Composite copper parts

Abstract

The present invention aims to provide a novel composite copper component. For example, a composite copper component is provided, wherein a layer containing copper oxide is formed on at least a portion of the surface of the copper component, wherein the surface of the composite copper component is thermocompressed to a resin substrate, and when the copper component is peeled off from the resin substrate after thermocompression bonding, metal contained in the layer containing copper oxide is transferred to the resin substrate.

Description

Technical Field

[0001] The invention relates to a composite copper component. Background Art

[0002] The copper foil used in the printed wiring board is required to have good adhesion with the insulating resin substrate. In order to improve the adhesion, a method is adopted in which the surface of the copper foil is roughened by etching, etc., so as to improve the mechanical bonding force by the so-called anchoring effect. From the perspective of the high density of the printed wiring board and the transmission loss under the high frequency band, the surface of the copper foil is required to be flat. In order to meet these opposite requirements, a copper surface treatment method (International Publication No. 2014 / 126193) has been developed, which includes an oxidation process and a reduction process. In this method, the copper foil is pretreated, and after oxidizing the surface of the copper foil by immersing it in a liquid containing an oxidant and forming the unevenness of copper oxide, it is immersed in a liquid containing a reducing agent to reduce the copper oxide, thereby adjusting the unevenness of the surface and trimming the roughness of the surface. In addition, as a method for improving the adhesion of copper foil during treatment by oxidation and reduction, a method of adding surfactant molecules during the oxidation process (Japanese Patent Publication No. 2013-534054) or a method of forming a protective film on the surface of the copper foil using aminothiazole compounds after the reduction process (Japanese Patent Application Publication No. 8-97559) has been developed.

[0003] It is also known that the longer and more protrusions formed by roughening treatment increase the mechanical bonding force between copper foil and resin, but at the same time, due to the insufficient strength of the protrusions, there is a problem that the protrusions fall off from the root or break in the middle. In order to increase its strength, it is reported that the surface of the protrusions is plated (Japanese Patent Publication No. 2016-188431).

[0004] The inventors of the present invention have also developed a composite copper foil in which Ni is plated on a roughened copper foil by electrolytic plating (International Publication No. 2019 / 093494).

[0005] With regard to the circuit formation process of printed wiring boards and semiconductor package substrates, with the further miniaturization of wiring in recent years, new processes such as the Semi-Additive Process (SAP method) or M-SAP (Modified Semi-Additive Process) (MSAP method) using the surface profile of copper foil have attracted much attention (Japanese Patent Publication No. 2017-034216).

[0006] As an example of a semi-additive process using the surface profile of the copper foil (i.e., a surface shape with concave and convex shapes formed by roughening treatment), the following method can be cited. First, the copper foil laminated on the resin substrate is etched on the entire surface, and the etched substrate surface to which the surface profile of the copper foil is transferred is opened with a laser or the like, and electroless copper plating is performed to make the opening portion conductive. The electroless copper-plated surface is covered with a dry film, and the dry film of the circuit forming portion is removed by UV exposure and development. The electroless copper-plated surface not covered by the dry film is electroplated with copper next time. Then, the dry film is peeled off, and finally the electroless copper-plated layer is etched (flash etching method, rapid etching method) using an etching solution containing sulfuric acid, hydrogen peroxide water, etc., thereby forming a fine circuit.

[0007] In this process, it is necessary to adhere the surface-treated copper foil to a resin substrate, peel off the surface-treated copper foil, and transfer the surface profile of the copper foil to the resin substrate. However, it is required that the profile of the copper foil surface is not damaged and is well transferred to the surface of the resin substrate. It is also necessary to improve the strength of maintaining the unevenness of the copper foil surface. Summary of the invention

[0008] Technical problem to be solved by the invention

[0009] In the previous process of using the surface profile of copper foil, for example, a copper foil with roughened particles is attached to a resin substrate from the roughened particle side surface, and then the copper foil is removed, thereby transferring the profile of the copper foil surface to the resin substrate surface, and applying a copper plating layer on the transferred surface. However, if the concave-convex shape of the surface becomes complicated, sometimes the plating liquid cannot enter. At this time, a gap is generated between the resin substrate and the (patterned) copper plating layer, and heating causes problems such as gap expansion, circuit peeling, or substrate expansion (Patent Document 6).

[0010] Therefore, an object of the present invention is to provide a composite copper component suitable for the SAP method or the MSAP method.

[0011] Technical solutions for solving technical problems

[0012] As a result of intensive studies, the inventors of the present invention have newly discovered that a composite copper part suitable for the SAP method or the MSAP method can be produced by reducing the strength of the protrusions produced by the roughening treatment instead of increasing the strength of the protrusions produced by the roughening treatment.

[0013] The present invention has the following embodiments: [1]

[0015] A composite copper component, wherein a layer containing copper oxide is formed on at least a portion of the surface of the copper component, wherein:

[0016] The surface of the composite copper component is thermally pressed onto a resin substrate under prescribed conditions, and after thermal pressing, the copper component is peeled off from the resin substrate under prescribed conditions. When the surface of the copper component peeled off from the resin substrate is analyzed using attenuated total reflection absorption Fourier transform infrared spectroscopy (FT-IR / ATR method), the wavelength range is 700-4000cm －1 In the above analysis, the S / N ratio of the peak detected corresponding to the substance derived from the resin substrate is 10 or less. [2]

[0018] The composite copper component according to [1], wherein the S / N ratio of the peak is 7 or less. [3]

[0020] A composite copper component, wherein a layer containing copper oxide is formed on at least a portion of the surface of the copper component, wherein:

[0021] The surface of the composite copper component is thermally pressed onto a resin substrate under prescribed conditions, and when the copper component is peeled off from the resin substrate under prescribed conditions after thermal pressing, metal atoms contained in the layer containing copper oxide are detected from the surface of the resin substrate from which the copper component is peeled off, in an X-ray photoelectron spectroscopy spectrum obtained by Surveyspectrum analysis using X-ray photoelectron spectroscopy (XPS). [4]

[0023] The composite copper member according to [3], wherein the total intensities of main peaks of metal elements detected from the surface of the resin substrate from which the copper member is peeled are greater than the peak intensity of C1s. [5]

[0025] The composite copper component according to [4], wherein, on the surface of the resin substrate from which the copper component is peeled off, [the total surface atomic composition percentage (Atom %) of metal elements] / [the surface atomic composition percentage (Atom %) of C1s] calculated from the measurement results of XPS

[0026] It is above 0.040. [6]

[0028] The composite copper component according to [4], wherein, on the surface of the resin substrate from which the copper component is peeled off, [the total surface atomic composition percentage (Atom %) of metal elements] / [the surface atomic composition percentage (Atom %) of C1s] calculated from the measurement results of XPS

[0029] It is 0.010 or more. [7]

[0031] A composite copper component as described in [4], wherein a survey spectrum analysis is performed using XPS on the surface of the resin substrate from which the copper component is peeled off, and when the composition ratio of the detected elements is calculated, the total surface atomic composition percentage of Cu2p3 and Ni2p3 is greater than 3.0 atom%. [8]

[0033] A composite copper component as described in [4], wherein, when Survey spectrum analysis is performed using XPS on the surface of the resin substrate from which the copper component is peeled off, the total surface atomic composition percentage of Cu2p3 and Ni2p3 when the composition ratio of the detected elements is calculated is greater than 1.5 atom%. [9]

[0035] A composite copper component as described in [4], wherein when Survey spectrum analysis is performed using XPS on the surface of the resin substrate from which the copper component is peeled off, and the composition ratio of the detected elements is determined, the surface atomic composition percentage of Cu2p3 is greater than 2.8 atom%.

[10]

[0037] A composite copper component as described in [4], wherein when Survey spectrum analysis is performed using XPS on the surface of the resin substrate from which the copper component is peeled off, and the composition ratio of the detected elements is determined, the surface atomic composition percentage of Cu2p3 is greater than 1.0 atom%.

[11]

[0039] The composite copper component as described in any one of [1] to

[10] , wherein Ra of the surface on which the layer containing copper oxide is formed is 0.04 μm or more, and the ratio of Ra of the surface of the copper component peeled off from the resin substrate to the Ra is less than 100%.

[12]

[0041] The composite copper member according to any one of [1] to

[11] , wherein a ratio of a surface area of ​​the copper member peeled from the resin substrate to a surface area of ​​a surface on which the layer containing copper oxide is formed is less than 100%.

[13]

[0043] The composite copper component according to any one of [1] to

[12] , wherein the color difference (ΔE ＊ ab) is 15 or more.

[14]

[0045] A composite copper component as described in any one of [1] to

[13] , wherein the resin substrate contains at least one insulating resin selected from polyphenylene ether (PPE), epoxy resin, polyphenylene oxide (PPO), polybenzoxazole (PBO), polytetrafluoroethylene (PTFE), liquid crystal polymer (LCP) or triphenyl phosphite (TPPI), fluororesin, polyetherimide, polyetheretherketone, polycycloolefin, bismaleimide resin, low dielectric constant polyimide and cyanate resin.

[15]

[0047] The composite copper component according to any one of [1] to

[14] , wherein the predetermined conditions for the thermocompression 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.

[16]

[0049] The composite copper member according to any one of [1] to

[15] , wherein the layer containing copper oxide contains a metal other than copper.

[17]

[0051] The composite copper component as described in

[16] , wherein the metal other than copper is Ni.

