JP5390852B2 - Rolled copper foil - Google Patents

Rolled copper foil Download PDF

Info

Publication number
JP5390852B2
JP5390852B2 JP2008327610A JP2008327610A JP5390852B2 JP 5390852 B2 JP5390852 B2 JP 5390852B2 JP 2008327610 A JP2008327610 A JP 2008327610A JP 2008327610 A JP2008327610 A JP 2008327610A JP 5390852 B2 JP5390852 B2 JP 5390852B2
Authority
JP
Japan
Prior art keywords
copper foil
measurement
rolled copper
rolled
plane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP2008327610A
Other languages
Japanese (ja)
Other versions
JP2010150578A (en
Inventor
岳海 室賀
元 佐々木
聡至 関
Original Assignee
株式会社Ｓｈカッパープロダクツ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社Ｓｈカッパープロダクツ filed Critical 株式会社Ｓｈカッパープロダクツ
Priority to JP2008327610A priority Critical patent/JP5390852B2/en
Publication of JP2010150578A publication Critical patent/JP2010150578A/en
Application granted granted Critical
Publication of JP5390852B2 publication Critical patent/JP5390852B2/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Parts Printed On Printed Circuit Boards (AREA)

Description

本発明は、圧延銅箔に関し、特に、フレキシブルプリント配線板等の可撓性配線部材に好適な優れた屈曲特性を有する圧延銅箔に関するものである。   The present invention relates to a rolled copper foil, and more particularly to a rolled copper foil having excellent bending characteristics suitable for a flexible wiring member such as a flexible printed wiring board.

フレキシブルプリント配線板（Flexible Printed Circuit、以下、FPCと称す）は、厚みが薄く可撓性に優れる特長から、電子機器等への実装形態における自由度が高い。そのため、現在では、折り畳み式携帯電話の折り曲げ部・デジタルカメラ・プリンターヘッドなどの可動部、ならびに、HDD （Hard Disk Drive）やDVD （Digital Versatile Disc），CD （Compact Disk）など、ディスク関連機器の可動部の配線等にFPCが広く用いられている。   A flexible printed circuit (hereinafter referred to as “FPC”) has a high degree of freedom in mounting on an electronic device or the like because of its thin thickness and excellent flexibility. For this reason, the folding parts of foldable mobile phones, movable parts such as digital cameras and printer heads, and disk-related equipment such as HDD (Hard Disk Drive), DVD (Digital Versatile Disc), and CD (Compact Disk) are now available. FPC is widely used for wiring of movable parts.

FPCの導電体としては、種々の表面処理が施された純銅箔または銅合金箔（以下、単に「銅箔」という）が一般的に用いられている。銅箔は、その製造方法の違いにより、電解銅箔と圧延銅箔に大別される。FPCは、前述のように繰り返し可動する部分の配線材として用いられることから優れた屈曲特性（例えば、100万回以上の屈曲特性）が要求され、銅箔としては圧延銅箔が使用されることが多い。   As the FPC conductor, pure copper foil or copper alloy foil (hereinafter simply referred to as “copper foil”) subjected to various surface treatments is generally used. Copper foils are roughly classified into electrolytic copper foils and rolled copper foils depending on the manufacturing method. FPC is used as a wiring material for parts that can be repeatedly moved as described above, and therefore excellent bending characteristics (for example, bending characteristics of 1 million times or more) are required, and rolled copper foil is used as the copper foil. There are many.

一般的に、圧延銅箔の製造は、原材料となるタフピッチ銅（JIS H3100 C1100）や無酸素銅（JIS H3100 C1020）の鋳塊に熱間圧延を施した後、所定の厚さまで冷間圧延と中間焼鈍を繰り返し施すことによって行われる。FPC用の圧延銅箔に要求される厚さは、通常、50μm以下であるが、最近では十数μm以下と更に薄くなる傾向にある。   In general, rolled copper foil is manufactured by hot rolling an ingot of tough pitch copper (JIS H3100 C1100) or oxygen-free copper (JIS H3100 C1020), which is a raw material, and then cold rolling to a predetermined thickness. It is performed by repeatedly performing intermediate annealing. The thickness required for the rolled copper foil for FPC is usually 50 μm or less, but recently, it has a tendency to be further reduced to a dozen μm or less.

FPCの製造工程は、概略的に、「FPC用銅箔と、ポリイミドなどの樹脂からなるベースフィルム（基材）とを貼り合わせてCCL （Copper Clad Laminate）を形成する工程（CCL工程）」と、「該CCLにエッチング等の手法により回路配線を形成する工程」と、「該回路上に配線保護のための表面処理を行う工程」などから構成されている。CCL工程には、接着剤を介して銅箔と基材を積層した後、熱処理により接着剤を硬化して密着させる（３層CCL）方法と、接着剤を介さず、表面処理の施された銅箔を基材に直接張り合わせた後、加熱・加圧により一体化する（２層CCL）方法の２種類がある。   The manufacturing process of FPC is roughly as follows: "Copper foil for FPC and base film (base material) made of resin such as polyimide to form CCL (Copper Clad Laminate) (CCL process)" , “A step of forming a circuit wiring on the CCL by a technique such as etching”, “a step of performing a surface treatment for protecting the wiring on the circuit”, and the like. In the CCL process, after laminating the copper foil and the base material via an adhesive, the adhesive was cured and adhered by heat treatment (three-layer CCL), and the surface treatment was applied without using the adhesive. There are two types of methods in which a copper foil is directly bonded to a substrate and then integrated by heating and pressing (two-layer CCL).

