WO2022255422A1 - 粗化処理銅箔、銅張積層板及びプリント配線板 - Google Patents

粗化処理銅箔、銅張積層板及びプリント配線板 Download PDF

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WO2022255422A1
WO2022255422A1 PCT/JP2022/022388 JP2022022388W WO2022255422A1 WO 2022255422 A1 WO2022255422 A1 WO 2022255422A1 JP 2022022388 W JP2022022388 W JP 2022022388W WO 2022255422 A1 WO2022255422 A1 WO 2022255422A1
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Prior art keywords
copper foil
roughened
frequency
frequency components
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PCT/JP2022/022388
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English (en)
French (fr)
Japanese (ja)
Inventor
翼 加藤
歩 立岡
博鈞 楊
彰太 川口
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三井金属鉱業株式会社
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Priority to KR1020237043498A priority Critical patent/KR20240017842A/ko
Priority to JP2023525899A priority patent/JPWO2022255422A1/ja
Priority to CN202280039183.0A priority patent/CN117480281A/zh
Publication of WO2022255422A1 publication Critical patent/WO2022255422A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • 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
    • 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
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/16—Electroplating with layers of varying thickness
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • 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
    • H05K1/03—Use of materials for the substrate
    • 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

Definitions

  • the present invention relates to roughened copper foils, copper clad laminates and printed wiring boards.
  • copper foil is widely used in the form of copper-clad laminates laminated with insulating resin substrates.
  • the copper foil and the insulating resin base material have high adhesive strength in order to prevent the wiring from being peeled off during the production of the printed wiring board. Therefore, in ordinary copper foils for manufacturing printed wiring boards, the bonding surface of the copper foil is roughened to form unevenness made of fine copper particles, and the unevenness is pressed into the insulating resin base material. Adhesion is improved by exerting an anchor effect.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2018-172785
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2018-172785
  • a surface-treated copper foil having an arithmetic mean roughness Ra of 0.08 ⁇ m or more and 0.20 ⁇ m or less on the roughened layer side surface and a TD (width direction) gloss of the roughened layer side surface of 70% or less. disclosed.
  • a printed wiring board comprises a copper foil processed into a wiring pattern and an insulating base material. losses.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2015-148011 describes a technique for providing a surface-treated copper foil with low signal transmission loss and a laminated board using the same, and the copper foil surface is improved by surface treatment. It discloses that the skewness Rsk based on JIS B0601-2001 is controlled within a predetermined range of -0.35 or more and 0.53 or less.
  • the present inventors have recently discovered a copper-clad laminate or printed wiring manufactured using a roughened copper foil by imparting a surface profile that satisfies a predetermined condition when the cross-sectional curve is Fourier transformed. We have found that the plate can achieve both excellent transmission characteristics and high peel strength.
  • an object of the present invention is to provide a roughened copper foil that can achieve both excellent transmission characteristics and high peel strength when used in copper-clad laminates or printed wiring boards.
  • a roughened copper foil having a roughened surface on at least one side When the cross-sectional curve with a horizontal target length of 64 ⁇ m on the roughened surface is decomposed into 512 frequency components by Fourier transformation with a frequency range of 0 to 511 and a frequency interval of 1, the frequency of 1 to 511 The ratio of the sum of frequency components of frequencies 1 to 5 in the sum of the components is 15.0% or more, and the average value of the frequency components of frequencies 13 to 511 is 0.010 ⁇ m or less.
  • FIG. 4 is a diagram for explaining that the surface unevenness of the roughening-treated copper foil is composed of roughening particle components and waviness components;
  • FIG. 4 is a diagram for explaining the relationship between frequency components after Fourier transform and waviness of a copper foil, and is a diagram showing a roughened surface of a roughened copper foil in which roughening particles are formed on a copper foil with large waviness. be.
  • FIG. 4 is a diagram for explaining the relationship between frequency components after Fourier transform and waviness of a copper foil, and is a diagram showing a roughened surface of a roughened copper foil in which roughening particles are formed on a smooth copper foil.
