WO2022255421A1 - 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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WO2022255421A1
WO2022255421A1 PCT/JP2022/022387 JP2022022387W WO2022255421A1 WO 2022255421 A1 WO2022255421 A1 WO 2022255421A1 JP 2022022387 W JP2022022387 W JP 2022022387W WO 2022255421 A1 WO2022255421 A1 WO 2022255421A1
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Prior art keywords
copper foil
roughened
less
cutoff
value
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PCT/JP2022/022387
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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 JP2023525898A priority Critical patent/JPWO2022255421A1/ja
Priority to CN202280039573.8A priority patent/CN117441039A/zh
Priority to KR1020237043495A priority patent/KR20240017841A/ko
Publication of WO2022255421A1 publication Critical patent/WO2022255421A1/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
    • B32B15/20—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
    • 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
    • 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 found that the Rdc/Rku, which is the ratio of the cutting level difference Rdc to the kurtosis Rku, and the maximum cross-sectional height Wt on the surface of the roughened copper foil are controlled within a predetermined range. It has been found that a copper-clad laminate or printed wiring board produced by using the compound is excellent in transmission characteristics and circuit linearity, and can achieve high peel strength.
  • an object of the present invention is to provide a roughened copper foil that is excellent in transmission characteristics and circuit linearity and capable of achieving high peel strength when used in copper-clad laminates or printed wiring boards. be.
  • a roughened copper foil having a roughened surface on at least one side In the roughened surface, Rdc/Rku, which is the ratio of the cutting level difference Rdc of the roughness curve to the kurtosis Rku of the roughness curve, is 0.180 ⁇ m or less, and the maximum cross-sectional height Wt of the undulation curve is 2.0 ⁇ m.
  • the Rku is a value measured in accordance with JIS B0601-2013 under the conditions of a magnification of 200, a cutoff wavelength of 0.3 ⁇ m with a cutoff value ⁇ s, and a cutoff wavelength of 5 ⁇ m with a cutoff value ⁇ c
  • the Rdc is measured in accordance with JIS B0601-2013 under the conditions of a magnification of 200, a cutoff wavelength of 0.3 ⁇ m with a cutoff value ⁇ s, and a cutoff wavelength of 5 ⁇ m with a cutoff value ⁇ c.
  • the roughened surface has an average height Rc of roughness curve elements of 0.70 ⁇ m or less, and the Rc is a cutoff wavelength of 0 at a magnification of 200 and a cutoff value ⁇ s in accordance with JIS B0601-2013. .3 ⁇ m and a cutoff wavelength of 5 ⁇ m with a cutoff value ⁇ c.
  • the roughened surface has a cutting level difference Wdc of the undulating curve of 1.20 ⁇ m or more and 3.10 ⁇ m or less, and the Wdc is cut off by a cutoff value ⁇ c at a magnification of 20 times in accordance with JIS B0601-2013.
  • the roughened copper foil according to any one of aspects 1 to 5, which is a value obtained as a difference in cutting level c (c(Wmr1)-c(Wmr2)).
  • the roughened surface has a roughness curve root-mean-square height Rq of 0.290 ⁇ m or less, and the Rq is a cutoff wavelength with a cutoff value ⁇ s at a magnification of 200 in accordance with JIS B0601-2013. 7.
  • FIG. 4 is a diagram for explaining a load curve of a roughness curve determined according to JIS B0601-2013;
  • FIG. 4 is a diagram for explaining a load length ratio Rmr(c) determined according to JIS B0601-2013;
  • FIG. 4 is a diagram for explaining a cutting level difference Rdc determined in compliance with JIS B0601-2013;
  • 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.
  • BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows an example of the roughening process copper foil of this invention.
  • the "load curve of the roughness curve” refers to the substantial part that appears when the roughness curve is cut at cutting level c, determined in accordance with JIS B0601-2013, as shown in FIG. is a curve representing the ratio of as a function of c. That is, the load curve of the roughness curve can also be said to be a curve representing the height at which the load length ratio Rmr(c) is from 0% to 100%.