ここで、FPCの製造工程においては、製造の容易性の観点から冷間圧延加工上がり（加工硬化した硬質な状態）の銅箔が用いられることが多い。銅箔が焼鈍された（軟化した）状態にあると、銅箔の裁断や基材との積層時に銅箔の変形（例えば、伸び、しわ、折れ、等）が生じ易く、製品不良になりやすいためである。   Here, in the manufacturing process of the FPC, a copper foil that has been cold-rolled (hardened after work hardening) is often used from the viewpoint of ease of manufacturing. When the copper foil is in an annealed (softened) state, the copper foil is likely to be deformed (for example, stretched, wrinkled, broken, etc.) during the cutting of the copper foil or the lamination with the base material, resulting in a defective product. Because.

一方、銅箔の屈曲特性は、再結晶焼鈍を行うことにより、圧延加工上がりの状態よりも著しく向上する。そこで、上述のCCL工程における基材と銅箔とを密着・一体化させるための熱処理で、銅箔の再結晶焼鈍を兼ねる製造方法が一般的に選択されている。なお、このときの熱処理条件は、180〜300℃で１〜60分間（代表的には200℃で30分間）であり、銅箔は再結晶組織に調質した状態となる。   On the other hand, the bending characteristics of the copper foil are remarkably improved as compared with the state after the rolling process by performing recrystallization annealing. Therefore, a manufacturing method that also serves as recrystallization annealing of the copper foil is generally selected in the heat treatment for bringing the base material and the copper foil into close contact and integration in the above-described CCL process. The heat treatment conditions at this time are 180 to 300 ° C. for 1 to 60 minutes (typically 200 ° C. for 30 minutes), and the copper foil is tempered into a recrystallized structure.

FPCの屈曲特性を高めるためには、その素材となる圧延銅箔の屈曲特性を高めることが有効である。また、一般的に、再結晶焼鈍後の銅箔の屈曲特性は、立方体集合組織が発達するほど向上することが知られている。なお、一般に言われている「立方体集合組織が発達」とは、圧延面において{２００}Cu面の占有率が高いこと（例えば、85％以上）のみを意味する。 In order to improve the bending characteristics of FPC, it is effective to increase the bending characteristics of the rolled copper foil as the material. In general, it is known that the bending characteristics of a copper foil after recrystallization annealing improve as the cubic texture develops. Note that “cubic texture development” generally referred to only means that the occupancy of the {200} Cu surface is high (for example, 85% or more) on the rolled surface.

従来、屈曲特性に優れた圧延銅箔やその製造方法として、次のようなものが報告されている。最終冷間圧延工程の総加工度を高くすること（例えば、90％以上）によって立方体集合組織を発達させる方法、および再結晶焼鈍後の立方体集合組織の発達度合を規定した銅箔（例えば、圧延面のＸ線回折で求めた(２００)面の強度が粉末Ｘ線回折で求めた(２００)面の強度の20倍より大きい銅箔）。最終冷間圧延工程前の中間焼鈍の際に立方体集合組織を発達させておき、最終冷間圧延工程の総加工度を93％以上にして再結晶後の立方体集合組織を更に発達させる方法。銅箔板厚方向の貫通結晶粒の割合を規定した銅箔（例えば、断面面積率で40％以上が貫通結晶粒である銅箔）。微量添加元素の添加により軟化温度を制御した銅箔（例えば、120〜150℃の半軟化温度に制御した銅箔）。双晶境界の長さを規定した銅箔（例えば、長さ５μmを超える双晶境界が１mm2の面積あたり合計長さ20 mm以下である銅箔）。微量添加元素の添加により再結晶組織を制御した銅箔（例えば、Snを0.01〜0.2質量％添加し、平均結晶粒径を５μm以下、最大結晶粒径を15μm以下に制御した銅箔）などが報告されている（例えば、特許文献１乃至７参照）。 Conventionally, the following has been reported as a rolled copper foil having excellent bending characteristics and a method for producing the same. A method of developing a cubic texture by increasing the total degree of work in the final cold rolling process (for example, 90% or more), and a copper foil that defines the degree of development of the cubic texture after recrystallization annealing (for example, rolling) A copper foil having a strength of (200) plane determined by X-ray diffraction of the plane greater than 20 times the strength of (200) plane determined by powder X-ray diffraction. A method in which a cube texture is developed during intermediate annealing before the final cold rolling step, and the total degree of work in the final cold rolling step is set to 93% or more to further develop the cube texture after recrystallization. A copper foil that defines the ratio of through crystal grains in the thickness direction of the copper foil plate (for example, a copper foil having a cross-sectional area ratio of 40% or more being through crystal grains). A copper foil whose softening temperature is controlled by adding a trace amount of additive elements (for example, a copper foil controlled to a semi-softening temperature of 120 to 150 ° C.). A copper foil having a defined twin boundary length (for example, a copper foil having a twin boundary exceeding 5 μm in length and having a total length of 20 mm or less per 1 mm 2 area). Copper foils whose recrystallized structure is controlled by adding trace elements (for example, copper foils with 0.01 to 0.2% by mass of Sn added, controlled to an average crystal grain size of 5 μm or less and a maximum crystal grain size of 15 μm or less), etc. Have been reported (for example, see Patent Documents 1 to 7).

