TW202134053A - Composite copper member having voids - Google Patents

Abstract

Provided is a composite copper member in which a copper-oxide-containing layer is formed on at least part of the surface of a copper member, the composite copper member being such that voids are present in the copper-oxide-containing layer.

Description

Composite copper components with voids

The present invention relates to a composite copper component with voids.

The copper foil used for the printed wiring board needs adhesion to the insulating resin substrate. In order to improve the adhesion, there has been a method of roughening the surface of the copper foil by etching or the like, that is, by using the so-called anchor effect to improve the mechanical adhesion. On the other hand, from the viewpoint of increased density of printed wiring boards or transmission loss in high frequency bands, the surface of the copper foil needs to be flattened. In order to meet the above-mentioned opposite requirements, a copper surface treatment method that performs an oxidation step and a reduction step has been developed (International Publication No. 2014/126193). In this method, the copper foil is pre-treated and immersed in a potion containing an oxidizing agent to oxidize the surface of the copper foil to form copper oxide bumps, and then immersed in a potion containing a reducing agent to reduce the copper oxide, thereby adjusting the surface bumps To adjust the surface roughness. In addition, a method of adding interfacial active molecules in the oxidation step has also been developed as a method for improving the adhesion of copper foil treatment by oxidation and reduction (Japanese Patent Application No. 2013-534054), and the use of aminothiazole after the reduction step A method of forming a protective film on the surface of a copper foil with a compound or the like (Japanese Patent Application Laid-Open No. 8-97559).

Generally speaking, in addition to mechanical adhesion, the adhesion between resin and metal is also related to 1) the physical bonding force generated by the intermolecular force between the resin and the metal or 2) the functional group of the resin and the metal. It is related to the chemical bonding force produced by covalent bonds. In order to achieve low permittivity and low dissipation factor, the insulating resin used in high-frequency circuits reduces the proportion of OH groups (hydroxy groups). The chemical bonding force becomes weaker (International Publication No. 2017/150043). Therefore, the adhesion of insulating resin and copper foil for high-frequency circuits requires stronger mechanical adhesion.

The inventors of this case have also developed a composite copper foil, which is electroplated with nickel on the roughened copper foil, and has excellent adhesion (International Publication No. 2019/093494).

The present invention provides a novel composite copper component, a printed wiring board using the same, and a copper component that functions as a carrier and is metal-plated.

As a result of intensive research, the inventors found that by creating voids in the copper oxide-containing layer formed by the roughening treatment, the strength of the copper oxide-containing layer forming the unevenness is not increased, but is reduced, thereby Can be used to make circuits suitable for forming printed wiring boards and semiconductor packaging substrates, especially suitable for semi-additive process (SAP method) or M-SAP (Modified Semi-Additive Process) (MSAP method) Copper components.

The present invention has the following implementation aspects: [1] A composite copper component in which a layer containing copper oxide is formed on at least a part of the surface of the copper component, and the layer containing copper oxide has several voids. [2] The composite copper component according to [1], wherein, among the plurality of voids, at least a part of the voids exists at the interface between the copper oxide-containing layer and the surface of the copper component. [3] The composite copper member according to [1] or [2], wherein the peel strength between the copper oxide-containing layer and the surface of the copper member is 0.001 kgf/cm or more and 0.30 kgf/cm or less. [4] The composite copper member as described in any one of [1] to [3], in which a cross-sectional image of the scanning electron microscope is taken, and when the captured image is binarized, it is compared with the copper oxide containing When the layers are measured in the direction parallel to each other, the number of the gaps detected in any 3.8 μm is more than 30. [5] The composite copper component according to any one of [1] to [4], wherein the surface of the copper oxide-containing layer of the composite copper component is thermocompression bonded to the resin substrate under predetermined conditions to form a laminate When measuring in a direction parallel to the layered surface, when the captured image is binarized by the scanning electron microscope cross-section of the laminated body, the amount of the gap detected in any 3.8μm The number is more than 30. [6] The composite copper member as in [4] or [5], wherein the average distance between the voids in the captured image of the binarized cross-section is 100 nm or less. [7] The composite copper member as in [4] or [5], wherein in the captured image of the binarized cross-section, the ratio of the distance between the voids of 50 nm or less accounts for more than 40% of the entire void. [8] The composite copper component as described in any one of [5] to [7], wherein the resin base material contains selected from the group consisting of polyphenylene ether, epoxy resin, polyoxyxylene, polybenzoxazole, and polytetrafluoroethylene Ethylene, liquid crystal polymer, triphenyl phosphite, fluororesin, polyetherimide, polyetheretherketone, polycyclic olefin, bismaleimide resin, low permittivity polyimide and cyanate resin At least one insulating resin in the composition group. [9] The composite copper component as described in any one of [5] to [8], wherein the prescribed conditions for the thermal compression bonding are at a temperature of 50°C to 400°C, a pressure of 0 to 20 MPa, and 1 minute to 5 hours Within the range of time. [10] The composite copper member according to any one of [5] to [9], wherein the Ra of the surface on which the copper oxide-containing layer is formed is 0.04 μm or more, and the resin base material The ratio of Ra on the surface of the peeled copper member is less than 100%. [11] The composite copper member according to any one of [5] to [10], wherein the surface area of the copper member peeled from the resin substrate after thermocompression bonding is relative to the surface area of the copper oxide-containing layer The ratio of the surface area of the surface is less than 100%. [12] The composite copper component according to any one of [1] to [11], wherein the layer containing copper oxide contains a metal other than copper. [13] The composite copper component as in [12], wherein the metal other than copper is nickel. [14] The composite copper component according to any one of [1] to [11], wherein the layer containing copper oxide includes a copper plating layer. [15] A metal foil with a carrier, comprising the composite copper member as described in any one of [12] to [14], the layer containing copper oxide is used as a metal foil, and the copper member is used as a carrier relative to the metal foil use. [16] A laminate in which at least a part of the surface area of the copper oxide-containing layer of the composite copper member according to any one of [1] to [14] is layered with a resin substrate. [17] The laminated body as in [16], wherein the resin base material contains three selected from the group consisting of polyphenylene ether, epoxy resin, polyoxyxylene, polybenzoxazole, polytetrafluoroethylene, liquid crystal polymer, and phosphorous acid. At least one insulation from the group consisting of phenyl ester, fluororesin, polyether imide, polyether ether ketone, polycyclic olefin, bismaleimide resin, low permittivity polyimide and cyanate resin性resin. [18] The composite copper component as in any one of [1] to [14] is used to make printed wiring boards. [19] The composite copper components such as [18] are used to make printed wiring boards by the semi-additive method or the M-SAP method.

