Composite copper component manufacturing system

Abstract

The purpose of the present invention is to provide a novel system for producing a composite copper member. The present invention provides a system having a first device for partially coating the surface of a copper member with a silane coupling agent or a rust inhibitor and a second device for forming a copper-oxide-containing layer through oxidation treatment of the partially coated surface, or a system having a fourth device for forming a copper-oxide-containing layer through oxidation treatment of the surface of a copper member and a fifth device for treating the oxidation-treated surface using a dissolving agent.

Description

[Technical Field]

[0001] The present invention relates to a manufacturing system for a composite copper component. [Background technology]

[0002] Copper foil used in printed wiring boards (PWBs) is required to have good adhesion to insulating resin substrates. To improve this adhesion, methods have been used to roughen the copper foil surface using etching or other methods, thereby increasing mechanical adhesion through the so-called anchor effect. Meanwhile, increasing the density of PWBs and reducing transmission loss in high-frequency bands have led to the need for flattened copper foil surfaces. To satisfy these conflicting requirements, copper surface treatment methods have been developed, including oxidation and reduction steps (see International Publication No. 2014 / 126193). In this method, copper foil is preconditioned and then immersed in a chemical solution containing an oxidizing agent to oxidize the surface and form copper oxide irregularities. The foil is then immersed in a chemical solution containing a reducing agent to reduce the copper oxide, thereby smoothing the surface irregularities and smoothing the surface roughness. Other methods for improving adhesion in copper foil treatment using oxidation / reduction include adding surface-active molecules in the oxidation process (JP Patent Publication No. 2013-534054) and forming a protective film on the surface of copper foil using an aminothiazole compound or the like after the reduction process (JP Patent Publication No. 8-97559).

[0003] Although the mechanical adhesive strength between the copper foil and the resin increases with the length and number of the protrusions formed by the roughening treatment, it has also been known that the protrusions may fall off from their bases or break off midway due to insufficient strength of the protrusions. To increase the strength, plating the surface of the protrusions has been reported (JP 2016-188431 A).

[0004] The present inventors have also developed a composite copper foil in which a roughened copper foil is plated with Ni by electrolytic plating (WO 2019 / 093494).

[0005] In recent years, the trend toward finer wiring has led to new circuit formation methods for printed wiring boards and semiconductor package substrates, such as the semi-additive process (SAP method) and the modified semi-additive process (M-SAP) (MSAP method), which use the surface profile of copper foil (Japanese Patent Application Laid-Open No. 2017-034216). An example of a semi-additive process using the copper foil surface profile (i.e., the uneven surface shape formed by roughening treatment) is as follows: First, copper foil laminated to a resin substrate is entirely etched, and the etched substrate surface to which the copper foil surface profile has been transferred is drilled with a laser or other device, followed by electroless copper plating to establish electrical continuity in the drilled holes. The electroless copper-plated surface is covered with a dry film, and the dry film in the circuit-forming area is removed by UV exposure and development. The electroless copper-plated surface not covered by the dry film is then electrolytically plated. The dry film is then peeled off, and finally, the electroless copper-plated layer is etched (flash etching, quick etching) using an etching solution containing sulfuric acid, hydrogen peroxide, or the like, to form a fine circuit. In this method, a resin substrate is laminated to the surface-treated copper foil, and the surface-treated copper foil is then peeled off to transfer the surface profile of the copper foil to the resin substrate. However, it is required to transfer the copper foil surface profile to the surface of the resin substrate well without damaging it, and further ingenuity has become necessary to maintain the strength of the irregularities on the copper foil surface. Summary of the Invention [Problem to be solved by the invention]

[0006] In a conventional method using a copper foil surface profile, for example, a copper foil having roughening particles is laminated to a resin substrate from the surface with the roughening particles, and then the copper foil is removed to transfer the copper foil surface profile to the resin substrate surface, and copper plating is then performed on the transferred surface. However, when the surface has a complex uneven shape, the plating solution may not be able to penetrate. In such cases, voids form between the resin substrate and the (patterned) copper plating layer, and the voids expand when heated, causing problems such as circuit peeling or board blistering. Therefore, an object of the present invention is to provide a manufacturing system for a composite copper member suitable for the SAP method or MSAP method. [Means for solving the problem]

[0007] As a result of extensive research, the present inventors have newly discovered that a composite copper member suitable for the SAP method or MSAP method can be produced by decreasing, rather than increasing, the strength of the protrusions formed by roughening treatment.

[0008] One embodiment of the present invention is a first system including a first device for partially coating a surface of a copper member with a silane coupling agent or a rust inhibitor, and a second device for forming a layer containing copper oxide by oxidizing the partially coated surface. The oxidation treatment may be performed with an oxidizing agent. The silane coupling agent may be selected from the group consisting of silane, tetraorganosilane, aminoethyl-aminopropyl-trimethoxysilane, (3-aminopropyl)trimethoxysilane, (1-[3-(trimethoxysilyl)propyl]urea), (3-aminopropyl)triethoxysilane, ((3-glycidyloxypropyl)trimethoxysilane), (3-chloropropyl)trimethoxysilane, and (3-glycidyloxypropyl)triethoxysilane.

[0033] The silane may be selected from the group consisting of (propyl)trimethoxysilane, dimethyldichlorosilane, 3-(trimethoxysilyl)propyl methacrylate, ethyltriacetoxysilane, triethoxy(isobutyl)silane, triethoxy(octyl)silane, tris(2-methoxyethoxy)(vinyl)silane, chlorotrimethylsilane, methyltrichlorosilane, silicon tetrachloride, tetraethoxysilane, phenyltrimethoxysilane, chlorotriethoxysilane, ethylene-trimethoxysilane.The rust inhibitor may be 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, pyrazolone The copper-containing metal may be selected from the group consisting of thiazole, 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, and 2-(methylthio)benzimidazole. The method may further include a third device for forming a layer containing a metal other than copper on the oxidized surface. The third device may include a conductive portion, and the ratio of the width of the conductive portion to the width of the copper member may be 0.8 or more. The metal other than copper may be Ni.

[0009] Another embodiment of the present invention is a second system including a fourth apparatus for oxidizing the surface of a copper member to form a layer containing copper oxide, and a fifth apparatus for treating the oxidized surface with a dissolving agent. The dissolving agent may be selected from the group consisting of nickel chloride, zinc chloride, iron 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, sodium 3-hydroxy-2,2'-iminodisuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, disodium N-(2-hydroxyethyl)iminodiacetate, sodium gluconate, tin(II) chloride, and citric acid. The system may further include a sixth apparatus for forming a layer containing a metal other than copper on the surface treated with the dissolving agent. The sixth device may have a current-carrying part, and the ratio of the width of the current-carrying part to the width of the copper member may be 0.8 or more. The metal other than copper may be Ni. The first system may further include a seventh device for thermocompression bonding a resin substrate onto the copper oxide-containing layer of the copper member, an eighth device for peeling the copper member from the resin substrate to obtain the resin substrate having some or all of the metals that form the copper oxide-containing layer, a ninth device for thermocompression bonding a resin substrate onto the copper member layer containing a metal other than copper, and a tenth device for peeling the copper member from the resin substrate to obtain the resin substrate having some or all of the metals that form the copper oxide-containing layer.

