Transcriptional defect is 80 μm ２ The following: The Rz of the surface of the metal layer other than copper is 1 μm or less. Copper component.

3. The copper member according to claim 1 or 2, wherein the metal other than copper is nickel and zinc.

4. The copper member according to claim 1 or 2, wherein the projection contains copper oxide.

5. The copper member according to claim 1 or 2, wherein the thickness of the metal layer other than copper is 17 to 50 nm.

6. A copper member according to claim 1 or 2, wherein a resin substrate is formed by heat-pressing a protrusion on the surface of the copper member to form a laminate, and then the copper member is peeled off from the resin substrate in the laminate, the thickness of the seed layer is 150 to 410 nm.

7. A laminate in which a copper member and a resin substrate according to claim 1 or 2 are laminated such that the resin substrate and a projection formed on the surface of the copper member are in contact with each other.

8. A process of obtaining a copper member by forming protrusions on part or all of the surface of a copper material, The process involves treating the aforementioned copper member with a release agent, The process involves plating the copper member using a plating solution to form a metal layer other than copper on its surface, A step of performing an alkali treatment on the metal layer other than copper of the copper member, A method for manufacturing a copper member according to claim 1, including the method described in claim 1.

9. The step of forming protrusions on part or all of the surface of the copper material is A method for manufacturing a copper member according to claim 8, comprising the step of forming protrusions containing copper oxide on part or all of the surface of the copper material by oxidation treatment.

10. A method for manufacturing a resin substrate with a seed layer, comprising a resin substrate and a seed layer formed on the surface of the resin substrate, A step of forming a laminate by laminating a resin substrate and a copper member according to claim 1 such that the resin substrate and the protrusions formed on the surface of the copper member come into contact with each other, The process involves separating the resin substrate and the copper member, and transferring the protrusions formed on the surface of the copper member to the resin substrate, thereby forming a seed layer on the surface of the resin substrate. A method for manufacturing a resin substrate with a seed layer, including the method described above.

11. A method for manufacturing a plated resin substrate comprising a resin substrate, a seed layer, and a plating layer in this order, A step of forming a laminate by laminating a resin substrate and a copper member according to claim 1 such that the resin substrate and the protrusions formed on the surface of the copper member come into contact with each other, The process involves separating the resin substrate and the copper member, and transferring the protrusions formed on the surface of the copper member to the resin substrate, thereby forming a seed layer on the surface of the resin substrate. The process involves plating the surface of the resin substrate using a plating solution, A method for manufacturing a resin substrate with a plated layer, including the method described above.

Images