JP5094834B2 - Copper foil manufacturing method, copper foil and copper clad laminate - Google Patents
Copper foil manufacturing method, copper foil and copper clad laminate Download PDFInfo
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- JP5094834B2 JP5094834B2 JP2009297461A JP2009297461A JP5094834B2 JP 5094834 B2 JP5094834 B2 JP 5094834B2 JP 2009297461 A JP2009297461 A JP 2009297461A JP 2009297461 A JP2009297461 A JP 2009297461A JP 5094834 B2 JP5094834 B2 JP 5094834B2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 146
- 239000011889 copper foil Substances 0.000 title claims description 94
- 229910052802 copper Inorganic materials 0.000 title claims description 51
- 239000010949 copper Substances 0.000 title claims description 51
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000005482 strain hardening Methods 0.000 claims description 38
- 238000005452 bending Methods 0.000 claims description 36
- 238000005097 cold rolling Methods 0.000 claims description 27
- 238000000137 annealing Methods 0.000 claims description 25
- 238000005096 rolling process Methods 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 230000003746 surface roughness Effects 0.000 claims description 19
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- 238000010030 laminating Methods 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims 1
- 239000003921 oil Substances 0.000 description 31
- 239000000463 material Substances 0.000 description 24
- 239000010410 layer Substances 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000010731 rolling oil Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005098 hot rolling Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/02—Alloys based on copper with tin as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Metal Rolling (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Laminated Bodies (AREA)
Description
本発明は、例えばフレキシブル配線板(FPC:Flexible Printed Circuit)に使用される銅箔の製造方法、銅箔及び銅張積層板に関する。 The present invention relates to a method for producing a copper foil , a copper foil, and a copper-clad laminate , for example, used for a flexible printed circuit (FPC).
デジタルカメラや携帯電話などの電子機器を駆動させる回路として、フレキシブル配線板(FPC:Flexible Printed Circuit)やCOF(chip of flexible circuit)が用いられている。このFPCやCOFは、樹脂層の片面又は両面に銅箔を積層した銅張積層板(CCL)を用い、銅箔に回路パターンを形成してなる。
そして、このような電子機器を小型化、高機能化するために、ケース内の狭い空間にFPCを折りたたんで収容する方法がとられる。また液晶ディスプレイ周辺に用いられるCOFの場合には、ベゼル(いわゆる「額縁」)を細くするために、COFの銅配線を液晶基板の裏側へ折り返している。
As a circuit for driving an electronic device such as a digital camera or a mobile phone, a flexible printed circuit (FPC) or a chip of flexible circuit (COF) is used. The FPC and COF are formed by using a copper clad laminate (CCL) in which a copper foil is laminated on one side or both sides of a resin layer and forming a circuit pattern on the copper foil.
In order to reduce the size and increase the functionality of such an electronic device, a method is adopted in which the FPC is folded and accommodated in a narrow space inside the case. In the case of the COF used around the liquid crystal display, the copper wiring of the COF is folded back to the back side of the liquid crystal substrate in order to make the bezel (so-called “frame”) thinner.
しかしながら、FPCやCOFを折り畳んだ際、銅箔部分に大きな変形荷重が加わり、破断し易くなるという問題がある。
そこで、柱状の銅結晶粒子を含み、25℃における伸び率5%以上の電解銅箔からFPCを構成することで、配線パターンが破断し難いFPCが得られることが報告されている(特許文献1)。
However, when FPC or COF is folded, there is a problem that a large deformation load is applied to the copper foil portion and it is easy to break.
Thus, it has been reported that an FPC in which the wiring pattern is not easily broken can be obtained by forming the FPC from an electrolytic copper foil containing columnar copper crystal particles and having an elongation of 5% or more at 25 ° C. (Patent Document 1). ).
従来、CCLの銅箔の曲げ性は銅箔の伸びと相関があると考えられており、そのため上記特許文献1に記載されているように、伸びの大きい電解銅箔が用いられている。
ところが、伸びの大きい圧延銅箔を用いても、CCLの曲げ性が向上しない場合があることを本発明者らは見出した。
すなわち、本発明は上記の課題を解決するためになされたものであり、銅張積層板に用いたときに曲げ性に優れた銅箔の製造方法、銅箔及び銅張積層板の提供を目的とする。
Conventionally, it has been considered that the bendability of a copper foil of CCL has a correlation with the elongation of the copper foil. Therefore, as described in Patent Document 1, an electrolytic copper foil having a large elongation is used.
However, the present inventors have found that even when a rolled copper foil having a large elongation is used, the bendability of CCL may not be improved.
That is, the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a copper foil manufacturing method, a copper foil, and a copper clad laminate that have excellent bendability when used in a copper clad laminate. And
本発明者らは種々検討した結果、CCLの曲げ性を向上させる因子として、銅箔の伸びではなく加工硬化指数(n値)が重要であることを見出した。 As a result of various studies, the present inventors have found that work hardening index (n value) is important as a factor for improving the bendability of CCL, not the elongation of copper foil .