[20] A method for manufacturing a printed wiring board, which is a method for manufacturing a printed wiring board using a composite copper member as described in any one of [1] to [14], including: 1) A step of thermocompression bonding a resin substrate under specified conditions on the copper oxide-containing layer of the composite copper component; 2) The step of peeling the copper member from the resin substrate under prescribed conditions to obtain a resin substrate having part or all of the metal forming the copper oxide-containing layer; and 3) A step of performing copper plating treatment on the surface of a resin substrate having part or all of the metal forming the copper oxide-containing layer. [21] A method for manufacturing a resin substrate with metal, including: 1) A step of thermocompression bonding a resin base material under prescribed conditions on the copper oxide-containing layer of the composite copper component as in any one of [1] to [14]; and 2) The step of peeling the copper member from the resin substrate under prescribed conditions to obtain a resin substrate having a part or all of the metal forming the copper oxide-containing layer. [22] A method for manufacturing a composite copper component, such as the method for manufacturing a composite copper component in any one of [1] to [11], including: 1) The step of partially coating the surface of the copper component with silane coupling agent; and 2) The step of oxidizing the partially coated surface. [23] A method for manufacturing a composite copper component, such as the method for manufacturing a composite copper component in any one of [1] to [11], including: 1) The step of partially coating the surface of the copper component with silane coupling agent; 2) The step of oxidizing the partially coated surface; and 3) The step of treating the surface of the formed copper oxide-containing layer with a modifier, where the modifier includes selected from the group consisting of nickel chloride, zinc chloride, iron chloride, chromium chloride, ammonium citrate, Ammonium chloride, potassium chloride, ammonium sulfate, nickel ammonium sulfate, ethylenediaminetetraacetic acid, dihydroxyethylglycine, tetrasodium L-glutamate diacetate, ethylenediamine-N,N'-disuccinate Acid, 3-hydroxy-2,2'-imino sodium disuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, N-(2-hydroxyethyl)imino A compound of the group consisting of disodium diacetate and sodium gluconate. [24] A method of manufacturing composite copper components, such as the method of manufacturing composite copper components in [12], including: 1) The step of partially coating the surface of the copper component with silane coupling agent; 2) The step of oxidizing the partially coated surface; and 3) A step of forming a layer containing a metal other than copper on the surface that has been oxidized. [25] A method for manufacturing composite copper components, such as the method for manufacturing composite copper components in [12], including: 1) The step of oxidizing the surface of the copper component; 2) The step of treating the surface after the oxidation treatment with a modifier; and 3) A step of forming a layer containing metals other than copper on the surface treated with the modifier, where the modifier includes selected from the group consisting of nickel chloride, zinc chloride, iron chloride, chromium chloride, and citric acid Ammonium, ammonium chloride, potassium chloride, ammonium sulfate, nickel ammonium sulfate, ethylenediaminetetraacetic acid, dihydroxyethylglycine, L-glutamic acid tetrasodium diacetate, ethylenediamine-N,N'- Disuccinic acid, sodium 3-hydroxy-2,2'-imino disuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, N-(2-hydroxyethyl) A compound of the group consisting of disodium amine diacetate and sodium gluconate. [26] A method of manufacturing composite copper components, such as the method of manufacturing composite copper components in [12], including: 1) The step of partially coating the surface of the copper component with a silane coupling agent; 2) The step of oxidizing the partially coated surface; 3) The step of treating the surface after the oxidation treatment with a modifier, and 4) A step of forming a layer containing metals other than copper on the surface treated with the modifier. Here, the modifier includes selected from the group consisting of nickel chloride, zinc chloride, iron chloride, chromium chloride, and citric acid Ammonium, ammonium chloride, potassium chloride, ammonium sulfate, nickel ammonium sulfate, ethylenediaminetetraacetic acid, dihydroxyethylglycine, L-glutamic acid tetrasodium diacetate, ethylenediamine-N,N'- Disuccinic acid, sodium 3-hydroxy-2,2'-imino disuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, N-(2-hydroxyethyl) A compound of the group consisting of disodium amine diacetate and sodium gluconate.

The preferred embodiments of the present invention will be described in detail below using additional drawings, but it is not limited thereto. In addition, based on the description of this specification, a person with ordinary knowledge in the technical field of the invention can understand the purpose, features, advantages, and concept of the present invention, and a person with ordinary knowledge in the technical field of the invention can easily reproduce it from the description of this specification. this invention. The embodiments and specific examples of the invention described below represent preferred embodiments of the invention, and are used for illustration and description, and do not limit the invention. Those having ordinary knowledge in the technical field to which the invention pertains will understand that various modifications can be made based on the description of this specification within the intent and scope of the invention disclosed in this specification.

Composite copper component: One embodiment of the present invention is a composite copper component. A layer containing copper oxide is formed on at least a part of the surface of the copper component. The copper member system contains copper as a main component and forms a part of the structure. The copper member specifically includes copper foil such as electrolytic copper foil, rolled copper foil, and copper foil with a carrier, copper wire, copper plate, copper lead frame, copper powder, etc., but is not limited to these. The copper member is preferably one that can be electroplated. The copper member is preferably a material made of pure copper with a copper purity of 99.9% by mass or more, more preferably made of toughened copper, deoxidized copper, and oxygen-free copper, and preferably has an oxygen content of 0.001% to 0.0005% by mass Oxygen-free copper is formed.

When the copper member is a copper foil, the thickness is not particularly limited, but is preferably 0.1 μm or more and 100 μm or less, more preferably 0.5 μm or more and 50 μm or less. When the copper member is a copper plate, the thickness thereof preferably exceeds 100 μm. Although not particularly limited, it is preferably 1 mm or more, 2 mm or more, or 10 mm or more, and more preferably 10 cm or less, 5 cm or less, or 2.5 cm or less.

The layer containing copper oxide is formed on the surface of the copper member, and contains copper oxide (CuO) and/or cuprous oxide (Cu ₂ O). The layer containing copper oxide can be formed by oxidizing the surface of the copper member. With this oxidation treatment, the surface of the copper member is roughened. For the layer containing copper oxide, a dissolving agent can be used to adjust the shape of the convex portion on the surface of the oxidized copper member. In addition, the surface of the copper oxide-containing layer can be reduced by a reducing agent. The resistivity of pure copper is 1.7×10 ^-8 (Ωm). In contrast, the resistivity of copper oxide is 1-10 ( Ωm), the resistivity of cuprous oxide is 1×10 ⁶ ～1×10 ⁷ (Ωm), so the conductivity of the copper oxide-containing layer is low, even if the amount of the copper oxide-containing layer transferred to the resin substrate In many cases, when a composite copper component is used to form a printed wiring board or a circuit of a semiconductor package substrate, it is difficult to produce transmission loss caused by the skin effect.

The layer containing copper oxide has several voids. The gap can be connected to the outside world or closed. Preferably, even if the resin substrate is thermally compressed on the layer containing copper oxide, the resin substrate does not enter the void and can maintain the void. The voids can be detected in the SEM cross-sectional image of the composite copper component. The voids are present in the layer containing copper oxide, and preferably also include those present at the interface between the layer containing copper oxide and the surface of the copper member. For example, this interface can be distinguished by the difference in density caused by the composition in the SEM cross-sectional image, or the difference in density caused by the presence or absence of the copper crystal structure that constitutes the copper component (Figure 3). Preferably, 50% or more, 60% or more, 70% or more, 80% or more, 90%, 95% or 100% of the number of voids are present at the interface between the copper oxide-containing layer and the surface of the copper member, but It is not particularly limited.

Specifically, the void system can be determined from the cross-sectional SEM image of the composite copper member by, for example, the following steps. 1) Obtain a SEM cross-sectional image, so that the copper oxide layer is on the top and the copper component is on the bottom in the image. 2) The area surrounded by copper and copper oxide that exists on the side closest to the copper member on the screen; or a straight line passing through the apex of the area surrounded by copper oxide and parallel to the layer containing copper oxide, and passing through the copper oxide The area surrounded by the apex of the highest protrusion of the layer of objects and a straight line parallel to the layer containing copper oxide is used as the measurement range. 3) After adjusting the contrast of the image in the measurement range, perform inversion processing to exchange the bright part and dark part of the image. 4) For automatic binarization, select the area surrounded by copper and copper oxide or the area surrounded by copper oxide. 5) The one with a side length of 1 pixel is regarded as noise and deleted. 6) Use the top left of the image as the origin, the downward direction in the image as the X axis, and the right direction as the Y axis. Take the area (1) with X=maximum and Y=minimum selected by automatic binarization as the starting point, and the area with the closest distance in the Y-axis direction as the area (2). The area closest to the area (2) in the Y-axis direction is taken as area (3), and then the same steps are used to determine areas (4) to (N) until Y=maximum in the measurement range. The regions (1) to (N) determined here are voids. Alternatively, the void can also be determined by the cross-sectional SEM image of the composite copper member after laminating the resin substrate in the same step. Binarization is to process the image by dividing the intensity of the image by a predetermined threshold, and the value above the threshold is 1, and the value below the threshold is 0. The binarization system can be binarized by the OTSU method (discriminatory analysis method), Sauvola method, Goto method, etc.

