WO2014003019A1 - Rolled copper foil, method for producing same, and laminate plate - Google Patents

Rolled copper foil, method for producing same, and laminate plate Download PDF

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Publication number
WO2014003019A1
WO2014003019A1 PCT/JP2013/067413 JP2013067413W WO2014003019A1 WO 2014003019 A1 WO2014003019 A1 WO 2014003019A1 JP 2013067413 W JP2013067413 W JP 2013067413W WO 2014003019 A1 WO2014003019 A1 WO 2014003019A1
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WIPO (PCT)
Prior art keywords
copper foil
rolling
rolled copper
less
final
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PCT/JP2013/067413
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French (fr)
Japanese (ja)
Inventor
嘉一郎 中室
拓摩 吉川
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Jx日鉱日石金属株式会社
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Application filed by Jx日鉱日石金属株式会社 filed Critical Jx日鉱日石金属株式会社
Priority to KR1020157002391A priority Critical patent/KR101669774B1/en
Priority to CN201380001896.9A priority patent/CN103636296B/en
Publication of WO2014003019A1 publication Critical patent/WO2014003019A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21BROLLING OF METAL
    • B21B1/00Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/40Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling foils which present special problems, e.g. because of thinness
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21BROLLING OF METAL
    • B21B3/00Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered 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
    • B32B15/08Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/28Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/09Use of materials for the conductive, e.g. metallic pattern
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/02Apparatus 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
    • H05K3/022Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/412Transparent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • B32B2457/08PCBs, i.e. printed circuit boards
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01Dielectrics
    • H05K2201/0137Materials
    • H05K2201/0154Polyimide
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03Conductive materials
    • H05K2201/0332Structure of the conductor
    • H05K2201/0335Layered conductors or foils
    • H05K2201/0355Metal foils
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03Conductive materials
    • H05K2201/0332Structure of the conductor
    • H05K2201/0335Layered conductors or foils
    • H05K2201/0358Resin coated copper [RCC]

Definitions

  • the present invention relates to a rolled copper foil and a method for producing the same, and a laminated board, and in particular, a rolled copper foil suitable for a field where transparency of the remaining resin after etching the copper foil is required, and a method for producing the same. , Relating to laminates.
  • FPC flexible printed wiring boards
  • the signal current propagates near the surface of the wiring. Therefore, if the surface of the copper foil used as the FPC wiring member is rough, the signal loss increases. Therefore, the smoothness of the surface is required for the high-frequency copper foil.
  • the marker position is confirmed by a CCD camera through a resin layer (for example, polyimide) serving as the base of the FPC, and the bonding position is adjusted.
  • the resin layer of FPC is obtained by removing the copper layer by etching after bonding the copper foil and the resin layer. Therefore, the resin layer surface is a replica to which the unevenness of the copper foil surface is transferred. That is, if the surface of the copper foil is rough, the surface of the resin layer is also rough, and light is irregularly reflected, so that the transparency is lowered. For this reason, in order to improve the light transmittance of a resin layer, it is necessary to make the adhesive surface with the resin layer of copper foil smooth. In general, the adhesive surface of the copper foil with the resin layer is subjected to roughening plating in order to increase the adhesive strength. Since the plating particles for the roughening treatment are larger than the surface roughness of the copper foil, the plating conditions have been mainly improved so far as means for smoothing the copper foil surface.
  • Patent Document 1 discloses an adhesion layer that is formed of chromium and zinc ions or oxides on the surface of a copper foil and is processed using an aqueous solution containing at least 0.5% of silane. The copper foil is shown.
  • the adhesion strength of the demonstration sample disclosed in Patent Document 1 is lower than that of a rough copper foil as a comparative sample.
  • the adhesion strength with the resin layer is lowered, and thus there is a limit to smoothing by improving the rough plating. For this reason, it is difficult to achieve both ensuring of the adhesion strength between the resin layer and the copper foil and improving the visibility of the resin layer.
  • the present invention is a rolled copper having a smooth surface even when subjected to the same roughening plating as before, excellent adhesion to the resin, and excellent transparency of the resin after the copper foil is removed by etching. It is an object to provide a foil, a manufacturing method thereof, and a laminated board.
  • the inventors smoothed the surface of the rolled copper foil as a base material for rough plating by a predetermined means, and by using the rolled copper foil whose gloss level was controlled within a predetermined range, It has been found that the transparency of the resin after removing the copper foil by etching is improved even when a roughening treatment for obtaining good adhesion with the resin is performed.
  • a 180 ° adhesive bending with the polyimide film surface inside is performed on a sample of a single-sided copper clad laminate having a width of 3 mm or more and 5 mm or less laminated, the number of times of bending until the copper foil breaks is 3 times. It is the rolled copper foil which is the above.
  • the oil film equivalent in the final rolling pass of the final cold rolling process is 17000 or less, the oil film equivalent in the rolling pass immediately before the final rolling pass is 15000 or less, and the oil film equivalent in the rolling pass immediately before is further reduced.
  • the present invention is a laminated plate configured by laminating the rolled copper foil of the present invention and a resin substrate.
  • a rolled copper foil a method for producing the same, and a laminated plate that are excellently bonded to a resin and excellent in transparency of the resin after the copper foil is removed by etching.
  • Example 3 is a SEM image of the copper foil surface of Example 2.
  • 6 is a SEM image of a copper foil surface of Comparative Example 2.
  • the rolled copper foil used in the present invention is useful for a rolled copper foil that is used by bonding a resin substrate to produce a laminate and partially removing the copper foil by etching.