特開２００１−２６２２９６号公報JP 2001-262296 A 特許第３００９３８３号公報Japanese Patent No. 3009383 特開２００１−３２３３５４号公報JP 2001-323354 A 特開２００６−１１７９７７号公報JP 2006-117777 A 特開２０００−２１２６６１号公報JP 2000-212661 A 特開２０００−２５６７６５号公報JP 2000-256765 A 特開２００５−６８４８４号公報JP 2005-68484 A

前述したように、従来技術では、最終冷間圧延工程の総加工度を高くするほど再結晶焼鈍後に圧延銅箔の立方体集合組織が発達して屈曲性が向上すると報告されている。しかしながら、冷間圧延加工においては、総加工度が高くなるほど加工硬化によって材料（銅箔）が硬くなることから、１パスあたりの加工度の制御が難しくなり圧延銅箔の製造効率が低下する問題がある。具体的には、冷間圧延の総加工度が約90％以上（特に93％以上）になると、１パスあたりの加工度制御や圧延加工自体が急激に難しくなる。   As described above, it has been reported in the prior art that the higher the total degree of work in the final cold rolling step, the more the cubic texture of the rolled copper foil develops after recrystallization annealing and the flexibility increases. However, in cold rolling, the higher the total degree of work, the harder the material (copper foil) by work hardening, so the control of the degree of work per pass becomes difficult and the production efficiency of the rolled copper foil decreases. There is. Specifically, when the total workability of cold rolling is about 90% or more (particularly 93% or more), control of the workability per pass and the rolling work itself become rapidly difficult.

一方、近年、電子機器類の小型化、高集積化（高密度実装化）や高性能化等の進展に伴い、FPCには従来よりも更なる高屈曲特性の要求が益々高まってきている。FPCの屈曲特性は実質的に銅箔のそれによって決まるため、要求を満たすためには銅箔の屈曲特性を更に向上させることが必須である。また、電子部品に対する低コスト化の要求は強まる一方である。   On the other hand, in recent years, with the progress of downsizing, high integration (high density mounting), high performance, etc. of electronic devices, demands for higher bending characteristics than ever are increasing. Since the bending characteristics of the FPC are substantially determined by that of the copper foil, it is essential to further improve the bending characteristics of the copper foil in order to satisfy the requirements. In addition, there is an increasing demand for cost reduction of electronic components.

従って、本発明の目的は、フレキシブルプリント配線板（FPC）等の可撓性配線部材に適しており、優れた屈曲特性を有する圧延銅箔を提供することにある。さらには、最終冷間圧延工程において従来のような高い総加工度を実施しなくても、高屈曲特性を有する圧延銅箔を安定して効率良く（すなわち、低コストで）製造できる製造方法を提供することにある。   Accordingly, an object of the present invention is to provide a rolled copper foil which is suitable for a flexible wiring member such as a flexible printed wiring board (FPC) and has excellent bending characteristics. Furthermore, a manufacturing method capable of stably and efficiently producing a rolled copper foil having high bending characteristics (ie, at low cost) without performing a high total workability as in the past in the final cold rolling process. It is to provide.

本発明者らは、圧延銅箔における金属結晶学的な詳細検討を行い、生地焼鈍の後で最終冷間圧延工程前の圧延銅箔および最終冷間圧延工程の後で再結晶焼鈍前の圧延銅箔における結晶粒の方位・配向状態が、再結晶焼鈍後の結晶粒配向状態および銅箔の屈曲特性との間に特定の相関関係を有することを見出した。また、その現象がこれまで考えられていた原理と異なる現象と思われることを見出したことに基づき、本発明を完成した（詳細は後述する）。   The present inventors have made detailed metallographic studies on rolled copper foil, rolled copper foil after dough annealing and before the final cold rolling step, and rolling before recrystallization annealing after the final cold rolling step It has been found that the orientation and orientation state of crystal grains in the copper foil have a specific correlation between the crystal grain orientation state after recrystallization annealing and the bending characteristics of the copper foil. Further, the present invention has been completed based on the finding that the phenomenon seems to be a phenomenon different from the previously considered principle (details will be described later).