本発明の銅箔の製造方法は、インゴットを熱間圧延後に冷間圧延と焼鈍を繰り返し、最終冷間圧延時の総加工度を85%以上とし、かつ前記最終冷間圧延における最終3パスでの油膜当量を以下の条件として圧延する厚み5〜30μmの銅箔の製造方法であって、前記銅箔は、無酸素銅若しくはタフピッチ銅からなり、又は無酸素銅若しくはタフピッチ銅にAg及びSnの群からなる1種以上を合計500質量ppm以下含む。但し、最終パスの2つ前の油膜当量;25000以下、最終パスの1つ前の油膜当量;30000以下、最終パスの油膜当量; 35000以下とする。ここで、インゴットを熱間圧延後、冷間圧延を経て銅箔を製造する際、冷間圧延において冷間圧延と焼鈍とを交互に行う。そして、最後の焼鈍後に最後に行う冷間圧延を「最終冷間圧延」とする。 The method for producing a copper foil according to the present invention repeats cold rolling and annealing after hot rolling an ingot, sets the total workability at the time of final cold rolling to 85% or more, and in the final three passes in the final cold rolling. The copper foil is made of oxygen-free copper or tough pitch copper, or the oxygen-free copper or tough pitch copper is made of Ag and Sn. 1 type or more which consists of a group is included in total 500 mass ppm or less . However, the oil film equivalent of the last two passes; 25000 or less, the oil film equivalent of the previous one of the final pass; 30000 or less, the oil film equivalent of the final pass; 35000 or less. Here, after manufacturing the copper foil through cold rolling after hot rolling the ingot, cold rolling and annealing are alternately performed in the cold rolling. The last cold rolling performed after the last annealing is referred to as “final cold rolling”.
本発明の銅箔は、厚み5〜30μm、圧延平行方向の表面粗さRa≦0.1μmで、かつ350℃で0.5時間焼鈍後の加工硬化指数が0.3以上0.45以下であって、無酸素銅若しくはタフピッチ銅からなり、又は無酸素銅若しくはタフピッチ銅にAg及びSnの群からなる1種以上を合計500質量ppm以下含む。
又、本発明の銅箔は、厚み5〜30μm、かつ350℃で0.5時間焼鈍後のI(220)/I(200)が0.11以下で、圧延平行方向の表面粗さRa≦0.1μmで、かつ350℃で0.5時間焼鈍後の加工硬化指数が0.3以上0.45以下であって、無酸素銅若しくはタフピッチ銅からなり、又は無酸素銅若しくはタフピッチ銅にAg及びSnの群からなる1種以上を合計500質量ppm以下含む。
本発明の銅箔において、半軟化温度が150℃以下であることが好ましい。
又、本発明の銅箔において、前記銅箔の片面に樹脂層を積層した合計厚みが50μm以下で、幅3mm以上5mm以下の試料を用い、前記銅箔の露出面を外側として180度密着曲げを行った場合に、前記銅箔が破断するまでの曲げ回数が4回以上であることが好ましい。
本発明の銅張積層板は、前記銅箔を、樹脂層の少なくとも片面に積層してなる。
The copper foil of the present invention has a thickness of 5 to 30 μm, a surface roughness Ra ≦ 0.1 μm in the rolling parallel direction, and a work hardening index after annealing at 350 ° C. for 0.5 hour is 0.3 or more and 0.45 or less, and oxygen-free copper or It is made of tough pitch copper, or contains oxygen and copper or tough pitch copper containing at least 500 ppm by mass in total of one or more members made of Ag and Sn.
Further, the copper foil of the present invention has a thickness of 5 to 30 μm, and I (220) / I (200) after annealing at 350 ° C. for 0.5 hour is 0.11 or less, and the surface roughness Ra ≦ 0.1 μm in the rolling parallel direction, In addition, the work hardening index after annealing at 350 ° C. for 0.5 hour is 0.3 to 0.45, and is made of oxygen free copper or tough pitch copper, or oxygen free copper or tough pitch copper is combined with one or more kinds of Ag and Sn. Contains 500 ppm by mass or less.
In the copper foil of the present invention, the semi-softening temperature is preferably 150 ° C. or lower.
Further, in the copper foil of the present invention, a sample having a total thickness of 50 μm or less and a width of 3 mm or more and 5 mm or less in which a resin layer is laminated on one side of the copper foil, and 180 degree adhesion bending with the exposed surface of the copper foil as the outside When performing this, it is preferable that the number of times of bending until the copper foil breaks is 4 times or more.
The copper clad laminate of the present invention is formed by laminating the copper foil on at least one surface of the resin layer.
本発明によれば、銅張積層板に用いたときに曲げ性に優れた銅箔が得られる。 According to the present invention, a copper foil excellent in bendability when used in a copper clad laminate can be obtained.
以下、本発明の実施形態に係る銅箔について説明する。なお、本発明において%とは、特に断らない限り、質量%を示すものとする。
本発明の実施形態に係る銅箔は、厚み5〜30μm、圧延平行方向の表面粗さRa≦0.1μmで、かつ350℃で0.5時間焼鈍後の加工硬化指数が0.3以上0.45以下である。
Hereinafter, the copper foil which concerns on embodiment of this invention is demonstrated. In the present invention, “%” means “% by mass” unless otherwise specified.
The copper foil according to the embodiment of the present invention has a thickness of 5 to 30 μm, a surface roughness Ra ≦ 0.1 μm in the rolling parallel direction, and a work hardening index after annealing at 350 ° C. for 0.5 hour is 0.3 or more and 0.45 or less.
加工硬化指数(n値)は、降伏点以上の塑性変形域における応力とひずみとの関係を、以下の式1(Hollomonの式)で近似した場合の指数nで表される。
[真応力]=[材料定数]×[真ひずみ]n (1)
加工硬化指数が大きいほど局所変形が起こりにくく、変形を行ったときに破断しにくい。又、加工硬化指数が高い材料は絞り加工性に優れ、プレス加工に適する。そして、銅箔を、樹脂層の少なくとも片面に積層して銅張積層板を製造し、この銅張積層板の曲げ性を評価した場合に、加工硬化指数が0.3以上の銅箔は局所変形が起こりにくく、曲げ部全体で変形を担うので、銅箔が破断しにくいと考えられる。但し、加工硬化指数が0.45を超える材料は、焼鈍後の強度が低く取り扱い性が悪化するため、銅張積層板用として適当でない。
The work hardening index (n value) is represented by an index n when the relationship between stress and strain in the plastic deformation region above the yield point is approximated by the following formula 1 (Hollomon formula).