[18]

[0053] A method for producing a printed wiring board, for producing a printed wiring board using the composite copper member described in any one of [1] to

[17] , the method comprising:

[0054] 1) a step of thermally pressing a resin substrate onto the layer containing copper oxide of the composite copper component under predetermined conditions;

[0055] 2) a step of peeling the copper component from the resin substrate under predetermined conditions to obtain a resin substrate having a part or all of the metal forming the layer containing copper oxide; and

[0056] 3) A step of performing copper plating on a part or all of the surface of the resin substrate having the metal forming the layer containing copper oxide.

[0057] [1A]

[0058] A method for manufacturing a resin substrate having metal, comprising:

[0059] 1) a step of thermally pressing a resin substrate onto the layer containing copper oxide of a composite copper member having a layer containing copper oxide formed on at least a portion of the surface of the copper member under predetermined conditions; and

[0060] 2) A step of peeling the copper member from the resin substrate under predetermined conditions to obtain a resin substrate having a part or all of the metal forming the layer containing copper oxide.

[0061] [2A]

[0062] The manufacturing method as described in [1A], wherein metal atoms contained in the layer containing copper oxide can be detected when the resin substrate having metal is subjected to survey spectrum analysis using X-ray photoelectron spectroscopy (XPS).

[0063] [3A]

[0064] The method for producing a resin substrate according to [2A], wherein the total intensities of the main peaks of the detected metal elements are larger than the peak intensity of the C1s spectrum.

[0065] [4A]

[0066] The method for producing a resin substrate as described in [3A], wherein the total surface atomic composition percentage (Atom %) of metal elements calculated by the XPS measurement is calculated as follows: [the total surface atomic composition percentage (Atom %) of metal elements] / [the surface atomic composition percentage (Atom %) of C1s]

[0067] It is above 0.040.

[0068] [5A]

[0069] The method for producing a resin substrate as described in [3A], wherein the total surface atomic composition percentage (Atom %) of metal elements calculated by the XPS measurement is calculated as follows: [the total surface atomic composition percentage (Atom %) of metal elements] / [the surface atomic composition percentage (Atom %) of C1s]

[0070] It is 0.010 or more.

[0071] [6A]

[0072] A method for manufacturing a resin substrate as described in [3A], wherein a Survey spectrum analysis is performed using XPS on the surface of the resin substrate from which the copper component has been peeled off, and when the composition ratio of the detected elements is determined, the total surface atomic composition percentage of Cu2p3 and Ni2p3 is greater than 3.0 atom%.

[0073] [7A]

[0074] A method for manufacturing a resin substrate as described in [3A], wherein Survey spectrum analysis is performed using XPS on the surface of the resin substrate from which the copper component has been peeled off, and when the composition ratio of the detected elements is determined, the total surface atomic composition percentage of Cu2p3 and Ni2p3 is greater than 1.5 atom%.

[0075] [8A]

[0076] A method for manufacturing a resin substrate as described in [3A], wherein Survey spectrum analysis is performed using XPS on the surface of the resin substrate from which the copper component has been peeled off, and when the composition ratio of the detected elements is determined, the surface atomic composition percentage of Cu2p3 is greater than 2.8 atom%.

[0077] [9A]

[0078] A method for manufacturing a resin substrate as described in [3A], wherein a Survey spectrum analysis is performed using XPS on the surface of the resin substrate from which the copper component has been peeled off, and when the composition ratio of the detected elements is determined, the surface atomic composition percentage of Cu2p3 is greater than 1.0 atom%.

[0079] [10A]

[0080] A method for producing a resin substrate as described in any one of [1A] to [9A], wherein the resin substrate comprises at least one insulating resin selected from polyphenylene ether (PPE), epoxy resin, polyphenylene oxide (PPO), polybenzoxazole (PBO), polytetrafluoroethylene (PTFE), liquid crystal polymer (LCP), triphenyl phosphite (TPPI), fluororesin, polyetherimide, polyetheretherketone, polycycloolefin, bismaleimide resin, low dielectric constant polyimide and cyanate resin.

[0081] [1B]

[0082] A method for producing a laminated body, for producing a laminated body comprising a composite copper part having a layer containing copper oxide formed on at least a portion of the surface of the copper part and a resin substrate, the method comprising:

[0083] a step of thermally pressing the resin substrate onto the layer containing copper oxide under predetermined conditions,

[0084] When the copper member is peeled off from the resin substrate under predetermined conditions, metal atoms contained in the layer containing copper oxide are detected from the surface of the resin substrate peeled off from the copper member by measurement using X-ray photoelectron spectroscopy (XPS).

[0085] [2B]

[0086] A method for producing a laminated body, for producing a laminated body comprising a composite copper part having a layer containing copper oxide formed on at least a portion of the surface of the copper part and a resin substrate, the method comprising:

[0087] a step of thermally pressing a resin substrate onto the layer containing copper oxide,

[0088] When the copper member is peeled off from the resin substrate under predetermined conditions, the attenuated total reflection absorption Fourier transform infrared spectroscopy (FT-IR / ATR method) in the wavelength range of 700-4000 cm －1 In the measurement of the range of , the S / N ratio of the peak corresponding to the substance derived from the resin substrate detected on the surface of the copper member peeled off from the resin substrate is 10 or less.

[0089] [1C]

[0090] A method for manufacturing a composite copper component, which is used to manufacture the composite copper component described in [1] or [3], the manufacturing method comprising:

[0091] 1) a step of locally coating the surface of the copper component with a silane coupling agent or a rust inhibitor; and

[0092] 2) A step of forming a layer containing the copper oxide by subjecting the surface after the partial coating to oxidation treatment.

[0093] [2C]

[0094] A method for manufacturing a composite copper component, which is used to manufacture the composite copper component described in

[16] , the manufacturing method comprising:

[0095] 1) a step of locally coating the surface of the copper component with a silane coupling agent or a rust inhibitor;

[0096] 2) a step of forming a layer containing the copper oxide by subjecting the surface after the partial coating to an oxidation treatment; and

[0097] 3) A step of forming a layer containing a metal other than copper on the surface after the oxidation treatment.

[0098] [3C]

[0099] A method for manufacturing a composite copper component, which is used to manufacture the composite copper component described in

[16] , the manufacturing method comprising:

[0100] 1) a step of forming a layer containing the copper oxide by oxidizing the surface of the copper member;

[0101] 2) a step of treating the surface after the oxidation treatment with a modifier; and

[0102] 3) forming a layer containing a metal other than copper on the surface treated with the modifying agent,

[0103] The above-mentioned modifier includes a compound selected from nickel chloride, zinc chloride, ferric chloride, chromium chloride, ammonium citrate, potassium chloride, ammonium sulfate, ammonium chloride, nickel ammonium sulfate, ethylenediaminetetraacetic acid, diethanolglycine, tetrasodium L-glutamate diacetate, ethylenediamine-N,N'-disuccinic acid, 3-hydroxy-2,2'-iminodisuccinate sodium, methylglycine diacetate trisodium, aspartic acid diacetate tetrasodium, N-(2-hydroxyethyl)iminodiacetic acid disodium and sodium gluconate.

[0104] [4C]

[0105] A method for manufacturing a composite copper component, which is used to manufacture the composite copper component described in

[16] , the manufacturing method comprising:

[0106] 1) a step of forming a layer containing the copper oxide by oxidizing the surface of the copper member;

[0107] 2) a step of treating the surface after the oxidation treatment with a modifier; and

[0108] 3) forming a layer containing a metal other than copper on the surface treated with the modifying agent,

[0109] The above-mentioned modifier comprises tin (II) chloride or citric acid.

[0110] ==Cross-references to related literature==

[0111] This application claims priority based on Japanese Patent Application No. 2019-194444 filed on October 25, 2019, and the contents of the basic application are incorporated into this specification by reference. BRIEF DESCRIPTION OF THE DRAWINGS

[0112] Figure 1 This is a schematic diagram schematically showing an example of the composite copper member of the present invention before thermocompression bonding and after peeling.

[0113] Figure 2-1 to Figure 2-2 The diagram shows the results of visual observation after peeling off after the composite copper foils of Examples 1 to 8 and Comparative Examples 2 to 4 were pressure-bonded to a resin substrate (the case where the surface of the copper foil was transferred to the resin side was marked as 0, and the case where there was no transfer was marked as ×), and representative photographs of the surfaces on both sides.

[0114] Figures 3-1 to 3-7 It is a figure which shows the result of XPS analysis of the resin base material of Examples 1-3 and Comparative Examples 1-4.

[0115] Figures 4-1 to 4-3 These are the results of thermally pressing the composite copper foils of Examples 1 to 3 and Comparative Examples 2 to 4 to a resin substrate (R5670KJ), peeling them off, and measuring the surfaces thereof by FT IR / ATR method.

[0116] Figure 5 These are the results of thermally pressing the composite copper foils of Example 3 and Comparative Example 3 to a resin substrate (R1551GG), peeling them off, and measuring their surfaces by FT IR / ATR method.

[0117] Figure 6-1 to 6-2 These are the results of thermally pressing the composite copper foils of Examples 4 to 8 onto a resin substrate (R5680J), peeling them off, and measuring the surfaces thereof by FT IR / ATR method.

[0118] Figure 7 The composite copper foils of Example 3 and Comparative Example 3 were thermocompression bonded to a resin substrate (NX9255), and then peeled off and the surfaces thereof were measured by FT IR / ATR method.

[0119] Figure 8 These are the results of thermally pressing the composite copper foils of Example 3 and Comparative Example 3 to a resin substrate (CT-Z), peeling the foils, and measuring the surfaces thereof by FT IR / ATR method.

