WO2016088884A1 - Surface-treated copper foil for forming high frequency signal transmission circuit, copper clad laminate board and printed wiring board - Google Patents
Surface-treated copper foil for forming high frequency signal transmission circuit, copper clad laminate board and printed wiring board Download PDFInfo
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- WO2016088884A1 WO2016088884A1 PCT/JP2015/084186 JP2015084186W WO2016088884A1 WO 2016088884 A1 WO2016088884 A1 WO 2016088884A1 JP 2015084186 W JP2015084186 W JP 2015084186W WO 2016088884 A1 WO2016088884 A1 WO 2016088884A1
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- copper foil
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- layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/02—Single bars, rods, wires, or strips
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
Definitions
- the present application relates to a surface-treated copper foil for forming a high-frequency signal transmission circuit, a copper-clad laminate for manufacturing a high-frequency signal transmission printed wiring board obtained by using the surface-treated copper foil, and a printed wiring board.
- the conductor loss that contributes to this transmission loss has a skin effect that the transmission signal flows on the surface of the circuit as the frequency of the transmission signal increases, and the cross-sectional area through which the transmission signal that is an electrical signal flows decreases. Since the resistance becomes high, a signal delay occurs, resulting in a failure to obtain a calculation speed as designed or a malfunction due to a signal knock-on phenomenon.
- Patent Document 1 discloses an “electrolytic copper foil” as a copper foil for a high-frequency circuit that has a small electrical resistance near the surface and can reduce transmission loss when used as a conductor for a high-frequency circuit.
- a copper foil for high frequency wherein at least one surface is roughened, and the high frequency copper foil and a resin base material are laminated and formed so that the roughened surface is in contact with the resin base material.
- the resistivity of the copper layer is 2.2 ⁇ 10 ⁇ 8 ⁇ m or less, preferably 2.0 ⁇ 10 ⁇ 8
- a high-frequency copper foil characterized by being ⁇ m or less is disclosed.
- the roughening treatment of the copper foil for high frequency disclosed in Patent Document 1 is not particularly limited as long as the resistivity of the copper foil after the roughening treatment is 2.2 ⁇ 10 ⁇ 8 ⁇ m or less. It can be understood that a roughened layer made of copper is formed on the foil surface.
- the roughening surface of the copper foil is indispensable for improving the adhesion when the copper foil and the insulating resin base material are bonded together, and it is not necessary to omit the roughening treatment from the copper foil. It is very difficult.
- the surface-treated copper foil for forming a high-frequency signal transmission circuit is a surface-treated copper foil having a roughened layer on the surface of the copper foil.
- the layer is made of needle-like or plate-like fine irregularities made of a copper composite compound containing copper oxide and cuprous oxide, and the copper foil has an average crystal grain size of 2.5 ⁇ m or more when observed in cross section. It is characterized by that.
- the copper-clad laminate for high-frequency signal transmission printed wiring board manufacture is a copper-clad laminate in which a surface-treated copper foil including a roughened layer and a copper layer is laminated.
- the surface-treated copper foil is made of needle-like or plate-like fine irregularities in which the roughened layer is made of a copper composite compound containing copper oxide and cuprous oxide, and the copper layer is a cross-section.
- the average crystal grain size when observed is 2.5 ⁇ m or more.
- the high-frequency signal transmission printed wiring board according to the present application is a printed wiring board including a high-frequency signal transmission circuit including a roughening layer and a copper layer, and the high-frequency signal transmission circuit is roughened.
- the treatment layer is composed of needle-like or plate-like fine irregularities made of a copper complex compound containing copper oxide and cuprous oxide, and the copper layer has an average crystal grain size of 2.5 ⁇ m or more when observed in cross section. It is characterized by being.
- the surface-treated copper foil for forming a high-frequency signal transmission circuit according to the present application is a "copper oxide and cuprous oxide" in which the needle-like or plate-like fine irregularities constituting the roughened layer are non-conductive components that do not conduct electricity. It consists of Therefore, the roughened layer of the surface-treated copper foil for forming a high-frequency signal transmission circuit according to the present application only plays a role for improving the adhesion with the insulating resin base material without flowing an electric signal.
- the copper foil constituting the surface-treated copper foil for forming a high-frequency signal transmission circuit according to the present application has a crystal structure having an average crystal grain size of 2.5 ⁇ m or more, and therefore has an extremely low electric resistance as compared with a normal copper foil. It is a good conductor.
- the circuit with which the high frequency signal transmission printed wiring board obtained using the copper clad laminate for manufacturing the high frequency signal transmission printed wiring board according to the present application has a high frequency of the transmission signal and a level at which the skin effect is manifested.
- the needle-like or plate-like fine irregularities constituting the roughening layer are nonconductors, a signal current due to the skin effect does not flow.
- the signal current flows through a low electrical resistance copper layer having an average crystal grain size of 2.5 ⁇ m or more, and a signal transmission speed as designed can be obtained.
- the surface-treated copper foil for forming a high-frequency signal transmission circuit is a surface-treated copper foil having a roughened layer on the surface of the copper foil,
- the treatment layer is made of needle-like or plate-like fine irregularities made of a copper composite compound containing copper oxide and cuprous oxide, and the copper foil has an average crystal grain size of 2.5 ⁇ m or more when observed in cross section. It is characterized by being.