[True stress] = [material constant] × [true strain] n (1)
As the work hardening index is larger, local deformation is less likely to occur and is less likely to break when deformed. In addition, a material having a high work hardening index is excellent in drawing workability and suitable for press working. And when copper foil is laminated on at least one side of the resin layer to produce a copper clad laminate, and the bendability of this copper clad laminate is evaluated, the copper foil having a work hardening index of 0.3 or more is not locally deformed. It is unlikely that the copper foil will break, because the entire bent part is deformed. However, a material having a work hardening index exceeding 0.45 is not suitable for a copper clad laminate because the strength after annealing is low and the handleability deteriorates.
ここで、350℃で0.5時間焼鈍後の加工硬化指数を規定した理由は、銅張積層板を製造する際の加熱条件がこの程度であるためである。なお、銅張積層板の樹脂層が樹脂組成物を銅箔に塗布、硬化して得られる場合(樹脂層と銅箔との間に接着層が介在しない2層CCLの場合)、上記加熱条件で樹脂の硬化を行うことになる。 Here, the reason why the work hardening index after annealing at 350 ° C. for 0.5 hour is defined is that the heating conditions for producing the copper clad laminate are about this level. In addition, when the resin layer of a copper clad laminated board is obtained by applying and curing a resin composition on a copper foil (in the case of a two-layer CCL in which no adhesive layer is interposed between the resin layer and the copper foil), the above heating conditions Thus, the resin is cured.
なお、銅箔の曲げ性を向上させる因子として、銅箔の伸びではなく加工硬化指数(n値)が重要である理由は以下のとおりと考えられる。
まず、加工硬化指数は、材料の加工硬化挙動を示す値のひとつであり、この値が大きいほど、材料は加工硬化しやすい性質を持つ。ここで、材料は引張変形を受けると、局部的にくびれを起こして破断するが、加工硬化係数が大きい材料では、くびれを起こした部分が加工硬化し、くびれ部が変形しにくくなる。そのため、変形しにくいくびれ部に代わって、それ以外の部分が変形しはじめる。これを繰り返すことで、材料全体が均等に変形する。一方、伸びはそのような状況を考慮せずにマクロ的に捕らえた指標なので、伸びが大きいものでも加工硬化指数が大きいとは限らない。
The reason why the work hardening index (n value) is important as a factor for improving the bendability of the copper foil, not the elongation of the copper foil, is considered as follows.
First, the work hardening index is one of the values indicating the work hardening behavior of a material. The larger this value, the easier the material is to work harden. Here, when the material is subjected to tensile deformation, the material is locally constricted and fractured. However, in a material having a large work hardening coefficient, the constricted portion is work hardened and the constricted portion is hardly deformed. Therefore, instead of the constricted portion that is difficult to deform, the other portions begin to deform. By repeating this, the entire material is uniformly deformed. On the other hand, since the elongation is an index captured macroscopically without considering such a situation, even if the elongation is large, the work hardening index is not always large.
従来、このような材料全体の均等な変形のしやすさの指標として、厚みのある材料の絞り加工において、加工硬化指数が用いられる例はあるものの、銅箔のように薄い材料は絞り加工などの加工を行わないので、加工硬化指数を指標とすることはこれまでなかった。そこで、本発明においては、銅箔の加工硬化指数を大きくすれば、CCLの180度密着曲げにおいても、曲げ部全体が均等に変形することによって破断を起こさずに曲がると考えた。 Conventionally, as an index of the ease of uniform deformation of the entire material, there is an example where work hardening index is used in drawing of a thick material, but thin material such as copper foil is drawn. In the past, no work hardening index was used as an index. Therefore, in the present invention, it was considered that if the work hardening index of the copper foil is increased, even in the 180 degree close contact bending of the CCL, the entire bent portion is deformed evenly so that it is bent without causing breakage.
さらに、200℃で0.5時間焼鈍後の加工硬化指数も0.3以上0.45以下であることが好ましい。これは、樹脂層としてフィルムを用い、フィルムと銅箔とを接着層を介して積層した3層CCLの製造時のラミネート温度が200℃程度であるからである。加工硬化指数は加熱によって銅箔が再結晶することによって大きくなるため、350℃より低温の200℃で加工硬化指数が0.3以上であれば、350℃でも0.3以上の加工硬化指数が得られる。また、上記焼鈍で充分に再結晶組織を得るためには、銅箔の半軟化温度は150℃以下であることが好ましい。 Furthermore, the work hardening index after annealing at 200 ° C. for 0.5 hour is also preferably 0.3 or more and 0.45 or less. This is because a laminating temperature at the time of producing a three-layer CCL in which a film is used as a resin layer and a film and a copper foil are laminated via an adhesive layer is about 200 ° C. Since the work hardening index increases when the copper foil is recrystallized by heating, if the work hardening index is 0.3 or more at 200 ° C. lower than 350 ° C., a work hardening index of 0.3 or more can be obtained even at 350 ° C. Further, in order to obtain a recrystallized structure sufficiently by the annealing, the semi-softening temperature of the copper foil is preferably 150 ° C. or less.