[0010] The second system may further include an eleventh device for thermocompression bonding a resin substrate onto the surface of the copper member treated with the solvent, a twelfth device for peeling the copper member from the resin substrate to obtain the resin substrate having some or all of the metals that form the copper oxide-containing layer, a thirteenth device for thermocompression bonding a resin substrate onto the layer containing a metal other than copper of the copper member, and a fourteenth device for peeling the copper member from the resin substrate to obtain the resin substrate having some or all of the metals that form the copper oxide-containing layer.

[0011] In the first and second systems, the resin substrate may contain at least one insulating resin selected from the group consisting of polyphenylene ether (PPE), epoxy, polyphenylene oxide (PPO), polybenzoxazole (PBO), polytetrafluoroethylene (PTFE), liquid crystal polymer (LCP), thermoplastic polyimide (TPI), fluororesin, polyetherimide, polyetheretherketone, polycycloolefin, bismaleimide resin, low-dielectric-constant polyimide, and cyanate resin. The composite copper member may be thermocompression bonded to the resin substrate at a temperature of 50°C to 400°C, a pressure of 0 to 20 MPa, and a time of 1 minute to 5 hours.

[0012] The first system and the second system may further include a fifteenth device for performing a copper plating process on the surface of the resin substrate having some or all of the metals forming the copper oxide-containing layer.

[0013] ==Cross-reference to related literature== This application claims priority based on Japanese Patent Application No. 2021-071459, filed on April 20, 2021, and the basic application is incorporated herein by reference. [Brief explanation of the drawings]

[0014] [Figure 1]FIG. 1 is a schematic diagram of an example of a composite copper member of the present invention before thermocompression bonding and after peeling. [Figure 2] FIG. 2 shows the results of visual observation after the composite copper foils of Examples 1 to 8 and Comparative Examples 2 to 4 were pressed onto a resin substrate and then peeled off (if the surface of the copper foil was transferred to the resin side, it was marked with ◯, and if not, it was marked with ×), as well as representative photographs of the surfaces on both sides. [Figure 3] FIG. 3 shows the results of XPS analysis of the resin substrates of Examples 1 to 3 and Comparative Examples 1 to 4. As shown in FIG. [Figure 4] FIG. 4 shows the results of measuring the surfaces of the composite copper foils of Examples 1 to 3 and Comparative Examples 2 to 4 by the FT-IR / ATR method after they were thermocompression bonded to a resin substrate (R5670KJ) and then peeled off. [Figure 5] FIG. 5 shows the results of measuring the surfaces of the composite copper foils of Example 3 and Comparative Example 3 by the FT-IR / ATR method after they were thermocompression bonded to a resin substrate (R1551GG) and then peeled off. [Figure 6] FIG. 6 shows the results of measuring the surfaces of the composite copper foils of Examples 4 to 8 by the FT-IR / ATR method after they were thermocompression bonded to a resin substrate (R5680J) and then peeled off. [Figure 7] FIG. 7 shows the results of measuring the surfaces of the composite copper foils of Example 3 and Comparative Example 3 by the FT-IR / ATR method after they were thermocompression bonded to a resin substrate (NX9255) and then peeled off. [Figure 8] FIG. 8 shows the results of measuring the surfaces of the composite copper foils of Example 3 and Comparative Example 3 by the FT-IR / ATR method after they were thermocompression bonded to a resin substrate (CT-Z) and then peeled off. [Figure 9] FIG. 9 is a schematic diagram showing the application of a composite copper foil ("transfer + transfer") according to one embodiment of the present invention and a conventional copper foil for transfer ("transfer only") to the SAP method. [Figure 10] FIG. 10 is a schematic diagram of a first production system for a composite copper foil according to one embodiment of the present invention. [Figure 11] 11 is a schematic diagram of a second manufacturing system for a composite copper foil according to one embodiment of the present invention, where A shows the case where the sixth device is not provided and B shows the case where the sixth device is provided. DETAILED DESCRIPTION OF THE INVENTION

[0015] Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings, but the present invention is not necessarily limited thereto. The objects, features, advantages, and concepts of the present invention will be apparent to those skilled in the art from the description in this specification, and those skilled in the art will be able to easily reproduce the present invention from the description in this specification. The embodiments and specific examples of the invention described below show preferred embodiments of the present invention and are presented for illustrative or explanatory purposes, and are not intended to limit the present invention thereto. It will be apparent to those skilled in the art that various changes and modifications can be made based on the description in this specification within the spirit and scope of the present invention disclosed herein.

[0016] ==Composite copper components== One embodiment of the present invention is a composite copper member in which a layer containing copper oxide is formed on at least a portion of the surface of a copper member. The copper member contains Cu as a main component, which becomes part of the structure. Specific examples of the copper member include, but are not limited to, copper foils such as electrolytic copper foil, rolled copper foil, and copper foil with a carrier, copper wire, copper plate, and copper lead frames. The copper member is preferably made of pure copper with a Cu purity of 99.9% by mass or more, more preferably made of tough pitch copper, deoxidized copper, or oxygen-free copper, and even more preferably made of oxygen-free copper with an oxygen content of 0.001% by mass to 0.0005% by mass.

[0017] When the copper member is a copper foil, its thickness is not particularly limited, but is preferably 0.1 μm or more and 100 μm or less, and more preferably 0.5 μm or more and 50 μm or less.

[0018] The copper oxide-containing layer is formed on the surface of a copper member and contains copper oxide (CuO) and / or cuprous oxide (CuO). This copper oxide-containing layer can be formed by oxidizing the surface of the copper member. This oxidation treatment roughens the surface of the copper member. The copper oxide-containing layer may be treated with a dissolving solution to adjust the protrusions on the oxidized surface of the copper member. The surface of the copper oxide-containing layer may also be reduced with a reducing agent, in which case cuprous oxide may be formed on the surface of the copper oxide-containing layer.

[0019] The resistivity of pure copper is 1.7 x 10 -8 (Ωm), whereas copper oxide is 1 to 10 (Ωm) , and cuprous oxide is 1×10 6 ~1×10 7 (Ωm), the layer containing copper oxide has low conductivity, and even if the amount of the layer containing copper oxide transferred to the resin substrate is large, transmission loss due to the skin effect is unlikely to occur when a circuit for a printed wiring board or a semiconductor package substrate is formed using the composite copper member according to the present invention.

[0020] The copper oxide-containing layer may contain a metal other than copper. The metal contained is not particularly limited, but may contain at least one metal selected from the group consisting of Sn, Ag, Zn, Al, Ti, Bi, Cr, Fe, Co, Ni, Pd, Au, and Pt. In particular, to provide acid resistance and heat resistance, it is preferable to contain a metal that is more acid-resistant and heat-resistant than copper, such as Ni, Pd, Au, and Pt.

[0021] Metals other than copper may be formed on the outermost surface of the copper member by plating. The plating method is not particularly limited, and examples include electrolytic plating, electroless plating, vacuum deposition, and chemical conversion treatment. However, electrolytic plating is preferred because it is preferable to form a uniform and thin plating layer. When electrolytic plating is performed on an oxidation-treated copper foil surface, the copper oxide on the surface is first reduced to cuprous oxide or pure copper, and an electric charge is used to convert it into pure copper. This results in a time lag before plating, after which the metal that forms the metal layer begins to precipitate. The amount of electric charge varies depending on the type of plating solution and the amount of copper oxide. For example, when applying Ni plating to a copper member, in order to keep the plating thickness within a preferred range, the area dm of the copper member to be electrolytically plated is required to be 1000 m / s. 2 It is preferable to apply a charge of 10 C or more and 90 C or less, and more preferable to apply a charge of 20 C or more and 65 C or less per charge.