  • FIG. 4 is a diagram for explaining the relationship between frequency components after Fourier transform and roughening particles, and is a diagram showing a roughening-treated surface of a roughening-treated copper foil having fine roughening particles.
  • FIG. 4 is a diagram for explaining the relationship between frequency components after Fourier transform and roughening particles, and is a diagram showing a roughening treatment surface of a roughening treatment copper foil having coarse roughening particles.
  • BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows an example of the roughening process copper foil of this invention.
  • cross-sectional curve refers to the curve that appears at the cut end when the actual surface of the sample is cut along a specified vertical plane. Equivalent to A cross-sectional curve can be obtained by measuring a surface profile of a predetermined measurement area on the roughened surface with a commercially available laser microscope. Preferable measurement conditions for the laser microscope will be shown in Examples below.
  • the term “Fourier transform” refers to transforming a curve f(x) of interest length L ( ⁇ m) in the horizontal direction into a sine wave at one frequency, or the sum of sine waves at two or more frequencies.
  • “Frequency” means the number of waves in length L (inverse of wavelength). Even if the curve f(x) looks very different from a sine wave at first glance, as in the example shown in Fig. 1, one or more can be expressed as a sum of sine waves of That is, when Fourier transform is performed on the curve f(x) under predetermined conditions, coefficients corresponding to each frequency are uniquely determined. In this specification, the above frequency coefficients are referred to as "frequency components". In the example shown in FIG.
  • frequency 1 (one wave in length L), frequency 2 (two waves in length L), frequency 3 (three waves in length L) ), frequency 4 (4 waves in length L) and frequency 5 (5 waves in length L) are 1.00, 0.05, 0.15, respectively. 0.03 and 0.10.
  • the frequency component is a numerical value that takes into account the amplitude (absolute value) of the original curve f(x), and as the amplitude of the curve f(x) increases, the frequency component of each frequency also increases.
  • the frequency component will be explained more specifically based on the example shown in FIG.
  • the Fourier transform of the example shown in FIG. 1 was performed on the curve f(x) of the horizontal target length L ( ⁇ m) under the conditions of frequencies of 1 to 5 and frequency intervals of 1. Assume that In this example, for the sake of simplification, it is assumed that there is no phase shift between the sine waves forming the curve f(x).
  • the frequency components of each frequency and their proportions are as shown in Table 1.
  • the Fourier transform described above can be performed using commercially available software (eg, "Mountains Map Imaging Topography 9.0” manufactured by Digital Surf). An analysis method using this software will be described later in Examples.
  • the "electrode surface” of the electrolytic copper foil refers to the surface that was in contact with the cathode when the electrolytic copper foil was manufactured.
  • the "deposition surface" of the electrolytic copper foil refers to the surface on which electrolytic copper is deposited during the production of the electrolytic copper foil, that is, the surface that is not in contact with the cathode.
  • the copper foil of the present invention is a roughened copper foil.
  • This roughened copper foil has a roughened surface on at least one side.
  • the frequency The proportion of the sum of frequency components of frequencies 1 to 5 in the sum of frequency components of 1 to 511 is 15.0% or more.
  • the average value of the frequency components of 13 or more and 511 or less is 0.010 ⁇ m or less.
  • the copper-clad laminate or printed wiring board manufactured using the roughened copper foil is excellent. It is possible to achieve both excellent transmission characteristics and high peel strength (for example, normal peel strength and peel strength against hydrochloric acid).
  • high peel strength for example, normal peel strength and peel strength against hydrochloric acid.
  • the unevenness on the roughened copper foil surface consists of a "roughening particle component” and a “waviness component” having a longer period than the roughening particle component.
  • the surface of a copper foil with small undulations (for example, the surface of a double-sided smooth foil or the electrode surface of an electrolytic copper foil) is subjected to a fine roughening treatment to remove small roughened particles.
  • a copper-clad laminate or a printed wiring board is produced using such a roughened copper foil, the peel strength between the copper foil and the substrate is generally low.
  • FIG. 3B shows an example of a roughened copper foil having roughening particles formed on the surface.