350℃で0.5時間焼鈍後の銅箔の加工硬化指数を0.3以上に管理する方法としては、最終冷間圧延時の総加工度を85%以上とすることが挙げられる。また再結晶組織を得る必要があることから、銅箔の半軟化温度を150℃以下に管理することが好ましい。一般に再結晶温度は、銅箔の組成と加工度によって決まるが、加工硬化指数を0.3以上とするためには、何れの手段によってもかまわない。
最終冷間圧延時の総加工度が85%未満であると、加工度が低くなって銅箔の軟化温度が高くなるため、CCL製造時の加熱による銅の再結晶が不十分になり、加工歪みが残って曲げ性が低下する傾向にある。
As a method for managing the work hardening index of the copper foil after annealing at 350 ° C. for 0.5 hour to 0.3 or more, the total work degree at the time of final cold rolling is 85% or more. In addition, since it is necessary to obtain a recrystallized structure, it is preferable to manage the semi-softening temperature of the copper foil at 150 ° C. or lower. In general, the recrystallization temperature is determined by the composition and degree of processing of the copper foil, but any means may be used in order to make the work hardening index 0.3 or more.
If the total degree of work during final cold rolling is less than 85%, the degree of work will be low and the softening temperature of the copper foil will be high, so copper recrystallization due to heating during CCL production will be insufficient, There is a tendency that the bendability is lowered due to remaining strain.
銅箔を銅張積層板に用いたときの曲げ性を向上させるためには、上記加工硬化指数に加え、表面粗さの影響を考慮する必要がある。ここで、加工硬化指数の大きさについては、「材料があとどれだけ加工硬化できるか」が重要な要素となる。そのため加工硬化指数を大きな値とするためには、初期段階では材料が加工硬化していない状態、つまり加工ひずみが除かれた状態であることが必要となる。CCL用銅箔においては、CCL製造工程の熱処理で銅箔が再結晶していることが必要となる。
そして、CCL製造工程の熱処理条件は樹脂の性質に依存するため、銅箔の再結晶温度を熱処理条件にあわせる必要がある。銅箔の再結晶温度は組成と加工度によって影響を受け、添加元素を多量に含む組成では軟化温度が高くなり過ぎる。また銅箔の組成が適正であっても、加工度が高過ぎれば常温軟化を招き、加工度が低過ぎれば軟化温度が高くなり過ぎる。
このような要因に加え、表面粗さは、加工硬化指数とは別の要因で曲げ性に影響する。表面粗さが大きく、銅箔の材料表面に切り欠き状の凹凸があると、曲げを行った際に切り欠き先端に応力が集中し、破断の原因となる。
In order to improve the bendability when the copper foil is used for a copper clad laminate, it is necessary to consider the influence of surface roughness in addition to the work hardening index. Here, with respect to the magnitude of the work hardening index, “how much work can be hardened further” is an important factor. Therefore, in order to increase the work hardening index, it is necessary that the material is not work hardened in the initial stage, that is, the work strain is removed. In the copper foil for CCL, it is necessary that the copper foil is recrystallized by the heat treatment in the CCL manufacturing process.
And since the heat processing conditions of a CCL manufacturing process depend on the property of resin, it is necessary to match the recrystallization temperature of copper foil with heat processing conditions. The recrystallization temperature of the copper foil is affected by the composition and the degree of processing, and the softening temperature becomes too high in a composition containing a large amount of additive elements. Even if the composition of the copper foil is appropriate, if the degree of work is too high, normal temperature softening is caused, and if the degree of work is too low, the softening temperature becomes too high.
In addition to these factors, the surface roughness affects bendability as a factor different from the work hardening index. If the surface roughness is large and there are notched irregularities on the material surface of the copper foil, stress is concentrated at the notch tip when bending, causing breakage.
このようなことから、本発明の実施形態に係る銅箔は、圧延平行方向の表面粗さRaが0.1μm以下である。この理由は、表面粗さRaが0.1μmを超えると、銅箔を曲げたときに、表面の凹凸が起点となって割れ(破断)が進行し易くなるためである。圧延によって銅箔表面に形成されるオイルピットと呼ばれるくぼみは、圧延直角方向に伸びた溝状に形成されることから、表面粗さは圧延平行方向で測定する。Raは、JIS-B0601に準拠して測定した算術平均粗さである。 For these reasons, the copper foil according to the embodiment of the present invention has a surface roughness Ra in the rolling parallel direction of 0.1 μm or less. This is because when the surface roughness Ra exceeds 0.1 μm, when the copper foil is bent, cracks (breaks) are likely to proceed due to the surface irregularities. Since the recess called oil pit formed on the copper foil surface by rolling is formed in a groove shape extending in the direction perpendicular to the rolling, the surface roughness is measured in the parallel direction of rolling. Ra is an arithmetic average roughness measured according to JIS-B0601.
銅箔の圧延平行方向の表面粗さRaを0.1μm以下に調整する方法として、最終冷間圧延における最終3パスにおける油膜当量を調整することが挙げられる。具体的には、最終冷間圧延における最終パスの2つ前の油膜当量;25000以下、最終パスの1つ前の油膜当量;30000以下、最終パスの油膜当量; 35000以下とする。
なお、材料厚みが薄くなると油膜当量は大きくなる傾向にあるため、最終3パスにおける油膜当量の値は、徐々に大きくなる。そこで、それぞれ厚みの異なる最終3パスについて、適正な油膜当量を設定する必要がある。
最終冷間圧延において圧延油粘度と材料降伏応力が全パスで等しいとすると、油膜当量は、(圧延速度)/(噛み込み角)に比例する。材料厚みが薄くなると噛み込み角は小さくなるために、最終パスに近づくほど油膜当量は大きくなる傾向にある。また生産性を保つためには、材料長さの長い最終パスに近づくほど圧延速度を上げる必要があり、これによっても最終パスに近づくほど油膜当量は大きくなる傾向にある。
As a method for adjusting the surface roughness Ra in the rolling parallel direction of the copper foil to 0.1 μm or less, adjusting the oil film equivalent in the final three passes in the final cold rolling can be mentioned. Specifically, the oil film equivalent of the last two passes in the final cold rolling: 25000 or less, the oil film equivalent of the one before the final pass; 30000 or less, the oil film equivalent of the final pass; 35000 or less.