[0022] The average thickness in the vertical direction of the metal 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, but is preferably 80 nm or less, more preferably 70 nm or less, or more preferably 60 nm or less.

[0023] The average vertical thickness of the metals other than copper contained in the copper oxide-containing layer can be calculated by dissolving the copper oxide-containing layer in an acidic solution, measuring the amount of metal by ICP analysis, and dividing the amount by the area of ​​the composite copper member. Alternatively, it can be calculated by dissolving the composite copper member itself and measuring the amount of metal only contained in the copper oxide-containing layer.

[0024] When the surface of a composite copper part on which a copper oxide-containing layer is formed is thermally press-fitted to a resin substrate, the surface profile of the composite copper part is transferred to the resin substrate. Then, when the composite copper part is peeled off from the resin substrate after thermal press-fitting, the metal contained in the copper oxide-containing layer adheres (transfers) to the resin substrate. One embodiment of a composite copper part is illustrated in FIG.

[0025] The resin substrate is a material containing resin as a primary component and can be used to form circuits such as printed wiring boards and semiconductor package substrates. The resin is not particularly limited, but may be a thermoplastic resin or a thermosetting resin, and is preferably polyphenylene ether (PPE), epoxy, polyphenylene oxide (PPO), polybenzoxazole (PBO), polytetrafluoroethylene (PTFE), liquid crystal polymer (LCP), thermoplastic polyimide (TPI), fluororesin, polyetherimide, polyetheretherketone, polycycloolefin, bismaleimide resin, low-dielectric-constant polyimide, cyanate resin, or a mixture thereof. The resin substrate may further contain inorganic fillers or glass fibers. The relative dielectric constant of the insulating substrate layer used is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.8 or less.

[0026] To thermocompression bond a resin substrate to the surface of a composite copper member, for example, the resin substrate and the composite copper member are laminated in close contact with each other, and then treated under predetermined conditions to bond the resin substrate and the composite copper member. The predetermined conditions (temperature, pressure, time) may be those recommended by each substrate manufacturer. Examples of the predetermined conditions include the following:

[0027] 1) When the resin substrate contains or is made of an epoxy resin, it is preferable to thermocompression bond the composite copper member to the resin substrate by applying a pressure of 0 to 20 MPa at a temperature of 50°C to 300°C for 1 minute to 5 hours.

[0028] for example, 1-1) If the resin substrate is R-1551 (manufactured by Panasonic), heat it under a pressure of 1 MPa, and after it reaches 100°C, hold it at that temperature for 5 to 10 minutes. Then, heat it further under a pressure of 3.3 MPa, and after it reaches 170 to 180°C, hold it at that temperature for 50 minutes to achieve thermocompression bonding.

[0029] 1-2) If the resin substrate is R-1410A (manufactured by Panasonic), heat it under a pressure of 1 MPa, and after it reaches 130°C, hold it at that temperature for 10 minutes. Then, heat it further under a pressure of 2.9 MPa, and after it reaches 200°C, hold it at that temperature for 70 minutes to achieve thermocompression bonding.

[0030] 1-3) If the resin substrate is EM-285 (manufactured by EMC), heat it under a pressure of 0.4 MPa, and after it reaches 100°C, increase the pressure to 2.4 to 2.9 MPa and heat it further. After it reaches 195°C, hold it at that temperature for 50 minutes to perform thermocompression bonding.

[0031] 1-4) When the resin substrate is GX13 (manufactured by Ajinomoto Fine-Techno), it is heated under pressure of 1.0 MPa and held at 180°C for 60 minutes to perform thermocompression bonding.

[0032] 2) When the resin substrate contains or consists of PPE resin, it is preferable to thermocompression bond the composite copper member to the resin substrate by applying a pressure of 0 to 20 MPa at a temperature of 50°C to 350°C for 1 minute to 5 hours.

[0033] for example, 2-1) If the resin substrate is R5620 (manufactured by Panasonic), it is thermocompression bonded by heating under a pressure of 0.5 MPa until the temperature reaches 100°C, and then the temperature and pressure are increased to 2.0 to 3.0 MPa and 200 to 210°C, and the substrate is held for 120 minutes for further thermocompression bonding.

[0034] 2-2) If the resin substrate is R5670 (manufactured by Panasonic), it is thermocompression bonded by heating it under a pressure of 0.49 MPa until it reaches 110°C, and then the temperature and pressure are increased to 2.94 MPa and 210°C, and the thermocompression bond is carried out by holding for 120 minutes.

[0035] 2-3) If the resin substrate is R5680 (manufactured by Panasonic), it is thermocompression bonded by heating it under a pressure of 0.5 MPa until it reaches 110°C, and then the temperature and pressure are increased to 3.0 to 4.0 MPa and 195°C, and the thermocompression bonding is carried out by holding for 75 minutes.

[0036] 2-4) If the resin substrate is N-22 (manufactured by Nelco), it is heated under pressure of 1.6 to 2.3 MPa, held at 177°C for 30 minutes, and then further heated and held at 216°C for 60 minutes to perform thermocompression bonding.

[0037] 3) When the resin substrate contains or is made of PTFE resin, it is preferable to heat-pressure bond the composite copper member to the resin substrate by applying a pressure of 0 to 20 MPa at a temperature of 50°C to 400°C for 1 minute to 5 hours.

[0038] for example, 3-1) If the resin substrate is NX9255 (manufactured by Park Electrochemical), heat it to 260°C while pressurizing it at 0.69 MPa, then increase the pressure to 1.03 to 1.72 MPa and heat it to 385°C, and hold it at 385°C for 10 minutes to perform thermocompression bonding.

[0039] 3-2) If the resin substrate is RO3003 (manufactured by Rogers), after 50 minutes from the start of pressing (approximately 220°C), the material is pressurized to 2.4 MPa and held at 371°C for 30 to 60 minutes to achieve thermocompression bonding.

[0040] The conditions for peeling the copper member from the resin substrate are not particularly limited, but can be based on a 90° peel test (Japanese Industrial Standard (JIS) C5016 "Test methods for flexible printed wiring boards"; corresponding international standards IEC249-1:1982, IEC326-2:1990).

[0041] After the copper member is peeled off, the metal contained in the copper oxide-containing layer is transferred to the resin substrate. The metal transferred to the surface of the resin substrate after the copper member is peeled off can be detected using various methods (for example, X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDS), and ICP optical emission spectroscopy (inductively coupled plasma optical emission spectroscopy, ICP-OES / ICP-AES)).

[0042] XPS is a method of irradiating an object with X-rays, and ionizing the object to release photoelectrons e -XPS is a technique for energy analysis by capturing electrons. It is possible to investigate the type, abundance, and chemical bonding state of elements present on the sample surface or to a specified depth from the surface (for example, up to a depth of 6 nm). The analysis spot diameter (i.e., the diameter of the cross section when an analyzable cylindrical part is cut so that the cross section is circular) should be between 1 μm and 1 mm.