  • the roughened copper foil having large undulations has a (simple) shape on the roughened surface that approximates a low frequency (long wavelength) sine wave. Therefore, as a result of performing the Fourier transform, it is considered that the proportion of low-frequency components with frequencies of 1 to 5 increases.
  • the roughened copper foil with small undulations has a complicated shape whose roughened surface is greatly different from a sine wave. Therefore, as a result of the Fourier transform, low-frequency components and high-frequency components are mixed (that is, the ratio of low-frequency components is reduced).
  • FIG. 3A the roughened copper foil having large undulations has a (simple) shape on the roughened surface that approximates a low frequency (long wavelength) sine wave. Therefore, as a result of performing the Fourier transform, it is considered that the proportion of low-frequency components with frequencies of 1 to 5 increases.
  • the roughened copper foil with small undulations has a complicated shape whose roughened surface is greatly different from a sine wave. Therefore, as a result of the Four
  • the roughened particles having a shorter period than the undulation can be represented by a high frequency (short wavelength) frequency component of 13 or more and 511 or less. Therefore, as shown in FIGS. 4A and 4B, it can be said that the smaller the roughening particles, the smaller the high-frequency component (the amplitude of the sine wave). Therefore, when the Fourier transform is performed, the roughened copper foil having a large ratio of low frequency components and a small average value of high frequency components contributes greatly to the adhesion reliability between the copper foil and the substrate. It can be said that fine roughening particles that contribute to excellent transmission characteristics are formed on the undulating copper foil surface. Thus, it is believed that the roughened copper foil of the present invention can achieve both excellent transmission characteristics and high peel strength when used in copper-clad laminates or printed wiring boards.
  • the ratio of frequency components of frequencies 1 to 5 in the result of Fourier transform is 15.0% or more, preferably 18.0% to 90.0%, more preferably 19.0%. It is 0% or more and 80.0% or less, more preferably 20.0% or more and 70.0% or less.
  • a roughened copper foil within the above range has undulations of a desired size, and can achieve high peel strength as well as excellent transmission characteristics.
  • the ratio of frequency components of frequencies 13 to 511 in the result of Fourier transformation is preferably 66.0% or less, more preferably 10.0% to 66.0%, and further It is preferably 15.0% or more and 65.0% or less, particularly preferably 20.0% or more and 64.0% or less.
  • a roughened copper foil within the above range has a more desirable size of undulations, and can achieve even higher peel strength while having excellent transmission characteristics.
  • the roughened copper foil preferably has an average value of 0.007 ⁇ m or more, more preferably 0.007 ⁇ m or more and 0.100 ⁇ m or less, still more preferably 0 0.007 ⁇ m or more and 0.050 ⁇ m or less, particularly preferably 0.008 ⁇ m or more and 0.030 ⁇ m or less.
  • the height (amplitude) of the entire copper foil which is the sum of the undulation component and the roughened particle component, is a desirable size, and even though it has excellent transmission characteristics, it has a higher peeling. strength can be achieved.
  • the roughened copper foil preferably has an average value of 0.150 ⁇ m or more, more preferably 0.160 ⁇ m or more and 2.000 ⁇ m or less, still more preferably 0 0.170 ⁇ m or more and 1.600 ⁇ m or less, particularly preferably 0.180 ⁇ m or more and 1.400 ⁇ m or less.
  • a roughened copper foil within the above range has a more desirable size of undulations, and can achieve even higher peel strength while having excellent transmission characteristics.
  • the roughened copper foil has an average value of 0.010 ⁇ m or less, preferably 0.001 ⁇ m or more and 0.010 ⁇ m or less, more preferably 0.002 ⁇ m or more and 0 0.010 ⁇ m or less.
  • a roughened copper foil having a surface roughness within the above range has roughening particles of a desired size, and can achieve excellent transmission characteristics while maintaining high peel strength.
  • the roughened copper foil preferably has an average value of 0.025 ⁇ m or less, more preferably 0.001 ⁇ m or more and 0.024 ⁇ m or less, still more preferably 0 0.003 ⁇ m or more and 0.022 ⁇ m or less, particularly preferably 0.005 ⁇ m or more and 0.020 ⁇ m or less.