- This “surface-treated copper foil for forming a high-frequency signal transmission circuit” is used for a printed wiring board or the like having a signal frequency of 1 GHz or more, more preferably 5 GHz or more, more preferably 10 GHz or more, and most preferably 15 GHz or more. It is suitable for.
- the high frequency signal does not flow through the needle-like or plate-like fine irregularities of the roughened layer of copper foil, and the high frequency signal flows only through the copper layer, the non-roughened copper foil without the roughened layer is used. High frequency characteristics similar to those used can be obtained.
- the surface-treated copper foil for forming a high-frequency signal transmission circuit according to the present application since the copper layer through which the high-frequency signal flows has a crystal structure with a low electrical resistance of 2.5 ⁇ m or more, good high-frequency characteristics Is obtained. Below, it explains in order of "copper foil” and "roughening process layer" which comprise the surface treatment copper foil for the said high frequency signal transmission circuit formation.
- Copper foil A copper foil having an average crystal grain size of 2.5 ⁇ m or more when observed in a cross section is used. When the average crystal grain size is 2.5 ⁇ m or more, the crystal grain boundaries are few, the intra-granular distortion of each crystal grain is small, and a remarkably excellent low electrical resistance is provided.
- the surface-treated copper foil for forming a high-frequency signal transmission circuit according to the present application is subjected to various thermal loads at the stage of lamination to the copper-clad laminate and the stage of processing to the printed wiring board, but at least the printed wiring that is the final product
- the average crystal grain size of the crystal structure of the copper layer constituting the circuit when it becomes a plate may be 2.5 ⁇ m or more.
- the impurity concentration contained in the copper foil is preferably 100 ppm or less.
- the impurities here are S, N, C, and Cl, and the total content is the impurity concentration.
- the copper purity of copper foil is 99.8 mass% or more. When the copper purity of the copper foil is 99.8% by mass or more, it is ensured that good conductive performance is provided.
- the surface roughness (Ra) and glossiness (Gs60 °) of the surface in close contact with the insulating resin substrate are preferably in the following ranges. .
- the surface characteristics of both surfaces of the circuit affect the high-frequency transmission characteristics. It is preferable that both surfaces are in the following range.
- the copper foil has a surface roughness (Ra) of 0.3 ⁇ m or less, more preferably 0.2 ⁇ m or less.
- adhering an insulating resin base material is preferable 40 or more, More preferably, it is 100 or more.
- the surface of the copper foil has a smooth surface with less irregularities and less waviness, and transmission loss can be suppressed.
- an acidic copper sulfate solution having a copper concentration of 50 g / L to 120 g / L and a free sulfuric acid concentration of 60 g / L to 250 g / L is used after activated carbon treatment, and a solution temperature of 20 ° C. to 70 ° C. It can be obtained by electrolysis under the conditions of ° C. and current density of 40 A / dm 2 to 100 A / dm 2 .
- an electrolytic copper foil, a copper foil with a carrier, or a rolled copper foil may be used. And there is no special limitation regarding the thickness of copper foil.
- Roughening treatment layer Containing a roughening treatment layer of the surface-treated copper foil for forming a high-frequency signal transmission circuit according to the present application “Acicular or plate-like fine irregularities made of a copper composite compound containing copper oxide and cuprous oxide” "Exhibits an anchor effect that improves the adhesion to an insulating resin base material having a low dielectric constant and low dielectric loss tangent used for a high-frequency substrate.
- no high-frequency signal flows in the roughened layer of the surface-treated copper foil for forming a high-frequency signal transmission circuit according to the present application.
- the surface-treated copper foil provided with a roughening treatment layer composed of “a needle-like or plate-like fine irregularity made of a copper composite compound containing copper oxide and cuprous oxide” as opposed to a copper foil having excellent conductive properties.
- a high-frequency signal transmission circuit forming material a high-frequency signal transmission circuit forming material.
- the surface-treated copper foil for forming a high-frequency signal transmission circuit according to the present application only needs to have a roughened layer on “at least the side of the copper foil that is in close contact with the insulating resin base material”. It may be a double-sided roughened copper foil provided with a surface treatment layer.
- the “copper composite compound containing copper oxide and cuprous oxide” constituting the fine irregularities of the roughened layer will be described.
- the reason why the “copper composite compound containing copper oxide and cuprous oxide” is used is that a component containing impurities other than copper oxide and cuprous oxide may be contained.
- the said roughening process layer is a needle-like or plate-like copper observed in the shape of a thin line so that it may become clear from cross-sectional observation of the surface treatment copper foil for high frequency signal transmission circuit formation concerning this application shown in FIG. It has fine irregularities composed of a composite compound.
- the maximum length of the “needle-like or plate-like fine irregularities made of a copper composite compound containing copper oxide and cuprous oxide” at this time is preferably 500 nm or less, more preferably 400 nm or less, still more preferably Is 300 nm or less.
- Such a maximum length of 500 nm or less “acicular or plate-like fine irregularities made of a copper composite compound containing copper oxide and cuprous oxide” exhibits a fine nano-anchor effect and forms a high-frequency signal transmission circuit. It is possible to obtain good adhesion between the surface treated copper foil and insulating resin base material and to form fine pitch circuits with the same good circuit shape as when using non-roughened copper foil. become.
- the powder from the roughened layer of the surface-treated copper foil for forming a high-frequency signal transmission circuit according to the present application is less likely to fall off, and the fine irregularities on the surface are less likely to be damaged.