The maximum horizontal chord length of the gap is preferably a size that can be detected when a SEM cross-sectional image with a magnification of 30,000 times and a resolution of 1024×768 pixels is binarized. Preferably, the side length is 500 nm or less, the side length is 400 nm or less, the side length is 300 nm or less, the side length is 200 nm or less, the side length is 100 nm or less, or the side length is 50 nm or less, and the side length is 4 nm or more, the side length is 5 nm or more, and the side length is 10 nm or more. The side length is 15 nm or more, the side length is 20 nm or more, the side length is 25 nm or more, the side length is 50 nm or more, the side length is 100 nm or more, or the side length is 200 nm or more, but it is not particularly limited. In the binarized SEM cross-sectional image, when measured in a direction parallel to the surface on which the copper oxide-containing layer is formed, the number of voids per 3.8 μm is preferably 25 or more, 30 or more, or 40 or more Or 50 or more, and 500 or less, 400 or less, 300 or less, 200 or less, 100 or less, 90 or less, 80 or less, 70 or less or 60 or less. In addition, the distance between the gaps can also be calculated on the image to calculate the distance between the gaps. The average distance between the voids is preferably 200 nm or less, 150 nm or less, 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, 60 nm or less or 50 nm or less, and 40 nm or more, 30 nm or more, 20 nm or more or 10 nm or more. In addition, the distance distribution between the gaps is preferably 50 nm or less, which accounts for 35%, 40%, 45%, or 50% or more of the entire gap.

With the existence of this void, the layer containing the copper oxide becomes easily separated from the copper member. The peel strength between the copper oxide-containing layer and the surface of the copper member is preferably 0.30kgf/cm or less, 0.20kgf/cm or less, 0.15kgf/cm or less, or 0.15kgf/cm or less, and 0.001kgf/cm or more , 0.002kgf/cm or more, 0.003kgf/cm or more, or 0.004kgf/cm or more, but not particularly limited. The peel strength can be based on a 90-degree peel test (Japanese Industrial Standards (JIS) C5016 "Test Method for Flexible Printed Wiring Boards"" after thermocompression bonding of the resin substrate on the layer containing copper oxide; the corresponding international standard IEC249-1 :1982, IEC326-2:1990), to measure the peel strength during peeling.

The layer containing copper oxide may contain metals other than copper. The included metal is not particularly limited, and may include at least one metal selected from the group consisting of tin, silver, zinc, aluminum, titanium, bismuth, chromium, iron, cobalt, nickel, palladium, gold, and platinum. In particular, in order to have acid resistance and heat resistance, it is preferable to include metals with higher acid resistance and heat resistance than copper, such as nickel, palladium, gold, and platinum. Metals other than copper can be formed on the surface of the copper member by plating. The method of plating is not particularly limited, and examples include electroplating, electroless plating, vacuum evaporation, chemical conversion treatment, and the like. It is preferable to form a uniform thin plating layer, so electroplating is preferred. When electroplating is applied to the surface of the copper foil after oxidation treatment, the copper oxide on the surface is first reduced to form cuprous oxide or pure copper. Therefore, there will be a time delay until the plating is formed, and then the metal layer is formed. Metal began to precipitate. The amount of charge varies depending on the type of plating solution or the amount of copper oxide. For example, when nickel plating is applied to a copper member, in order to make the thickness within a preferable range, it is better to give every dm of the copper member to be electroplated ² Charges with an area of 15C or more and 75C or less are more preferably given with a charge of 25C or more and 65C or less. The average thickness in the vertical direction of metals other than copper formed on the outermost surface of the copper member by plating is not particularly limited, but is preferably 6 nm or more, more preferably 10 nm or more, 14 nm or more, 18 nm or more, or 20 nm or more. However, it is preferably 80 nm or less, more preferably 70 nm or less or 60 nm or less. In addition, the average thickness in the vertical direction of the metal other than copper contained in the copper oxide-containing layer can be obtained by dissolving the copper oxide-containing layer in an acid solution, and measuring the amount of metal by ICP analysis, and dividing the measured amount by the composite Calculate the area of the copper member. Alternatively, it can also be calculated by dissolving the composite copper member itself and measuring only the amount of metal contained in the layer containing copper oxide.

When the surface of the composite copper member formed with the layer containing copper oxide is thermally press-fitted to the resin base material, the surface profile of the composite copper member is transferred to the resin base material. In addition, when the composite copper member is peeled from the resin substrate after thermocompression bonding, the metal contained in the copper oxide-containing layer is transferred from the composite copper member to the resin substrate. An example of an embodiment of the composite copper member is shown in Fig. 1.

The resin base material contains resin as a main component, and can be used to form circuits such as printed wiring boards and semiconductor package substrates. The resin is not particularly limited, and may be a thermoplastic resin or a thermosetting resin, preferably polyphenylene ether (PPE), epoxy resin, polyoxyxylene (PPO), polybenzoxazole (PBO), polytetrafluoroethylene (PTFE) , Liquid crystal polymer (LCP), triphenyl phosphite (TPPI), fluororesin, polyetherimide, polyetheretherketone, polycyclic olefin, bismaleimide resin, low permittivity polyimide , Cyanate resin or mixed resins of these. The resin substrate may additionally contain inorganic fillers or glass fibers.

In order to thermocompression-bond the resin substrate to the surface of the composite copper member, for example, the resin substrate and the composite copper member are laminated in close contact with each other, and then processed under predetermined conditions to adhere the resin substrate and the composite copper member. The specified conditions (such as temperature, pressure, time) can be the conditions recommended by each substrate manufacturer. The prescribed conditions may consider the following conditions, for example.

1) In the case where the resin substrate contains epoxy resin or is formed of epoxy resin, it is preferable to apply a pressure of 0-20 MPa at a temperature of 50°C to 300°C for 1 minute to 5 hours to heat the composite copper component. Crimped to the resin substrate. E.g, 1-1) When the resin substrate is R-1551 (manufactured by Panasonic), it is heated at a pressure of 1 MPa, and after reaching 100°C, the temperature is maintained at that temperature for 5 to 10 minutes, and then further heated at a pressure of 3.3 MPa to reach After 170-180°C, maintain the temperature for 50 minutes to perform thermocompression bonding. 1-2) When the resin substrate is R-1410A (manufactured by Panasonic), heat it at a pressure of 1 MPa. After reaching 130°C, maintain the temperature for 10 minutes, and then further heat it at a pressure of 2.9 MPa to reach 200°C. After that, the temperature was maintained for 70 minutes to perform thermocompression bonding. 1-3) When the resin base material is EM-285 (manufactured by EMC), heat it at a pressure of 0.4 MPa. After reaching 100°C, increase the pressure to 2.4 to 2.9 MPa and then further heat it. After reaching 195°C, it will be heated at this temperature. Maintain for 50 minutes for thermocompression bonding. 1-4) When the resin substrate is GX13 (manufactured by Ajinomoto), heat it while applying pressure at 1.0 MPa, and maintain it at 180°C for 60 minutes to perform thermocompression bonding.