本発明は、上記目的を達成するため、最終冷間圧延工程の後で再結晶焼鈍前の圧延銅箔であって、圧延面を基準としたＸ線回折極点図測定による銅結晶の{２２０}Cu面回折の正極点図結果で、α角度が40〜50°の範囲において、β角度の少なくとも90±５°毎に存在して４回対称性を示す結晶粒群に起因する回折ピークが存在し、さらに、前記β角度の90±10°毎に存在して４回対称性を示す別の結晶粒群に起因する回折ピークが存在することを特徴とする圧延銅箔を提供する。なお、圧延銅箔の素材としては、タフピッチ銅（例えばJIS H3100 C1100）や無酸素銅（例えばJIS H3100 C1020）等のような銅純度が99.9％以上の銅を用いることが好ましい。また、銅純度が99.9％以上である銅合金を用いてもよい。 In order to achieve the above object, the present invention is a rolled copper foil after the final cold rolling process and before recrystallization annealing, and the copper crystal {220} by X-ray diffraction pole figure measurement based on the rolled surface In the positive electrode dot diagram of Cu plane diffraction, there is a diffraction peak due to a group of crystal grains having a 4-fold symmetry that exists at every 90 ± 5 ° of β angle in the range of α angle of 40-50 °. Furthermore, the present invention provides a rolled copper foil characterized in that there is a diffraction peak due to another crystal grain group presenting every four times the β angle of 90 ± 10 ° and exhibiting 4-fold symmetry. As the material of the rolled copper foil, it is preferable to use copper having a copper purity of 99.9% or more, such as tough pitch copper (for example, JIS H3100 C1100) and oxygen-free copper (for example, JIS H3100 C1020). Moreover, you may use the copper alloy whose copper purity is 99.9% or more.

また、本発明は、上記目的を達成するため、上記の本発明に係る圧延銅箔において、以下のような改良や変更を加えることができる。
（１）前記圧延面を基準としたＸ線回折極点図測定により得られる結果で、極点図測定のα角度を横軸とし各α角度におけるβ走査で得られる銅結晶の{２２０}Cu面回折ピークの規格化強度を縦軸としてグラフ表記した際に、α＝25〜35°の間に前記規格化強度の極大値Ｐが存在し、α＝40〜50°の間に前記規格化強度の極大値Ｑが存在し、α＝85〜90°の間は前記規格化強度が単調増加しており、前記極大値Ｐと前記極大値Ｑと前記α＝90°における前記規格化強度の値Ｒとが「Ｑ≦Ｐ≦Ｒ」である。
（２）前記圧延面に対するＸ線回折２θ/θ測定により得られる結果で、銅結晶の回折ピークの強度が「I{200}Cu ≧ I{220}Cu」であることを特徴とする圧延銅箔を提供する。
（３）前記圧延銅箔に対して再結晶焼鈍を施した後の圧延銅箔であって、
前記圧延面に対するＸ線回折２θ/θ測定から算出される立方体集合組織の比率[Ａ]と、当該立方体集合組織の結晶粒についてＸ線回折ロッキングカーブ測定から算出される面外配向比率[Ｂ]と、前記立方体集合組織の結晶粒について前記圧延面を基準としたＸ線回折極点図測定から算出される面内配向比率[Ｃ]との積が、「[Ａ]×[Ｂ]×[Ｃ] ≧ 0.5」であることを特徴とする圧延銅箔を提供する。 Moreover, in order to achieve the said objective, this invention can add the following improvements and changes in the rolled copper foil which concerns on said this invention.
(1) {220} Cu surface diffraction of copper crystals obtained by X-ray diffraction pole figure measurement based on the rolled surface, obtained by β scanning at each α angle with the α angle of the pole figure measurement as the horizontal axis When the normalized intensity of the peak is shown as a graph on the vertical axis, there is a maximum value P of the normalized intensity between α = 25 to 35 °, and the normalized intensity of the peak between α = 40 to 50 °. There is a maximum value Q, and the normalized strength monotonically increases between α = 85 and 90 °, and the normalized strength value R at the maximum value P, the maximum value Q, and α = 90 °. And “Q ≦ P ≦ R”.
(2) Rolled copper characterized in that the intensity of the diffraction peak of the copper crystal is “I {200} Cu ≧ I {220} Cu ” as a result of X-ray diffraction 2θ / θ measurement on the rolled surface. Provide foil.
(3) A rolled copper foil after being subjected to recrystallization annealing on the rolled copper foil,
The ratio [A] of the cube texture calculated from the X-ray diffraction 2θ / θ measurement with respect to the rolled surface, and the out-of-plane orientation ratio [B] calculated from the X-ray diffraction rocking curve measurement for the crystal grains of the cube texture And the in-plane orientation ratio [C] calculated from the X-ray diffraction pole figure measurement based on the rolling surface for the crystal grains of the cubic texture is “[A] × [B] × [C A rolled copper foil is provided, wherein ≧ 0.5 ”.

本発明によれば、フレキシブルプリント配線板（FPC）等の可撓性配線部材に適しており、優れた屈曲特性を有する圧延銅箔を提供することができる。さらには、高屈曲特性を有する圧延銅箔を安定して効率良く（すなわち、低コストで）製造する製造方法を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, it is suitable for flexible wiring members, such as a flexible printed wiring board (FPC), and can provide the rolled copper foil which has the outstanding bending characteristic. Furthermore, the manufacturing method which manufactures the rolled copper foil which has a high bending characteristic stably and efficiently (namely, low cost) can be provided.