  • a roughened copper foil within the above range has roughening particles of a more desirable size, and can achieve excellent transmission characteristics while maintaining high peel strength.
  • the thickness of the roughened copper foil is not particularly limited, it is preferably 0.1 ⁇ m or more and 210 ⁇ m or less, more preferably 0.3 ⁇ m or more and 105 ⁇ m or less, and still more preferably 7 ⁇ m or more and 70 ⁇ m or less.
  • the roughened copper foil of the present invention is not limited to the ordinary copper foil whose surface has been roughened, but the copper foil surface of the carrier-attached copper foil has been roughened or finely roughened. can be anything.
  • the roughened copper foil of the present invention is obtained by subjecting a copper foil surface having predetermined undulations (for example, a deposition surface of an electrolytic copper foil) to a roughening treatment under desired low-roughening conditions. It can be produced preferably by carrying out to form fine roughened particles. Therefore, according to a preferred aspect of the present invention, the roughened copper foil is an electrolytic copper foil, and the roughened surface is present on the deposition surface side of the electrolytic copper foil.
  • the roughened copper foil may have roughened surfaces on both sides, or may have a roughened surface only on one side.
  • the roughened surface is typically provided with a plurality of roughened particles, and preferably each of these roughened particles is made of copper particles.
  • the copper particles may consist of metallic copper, or may consist of a copper alloy.
  • the roughening treatment for forming the roughened surface can be preferably carried out by forming roughening particles with copper or a copper alloy on the copper foil.
  • the copper foil before the roughening treatment may be a non-roughened copper foil or a pre-roughened copper foil.
  • the surface of the copper foil to be roughened preferably has a ten-point average roughness Rz measured in accordance with JIS B0601-1994 of 1.30 ⁇ m or more and 15.00 ⁇ m or less, more preferably It is 1.50 ⁇ m or more and 10.00 ⁇ m or less. Within the above range, it becomes easier to impart the surface profile required for the roughened copper foil of the present invention to the roughened surface.
  • the roughening treatment is performed, for example, in a copper sulfate solution containing a copper concentration of 7 g/L or more and 17 g/L or less and a sulfuric acid concentration of 50 g/L or more and 200 g/L or less at a temperature of 20 ° C. or more and 40 ° C. or less at 10 A / dm 2 or more and 50 A. /dm 2 or less.
  • This electrolytic deposition is preferably carried out for 0.5 to 30 seconds, more preferably 1 to 30 seconds, and even more preferably 1 to 3 seconds.
  • the roughened copper foil according to the present invention is not limited to the method described above, and may be manufactured by any method.
  • R L L/D C (Wherein, R L is the liquid resistance index (mm L/mol), L is the distance between the electrodes (anode-cathode) (mm), and D C is the charge carrier density (mol/L).)
  • the liquid resistance index RL defined by is preferably 9.0 mm L / mol or more and 20.0 mm L / mol or less, and 11.0 mm L / mol or more and 17.0 mm L / mol or less is more preferred.
  • the bumps can be preferably formed in a shape suitable for imparting the surface profile required for the roughened copper foil of the present invention.
  • the charge carrier density Dc can be calculated by totaling the product of each ion concentration and valence for all ions present in the plating solution.
  • the liquid resistance index is an index that correlates with the resistance of the solution.
  • the roughened copper foil may be subjected to antirust treatment and may have an antirust treatment layer formed thereon.
  • the antirust treatment preferably includes plating with zinc.
  • the plating treatment using zinc may be either zinc plating treatment or zinc alloy plating treatment, and the zinc alloy plating treatment is particularly preferably zinc-nickel alloy treatment.
  • the zinc-nickel alloy treatment may be a plating treatment containing at least Ni and Zn, and may further contain other elements such as Sn, Cr, Co and Mo.
  • the antirust treatment layer further contains Mo in addition to Ni and Zn, so that the treated surface of the roughened copper foil has excellent adhesion to resin, chemical resistance, and heat resistance, and etching residue is removed. It becomes difficult to remain.