- the “maximum length” referred to here is a cross-section of the surface-treated copper foil for forming a high-frequency signal transmission circuit, from the base end to the tip on the copper foil surface side observed in a linear shape.
- the maximum value when the length is measured.
- this “maximum length” becomes shorter, a finer uneven structure can be imparted to the surface of the copper foil, and the shape of the copper foil surface before the roughening treatment can be maintained. Therefore, the fluctuation
- the “needle-like or plate-like fine irregularities made of a copper composite compound containing copper oxide and cuprous oxide” of the surface-treated copper foil for forming a high-frequency signal transmission circuit is an X-ray photoelectron spectroscopy ( X-ray Photoelectron Spectroscopy (hereinafter referred to as “XPS”))
- XPS X-ray Photoelectron Spectroscopy
- the constituent elements of the fine unevenness are analyzed using XPS, Cu (I) appearing at 932.4 eV corresponding to the binding energy of Cu 2p 3/2, and Cu (II) appearing at 934.3 eV ) Is obtained by waveform separation, and the occupied area ratio of the Cu (I) peak is specified from the peak area of each component.
- Quantum 2000 (beam condition: 40 W, 200 ⁇ m diameter) manufactured by ULVAC-PHI Co., Ltd. is used as an XPS analyzer, and “MultiPack ver. Measure.
- the Cu (I) peak obtained as described above is considered to be derived from monovalent copper constituting cuprous oxide (cuprous oxide: Cu2O). And it is thought that a Cu (II) peak originates in the bivalent copper which comprises copper oxide (cupric oxide: CuO). Furthermore, it is considered that the Cu (0) peak is derived from zero-valent copper constituting metallic copper. Therefore, when the occupation area ratio of the Cu (I) peak is less than 50%, the occupation ratio of cuprous oxide in the fine irregularities is smaller than the occupation ratio of copper oxide. Copper oxide has higher solubility in acids such as an etchant than cuprous oxide.
- the occupied area ratio of the Cu (I) peak when the occupied area ratio of the Cu (I) peak is less than 50%, the roughened layer side of the surface-treated copper foil for forming the high-frequency signal transmission circuit is bonded to the insulating resin substrate, and the circuit is formed by etching.
- the roughening treatment layer is easily dissolved in the etching solution, and the adhesion between the circuit and the insulating resin base material may be lowered.
- the occupied area ratio of the Cu (I) peak when the constituent elements of the fine unevenness are analyzed by XPS is more preferably 70% or more, and further preferably 80% or more.
- the component ratio of cuprous oxide having higher acid solubility resistance to the etching solution or the like becomes higher than that of copper oxide. Accordingly, the acid solubility resistance of the roughened layer to the etching solution is improved, and the insertion of the etching solution at the time of circuit formation can be reduced, and a circuit having good adhesion to the insulating resin substrate can be formed.
- the upper limit value of the occupied area ratio of the Cu (I) peak is not particularly limited, but is 99% or less.
- the exclusive area ratio of the Cu (I) peak is preferably 98% or less, and more preferably 95% or less.
- the occupation area ratio of the Cu (I) peak was calculated by a calculation formula of Cu (I) / ⁇ Cu (I) + Cu (II) ⁇ ⁇ 100 (%).
- the roughening treatment layer according to the present application described above can be formed by the following wet method as an example.
- a copper compound containing copper oxide cupric oxide
- a copper compound containing copper oxide cupric oxide
- the copper compound is reduced, and a part of the copper oxide is converted into cuprous oxide (cuprous oxide), thereby forming a “needle or plate comprising a copper composite compound containing copper oxide and cuprous oxide.
- Shaped fine irregularities can be formed on the surface of the copper foil.
- the “fine unevenness” itself referred to in the present application is formed of a copper compound containing copper oxide at the stage where the surface of the copper foil is oxidized by a wet method.
- alkaline solutions such as a sodium hydroxide solution.
- an alkaline solution By oxidizing the surface of the copper foil with an alkaline solution, fine irregularities made of a copper compound containing needle-like or plate-like copper oxide can be formed on the surface of the copper foil.
- an alkaline solution containing an oxidation inhibitor for properly controlling the oxidation of the copper foil surface is used. It is preferable.
- amino-2-silane coupling agents such as N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, etc. Can be used.
- amino silane coupling agents can be dissolved in an alkaline solution and are stable in an alkaline solution. Therefore, the amino silane coupling agent is adsorbed on the surface of the copper foil and exhibits an effect of accurately controlling the oxidation of the copper foil surface. To do. As a result, excessive growth of copper oxide needle-like crystals can be suppressed, and a roughened layer having fine irregularities with a maximum length of 500 nm or less can be formed.
- the fine irregularities provided on the surface of the copper foil using the alkaline solution containing the amino-based silane coupling agent are almost maintained even after the reduction treatment.
- a roughened layer having fine irregularities with a needle-like or plate-like maximum length of 500 nm or less made of a copper composite compound containing copper oxide and cuprous oxide can be stably obtained.
- the peak of Cu (I) obtained when XPS qualitatively analyzes the constituent elements of the fine irregularities constituting the roughening treatment layer by adjusting the reducing agent concentration, solution pH, solution temperature, etc.
- the occupied area ratio of the Cu (I) peak can be appropriately adjusted with respect to the total area of the area and the peak area of Cu (II).