本発明に関係する銅結晶の主な結晶面を示す模式図を図１に示す。銅の結晶構造は立方晶であることから、{２００}Cu面と{２２０}Cu面のなす角度は45°になる。なお、{ }は等価な面を表すものとする（図１参照）。 A schematic diagram showing main crystal planes of a copper crystal related to the present invention is shown in FIG. Since the crystal structure of copper is cubic, the angle between the {200} Cu face and the {220} Cu face is 45 °. Note that {} represents an equivalent surface (see FIG. 1).

図２は、Ｘ線回折（以下、XRDと表記する場合もある）における入射Ｘ線・検出器・試料・走査軸の関係を示す概略図である。以下、図２を用いてXRDによる圧延銅箔の結晶粒配向状態に関する評価方法を説明する。なお、図２における３つの走査軸は、一般的に、θ軸が試料軸、α軸があおり軸、β軸が面内回転軸と呼ばれている。また、本発明におけるＸ線回折は、すべてCu Kα線によるものとする。   FIG. 2 is a schematic diagram showing a relationship among incident X-rays, detectors, samples, and scanning axes in X-ray diffraction (hereinafter sometimes referred to as XRD). Hereafter, the evaluation method regarding the crystal grain orientation state of the rolled copper foil by XRD is demonstrated using FIG. Note that the three scanning axes in FIG. 2 are generally called a sample axis, an α axis having a θ axis, and a β axis being an in-plane rotation axis. Further, all X-ray diffraction in the present invention is based on Cu Kα rays.

入射Ｘ線に対して、試料と検出器をθ軸で走査し、試料の走査角をθ、検出器の走査角を２θで走査する測定方法を２θ/θ測定という。２θ/θ測定による回折ピークの強度よって、多結晶体である圧延銅箔の試料面（本発明では圧延面）において、どの結晶面が優勢であるのかを評価できる。   A measurement method in which a sample and a detector are scanned with respect to incident X-rays along the θ axis, the scanning angle of the sample is scanned with θ, and the scanning angle of the detector with 2θ is called 2θ / θ measurement. Based on the intensity of the diffraction peak by 2θ / θ measurement, it is possible to evaluate which crystal plane is dominant on the sample surface (rolled surface in the present invention) of a rolled copper foil that is a polycrystalline body.

ある１つの回折面{ｈｋｌ}Cuに着目して、着目した{ｈｋｌ}Cu面の２θ値に対し（検出器の走査角２θを固定し）、試料のみをθ軸走査させる測定方法をロッキングカーブ測定という。この測定による{ｈｋｌ}Cu面ピークの半価幅または積分幅で{ｈｋｌ}Cu面の圧延面垂直方向の配向度を評価できる。このとき、半価幅または積分幅の値が小さいほど圧延面に垂直方向の結晶配向性に優れているといえる（以下、「圧延面に垂直方向の結晶配向性」を「面外配向性」と称する）。なお、半価幅は回折ピークの最大強度の半分の強度におけるピーク幅、積分幅は回折ピークの積分強度を該回折ピークの最大強度で除したものと定義する。 Focusing on a certain diffractive surface {hkl} Cu , the rocking curve is a measurement method that scans only the sample with the θ-axis relative to the 2θ value of the focused {hkl} Cu surface (with the detector scanning angle 2θ fixed) This is called measurement. The degree of orientation of the {hkl} Cu plane in the direction perpendicular to the rolling plane can be evaluated by the half width or integral width of the {hkl} Cu plane peak obtained by this measurement. At this time, it can be said that the smaller the value of the half width or the integral width, the better the crystal orientation in the direction perpendicular to the rolling surface (hereinafter referred to as “crystal orientation in the direction perpendicular to the rolling surface” as “out-of-plane orientation”). Called). The half width is defined as the peak width at half the maximum intensity of the diffraction peak, and the integral width is defined as the integral intensity of the diffraction peak divided by the maximum intensity of the diffraction peak.

ある１つの回折面{ｈ'ｋ'ｌ'}Cuに着目して、着目した{ｈ'ｋ'ｌ'}Cu面の２θ値に対し（検出器の走査角２θを固定し）、α軸走査をステップで行い、各α値に対して試料をβ軸走査（０〜３６０°まで面内回転（自転））させる測定方法を極点図測定という。この測定により、着目した{ｈ'ｋ'ｌ'}Cu面が圧延面の垂直方向から傾いている程度を評価できる。なお、本発明のXRD極点図測定では、試料面に垂直な方向をα＝90°と定義し、測定の基準とする。また、極点図測定には、反射法（α＝15〜90°）と透過法（α＝０〜15°）があるが、本発明における極点図測定は、反射法（α＝15〜90°）のみの測定を考慮する。 Focusing on a certain diffractive surface {h'k'l '} Cu , with respect to the 2θ value of the focused {h'k'l'} Cu surface (fixed detector scanning angle 2θ), α axis A measurement method in which scanning is performed in steps and the sample is β-axis scanned (in-plane rotation (rotation) from 0 to 360 °) with respect to each α value is referred to as pole figure measurement. By this measurement, it is possible to evaluate the degree to which the focused {h′k′l ′} Cu surface is tilted from the vertical direction of the rolling surface. In the XRD pole figure measurement of the present invention, the direction perpendicular to the sample surface is defined as α = 90 °, which is used as a measurement reference. The pole figure measurement includes a reflection method (α = 15 to 90 °) and a transmission method (α = 0 to 15 °). The pole figure measurement in the present invention is performed by the reflection method (α = 15 to 90 °). ) Only the measurement is considered.