  • Ni/(Zn+Ni) which is the ratio of the Ni deposition amount to the total amount of the Zn deposition amount and the Ni deposition amount, is preferably 0.3 or more and 0.9 or less, more preferably It is 0.4 or more and 0.9 or less, more preferably 0.4 or more and 0.8 or less.
  • the total amount of Zn and Ni deposited in the zinc-nickel alloy plating is preferably 8 mg/m 2 or more and 160 mg/m 2 or less, more preferably 13 mg/m 2 or more and 130 mg/m 2 or less, and still more preferably 19 mg/m 2 . 80 mg/ m2 or less.
  • Ni/(Zn+Ni+Mo) which is the ratio of the Ni deposition amount to the total amount of the Zn deposition amount, the Ni deposition amount and the Mo deposition amount, is 0.20 or more and 0.20 to 0.20. It is preferably 80 or less, more preferably 0.25 or more and 0.75 or less, still more preferably 0.30 or more and 0.65 or less.
  • the total deposition amount of Zn, Ni and Mo in the zinc-nickel-molybdenum alloy plating is preferably 10 mg/m 2 or more and 200 mg/m 2 or less, more preferably 15 mg/m 2 or more and 150 mg/m 2 or less, further preferably 20 mg/m 2 or more and 90 mg/m 2 or less.
  • the amounts of Zn, Ni, and Mo deposited were obtained by dissolving a predetermined area (for example, 25 cm 2 ) on the roughened surface of the roughened copper foil with acid, and measuring the concentration of each element in the resulting solution by ICP emission spectrometry. It can be calculated by analyzing based on the law.
  • the antirust treatment preferably further includes chromate treatment, and this chromate treatment is more preferably performed on the surface of the zinc-containing plating after the plating treatment using zinc. By doing so, the rust resistance can be further improved.
  • a particularly preferred antirust treatment is a combination of zinc-nickel alloy plating treatment (or zinc-nickel-molybdenum alloy plating treatment) and subsequent chromate treatment.
  • the surface of the roughened copper foil may be treated with a silane coupling agent to form a silane coupling agent-treated layer.
  • a silane coupling agent-treated layer can be formed by appropriately diluting a silane coupling agent, coating it, and drying it.
  • silane coupling agents include epoxy-functional silane coupling agents such as 4-glycidylbutyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, or 3-aminopropyltriethoxysilane, N-(2- aminoethyl)-3-aminopropyltrimethoxysilane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, etc.
  • epoxy-functional silane coupling agents such as 4-glycidylbutyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, or 3-aminopropyltriethoxysilane, N-(2- aminoethyl)-3-aminopropyltrimethoxysilane, N-3-(4-(3-aminopropoxy)but
  • amino-functional silane coupling agents or mercapto-functional silane coupling agents such as 3-mercaptopropyltrimethoxysilane or olefin-functional silane coupling agents such as vinyltrimethoxysilane, vinylphenyltrimethoxysilane, or 3-methacrylic acrylic functional silane coupling agents such as roxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, or imidazole functional silane coupling agents such as imidazole silane, or triazine functional silane coupling agents such as triazine silane, and the like. is mentioned.
  • the roughened copper foil preferably has an anticorrosive layer and/or a silane coupling agent-treated layer on the roughened surface, more preferably an anticorrosive layer and a silane coupling agent-treated layer.
  • each numerical value of the frequency component parameter after Fourier transformation in this specification is the antirust treatment layer and/or the silane coupling agent. It means a numerical value obtained by measuring and analyzing the surface of the roughened copper foil after the ring agent treatment layer is formed.
  • the anticorrosion treatment layer and the silane coupling agent treatment layer may be formed not only on the roughened surface side of the roughened copper foil, but also on the side where the roughened surface is not formed.
  • the roughened copper foil of the present invention is preferably used for producing a copper-clad laminate for printed wiring boards. That is, according to a preferred aspect of the present invention, there is provided a copper-clad laminate comprising the roughened copper foil.
  • This copper-clad laminate comprises the roughened copper foil of the present invention and a resin layer provided in close contact with the roughened surface of the roughened copper foil.