- the constituent elements of the fine irregularities of the roughened layer formed by the above method are analyzed by XPS, the presence of “—COOH” may be detected.
- the oxidation treatment and reduction treatment of the copper foil surface can be performed by a wet method using a treatment solution. Accordingly, the roughened layer can be easily formed on both sides of the copper foil by a method such as immersing the copper foil in the treatment solution. Therefore, the double-sided roughened layer suitable for forming the inner layer circuit of the multilayer printed wiring board can be used. It becomes possible to easily obtain a heat-treated copper foil.
- any surface treatment may be performed as long as the characteristics of the roughened layer are not impaired.
- a silane coupling agent treatment layer on the surface of the roughening treatment layer described above, it is possible to improve the moisture absorption resistance deterioration characteristics when processed into a printed wiring board.
- This silane coupling agent treatment layer uses any one of olefin functional silane, epoxy functional silane, vinyl functional silane, acrylic functional silane, amino functional silane and mercapto functional silane as the silane coupling agent. It is preferable to form.
- silane coupling agents are represented by the general formula R—Si (OR ′) n (where R: an organic functional group typified by an amino group or vinyl group, OR ′: a methoxy group or an ethoxy group) And the like, n: 2 or 3.
- usable silane coupling agents include vinyltrimethoxysilane, vinylphenyltrimethoxylane, ⁇ -----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
- silane coupling agents listed here are used on the surface of the copper foil that is in close contact with the insulating resin base material, they do not adversely affect the characteristics after the subsequent etching process and printed wiring board. is there.
- Which type is used in the silane coupling agent can be appropriately selected according to the type of the insulating resin base material, the method of using the copper foil, and the like.
- the method of forming the silane coupling agent treatment layer, and the roughening treatment layer and the silane coupling agent treatment liquid are most uniformly applied by employing an immersion method, a showering method, a spraying method, or the like. Any method that can be brought into contact and adsorbed may be used.
- Copper clad laminate for high frequency signal transmission printed wiring board manufacture is a copper clad laminated with a surface-treated copper foil including a roughened layer and a copper layer.
- the surface-treated copper foil is a laminate, and the roughened layer is made of needle-like or plate-like fine irregularities made of a copper composite compound containing copper oxide and cuprous oxide, and the copper layer has a cross-section
- the average crystal grain size when observed with the above is 2.5 ⁇ m or more.
- the surface-treated copper foil used here means the above-mentioned surface-treated copper foil for forming a high-frequency signal transmission circuit, and is obtained by laminating the surface-treated copper foil for forming a high-frequency signal transmission circuit and an insulating resin base material. It is what And the copper clad laminated board for high frequency signal transmission printed wiring board manufacture which concerns on this application is "a copper compound compound containing a copper oxide and a cuprous oxide which is a non-conductor component in the roughening process layer of the laminated surface treatment copper foil. Therefore, high-frequency signals are present on the needle-like or plate-like fine irregularities of the roughened layer of the copper foil while ensuring good adhesion to the insulating resin substrate.
- a low electrical resistance crystal structure having an average crystal grain size of 2.5 ⁇ m or more is formed on the copper layer. Therefore, it exhibits excellent high frequency characteristics.
- the insulating resin base material at this time any material that can be used for manufacturing a printed wiring board such as an insulating resin base material for a rigid substrate and a resin base material for a flexible substrate can be used.
- the lamination method any method such as a press molding method, a continuous laminating method, and a casting method can be used.
- the high-frequency signal transmission printed wiring board according to the present application is a printed wiring board including a high-frequency signal transmission circuit including a roughening treatment layer and a copper layer, and the high-frequency signal transmission circuit
- the treatment layer is composed of needle-like or plate-like fine irregularities made of a copper composite compound containing copper oxide and cuprous oxide, and the copper layer has an average crystal grain size of 2.5 ⁇ m or more when observed in cross section It is characterized by being.
- the “high-frequency signal transmission printed wiring board” here is obtained through a printed wiring board manufacturing process such as etching using the above-mentioned “copper-clad laminate for manufacturing a high-frequency signal transmission printed wiring board”.
- the high-frequency signal transmission circuit provided in the high-frequency signal transmission printed wiring board according to the present application is a needle-like or plate-like made of a copper composite compound containing copper oxide and cuprous oxide whose roughening layer is a non-conductive component. Because it has ⁇ fine irregularities '', no current flows through the roughened layer even if a signal with a frequency at which the skin effect appears, and the inside of the low electrical resistance copper layer with an average crystal grain size of 2.5 ⁇ m or more The transmission loss is reduced.
- Copper foil In the examples, a titanium plate electrode whose surface was polished with # 2000 polishing paper as the cathode and DSA as the anode was adjusted to a copper concentration of 80 g / L and a free sulfuric acid concentration of 150 g / L. After preparing an acid-sulfuric acid copper electrolytic solution and treating the activated carbon so that about 3.0 g of activated carbon is in contact with 1 liter of the acid-sulfuric acid copper electrolyte for about 20 seconds, the liquid temperature is 50 ° C., and the current density is 100 A / dm 2. Then, an electrolytic copper foil having a thickness of 18 ⁇ m was produced.
- the “electrode surface” of the surface roughness in Table 1 is the surface in contact with the cathode of the electrolytic copper foil, and the “deposition surface” is the surface on the side where copper is deposited.