  • the load length ratio Rmr(c) is the ratio of the load length of the roughness curve element at the cutting level c to the evaluation length, determined in accordance with JIS B0601-2013, as shown in FIG. is a parameter that represents
  • cutting level difference Rdc of roughness curve refers to roughness measured in accordance with JIS B0601-2013, as shown in FIG. A parameter that represents the difference (c(Rmr1)-c(Rmr2)) in the cutting level c in the height direction between the two load length ratios Rmr1 and Rmr2 (where Rmr1 ⁇ Rmr2) in the load curve of the curve. . Assume herein that Rdc is calculated by specifying Rmr1 as 20% and Rmr2 as 80%.
  • roughness curve root mean square height Rq means that the reference length measured in accordance with JIS B0601-2013 is Z (x) is a parameter representing the root mean square of (Z(x) represents the height of the roughness curve at an arbitrary position x).
  • the terms "roughness curve kurtosis Rku”, “kurtosis Rku” or “Rku” are dimensionless by the square root mean square height Rq measured in accordance with JIS B0601-2013. It is a parameter representing the mean square of Z(x) in the reference length.
  • Rku means kurtosis, which is a measure of the sharpness of the surface, and represents the sharpness of the height distribution.
  • Rku>3 means that the height distribution is sharp
  • Rku ⁇ 3 means that the height distribution is flat. do.
  • Rdc/Rku is a parameter representing the ratio of the cleavage level difference Rdc to the kurtosis Rku.
  • average height Rc of the roughness curve element refers to the roughness curve element at the reference length measured in accordance with JIS B0601-2013. This parameter represents the average height.
  • Roughness curve element means a set of adjacent peaks and valleys in the roughness curve. A minimum height and a minimum length are specified for the peaks or valleys that constitute the roughness curve element, and the height is 10% or less of the maximum height Rz, or the length is 1% or less of the reference length. Some are considered noise and are part of the valleys or mountains that follow.
  • maximum cross-sectional height Wt of undulation curve refers to the crest height of the undulation curve at the evaluation length measured in accordance with JIS B0601-2013. This parameter represents the sum of the maximum depth and the maximum valley depth.
  • maximum peak height Wp of the undulation curve refers to the peak height of the undulation curve at the reference length measured in accordance with JIS B0601-2013. This parameter represents the maximum value.
  • the "load curve of the undulation curve” is a curve that expresses the ratio of the substantial part that appears when the undulation curve is cut at the cutting level c as a function of c, which is determined in accordance with JIS B0601-2013. is. That is, the load curve of the undulation curve can also be said to be a curve representing the height at which the load length ratio Wmr(c) is from 0% to 100%.
  • the load length ratio Wmr(c) is a parameter representing the ratio of the load length of the undulating curve element at the cut level c to the evaluation length determined in accordance with JIS B0601-2013.
  • cutting level difference Wdc of waviness curve refers to two load lengths in a waviness curve load curve measured in accordance with JIS B0601-2013. This is a parameter representing the difference (c(Wmr1)-c(Wmr2)) in the cutting level c in the height direction between the depth ratios Wmr1 and Wmr2 (where Wmr1 ⁇ Wmr2). Assume herein that Wdc is calculated by specifying Wmr1 as 20% and Wmr2 as 80%.
  • Rdc, Rq, Rku, Rc, Wt, Wp and Wdc can be calculated by measuring a surface profile of a predetermined measurement length on the roughened surface with a commercially available laser microscope.
  • the roughness parameters Rdc, Rq, Rku, and Rc are measured under the conditions of a magnification of 200, a cutoff wavelength of 0.3 ⁇ m with a cutoff value ⁇ s, and a cutoff wavelength of 5 ⁇ m with a cutoff value ⁇ c.
  • the reference length and the evaluation length used for calculating the roughness parameter are set to 5 ⁇ m and 25 ⁇ m, respectively.
  • the waviness parameters Wt, Wp, and Wdc are measured under the conditions of a magnification of 20, a cutoff wavelength of 5 ⁇ m with a cutoff value ⁇ c, and no cutoff with a cutoff value ⁇ f.
  • the reference length and the evaluation length used to calculate the waviness parameter are both the same as the measured length of the roughened surface.