  • the surface of the copper foil that adheres to the resin substrate that is, the roughened surface, has a fist-like electric surface on the surface of the copper foil after degreasing in order to improve the peel strength of the copper foil after lamination.
  • a roughening process is carried out to wear. This roughening treatment can be performed by copper-cobalt-nickel alloy plating, copper-nickel-phosphorus alloy plating, or the like.
  • the rolled copper foil according to the present invention includes a copper alloy foil containing one or more elements such as Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V.
  • a copper alloy containing 10 to 2000 ppm of the above element or a copper alloy containing 10 to 500 ppm is included.
  • the conductivity of the rolled copper foil is preferably 50% IACS or more, more preferably 60% IACS or more, and still more preferably 80% IACS or more.
  • the thickness of the copper foil is not particularly limited, but is preferably 5 to 50 ⁇ m, more preferably 5 to 35 ⁇ m.
  • the rolled copper foil of the present invention has a 60-degree glossiness G in the rolling parallel direction of more than 500. For this reason, the smoothness of the copper foil surface becomes good, and the transparency of the resin after removing the copper foil by etching becomes good even if a roughening treatment for obtaining good adhesion with the resin is performed.
  • the 60-degree glossiness G in the rolling parallel direction is 500 or less, when the roughening treatment is performed to obtain good adhesion to the resin, the transparency of the resin after removing the copper foil by etching is good. It becomes difficult to obtain.
  • the 60-degree glossiness G in the rolling parallel direction is preferably 520 or more, and more preferably 550 or more.
  • the 60 degree glossiness G in the rolling parallel direction is 600 or more. Although there is no upper limit on the 60-degree glossiness G in terms of the characteristics of the copper foil, the 60-degree glossiness G in the rolling parallel direction can be 900 or less in consideration of manufacturability and the like.
  • the rolled copper foil of the present invention performs 180 ° adhesion bending with a polyimide film surface on the inside of a sample of a single-sided copper clad laminate having a width of 3 mm or more and 5 mm or less obtained by laminating a copper foil and a polyimide film having a film thickness of 25 ⁇ m.
  • the number of times of bending until the copper foil breaks is preferably 3 times or more, and more preferably 5 times or more. If the flexibility is good so as to satisfy such conditions, it can be suitably used as an LCD module FPC.
  • a raw material is first melt
  • the oil film equivalent in the final rolling pass of the final cold rolling step is 17000 or less
  • the oil film equivalent in the rolling pass immediately before the final rolling pass is 15000 or less
  • the oil film equivalent is defined by the following equation.
  • Oil film equivalent ⁇ (rolling oil viscosity [cSt]) ⁇ (sheet feeding speed [mpm] + roll peripheral speed [mpm]) ⁇ / ⁇ (roll biting angle [rad]) ⁇ (yield stress of material [kg / mm 2 ]) ⁇
  • the rolling oil viscosity [cSt] is a kinematic viscosity at 40 ° C.
  • a known method such as using a low-viscosity rolling oil or slowing the sheet passing speed may be used. By controlling the oil film equivalent, deformation of the material surface is constrained by the roll, and an increase in surface roughness accompanying a change in thickness due to rolling can be suppressed.
  • the gloss level after the final pass can be controlled within a desired range. If the gloss level is low immediately before the final pass, even if the material surface is smoothed in the final pass, deep irregularities formed up to the previous pass remain, and the desired surface shape cannot be obtained.
  • the surface of the rolling roll is preferably smooth.
  • the average roughness Ra when the rolling roll used with the manufacturing method of the rolled copper foil of this invention is measured in the direction parallel to the rotating shaft of a roll is 0.1 micrometer or less.
  • the laminated copper foil can be manufactured by bonding the rolled copper foil of the present invention to the resin substrate from the roughened surface side.
  • the resin substrate is not particularly limited as long as it has characteristics applicable to a printed wiring board and the like.
  • a polyester film such as polyethylene terephthalate (PET), a polyimide film, a liquid crystal polymer (LCP) film, etc. are used. I can do it.
  • the method of laminating can be applied to a substrate such as a polyimide film via an adhesive, or laminated and bonded to a rolled copper foil under high temperature and high pressure without using an adhesive, or a polyimide precursor is applied and dried.
  • a substrate such as a polyimide film via an adhesive
  • laminated and bonded to a rolled copper foil under high temperature and high pressure without using an adhesive or a polyimide precursor is applied and dried.
  • -A laminated board can be manufactured by performing hardening etc.
  • each rolled copper foil was prepared as follows. First, after producing a copper ingot having the composition shown in Table 1 and performing hot rolling, cold rolling and annealing in an annealing furnace set to a temperature of 300 to 800 ° C. are repeated at least once, and then cold rolling is performed. Thus, a rolled plate having a thickness of 1 to 2 mm was obtained. This rolled sheet was annealed and recrystallized in an annealing furnace set to a temperature of 300 to 800 ° C., and finally cold-rolled to the thickness shown in Table 1.
  • the conditions for the roughening treatment were set as follows. The conditions for the roughening treatment were generally used for FPC applications as those that would give practically sufficient peel strength.
  • -Plating bath composition Cu 15 g / L, Co 8.5 g / L, Ni 8.6 g / L -Treatment solution pH: 2.5 ⁇ Processing temperature: 38 °C ⁇ Current density: 20 A / dm 2 ⁇ Plating time: 2.0 seconds
  • haze value (%) is a value calculated by (diffuse transmittance) / (total light transmittance) ⁇ 100.
  • One surface of each sample copper foil was plated under the following conditions as a roughening treatment.