  • the roughened copper foil may be provided on one side of the resin layer, or may be provided on both sides.
  • the resin layer comprises resin, preferably insulating resin.
  • the resin layer is preferably prepreg and/or resin sheet.
  • Prepreg is a general term for composite materials in which synthetic resin is impregnated into a base material such as a synthetic resin plate, a glass plate, a glass woven fabric, a glass non-woven fabric, or paper.
  • insulating resins include epoxy resins, cyanate resins, bismaleimide triazine resins (BT resins), polyphenylene ether resins, and phenol resins.
  • the insulating resin forming the resin sheet include insulating resins such as epoxy resins, polyimide resins, and polyester resins.
  • the resin layer may contain filler particles made of various inorganic particles such as silica and alumina from the viewpoint of improving insulation.
  • the thickness of the resin layer is not particularly limited, it is preferably 1 ⁇ m or more and 1000 ⁇ m or less, more preferably 2 ⁇ m or more and 400 ⁇ m or less, and still more preferably 3 ⁇ m or more and 200 ⁇ m or less.
  • the resin layer may be composed of multiple layers.
  • a resin layer such as a prepreg and/or a resin sheet may be provided on the roughened copper foil in advance via a primer resin layer that is applied to the surface of the copper foil.
  • the roughened copper foil of the present invention is preferably used for manufacturing printed wiring boards. That is, according to a preferred aspect of the present invention, there is provided a printed wiring board comprising the roughened copper foil.
  • the printed wiring board according to this aspect includes a layer structure in which a resin layer and a copper layer are laminated.
  • the copper layer is a layer derived from the roughened copper foil of the present invention.
  • the resin layer is as described above for the copper-clad laminate. In any case, a known layer structure can be adopted for the printed wiring board.
  • printed wiring boards include a single-sided or double-sided printed wiring board formed by bonding the roughened copper foil of the present invention to one or both sides of a prepreg to form a cured laminate, and then forming a circuit on the printed wiring board.
  • a multilayer printed wiring board etc. are mentioned.
  • other specific examples include flexible printed wiring boards, COF, TAB tapes, etc., in which the roughened copper foil of the present invention is formed on a resin film to form a circuit.
  • a resin-coated copper foil (RCC) is formed by applying the above resin layer to the roughened copper foil of the present invention, and the resin layer is used as an insulating adhesive layer and laminated on the above printed circuit board.
  • the roughened copper foil is used as all or part of the wiring layer, and the circuit is formed by the modified semi-additive method (MSAP), the subtractive method, etc., and the roughened copper foil is removed.
  • MSAP modified semi-additive method
  • Examples 1-11 The roughened copper foil of the present invention was manufactured as follows.
  • Example 9 an electrolytic copper foil B with a thickness of 18 ⁇ m was obtained using a sulfuric acid copper sulfate solution having the composition shown below as the copper electrolyte. At this time, conditions other than the composition of the sulfuric acid copper sulfate solution were the same as those for the electrolytic copper foil A.
  • Examples 1 to 6 and 9 to 11 are on the deposition surface side
  • Examples 7 and 8 are on the electrode surface side.
  • the deposition surface of the electrolytic copper foil used in Examples 1 to 6 and 9 to 11 and the electrode surface of the electrolytic copper foil used in Examples 7 and 8 were measured using a contact surface roughness meter to JIS B0601-1994.
  • the ten-point average roughness Rz measured according to the standard was as shown in Table 2.
  • first roughening treatment For Examples 1 to 7, the following roughening treatment (first roughening treatment) was performed. This roughening treatment is performed in a copper electrolytic solution for roughening treatment (copper concentration: 7 g / L or more and 17 g / L or less, sulfuric acid concentration: 50 g / L or more and 200 g / L or less, liquid temperature: 30 ° C.) for each example Electrolysis was carried out under the liquid resistance index, current density and time conditions shown in Table 2, followed by washing with water.
  • Examples 8 to 11 the following first roughening treatment, second roughening treatment and third roughening treatment were performed in this order.