[0120] Fig. 9 This is a schematic diagram when the composite copper foil (“transfer + transfer”) according to one embodiment of the present invention and the conventional transfer copper foil (“transfer only”) are applied to the SAP method. DETAILED DESCRIPTION

[0121] Hereinafter, preferred embodiments of the present invention will be described in detail using the accompanying drawings, but are not necessarily limited thereto. Among them, through the description of this specification, the purpose, features, advantages and concepts of the present invention are clear to those skilled in the art, and as long as they are skilled in the art, they can easily reproduce the present invention according to the description of this specification. The embodiments of the invention described below and specific examples, etc. represent preferred embodiments of the present invention, and are intended to illustrate or explain, and the present invention is not limited thereto. Those skilled in the art can clearly know that various changes and modifications can be made based on the description of this specification within the intent and scope of the present invention disclosed in this specification.

[0122] ==Composite Copper Parts==

[0123] One embodiment of the present invention is a composite copper component having a layer containing copper oxide formed on at least a portion of the surface of the copper component. The copper component contains Cu as a main component that forms a part of the structure. The copper component is specifically a copper foil such as electrolytic copper foil or rolled copper foil and copper foil with a carrier, a copper wire, a copper plate, and a copper lead frame, but is not limited to this. The copper component is preferably made of a material composed of pure copper with a Cu purity of 99.9% by mass or more, more preferably formed of tough-pitch copper, deoxidized copper, and oxygen-free copper, and further preferably formed of oxygen-free copper with an oxygen content of 0.001% to 0.0005% by mass.

[0124] When the copper member is a copper foil, the thickness thereof is not particularly limited, but is preferably 0.1 μm to 100 μm, and more preferably 0.5 μm to 50 μm.

[0125] The layer containing copper oxide is formed on the surface of the copper part, and contains copper oxide (CuO) and / or cuprous oxide (Cu2O). The layer containing copper oxide can be formed by oxidizing the surface of the copper part. The surface of the copper part is roughened by the oxidation treatment. The layer containing copper oxide can also be treated with a dissolving agent to adjust the convex portion of the surface of the oxidized copper part. In addition, the surface of the layer containing copper oxide can also be reduced using a reducing agent, in which case cuprous oxide can be formed on the surface of the layer containing copper oxide. The resistivity of pure copper is 1.7×10 －8 (Ωm), compared to 1 to 10 (Ωm) for copper oxide and 1×10 6 ~1×10 7 (Ωm), the conductivity of the layer containing copper oxide is low. For example, even if the amount of the layer containing copper oxide transferred to the resin substrate is large, when a circuit of a printed wiring board or a semiconductor package substrate is formed using the composite copper component according to the present invention, transmission loss due to the skin effect is unlikely to occur.

[0126] The layer containing copper oxide may contain metals other than copper. The metal contained is not particularly limited, and may contain at least one metal selected from Sn, Ag, Zn, Al, Ti, Bi, Cr, Fe, Co, Ni, Pd, Au, and Pt. In particular, in order to have acid resistance and heat resistance, it is preferable to contain a metal having higher acid resistance and heat resistance than copper, such as Ni, Pd, Au, and Pt.

[0127] Metals other than copper can be formed on the outermost surface of the copper component by plating. The plating method is not particularly limited, and examples thereof include electrolytic plating, electroless plating, vacuum evaporation, chemical surface treatment, etc., but electrolytic plating is preferred because it is preferred to form a uniform and thin plating layer. When electrolytic plating is performed on the surface of the oxidized copper foil, first, the copper oxide on the surface is reduced, and the charge is consumed to become cuprous oxide or pure copper, so there is a time delay before plating, and then the metal forming the metal layer begins to precipitate. The amount of charge varies depending on the type of plating solution and the amount of copper oxide, but for example, in the case of Ni plating on a copper component, in order to make its thickness within the preferred range, the area of ​​the copper component treated with electrolytic plating is 1 dm2 per dm2. 2 It is preferred to give a charge of 15C to 75C, and more preferably a charge of 25C to 65C.

[0128] The average thickness in the vertical direction of the metal other than copper formed on the outermost surface of the copper component 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.

[0129] In addition, the average thickness of the metal other than copper contained in the layer containing copper oxide in the vertical direction can be calculated by dissolving the layer containing copper oxide with an acidic solution, measuring the amount of metal by ICP analysis, and dividing the result by the area of ​​the composite copper member. Alternatively, it can be calculated by dissolving the composite copper member itself and measuring only the amount of metal contained in the layer containing copper oxide.

[0130] If the surface of the composite copper component having the layer containing copper oxide formed thereon is thermally pressed (thermal press fitting) to a resin substrate, the surface profile of the composite copper component is transferred to the resin substrate. Furthermore, when the composite copper component is peeled off from the resin substrate after thermal pressing, the metal contained in the layer containing copper oxide adheres (transferred) to the resin substrate. An embodiment of the composite copper component is illustrated in Figure 1 .

[0131] Resin substrate is the material containing resin as main component, can be used for the circuit formation of printed wiring substrate and semiconductor package substrate etc. Resin is not particularly limited, can be thermoplastic resin, can also be thermosetting resin, preferably polyphenylene ether (PPE), epoxy resin, polyphenylene oxide (PPO), polybenzoxazole (PBO), polytetrafluoroethylene (PTFE), liquid crystal polymer (LCP), triphenyl phosphite (TPPI), fluororesin, polyetherimide, polyetheretherketone, polycycloolefin, bismaleimide resin, low dielectric constant polyimide, cyanate resin or their mixed resin. Resin substrate can also contain inorganic filler, glass fiber.

[0132] In order to thermally press-bond the resin substrate to the surface of the composite copper component, for example, after the resin substrate and the composite copper component are tightly bonded and laminated, they are treated under prescribed conditions to bond the resin substrate and the composite copper component. As prescribed conditions (temperature, pressure, time), the recommended conditions of each substrate manufacturer can be used. The prescribed conditions can be considered as follows, for example.

[0133] 1) When the resin substrate contains or consists of epoxy resin, the composite copper component is preferably thermally compressed onto the resin substrate by applying a pressure of 0 to 20 MPa at a temperature of 50 to 300° C. for 1 minute to 5 hours.

[0134] For example,

[0135] 1-1) When the resin substrate is R-1551 (manufactured by Panasonic),

[0136] Heat at a pressure of 1 MPa to 100°C and keep at this temperature for 5 to 10 minutes.

[0137] Then, the material was further heated under a pressure of 3.3 MPa to 170 to 180° C. and then maintained at that temperature for 50 minutes to perform thermocompression bonding.

[0138] 1-2) When the resin substrate is R-1410A (manufactured by Panasonic),

[0139] The thermocompression bonding was performed by heating to 130° C. under a pressure of 1 MPa and then maintaining the temperature for 10 minutes, and then further heating to 200° C. under a pressure of 2.9 MPa and then maintaining the temperature for 70 minutes.

[0140] 1-3) When the resin base material is EM-285 (manufactured by EMC),

[0141] The steel sheets were heated at a pressure of 0.4 MPa until the temperature reached 100°C, and then the pressure was increased to 2.4 to 2.9 MPa. The steel sheets were further heated until the temperature reached 195°C, and then the temperature was maintained for 50 minutes for thermocompression bonding.

[0142] 1-4) When the resin substrate is GX13 (manufactured by Ajinomoto Fine Chemicals Co., Ltd.), the substrate is heated while being pressurized at 1.0 MPa and maintained at 180° C. for 60 minutes to perform thermocompression bonding.

[0143] 2) When the resin substrate contains a PPE resin or consists of a PPE resin, it is preferred to thermally press-bond the composite copper component to the resin substrate by applying a pressure of 0 to 20 MPa at a temperature of 50 to 350° C. for 1 minute to 5 hours.

[0144] For example,

[0145] 2-1) When the resin substrate is R5620 (manufactured by Panasonic),

[0146] The thermocompression bonding was performed while heating to 100° C. under a pressure of 0.5 MPa, and then the temperature and pressure were increased to maintain at 2.0 to 3.0 MPa and 200 to 210° C. for 120 minutes, thereby further thermocompression bonding was performed.

[0147] 2-2) When the resin substrate is R5670 (manufactured by Panasonic),

[0148] The thermocompression bonding was performed while heating to 110° C. under a pressure of 0.49 MPa, and then the temperature and pressure were increased and maintained at 2.94 MPa and 210° C. for 120 minutes, thereby performing thermocompression bonding.

[0149] 2-3) When the resin substrate is R5680 (manufactured by Panasonic), thermocompression bonding is performed while heating to 110° C. under a pressure of 0.5 MPa, and then the temperature and pressure are increased to maintain at 3.0 to 4.0 MPa and 195° C. for 75 minutes.

[0150] 2-4) When the resin substrate is N-22 (manufactured by Nelco), the substrate is heated and held at 177° C. for 30 minutes while being pressurized at 1.6 to 2.3 MPa, and then further heated and held at 216° C. for 60 minutes to perform thermocompression bonding.

[0151] 3) When the resin substrate contains or consists of PTFE resin, it is preferred to thermally press-bond the composite copper component to the resin substrate by applying a pressure of 0 to 20 MPa at a temperature of 50 to 400° C. for 1 minute to 5 hours.

[0152] For example,

[0153] 3-1) When the resin substrate is NX9255 (manufactured by Park Electrochemica L Corp.), the substrate is heated to 260° C. while being pressurized at 0.69 MPa, and the pressure is increased to 1.03 to 1.72 MPa, and the substrate is heated to 385° C. and maintained at 385° C. for 10 minutes to perform thermocompression bonding.