  • ⁇ Peel strength (adhesive strength);
  • the normal peel strength is measured with a tensile tester Autograph 100, and the normal peel strength is 0.7 N / mm or more that can be used for laminated substrate applications (judgment “ ⁇ ”). Those with less than 0.7 N / mm could not be used (judgment “x”).
  • FIG. 2 shows an SEM image of the copper foil surface of Comparative Example 2.
  • the 60-degree glossiness G in the rolling parallel direction was greater than 500, and the adhesion to the resin, the visibility of the resin, and the bendability were good.
  • the 60-degree glossiness G in the rolling parallel direction was 500 or less, and the visibility of the resin was poor. Some also had poor bendability.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Thermal Sciences (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)
  • Metal Rolling (AREA)
  • Manufacturing & Machinery (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Structure Of Printed Boards (AREA)

Abstract

Provided are: a rolled copper foil that adheres favorably to resin, and is such that the resin transparency is superior after removing the copper foil by means of etching; a method for producing the rolled copper foil; and a laminate plate. In the rolled copper foil, of which the 60° glossiness (G) in the direction parallel to rolling is greater than 500 and no greater than 900, when a 180° tight rolling is performed with the polyimide film surface on the inside of a sample of a one-sided-copper-clad laminate plate having a width of 3-5 mm inclusive and resulting from laminating a copper foil and a polyimide film having a thickness of 25 μm, the number of bending repetitions until the copper foil breaks is at least three.

Description

圧延銅箔及びその製造方法、並びに、積層板Rolled copper foil, method for producing the same, and laminate
 本発明は、圧延銅箔及びその製造方法、並びに、積層板に関し、特に、銅箔をエッチングした後の残部の樹脂の透明性が要求される分野に好適な圧延銅箔及びその製造方法、並びに、積層板に関する。 TECHNICAL FIELD The present invention relates to a rolled copper foil and a method for producing the same, and a laminated board, and in particular, a rolled copper foil suitable for a field where transparency of the remaining resin after etching the copper foil is required, and a method for producing the same. , Relating to laminates.
 近年、電子機器の高機能化に伴い、信号の高周波化が進んでおり、それに伴い信号配線として用いられるフレキシブルプリント配線板(以下、FPC)にも高周波対応が求められてきている。信号が高周波化すると、信号電流は配線の表面近傍を伝播するために、FPCの配線部材として用いられる銅箔の表面が粗いと信号の損失が大きくなる。そのため高周波対応の銅箔には表面の平滑性が求められる。
 また、FPCをLCDとACF接合する際に、FPCのベースとなる樹脂層(例えば、ポリイミド)越しにCCDカメラでマーカー位置を確認し、接合位置合わせを行う。このため樹脂層の透明度が低いと位置合わせができない。
 FPCの樹脂層は、銅箔と樹脂層とを接合した後にエッチングによって銅層を除去したものである。そのため樹脂層表面は、銅箔表面の凹凸を転写したレプリカとなっている。つまり、銅箔表面が粗いと樹脂層表面も粗くなり、光を乱反射するために透明度が低下する。このため、樹脂層の光透過性を改善するためには、銅箔の樹脂層との接着面を平滑にする必要がある。
 一般に、銅箔の樹脂層との接着面は、接着強度を増すために粗化めっき処理される。銅箔の表面粗さに比べて粗化処理のめっき粒子が大きいことから、銅箔表面を平滑にする手段として、これまで主としてめっき条件の改良が行われてきた。
In recent years, with the increase in functionality of electronic devices, the frequency of signals has been increased, and accordingly, flexible printed wiring boards (hereinafter referred to as FPC) used as signal wiring have been required to support high frequencies. When the frequency of the signal is increased, the signal current propagates near the surface of the wiring. Therefore, if the surface of the copper foil used as the FPC wiring member is rough, the signal loss increases. Therefore, the smoothness of the surface is required for the high-frequency copper foil.
Further, when the FPC is bonded to the LCD by the ACF, the marker position is confirmed by a CCD camera through a resin layer (for example, polyimide) serving as the base of the FPC, and the bonding position is adjusted. For this reason, if the transparency of the resin layer is low, alignment cannot be performed.
The resin layer of FPC is obtained by removing the copper layer by etching after bonding the copper foil and the resin layer. Therefore, the resin layer surface is a replica to which the unevenness of the copper foil surface is transferred. That is, if the surface of the copper foil is rough, the surface of the resin layer is also rough, and light is irregularly reflected, so that the transparency is lowered. For this reason, in order to improve the light transmittance of a resin layer, it is necessary to make the adhesive surface with the resin layer of copper foil smooth.
In general, the adhesive surface of the copper foil with the resin layer is subjected to roughening plating in order to increase the adhesive strength. Since the plating particles for the roughening treatment are larger than the surface roughness of the copper foil, the plating conditions have been mainly improved so far as means for smoothing the copper foil surface.
 このような技術として、例えば、特許文献1には、銅箔表面にクロム及び亜鉛のイオンまたは酸化物から形成され、少なくとも0.5%のシランを含有する水溶液を用いて処理される付着層を持つ銅箔が示されている。 As such a technique, for example, Patent Document 1 discloses an adhesion layer that is formed of chromium and zinc ions or oxides on the surface of a copper foil and is processed using an aqueous solution containing at least 0.5% of silane. The copper foil is shown.