  • the first roughening treatment is performed in a copper electrolytic solution for roughening treatment (copper concentration: 7 g / L or more and 17 g / L or less, sulfuric acid concentration: 50 g / L or more and 200 g / L or less, liquid temperature: 30 ° C.)
  • Table 2 Electrolysis was carried out under the liquid resistance index, current density and time conditions shown in , followed by washing with water.
  • the second roughening treatment is performed by electrolyzing under the conditions of liquid resistance index, current density and time shown in Table 2 in a copper electrolytic solution for roughening treatment having the same composition as the first roughening treatment, and washing with water. gone.
  • the third roughening treatment is performed in a copper electrolytic solution for roughening treatment (copper concentration: 65 g / L or more and 80 g / L or less, sulfuric acid concentration: 50 g / L or more and 200 g / L or less, liquid temperature: 45 ° C.) Table 2 Electrolysis was carried out under the liquid resistance index, current density and time conditions shown in , followed by washing with water.
  • Anticorrosive treatment shown in Table 2 was performed on the electrolytic copper foil after the roughening treatment.
  • a pyrophosphate bath was used on the roughened surface of the electrolytic copper foil, and the concentration of potassium pyrophosphate was 100 g / L, the concentration of zinc was 1 g / L, and nickel Rust prevention treatment A (zinc-nickel-molybdenum system rust prevention treatment) was performed at a concentration of 2 g/L, a molybdenum concentration of 1 g/L, a liquid temperature of 40°C, and a current density of 0.5 A/dm 2 .
  • a pyrophosphate bath was applied to the surface of the electrodeposited copper foil that had not been roughened, and the concentration of potassium pyrophosphate was 80 g/L, the concentration of zinc was 0.2 g/L, the concentration of nickel was 2 g/L, the liquid temperature was 40°C.
  • Antirust treatment B (zinc-nickel antirust treatment) was performed at a current density of 0.5 A/dm 2 .
  • both surfaces of the electrolytic copper foil were subjected to rust prevention treatment B under the same conditions as the surface of the electrolytic copper foil not subjected to the roughening treatment in Examples 1 and 5 to 8. .
  • Chromate treatment was performed on both surfaces of the antirust-treated electrolytic copper foil to form a chromate layer on the antirust treatment layer. This chromate treatment was performed under the conditions of a chromic acid concentration of 1 g/L, a pH of 11, a liquid temperature of 25° C. and a current density of 1 A/dm 2 .
  • Silane Coupling Agent Treatment The chromate-treated copper foil was washed with water and then immediately treated with a silane coupling agent to adsorb the silane coupling agent onto the chromate layer on the roughened surface.
  • This silane coupling agent treatment was carried out by spraying a solution of a silane coupling agent using pure water as a solvent onto the roughened surface by showering for adsorption treatment.
  • the silane coupling agent 3-aminopropyltrimethoxysilane was used in Examples 1 and 3-7, and 3-glycidoxypropyltrimethoxysilane was used in Examples 2 and 8-11.
  • the concentration of the silane coupling agent was 3 g/L in each case. After adsorption of the silane coupling agent, water was finally evaporated by an electric heater to obtain a roughened copper foil with a predetermined thickness.
  • (a) Frequency component parameter after Fourier transform of the cross-sectional curve on the roughened surface was calculated as follows. First, the roughened surface of the roughened copper foil was measured using a laser microscope (OLS-5000, manufactured by Olympus Corporation) to obtain surface profile data. The measurement conditions of the laser microscope were as follows: objective lens magnification of 100 times, optical zoom of 2 times, measurement area of 64.419 ⁇ m in length ⁇ 64.397 ⁇ m in width, and an acquisition mode of accuracy priority mode. The direction of observation was such that the treatment streaks of the copper foil (the width direction when the copper foil was manufactured) were perpendicular (not oblique) to the field of view.