[0154] 3-2) When the resin substrate is RO3003 (manufactured by Rogers), 50 minutes after the start of pressurization (about 220° C.), the pressure is increased to 2.4 MPa and maintained at 371° C. for 30 to 60 minutes to perform thermocompression bonding.

[0155] The conditions for peeling the copper member from the resin substrate are not particularly limited, and can be performed according to a 90° peel test (Japanese Industrial Standard (JIS) C5016 "Flexible Printed Wiring Board Test Methods"; corresponding international standards IEC249-1:1982, IEC326-2:1990).

[0156] The metal contained in the layer containing copper oxide is transferred to the resin substrate after the copper component is peeled off. The metal transferred to the surface of the resin substrate after the copper component is peeled off can be detected by various methods (for example, X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDS), ICP emission spectrometry (high-frequency inductively coupled plasma emission spectrometry, ICP-OES / ICP-AES)).

[0157] XPS is a method of irradiating an object with X-rays and capturing the photoelectrons released as the object is ionized. - XPS is a method for energy analysis. Through XPS, the type, amount, chemical bonding state, etc. of elements present on the sample surface or at a specified depth from the surface (for example, up to a depth of 6 nm) can be studied. The analysis spot diameter (i.e., the diameter of the cross section when the cylindrical part that can be analyzed is cut in a circular manner) is preferably 1 μm or more and 1 mm or less.

[0158] The metal contained in the layer containing copper oxide is preferably transferred to the resin substrate in a manner that fills more than 80%, more than 90%, more than 95%, more than 99%, or more than 99.9% of the concave portions of the transferred surface profile. In the case of a manner that fills most of the concave portions, when the surface of the resin substrate is measured by XPS, which is an elemental analysis of the sample surface, the total of the peak intensities of the spectra of metal atoms (copper atoms and atoms of metals other than copper) is greater than the peak intensity of the spectrum of C1s. There are many types of peaks of metal elements, but here we refer to the main peaks of each metal element. For example, the peaks of Cu for 2p3 orbital, Sn for 3d5 orbital, Ag for 3d5 orbital, Zn for 2p3 orbital, Al for 2p orbital, Ti for 2p3 orbital, Bi for 4f7 orbital, Cr for 2p3 orbital, Fe for 2p3 orbital, Co for 2p3 orbital, Ni for 2p3 orbital, Pd for 3d5 orbital, Au for 4f7 orbital, and Pt for 4f7 orbital are the main peaks. In addition, the intensity of the peak of the spectrum mentioned here refers to Figure 3-1 to Figure 3-7 The XPS spectrum data are shown as height on the vertical axis.

[0159] Regarding the amount of metal contained in the layer containing copper oxide, the ratio of Cu2p3 to all surface atoms in the surface of the resin substrate from which the copper component has been peeled off, as measured by X-ray photoelectron spectroscopy (XPS), is preferably 1.0 atom% or more, 1.8 atom% or more, 2.8 atom% or more, 3.0 atom% or more, 4.0 atom% or more, 5.0 atom% or more, or 6.0 atom%. Alternatively, when the surface of the copper component after transfer is measured by XPS, the ratio of the surface atomic composition percentage of Cu2p3 / the surface atomic composition percentage of C1s is preferably 0.010 or more, 0.015 or more, 0.020 or more, 0.025 or more, 0.030 or more, 0.035 or more, 0.040 or more, 0.045 or more, 0.050 or more, or 0.10 or more.

[0160] When the layer containing copper oxide contains a metal other than copper, the total surface atomic composition percentage of metal atoms (copper atoms and atoms of metal other than copper) in the surface of the above-mentioned peeled resin substrate measured by X-ray photoelectron spectroscopy (XPS) is preferably 1.0 atom% or more, 1.5 atom% or more, 1.8 atom% or more, 2.8 atom% or more, 3.0 atom% or more, 4.0 atom% or more, 5.0 atom% or more, or 6.0 atom%. Alternatively, the ratio of the total surface atomic composition percentage of metal atoms (copper atoms and atoms of metal other than copper) / the surface atomic composition percentage of C1s is preferably 0.010 or more, 0.015 or more, 0.020 or more, 0.025 or more, 0.030 or more, 0.035 or more, 0.040 or more, 0.045 or more, 0.050 or more, or 0.10 or more.

[0161] It is preferred that no organic matter originating from the resin substrate is detected from the surface of the copper component after being peeled off from the resin substrate, or even if detected, it is only a small amount. This means that no cracking occurs on the resin substrate side during peeling. The method for detecting organic matter originating from the resin substrate is not particularly limited, and can be performed, for example, by detecting a peak originating from the resin substrate using attenuated total reflection absorption Fourier transform infrared spectroscopy (FT-IR method).

[0162] The FT-IR method is an infrared spectrometry method that irradiates a substance to be measured with infrared rays and uses the infrared absorption spectrum to identify and / or quantify the compound. In the present invention, it can be used to detect organic matter derived from a resin substrate.

[0163] The peaks derived from the resin matrix are exemplified in "Infrared and Raman Spectroscopy: Principles and SpectraL Interpretation (by Peter Larkin)". －1 The S / N ratio is preferably 10 or less, 9 or less, more preferably 8 or less, 7 or less, and preferably no peak derived from the resin substrate is detected.

[0164] The arithmetic mean roughness (Ra) of the surface of the composite copper member having the layer containing copper oxide formed thereon is preferably 0.04 μm or more, more preferably 0.1 μm or more, and is preferably 0.3 μm or less, more preferably 0.2 μm or less.

[0165] The maximum height roughness (Rz) of the surface of the composite copper member having the layer containing copper oxide formed thereon is preferably 0.2 μm or more, more preferably 1.0 μm or more, and is preferably 2.0 μm or less, more preferably 1.7 μm or less.

[0166] If Ra and Rz are too small, the adhesion with the resin base material will be insufficient, and if they are too large, the fine wiring formability and high-frequency characteristics will deteriorate.

[0167] Here, the arithmetic mean roughness (Ra) is the average of the absolute values ​​of Z(x) (ie, the height of the mountain and the depth of the valley) in the profile curve (y=Z(x)) represented by the following equation in the reference length l.

[0168]

[0169] The maximum height roughness (Rz) indicates 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.

[0170] Ra and Rz can be calculated by the method prescribed in JIS B0601:2001 (based on the international standard ISO4287-1997).

[0171] The ratio of Ra after peeling of the surface of the composite copper component having the layer containing copper oxide formed thereon to Ra before thermocompression bonding is preferably less than 100%, less than 96%, less than 95%, less than 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 the ratio, the more the metal forming the layer containing copper oxide is transferred to the resin substrate.

[0172] The ratio of the surface area after peeling of the composite copper component having the layer containing copper oxide formed thereon to the surface area before thermocompression bonding 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 the ratio, the more the metal forming the layer containing copper oxide is transferred to the resin substrate.

[0173] Surface area can be measured using confocal microscopy or atomic force microscopy.

[0174] In a composite copper component of one embodiment of the present invention, the average length (RSm) of the roughness curve element of the surface of the composite copper component having a layer containing copper oxide is not particularly limited, and is preferably 1500 nm or less, 1400 nm or less, 1300 nm or less, 1200 nm or less, 1100 nm or less, 1000 nm or less, 900 nm or less, 800 nm or less, 750 nm or less, 700 nm or less, 650 nm or less, 600 nm or less, 550 nm or less, 450 nm or less, or 350 nm or less, and preferably 100 nm or more, 200 nm or more, or 300 nm or more. RSm represents the average length of the roughness curve corresponding to one period (i.e., the length of the profile curve element: Xs1 to Xsm) in a certain reference length (lr), and is calculated by the following formula.

[0175]

[0176] Here, 10% of the arithmetic mean roughness (Ra) is used as the minimum height of the concavity and convexity, and 1% of the reference length (lr) is used as the minimum length to define the concavity and convexity of one cycle. As an example, Rsm can be measured and calculated according to the "Surface roughness measurement method of fine ceramic film by atomic force microscope (JIS R 1683: 2007)".

[0177] ΔE of the surface of the composite copper component before thermocompression bonding and the surface of the copper component after peeling ＊ ab is preferably 13 or more, 15 or more, 20 or more, 25 or more, 30 or more, or 35 or more. A larger difference means that the metal forming the layer containing copper oxide (that is, the metal forming the irregularities) is more transferred to the resin substrate.

[0178] ==Method for manufacturing composite copper component==

[0179] One embodiment of the present invention is a method for producing a composite copper member, including a step of making it easier for a layer containing a copper oxide to break (break) from the copper member.

[0180] In this process, the method for making the layer containing copper oxide easy to break from the copper part is not particularly limited, and is carried out by 1) locally coating the surface of the copper part with a coating agent such as a silane coupling agent or a rust inhibitor before oxidation treatment; 2) treating the layer containing copper oxide with nickel chloride after oxidation treatment, etc.

[0181] The layer containing copper oxide is preferably formed by treating the surface of the copper part with an oxidizing agent. The oxidizing agent is not particularly limited, and for example, an aqueous solution of sodium chlorite, sodium hypochlorite, potassium chlorate, potassium perchlorate, etc. can be used. Various additives (for example, phosphates such as trisodium phosphate dodecahydrate) can be added to the oxidizing agent.

[0182] The oxidation reaction conditions are not particularly limited, but 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.