Since the oil film equivalent tends to increase as the material thickness decreases, the oil film equivalent value in the final three passes gradually increases. Therefore, it is necessary to set an appropriate oil film equivalent for the final three passes having different thicknesses.
If the rolling oil viscosity and the material yield stress are equal in all passes in the final cold rolling, the oil film equivalent is proportional to (rolling speed) / (engagement angle). As the material thickness decreases, the bite angle decreases, so the oil film equivalent tends to increase as the material approaches the final pass. In order to maintain productivity, it is necessary to increase the rolling speed as the material passes closer to the final pass, and the oil film equivalent tends to increase as the material approaches the final pass.
そして、最終冷間圧延における中間パスでの材料表面粗さが粗いと、最終パスで油膜当量を低く抑えても材料表面を充分に平滑にすることができない。このようなことから、最終冷間圧延における最終3パスにおける油膜当量を管理している。
一方、最終冷間圧延における最終3パスにおいて、最終パスの2つ前の油膜当量;25000以下、最終パスの1つ前の油膜当量;30000以下、最終パスの油膜当量; 35000以下をすべて満たさないと(最終3パスのいずれかのパスで油膜当量が上記値を超えると)、銅箔の表面が粗くなり、圧延平行方向の表面粗さRaが0.1μmを超えて以下の不具合が生じる。
油膜当量を低減するために、最終パスの圧延加工度を25%以上にするのが良い。
If the material surface roughness in the intermediate pass in the final cold rolling is rough, the material surface cannot be sufficiently smoothed even if the oil film equivalent is kept low in the final pass. For this reason, the oil film equivalent in the final three passes in the final cold rolling is managed.
On the other hand, in the final three passes in the final cold rolling, the oil film equivalent of the last two before the final pass; 25000 or less, the oil film equivalent of the last one before the final pass; 30000 or less, the oil film equivalent of the final pass; (If the oil film equivalent exceeds the above value in any of the last three passes), the surface of the copper foil becomes rough, and the surface roughness Ra in the rolling parallel direction exceeds 0.1 μm, resulting in the following problems.
In order to reduce the oil film equivalent, the rolling degree of the final pass should be 25% or more.
なお、上記油膜当量は下記式で表される。(油膜当量)={(圧延油粘度、40℃の動粘度;cSt)×(圧延速度;m/分)}/{(材料の降伏応力;kg/mm2)×(ロール噛込角;rad)}
圧延油粘度は4.0〜8.0cSt程度、圧延速度200〜600m/分、ロールの噛込角は例えば0.0005〜0.005rad、好ましくは0.001〜0.04radとすることができる。
The oil film equivalent is represented by the following formula. (Oil film equivalent) = {(rolling oil viscosity, kinematic viscosity at 40 ° C .; cSt) × (rolling speed; m / min)} / {(yield stress of material; kg / mm 2) × (roll biting angle; rad) }
The rolling oil viscosity is about 4.0 to 8.0 cSt, the rolling speed is 200 to 600 m / min, and the biting angle of the roll is, for example, 0.0005 to 0.005 rad, preferably 0.001 to 0.04 rad.
本発明の実施形態に係る銅箔において、銅箔を350℃×0.5時間で大気焼鈍した後,圧延面のX線回折を行ったとき、それぞれ(220)面及び(200)面の強度の積分値(I)の比I(220)/I(200)が0.11以下であると好ましい。この場合、銅箔中の(220)面の割合が多くなり、350℃×0.5時間の焼鈍で銅箔の再結晶が進行し、加工ひずみが減少して曲げ性が向上すると考えられる。 In the copper foil according to the embodiment of the present invention, when the copper foil is subjected to atmospheric annealing at 350 ° C. for 0.5 hour and then subjected to X-ray diffraction of the rolled surface, the integration of the strengths of the (220) plane and (200) plane, respectively. The ratio I (220) / I (200) of the value (I) is preferably 0.11 or less. In this case, the proportion of the (220) plane in the copper foil increases, and recrystallization of the copper foil proceeds by annealing at 350 ° C. for 0.5 hour, so that the work strain is reduced and the bendability is improved.
さらに、本発明の実施形態に係る銅箔の片面に樹脂層を積層した合計厚みが50μm以下で、幅3mm以上5mm以下の試料を用い、銅箔の露出面を外側として180度密着曲げを行った場合に、銅箔が破断するまでの曲げ回数が4回以上であることが好ましい。
銅箔の片面に樹脂層を積層した合計厚みが50μm以下の試料は、銅張積層板を模したものであり、その180度密着曲げの曲げ回数は、銅張積層板の曲げ性を評価したことになる。
樹脂層としては、ポリイミド;PET(ポリエチレンテレフタレート);エポキシ樹脂、フェノール樹脂等の熱硬化性樹脂;飽和ポリエステル樹脂等の熱可塑性樹脂を用いることができるがこれらに限定されない。又、これら樹脂層の成分を溶剤に溶かしたワニス(例えば、ポリイミドの前駆体のポリアミック酸溶液)を銅箔の片面に塗布し、加熱することで溶媒を除去して反応(例えばイミド化反応)を進行させ、硬化させてもよい。
Furthermore, the total thickness of the resin layers laminated on one side of the copper foil according to the embodiment of the present invention is 50 μm or less, and a sample having a width of 3 mm or more and 5 mm or less is used, and 180 ° adhesion bending is performed with the exposed surface of the copper foil as the outside In this case, the number of times of bending until the copper foil breaks is preferably 4 times or more.
A sample having a total thickness of 50 μm or less, in which a resin layer is laminated on one side of a copper foil, imitates a copper-clad laminate, and the number of bends of 180-degree contact bending evaluated the bendability of the copper-clad laminate. It will be.