2) When the resin base material contains PPE resin or is formed of PPE resin, it is preferable to apply a pressure of 0-20 MPa at a temperature of 50°C to 350°C for 1 minute to 5 hours, thereby thermocompression bonding of the composite copper member For resin substrate. E.g, 2-1) When the resin substrate is R5620 (manufactured by Panasonic), after heating to 100°C under a pressure of 0.5 MPa, after thermo-compression bonding, raise the temperature and pressure to maintain at 2.0 to 3.0 MPa and 200 to 210°C 120 minutes for further thermal compression bonding. 2-2) When the resin substrate is R5670 (manufactured by Panasonic), after heating to 110°C under a pressure of 0.49 MPa, after thermo-compression bonding, raise the temperature and pressure and maintain at 2.94 MPa and 210°C for 120 minutes. Hot crimping. 2-3) When the resin base material is R5680 (manufactured by Panasonic), after heating to 110°C under a pressure of 0.5 MPa, after thermo-compression bonding, raise the temperature and pressure and maintain at 3.0 to 4.0 MPa at 195°C for 75 minutes For thermal compression. 2-4) When the resin base material is N-22 (manufactured by Nelco), heat it while applying pressure at 1.6 to 2.3 MPa. After maintaining it at 177°C for 30 minutes, it is further heated and heated at 216°C for 60 minutes. Crimping.

3) When the resin base material contains PTFE resin or is formed of PTFE resin, it is preferable to apply a pressure of 0-20 MPa at a temperature of 50°C to 400°C for 1 minute to 5 hours, thereby thermocompression bonding of the composite copper member For resin substrate. E.g, 3-1) When the resin substrate is NX9255 (manufactured by Park Electrochemical), heat to 260°C while applying pressure at 0.69 MPa, increase the pressure to 1.03 to 1.72 MPa and heat to 385°C, and maintain at 385°C for 10 minutes Perform thermo-compression bonding. 3-2) When the resin substrate is RO3003 (manufactured by Rogers), 50 minutes (approximately 220°C) after the start of pressing, pressurize to 2.4 MPa and maintain at 371°C for 30 to 60 minutes to perform thermocompression bonding.

The conditions for peeling the copper member from the resin base material are not particularly limited, and it can be based on a 90° peel test (Japanese Industrial Standards (JIS) C5016 "Test Method for Flexible Printed Wiring Boards"; International Standards IEC249-1:1982, IEC326-2) :1990) to proceed.

The metal contained in the copper oxide-containing layer is transferred to the resin substrate after peeling off the copper member. Various methods (such as X-ray photoelectron spectroscopy (XPS), energy scattering X-ray spectroscopy (EDS), ICP emission spectroscopy (inductively coupled plasma emission) Spectroscopy, ICP-OES/ICP-AES)). XPS is a technique in which X-rays are irradiated to an object, and the photoelectrons emitted by the ionization of the object are e-captured for energy analysis. With XPS, it is possible to detect the type, amount, chemical bonding state, etc. of the elements present on the surface of the sample or from the surface to a predetermined depth (for example, to a depth of 6nm). The analysis point diameter (that is, the cross-sectional diameter when the cylindrical part that can be analyzed is cut to make the cross-section circular) is suitable for 1μm or more to 1mm or less.

最大高度粗度（Rz）係表示基準長度l中，輪廓曲線（y=Z(x)）的峰高Zp之最大值與谷深Zv之最大值的和。Ra、Rz係根據JIS B 0601:2001（基於國際標準ISO4287-1997）規定之方法算出。形成有包含銅氧化物之層的複合銅構件之表面，其剝離後之Ra相對於熱壓接前之Ra的比例，較佳為未滿100%、未滿96%、未滿95%、未滿94%、未滿93%、未滿92%、未滿91%、未滿90%、未滿80%、未滿70%、未滿65%或未滿60%。此比例越小，則越表示形成包含銅氧化物之層的金屬已轉移至樹脂基材。The arithmetic average roughness (Ra) of the surface of the composite copper member on which the layer containing copper oxide is formed is preferably 0.04 μm or more, more preferably 0.1 μm or more, more preferably 0.3 μm or less, more preferably 0.2 μm the following. The maximum height roughness (Rz) of the surface of the composite copper member on which the layer containing copper oxide is formed is preferably 0.2 μm or more, more preferably 1.0 μm or more, more preferably 2.0 μm or less, more preferably 1.7 μm the following. If Ra and Rz are too small, the adhesion to the resin substrate will be insufficient, and if they are too large, the fine wiring formation and high-frequency characteristics will be poor. Here, the arithmetic average roughness (Ra) represents the average value of the absolute value of Z(x) (ie peak height and valley depth) in the profile curve (y=Z(x)) expressed by the following formula in the reference length l . Mathematical formula 1:

The maximum height roughness (Rz) is the sum of the maximum value of the peak height Zp and the maximum value of the valley depth Zv of the profile curve (y=Z(x)) in the reference length l. Ra and Rz are calculated according to the method stipulated in JIS B 0601:2001 (based on the international standard ISO4287-1997). On the surface of the composite copper member on which the layer containing copper oxide is formed, the ratio of the Ra after peeling to the Ra before the thermocompression bonding is preferably less than 100%, less than 96%, less than 95%, and less than 100%. Full 94%, less than 93%, less than 92%, less than 91%, less than 90%, less than 80%, less than 70%, less than 65%, or less than 60%. The smaller this ratio is, the more it means that the metal forming the layer containing copper oxide has been transferred to the resin substrate.

The ratio of the surface area after peeling to the surface area before thermocompression bonding of the composite copper member formed with a layer containing copper oxide is preferably less than 100%, less than 98%, less than 97%, less than 96 %, less than 95%, less than 94%, less than 93%, less than 92%, less than 91%, less than 90%, less than 80%, or less than 75%. The smaller this ratio is, the more it means that the metal forming the layer containing copper oxide has been transferred to the resin substrate. The surface area can be measured with a conjugate focus microscope or an atomic force microscope.

在此，算數平均粗度（Ra）的10%作為凹凸的最小高度，基準長度（lr）的1%作為最小長度以定義一個週期量的凹凸。舉例如，Rsm可根據「利用原子力顯微鏡之精密陶瓷薄膜的表面粗度測定方法（JIS R 1683:2007）」來測定並算出。In the composite copper member of one embodiment of the present invention, the average length (RSm) of the roughness curve parameter of the surface of the composite copper member on which the layer containing copper oxide is formed is not particularly limited, and is preferably 1500 nm or less and 1400 nm or less , 1300nm or less, 1200nm or less, 1100nm or less, 1000nm or less, 900nm or less, 800nm or less, 750nm or less, 700nm or less, 650nm or less, 600nm or less, 550nm or less, 450nm or less, or 350nm or less, and preferably 100nm or more, 200nm or more 300nm or more. Here, RSm represents the average length (that is, the length of the profile curve parameter: Xs1 to Xsm) of the unevenness of one period included in the roughness curve of one reference length (lr), and is calculated by the following formula. Mathematical formula 2:

Here, 10% of the arithmetic average roughness (Ra) is taken as the minimum height of the concavity and convexity, and 1% of the reference length (lr) is taken as the minimum length to define one period of concavity and convexity. For example, Rsm can be measured and calculated according to "Method for Measuring Surface Roughness of Precision Ceramic Thin Films Using Atomic Force Microscope (JIS R 1683:2007)".

The ΔE*ab of the surface of the composite copper member before thermocompression bonding and the surface of the copper member after peeling is preferably 13 or more, 15 or more, 20 or more, 25 or more, 30 or more or 35 or more. The larger the difference, the more it means that the metal forming the layer containing copper oxide (that is, the metal forming the unevenness) has been transferred to the resin substrate.

Method for manufacturing a composite copper component: One embodiment of the present invention is a method for manufacturing a composite copper component, including the step of providing a gap in the layer containing copper oxide so that the layer containing copper oxide is easily broken from the copper component.

In this step, the method of providing voids in the copper oxide-containing layer so that the copper oxide-containing layer can be easily broken from the copper member is not particularly limited. There are 1) The surface of the copper member is coated with a coating agent such as a silane coupling agent before the oxidation treatment. For partial coating, 2) After oxidation treatment, treat the layer containing copper oxide with a modifier such as nickel chloride, or a combination of the above methods.