[0183] Before the oxidation treatment, a degreasing treatment or an acid wash for uniform treatment to remove the natural oxide film may be performed, or an alkali treatment may be performed after the acid wash to prevent acid from being introduced into the oxidation process. The method of the alkali treatment is not particularly limited, and the treatment may be performed at 30 to 50° C. for about 0.5 to 2 minutes using an alkali aqueous solution, preferably 0.1 to 10 g / L, more preferably 1 to 2 g / L, such as a sodium hydroxide aqueous solution.

[0184] Alternatively, the copper oxide layer may be dissolved with a dissolving solution containing a dissolving agent to adjust the convex portions on the surface of the copper member, or the copper oxide in the copper oxide layer may be reduced with a reducing solution containing a reducing agent.

[0185] The dissolving agent is not particularly limited, but is preferably a chelating agent, particularly a biodegradable chelating agent, and examples thereof include tetrasodium L-glutamate diacetate (CMG-40), ethylenediaminetetraacetic acid (sodium salt), diethanolglycine, tetrasodium L-glutamate diacetate, ethylenediamine-N,N'-disuccinic acid, sodium 3-hydroxy-2,2'-iminodisuccinate, trisodium methylglycine diacetate, tetrasodium aspartic acid diacetate, disodium N-(2-hydroxyethyl)iminodiacetate, and sodium gluconate.

[0186] As the reducing agent, DMAB (dimethylamine borane), diborane, sodium borohydride, hydrazine, etc. can be used. The reducing chemical solution is a liquid containing a reducing agent, an alkaline compound (such as sodium hydroxide, potassium hydroxide, etc.) and a solvent (such as pure water, etc.).

[0187] A layer containing a metal other than copper can be formed on a layer containing copper oxide. The layer containing a metal other than copper can be formed, for example, by plating with a metal other than copper. The plating method can use a known technique, for example, as a metal other than copper, Sn, Ag, Zn, Al, Ti, Bi, Cr, Fe, Co, Ni, Pd, Au, Pt or various alloys can be used. The plating process is also not particularly limited, and plating can be performed by electrolytic plating, electroless plating, vacuum evaporation, chemical surface treatment, etc., but since it is preferred to form a uniform and thin plating layer, electrolytic plating is preferred.

[0188] In the case of electrolytic plating, nickel plating and nickel alloy plating are preferred. Examples of metals formed by nickel plating and nickel alloy plating include pure nickel, Ni-Cu alloy, Ni-Cr alloy, Ni-Co alloy, Ni-Zn alloy, Ni-Mn alloy, Ni-Pb alloy, and Ni-P alloy.

[0189] Examples of the metal salt used for plating include nickel sulfate, nickel sulfamate, nickel chloride, nickel bromide, zinc oxide, zinc chloride, diamminedichloropalladium, ferric sulfate, ferric chloride, anhydrous chromic acid, chromium chloride, sodium chromium sulfate, copper sulfate, copper pyrophosphate, cobalt sulfate, and manganese sulfate.

[0190] In nickel plating, the bath composition preferably contains nickel sulfate (100 g / L to 350 g / L), nickel sulfamate (100 g / L to 600 g / L), nickel chloride (0 g / L to 300 g / L) and mixtures thereof, and may also contain sodium citrate (0 g / L to 100 g / L) and boric acid (0 g / L to 60 g / L) as additives.

[0191] In the case of electroless nickel plating, electroless plating using a catalyst is preferred. As the catalyst, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or their salts are preferably used. By performing electroless plating using a catalyst, a uniform metal layer in which particles do not exist in a dotted state can be obtained, thereby improving the heat resistance of the composite copper foil.

[0192] One embodiment of the method for manufacturing a composite copper component of the present invention is a method for manufacturing a composite copper component, which includes: 1) a step of locally coating the surface of the copper component with a silane coupling agent or a rust inhibitor; and 2) a step of oxidizing the surface of the copper component after the local coating to form a layer containing copper oxide, or includes: 1) a step of locally coating the surface of the copper component with a silane coupling agent or a rust inhibitor; 2) a step of oxidizing the surface of the copper component after the local coating to form a layer containing copper oxide; and 3) a step of forming a layer containing a metal other than copper on the surface of the composite copper component on which the layer containing copper oxide is formed.

[0193] By partially coating the surface of the copper member with a coating agent such as a silane coupling agent or a rust inhibitor, the portion is protected from oxidation treatment, and voids are generated in the layer containing copper oxide, so that the layer containing copper oxide is easily broken from the copper member.

[0194] 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-glycidyloxypropyl)trimethoxysilane), (3-chloropropyl)triethoxysilane Methoxysilane, (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, and ethylene-trimethoxysilane.

[0195] The rust inhibitor is not particularly limited, and can be selected from 1H-tetrazole, 5-methyl-1H-tetrazole, 5-amino-1H-tetrazole, 5-phenyl-1H-tetrazole, 1,2,3-triazole, 1,2,4-triazole, 1,2,3-benzotriazole, 5-methyl-1H-benzotriazole, 5-amino-1H-benzotriazole, 2-mercaptobenzothiazole, 1,3-dimethyl-5-pyrazolone, pyrrole, 3-methylpyrrole, 2,4-dimethylpyrrole, 2-ethylpyrrole, pyrazole, 3-aminopyrazole, 4-methylpyrazole, 3-amino-5-hydroxypyrazole, thiazole, 2-aminothiazole, 2-methylthiazole, 2-amino-5-methylthiazole, 2-ethylthiazole, benzothiazole, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-butylimidazole, 5-aminoimidazole, 6-aminoimidazole, benzimidazole, 2-(methylthio)benzimidazole.

[0196] Treatment with a silane coupling agent or a rust inhibitor can be performed at any time before oxidation treatment, and can also be performed together with degreasing treatment, acid cleaning for uniform treatment by removing the natural oxide film, or alkaline treatment after acid cleaning to prevent oxygen from being introduced into the oxidation process.

[0197] The surface of the copper part is preferably locally coated (for example, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90% or more, less than 100%) by treatment with a silane coupling agent or a rust inhibitor, and for this purpose, it is preferably reacted at room temperature for 30 seconds, 1 minute or 2 minutes or more at a concentration of 0.1%, 0.5%, 1% or 2%.

[0198] One embodiment of the method for producing a composite copper component of the present invention is a method for producing a composite copper component comprising: 1) a step of forming a layer containing copper oxide by subjecting the surface of the copper component to oxidation treatment; and 2) a step of treating the surface of the copper component on which the layer containing copper oxide is formed with a modifier, or a method for producing a composite copper component comprising: 1) a step of forming a layer containing copper oxide by subjecting the surface of the copper component to oxidation treatment; 2) a step of treating the surface of the copper component on which the layer containing copper oxide is formed with a modifier; and 3) a step of forming a layer containing a metal other than copper on the surface of the composite copper component on which the layer containing copper oxide is formed after being treated with the modifier.

[0199] It is considered that the copper oxide portion near the interface between the copper member and the layer containing copper oxide is dissolved by the treatment with the modifying agent, and the layer containing copper oxide is easily broken from the copper member.

[0200] The modifier for making the layer containing copper oxide easy to break from the copper part only needs to contain a component that dissolves copper oxide, and is not limited to nickel chloride, and can be selected from chlorides (zinc chloride, ferric chloride, chromium chloride, etc.), ammonium salts (ammonium citrate, potassium chloride, ammonium sulfate, ammonium chloride, nickel ammonium sulfate, etc.), chelating agents (ethylenediaminetetraacetic acid, diethanolglycine, tetrasodium L-glutamic acid diacetate, ethylenediamine-N,N'-disuccinic acid, sodium 3-hydroxy-2,2'-iminodisuccinate, trisodium methylglycine diacetate, tetrasodium aspartic acid diacetate, disodium N-(2-hydroxyethyl)iminodiacetic acid, sodium gluconate, etc.), tin (II) chloride and citric acid.

[0201] In the case of treatment with nickel chloride, there is no particular limitation, but it is preferred to immerse the copper part having a layer containing copper oxide in a nickel chloride solution (concentration 45 g / L or more) at room temperature for more than 5 seconds. In addition, the nickel chloride treatment may be performed not only alone, but also simultaneously with the oxidation treatment, or simultaneously with the plating treatment after the oxidation treatment. For example, nickel chloride may be contained in the plating solution, and the copper part having a layer containing copper oxide may be immersed in the plating solution for 5 seconds, 10 seconds, 15 seconds, 20 seconds, 30 seconds, 1 minute or 2 minutes before plating. The immersion time may be appropriately changed according to the thickness of the oxide film.

[0202] ==How to use composite copper parts==

[0203] The composite copper component according to the present invention can be used for:

[0204] (1) Pressing onto a resin substrate to produce a laminate;

[0205] (2) pressing and bonding to a resin substrate, and peeling off to obtain a resin substrate having a part or all of the metal forming a layer containing copper oxide;

[0206] (3) In the SAP method or the MSAP method, the resin substrate is pressed and peeled off to obtain a resin substrate having a part or all of the metal forming a layer containing copper oxide, and the surface of the peeled resin substrate is copper-plated to manufacture a printed wiring board; etc.

[0207] In (1) to (3), the resin substrate and the method of heat-compression bonding to the resin substrate may be the same as or different from the conditions in the X-ray photoelectron spectroscopy measurement.

[0208] In (2) to (3), the method of exfoliation may be the same as or different from the conditions in the X-ray photoelectron spectroscopy measurement.

[0209] In (3), the copper plating method may be electrolytic plating or electroless plating.