  • OLS-5000 manufactured by Olympus Corporation
  • the obtained surface shape data was analyzed using the image analysis software "MountainsMap Imaging Topography 9.0" (manufactured by Digital Surf). Specifically, open the surface shape data (Lext file format) with the image analysis software, execute "extract cross section” in the function "operator” on the software, 64 ⁇ m perpendicular to the processing streak (whole area) The cross-sectional curve of is extracted. Fourier transform (frequency range: 0 to 511, frequency interval: 1) was performed on this cross-sectional curve by executing "frequency spectrum” in the function "analysis” on the software.
  • Example 1 the surface of the copper-clad laminate on the copper foil side was plated with copper until the thickness of the copper foil reached 18 ⁇ m before forming the circuit.
  • Example 4 to 6 and 11 the surface of the copper-clad laminate on the copper foil side was etched until the copper foil had a thickness of 18 ⁇ m before forming the circuit.
  • the linear circuit thus obtained was peeled off from the insulating substrate according to JIS C 5016-1994 A method (90° peeling), and the normal peel strength (kgf/cm) was measured.
  • the quality of the normal peel strength obtained was evaluated according to the following criteria. The results were as shown in Table 3.
  • a base material for high frequency (MEGTRON6N manufactured by Panasonic) was prepared as an insulating resin base material.
  • a roughened copper foil is laminated on both sides of this insulating resin substrate so that the roughened surface is in contact with the insulating resin substrate, and a vacuum press is used at a temperature of 190 ° C. for a pressing time of 120 minutes. to obtain a copper-clad laminate having an insulation thickness of 136 ⁇ m.
  • the copper-clad laminate was subjected to an etching process to obtain a transmission loss measuring board on which microstrip lines were formed so as to have a characteristic impedance of 50 ⁇ .
  • the transmission loss (dB/cm) at 16 GHz was measured on the obtained transmission loss measuring board using a network analyzer (N5225B manufactured by Keysight Technologies). The quality of the obtained transmission loss was evaluated according to the following criteria. The results were as shown in Table 3. ⁇ Transmission loss evaluation criteria> -Good: Transmission loss is -0.23 dB/cm or more -Bad: Transmission loss is less than -0.23 dB/cm

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  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Manufacturing Of Printed Wiring (AREA)
PCT/JP2022/022388 2021-06-03 2022-06-01 粗化処理銅箔、銅張積層板及びプリント配線板 WO2022255422A1 (ja)

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WO2018110579A1 (ja) * 2016-12-14 2018-06-21 古河電気工業株式会社 表面処理銅箔および銅張積層板
CN113099605A (zh) * 2021-06-08 2021-07-09 广州方邦电子股份有限公司 金属箔、带载体金属箔、覆铜层叠板及印刷线路板

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JP2006210689A (ja) * 2005-01-28 2006-08-10 Fukuda Metal Foil & Powder Co Ltd 高周波プリント配線板用銅箔及びその製造方法
JP2015028197A (ja) * 2013-07-30 2015-02-12 株式会社Ｓｈカッパープロダクツ 粗化銅箔、銅張積層板及びプリント配線板
JP5758035B2 (ja) 2013-08-20 2015-08-05 Jx日鉱日石金属株式会社 表面処理銅箔及びそれを用いた積層板、プリント配線板、電子機器、並びに、プリント配線板の製造方法
WO2016174998A1 (ja) * 2015-04-28 2016-11-03 三井金属鉱業株式会社 粗化処理銅箔及びプリント配線板
JP2018145519A (ja) * 2017-03-03 2018-09-20 Ｊｘ金属株式会社 表面処理銅箔、キャリア付銅箔、積層体、プリント配線板の製造方法及び電子機器の製造方法
JP7356209B2 (ja) 2017-03-31 2023-10-04 Ｊｘ金属株式会社 表面処理銅箔、樹脂層付き表面処理銅箔、キャリア付銅箔、積層体、プリント配線板の製造方法及び電子機器の製造方法

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WO2018110579A1 (ja) * 2016-12-14 2018-06-21 古河電気工業株式会社 表面処理銅箔および銅張積層板
CN113099605A (zh) * 2021-06-08 2021-07-09 广州方邦电子股份有限公司 金属箔、带载体金属箔、覆铜层叠板及印刷线路板

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