特開2012-39126号公報JP 2012-39126 A
 しかしながら、特許文献1に開示された実証サンプルの密着強度は比較サンプルである粗い銅箔と比較すると接着強度は低い値にとどまっている。このように、粗化粒子を過度に微細化すると樹脂層との密着強度が低下することから、粗化めっきの改良による平滑化には限界があった。このため、樹脂層と銅箔との密着強度の確保と、樹脂層の視認性の向上とを両立することが困難となっている。
 本発明は、従来と同じ粗化めっきを施した場合にも平滑な表面を有し、樹脂と良好に接着し、且つ、銅箔をエッチングで除去した後の樹脂の透明性に優れた圧延銅箔及びその製造方法、並びに、積層板を提供することを課題とする。
However, the adhesion strength of the demonstration sample disclosed in Patent Document 1 is lower than that of a rough copper foil as a comparative sample. As described above, when the coarse particles are excessively refined, the adhesion strength with the resin layer is lowered, and thus there is a limit to smoothing by improving the rough plating. For this reason, it is difficult to achieve both ensuring of the adhesion strength between the resin layer and the copper foil and improving the visibility of the resin layer.
The present invention is a rolled copper having a smooth surface even when subjected to the same roughening plating as before, excellent adhesion to the resin, and excellent transparency of the resin after the copper foil is removed by etching. It is an object to provide a foil, a manufacturing method thereof, and a laminated board.
 本発明者らは鋭意研究を重ねた結果、粗化めっきの母材となる圧延銅箔の表面を所定の手段で平滑化し、光沢度を所定の範囲に制御した圧延銅箔を用いることで、樹脂との良好な密着性を得るための粗化処理を行っても、銅箔をエッチングで除去した後の樹脂の透明性が良好となることを見出した。 As a result of intensive research, the inventors smoothed the surface of the rolled copper foil as a base material for rough plating by a predetermined means, and by using the rolled copper foil whose gloss level was controlled within a predetermined range, It has been found that the transparency of the resin after removing the copper foil by etching is improved even when a roughening treatment for obtaining good adhesion with the resin is performed.
 以上の知見を基礎として完成された本発明は一側面において、圧延平行方向の60度光沢度Gが500以上且つ900以下である圧延銅箔であり、前記銅箔とフィルム厚25μmのポリイミドフィルムとを積層した幅3mm以上5mm以下の片面銅張積層板の試料に対し、前記ポリイミドフィルム面を内側とした180°密着曲げを行ったときに、前記銅箔が破断するまでの曲げ回数が3回以上である圧延銅箔である。 The present invention completed on the basis of the above knowledge is, in one aspect, a rolled copper foil having a 60-degree gloss G in the rolling parallel direction of 500 or more and 900 or less, the copper foil and a polyimide film having a film thickness of 25 μm, When a 180 ° adhesive bending with the polyimide film surface inside is performed on a sample of a single-sided copper clad laminate having a width of 3 mm or more and 5 mm or less laminated, the number of times of bending until the copper foil breaks is 3 times. It is the rolled copper foil which is the above.
 本発明は別の一側面において、最終冷間圧延工程の最終圧延パスにおける油膜当量を17000以下、最終圧延パスの直前の圧延パスにおける油膜当量を15000以下、更にその直前の圧延パスにおける油膜当量を10000以下とし、且つ、最終圧延工程において、最終圧延パスの直前で圧延平行方向の60度光沢度が500より大になるように調整した後、最終圧延パスを行う本発明に記載の圧延銅箔の製造方法である。 In another aspect of the present invention, the oil film equivalent in the final rolling pass of the final cold rolling process is 17000 or less, the oil film equivalent in the rolling pass immediately before the final rolling pass is 15000 or less, and the oil film equivalent in the rolling pass immediately before is further reduced. The rolled copper foil according to the present invention, in which the final rolling pass is performed after the final rolling pass is adjusted so that the 60-degree glossiness in the rolling parallel direction is greater than 500 immediately before the final rolling pass. It is a manufacturing method.
 本発明は更に別の一側面において、本発明の圧延銅箔と樹脂基板とを積層して構成した積層板である。 In yet another aspect, the present invention is a laminated plate configured by laminating the rolled copper foil of the present invention and a resin substrate.
 本発明によれば、樹脂と良好に接着し、且つ、銅箔をエッチングで除去した後の樹脂の透明性に優れた圧延銅箔及びその製造方法、並びに、積層板を提供することができる。 According to the present invention, it is possible to provide a rolled copper foil, a method for producing the same, and a laminated plate that are excellently bonded to a resin and excellent in transparency of the resin after the copper foil is removed by etching.
実施例2の銅箔表面のSEM像である。3 is a SEM image of the copper foil surface of Example 2. 比較例2の銅箔表面のSEM像である。6 is a SEM image of a copper foil surface of Comparative Example 2.
 〔圧延銅箔の形態及び製造方法〕
 本発明において使用する圧延銅箔は、樹脂基板と接着させて積層体を作製し、エッチングにより部分的に銅箔を除去することで使用される圧延銅箔に有用である。
 通常、銅箔の、樹脂基板と接着する面、即ち粗化面には積層後の銅箔の引き剥し強さを向上させることを目的として、脱脂後の銅箔の表面にふしこぶ状の電着を行う粗化処理が施される。この粗化処理は銅-コバルト-ニッケル合金めっきや銅-ニッケル-りん合金めっき等により行うことができる。
 本発明に係る圧延銅箔にはAg、Sn、In、Ti、Zn、Zr、Fe、P、Ni、Si、Te、Cr、Nb、V等の元素を一種以上含む銅合金箔も含まれる。例えば、上記元素を10~2000ppm含む銅合金、あるいは10~500ppm含む銅合金が含まれる。上記元素の濃度が高くなる(例えば合計で10質量%以上)と、導電率が低下する場合がある。圧延銅箔の導電率は、好ましくは50%IACS以上、より好ましくは60%IACS以上、更に好ましくは80%IACS以上である。また銅箔厚みは特に限定されないが、好ましくは5~50μm、さらに好ましくは5~35μmである。
[Form and manufacturing method of rolled copper foil]
The rolled copper foil used in the present invention is useful for a rolled copper foil that is used by bonding a resin substrate to produce a laminate and partially removing the copper foil by etching.