[0210] Example

[0211] <1. Manufacturing of composite copper foil>

[0212] Examples 1 to 9 and Comparative Examples 2 to 3 used the shiny side (shiny side. A relatively flat side compared to the opposite side) of copper foil (DR-WS, thickness: 18 μm) manufactured by Furukawa Electric Co., Ltd. Comparative Example 4 used the matte side of copper foil (FV-WS, thickness: 18 μm) manufactured by Furukawa Electric Co., Ltd., and used it as a test piece in an untreated state.

[0213] (1) Pretreatment (PS)

[0214] First, the copper foil was immersed in the following solution at 25°C for 1 minute.

[0215] Examples 1 and 2 used 2.5 g / L of potassium carbonate and 1 vol% of KBE-903 (3-aminopropyltriethoxysilane; manufactured by Shin-Etsu Silicone Co., Ltd.).

[0216] In Example 3, 2.5 g / L potassium carbonate and 0.06 g / L potassium bicarbonate were used.

[0217] In Examples 4 to 6, 5 g / L of potassium hydroxide was used.

[0218] In Example 7, 5 g / L of potassium hydroxide and 5 vol% of KBM-603 (N-2-(aminoethyl)-3-aminopropyltrimethoxysilane; manufactured by Shin-Etsu Silicone Co., Ltd.) were used.

[0219] In Example 8, 5 g / L potassium hydroxide and 1 wt% BTA (benzotriazole) were used.

[0220] Comparative Example 2 used a solution of 2.5 g / L potassium carbonate.

[0221] Comparative Example 3 used a solution of 2.5 g / L potassium carbonate and 0.06 g / L potassium bicarbonate.

[0222] (2) Oxidation treatment (AS)

[0223] The pre-treated copper foil is immersed in an oxidizing agent for oxidation treatment.

[0224] In Examples 1, 2, 7, 8 and Comparative Example 2, a solution of 58.3 g / L sodium chlorite, 20 g / L potassium hydroxide and 39.1 g / L potassium carbonate was used as an oxidant.

[0225] In Examples 3 to 6, a solution of 45 g / L sodium chlorite, 12 g / L potassium hydroxide, and 2 g / L KBM-403 (3-glycidoxypropyltrimethoxysilane; manufactured by Shin-Etsu Silicone Co., Ltd.) was used as an oxidant.

[0226] In Comparative Example 3, as the oxidant, a solution of 58.8 g / L sodium chlorite, 8.8 g / L potassium hydroxide, 3 g / L potassium carbonate, and 2 g / L KBM-403 (3-glycidoxypropyltrimethoxysilane; manufactured by Shin-Etsu Silicone Co., Ltd.) was used.

[0227] In Examples 1, 2, 7, and 8, the samples were immersed in the oxidizing agent at 73° C. for 6 minutes, and in Examples 3 to 6 and Comparative Examples 2 and 3, the samples were immersed in the oxidizing agent at 73° C. for 2 minutes.

[0228] (3) Plating pretreatment

[0229] After the oxidation treatment, in Examples 4 to 6, the following modifying agents were used for plating pretreatment.

[0230] In Example 4, a solution of 45 g / L of tin (II) chloride dihydrate and 1 mL / L of hydrochloric acid was used and the mixture was treated at 45° C. for 10 seconds.

[0231] In Example 5, a 45 g / L ammonium chloride solution was used and the treatment was performed at 45° C. for 60 seconds.

[0232] In Example 6, 5 mL / L of a 50% citric acid solution was used and the treatment was performed at 45° C. for 60 seconds.

[0233] (4) Electrolytic plating

[0234] After oxidation treatment, Examples 2, 3 and Comparative Example 3 were electroplated using a first electrolytic nickel plating solution (240 g / L nickel sulfate; 45 g / L nickel chloride; 20 g / L sodium citrate). After pre-plating, Examples 4 to 7 were electroplated using a second electrolytic nickel plating solution (240 g / L nickel sulfate; 20 g / L sodium citrate). Example 3 was immersed in the electrolytic nickel plating solution for 1 minute before electroplating. The samples were heated at 50°C and a current density of 0.5 A / dm 2 ×45 seconds (=22.5C / dm 2 Copper foil area) is electroplated.

[0235] Regarding the examples and comparative examples, a plurality of test pieces were prepared under the same conditions as above. The conditions are summarized in Table 1.

[0236] [Table 1]

[0237]

[0238] <2. Pressing and peeling of resin substrate>

[0239] (1) Methods

[0240] The test pieces of Examples 1 to 8 and Comparative Examples 2 to 4 were subjected to a peeling test of the resin substrate using R5670KJ (Panasonic), R5680J (Panasonic), CT-Z (Kuraray), NX9255 (Park ElectrochemicaL Corp.), and R1551GG (Panasonic) as prepregs.

[0241] First, for the test piece, the laminated prepreg is heat-pressed in a vacuum using a vacuum high-pressure press to obtain a laminated body sample. In addition, when the resin substrate is R5670KJ (manufactured by Panasonic), after being heat-pressed while heating to 110°C under a pressure of 0.49MPa, the temperature and pressure are increased, and the heat is pressed at 2.94MPa and 210°C for 120 minutes. In the case of R5680J (manufactured by Panasonic), after being heat-pressed while heating to 110°C under a pressure of 0.5MPa, the temperature and pressure are increased, and the heat is pressed at 3.5MPa and 195°C for 75 minutes. In the case of NX9255 (manufactured by Park ElectrochemicaL Corp.), the resin substrate is heated to 260°C while being pressurized at 0.69MPa, the pressure is increased to 1.5MPa, heated to 385°C, and kept at 385°C for 10 minutes. When the resin substrate is R1551GG (manufactured by Panasonic), it is heated at a pressure of 1 MPa, and after reaching 100°C, it is maintained at this temperature for 10 minutes, and then further heated at a pressure of 3.3 MPa, and after reaching 180°C, it is maintained at this temperature for 50 minutes, thereby performing thermocompression bonding. When the resin substrate is CT-Z (manufactured by Kuraray), it is heated at a pressure of 0 MPa, maintained at 260°C for 15 minutes, and then further heated at 300°C while applying a pressure of 4 MPa and maintained at 10 minutes, thereby performing thermocompression bonding. For these laminated body samples, the copper parts were peeled off from the resin substrate according to the 90° peel test (Japanese Industrial Standard (JIS) C5016). Figure 1 ). The results of visual observation are shown in Figure 2-1 In addition, regarding a representative combination, photographs of the surfaces of the resin side and the copper foil side after peeling are shown in Figure 2-2 .

[0242] from Figure 2-1 to Figure 2-2 It is known that in Examples, the surface of the copper foil was easily observed to be transferred to the resin side, whereas in Comparative Examples, the surface of the copper foil was not transferred to the resin side. In order to verify this phenomenon in a material form, the following surface analysis was performed.

[0243] <3. Surface analysis of the resin substrate after peeling>

[0244] The surface of the peeled resin substrate was subjected to elemental analysis. Specifically, the obtained resin substrate was analyzed using Quantera SXM (manufactured by ULVAC-PHI) under the following conditions. As a negative control, a resin substrate (R5670KJ; MEGTRON 6) that was not treated was analyzed (Comparative Example 1).

[0245] (1)Survey spectrum

[0246] First, check the elements under the following conditions.

[0247] X-ray source: monochromated ALKα (1486.6 eV)

[0248] X-ray beam diameter: 100μm (25w15kV)

[0249] Optical path energy: 280eV, 1eVstep

[0250] Point analysis:

[0251] Total times: 8 times

[0252] (2) Results

[0253] The results are shown in Table 2 and Figure 3-1 to Figure 3-7 .

[0254] In the example, the peak intensity of the spectrum of Cu2p3 derived from the transferred copper atoms is greater than the peak intensity of the spectrum of C1s formed by the resin substrate, whereas in the comparative example, no peak of the spectrum of Cu2p3 is detected, or its intensity is less than the peak intensity of the spectrum of C1s. This indicates that in the comparative example, the copper atoms are not substantially transferred to the resin substrate, or are substantially absent in the surface layer of the resin substrate detectable by XPS.

[0255] In Example 1, the composite copper foil was not plated, so only Cu atoms migrated and were detected on the resin substrate side. In Examples 2 and 3, nickel plating was performed, so Cu atoms and Ni atoms migrated and were detected on the resin side.

[0256] In addition, the ratio of C1s in the examples is smaller than that in the comparative examples. In the examples, it is considered that the ratio of C1s on the surface becomes relatively smaller due to the transfer of copper oxide or cuprous oxide.

[0257] [Table 2]

[0258]

[0259] <4. Measurement of Ra and surface area of ​​composite copper foil before and after thermal compression bonding>

[0260] (1) Methods

[0261] For the composite copper foil test pieces of Examples 1 to 8 and Comparative Examples 2 to 4, the surface area before and after thermal compression bonding was calculated using a confocal scanning electron microscope OPTELICS H1200 (manufactured by Lasertec Co., Ltd.). As measurement conditions, the mode was set to confocal mode, the scanning area was set to 100 μm×100 μm, the light source was set to blue, and the cutoff value was set to 1 / 5. The objective lens was set to x100, the eyepiece was set to x14, the digital zoom was set to x1, the Z pitch was set to 10 nm, and data from 3 locations was obtained, and the surface area was set to the average value of the 3 locations.

[0262] (2) Results

[0263] As shown in Table 3, before thermocompression bonding and after peeling, Ra and surface area decreased in the examples, but increased in the comparative examples. This indicates that in the examples, all or part of the convex portion of the composite copper component was transferred to the resin side, while in the comparative examples, part of the resin was transferred to the composite copper component.