  • the waviness parameter is measured for a region of 643.973 ⁇ m long ⁇ 643.393 ⁇ m wide on the roughened surface. 643.973 ⁇ m in case and 643.393 ⁇ m in lateral direction.
  • the above magnification corresponds to the value obtained by multiplying the magnification of the objective lens by the magnification of the optical zoom.
  • preferable measurement conditions and analysis conditions for the surface profile by the laser microscope will be shown in Examples below.
  • 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.
  • Rdc/Rku which is the ratio of the cutting level difference Rdc of the roughness curve to the kurtosis Rku of the roughness curve, is 0.180 ⁇ m or less.
  • the roughened surface has a maximum cross-sectional height Wt of an undulating curve of 2.50 ⁇ m or more and 10.00 ⁇ m or less.
  • a copper clad laminate or a printed wiring board manufactured using the roughened copper foil can achieve transmission It is excellent in characteristics (high frequency characteristics) and circuit linearity, and can achieve high peel strength.
  • 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.
  • a copper foil surface with small undulations for example, the surface of a double-sided smooth foil or the electrode surface of an electrolytic copper foil
  • the peel strength between the copper foil and the substrate is generally low.
  • the present inventors studied the effects of roughened particles and undulations on the copper foil surface on transmission characteristics, circuit linearity, and peel strength. As a result, it was found that, contrary to expectations, the waviness component of the copper foil had little effect on the transmission characteristics, and that the size of the roughening particles mainly affected the transmission characteristics. Then, the present inventors made the bumps (roughened particles) finer in order to improve the transmission characteristics, and compensated for the insufficient adhesion by undulating the copper foil, which has a small effect on the transmission characteristics. , it was found that both excellent transmission characteristics and adhesion reliability due to high peel strength can be achieved.
  • Roughened particle components and waviness components on the copper foil surface that affect transmission characteristics, circuit linearity, or peel strength can be distinguished by properly using the measurement magnification in a laser microscope and the cutoff values ⁇ s, ⁇ c, and ⁇ f. .
  • the roughened surface by measuring the roughened surface at a high magnification of 200 times, it is possible to accurately evaluate the fine irregularities of the roughened surface that affect the transmission characteristics.
  • the influence of the waviness component can be reduced.
  • a cut roughness parameter can be calculated.
  • the roughness parameters in the present invention are parameters that accurately reflect the roughened particle component on the copper foil surface.
  • Rdc, Rku, Rdc/Rku, Rc and Rq are parameters that accurately reflect the roughened particle component on the copper foil surface.
  • the roughened surface can be evaluated accurately.
  • by measuring the roughened surface at a low magnification of 20 times it is possible to extensively evaluate the height (undulation) of the entire roughened surface that affects circuit linearity and adhesion reliability. can.
  • the undulation curve obtained by measuring the roughened surface under the conditions where the cutoff wavelength is 5 ⁇ m with the cutoff value ⁇ c and the cutoff value ⁇ f is not performed the effect of the roughened particle component is cut. undulation parameters can be calculated.
  • the waviness parameters in the present invention are parameters that adequately reflect waviness components on the copper foil surface, and by using these indices, circuit linearity and peel strength can be accurately evaluated. can do.
  • the roughened surface of the roughened copper foil has a maximum cross-sectional height Wt of the undulating curve of 2.50 ⁇ m or more and 10.00 ⁇ m or less, preferably 2.90 ⁇ m or more and 10.00 ⁇ m or less, more preferably 3.10 ⁇ m or more. It is 9.00 ⁇ m or less, more preferably 3.30 ⁇ m or more and 7.00 ⁇ m or less.
  • Wt is within the above range, excellent circuit linearity and high peel strength can be achieved in a well-balanced manner while ensuring excellent transmission characteristics.
  • Rdc/Rku of the roughened surface of the roughened copper foil is 0.180 ⁇ m or less, preferably 0.015 ⁇ m or more and 0.150 ⁇ m or less, more preferably 0.030 ⁇ m or more and 0.110 ⁇ m or less, and still more preferably 0 0.045 ⁇ m or more and 0.080 ⁇ m or less.
  • Rdc/Rku is within the above range, excellent transmission characteristics can be achieved while maintaining excellent circuit linearity and high peel strength.