- Table 1 shows the results of surface roughness (Ra), glossiness, impurity concentration, and copper purity of this electrolytic copper foil. The evaluation method will be described below.
- Formation of roughening treatment layer The above-mentioned electrolytic copper foil was immersed in a sulfuric acid solution having a sulfuric acid concentration of 5% by mass for 1 minute, and then washed with water. And the electrolytic copper foil which this pickling process was complete
- finished was immersed in sodium hydroxide aqueous solution, the alkali degreasing process was performed, and the water washing was performed.
- An oxidation treatment was performed on the electrode surface of the electrolytic copper foil after the preliminary treatment.
- the electrolytic copper foil is treated with sodium hydroxide containing a liquid temperature of 70 ° C., pH 12, chlorous acid concentration of 150 g / L, and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane concentration of 10 g / L. It was immersed in the solution for 2 minutes to form fine irregularities made of a copper compound on the surface of the electrolytic copper foil.
- the main component of the copper compound at this time is copper oxide.
- a reduction treatment was performed on the electrolytic copper foil that had been subjected to the oxidation treatment.
- a part of the copper oxide is reduced to the cuprous oxide by reducing a part of the copper oxide on the surface of the electrolytic copper foil, so that the maximum length of 500 nm composed of “copper composite compound containing copper oxide and cuprous oxide” can be obtained.
- a roughening treatment layer having irregularities was formed.
- Silane coupling agent treatment When the reduction treatment is completed, after washing with water, a silane coupling agent treatment solution (an aqueous solution containing 5 g / L of ⁇ -glycidoxypropyltrimethoxysilane using ion-exchanged water as a solvent) It sprayed on the roughening surface of the electrolytic copper foil after the said roughening process by the showering method, and adsorption
- a silane coupling agent treatment solution an aqueous solution containing 5 g / L of ⁇ -glycidoxypropyltrimethoxysilane using ion-exchanged water as a solvent
- Silane coupling agent for surface-treated copper foil for forming a high-frequency signal transmission circuit using the surface-treated copper foil for forming the high-frequency signal transmission circuit and a high-frequency prepreg (MEGTRON 6 manufactured by Panasonic)
- the treated roughened surface was brought into contact with the prepreg and laminated using a vacuum press at a temperature of 190 ° C. and a pressing time of 120 minutes to obtain a copper-clad laminate having an insulation thickness of 0.2 mm.
- the copper-clad laminate was etched to obtain a high-frequency characteristic measurement substrate which is a printed wiring board in which microstrip lines are formed so that the characteristic impedance is 50 ⁇ for single and 100 ⁇ for differential.
- the average crystal grain size of the copper layer was 3.09 ⁇ m.
- the average crystal grain size was measured as follows.
- the copper foil cross section is processed using a focused ion beam processing and observation apparatus (SIM2050) manufactured by Seiko Instruments Inc., crystal orientation analysis is performed by an EBSD (Electron Backscatter Diffraction) method, and a grain boundary is detected.
- a region surrounded by the boundary is defined as a crystal grain, and the diameter of a circle having the same area as the area of the region is defined as the crystal grain size of each crystal grain.
- the average crystal grain size means an average value of crystal grain sizes of crystal grains existing within a predetermined measurement field.
- an acidic copper electrolytic solution containing a copper concentration of 80 g / L, a free sulfuric acid concentration of 250 g / L, a chlorine concentration of 1.1 ppm and gelatin of 2 ppm was used. Electrolysis was performed at a temperature of 60 ° C./dm 2 and a copper foil having a thickness of 18 ⁇ m was produced. In addition, the high frequency characteristic measuring substrate was obtained in the same manner as in the example.
- the high frequency signal transmission circuit formed on the high frequency characteristic measurement substrate obtained in Comparative Example 1 had an average crystal grain size of the copper layer of 0.73 ⁇ m. Moreover, the measurement result of a high frequency characteristic is shown in FIG.2 and FIG.3.
- FIG. 2 shows the relationship between transmission loss and signal frequency using a single microstrip line designed to have a characteristic impedance of 50 ⁇ .
- the upper part of FIG. 2 shows the frequency range of 0 GHz to 20 GHz, and the lower part shows the enlarged range of the frequency range of 15 GHz to 20 GHz.
- the transmission loss of the embodiment is smaller than that of the comparative example in the entire frequency range of 0 GHz to 20 GHz, and in particular, the transmission loss of the embodiment is small in the frequency range of 15 GHz to 20 GHz.
- Fig. 3 shows the relationship between transmission loss and transmission frequency using a microstrip line designed so that the differential is 100 ⁇ by arranging two single microstrip lines with a characteristic impedance of 50 ⁇ in parallel. It is.
- the upper part of FIG. 3 shows the frequency range of 0 GHz to 20 GHz, and the lower part shows the enlarged range of the frequency of 15 GHz to 20 GHz.
- the transmission loss of the example starts to decrease from around 7 GHz in the entire frequency range of 0 GHz to 20 GHz, and the transmission loss of the example is more remarkable in the frequency range of 15 GHz to 20 GHz than the comparative example. It can be understood that it will be less. Then, as the frequency becomes higher, it can be confirmed that the difference from the transmission loss of the embodiment is widened as compared with the comparative example.
- the surface-treated copper foil for forming a high-frequency signal transmission circuit according to the present application is a “copper oxide and cuprous oxide” which is a non-conductive component in which the needle-like or plate-like fine irregularities constituting the roughening treatment layer do not conduct electricity.