[0043] The metal contained in the copper oxide-containing layer is preferably transferred to the resin substrate in such a way that it fills at least 80%, 90%, 95%, 99%, or 99.9% of the recesses in the transferred surface profile. In this case, when the resin substrate surface is measured using XPS, which performs elemental analysis of the sample surface, the sum 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 C1s spectrum. While metal elements have multiple peaks, the main peaks referred to here refer to the main peaks of each metal element. For example, the main peaks are the 2p3 orbital for Cu, the 3d5 orbital for Sn, the 3d5 orbital for Ag, the 2p3 orbital for Zn, the 2p7 orbital for Al, the 2p3 orbital for Ti, the 4f7 orbital for Bi, the 2p3 orbital for Cr, the 2p3 orbital for Fe, the 2p3 orbital for Co, the 2p3 orbital for Ni, the 3d5 orbital for Pd, the 4f7 orbital for Au, and the 4f7 orbital for Pt. The intensity of the spectral peak referred to here is the height of the vertical axis of the XPS spectral data shown in FIG.

[0044] Regarding the amount of metal contained in the copper oxide-containing layer, the ratio of Cu2p3 to all surface atoms on the surface of the resin substrate from which the copper member has been peeled, 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 member after transfer is measured by XPS, the ratio of the surface atomic composition percentage of Cu2p3 to 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.

[0045] When the copper oxide-containing layer contains a metal other than copper, the total surface atomic composition percentage of metal atoms (copper atoms and atoms of metals other than copper) on the surface of the 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 metals other than copper) to 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.

[0046] It is preferable that no organic matter derived from the resin substrate is detected on the surface of the copper member peeled from the resin substrate, or even if it is detected, it is only in a small amount. This indicates that no breakage occurs on the resin substrate side during peeling. The method for detecting organic matter derived from the resin substrate is not particularly limited, but can be performed, for example, by detecting peaks derived from the resin substrate using attenuated total reflection absorption Fourier transform infrared spectroscopy (FT-IR method).

[0047] The FT-IR method is an infrared spectroscopy method in which infrared light is irradiated onto a substance to be measured and the compounds are identified and / or quantified using the infrared absorption spectrum. In the present invention, it can be used to detect organic substances derived from resin substrates.

[0048] The peaks derived from resin substrates are illustrated in "Infrared and Raman Spectroscopy: Principles and Spectral Interpretation" by Peter Larkin. Wavelength range: 700-4000 cm -1 In the above, the S / N ratio is preferably 10 or less, more preferably 9 or less, and even more preferably 8 or less, more preferably 7 or less, and it is preferable that no peak derived from the resin substrate is detected.

[0049] The arithmetic mean roughness (Ra) of the surface of the composite copper member on which the copper oxide-containing layer is formed is preferably 0.03 μm or more, more preferably 0.05 μm or more, and is preferably 0.3 μm or less, more preferably 0.2 μm or less.

[0050] The surface roughness in maximum height (Rz) of the composite copper member on which the copper oxide-containing layer is formed 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.

[0051] 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 formability and high frequency characteristics will be poor.

[0052] Here, the arithmetic mean roughness (Ra) represents the average absolute value of Z(x) (i.e., the height of peaks and the depth of valleys) in the profile curve (y=Z(x)) expressed by the following formula over a reference length l.

number

[0053] The maximum height roughness (Rz) represents the sum of the maximum peak height Zp and the maximum valley depth Zv of the profile curve (y = Z(x)) over the reference length l.

[0054] Ra and Rz can be calculated using the method specified in JIS B 0601:2001 (based on the international standard ISO4287-1997).

[0055] The ratio of Ra after peeling to Ra before thermocompression bonding on the surface of the composite copper member on which the copper oxide-containing layer is formed 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 this ratio, the more the metal forming the copper oxide-containing layer is transferred to the resin substrate.

[0056] The ratio of the surface area of ​​the composite copper member having the copper oxide-containing layer formed thereon to the surface area before thermocompression bonding after peeling 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, the more the metal forming the copper oxide-containing layer is transferred to the resin substrate. The surface area can be measured using a confocal microscope or an atomic force microscope.

[0057] In one embodiment of the present invention, the average length (RSm) of the roughness curve element of the surface of the composite copper member having a copper oxide-containing layer formed thereon is not particularly limited, but 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. Here, RSm represents the average length of one cycle of unevenness in the roughness curve over a certain reference length (lr) (i.e., the length of the profile curve element: Xs1 to Xsm), and is calculated using the following formula:

number

[0058] Here, the minimum height of the irregularities is defined as 10% of the arithmetic mean roughness (Ra), and the minimum length is defined as 1% of the reference length (lr).As an example, RSm can be measured and calculated in accordance with the "Method for measuring surface roughness of fine ceramic thin films using an atomic force microscope (JIS R 1683:2007)."

[0059] ΔE of the surface of the composite copper part before thermocompression bonding and the surface of the copper part after peeling *It is preferable that ab is 13 or more, 15 or more, 20 or more, 25 or more, 30 or more, or 35 or more. The larger this difference is, the more the metal forming the copper oxide-containing layer (i.e., the metal forming the unevenness) has been transferred to the resin substrate.

[0060] ==Method of manufacturing composite copper components== One embodiment of the present invention is a method for manufacturing a composite copper component, comprising the step of facilitating fracture of a layer comprising copper oxide from the copper component.

[0061] In this process, the method for making the copper oxide-containing layer more easily ruptured from the copper member is not particularly limited, but may include 1) partially coating the surface of the copper member with a coating agent such as a silane coupling agent or a rust inhibitor before the oxidation treatment, or 2) treating the copper oxide-containing layer with Ni chloride after the oxidation treatment.

[0062] 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, and for example, an aqueous solution of sodium chlorite, sodium hypochlorite, potassium chlorate, potassium perchlorate, or the like can be used. Various additives (for example, phosphates such as trisodium phosphate dodecahydrate) may be added to the oxidizing agent.

[0063] 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.

[0064] Before the oxidation treatment, degreasing treatment, removal of natural oxide films, and acid washing for uniform treatment may be performed, or after the acid washing, alkali treatment may be performed to prevent the acid from being carried over into the oxidation step. The alkali treatment method is not particularly limited, but it is preferable to treat with a 0.1 to 10 g / L, more preferably a 1 to 2 g / L, aqueous alkali solution, such as a sodium hydroxide solution, at 30 to 50°C for about 0.5 to 2 minutes.

[0065] Alternatively, the layer containing copper oxide may be dissolved with a dissolving chemical to adjust the protrusions on the surface of the copper member, or the copper oxide in the layer containing copper oxide may be reduced with a reducing chemical.

[0066] The dissolving solution is not particularly limited, but a chelating agent, particularly a biodegradable chelating agent, is preferred. Examples of the dissolving solution include solutions of 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 aspartate diacetate, disodium N-(2-hydroxyethyl)iminodiacetate, and sodium gluconate.

[0067] Examples of the reducing chemical solution include solutions of reducing agents such as DMAB (dimethylamine borane), diborane, sodium borohydride, and hydrazine, and alkaline compounds (for example, sodium hydroxide, potassium hydroxide, etc.).

[0068] A layer containing a metal other than copper may be formed on the 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. Known plating techniques can be used, and examples of metals other than copper that can be used include Sn, Ag, Zn, Al, Ti, Bi, Cr, Fe, Co, Ni, Pd, Au, Pt, and various alloys. The plating process is also not particularly limited, and plating can be performed by electroplating, electroless plating, vacuum deposition, chemical conversion treatment, etc., but electroplating is preferred because it is preferable to form a uniform and thin plating layer.