Usually, the surface of the copper foil that adheres to the resin substrate, that is, the roughened surface, has a fist-like electric surface on the surface of the copper foil after degreasing in order to improve the peel strength of the copper foil after lamination. A roughening process is carried out to wear. This roughening treatment can be performed by copper-cobalt-nickel alloy plating, copper-nickel-phosphorus alloy plating, or the like.
The rolled copper foil according to the present invention includes a copper alloy foil containing one or more elements such as Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V. For example, a copper alloy containing 10 to 2000 ppm of the above element or a copper alloy containing 10 to 500 ppm is included. When the concentration of the above elements increases (for example, 10% by mass or more in total), the conductivity may decrease. The conductivity of the rolled copper foil is preferably 50% IACS or more, more preferably 60% IACS or more, and still more preferably 80% IACS or more. The thickness of the copper foil is not particularly limited, but is preferably 5 to 50 μm, more preferably 5 to 35 μm.
 本発明の圧延銅箔は、圧延平行方向の60度光沢度Gが500より大である。このため、銅箔表面の平滑性が良好となり、樹脂との良好な密着性を得るための粗化処理を行っても、銅箔をエッチングで除去した後の樹脂の透明性が良好となる。圧延平行方向の60度光沢度Gが500以下であると、樹脂との良好な密着性を得るための粗化処理を行った場合、銅箔をエッチングで除去した後の樹脂の良好な透明性を得ることが困難となる。
 また、圧延平行方向の60度光沢度Gが520以上であるのが好ましく、550以上であるのが更に好ましい。圧延平行方向の60度光沢度Gが600以上であるのが更により好ましい。銅箔の特性上は、60度光沢度Gについて上限に制限はないが、製造性等を考慮すると圧延平行方向の60度光沢度Gが900以下とすることができる。
The rolled copper foil of the present invention has a 60-degree glossiness G in the rolling parallel direction of more than 500. For this reason, the smoothness of the copper foil surface becomes good, and the transparency of the resin after removing the copper foil by etching becomes good even if a roughening treatment for obtaining good adhesion with the resin is performed. When the 60-degree glossiness G in the rolling parallel direction is 500 or less, when the roughening treatment is performed to obtain good adhesion to the resin, the transparency of the resin after removing the copper foil by etching is good. It becomes difficult to obtain.
Further, the 60-degree glossiness G in the rolling parallel direction is preferably 520 or more, and more preferably 550 or more. It is even more preferable that the 60 degree glossiness G in the rolling parallel direction is 600 or more. Although there is no upper limit on the 60-degree glossiness G in terms of the characteristics of the copper foil, the 60-degree glossiness G in the rolling parallel direction can be 900 or less in consideration of manufacturability and the like.
 本発明の圧延銅箔は、銅箔とフィルム厚25μmのポリイミドフィルムとを積層した幅3mm以上5mm以下の片面銅張積層板の試料に対し、ポリイミドフィルム面を内側とした180°密着曲げを行ったときに、銅箔が破断するまでの曲げ回数が3回以上であるのが好ましく、5回以上であるのがより好ましい。このような条件を満たすように屈曲性が良好であれば、LCDモジュール用FPCとして好適に用いることができる。 The rolled copper foil of the present invention performs 180 ° adhesion bending with a polyimide film surface on the inside of a sample of a single-sided copper clad laminate having a width of 3 mm or more and 5 mm or less obtained by laminating a copper foil and a polyimide film having a film thickness of 25 μm. The number of times of bending until the copper foil breaks is preferably 3 times or more, and more preferably 5 times or more. If the flexibility is good so as to satisfy such conditions, it can be suitably used as an LCD module FPC.