The layer containing copper oxide is preferably formed by treating the surface of the copper member with an oxidizing agent. The oxidizing agent is not particularly limited. For example, aqueous solutions such as sodium chlorite, sodium hypochlorite, potassium chlorate, potassium perchlorate, and potassium persulfate can be used. Various additives (such as phosphate such as trisodium phosphate dodecahydrate) can be added to the oxidizing agent.

The oxidation reaction conditions are not particularly limited, and the reaction temperature is preferably 40 to 95°C, more preferably 45 to 80°C. The reaction time is preferably 0.5 to 30 minutes, more preferably 1 to 10 minutes.

Before oxidation treatment, degreasing treatment, removal of natural oxide film for acid cleaning for homogenization treatment, or alkali treatment after acid cleaning can be carried out to prevent acid from being carried into the oxidation step. The pickling can be performed by immersing the copper surface in sulfuric acid at a liquid temperature of 20 to 50°C and 5 to 20% by weight for 1 to 5 minutes, and then washing with water. After the acid treatment, in order to reduce the unevenness of the treatment and prevent the acid used in the cleaning treatment from being mixed with the oxidant, further alkali treatment can be carried out. The method of alkali treatment is not particularly limited, preferably 0.1-10g/L alkaline aqueous solution, more preferably 1-2g/L alkaline aqueous solution, alkaline aqueous solution such as sodium hydroxide aqueous solution, treated at 30-50°C for 0.5 ~2 minutes is enough. In addition, the copper oxide-containing layer can be dissolved with a dissolving chemical solution containing a dissolving agent to adjust the protrusions on the surface of the copper member, and the reducing chemical solution containing a reducing agent can also be used to reduce the copper oxide of the copper oxide-containing layer.

The dissolving agent is not particularly limited. It is preferably a chelating agent, particularly a biodegradable chelating agent, such as L-glutamic acid tetrasodium diacetate (CMG-40), ethylenediaminetetraacetic acid (sodium salt), dihydroxy Ethylglycine, tetrasodium L-glutamate diacetate, ethylenediamine-N,N'-disuccinic acid, 3-hydroxy-2,2'-imino sodium disuccinate, methylglycamine Trisodium diacetate, tetrasodium aspartate diacetate, disodium N-(2-hydroxyethyl) iminodiacetate, sodium gluconate, etc.

The reducing agent can be DMAB (dimethylamine borane), diborane, sodium borohydride, hydrazine, etc. In addition, the chemical solution for reduction is a liquid containing a reducing agent, an alkaline compound (for example, sodium hydroxide, potassium hydroxide, etc.), and a solvent (for example, pure water, etc.).

The layer containing copper oxide may contain metals other than copper. Metals other than copper can be included, for example, by plating a layer containing copper oxide with a metal other than copper. The plating treatment method can use the conventional technology, and the metal other than copper can be tin, silver, zinc, aluminum, titanium, bismuth, chromium, iron, cobalt, nickel, palladium, gold, platinum or various alloys. The plating step is also not particularly limited, and plating, electroless plating, vacuum evaporation, chemical conversion treatment, etc. can be used, and it is preferable to form a uniform thin plating layer, so electroplating is preferred.

In the case of electroplating, nickel plating and nickel alloy plating are preferable. Metals formed by nickel plating and nickel alloy plating include, for example, pure nickel, nickel-copper alloys, nickel-chromium alloys, nickel-cobalt alloys, nickel-zinc alloys, nickel-manganese alloys, nickel-lead alloys, and nickel-phosphorus alloys. Metal salts used for plating include, for example, nickel sulfate, nickel sulfamate, nickel chloride, nickel bromide, zinc oxide, zinc chloride, diamine dichloropalladium, iron sulfate, iron chloride, anhydrous chromic acid, Chromium chloride, sodium chromium sulfate, copper sulfate, copper pyrophosphate, cobalt sulfate, manganese sulfate, etc. In nickel plating, the bath composition preferably contains, for example, nickel sulfate (100g/L or more and 350g/L or less), nickel sulfamate (100g/L or more and 600g/L or less), nickel chloride (0g/L or more) And 300g/L or less) and these mixtures may also contain sodium citrate (0 g/L or more and 100 g/L or less) or boric acid (0 g/L or more and 60 g/L or less) as additives.

In the case of electroless nickel plating, electroless plating using a catalyst is preferred. The catalyst can use iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, or their salts. By performing electroless plating using a catalyst, the heat resistance of the composite copper foil can be improved.

An embodiment of the method for manufacturing a composite copper component of the present invention includes 1) the step of partially coating the surface of the copper component with a silane coupling agent; and 2) the step of oxidizing the surface of the partially coated copper component; Or, it includes 1) the step of partially coating the surface of the copper component with a silane coupling agent; 2) the step of oxidizing the surface of the partially coated copper component; and 3) forming a copper component on the surface of the oxidized copper component. Steps other than the metal layer. By partially coating the surface of the copper component with a coating agent such as silane coupling agent, the part is protected from oxidation treatment, and voids are generated in the layer containing copper oxide, especially near the interface with the copper component, including copper oxide The layer becomes easy to break from the copper component. Therefore, the treatment of the silane coupling agent is better to remove the part of the surface of the copper component (such as 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%). Above and less than 100%) coating. For this, it is better to make the silane coupling agent at a concentration of 0.1%, 0.5%, 1% or 2% at room temperature to react for 30 seconds, 1 minute or 2 minutes or more .

The silane coupling agent is not particularly limited, and can be selected from silane, tetraorgano-silane, aminoethyl-aminopropyl-trimethoxysilane, (3-aminopropyl)trimethoxysilane, (1-[ 3-(Trimethoxysilyl)propyl]urea) (l-[3-(Trimethoxysilyl)propyl]urea), (3-aminopropyl)triethoxysilane, (3-epoxypropyl oxygen Propyl)trimethoxysilane, (3-chloropropyl)trimethoxysilane, (3-epoxypropyloxypropyl)trimethoxysilane, dimethyldichlorosilane, 3-(trimethoxysilane) Yl) propyl methacrylate, ethyl triacetoxysilane, triethoxy (isobutyl) silane, triethoxy (octyl) silane, ginseng (2-methoxyethoxy) (Vinyl) Silane, chlorotrimethylsilane, methyltrichlorosilane, silicon tetrachloride, tetraethoxysilane, phenyltrimethoxysilane, chlorotriethoxysilane, vinyl-trimethoxysilane Wait. The treatment of the silane coupling agent can be carried out at any time as long as it is carried out before the oxidation treatment. It can be combined with degreasing treatment, acid washing by removing natural oxide film for homogenization treatment, or after acid washing to prevent acid from being carried in The alkali treatment in the oxidation step is carried out at the same time.

An embodiment of the method for manufacturing a composite copper member of the present invention includes 1) the step of oxidizing the surface of the copper member; and 2) the step of treating the surface of the oxidized copper member with a modifier, or, including 1) The step of oxidizing the surface of the copper component; 2) the step of treating the surface of the oxidized copper component with a modifier; and 3) the step of forming a layer containing a metal other than copper on the surface of the composite copper component treated with the modifier . It is presumed that part of the copper oxide system near the interface between the copper member and the copper oxide-containing layer is dissolved by the treatment with the modifier, resulting in voids, and the copper oxide-containing layer becomes easy to break from the copper member. The modifier used to make the layer containing copper oxide easy to break from the copper member is not limited to nickel chloride, but may also be chloride (zinc chloride, iron chloride, chromium chloride, etc.), ammonium salt ( Ammonium citrate, ammonium chloride, ammonium sulfate, nickel ammonium sulfate, etc.), chelating agents (ethylenediaminetetraacetic acid, dihydroxyethylglycine, tetrasodium L-glutamic acid diacetate, ethylenediamine-N, N'-disuccinic acid, sodium 3-hydroxy-2,2'-imino disuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, N-(2-hydroxyethyl Group) disodium iminodiacetate, sodium gluconate) and so on. It is not particularly limited when treated with nickel chloride. It is preferable to immerse the copper member on which the layer containing copper oxide is formed in a nickel chloride solution (concentration of 45g/L or more) at room temperature or a temperature higher than room temperature. ) More than 5 seconds. Moreover, not only the nickel chloride treatment alone, but also the oxidation treatment may be performed simultaneously, or the plating treatment may be performed simultaneously after the oxidation treatment. For example, nickel chloride can be contained in the plating solution, and the copper member on which the layer containing copper oxide is formed is immersed in the plating solution for 5 seconds, 10 seconds, 15 seconds, 20 seconds, 30 seconds, 1 minute or 2 minutes. The immersion time can be appropriately changed according to the thickness of the oxide film.