As the resin layer, polyimide; PET (polyethylene terephthalate); thermosetting resin such as epoxy resin and phenol resin; thermoplastic resin such as saturated polyester resin can be used, but is not limited thereto. In addition, varnish (for example, polyamic acid solution of polyimide precursor) in which the components of these resin layers are dissolved in a solvent is applied to one side of a copper foil, and the solvent is removed by heating to react (for example, imidization reaction). May be allowed to proceed and cured.
180度密着曲げは、折り目が自身の幅方向に平行になるように試料を折り返し、ハンドプレスで潰して重ねて行う。そして、曲げ部の断面の銅箔部分の破断の有無を光学顕微鏡で観察する。破断がなければ、密着曲げ後の試料を開き、ハンドプレスを用いて平らに伸ばした後に、同じ場所でもう一度折り返してハンドプレスで潰す。このようにして、銅箔が破断するまでの曲げ回数を求める。 180 degree contact bending is performed by folding the sample so that the crease is parallel to its own width direction, and crushing and stacking with a hand press. And the presence or absence of a fracture | rupture of the copper foil part of the cross section of a bending part is observed with an optical microscope. If there is no break, the sample after close contact bending is opened, stretched flat using a hand press, then folded back at the same place and crushed with a hand press. In this way, the number of times of bending until the copper foil breaks is determined.
本発明の実施形態に係る銅箔の組成は、無酸素銅若しくはタフピッチ銅(いずれもJIS-H3100に規定)からなることが好ましい。又、上記無酸素銅若しくはタフピッチ銅にAg及びSnの群からなる1種以上を合計500質量ppm以下含むものであってもよい。本発明の実施形態に係る銅箔において、Ag及びSnの群からなる1種以上を合計500質量ppmを超えて添加すると、再結晶温度が過度に高くなり、CCL製造工程の熱処理での再結晶が不十分となる場合がある。 The composition of the copper foil according to the embodiment of the present invention is preferably made of oxygen-free copper or tough pitch copper (both defined in JIS-H3100). Further, the oxygen-free copper or tough pitch copper may contain a total of 500 mass ppm or less of at least one member of the group consisting of Ag and Sn. In the copper foil according to the embodiment of the present invention, when one or more of the group consisting of Ag and Sn is added in excess of 500 ppm by mass, the recrystallization temperature becomes excessively high, and the recrystallization in the heat treatment in the CCL manufacturing process May become insufficient.
本発明の銅張積層板は、上記した銅箔を、上記樹脂層の少なくとも片面に積層してなる。本発明の実施形態に係る銅箔は、曲げ性に優れるため、これを用いた銅張積層板も曲げ性に優れる。例えば、本発明の銅張積層板は、半径5mm以下で90〜180度折り曲げる用途に好適に使用できる。 The copper clad laminate of the present invention is formed by laminating the above copper foil on at least one surface of the resin layer. Since the copper foil which concerns on embodiment of this invention is excellent in bendability, the copper clad laminated board using this is also excellent in bendability. For example, the copper-clad laminate of the present invention can be suitably used for applications that bend 90 to 180 degrees with a radius of 5 mm or less.
無酸素銅またはタフピッチ銅(JIS H3100)を溶解し、必要に応じてAg、Snを表1に示す量添加して鋳造し、インゴットを作製した。インゴットを熱間圧延後に冷間圧延と焼鈍を適宜繰り返して銅箔を作製した。軟化温度を調整するため、最終冷間圧延時の総加工度を85%以上とし、かつ表面粗さを低減するために、表面が平滑(ロール軸方向でRa≦0.1μm)なロールを用いて最終冷間圧延し、銅箔を製造した。圧延油粘度を4.0〜8.0cSt程度とし、圧延速度200〜600m/分、ロールの噛込角0.003〜0.03radの範囲で調整し、最終冷間圧延における最終3パスでの油膜当量をいずれも35000以下となるようにした。 Oxygen-free copper or tough pitch copper (JIS H3100) was dissolved, and if necessary, Ag and Sn were added in amounts shown in Table 1 and cast to prepare an ingot. After hot rolling the ingot, cold rolling and annealing were repeated as appropriate to produce a copper foil. In order to adjust the softening temperature, use a roll with a smooth surface (Ra ≦ 0.1μm in the roll axis direction) in order to reduce the surface roughness to a total workability of 85% or more during final cold rolling. Final cold rolling was performed to produce a copper foil. The rolling oil viscosity is about 4.0 to 8.0 cSt, the rolling speed is adjusted to 200 to 600 m / min, and the roll bite angle is 0.003 to 0.03 rad, and the oil film equivalent in the final three passes in the final cold rolling is 35000 It was made to become the following.
<加工硬化指数>
得られた銅箔を、それぞれ200℃×0.5時間、及び350℃×0.5時間で大気焼鈍した後に引張試験(JIS-Z2241に準拠)を行い、加工硬化指数を求めた。なお、加工硬化指数は、材料が降伏した後の均一伸びと応力とを用いて求める必要があるため、伸び2%から最大応力点までの値を用いた。そして、測定した伸び及び応力から求めた真ひずみと、真応力との両対数グラフを最小自乗法で近似し、グラフの傾きから加工硬化指数を求めた。真ひずみと真応力は以下の式で求めた。
[真ひずみ]=ln(1+[ひずみ])
[真応力]=(1+[真ひずみ])×[応力]
<半軟化温度>
得られた銅箔を、それぞれ100〜400℃×0.5時間で大気焼鈍した後に引張試験を行い、熱処理条件に対する強度(引張り強さ)を求めた。焼鈍後の強度TShが、圧延上がり(焼鈍前)の強度TSasrollと、完全に軟化した状態の強度TSannealとの平均値となる焼鈍温度を、半軟化温度とした。
<Work hardening index>
The obtained copper foils were each annealed at 200 ° C. × 0.5 hours and 350 ° C. × 0.5 hours, and then subjected to a tensile test (based on JIS-Z2241) to obtain a work hardening index. Note that the work hardening index needs to be obtained using the uniform elongation and stress after the material yields, so the value from the elongation of 2% to the maximum stress point was used. Then, a logarithmic graph of true strain and true stress obtained from the measured elongation and stress was approximated by the method of least squares, and a work hardening index was obtained from the slope of the graph. True strain and true stress were determined by the following formulas.