[0069] 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.

[0070] Examples of metal salts used for plating include nickel sulfate, nickel sulfamate, nickel chloride, nickel bromide, zinc oxide, zinc chloride, diamminedichloropalladium, iron sulfate, iron chloride, chromic anhydride, chromium chloride, sodium chromium sulfate, copper sulfate, copper pyrophosphate, cobalt sulfate, and manganese sulfate.

[0071] In nickel plating, the bath composition preferably contains, for example, nickel sulfate (100 g / L or more and 350 g / L or less), nickel sulfamate (100 g / L or more and 600 g / L or less), nickel chloride (0 g / L or more and 300 g / L or less), or a mixture thereof, but may also contain additives such as 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).

[0072] In the case of electroless nickel plating, electroless plating using a catalyst is preferred. The catalyst preferably used is iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, or a salt thereof. By performing electroless plating using a catalyst, a uniform metal layer without scattered particles can be obtained, thereby improving the heat resistance of the composite copper member.

[0073] One embodiment of the method for producing a composite copper member of the present invention includes: 1) a step of partially coating the surface of a copper member with a silane coupling agent or a rust inhibitor; and 2) a step of forming a layer containing copper oxide by oxidizing the partially coated surface of the copper member; or a method for producing a composite copper member including: 1) a step of partially coating the surface of a copper member with a silane coupling agent or a rust inhibitor; 2) a step of forming a layer containing copper oxide by oxidizing the surface of the partially coated copper member; and 3) a step of forming a layer containing a metal other than copper on the surface of the composite copper member on which the layer containing copper oxide has been formed.

[0074] By partially coating the surface of a copper member with a coating agent such as a silane coupling agent or a rust inhibitor, that portion is prevented from being subjected to oxidation treatment, and voids are generated in the layer containing copper oxide, making the layer containing copper oxide more likely to break away from the copper member.

[0075] The silane coupling agent is not particularly limited, but examples thereof include silane, tetraorgano-silane, aminoethyl-aminopropyl-trimethoxysilane, (3-aminopropyl)trimethoxysilane, (1-[3-(trimethoxysilyl)propyl]urea), (3-aminopropyl)triethoxysilane, ((3-glycidyloxypropyl)trimethoxysilane), (3-chloropropyl)trimethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, The silane may be selected from (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.

[0076] The rust inhibitor is not particularly limited, but examples thereof include 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, and 2-ethylpyrrole. The benzothiazole may be selected from the group consisting of benzothiazole, 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.

[0077] The treatment with a silane coupling agent or a rust inhibitor may be carried out at any time before the oxidation treatment, and may be carried out together with a degreasing treatment, an acid wash for removing a natural oxide film and achieving a uniform treatment, or an alkali treatment after the acid wash for preventing the introduction of acid into the oxidation step.

[0078] The treatment with the silane coupling agent or rust inhibitor is preferably carried out to coat only a portion of the copper surface (e.g., 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% or more, but less than 100%), and for this purpose, it is preferable to react the agent at a concentration of 0.1%, 0.5%, 1%, or 2% or more at room temperature for 30 seconds, 1 minute, or 2 minutes or more.

[0079] One embodiment of the method for producing a composite copper member of the present invention comprises: 1) a step of forming a layer containing copper oxide by oxidizing the surface of a copper member; and 2) a step of treating the surface of the copper member on which the layer containing copper oxide has been formed with a solvent; or a method for producing a composite copper member comprising: 1) a step of forming a layer containing copper oxide by oxidizing the surface of a copper member; 2) a step of treating the surface of the copper member on which the layer containing copper oxide has been formed with a solvent; and 3) a step of forming a layer containing a metal other than copper on the surface of the composite copper member on which the layer containing copper oxide has been formed and which has been treated with the solvent.

[0080] It is believed that treatment with a solvent partially dissolves copper oxide near the interface between the copper member and the layer containing copper oxide, making it easier for the layer containing copper oxide to break away from the copper member.

[0081] The dissolving agent for facilitating the fracture of the copper oxide-containing layer from the copper member need only contain a component that dissolves copper oxide, and is not limited to Ni chloride. It may be selected from chlorides (potassium chloride, zinc chloride, iron chloride, chromium chloride, etc.), ammonium salts (ammonium citrate, ammonium sulfate, ammonium chloride, nickel ammonium sulfate, etc.), chelating agents (ethylenediaminetetraacetic acid, diethanolglycine, tetrasodium L-glutamate diacetate, ethylenediamine-N,N'-disuccinic acid, sodium 3-hydroxy-2,2'-iminodisuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, disodium N-(2-hydroxyethyl)iminodiacetate, sodium gluconate, etc.), tin(II) chloride, and citric acid.

[0082] When treating with Ni chloride, although not particularly limited, it is preferable to immerse the copper member on which the copper oxide-containing layer has been formed in a Ni chloride solution (concentration of 45 g / L or more) at room temperature or a temperature higher than room temperature for 5 seconds or more. Furthermore, instead of treating with Ni chloride alone, the treatment may be performed simultaneously with oxidation treatment, or after oxidation treatment, simultaneously with plating treatment. For example, Ni chloride may be added to the plating solution, and the copper member on which the copper oxide-containing layer has been formed may be immersed in the plating solution for 5, 10, 15, 20, 30 seconds, 1 minute, or 2 minutes before plating. The immersion time can be adjusted as appropriate depending on the thickness of the oxide film.

[0083] ==How to use composite copper parts== The composite copper member according to the present invention is (1) Pressing onto a resin substrate to produce a laminate; (2) Pressing the metal film onto a resin substrate and peeling it off to obtain a resin substrate having a part or all of the metal forming the copper oxide-containing layer; (3) In the SAP method or MSAP method, a printed wiring board is produced by pressing a resin substrate and peeling it off to obtain a resin substrate having all or part of the metal that forms the copper oxide-containing layer, and then copper plating the peeled surface of the resin substrate; It can be used for the following purposes: In (1) to (3), the resin substrate and the method of thermocompression bonding to the resin substrate may be the same as or different from the conditions used in measuring the X-ray photoelectron spectroscopy spectrum. In (2) and (3), the peeling method may be the same as or different from the conditions used in measuring the X-ray photoelectron spectroscopy spectrum. In (3), the copper plating method may be electrolytic plating or electroless plating.

[0084] ==Composite copper component manufacturing system== <Major components of the manufacturing system> One embodiment of the manufacturing system for a composite copper member of the present invention is a first manufacturing system having a first device for partially coating the surface of the copper member with a silane coupling agent or a rust inhibitor and a second device for oxidizing the partially coated surface to form a layer containing copper oxide. The first and second devices may have a first and second tanks for treating the copper member. As an example, Figure 10 shows a schematic diagram of the first manufacturing system using a roll-to-roll transport system. However, the copper member may be transported between the tanks by any method other than a roll-to-roll transport system, such as manually or by a conveyor such as a belt conveyor.

[0085] Here, the method of partially coating the surface of a copper member with a silane coupling agent or a rust inhibitor using a first device, and the method of forming a layer containing copper oxide by oxidizing the partially coated surface using a second device are as described in the section "Composite Copper Member."

[0086] In the first manufacturing system, a layer containing a metal other than copper may be formed on the oxidized surface. The formation of the layer containing a metal other than copper is performed using a third apparatus. The third apparatus may have a third tank for treating the copper member.