極点図測定の特徴を利用した評価方法の１つに面内配向測定がある。これは、着目した{ｈｋｌ}Cu面と幾何学的に対応する結晶面{ｈ'ｋ'ｌ'}Cuが該{ｈｋｌ}Cu面となす角度をα'とした場合、「α＝９０−α'」となるようにα軸走査し（試料を傾け）、{ｈ'ｋ'ｌ'}Cu面の２θ値に対して（検出器の走査角２θを固定して）、試料をβ軸走査（０〜360°まで面内回転（自転））させる測定方法である。この測定による{ｈ'ｋ'ｌ'}Cu面ピークの半価幅または積分幅で、{ｈ'ｋ'ｌ'}Cu面と幾何学的に対応する{ｈｋｌ}Cu面の圧延面内２軸方向の配向度が評価できる。このとき、前述と同様に、該回折ピークの半価幅または積分幅の値が小さいほど圧延面内方向の結晶配向性に優れているといえる（以下、「圧延面内方向の結晶配向性」を「面内配向性」と称する）。 One of evaluation methods using the characteristics of pole figure measurement is in-plane orientation measurement. This is because when the angle between the {hkl} Cu plane of interest and the crystal plane {h'k'l '} Cu geometrically corresponding to the {hkl} Cu plane is α ′, “α = 90− Scan the α axis so that it becomes “α ′” (tilt the sample), and fix the sample to the β axis with respect to the 2θ value of the {h′k′l ′} Cu surface (fixing the scanning angle 2θ of the detector) This is a measurement method of scanning (in-plane rotation (rotation) from 0 to 360 °). 'In Cu surface half width or integration width of a peak, {h'k'l {h'k'l}' by this measure} Cu plane geometrically corresponding {hkl} Cu plane of the rolling plane 2 The degree of orientation in the axial direction can be evaluated. At this time, as described above, it can be said that the smaller the half width or integral width of the diffraction peak, the better the crystal orientation in the in-rolling plane direction (hereinafter referred to as “crystalline orientation in the in-rolling plane direction”). Is referred to as “in-plane orientation”).

〔本発明の第１の実施形態〕
（面内配向測定）
本実施の形態における圧延銅箔は、最終冷間圧延工程の後で再結晶焼鈍前の圧延銅箔であって、圧延面を基準としたＸ線回折極点図測定により得られる結果で、極点図測定のα角度＝45°におけるβ走査で得られる銅結晶の{２２０}Cu面回折ピークがβ角度の少なくとも90±５°毎に存在して４回対称性を示すことを特徴とする。例えば、極点図測定において銅箔の圧延方向をβ＝０°とした場合、４回対称の回折ピークの中心はそれぞれβ≒０°（360°）, 90°, 180°, 270°となる。 [First embodiment of the present invention]
(In-plane orientation measurement)
The rolled copper foil in the present embodiment is a rolled copper foil after the final cold rolling process and before recrystallization annealing, and is a result obtained by X-ray diffraction pole figure measurement based on the rolled surface. A {220} Cu plane diffraction peak of a copper crystal obtained by β scanning at a measurement α angle = 45 ° exists at every 90 ± 5 ° of the β angle and exhibits fourfold symmetry. For example, when the rolling direction of the copper foil is β = 0 ° in the pole figure measurement, the centers of the four-fold symmetric diffraction peaks are β≈0 ° (360 °), 90 °, 180 °, and 270 °, respectively.

上述の面内配向測定結果において、{２２０}Cu面回折ピークが90±５°毎の４回対称性を示さない場合、再結晶焼鈍を施しても高屈曲特性を有する圧延銅箔が得られない。よって、上記のように規定する。なお、極点図測定のα角度＝45°においてβ走査で得られる銅結晶の{２２０}Cu面回折ピークが90±５°毎の４回対称性を示すということは、該{２２０}Cu面と結晶幾何学的に45°の角度をなす{２００}Cu面が銅箔の圧延面で面内配向していることを意味する。また、当該４回対称性の回折ピークは、それぞれの回折ピーク強度がβ軸走査（０〜360°までの面内回転）で得られる{２２０}Cu面回折の最小強度に対して1.5倍以上を有することが望ましい。 In the above in-plane orientation measurement results, when the {220} Cu plane diffraction peak does not show the 4-fold symmetry every 90 ± 5 °, a rolled copper foil having high bending properties can be obtained even if recrystallization annealing is performed. Absent. Therefore, it is defined as described above. It should be noted that the {220} Cu plane diffraction peak of the copper crystal obtained by β scanning at the α angle = 45 ° of the pole figure measurement shows the 4-fold symmetry every 90 ± 5 ° indicates that the {220} Cu plane The {200} Cu plane, which forms an angle of 45 ° with respect to the crystal geometry, means that the in-plane orientation is in the rolled plane of the copper foil. In addition, the diffraction peak of the 4-fold symmetry is 1.5 times or more than the minimum intensity of {220} Cu- plane diffraction, where each diffraction peak intensity is obtained by β-axis scanning (in-plane rotation from 0 to 360 °). It is desirable to have