[True strain] = ln (1+ [Strain])
[True stress] = (1+ [true strain]) x [stress]
<Semi-softening temperature>
The obtained copper foils were each annealed at 100 to 400 ° C. for 0.5 hours and then subjected to a tensile test to determine the strength (tensile strength) with respect to the heat treatment conditions. The annealing temperature at which the strength TSh after annealing was an average value of the strength TSasroll after rolling (before annealing) and the strength TSanneal in a completely softened state was defined as a semi-softening temperature.
<銅張積層板の折曲回数>
次に、得られた銅箔の片面に、キャスト法で厚み約20μmのポリイミド層を製膜し、片面CCLを作製した。具体的には、得られた銅箔の片面を化学処理(めっき)し、この面にポリイミド樹脂の前駆体ワニス(宇部興産製U−ワニスA)を厚さ20μmになるように塗布した。この後、130℃に設定した熱風循環式高温槽で30分乾燥し、段階的に350℃まで2000秒かけて昇温して硬化(イミド化)して樹脂層(ポリイミド層)を形成し、片面CCLを作製した。
180度密着曲げは以下の手順で行った。まず、この片面CCLを幅3.2mm、長さ30mmで試験片の長さ方向が圧延方向と平行になるように切り出して試験片とし、樹脂層面を内側にしてループ状にし、ハンドプレスで潰して180度密着曲げを行った。そして、曲げ部の断面の銅箔部分の破断の有無を光学顕微鏡で観察した。破断がなければ、密着曲げ後の試料を開き、ハンドプレスを用いて平らに伸ばした後に、同じ場所でもう一度折り返してハンドプレスで潰した。このようにして、銅箔が破断するまでの曲げ回数を求めた。
<Number of bending of copper clad laminate>
Next, a polyimide layer having a thickness of about 20 μm was formed on one side of the obtained copper foil by a casting method to produce a single-sided CCL. Specifically, one side of the obtained copper foil was chemically treated (plated), and a polyimide resin precursor varnish (U-Vanice A-U Varnish A) was applied to this side so as to have a thickness of 20 μm. After that, it is dried for 30 minutes in a hot air circulation high temperature bath set at 130 ° C., and heated up to 350 ° C. over 2000 seconds and cured (imidized) to form a resin layer (polyimide layer). Single-sided CCL was prepared.
180 degree contact bending was performed according to the following procedure. First, this single-sided CCL is 3.2 mm wide, 30 mm long, cut out so that the length direction of the test piece is parallel to the rolling direction, and made into a test piece, looped with the resin layer side inside, and crushed with a hand press 180 degree close contact bending was performed. And the presence or absence of the fracture | rupture of the copper foil part of the cross section of a bending part was observed with the optical microscope. If there was no break, the sample after close contact bending was opened and stretched flat using a hand press, then folded back at the same place and crushed with a hand press. In this way, the number of bendings until the copper foil broke was determined.
<銅箔の摺動屈曲回数>
次に、得られた銅箔を、幅12.7 mm,長さ200 mmで試験片の長さ方向が圧延方向と平行になるように切り出して試験片とし、200℃で30分間加熱して再結晶させた。このものを、図1に示すIPC(アメリカプリント回路工業会)摺動屈曲装置により,IPC摺動屈曲回数の測定を行った。この装置は,発振駆動体4に振動伝達部材3を結合した構造になっており,試験片1は,矢印で示したねじ2の部分と3の先端部の計4点で装置に固定される。振動部3が上下に駆動すると,試験片1の中間部は,所定の曲率半径rでヘアピン状に屈曲される。本試験では,以下の条件下で屈曲を繰り返した時の破断までの回数を求めた。
曲率半径r:2.5 mm,振動ストローク:25mm,振動速度:1500回/分の条件で試験を行った。
<Number of sliding and bending of copper foil>
Next, the obtained copper foil was cut out to have a width of 12.7 mm and a length of 200 mm so that the length direction of the test piece was parallel to the rolling direction, and it was recrystallized by heating at 200 ° C. for 30 minutes. I let you. This was measured for the number of IPC sliding bends using an IPC (American Printed Circuit Industry Association) slide bending apparatus shown in FIG. This apparatus has a structure in which a
The test was performed under the conditions of a radius of curvature r: 2.5 mm, a vibration stroke: 25 mm, and a vibration speed: 1500 times / minute.
<I(220)/I(200)>
得られた銅箔を、350℃×0.5時間で大気焼鈍した後,圧延面のX線回折を行い、それぞれ(220)面及び(200)面の回折ピーク強度の積分値(I)を求めた。
<I (220) / I (200)>
The obtained copper foil was annealed at 350 ° C for 0.5 hours, and then X-ray diffraction was performed on the rolled surface, and the integrated values (I) of diffraction peak intensities on the (220) plane and (200) plane were obtained. .
得られた結果を表1に示す。なお、表1の組成において、OFC及びTPCは、それぞれ無酸素銅及びタフピッチ銅(JIS H3100)を示し、Ag100ppmTPCは、タフピッチ銅にAgを100質量ppm添加したものを示す。 The obtained results are shown in Table 1. In the composition of Table 1, OFC and TPC indicate oxygen-free copper and tough pitch copper (JIS H3100), respectively, and Ag100 ppm TPC indicates that 100 mass ppm of Ag is added to tough pitch copper.