[0087] Here, the method for forming a layer containing a metal other than copper on the oxidized surface using the third apparatus is as described in the section "Composite copper member." When forming a layer containing a metal other than copper by electroplating, the third apparatus may be provided with electrodes and a power supply for electroplating.

[0088] This first manufacturing system may further include a thermocompression bonding device for thermocompression bonding a resin substrate onto a layer containing copper oxide or a layer containing a metal other than copper of a copper member, and a peeling device for peeling the copper member from the resin substrate to obtain a resin substrate having some or all of the metal that forms the layer containing copper oxide.

[0089] Another embodiment of the composite copper component manufacturing system of the present invention is a second manufacturing system having a fourth apparatus for oxidizing the surface of the copper component to form a layer containing copper oxide on the surface of the copper component, and a fifth apparatus for treating the oxidized surface with a dissolving agent. The fourth and fifth apparatuses may have fourth and fifth tanks for treating the copper component. As an example, FIG. 11 shows a schematic diagram of the second manufacturing system using a roll-to-roll transport system. However, the copper component may be transported between the tanks by any method other than the roll-to-roll transport system, such as manually or by a conveyor such as a belt conveyor.

[0090] Here, the method of forming a layer containing copper oxide on the surface of a copper member using the fourth device and the method of treating the oxidized surface with a dissolving agent using the fifth device are as described in the section "Composite copper member."

[0091] In the second manufacturing system, a layer containing a metal other than copper may be formed on the surface treated with the dissolving agent. The formation of this layer containing a metal other than copper may be performed in a fifth apparatus, or a sixth apparatus separate from the fifth apparatus may be provided and the layer containing a metal other than copper may be formed using the sixth apparatus. The sixth apparatus may have a sixth tank for treating the copper member.

[0092] Here, the method of forming a layer containing a metal other than copper on the oxidation-treated surface using the fifth or sixth apparatus is as described in the section "Composite copper member." When forming a layer containing a metal other than copper by electroplating, electrodes and a power supply for electroplating may be provided in the sixth apparatus if the sixth apparatus is provided, or in the fifth apparatus if the sixth apparatus is not provided.

[0093] This second manufacturing system may further include a thermocompression bonding device for thermocompression bonding a resin substrate onto the surface of the copper member treated with a solvent or onto a layer containing a metal other than copper, and a peeling device for peeling the copper member from the resin substrate to obtain a resin substrate having some or all of the metal that forms the layer containing copper oxide.

[0094] In the first manufacturing system and the second manufacturing system, the method of thermocompression bonding using an apparatus for thermocompression bonding a resin substrate to a composite copper member, and the method of peeling using an apparatus for peeling a copper member from a resin substrate are as described in the section "Composite copper member."

[0095] The first and second manufacturing systems may further include an apparatus for performing a copper plating process on the surface of the resin substrate having a part or all of the metal that forms the layer containing copper oxide.

[0096] Here, the method of plating using the apparatus for copper plating the surface of the resin substrate is as described in the section "Method of using the composite copper member."

[0097] <Other components of the manufacturing system> Each device may have one or more first to sixth tanks. One or more washing tanks may be provided between each device and / or at the beginning and end of the entire process. The water in the washing tank may be heated to the same temperature as or close to the temperature of the preceding and following tanks, thereby preventing wrinkles due to differences in thermal expansion.

[0098] Each device is preferably equipped with a heating unit and a timer, which allow the temperature and time of processing in each device to be set.

[0099] When copper members are processed continuously, such as in a roll-to-roll transport system, electricity is applied to the copper members for electrolytic plating from a current-carrying unit provided on the roll. This current-carrying unit is provided so that the longitudinal direction of the electrode is parallel to the width direction of the roll. The current-carrying unit is not limited to being located immediately before or after the bath for electrolytic plating treatment, but may also be provided on the roll of another bath. The ratio of the width of the current-carrying part to the width of the copper member, i.e., the length in the longitudinal direction, is preferably 0.8 or more, more preferably 0.9 or more, and even more preferably 1.0 or more. If the width of the current-carrying part is much narrower than the width of the copper member, electrolytic plating will be insufficient at the end of the copper member that is distant from the current-carrying part, and the plating effect will not be exerted.

[0100] The solution used in each tank may be stored in the tank and the copper surface may be immersed in the solution, or may be sprayed onto the copper surface using a shower device attached to the tank. When the solution is stored in the tank, it is preferable to provide a liquid circulation device for the tank. This can reduce unevenness in the treatment caused by the solution.

[0101] The manufacturing system may be provided with a drying device for drying the copper member after all processes have been completed. The drying temperature is not particularly limited, but the copper surface may be dried at room temperature to about 230°C. [Example]

[0102] <1. Manufacturing of composite copper foil> In Examples 1 to 9 and Comparative Examples 2 and 3, the shiny side (the glossy side, the side that is flat compared to the opposite side) of copper foil (DR-WS, thickness: 18 μm) manufactured by Furukawa Electric Co., Ltd. was used. In Comparative Example 4, the matte side of copper foil (FV-WS, thickness: 18 μm) manufactured by Furukawa Electric Co., Ltd. was used as the test piece without any treatment.

[0103] (1) Pretreatment First, the copper foil was immersed in the following solution at 25°C for 1 minute. In Examples 1 and 2, potassium carbonate was used at 2.5 g / L; KBE-903 (3-aminopropyltriethoxysilane; manufactured by Shin-Etsu Silicone Co., Ltd.) was used at 1 vol %; Example 3 contains potassium carbonate 2.5 g / L; potassium bicarbonate 0.06 g / L; In Examples 4 to 6, potassium hydroxide was used at 5 g / L, Example 7 contains 5 g / L of potassium hydroxide; 5 vol% of KBM-603 (N-2-(aminoethyl)-3-aminopropyltrimethoxysilane; manufactured by Shin-Etsu Silicone Co., Ltd.); Example 8 contains potassium hydroxide 5 g / L; BTA (benzotriazole) 1 wt %; Comparative Example 2 is a solution of potassium carbonate 2.5 g / L, Comparative Example 3 is a solution of potassium carbonate 2.5 g / L; potassium bicarbonate 0.06 g / L; was used.

[0104] (2) Oxidation treatment The pretreated copper foil was immersed in an oxidizing agent to carry out an oxidation treatment. In Examples 1, 2, 7, and 8 and Comparative Example 2, a solution of sodium chlorite 58.3 g / L, potassium hydroxide 20 g / L, and potassium carbonate 39.1 g / L was used as the oxidizing agent. 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 Silicones Co., Ltd.) was used as the oxidizing agent. In Comparative Example 3, 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 Silicones Co., Ltd.) was used as the oxidizing agent. Examples 1, 2, 7, and 8 were immersed in the oxidizing agent at 73°C for 6 minutes, and Examples 3 to 6 and Comparative Examples 2 and 3 were immersed in the oxidizing agent at 73°C for 2 minutes.

[0105] (3) Plating pretreatment After the oxidation treatment, in Examples 4 to 6, a pre-plating treatment was carried out using a dissolving agent as follows. In Example 4, the sample was treated with a solution of 45 g / L tin(II) chloride dihydrate and 1 mL / L hydrochloric acid at 45°C for 10 seconds. In Example 5, the sample was treated with a 45 g / L solution of ammonium chloride at 45° C. for 60 seconds. In Example 6, the sample was treated with 5 mL / L of 50% citric acid solution at 45° C. for 60 seconds.