- the copper foil has a low electrical resistance crystal structure having an average crystal grain size of 2.5 ⁇ m or more. Therefore, the roughened layer of the surface-treated copper foil for forming a high-frequency signal transmission circuit according to the present application does not flow an electrical signal, plays a role for improving the adhesion with the insulating resin base material, and has a good quality.
- a copper clad laminate for manufacturing a high-frequency signal transmission printed wiring board can be provided.
- the circuit with the high-frequency signal transmission printed wiring board obtained by using such a copper-clad laminate for high-frequency signal transmission printed wiring board manufacture even if the frequency of the transmission signal is high and the skin effect level is achieved, Since the copper composite compound constituting the roughening layer is a non-conductor, no signal current due to the skin effect flows through the roughening layer, and the signal current is a low electric current with an average crystal grain size of 2.5 ⁇ m or more inside the circuit. Since only the copper layer of the resistor flows, it is possible to obtain a signal transmission speed as designed.
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Abstract
Description
本件出願に係る高周波信号伝送回路形成用表面処理銅箔は、銅箔の表面に粗化処理層を備える表面処理銅箔であって、当該粗化処理層は酸化銅及び亜酸化銅を含有する銅複合化合物からなる針状又は板状の微細凹凸からなり、かつ、当該銅箔は断面で観察したときの平均結晶粒径が2.5μm以上であることを特徴とする。この「高周波信号伝送回路形成用表面処理銅箔」は、信号の周波数が1GHz以上、より好ましくは5GHz以上、さらに好ましくは10GHz以上、もっとも好ましくは15GHz以上の帯域で使用するプリント配線板等の用途に好適なものである。 1. Form of surface-treated copper foil for forming a high-frequency signal transmission circuit The surface-treated copper foil for forming a high-frequency signal transmission circuit according to the present application is a surface-treated copper foil having a roughened layer on the surface of the copper foil, The treatment layer is made of needle-like or plate-like fine irregularities made of a copper composite compound containing copper oxide and cuprous oxide, and the copper foil has an average crystal grain size of 2.5 μm or more when observed in cross section. It is characterized by being. This “surface-treated copper foil for forming a high-frequency signal transmission circuit” is used for a printed wiring board or the like having a signal frequency of 1 GHz or more, more preferably 5 GHz or more, more preferably 10 GHz or more, and most preferably 15 GHz or more. It is suitable for.
以下に、当該高周波信号伝送回路形成用表面処理銅箔を構成する「銅箔」、「粗化処理層」の順で説明する。 Conventionally, in order to improve the adhesion between the copper foil and the insulating resin base material, roughening treatments such as “adhesion of fine copper particles” and “unevenness formation by etching” have been performed on the surface of the copper foil. However, when this conventional roughened copper foil is used to form a high-frequency signal transmission circuit, the roughened layer provided on the copper foil surface is a conductor, so transmission loss of high-frequency signals due to the skin effect Occurs. In contrast, in the surface-treated copper foil for forming a high-frequency signal transmission circuit according to the present application, the needle-like or plate-like fine irregularities constituting the roughened layer are non-conductive components that do not conduct electricity "copper oxide and It is composed of “cuprous oxide”. Therefore, since the high frequency signal does not flow through the needle-like or plate-like fine irregularities of the roughened layer of copper foil, and the high frequency signal flows only through the copper layer, the non-roughened copper foil without the roughened layer is used. High frequency characteristics similar to those used can be obtained. In the case of the surface-treated copper foil for forming a high-frequency signal transmission circuit according to the present application, since the copper layer through which the high-frequency signal flows has a crystal structure with a low electrical resistance of 2.5 μm or more, good high-frequency characteristics Is obtained.
Below, it explains in order of "copper foil" and "roughening process layer" which comprise the surface treatment copper foil for the said high frequency signal transmission circuit formation.