  • the roughened surface of the roughened copper foil preferably has a roughness curve cutting level difference Rdc of 0.45 ⁇ m or less, more preferably 0.04 ⁇ m or more and 0.40 ⁇ m or less, and still more preferably 0.08 ⁇ m or more. It is 0.35 ⁇ m or less, particularly preferably 0.12 ⁇ m or more and 0.30 ⁇ m or less.
  • Rdc is within the above range, it becomes easier to control Rdc/Rku within the above range, and further excellent transmission characteristics can be achieved.
  • the roughened surface of the roughened copper foil preferably has a roughness curve kurtosis Rku of 1.30 or more and 8.00 or less, more preferably 1.50 or more and 5.50 or less, and still more preferably 2.50 or more. 00 or more and 4.50 or less, particularly preferably 2.50 or more and 3.20 or less.
  • Rku is within the above range, it becomes easier to control Rdc/Rku within the above range, and further excellent transmission characteristics can be achieved.
  • the roughened surface of the roughened copper foil preferably has a peak height Wp of 1.00 ⁇ m or more and 6.00 ⁇ m or less, more preferably 1.20 ⁇ m or more and 5.00 ⁇ m or less, and still more preferably 1 .30 ⁇ m or more and 4.30 ⁇ m or less, particularly preferably 1.40 ⁇ m or more and 3.70 ⁇ m or less.
  • Wp is within the above range, excellent circuit linearity and high peel strength can be achieved in a better balance while ensuring excellent transmission characteristics.
  • the roughened surface of the roughened copper foil preferably has an average height Rc of roughness curve elements of 0.70 ⁇ m or less, more preferably 0.06 ⁇ m or more and 0.60 ⁇ m or less, and still more preferably 0.12 ⁇ m. 0.50 ⁇ m or less, particularly preferably 0.18 ⁇ m or more and 0.50 ⁇ m or less.
  • Rc is within the above range, even better transmission characteristics can be achieved while maintaining excellent circuit linearity and high peel strength.
  • the roughened surface of the roughened copper foil preferably has a cutting level difference Wdc of the undulating curve of 1.20 ⁇ m or more and 3.10 ⁇ m or less, more preferably 1.20 ⁇ m or more and 2.70 ⁇ m or less, still more preferably 1 .30 ⁇ m or more and 2.30 ⁇ m or less, particularly preferably 1.60 ⁇ m or more and 2.00 ⁇ m or less.
  • Wdc is within the above range, it is possible to achieve excellent circuit linearity and high peel strength in a well-balanced manner while ensuring excellent transmission characteristics.
  • the roughened surface of the roughened copper foil preferably has a roughness curve with a root-mean-square height Rq of 0.290 ⁇ m or less, more preferably 0.030 ⁇ m or more and 0.260 ⁇ m or less, still more preferably 0.290 ⁇ m or less. 060 ⁇ m or more and 0.220 ⁇ m or less, particularly preferably 0.090 ⁇ m or more and 0.200 ⁇ m or less.
  • Rq is within the above range, it is possible to achieve even better transmission characteristics while maintaining excellent circuit linearity and high peel strength.
  • the thickness of the roughened copper foil is not particularly limited, but is preferably 0.1 ⁇ m or more and 210 ⁇ m or less, more preferably 0.3 ⁇ m or more and 105 ⁇ m or less, still more preferably 7 ⁇ m or more and 70 ⁇ m or less, and particularly preferably 9 ⁇ m or more and 35 ⁇ 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 each of these roughened particles preferably consists 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 10.00 ⁇ m or less, more preferably It is 1.50 ⁇ m or more and 8.00 ⁇ 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.
  • an anticorrosive layer and/or a silane coupling agent-treated layer are formed on the roughened surface, more preferably an anticorrosive layer and a silane coupling agent-treated layer.
  • each numerical value of the roughness parameter and waviness parameter in this specification is It means a numerical value obtained by measuring the surface of the roughened copper foil after the agent-treated 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.
  • first roughening treatment For Examples 1 to 8, 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 conditions of liquid resistance index, current density and time shown in Table 1, followed by washing with water.