[0106] (4) Electroplating After the oxidation treatment, in Examples 2 and 3 and Comparative Example 3, electroplating was performed using a first Ni electroplating solution (nickel sulfate 240 g / L; nickel chloride 45 g / L; sodium citrate 20 g / L). In Examples 4 to 7, after plating pretreatment, electroplating was performed using a second Ni electroplating solution (nickel sulfate 240 g / L; sodium citrate 20 g / L). In Example 3, the plate was immersed in the Ni electroplating solution for 1 minute before electroplating. The plate was immersed in the Ni electroplating solution at 50°C with a current density of 0.5 A / dm 2 ×45 seconds (=22.5C / dm 2 Electrolytic plating was performed on the copper foil area.

[0107] For each of 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. [Table 1]

[0108] Here, for Example 3, composite copper foils were produced by changing the width of the current-carrying portion during electrolytic plating. The composite copper foil was divided into 12 equal sections widthwise and dissolved in 12% nitric acid. The solution was then measured for the amount of plated metal at each measurement point using an ICP-OES 5100 SVDV (Agilent Technologies). The highest measured metal amount was assigned a value of 100, and the percentage of measurement points with a metal amount ratio of 70 or greater was calculated. Measurement points with a metal amount ratio of 70 or greater were assigned a ○ if 70% or greater of all measurement points were satisfied, a △ if 40% to 70% were satisfied, and an × if less than 40% were satisfied. As a result, as shown in Table 2, the amount of plated metal was 40% or greater when the ratio of the width of the conductive portion to the width of the copper member was 0.8 or greater, and 70% or greater when 1.0 or greater. [Table 2]

[0109] <2. Pressing and peeling of resin substrate> (1) Method For the test specimens of Examples 1 to 8 and Comparative Examples 2 to 4, peel tests of the resin substrate were performed using R5670KJ (manufactured by Panasonic), R5680J (manufactured by Panasonic), CT-Z (manufactured by Kuraray), NX9255 (manufactured by Park Electrochemical), and R1551GG (manufactured by Panasonic) as prepregs.

[0110] First, a prepreg was laminated onto the test piece and thermocompression-bonded in a vacuum using a vacuum high-pressure press to obtain a laminate sample. When the resin substrate was R5670KJ (Panasonic), the test piece was thermocompression-bonded under a pressure of 0.49 MPa until the temperature reached 110°C. The temperature and pressure were then increased to 2.94 MPa and 210°C for 120 minutes. When the resin substrate was R5680J (Panasonic), the test piece was thermocompression-bonded under a pressure of 0.5 MPa until the temperature reached 110°C. The temperature and pressure were then increased to 3.5 MPa and 195°C for 75 minutes. When the resin substrate was NX9255 (Park Electrochemical), the test piece was thermocompression-bonded under a pressure of 0.69 MPa until the temperature reached 260°C, then increased to 1.5 MPa and heated to 385°C, and held at 385°C for 10 minutes. When the resin substrate was R1551GG (Panasonic), the samples were heated under 1 MPa pressure, reached 100°C, and held at that temperature for 10 minutes. Then, the samples were further heated under 3.3 MPa pressure, reached 180°C, and held at that temperature for 50 minutes. When the resin substrate was CT-Z (Kuraray), the samples were heated under 0 MPa pressure, held at 260°C for 15 minutes, and then further heated under 4 MPa pressure and held at 300°C for 10 minutes. The copper components were peeled from the resin substrate using these laminate samples according to the 90° peel test (Japanese Industrial Standard (JIS) C5016) (Figure 1). Visual observation results are shown in Figure 2-1. Photographs of the resin and copper foil surfaces after peeling are shown in Figure 2-2 for a representative combination.

[0111] 2, it is easy to observe that the copper foil surface has been transferred to the resin side in the example, whereas the copper foil surface has not been transferred to the resin side in the comparative example. To prove this as a substance, the following surface analysis was performed.

[0112] <3. Surface analysis of resin substrate after peeling> After peeling, the surface of the resin substrate was subjected to elemental analysis. Specifically, the obtained resin substrate was analyzed using a QuanteraSXM (manufactured by ULVAC-PHI) under the following conditions. As a negative control, an untreated resin substrate (R5670KJ; MEGTRON6) was analyzed (Comparative Example 1). (1) Survey spectrum First, elements were detected under the following conditions. X-ray light source: Monochromatic Al Kα (1486.6eV) X-ray beam diameter: 100μm (25w15kV) Pass energy: 280 eV, 1 eV step Point analysis: φ100μm Accumulation count: 8 times

[0113] (2) Results The results are shown in Table 3 and FIG. In the Examples, the peak intensity of the Cu2p3 spectrum derived from the transferred copper atoms was greater than the peak intensity of the C1s spectrum derived from the resin substrate, whereas in the Comparative Examples, the Cu2p3 spectrum peak was not detected or its intensity was smaller than the peak intensity of the C1s spectrum. This indicates that in the Comparative Examples, almost no copper atoms were transferred to the resin substrate or that almost no copper atoms were present in the surface layer of the resin substrate that could be detected by XPS.

[0114] In Example 1, the composite copper foil was not plated, so only Cu atoms were transferred and detected on the resin substrate side. In Examples 2 and 3, the composite copper foil was plated with Ni, so both Cu and Ni atoms were transferred and detected on the resin side.

[0115] Furthermore, the proportion of C1s was smaller in all of the Examples than in the Comparative Examples. It is believed that in the Examples, the proportion of C1s on the surface became relatively smaller due to the transfer of copper oxide or cuprous oxide. [Table 3]

[0116] <4. Measurement of Ra and surface area of ​​composite copper foil before thermocompression bonding and after peeling> (1) Method The surface areas of the composite copper foil test pieces of Examples 1 to 8 and Comparative Examples 2 to 4 before thermocompression bonding and after peeling were calculated using a confocal microscope, OPTELICS H1200 (manufactured by Lasertec Corporation). The measurement conditions were confocal mode, scan area 100 μm × 100 μm, light source Blue, and cutoff value 1 / 5. The object lens was set to x100, contact lens to x14, digital zoom to x1, and Z pitch to 10 nm. Data was obtained at three locations, and the surface area was calculated as the average value of the three locations.