[0264] [Table 3]

[0265]

[0266] <5.ΔE of composite copper foil before and after thermal compression bonding ＊ Calculation of ab>

[0267] (1) Methods

[0268] The color difference (L ＊ 、a ＊ , b ＊ ), and ΔE is calculated from the obtained value according to the following formula: ＊ ab.

[0269] ΔE ＊ ab=[(ΔL ＊ ) 2 +(Δa ＊ ) 2 +(Δb ＊ ) 2 ] 1 / 2

[0270] (2) Results

[0271] As shown in Table 4, before thermal compression bonding and after peeling, in the examples, ΔE ＊ab is 15 or more, while in the comparative example, it is less than 15. This is because in the example, the metal contained in the layer containing copper oxide is transferred to the resin substrate, so the color change of the copper part becomes large, while in the comparative example, the layer containing copper oxide remains on the copper part as it is, so the color change of the copper part is small, so the more the metal contained in the layer containing copper oxide is transferred, the greater the difference between them. In fact, in Figure 2-1 to Figure 2-2 In the photograph, after peeling, the resin side of the example is greatly colored, but the resin side of the comparative example remains almost white.

[0272] [Table 4]

[0273]

[0274] <5. Analysis of the surface of the composite copper foil after transfer by attenuated total reflection absorption Fourier transform infrared spectroscopy (FT IR / ATR method)>

[0275] (1) Methods

[0276] As the resin substrate, R1551GG (epoxy), R5670KJ, R5680J (the above, PPE), NX9255 (PTFE) or CT-Z (LCP) was used for thermocompression bonding, and each composite copper component test piece after peeling was analyzed by FT-IR / ATR method under the following measurement conditions.

[0277] Measurement conditions

[0278] Parkin Elmer Specrtum 100

[0279] ATR method

[0280] Crystal: Germanium

[0281] Resolution: 4

[0282] Scan number: 4 times

[0283] Pressure (dynamometer): 40±5[N]

[0284] Spectral representation: absorbance

[0285] (2) Calculation of S / N (signal / noise) ratio

[0286] The same conditions as those for hot pressing of composite copper parts were used to heat and pressurize the resin substrate. The resin substrate was measured by FT-IR at 50 cm －1 The range of 3800-3850cm is selected as any wavelength without a peak derived from the resin. －1As a wavelength without a peak derived from the resin. Furthermore, in the wavelength range of 700-4000cm －1 In the case of using R1551GG as the resin substrate, the wavelength of 1200 cm －1 As the maximum peak detection wavelength, when using R5670KJ and R5680J, 1190cm －1 As the maximum peak detection wavelength, when using NX9255, 1232cm －1 When using CT-Z as the maximum peak detection wavelength, the wavelength of 1741 cm －1 The maximum peak detection wavelength is near Figure 4-1 to Figure 4-3 , Figure 5 , Figure 6-1 to Figure 6-2 , Figure 7 and Figure 8 The arrow indicates the maximum peak detection wavelength).

[0287] The surface of the copper part after transfer was measured by FT-IR, and a baseline was drawn connecting the two extreme points of the peak at the maximum peak detection wavelength with a straight line, and the difference between the baseline and the maximum height of the peak was taken as the signal value (S). －1 The difference between the maximum value and the minimum value of the detected peak is taken as the noise value (N) and the S / N ratio is calculated.

[0288] (3) Results

[0289] The results are expressed in Figure 4-1 to Figure 4-3 , Figure 5 , Figure 6-1 to Figure 6-2 , Figure 7 and Figure 8 and Table 5.

[0290] [Table 5]

[0291]

[0292] As shown in Table 5, in the example, no peak with an S / N ratio of 10 or more corresponding to the organic matter derived from the resin was detected on the composite copper foil side, but in the comparative example, a peak with an S / N ratio of 10 or more corresponding to the organic matter derived from the resin was detected on the composite copper foil side.

[0293] This is because in the comparative example, the metal on the surface of the composite copper component is hardly transferred, and when the composite copper component is peeled off from the resin substrate, the resin is coagulated and destroyed, and the destroyed resin adheres to the surface of the composite copper component, so the peak corresponding to the organic matter derived from the resin is detected. On the other hand, in the example, since the metal on the surface of the composite copper component is transferred to the resin substrate, there is hardly any resin attached to the composite copper component after the composite copper component is peeled off from the resin substrate, and no peak corresponding to the organic matter derived from the resin with an S / N ratio of 10 or more is detected.

[0294] That is, in the comparative example, since the strength of the resin substrate is greater than the strength of the protrusion formed by the layer containing copper oxide, the metal on the surface of the composite copper part is not transferred, and the cohesive failure of the resin occurs. On the other hand, in the example, since the strength of the protrusion formed by the layer containing copper oxide is lower than the strength of the resin substrate, the metal on the surface of the composite copper part is transferred, and thus there is almost no adhesion of the resin.

[0295] Industrial Applicability

[0296] According to the present invention, a novel composite copper component can be provided. The composite copper component is suitable for the SAP method or the MSAP method ( Fig. 9 ). In order for the plating solution to penetrate into the deepest part of the end of the concave portion, the shape of the concave portion needs to be large to a certain extent, which is not suitable for the formation of fine wiring. However, when using the composite copper foil of the present invention, the layer containing copper oxide that forms the concave and convex is transferred itself, so it is not necessary to allow the plating solution to penetrate into the deepest part of the concave portion. It is sufficient to perform (pattern) copper plating on the concave and convex layer containing the transferred copper oxide. Even if the shape of the concave portion located on the surface of the original composite copper component is long and thin, the possibility of generating a gap between the resin substrate and the (pattern) copper plating layer is small, which is suitable for the formation of fine wiring.

[0297] Furthermore, since copper plating is performed on the layer containing copper oxide, the copper plating has a high bonding affinity to the layer containing copper oxide, and the bonding of the layer containing copper oxide bonded to the copper plating layer ensures the peel strength between the resin substrate and the (patterned) copper plating layer.

Claims

1. A composite copper component, wherein a layer containing copper oxide is formed on at least a portion of the surface of the copper component, characterized in that: The surface of the composite copper component is thermally pressed onto a resin substrate under predetermined conditions, and after thermal pressing, the copper component is peeled off from the resin substrate under predetermined conditions. When the surface of the copper component peeled off from the resin substrate is analyzed using attenuated total reflection absorption Fourier transform infrared spectroscopy (FT-IR / ATR method), the wavelength range is 700-4000cm －1 In the above analysis, the S / N ratio of the peak corresponding to the substance derived from the resin substrate detected was 10 or less.

2. The composite copper component according to claim 1, characterized in that: The S / N ratio of the peak is 7 or less.

3. The composite copper component according to claim 1 or 2, characterized in that: The Ra of the surface on which the layer containing copper oxide is formed is 0.04 μm or more, and the ratio of the Ra of the surface of the copper member peeled off from the resin substrate to the Ra is less than 100%.

4. The composite copper component according to claim 1 or 2, characterized in that: A ratio of a surface area of ​​the copper member peeled from the resin substrate to a surface area of ​​a surface on which the layer containing copper oxide is formed is less than 100%.

5. The composite copper component according to claim 1 or 2, characterized in that: The color difference (ΔE) between the surface on which the layer containing copper oxide is formed and the surface of the copper member peeled off from the resin substrate ＊ ab) is 15 or more.

6. The composite copper component according to claim 1 or 2, characterized in that: The resin substrate contains at least one insulating resin selected from polyphenylene ether (PPE), epoxy resin, polyphenylene oxide (PPO), polybenzoxazole (PBO), polytetrafluoroethylene (PTFE), liquid crystal polymer (LCP) or triphenyl phosphite (TPPI), fluororesin, polyetherimide, polyetheretherketone, polycycloolefin, bismaleimide resin, low dielectric constant polyimide and cyanate resin.

7. The composite copper component according to claim 1 or 2, characterized in that: The predetermined conditions for 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.

8. The composite copper component according to claim 1 or 2, characterized in that: The layer containing copper oxide contains a metal other than copper.

9. The composite copper component according to claim 8, characterized in that: The metal other than copper is Ni.

10. A composite copper component, wherein a layer containing copper oxide is formed on at least a portion of the surface of the copper component, characterized in that: The surface of the composite copper component is heat-pressed onto a resin substrate under prescribed conditions, and when the copper component is peeled off from the resin substrate under prescribed conditions after heat-pressing, in an X-ray photoelectron spectroscopy spectrum obtained by Surveyspectrum analysis of X-ray photoelectron spectroscopy (XPS), metal atoms contained in the layer containing copper oxide are detected from the surface of the resin substrate from which the copper component is peeled off, and the total intensities of the main peaks of the metal elements detected from the surface of the resin substrate from which the copper component is peeled off are greater than the peak intensity of C1s.

11. The composite copper component according to claim 10, characterized in that: On the surface of the resin substrate from which the copper member was peeled, the [Total surface atomic composition percentage (Atom%) of metal elements] / [Surface atomic composition percentage (Atom%) of C1s] It is above 0.

040.

12. The composite copper component according to claim 10, characterized in that: On the surface of the resin substrate from which the copper member was peeled, the [Total surface atomic composition percentage (Atom%) of metal elements] / [Surface atomic composition percentage (Atom%) of C1s] It is 0.010 or more.

13. The composite copper component according to claim 10, characterized in that: When Survey spectrum analysis was performed using XPS on the surface of the resin substrate from which the copper component was peeled off and the composition ratio of the detected elements was calculated, the total surface atomic composition percentage of Cu2p3 and Ni2p3 was greater than 3.0 atom%.