  • 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 1 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 electrolysis under the conditions of liquid resistance index, current density and time shown in Table 1 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 1 Electrolysis was carried out under the liquid resistance index, current density and time conditions shown in , followed by washing with water.
  • the antirust treatment shown in Table 1 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, with a potassium pyrophosphate concentration of 100 g / L, a zinc concentration of 1 g / L, 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 antirust treatment B under the same conditions as the surface of the electrolytic copper foil not subjected to roughening treatment in Examples 1 and 5 to 8. gone.
  • 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, 3, 4 and 6-8, and 3-glycidoxypropyltrimethoxysilane was used in Examples 2, 5 and 9-11.
  • 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.
  • the obtained surface profile of the roughened surface was analyzed according to the conditions shown in Tables 2 and 3, and Rdc, Rku, Rc, Rq, Wdc, Wt and Wp were calculated. Also, Rdc/Rku was calculated based on the obtained Rdc and Rku values. The results were as shown in Table 4.
  • ⁇ Preparation of copper-clad laminate Two prepregs (thickness: 100 ⁇ m) mainly composed of polyphenylene ether, triallyl isocyanurate, and bismaleimide resin were prepared and stacked as insulating substrates.
  • the manufactured surface-treated copper foil was laminated on the stacked prepreg so that the roughened surface was in contact with the prepreg, and pressed at 32 kgf/cm 2 and 205° C. for 120 minutes to obtain a 34 cm ⁇ 34 cm copper clad.
  • a laminate was produced.
  • Circuit linearity was evaluated as follows. First, for Examples 4 to 7, etching was performed on the copper-foil-side surface of the above-described copper-clad laminate until the thickness of the copper foil reached 12 ⁇ m. For Examples 1 to 11, a dry film was attached to the surface of the copper-clad laminate on the copper foil side, followed by exposure and development to form an etching resist. By treating with a copper chloride etchant, copper was dissolved and removed from between the resists to form linear circuits each having a width of 300 ⁇ m, a height of 12 ⁇ m, and a length of 10 cm or 15 cm (six in total).
  • the linear circuit thus obtained was observed with an optical microscope, and the circuit width was measured by randomly selecting 30 points per circuit. An average value and a standard deviation were calculated for the obtained 30 sets of circuit width data, and the coefficient of variation (%) for each circuit was calculated by dividing the standard deviation by the average value. The average value of the variation coefficients in the six circuits was obtained and used as the circuit width variation coefficient in each example. The quality of the obtained circuit width variation coefficient was evaluated according to the following criteria. The results were as shown in Table 4. ⁇ Circuit Width Variation Coefficient Evaluation Criteria> -Good: Circuit width variation coefficient is 1.50% or less -Bad: Circuit width variation coefficient is over 1.50%
  • ⁇ Peel strength between copper foil and substrate> In order to evaluate the adhesion between the roughened copper foil and the insulating substrate, the normal peel strength was measured as follows. First, for Examples 4 to 7, etching was performed on the copper-foil-side surface of the above-described copper-clad laminate until the thickness of the copper foil reached 12 ⁇ m. For Examples 1 to 11, circuit formation was performed on the copper-clad laminate by an etching method to produce a test substrate having a straight circuit with a width of 3 mm. 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.
  • 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 28 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 4. ⁇ Transmission loss evaluation criteria> -Good: Transmission loss is -0.33 dB/cm or more -Bad: Transmission loss is less than -0.33 dB/cm

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  • Laminated Bodies (AREA)
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PCT/JP2022/022387 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 WO2022255421A1 (ja)

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JP2014201777A (ja) * 2013-04-02 2014-10-27 Jx日鉱日石金属株式会社 キャリア付き銅箔
WO2019188087A1 (ja) * 2018-03-30 2019-10-03 三井金属鉱業株式会社 銅張積層板

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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
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
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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WO2014042201A1 (ja) * 2012-09-11 2014-03-20 Jx日鉱日石金属株式会社 キャリア付き銅箔
JP2014201777A (ja) * 2013-04-02 2014-10-27 Jx日鉱日石金属株式会社 キャリア付き銅箔
WO2019188087A1 (ja) * 2018-03-30 2019-10-03 三井金属鉱業株式会社 銅張積層板

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