 本発明の圧延銅箔の製造方法としては、まず溶解炉で原料を溶解し、所望の組成の溶湯を得る。そして、この溶湯をインゴットに鋳造する。その後、熱間圧延、冷間圧延、及び、焼鈍を適宜行い、所定の厚みを有する箔に仕上げる。熱処理後には、熱処理時に生成した表面酸化膜を除去するために、表面の酸洗や研磨等を行ってもよい。最終冷間圧延では、熱処理後の材料を繰り返し圧延機に通板(パス)することで所定の厚みに仕上げる。本発明の圧延銅箔の製造方法では、最終冷間圧延工程の最終圧延パスにおける油膜当量を17000以下、最終圧延パスの直前の圧延パスにおける油膜当量を15000以下、更にその直前の圧延パスにおける油膜当量を10000以下とし、且つ、最終圧延工程において、最終圧延パスの直前で圧延平行方向の60度光沢度が500より大になるように調整した後、最終圧延パスを行うことが重要である。
 ここで、油膜当量は下記の式で規定される。
 油膜当量={(圧延油粘度[cSt])×(通板速度[mpm]+ロール周速度[mpm])}/{(ロールの噛み込み角[rad])×(材料の降伏応力[kg/mm2])}
 圧延油粘度[cSt]は40℃での動粘度である。
 油膜当量を制御するためには、低粘度の圧延油を用いたり、通板速度を遅くしたりする等、公知の方法を用いればよい。
 油膜当量を制御することによって、材料表面の変形がロールによって拘束され、圧延による厚みの変化に伴う表面粗さの増加を抑制することができる。また、最終圧延パスの直前で光沢度を高くすることで、最終パス後の光沢度を所期の範囲に制御できる。最終パス直前で光沢度が低いと、最終パスで材料表面を平滑にしても、前パスまでに形成された深い凹凸が残留するため、所期の表面形状が得られない。
As a manufacturing method of the rolled copper foil of this invention, a raw material is first melt | dissolved in a melting furnace and the molten metal of a desired composition is obtained. Then, this molten metal is cast into an ingot. Thereafter, hot rolling, cold rolling, and annealing are appropriately performed to finish a foil having a predetermined thickness. After the heat treatment, surface pickling, polishing, or the like may be performed in order to remove the surface oxide film generated during the heat treatment. In the final cold rolling, the material after the heat treatment is repeatedly passed through a rolling mill to be finished to a predetermined thickness. In the method for producing rolled copper foil of the present invention, the oil film equivalent in the final rolling pass of the final cold rolling step is 17000 or less, the oil film equivalent in the rolling pass immediately before the final rolling pass is 15000 or less, and the oil film in the rolling pass immediately before that It is important to perform the final rolling pass after adjusting the equivalent rolling to 10000 or less and adjusting the 60 degree gloss in the rolling parallel direction to be greater than 500 immediately before the final rolling pass in the final rolling step.
Here, the oil film equivalent is defined by the following equation.
Oil film equivalent = {(rolling oil viscosity [cSt]) × (sheet feeding speed [mpm] + roll peripheral speed [mpm])} / {(roll biting angle [rad]) × (yield stress of material [kg / mm 2 ])}
The rolling oil viscosity [cSt] is a kinematic viscosity at 40 ° C.
In order to control the oil film equivalent, a known method such as using a low-viscosity rolling oil or slowing the sheet passing speed may be used.
By controlling the oil film equivalent, deformation of the material surface is constrained by the roll, and an increase in surface roughness accompanying a change in thickness due to rolling can be suppressed. Further, by increasing the gloss level immediately before the final rolling pass, the gloss level after the final pass can be controlled within a desired range. If the gloss level is low immediately before the final pass, even if the material surface is smoothed in the final pass, deep irregularities formed up to the previous pass remain, and the desired surface shape cannot be obtained.
 また、油膜当量が小さい場合には、圧延に用いる圧延ロール表面の凹凸が材料表面に転写しやすいため、圧延ロール表面も平滑であるのが好ましい。このため、本発明の圧延銅箔の製造方法で用いる圧延ロールは、ロールの回転軸に平行な方向に測定したときの平均粗さRaが0.1μm以下であるのが好ましい。 In addition, when the oil film equivalent is small, the unevenness on the surface of the rolling roll used for rolling is easily transferred to the material surface, and therefore, the surface of the rolling roll is preferably smooth. For this reason, it is preferable that the average roughness Ra when the rolling roll used with the manufacturing method of the rolled copper foil of this invention is measured in the direction parallel to the rotating shaft of a roll is 0.1 micrometer or less.
 本発明の圧延銅箔を、粗化処理面側から樹脂基板に貼り合わせて積層体を製造することができる。樹脂基板はプリント配線板等に適用可能な特性を有するものであれば特に制限を受けないが、例えば、ポリエチレンテレフタラート(PET)等のポリエステルフィルムやポリイミドフィルム、液晶ポリマー(LCP)フィルム等を使用する事ができる。 The laminated copper foil can be manufactured by bonding the rolled copper foil of the present invention to the resin substrate from the roughened surface side. The resin substrate is not particularly limited as long as it has characteristics applicable to a printed wiring board and the like. For example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a liquid crystal polymer (LCP) film, etc. are used. I can do it.
 貼り合わせの方法は、ポリイミドフィルム等の基材に接着剤を介して、又は、接着剤を使用せずに高温高圧下で圧延銅箔に積層接着して、又は、ポリイミド前駆体を塗布・乾燥・硬化等を行うことで積層板を製造することができる。 The method of laminating can be applied to a substrate such as a polyimide film via an adhesive, or laminated and bonded to a rolled copper foil under high temperature and high pressure without using an adhesive, or a polyimide precursor is applied and dried. -A laminated board can be manufactured by performing hardening etc.
 実施例1~11及び比較例1~5として、各圧延銅箔を以下のように準備した。
 まず、表1に記載の組成の銅インゴットを製造し、熱間圧延を行った後、冷間圧延と300~800℃の温度に設定した焼鈍炉における焼鈍を1回以上繰り返し、その後冷間圧延して1~2mm厚の圧延板を得た。この圧延板を300~800℃の温度に設定した焼鈍炉で焼鈍して再結晶させ、表1に記載の厚みまで最終冷間圧延した。このとき、実施例1~11については最終冷間圧延工程において、最終圧延パスにおいて油膜当量が17000以下、最終圧延パスの直前の圧延パスにおける油膜当量を15000以下、更にその直前の圧延パスにおける油膜当量を10000以下となるように圧延条件を整え、最終圧延パスの直前で圧延平行方向の60度光沢度が表1に記載の値になるように圧延条件を整えて行った。表1において、最終圧延パスにおける油膜当量を「最終パス油膜当量」、最終圧延パスの直前の圧延パスにおける油膜当量を「最終1パス前油膜当量」、更にその直前の圧延パスにおける油膜当量を「最終2パス前油膜当量」と記載している。
 また、比較例1~5については表1に記載の条件で最終冷間圧延を行った。
 また、このとき用いた圧延ロールは、ロールの回転軸に平行な方向に測定したときの平均粗さRaが0.08μmであった。
As Examples 1 to 11 and Comparative Examples 1 to 5, each rolled copper foil was prepared as follows.