An embodiment of the method for manufacturing a composite copper component of the present invention includes 1) the step of partially coating the surface of the copper component with a silane coupling agent; 2) the step of oxidizing the surface of the partially coated copper component; and 3) The step of treating the surface of the oxidized copper component with a modifier, or including 1) the step of partially coating the surface of the copper component with a silane coupling agent; 2) oxidizing the surface of the partially coated copper component 3) the step of treating the surface of the oxidized copper member with a modifier; and 4) the step of forming a layer containing a metal other than copper on the surface of the copper member treated with the modifier.

Use method of composite copper component: The composite copper component of the present invention can be used for (1) Crimping on the resin base material to manufacture a laminate; (2) It is crimped on the resin substrate and peeled off to obtain a part or all of the metal that forms the layer containing copper oxide on the resin substrate; (3) In the SAP method or the MSAP method, the resin substrate is crimped and peeled to obtain a resin substrate with a part or all of the metal forming the layer containing copper oxide. Copper is applied to the surface of the peeled resin substrate. Plating treatment to manufacture printed wiring boards; (4) On the layer containing copper oxide, plating of copper or a metal other than copper is applied to form a metal foil, the copper member is used as a carrier, and the layer containing copper oxide and the plating of copper or a metal other than copper are used as Metal foil is used to manufacture metal foil with a carrier, etc. In (1) to (3), the resin base material and the conditions for thermocompression bonding to the resin base material may be the same as or different from the conditions when the SEM cross-sectional image is obtained. In (2) to (3), the peeling conditions may be the same as or different from the conditions when the SEM cross-sectional image is obtained. In (3), the copper plating method can be electroplating or electroless plating. In (4), the method of applying plating to the outermost surface of the layer containing copper oxide may be electroplating or electroless plating, and the metal may be an alloy.

<1. Manufacturing of composite copper foil>: In Examples 1 to 3, Comparative Examples 2 and 3, the bright surface (glossy surface) of the copper foil (DR-WS, thickness: 18μm) manufactured by Furukawa Electric Co., Ltd. was used. When comparing the surface, it is a flat surface). In Comparative Example 1, the matte surface of copper foil (FV-WS, thickness: 18 μm) manufactured by Furukawa Electric Co., Ltd. was used, and the untreated state was used as a test piece.

(1) Pretreatment: Examples 1 and 2 are made in potassium carbonate 5g/L; KBE-903 (3-aminopropyl triethoxysilane; manufactured by Shin-Etsu Silicone) 1 vol% solution, immersed at 25°C minute. Comparative Examples 2, 3, and Example 3 were immersed in a solution of 5 g/L of potassium carbonate at 25°C for 1 minute.

(2) Oxidation treatment: the pre-treated copper foil is immersed in an oxidant for oxidation treatment. Examples 1 and 2 used sodium chlorite 52.5g/L; potassium hydroxide 18g/L; potassium carbonate 35g/L solution as the oxidant. Example 3 uses 37.5g/L sodium chlorite; 10g/L potassium hydroxide; KBM-403 (3-epoxypropyloxypropyltrimethoxysilane; manufactured by Shin-Etsu Silicone) 1.5g/L solution As an oxidant. Comparative Example 2 uses 53.5g/L of sodium chlorite; 8g/L of potassium hydroxide; 2g/L of potassium carbonate; KBM-403 (3-epoxypropyloxypropyltrimethoxysilane; manufactured by Shin-Etsu Silicone) 1.5g/L solution is used as oxidant. Comparative example 3 uses sodium chlorite 195g/L; potassium hydroxide 18g/L; KBM-403 (3-epoxypropyloxypropyltrimethoxysilane; Shin-Etsu Silicone) 0.5g/L solution as Oxidant. Examples 1 and 2 were immersed in the oxidizing agent at 73°C for 6 minutes, and Example 3 and Comparative Example 2 were immersed in the oxidizing agent at 73°C for 2 minutes. Comparative Example 3 was immersed in the oxidizing agent at 50°C for 1 minute. (3) Electroplating treatment: After oxidation treatment, Examples 2, 3 and Comparative Example 2 used nickel electroplating solution (nickel sulfate 250g/L; nickel chloride 50g/L; sodium citrate 25g/L) for electroplating. Comparative Example 3 uses nickel electroplating solution (nickel sulfate 250g/L; boric acid 35g/L) for electroplating. In Example 3, immersion in a nickel electroplating solution for 1 minute before electroplating. Comparative Examples 2 and 3 and Examples 2 and 3 were electroplated at 50° C. and a current density of 0.5 A/dm ² ×45 seconds (=22.5 C/dm ² copper foil area).

Regarding the Examples and Comparative Examples, several test pieces were produced under the same conditions (Table 1). Table 1 Example Comparative example Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Comparative example 3 Pretreatment Deployment Potassium Carbonate g/L 5 5 5 - 5 5 KBE-903 vol% 1 1 0 - 0 0 deal with temperature °C 25 25 25 - 25 25 time minute 1 1 1 - 1 1 Oxidation treatment Deployment Sodium chlorite g/L 52.5 52.5 37.5 - 53.5 195 Potassium hydroxide g/L 18 18 10 - 8 18 Potassium Carbonate g/L 35 35 0 - 2 0 KBM-403 g/L 0 0 1.5 - 1.5 0.5 deal with temperature °C 73 73 73 - 73 50 time minute 6 6 2 - 2 1 Plating treatment Deployment Nickel Sulfate g/L - 250 250 - 250 250 Nickel chloride g/L - 50 50 - 50 0 Sodium citrate g/L - 25 25 - 25 0 Boric acid g/L - 0 0 - 0 35 Soaking time before power on - minute - 0 1 - 0 0

<2. Crimping and peeling of resin base material>: The test pieces of Examples 1 to 3 and Comparative Examples 1 to 3 removed the solution used in the treatment before the build-up prepreg and dried it sufficiently. The laminated prepregs (R5670KJ, manufactured by Panasonic) of these test pieces were thermocompression bonded in a vacuum with a vacuum high-pressure press under the conditions of a pressure of 2.9 MPa, a temperature of 210°C, and a pressing time of 120 minutes to obtain a sample of the laminated body. . The cross section of the obtained laminate sample was obtained by FIB (focused ion beam) processing under the conditions of an acceleration voltage of 30 kV and a probe current of 4 nA. A focused ion beam scanning electron microscope (Auriga, manufactured by Carl Zeiss) was used to observe the obtained cross section at a magnification of 30,000 times and a resolution of 1024×768 to obtain an SEM cross-sectional image (Figure 3). With respect to these laminate samples, the copper member was peeled from the resin base material based on a 90-degree peel test (Japanese Industrial Standards (JIS) C5016). The image and peel strength (kgf/cm) of the test piece after peeling are shown in Figure 2, and the SEM cross-sectional image of the laminate sample before and after peeling is shown in Figure 6. In Fig. 6, with regard to Comparative Example 3, Pt deposits for protecting the processed surface were layered on the resin substrate side, and then an image was taken. As shown in Figures 2 and 6, in only the embodiment, the needle-shaped crystalline copper oxide or the needle-shaped crystalline copper oxide derived from the needle-shaped crystalline copper oxide has almost the same thickness and the needle-shaped protrusions coated with nickel are almost made of copper The foil is separated and transferred to the resin substrate side. In addition, the peel strength of the examples is also very small compared with the comparative examples.