表1から明らかなように、半軟化温度が150℃以下で、圧延平行方向の表面粗さRa≦0.1μmで、かつ350℃で0.5時間焼鈍後の加工硬化指数が0.3以上である実施例1〜8の場合、180度密着曲げを行ったときの曲げ回数が4回以上であり、曲げ性に優れたものとなった。
一方、最終冷間圧延時の総加工度を85%未満とした比較例3、6、7、8の場合、350℃で0.5時間焼鈍後の加工硬化指数が0.3未満となり、180度密着曲げを行ったときの曲げ回数が4回未満となって曲げ性が劣化した。なお、比較例1の場合、銅箔中のSnの添加量が500質量ppmを超えたために半軟化温度が150℃を超え、加工硬化指数が0.3未満となったものと考えられる。
また半軟化温度が150℃を超えた比較例1、7、8の場合、350℃で0.5時間焼鈍後の加工硬化指数が0.3未満となり、180度密着曲げを行ったときの曲げ回数が4回未満となって曲げ性が劣化した。
As is apparent from Table 1, the semi-softening temperature is 150 ° C. or less, the surface roughness Ra ≦ 0.1 μm in the rolling parallel direction, and the work hardening index after annealing at 350 ° C. for 0.5 hour is 0.3 or more. In the case of ˜8, the number of bending when the 180-degree contact bending was performed was 4 times or more, and the bendability was excellent.
On the other hand, in Comparative Examples 3, 6, 7, and 8 in which the total degree of work during the final cold rolling was less than 85%, the work hardening index after annealing at 350 ° C. for 0.5 hours was less than 0.3, and 180 degree contact bending was performed. The number of bendings performed was less than 4 and the bendability deteriorated. In addition, in the case of the comparative example 1, since the addition amount of Sn in copper foil exceeded 500 mass ppm, it is thought that the semisoftening temperature exceeded 150 degreeC and the work hardening index became less than 0.3.
In Comparative Examples 1, 7, and 8 where the semi-softening temperature exceeds 150 ° C., the work hardening index after annealing at 350 ° C. for 0.5 hours is less than 0.3, and the number of times of bending when performing 180 ° contact bending is 4 times. As a result, the bendability deteriorated.
最終冷間圧延における最終3パスでの油膜当量として、最終パスの2つ前の油膜当量;25000を超え、最終パスの1つ前の油膜当量;30000を超え、最終パスの油膜当量; 35000を超えた比較例2の場合、圧延平行方向の表面粗さRaが0.1μmを超え、180度密着曲げを行ったときの曲げ回数が4回未満となって曲げ性が劣化した。
最終冷間圧延における最終3パスでの油膜当量のうち、最終パスの1つ前の油膜当量が30000を超えた比較例4の場合、圧延平行方向の表面粗さRaが0.1μmを超え、180度密着曲げを行ったときの曲げ回数が4回未満となって曲げ性が劣化した。
最終冷間圧延における最終3パスでの油膜当量のうち、最終パスの2つ前の油膜当量が25000を超えた比較例5の場合も、圧延平行方向の表面粗さRaが0.1μmを超え、180度密着曲げを行ったときの曲げ回数が4回未満となって曲げ性が劣化した。
As the oil film equivalent in the final three passes in the final cold rolling, the oil film equivalent in the last two passes; over 25000, the oil film equivalent in the previous one in the final pass; over 30000, the oil film equivalent in the final pass; 35000 In the case of the comparative example 2 that exceeded, the surface roughness Ra in the rolling parallel direction exceeded 0.1 μm, and the number of bendings when the 180 degree contact bending was performed was less than 4 times, and the bendability deteriorated.
In the case of Comparative Example 4 in which the oil film equivalent of the last three passes in the final cold rolling exceeds 30000, the surface roughness Ra in the rolling parallel direction exceeds 0.1 μm, 180 When the tight bending was performed, the number of bendings was less than 4 and the bendability deteriorated.
Of the oil film equivalents in the final three passes in the final cold rolling, the surface roughness Ra in the rolling parallel direction exceeds 0.1 μm in the case of Comparative Example 5 in which the oil film equivalent two previous to the final pass exceeded 25000, When the 180 degree contact bending was performed, the number of bendings was less than 4 and the bendability deteriorated.
なお、比較例1〜8の場合も、従来の屈曲性の評価であるIPC摺動屈曲回数は各実施例と同等であり、摺動屈曲試験では銅張積層板の曲げ性を評価できないことがわかる。 In addition, in the case of Comparative Examples 1 to 8, the number of IPC sliding bends, which is the conventional evaluation of bendability, is equivalent to each example, and the bendability of the copper-clad laminate cannot be evaluated by the slide bend test. Recognize.
Claims (6)
但し、最終パスの2つ前の油膜当量;25000以下、最終パスの1つ前の油膜当量;30000以下、最終パスの油膜当量; 35000以下 Cold rolling and annealing are repeated after the ingot is hot-rolled, the total workability at the time of final cold rolling is 85% or more, and the oil film equivalent in the final three passes in the final cold rolling is rolled under the following conditions A method for producing a copper foil having a thickness of 5 to 30 μm , wherein the copper foil is made of oxygen-free copper or tough pitch copper, or a total of 500 masses of one or more kinds consisting of Ag and Sn in oxygen-free copper or tough pitch copper. A method for producing copper foil containing ppm or less .
However, the oil film equivalent before the final pass; 25000 or less, the oil film equivalent before the final pass; 30000 or less, the oil film equivalent of the final pass; 35000 or less
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