[0117] (2) Results As shown in Table 4, before and after thermocompression bonding, Ra and surface area decreased in the Examples, whereas they increased in the Comparative Examples. This indicates that in the Examples, all or part of the protrusions of the composite copper part were transferred to the resin side, whereas in the Comparative Examples, part of the resin was transferred to the composite copper part. [Table 4]

[0118] <5. ΔE of composite copper foil before thermocompression bonding and after peeling * Calculation of ab> (1) Method The color difference (L * , a * , b * ) and calculate ΔE from the obtained value according to the following formula: * ab was calculated. ΔE * ab = [(ΔL * ) 2 + (Δa * ) 2 + (Δb * ) 2 ] 1 / 2

[0119] (2) Results As shown in Table 5, in the examples, ΔE * While ab was 15 or more, it was less than 15 in the comparative example. This is because in the example, the metal contained in the copper oxide-containing layer was transferred to the resin substrate, resulting in a significant color change in the copper member, whereas in the comparative example, the copper oxide-containing layer remained intact on the copper member, resulting in a smaller color change in the copper member. Therefore, the more metal contained in the copper oxide-containing layer was transferred, the greater the difference. In fact, in the photograph of Figure 2, after peeling, the resin side was significantly colored in the example, while the resin side remained almost white in the comparative example. [Table 5]

[0120] 5. Analysis of the Composite Copper Foil Surface After Transfer Using Attenuated Total Reflection / Absorption Fourier Transform Infrared Spectroscopy (FT-IR / ATR Method) (1) Method The resin substrates were R1551GG (epoxy-based), R5670KJ, R5680J (all PPE-based), NX9255 (PTFE-based), or CT-Z (LCP-based), and the composite copper component specimens were thermocompression bonded and then peeled off. The specimens were analyzed using the FT-IR / ATR method under the following measurement conditions. Measurement conditions Parkin Elmer Specrtum100 ATR method Crystal: Germanium Resolution: 4 Number of scans: 4 Pressure (force gauge): 40±5 [N] Spectral display: absorbance

[0121] (2) Calculation of S / N (signal / noise) ratio After heating and pressurizing only the resin substrate under the same conditions as when thermocompression bonding with the composite copper material, the resin substrate was measured by FT-IR, and an arbitrary wavelength of 50 cm was used where there was no peak derived from the resin. -1 In this example, the range was selected as 3800-3850 cm -1 was set as a wavelength where there was no peak derived from the resin. -1 The wavelength at which the maximum peak was detected was identified. When R1551GG was used as the resin substrate, the wavelength was 1200 cm -1 1190cm when using R5670KJ and R5680J -1 When using NX9255, the temperature is 1232 cm -1 When CT-Z is used, the -1 The area around this wavelength was determined as the maximum peak detection wavelength (the arrows in FIGS. 4 to 8 indicate the maximum peak detection wavelength).

[0122] The copper surface after the transfer was measured by FT-IR, and a baseline was drawn by connecting the extreme points of the peak at the maximum peak detection wavelength. 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 and minimum values ​​of the detected peak was taken as the noise value (N) and the S / N ratio was calculated.

[0123] (3) Results The results are shown in FIGS. [Table 6]

[0124] As shown in Table 6, in the examples, no peaks with an S / N ratio of 10 or more corresponding to organic substances derived from the resin were detected on the composite copper foil side, whereas in the comparative examples, peaks with an S / N ratio of 10 or more corresponding to organic substances derived from the resin were detected on the composite copper foil side.

[0125] This is because in the comparative example, almost no metal was transferred from the surface of the composite copper member, and cohesive failure of the resin occurred when the composite copper member was peeled from the resin substrate, resulting in the detection of a peak corresponding to organic matter derived from the resin. On the other hand, in the example, the metal on the surface of the composite copper member was transferred to the resin substrate, so almost no resin adhered to the composite copper member after peeling it from the resin substrate, and no peaks with an S / N ratio of 10 or more corresponding to organic matter derived from the resin were detected.

[0126] That is, in the comparative example, the strength of the protrusions formed by the copper oxide-containing layer is greater than the strength of the resin substrate, so the metal on the surface of the composite copper member does not transfer, resulting in cohesive failure of the resin.On the other hand, in the example, the strength of the protrusions formed by the copper oxide-containing layer is less than the strength of the resin substrate, so the metal on the surface of the composite copper member transfers, resulting in almost no resin adhesion. [Industrial Applicability]

[0127] The present invention provides a novel manufacturing system for composite copper members. Such composite copper members are suitable for the SAP and MSAP processes (Figure 9). To allow the plating solution to penetrate to the deepest part of the recesses, the recesses must be relatively large, making them unsuitable for forming fine wiring. However, when using the composite copper member of the present invention, the copper oxide-containing layer that forms the recesses is itself transferred, eliminating the need for the plating solution to penetrate to the deepest part of the recesses. Instead, copper plating can be performed on the transferred copper oxide-containing layer, which has no recesses or recesses. Even if the recesses on the surface of the original composite copper member are long and narrow, there is little chance of voids forming between the resin substrate and the copper plating layer, making this suitable for forming fine wiring. The copper plating may be patterned. In addition, since copper is plated onto the layer containing copper oxide, the peel strength between the resin substrate and the copper-plated layer is ensured by the unevenness formed by the layer containing copper oxide.

Claims

1. a first device for partially coating the surface of a copper member with a silane coupling agent or a rust inhibitor; a second device for forming a layer containing copper oxide by oxidizing the partially coated surface; a seventh device for thermocompression bonding a resin substrate onto the copper oxide-containing layer of the copper member; an eighth device for peeling the copper member from the resin substrate to obtain the resin substrate having a part or all of the metal forming the copper oxide-containing layer; a fifteenth apparatus for performing copper plating on the surface of the resin substrate having a part or all of the metal forming the copper oxide-containing layer; and A system for manufacturing a printed wiring board, in which the copper member is thermocompression bonded to the resin substrate at a temperature of 50°C to 400°C, a pressure of 0 to 20 MPa, and a time of 1 minute to 5 hours; or a first device for partially coating the surface of a copper member with a silane coupling agent or a rust inhibitor; a second device for forming a layer containing copper oxide by oxidizing the partially coated surface; a third device for forming a layer containing a metal other than copper on the oxidized surface; a ninth device for thermocompression bonding a resin substrate onto the layer containing a metal other than copper of the copper member; a tenth device for peeling the copper member from the resin substrate to obtain the resin substrate having a part or all of the metal forming the copper oxide-containing layer; a fifteenth apparatus for performing copper plating on the surface of the resin substrate having a part or all of the metal forming the copper oxide-containing layer; and A system for manufacturing a printed wiring board, wherein the copper member is thermocompression bonded to the resin substrate at a temperature of 50°C to 400°C, a pressure of 0 to 20 MPa, and a time of 1 minute to 5 hours.

2. The system of claim 1 , wherein the oxidation treatment is performed by an oxidizing agent.

3. The silane coupling agent may be selected from the group consisting of silane, tetraorgano-silane, aminoethyl-aminopropyl-trimethoxysilane, (3-aminopropyl)trimethoxysilane, 1-[3-(trimethoxysilyl)propyl]urea, (3-aminopropyl)triethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, (3-chloropropyl)trimethoxysilane, (3-glycidyloxypropyl)trimethysilane, 3. The system of claim 1, wherein the silane is selected from the group consisting of dimethylsilane, 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 ethylenetrimethoxysilane.

4. The rust inhibitor may be 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-aminopyrrole The system according to any one of claims 1 to 3, wherein the compound is selected from the group consisting of pyrazole, 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, and 2-(methylthio)benzimidazole.

5. the third device has a current-carrying unit, The system according to any one of claims 1 to 4, wherein the ratio of the width of the current-carrying portion to the width of the copper member is 0.8 or more.

6. The system according to any one of claims 1 to 5, wherein the metal other than copper is Ni.

7. The system according to any one of claims 1 to 6, wherein the resin substrate contains at least one insulating resin selected from the group consisting of polyphenylene ether (PPE), epoxy, polyphenylene oxide (PPO), polybenzoxazole (PBO), polytetrafluoroethylene (PTFE), liquid crystal polymer (LCP), thermoplastic polyimide (TPI), fluororesin, polyetherimide, polyetheretherketone, polycycloolefin, bismaleimide resin, low dielectric constant polyimide, and cyanate resin.

Images