<3. Binarization of the SEM cross-sectional image after thermocompression bonding>: The SEM cross-sectional image of the obtained laminate sample (arranged so that the needle-shaped convex part faces upwards of the image; image size=3.78μm×2.61μm; resolution 1024×768) Use the image analysis software WinROOF2018 (Mitsukoshi Corporation, ver4.5.5) to perform binarization through the following steps. <Operation> 1) Selection range (rectangular ROI): a straight line parallel to the lapped plane passing through the apex of the void closest to the copper side, and a line parallel to the lapped plane passing through the apex of the highest protrusion formed on the copper surface The area enclosed by the straight line serves as the measurement range. 2) Image processing → Emphasis (lightness ±0, contrast +20): In order to facilitate image processing, adjust the contrast. 3) Image processing → Emphasis → Inversion: In order to select the gap in the binarization process, perform inversion processing so that the bright part and the dark part of the image are interchanged. 4) Automatic binarization (discrimination analysis method): Perform automatic binarization, select the area surrounded by copper and copper oxide and the area surrounded by copper oxide. The decision of the threshold is carried out by discriminant analysis. 5) Removal of noise: treat those with a side length of 1 pixel as noise, and delete those with an area of 15nm ² or less. 6) Calculate the distance between the gaps: When arranging the image so that the direction of the convex part is toward the top of the image, use the upper left of the image as the origin, the downward direction in the image as the X axis, and the right direction as the Y axis. The area where X=maximum and Y=minimum selected by automatic binarization is taken as the starting point, and the distance between the area and the area at the closest distance in the Y-axis direction is calculated as the distance between two points. When calculating the distance between two points, the selected areas are defined as gaps. 7) Measurement of gap size: Find the maximum horizontal chord length of the gap and use this as the size of each gap. The SEM cross-sectional image of each laminate sample after inversion binarization is shown in Fig. 4. In addition, the result of calculating the gap and the average distance between the gaps is shown in Fig. 5.

In Comparative Examples 2 and 3, only the area surrounded by copper oxide (that is, the gap between the unevenness of the copper oxide layer) is calculated as the void. In contrast, in the embodiment, the area surrounded by the copper oxide and the copper and copper oxidation are calculated. The area surrounded by the object (that is, the area existing at the interface between the copper oxide-containing layer and the copper foil) serves as a void. Therefore, the number of voids calculated in the embodiment is larger, and the distance between the voids is also short. In addition, in the examples, the proportion of the distance between the gaps of 50 nm or less accounted for 40% or more of the whole.

<4. Measurement of Ra and surface area of composite copper foil before thermocompression bonding and after peeling> (1) Method For the composite copper foil test pieces of Examples 1 to 3 and Comparative Examples 1 and 2, conjugate focus scanning electrons were used Microscope OPTELICS H1200 (manufactured by Lasertec Co., Ltd.) calculates the surface area before and after thermal compression bonding. Measurement conditions: The mode is conjugate focus mode, the scanning area is 100μm×100μm, the light source is blue light, and the Cut-off value is 1/5. Attach objective lens x100, eyepiece x14, digital zoom x1, and set Z pitch to 10nm. Obtain data from 3 positions, and the surface area is the average of 3 positions. (2) Results As described in Table 2, before and after the thermocompression bonding, the Ra and the surface area decreased in the examples, while the comparative examples increased instead. This indicates that all or part of the convex portions of the composite copper member in the examples are transferred to the resin side, while in the comparative example, instead, part of the resin is transferred to the composite copper member. Table 2 Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Before thermal crimping roughness Ra μm 0.18 0.21 0.04 0.18 0.04 After peeling roughness Ra μm 0.12 0.12 0.03 0.21 0.05 Rate of change After peeling/before thermocompression % 64.48 59.42 94.29 117.71 130.56 Before thermal crimping Surface area μm ² 21453 21578 10897 19033 10915 After peeling Surface area μm ² 15573 16,157 10642 21839 11599 Rate of change After peeling/before thermocompression % 72.59 74.88 97.66 114.74 106.27

According to the present invention, a novel composite copper member can be provided. This composite copper member is suitable for SAP method or MSAP method (Figure 7). In order for the plating solution to infiltrate the bottommost part of the recess, the shape of the recess needs to be large to a certain extent, which is not suitable for forming fine wiring (Japanese Patent Application Laid-Open No. 2017-034216). However, in the case of using the composite copper foil of the present invention, the copper oxide-containing layer that forms the unevenness will transfer itself, so there is no need to dip the plating solution into the bottom of the recessed portion, and it contains the transferred copper oxide without unevenness. (Pattern) copper plating is sufficient on the layer of, even if the concave shape on the surface of the original composite copper member is elongated, the possibility of voids between the resin substrate and the (pattern) copper plating layer is low, and it is suitable for the formation of fine wiring. In addition, since copper plating is performed on the layer containing copper oxide, the bonding affinity of copper plating to the layer containing copper oxide is high, and the peel strength between the resin substrate and the (pattern) copper plating layer The bonding of the bonded copper oxide-containing layer is ensured. It is known that using an oxidized metal as a peeling layer to make a carrier foil cannot stabilize the peel strength (International Publication No. 2010/027052). However, by forming voids in the layer containing copper oxide, the composite copper component of the present invention can be used directly as a copper component with a metal foil with a carrier, or used to manufacture the copper component. Even with carrier foil, because of its too thin metal foil, it cannot withstand the thermal compression bonding step to the resin substrate from the standpoint of strength. For example, the composite copper foil of Example 2 or 3 shows that the part of the copper foil acts as a carrier and can transfer the layer containing copper oxide and the nickel plating layer, so that conductive nickel with a thickness of only tens of nm can be thermally compressed on Resin substrate. The copper oxide-containing layer is also transferred together, so the physical strength of the nickel layer is reinforced by the presence of the copper oxide-containing layer transferred together. On the other hand, the conductivity of the copper oxide-containing layer is extremely high. Low, so non-conductive, almost no transmission loss caused by the presence of copper oxide-containing layers.

without

[Figure 1] A schematic view of an example of the cross section of the composite copper member of the present invention before and after thermal compression bonding. [Figure 2] The image of the peeled surface after the composite copper foil of the example and the comparative example is crimped on the resin substrate and peeled off. The numerical value indicates the peel strength during peeling. [Figure 3] The cross-sectional image of the composite copper foils of Examples 1 to 3 and Comparative Examples 2 and 3 that were thermally bonded to a resin substrate and observed with a scanning electron microscope (SEM) (30000 times magnification). The dashed line indicates the interface between the copper oxide-containing layer and the copper member. [Picture 4] The cross-sectional image of Fig. 3 is inverted and binarized. The inverted part is a gap. Only a straight line showing the distance between the gaps is added to the image of Example 1. [Picture 5] The number and size of gaps (A), the average distance between gaps (B), and the distribution of gap distances (C) obtained by image analysis in Fig. 4. [Figure 6] The cross-sections of the composite copper foils of Example 3 and Comparative Example 3 after thermal compression bonding to the resin substrate and peeling off were observed with SEM. [Figure 7] When the composite copper foil ("transfer + transfer") of one embodiment of the present invention and the conventional copper foil for transfer (only "transfer") are used in the SAP method, each processing step Schematic drawing of the middle section.