First, after producing a copper ingot having the composition shown in Table 1 and performing hot rolling, cold rolling and annealing in an annealing furnace set to a temperature of 300 to 800 ° C. are repeated at least once, and then cold rolling is performed. Thus, a rolled plate having a thickness of 1 to 2 mm was obtained. This rolled sheet was annealed and recrystallized in an annealing furnace set to a temperature of 300 to 800 ° C., and finally cold-rolled to the thickness shown in Table 1. At this time, in Examples 1 to 11, in the final cold rolling step, the oil film equivalent was 17000 or less in the final rolling pass, the oil film equivalent in the rolling pass immediately before the final rolling pass was 15000 or less, and the oil film in the rolling pass immediately before that The rolling conditions were adjusted so that the equivalent was 10,000 or less, and the rolling conditions were adjusted so that the 60-degree glossiness in the rolling parallel direction was the value shown in Table 1 immediately before the final rolling pass. In Table 1, an oil film equivalent in the final rolling pass is “final pass oil film equivalent”, an oil film equivalent in the rolling pass immediately before the final rolling pass is “oil film equivalent in the last one pass”, and an oil film equivalent in the rolling pass immediately before is “ The final two-pass pre-oil film equivalent ”.
In Comparative Examples 1 to 5, final cold rolling was performed under the conditions described in Table 1.
Moreover, the average roughness Ra when the rolling roll used at this time measured in the direction parallel to the rotating shaft of a roll was 0.08 micrometer.
 粗化処理の条件は以下のように設定した。粗化処理の条件は、実用上十分なピール強度が得られるものとして一般的にFPC用途で用いられているものとした。
・めっき浴組成:Cu15g/L、Co8.5g/L、Ni8.6g/L
・処理液pH:2.5
・処理温度:38℃
・電流密度:20A/dm2
・めっき時間:2.0秒
The conditions for the roughening treatment were set as follows. The conditions for the roughening treatment were generally used for FPC applications as those that would give practically sufficient peel strength.
-Plating bath composition: Cu 15 g / L, Co 8.5 g / L, Ni 8.6 g / L
-Treatment solution pH: 2.5
・ Processing temperature: 38 ℃
・ Current density: 20 A / dm 2
・ Plating time: 2.0 seconds
 上述のようにして作製した実施例及び比較例の各サンプルについて、各種評価を下記の通り行った。
 ・光沢度;
 JIS Z8741に準拠した日本電色工業株式会社製光沢度計ハンディーグロスメーターPG-1を使用し、圧延方向の入射角60度で表面処理前の銅箔の光沢度を求めた。
Various evaluation was performed as follows about each sample of the Example and comparative example which were produced as mentioned above.
・ Glossiness;
Using a gloss meter Handy Gloss Meter PG-1 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS Z8741, the glossiness of the copper foil before the surface treatment was determined at an incident angle of 60 degrees in the rolling direction.
・視認性(樹脂透明性);
 樹脂透明性の評価はヘイズ値を用いて行った。ここで、ヘイズ値(%)は、(拡散透過率)/(全光線透過率)×100で算出される値である。
 各サンプル銅箔の一方の表面に、粗化処理として以下の条件でめっき処理を行った。
・めっき浴組成:Cu15g/L、Co8.5g/L、Ni8.6g/L
・処理液pH:2.5
・処理温度:38℃
・電流密度:20A/dm2
・めっき時間:2.0秒
 次に、粗化処理銅箔について、ラミネート用熱硬化性接着剤付きポリイミドフィルム(厚み50μm、宇部興産製ユーピレックス)の両面に粗化面側を貼り合わせ、銅箔をエッチング(塩化第二鉄水溶液)で除去してサンプルフィルムを作成した。JIS K7136(2000)に準拠した村上色彩技術研究所製ヘイズメーターHM-150を使用し、サンプルフィルムのヘイズ値を測定した。
・ Visibility (resin transparency);
Evaluation of resin transparency was performed using haze values. Here, the haze value (%) is a value calculated by (diffuse transmittance) / (total light transmittance) × 100.
One surface of each sample copper foil was plated under the following conditions as a roughening treatment.
-Plating bath composition: Cu 15 g / L, Co 8.5 g / L, Ni 8.6 g / L
-Treatment solution pH: 2.5
・ Processing temperature: 38 ℃
・ Current density: 20 A / dm 2
-Plating time: 2.0 seconds Next, about the roughened copper foil, the roughened surface side was bonded to both surfaces of the polyimide film with a thermosetting adhesive for lamination (thickness 50 μm, Ube Industries Upilex), and the copper foil Was removed by etching (ferric chloride aqueous solution) to prepare a sample film. The haze value of the sample film was measured using a haze meter HM-150 manufactured by Murakami Color Research Laboratory based on JIS K7136 (2000).
 ・ピール強度(接着強度);
 PC-TM-650に準拠し、引張り試験機オートグラフ100で常態ピール強度を測定し、上記常態ピール強度が0.7N/mm以上を積層基板用途に使用できるもの(判定「○」)とし、0.7N/mm未満のものを使用できないもの(判定「×」)とした。
・ Peel strength (adhesive strength);
In accordance with PC-TM-650, the normal peel strength is measured with a tensile tester Autograph 100, and the normal peel strength is 0.7 N / mm or more that can be used for laminated substrate applications (judgment “◯”). Those with less than 0.7 N / mm could not be used (judgment “x”).