〔本発明の第２の実施形態〕
（規格化強度）
本実施の形態における圧延銅箔は、最終冷間圧延工程の後で再結晶焼鈍前の圧延銅箔であって、前記圧延面を基準としたＸ線回折極点図測定により得られる結果で、極点図測定のα角度を横軸とし各α角度におけるβ走査で得られる銅結晶の{２２０}Cu面回折ピークの規格化強度を縦軸としてグラフ表記した際に、α＝25〜35°の間に前記規格化強度の極大値Ｐが存在し、α＝40〜50°の間に前記規格化強度の極大値Ｑが存在し、α＝85〜90°の間は前記規格化強度が単調増加しており、前記極大値Ｐと前記極大値Ｑと前記α＝90°における前記規格化強度の値Ｒとが「Ｑ≦Ｐ≦Ｒ」であることを特徴とする。上述のXRD極点図測定の結果において、{２２０}Cu面回折ピークの規格化強度がα＝25〜35°の極大値Ｐとα＝40〜50°の極大値Ｑとα＝85〜90°の単調増加とを示さず、前記極大値Ｐと前記極大値Ｑと前記α＝90°における規格化強度の値Ｒとが「Ｑ≦Ｐ≦Ｒ」の関係を示さない場合、再結晶焼鈍を施しても高屈曲特性を有する圧延銅箔が得られない。よって、上記のように規定する。 [Second Embodiment of the Present Invention]
(Standardized strength)
The rolled copper foil in the present embodiment is a rolled copper foil after the final cold rolling process and before recrystallization annealing, and is a result obtained by X-ray diffraction pole figure measurement based on the rolled surface. When graphed with the normalized intensity of the {220} Cu- plane diffraction peak of the copper crystal obtained by β scanning at each α angle as the abscissa and α = 25 to 35 ° There is a maximum value P of the normalized strength, and there is a maximum value Q of the standardized strength between α = 40 to 50 °, and the normalized strength increases monotonously between α = 85 to 90 °. The maximum value P, the maximum value Q, and the normalized strength value R at α = 90 ° satisfy “Q ≦ P ≦ R”. As a result of the above XRD pole figure measurement, the normalized intensity of the {220} Cu plane diffraction peak is a maximum value P of α = 25 to 35 °, a maximum value Q of α = 40 to 50 °, and α = 85 to 90 °. If the maximum value P, the maximum value Q, and the normalized strength value R at α = 90 ° do not show the relationship of “Q ≦ P ≦ R”, the recrystallization annealing is not performed. Even if applied, a rolled copper foil having high bending properties cannot be obtained. Therefore, it is defined as described above.

なお、規格化強度Ｒｃとは、XRD極点図測定において、各α角度におけるβ軸走査（面内回転軸走査）による所定の{ｈｋｌ}Cu回折ピーク強度を平均化したカウント数であり、次式（詳細は下記文献を参照）により算出することができる。なお、規格化の計算は通常コンピューターで実施される。また、XRDピーク強度を規格化して用いる理由は、XRD測定の際の管電圧や管電流などの条件設定の違いによる影響をなくして比較できるようにするためである（実質的に装置依存性がなくなる）。
Ｒｃ＝Ｉｃ / Ｉstd
ここで、
Ｉｃ：補正強度（バックグラウンド補正、吸収補正）
Ｉstd：計算で求めた規格化するための強度
である。
（文献名）「RAD システム応用ソフトウェア 集合組織解析プログラム 取扱説明書（説明書番号：MJ201RE）」，理学電機株式会社，ｐ．22〜23．
（文献名）「CN9258E101 RINT2000シリーズ アプリケーションソフトウェア 正極点 取扱説明書（説明書番号：MJ10102A01）」理学電機株式会社，ｐ．８〜10． Note that the normalized intensity R c is a count number obtained by averaging predetermined {hkl} Cu diffraction peak intensities by β-axis scanning (in-plane rotation axis scanning) at each α angle in the XRD pole figure measurement. It can be calculated by an equation (refer to the following document for details). The normalization calculation is usually performed by a computer. The reason for using the standardized XRD peak intensity is to allow comparison without the influence of differences in conditions such as tube voltage and tube current during XRD measurement. Disappear).
R c = I c / I std
here,
I c : correction intensity (background correction, absorption correction)
I std : strength for normalization obtained by calculation.
(Literature name) “RAD system application software texture analysis program instruction manual (manual number: MJ201RE)”, Rigaku Corporation, p. 22-23.
(Literature name) “CN9258E101 RINT2000 Series Application Software Positive Point Instruction Manual (manual number: MJ10102A01)” Rigaku Corporation, p. 8-10.