Claims (26)

A composite copper component has a layer containing copper oxide formed on at least a part of the surface of the copper component, and the layer containing copper oxide has several voids. The composite copper component of claim 1, wherein, among the plurality of voids, at least a part of the voids exists at the interface between the copper oxide-containing layer and the surface of the copper component. The composite copper member of claim 1 or 2, wherein the peel strength between the copper oxide-containing layer and the surface of the copper member is 0.001 kgf/cm or more and 0.30 kgf/cm or less. The composite copper component of any one of claims 1 to 3, wherein a photographed image of a cross-section of a scanning electron microscope is obtained, the photographed image is binarized, and the measurement is performed in a direction parallel to the copper oxide-containing layer , The number of the gaps detected in any 3.8μm is more than 30. The composite copper component according to any one of claims 1 to 4, wherein the surface of the copper oxide-containing layer of the composite copper component is thermocompression-bonded to a resin substrate under prescribed conditions to form a laminate, and the laminate is obtained A cross-sectional image taken by a scanning electron microscope of a body. When the taken image is binarized, when measured in a direction parallel to the layered surface, the number of gaps detected in any 3.8μm is more than 30 . The composite copper member of claim 4 or 5, wherein in the captured image of the binarized cross-section, the average distance between the voids is 100 nm or less. The composite copper member of claim 4 or 5, wherein, in the captured image of the binarized cross-section, the ratio of the distance between the voids of 50 nm or less accounts for more than 40% of the entire void. The composite copper component according to any one of claims 5 to 7, wherein the resin base material contains selected from the group consisting of polyphenylene ether, epoxy resin, polyoxyxylene, polybenzoxazole, polytetrafluoroethylene, and liquid crystal polymer , Triphenyl phosphite, fluororesin, polyetherimide, polyetheretherketone, polycyclic olefin, bismaleimide resin, low permittivity polyimide and cyanate resin At least one insulating resin. The composite copper component of any one of claims 5 to 8, wherein the prescribed conditions of the thermal compression bonding are within the range of a temperature of 50°C to 400°C, a pressure of 0 to 20 MPa, and a time of 1 minute to 5 hours . The composite copper member according to any one of claims 5 to 9, wherein Ra of the surface on which the copper oxide-containing layer is formed is 0.03 μm or more, and the copper member peeled from the resin substrate with respect to the Ra The ratio of Ra on the surface is less than 100%. The composite copper component according to any one of claims 5 to 10, wherein the ratio of the surface area of the copper component peeled from the resin substrate after thermocompression bonding to the surface area of the surface on which the copper oxide-containing layer is formed Is less than 100%. The composite copper component according to any one of claims 1 to 11, wherein the layer containing copper oxide contains a metal other than copper. Such as the composite copper component of claim 12, wherein the metal other than copper is nickel. The composite copper component according to any one of claims 1 to 11, wherein the layer containing copper oxide includes a copper plating layer. A metal foil with a carrier, comprising the composite copper member according to any one of claims 12 to 14, the layer containing copper oxide is used as a metal foil, and the copper member is used as a carrier with respect to the metal foil. A laminate in which at least a part of the surface area of the copper oxide-containing layer of the composite copper member according to any one of claims 1 to 14 is layered with a resin substrate. The laminate of claim 16, wherein the resin base material contains selected from the group consisting of polyphenylene ether, epoxy resin, polyoxyxylene, polybenzoxazole, polytetrafluoroethylene, liquid crystal polymer, triphenyl phosphite, At least one insulating resin selected from the group consisting of fluororesin, polyetherimide, polyetheretherketone, polycyclic olefin, bismaleimide resin, low permittivity polyimide, and cyanate resin. The composite copper component of any one of claims 1 to 14 is used to make printed wiring boards. For example, the composite copper component of claim 18 is used to make printed wiring boards by the semi-additive method or the M-SAP method. A method for manufacturing a printed wiring board is a method for manufacturing a printed wiring board using a composite copper member as claimed in any one of claims 1 to 14, comprising: 1) A step of thermocompression bonding a resin substrate under specified conditions on the copper oxide-containing layer of the composite copper component; 2) The step of peeling the copper member from the resin substrate under prescribed conditions to obtain a resin substrate having part or all of the metal forming the copper oxide-containing layer; and 3) A step of performing copper plating treatment on the surface of a resin substrate having part or all of the metal forming the copper oxide-containing layer. A method for manufacturing a resin substrate with metal, including: 1) A step of thermocompression bonding a resin base material under prescribed conditions on the copper oxide-containing layer of the composite copper component according to any one of claims 1 to 14; and 2) The step of peeling the copper member from the resin substrate under prescribed conditions to obtain a resin substrate having a part or all of the metal forming the copper oxide-containing layer. A method for manufacturing a composite copper component is the method for manufacturing a composite copper component according to any one of claims 1 to 11, comprising: 1) The step of partially coating the surface of the copper component with silane coupling agent; and 2) The step of forming the layer containing copper oxide by oxidizing the partially coated surface. A method for manufacturing a composite copper component is the method for manufacturing a composite copper component according to any one of claims 1 to 11, comprising: 1) The step of partially coating the surface of the copper component with silane coupling agent; 2) The step of oxidizing the partially coated surface; and 3) The step of treating the surface of the formed copper oxide-containing layer with a modifier, where the modifier includes selected from the group consisting of nickel chloride, zinc chloride, iron chloride, chromium chloride, ammonium citrate, Ammonium chloride, potassium chloride, ammonium sulfate, nickel ammonium sulfate, ethylenediaminetetraacetic acid, dihydroxyethylglycine, tetrasodium L-glutamate diacetate, ethylenediamine-N,N'-disuccinate Acid, 3-hydroxy-2,2'-imino sodium disuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, N-(2-hydroxyethyl)imino A compound of the group consisting of disodium diacetate and sodium gluconate. A method for manufacturing a composite copper component, such as the method for manufacturing a composite copper component in claim 12, including: 1) The step of partially coating the surface of the copper component with silane coupling agent; 2) The step of oxidizing the partially coated surface; and 3) A step of forming a layer containing a metal other than copper on the surface that has been oxidized. A method for manufacturing a composite copper component, such as the method for manufacturing a composite copper component in claim 12, including: 1) The step of oxidizing the surface of the copper component; 2) The step of treating the surface after the oxidation treatment with a modifier; and 3) A step of forming a layer containing metals other than copper on the surface treated with the modifier, where the modifier includes selected from the group consisting of nickel chloride, zinc chloride, iron chloride, chromium chloride, and citric acid Ammonium, ammonium chloride, potassium chloride, ammonium sulfate, nickel ammonium sulfate, ethylenediaminetetraacetic acid, dihydroxyethylglycine, L-glutamic acid tetrasodium diacetate, ethylenediamine-N,N'- Disuccinic acid, sodium 3-hydroxy-2,2'-imino disuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, N-(2-hydroxyethyl) A compound of the group consisting of disodium amine diacetate and sodium gluconate. A method for manufacturing a composite copper component, such as the method for manufacturing a composite copper component in claim 12, including: 1) The step of partially coating the surface of the copper component with a silane coupling agent; 2) The step of oxidizing the partially coated surface; 3) The step of treating the surface after the oxidation treatment with a modifier, and 4) A step of forming a layer containing metals other than copper on the surface treated with the modifier. Here, the modifier includes selected from the group consisting of nickel chloride, zinc chloride, iron chloride, chromium chloride, and citric acid Ammonium, ammonium chloride, potassium chloride, ammonium sulfate, nickel ammonium sulfate, ethylenediaminetetraacetic acid, dihydroxyethylglycine, L-glutamic acid tetrasodium diacetate, ethylenediamine-N,N'- Disuccinic acid, sodium 3-hydroxy-2,2'-imino disuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, N-(2-hydroxyethyl) A compound of the group consisting of disodium amine diacetate and sodium gluconate.

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