 ・曲げ性;
 各銅箔とフィルム厚25μmのポリイミドフィルムとを積層した幅3mm以上5mm以下の片面銅張積層板の試料を作製し、ポリイミドフィルム面を内側とした180°密着曲げを行ったときに、銅箔が破断するまでの曲げ回数を測定した。
 上記各試験の条件及び評価を表1に示す。
・ Bendability;
When a sample of a single-sided copper-clad laminate with a width of 3 mm or more and 5 mm or less, in which each copper foil and a polyimide film with a film thickness of 25 μm were laminated, was subjected to 180 ° adhesion bending with the polyimide film surface inside, the copper foil The number of bendings until the fracture occurred was measured.
Table 1 shows the conditions and evaluation of each test.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 (評価結果)
 図1に実施例2の銅箔表面のSEM像を示す。図2に比較例2の銅箔表面のSEM像を示す。
 実施例1~11は、いずれも圧延平行方向の60度光沢度Gが500より大であり、樹脂との密着性、樹脂の視認性及び曲げ性が良好であった。
 比較例1~5は、いずれも圧延平行方向の60度光沢度Gが500以下であり、樹脂の視認性が不良であった。また、曲げ性が不良であるものもあった。
(Evaluation results)
The SEM image of the copper foil surface of Example 2 is shown in FIG. FIG. 2 shows an SEM image of the copper foil surface of Comparative Example 2.
In each of Examples 1 to 11, the 60-degree glossiness G in the rolling parallel direction was greater than 500, and the adhesion to the resin, the visibility of the resin, and the bendability were good.
In each of Comparative Examples 1 to 5, the 60-degree glossiness G in the rolling parallel direction was 500 or less, and the visibility of the resin was poor. Some also had poor bendability.

Claims (6)

  1.  圧延平行方向の60度光沢度Gが500以上且つ900以下である圧延銅箔であり、
     前記銅箔とフィルム厚25μmのポリイミドフィルムとを積層した幅3mm以上5mm以下の片面銅張積層板の試料に対し、前記ポリイミドフィルム面を内側とした180°密着曲げを行ったときに、前記銅箔が破断するまでの曲げ回数が3回以上である圧延銅箔。
    It is a rolled copper foil whose 60 degree gloss G in the rolling parallel direction is 500 or more and 900 or less,
    When a single-sided copper clad laminate having a width of 3 mm or more and 5 mm or less obtained by laminating the copper foil and a polyimide film having a film thickness of 25 μm was subjected to 180 ° adhesion bending with the polyimide film surface inside, the copper A rolled copper foil in which the number of bending times until the foil breaks is 3 or more.
  2.  前記圧延平行方向の60度光沢度Gが600以上且つ900以下である請求項1に記載の圧延銅箔。 The rolled copper foil according to claim 1, wherein the 60-degree glossiness G in the rolling parallel direction is 600 or more and 900 or less.
  3.  前記銅箔が破断するまでの曲げ回数が5回以上である請求項1又は2に記載の圧延銅箔。 The rolled copper foil according to claim 1 or 2, wherein the number of times of bending until the copper foil breaks is 5 or more.
  4.  最終冷間圧延工程の最終圧延パスにおける油膜当量を17000以下、最終圧延パスの直前の圧延パスにおける油膜当量を15000以下、更にその直前の圧延パスにおける油膜当量を10000以下とし、且つ、最終圧延工程において、最終圧延パスの直前で圧延平行方向の60度光沢度が500より大になるように調整した後、最終圧延パスを行う請求項1~3のいずれかに記載の圧延銅箔の製造方法。 The oil film equivalent in the final rolling pass of the final cold rolling step is 17000 or less, the oil film equivalent in the rolling pass immediately before the final rolling pass is 15000 or less, and the oil film equivalent in the immediately preceding rolling pass is 10,000 or less, and the final rolling step The method for producing a rolled copper foil according to any one of claims 1 to 3, wherein the final rolling pass is performed after adjusting so that the 60 ° gloss in the rolling parallel direction is greater than 500 immediately before the final rolling pass. .
  5.  ロールの回転軸に平行な方向に測定したときの平均粗さRaが0.1μm以下である圧延ロールを用いて圧延を行う請求項4に記載の圧延銅箔の製造方法。 The method for producing a rolled copper foil according to claim 4, wherein rolling is performed using a rolling roll having an average roughness Ra of 0.1 µm or less when measured in a direction parallel to the rotation axis of the roll.
  6.  請求項1~3のいずれかに記載の圧延銅箔と樹脂基板とを積層して構成した積層板。 A laminate comprising the rolled copper foil according to any one of claims 1 to 3 and a resin substrate.
PCT/JP2013/067413 2012-06-29 2013-06-25 Rolled copper foil, method for producing same, and laminate plate WO2014003019A1 (en)

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JP6612168B2 (en) * 2016-03-30 2019-11-27 Jx金属株式会社 Copper foil, copper clad laminate, flexible printed circuit board and electronic device
JP6611751B2 (en) * 2017-03-31 2019-11-27 Jx金属株式会社 Rolled copper foil for lithium ion battery current collector and lithium ion battery
JP6856688B2 (en) * 2019-03-26 2021-04-07 Jx金属株式会社 Copper foil for flexible printed circuit boards, copper-clad laminates using it, flexible printed circuit boards, and electronic devices
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