14. The composite copper component according to claim 10, characterized in that: When Survey spectrum analysis was performed using XPS on the surface of the resin substrate from which the copper component was peeled off and the composition ratio of the detected elements was determined, the total surface atomic composition percentage of Cu2p3 and Ni2p3 was greater than 1.5 atom%.

15. The composite copper component according to claim 10, characterized in that: When Survey spectrum analysis was performed using XPS on the surface of the resin substrate from which the copper component was peeled off and the composition ratio of the detected elements was determined, the surface atomic composition percentage of Cu2p3 was greater than 2.8 atom%.

16. The composite copper component according to claim 10, characterized in that: When Survey spectrum analysis was performed using XPS on the surface of the resin substrate from which the copper component was peeled off and the composition ratio of the detected elements was determined, the surface atomic composition percentage of Cu2p3 was greater than 1.0 atom%.

17. The composite copper component according to any one of claims 10 to 16, characterized in that: The Ra of the surface on which the layer containing copper oxide is formed is 0.04 μm or more, and the ratio of the Ra of the surface of the copper member peeled off from the resin substrate to the Ra is less than 100%.

18. The composite copper component according to any one of claims 10 to 16, characterized in that: A ratio of a surface area of ​​the copper member peeled from the resin substrate to a surface area of ​​a surface on which the layer containing copper oxide is formed is less than 100%.

19. The composite copper component according to any one of claims 10 to 16, characterized in that: The color difference (ΔE) between the surface on which the layer containing copper oxide is formed and the surface of the copper member peeled off from the resin substrate ＊ ab) is 15 or more.

20. The composite copper component according to any one of claims 10 to 16, characterized in that: The resin substrate contains at least one insulating resin selected from polyphenylene ether (PPE), epoxy resin, polyphenylene oxide (PPO), polybenzoxazole (PBO), polytetrafluoroethylene (PTFE), liquid crystal polymer (LCP) or triphenyl phosphite (TPPI), fluororesin, polyetherimide, polyetheretherketone, polycycloolefin, bismaleimide resin, low dielectric constant polyimide and cyanate resin.

21. The composite copper component according to any one of claims 10 to 16, characterized in that: The predetermined conditions for 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.

22. The composite copper component according to any one of claims 10 to 16, characterized in that: The layer containing copper oxide contains a metal other than copper.

23. The composite copper component according to claim 22, characterized in that: The metal other than copper is Ni.

24. A method for producing a printed wiring board, for producing a printed wiring board using the composite copper member according to any one of claims 1 to 23, the method comprising: 1) a step of thermally pressing a resin substrate onto the layer containing copper oxide of the composite copper component under predetermined conditions; 2) a step of peeling the copper component from the resin substrate under predetermined conditions to obtain a resin substrate having a part or all of the metal forming the layer containing copper oxide; and 3) A step of performing copper plating on a surface of a part or all of a resin substrate having a metal forming the layer containing copper oxide.

25. A method for producing a resin substrate having a metal, characterized in that: include: 1) a step of thermally pressing a resin base material onto the layer containing copper oxide of a composite copper member having a layer containing copper oxide formed on at least a portion of the surface of the copper member under predetermined conditions; and 2) a step of peeling the copper component from the resin substrate under predetermined conditions to obtain a resin substrate having a part or all of the metal forming the layer containing copper oxide, When the metal-containing resin substrate is subjected to survey spectrum analysis using X-ray photoelectron spectroscopy (XPS), metal atoms contained in the layer containing copper oxide can be detected. The total intensities of the main peaks of the detected metal elements are greater than the peak intensity of the spectrum of C1s.

26. The method for producing a resin substrate according to claim 25, wherein: The XPS measurement calculated [Total surface atomic composition percentage (Atom%) of metal elements] / [Surface atomic composition percentage (Atom%) of C1s] It is above 0.

040.

27. The method for producing a resin substrate according to claim 25, wherein: The XPS measurement calculated [Total surface atomic composition percentage (Atom%) of metal elements] / [Surface atomic composition percentage (Atom%) of C1s] It is 0.010 or more.

28. The method for producing a resin substrate according to claim 25, wherein: When Survey spectrum analysis was performed using XPS on the surface of the resin substrate from which the copper component was peeled off and the composition ratio of the detected elements was calculated, the total surface atomic composition percentage of Cu2p3 and Ni2p3 was greater than 3.0 atom%.

29. The method for producing a resin substrate according to claim 25, wherein: When Survey spectrum analysis was performed using XPS on the surface of the resin substrate from which the copper component was peeled off and the composition ratio of the detected elements was determined, the total surface atomic composition percentage of Cu2p3 and Ni2p3 was greater than 1.5 atom%.

30. The method for producing a resin substrate according to claim 25, wherein: When Survey spectrum analysis was performed using XPS on the surface of the resin substrate from which the copper component was peeled off and the composition ratio of the detected elements was determined, the surface atomic composition percentage of Cu2p3 was greater than 2.8 atom%.

31. The method for producing a resin substrate according to claim 25, wherein: When Survey spectrum analysis was performed using XPS on the surface of the resin substrate from which the copper component was peeled off and the composition ratio of the detected elements was determined, the surface atomic composition percentage of Cu2p3 was greater than 1.0 atom%.

32. The method for producing a resin substrate according to any one of claims 25 to 29, wherein: The resin substrate includes at least one insulating resin selected from the group consisting of polyphenylene ether (PPE), epoxy resin, polyphenylene oxide (PPO), polybenzoxazole (PBO), polytetrafluoroethylene (PTFE), liquid crystal polymer (LCP), triphenyl phosphite (TPPI), fluororesin, polyetherimide, polyetheretherketone, polycycloolefin, bismaleimide resin, low dielectric constant polyimide and cyanate resin.

33. A method for producing a laminated body comprising a composite copper member having a layer containing copper oxide formed on at least a portion of the surface of the copper member and a resin substrate, the method comprising: The method comprises the step of thermally pressing the resin substrate onto the layer containing copper oxide under predetermined conditions, When the copper component is peeled off from the resin substrate under specified conditions, when a survey spectrum analysis is performed using X-ray photoelectron spectroscopy (XPS), metal atoms contained in the layer containing copper oxide are detected from the surface of the resin substrate peeled off from the copper component, and the total intensity of the main peaks of the detected metal elements is greater than the peak intensity of the C1s spectrum.

34. A method for producing a laminated body comprising a composite copper member having a layer containing copper oxide formed on at least a portion of the surface of the copper member and a resin substrate, the method comprising: The method comprises the step of thermally pressing a resin substrate onto the layer containing copper oxide, When the copper member is peeled off from the resin substrate under predetermined conditions, the attenuated total reflection absorption Fourier transform infrared spectroscopy (FT-IR / ATR method) in the wavelength range of 700-4000 cm －1 In the measurement of the range of , the S / N ratio of the peak corresponding to the substance derived from the resin substrate detected on the surface of the copper member peeled off from the resin substrate is 10 or less.

35. A method for manufacturing a composite copper component, used for manufacturing the composite copper component according to claim 1 or 10, wherein the method comprises: 1) a step of locally coating the surface of the copper component with a silane coupling agent or a rust inhibitor; and 2) A step of forming a layer including the copper oxide by subjecting the surface after the partial coating to an oxidation treatment.

36. A method for manufacturing a composite copper component, used for manufacturing the composite copper component according to claim 22, the manufacturing method comprising: 1) a step of locally coating the surface of the copper component with a silane coupling agent or a rust inhibitor; 2) a step of forming a layer containing the copper oxide by subjecting the surface after the partial coating to an oxidation treatment; and 3) A step of forming a layer containing a metal other than copper on the surface after the oxidation treatment.

37. A method for manufacturing a composite copper component, used for manufacturing the composite copper component according to claim 22, the manufacturing method comprising: 1) a step of forming a layer including the copper oxide by subjecting the surface of the copper member to an oxidation treatment; 2) a step of treating the surface after the oxidation treatment with a modifying agent; and 3) forming a layer containing a metal other than copper on the surface treated with the modifying agent, The modifier includes a component that dissolves the copper oxide.

38. A method for manufacturing a composite copper component, used for manufacturing the composite copper component according to claim 22, the manufacturing method comprising: 1) a step of forming a layer including the copper oxide by subjecting the surface of the copper member to an oxidation treatment; 2) a step of treating the surface after the oxidation treatment with a modifying agent; and 3) forming a layer containing a metal other than copper on the surface treated with the modifying agent, The modifier comprises a compound selected from nickel chloride, zinc chloride, ferric chloride, chromium chloride, ammonium citrate, potassium chloride, ammonium sulfate, ammonium chloride, nickel ammonium sulfate, ethylenediaminetetraacetic acid, diethanolglycine, tetrasodium L-glutamate diacetate, ethylenediamine-N,N'-disuccinic acid, 3-hydroxy-2,2'-iminodisuccinate sodium, methylglycine diacetate trisodium, aspartic acid diacetate tetrasodium, N-(2-hydroxyethyl)iminodiacetic acid disodium and sodium gluconate.

39. A method for manufacturing a composite copper component, used for manufacturing the composite copper component according to claim 22, the manufacturing method comprising: 1) a step of forming a layer including the copper oxide by subjecting the surface of the copper member to an oxidation treatment; 2) a step of treating the surface after the oxidation treatment with a modifying agent; and 3) forming a layer containing a metal other than copper on the surface treated with the modifying agent, The modifying agent comprises tin(II) chloride or citric acid.

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