本件出願に係る高周波信号伝送プリント配線板製造用銅張積層板は、粗化処理層及び銅層を含む表面処理銅箔を積層した銅張積層板であって、当該表面処理銅箔は、粗化処理層が酸化銅及び亜酸化銅を含有する銅複合化合物からなる針状又は板状の微細凹凸からなり、かつ、当該銅層は断面で観察したときの平均結晶粒径が2.5μm以上であることを特徴とする。ここで用いる表面処理銅箔は、上述の高周波信号伝送回路形成用表面処理銅箔を意味するものであり、この高周波信号伝送回路形成用表面処理銅箔と絶縁樹脂基材とを積層して得られるものである。そして、本件出願に係る高周波信号伝送プリント配線板製造用銅張積層板は、積層した表面処理銅箔の粗化処理層に不導体成分である「酸化銅及び亜酸化銅を含有する銅複合化合物からなる針状又は板状の微細凹凸」が存在するため、絶縁樹脂基材と良好な密着性を確保しつつ、銅箔の粗化処理層の針状又は板状の微細凹凸には高周波信号が流れないため無粗化銅箔を用いたと同様の表皮効果を低減する効果が得られる。そして、本件出願に係る高周波信号伝送プリント配線板製造用銅張積層板を用いて形成した高周波信号伝送回路の場合、銅層に平均結晶粒径が2.5μm以上の低電気抵抗の結晶組織を備えるため、優れた高周波特性を示すことになる。なお、このときの絶縁樹脂基材に関して特段の限定は無く、リジッド基板用絶縁樹脂基材、フレキシブル基板用樹脂基材等のプリント配線板製造に使用可能なあらゆるものの使用が可能である。また、積層方法に関しても、プレス成形法、連続ラミネート法、キャスティング法等のあらゆる方法の使用が可能である。 2. Form of copper clad laminate for high frequency signal transmission printed wiring board manufacture Copper clad laminate for high frequency signal transmission printed wiring board manufacture according to the present application is a copper clad laminated with a surface-treated copper foil including a roughened layer and a copper layer. The surface-treated copper foil is a laminate, and the roughened layer is made of needle-like or plate-like fine irregularities made of a copper composite compound containing copper oxide and cuprous oxide, and the copper layer has a cross-section The average crystal grain size when observed with the above is 2.5 μm or more. The surface-treated copper foil used here means the above-mentioned surface-treated copper foil for forming a high-frequency signal transmission circuit, and is obtained by laminating the surface-treated copper foil for forming a high-frequency signal transmission circuit and an insulating resin base material. It is what And the copper clad laminated board for high frequency signal transmission printed wiring board manufacture which concerns on this application is "a copper compound compound containing a copper oxide and a cuprous oxide which is a non-conductor component in the roughening process layer of the laminated surface treatment copper foil. Therefore, high-frequency signals are present on the needle-like or plate-like fine irregularities of the roughened layer of the copper foil while ensuring good adhesion to the insulating resin substrate. Therefore, the effect of reducing the skin effect similar to the case of using the non-roughened copper foil is obtained. In the case of a high-frequency signal transmission circuit formed using the copper-clad laminate for manufacturing a high-frequency signal transmission printed wiring board according to the present application, a low electrical resistance crystal structure having an average crystal grain size of 2.5 μm or more is formed on the copper layer. Therefore, it exhibits excellent high frequency characteristics. In addition, there is no particular limitation regarding the insulating resin base material at this time, and any material that can be used for manufacturing a printed wiring board such as an insulating resin base material for a rigid substrate and a resin base material for a flexible substrate can be used. In addition, regarding the lamination method, any method such as a press molding method, a continuous laminating method, and a casting method can be used.
本件出願に係る高周波信号伝送プリント配線板は、粗化処理層及び銅層を含む高周波信号伝送回路を備えるプリント配線板であって、当該高周波信号伝送回路は、粗化処理層が酸化銅及び亜酸化銅を含有する銅複合化合物からなる針状又は板状の微細凹凸からなり、かつ、当該銅層は断面で観察したときの平均結晶粒径が2.5μm以上であることを特徴とする。ここでいう「高周波信号伝送プリント配線板」は、上述の「高周波信号伝送プリント配線板製造用銅張積層板」を用いて、エッチング加工等のプリント配線板製造プロセスを経て得られるものである。この本件出願に係る高周波信号伝送プリント配線板の備える高周波信号伝送回路は、粗化処理層が不導体成分である「酸化銅及び亜酸化銅を含有する銅複合化合物からなる針状又は板状の微細凹凸」を備えるため、表皮効果が発現するレベルの周波数の信号が流れても、粗化処理層に電流が流れず、平均結晶粒径が2.5μm以上の低電気抵抗の銅層の内部を流れるため伝送損失が少なくなる。 3. Form of high-frequency signal transmission printed wiring board The high-frequency signal transmission printed wiring board according to the present application is a printed wiring board including a high-frequency signal transmission circuit including a roughening treatment layer and a copper layer, and the high-frequency signal transmission circuit The treatment layer is composed of needle-like or plate-like fine irregularities made of a copper composite compound containing copper oxide and cuprous oxide, and the copper layer has an average crystal grain size of 2.5 μm or more when observed in cross section It is characterized by being. The “high-frequency signal transmission printed wiring board” here is obtained through a printed wiring board manufacturing process such as etching using the above-mentioned “copper-clad laminate for manufacturing a high-frequency signal transmission printed wiring board”. The high-frequency signal transmission circuit provided in the high-frequency signal transmission printed wiring board according to the present application is a needle-like or plate-like made of a copper composite compound containing copper oxide and cuprous oxide whose roughening layer is a non-conductive component. Because it has `` fine irregularities '', no current flows through the roughened layer even if a signal with a frequency at which the skin effect appears, and the inside of the low electrical resistance copper layer with an average crystal grain size of 2.5 μm or more The transmission loss is reduced.
光沢度: 日本電色工業株式会社製光沢計PG-1M型を用い、光沢度の測定方法であるJIS Z 8741-1997に準拠して測定した。
表面粗さ(Ra): 小坂研究所製の触針式表面粗さ計 SE3500(触針曲率半径:2μm)を用い、JIS B0601に準拠して測定した。
銅箔中の微量元素分析: 炭素および硫黄の含有量は、堀場製作所製EMIA-920V 炭素・硫黄分析装置を用いて分析した。そして、窒素の含有量は、堀場製作所製 EMGA-620 酸素・窒素分析装置を用いて分析した。また、銅箔中の塩素の含有量は、塩化銀比濁法により 日立ハイテクフィールディング製 U-3310 分光光度計を用いて分析した。
銅純度分析: JIS H1101に準拠して行った。 [Evaluation method for copper foil]
Glossiness: A gloss meter PG-1M manufactured by Nippon Denshoku Industries Co., Ltd. was used, and the glossiness was measured in accordance with JIS Z 8741-1997, which is a glossiness measurement method.
Surface roughness (Ra): Measured in accordance with JIS B0601, using a stylus type surface roughness meter SE3500 (stylus curvature radius: 2 μm) manufactured by Kosaka Laboratory.
Trace element analysis in copper foil: The carbon and sulfur contents were analyzed using an EMIA-920V carbon / sulfur analyzer manufactured by Horiba. The nitrogen content was analyzed using an EMGA-620 oxygen / nitrogen analyzer manufactured by Horiba. Further, the chlorine content in the copper foil was analyzed by a silver chloride turbidimetric method using a U-3310 spectrophotometer manufactured by Hitachi High-Tech Fielding.
Copper purity analysis: Performed according to JIS H1101.
以下に、実施例と比較例との対比結果を、使用した銅箔の差異及び平均結晶粒径の差異が明瞭となるよう表1に示す。 [Contrast between Example and Comparative Example]
The results of comparison between the examples and the comparative examples are shown in Table 1 so that the difference in the used copper foil and the difference in the average crystal grain size become clear.
Claims (7)
- 銅箔の表面に粗化処理層を備える表面処理銅箔であって、
当該粗化処理層は酸化銅及び亜酸化銅を含有する銅複合化合物からなる針状又は板状の微細凹凸からなり、かつ、
当該銅箔は断面で観察したときの平均結晶粒径が2.5μm以上であることを特徴とする高周波信号伝送回路形成用表面処理銅箔。 A surface-treated copper foil having a roughened layer on the surface of the copper foil,
The roughening treatment layer is composed of needle-like or plate-like fine irregularities made of a copper composite compound containing copper oxide and cuprous oxide, and
A surface-treated copper foil for forming a high-frequency signal transmission circuit, wherein the copper foil has an average crystal grain size of 2.5 μm or more when observed in a cross section. - 前記銅箔の粗化処理層を設ける表面は、Ra≦0.3μmである請求項1に記載の高周波信号伝送回路形成用表面処理銅箔。 The surface-treated copper foil for forming a high-frequency signal transmission circuit according to claim 1, wherein the surface on which the roughened layer of the copper foil is provided satisfies Ra ≦ 0.3 μm.
- 前記粗化処理層を構成する針状又は板状の微細凹凸は、最大長さが500nm以下である請求項1又は請求項2に記載の高周波信号伝送回路形成用表面処理銅箔。 3. The surface-treated copper foil for forming a high-frequency signal transmission circuit according to claim 1, wherein a maximum length of the needle-like or plate-like fine irregularities constituting the roughening treatment layer is 500 nm or less.
- 前記酸化銅及び亜酸化銅を含有する銅複合化合物は、XPS分析におけるCu(I)及びCu(II)の各ピーク面積の合計面積を100%としたとき、Cu(I)ピークの占有面積率が50%以上である請求項1~請求項3のいずれかに記載の高周波信号伝送回路形成用表面処理銅箔。 The copper composite compound containing copper oxide and cuprous oxide has an occupied area ratio of Cu (I) peak when the total area of each peak area of Cu (I) and Cu (II) in XPS analysis is 100%. The surface-treated copper foil for forming a high-frequency signal transmission circuit according to any one of claims 1 to 3, wherein the surface treatment copper foil is 50% or more.
- 前記銅箔は、銅純度が99.8質量%以上である請求項1~請求項4のいずれかに記載の高周波信号伝送回路形成用表面処理銅箔。 The surface-treated copper foil for forming a high-frequency signal transmission circuit according to any one of claims 1 to 4, wherein the copper foil has a copper purity of 99.8% by mass or more.
- 粗化処理層及び銅層を含む表面処理銅箔を積層した銅張積層板であって、
当該表面処理銅箔は、粗化処理層が酸化銅及び亜酸化銅を含有する銅複合化合物からなる針状又は板状の微細凹凸からなり、かつ、当該銅層は断面で観察したときの平均結晶粒径が2.5μm以上であることを特徴とする高周波信号伝送プリント配線板製造用銅張積層板。 A copper clad laminate in which a surface-treated copper foil including a roughened layer and a copper layer is laminated,
The surface-treated copper foil is composed of needle-like or plate-like fine irregularities in which the roughened layer is made of a copper composite compound containing copper oxide and cuprous oxide, and the copper layer is an average when observed in cross section. A copper-clad laminate for producing a high-frequency signal transmission printed wiring board, wherein the crystal grain size is 2.5 μm or more. - 粗化処理層及び銅層を含む高周波信号伝送回路を備えるプリント配線板であって、
当該高周波信号伝送回路は、粗化処理層が酸化銅及び亜酸化銅を含有する銅複合化合物からなる針状又は板状の微細凹凸からなり、かつ、当該銅層は断面で観察したときの平均結晶粒径が2.5μm以上であることを特徴とする高周波信号伝送プリント配線板。 A printed wiring board including a high-frequency signal transmission circuit including a roughened layer and a copper layer,
The high-frequency signal transmission circuit is composed of needle-like or plate-like fine irregularities in which the roughening layer is made of a copper composite compound containing copper oxide and cuprous oxide, and the copper layer is an average when observed in cross section. A high-frequency signal transmission printed wiring board having a crystal grain size of 2.5 μm or more.
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