〔本発明の第３の実施形態〕
（２θ/θ測定）
本実施の形態における圧延銅箔は、最終冷間圧延工程の後で再結晶焼鈍前の状態において、前記圧延面に対するＸ線回折２θ/θ測定により得られる結果で、銅結晶の回折ピークの強度Ｉが「I{200}Cu ≧ I{220}Cu」であることを特徴とする。 [Third embodiment of the present invention]
(2θ / θ measurement)
The rolled copper foil in the present embodiment is a result obtained by X-ray diffraction 2θ / θ measurement on the rolled surface in the state after the final cold rolling process and before recrystallization annealing, and the intensity of the diffraction peak of the copper crystal. I is characterized by “I {200} Cu ≧ I {220} Cu ”.

前述したように本発明に係る圧延銅箔は、最終冷間圧延工程の後で再結晶焼鈍前の状態において、{２００}Cu面が銅箔の圧延面で配向している。このことは、多結晶体である銅箔の圧延面に{２００}Cu面配向した結晶粒が相当量存在することを意味する。図３は、本発明に係る圧延銅箔において、最終冷間圧延工程の後かつ再結晶焼鈍前の状態で、圧延面に対してＸ線回折２θ/θ測定を行った結果の１例である。 As described above, in the rolled copper foil according to the present invention, the {200} Cu plane is oriented with the rolled surface of the copper foil in the state after the final cold rolling step and before the recrystallization annealing. This means that a considerable amount of {200} Cu face-oriented crystal grains are present on the rolled surface of the copper foil which is a polycrystal. FIG. 3 is an example of the result of X-ray diffraction 2θ / θ measurement performed on the rolled surface in the rolled copper foil according to the present invention after the final cold rolling step and before recrystallization annealing. .

図３から明らかなように、圧延面は{２００}Cu面の回折強度が強く、{２００}Cu面配向した結晶粒が多く存在していることを示している。銅箔の圧延面において{２００}Cu面が強く配向していないと、再結晶焼鈍を施しても高屈曲特性を有する圧延銅箔が得られない。よって、上記のように規定する。 As apparent from FIG. 3, the diffraction intensity of the rolled surface is {200} Cu surface is strong, indicating that there exists a number {200} Cu plane oriented crystal grains. If the {200} Cu surface is not strongly oriented on the rolled surface of the copper foil, a rolled copper foil having high bending properties cannot be obtained even if recrystallization annealing is performed. Therefore, it is defined as described above.

〔本発明の第４の実施形態〕
（極点図測定）
本実施の形態における圧延銅箔は、最終冷間圧延工程の後で再結晶焼鈍前の状態において、圧延面を基準としたＸ線回折極点図測定による銅結晶の{２２０}Cu面回折の正極点図結果で、α角度が40〜50°の範囲において、β角度の少なくとも90±５°毎に存在して４回対称性を示す結晶粒群に起因する回折ピークが存在し、さらに、前記β角度の90±10°毎に存在して４回対称性を示す別の結晶粒群に起因する回折ピークが存在することを特徴とする。例えば、正極点図におけるβ＝０°を銅箔の圧延方向とした場合、α角度＝40〜50°において第１の実施形態に係る４回対称性の回折（回折ピーク）がβ＝０±５°, 90±５°, 180±５°, 270±５°に観察されるのに加えて、別の４回対称性の回折（回折ピーク）がβ＝45±10°, 135±10°, 225±10°, 315±10°に観察される場合などがその１例である。なお、本実施の形態における「別の４回対称性を示す結晶粒」では、上記４つの回折ピーク（β＝45±10°, 135±10°, 225±10°, 315±10°）のうち少なくとも３つが観察されればよいものとする。 [Fourth Embodiment of the Present Invention]
(Pole figure measurement)
The rolled copper foil in the present embodiment is a positive electrode of {220} Cu surface diffraction of copper crystal by X-ray diffraction pole figure measurement based on the rolled surface in the state after the final cold rolling process and before recrystallization annealing. As a result of the dot diagram, in the range of α angle of 40 to 50 °, there is a diffraction peak due to a group of crystal grains presenting at least 90 ± 5 ° of β angle and exhibiting 4-fold symmetry, It is characterized in that there is a diffraction peak due to another group of crystal grains present at every 90 ± 10 ° of the β angle and exhibiting 4-fold symmetry. For example, when β = 0 ° in the positive dot diagram is the rolling direction of the copper foil, the four-fold symmetry diffraction (diffraction peak) according to the first embodiment is β = 0 ± at α angle = 40-50 °. In addition to being observed at 5 °, 90 ± 5 °, 180 ± 5 °, 270 ± 5 °, another four-fold diffraction (diffraction peak) is β = 45 ± 10 °, 135 ± 10 ° , 225 ± 10 °, 315 ± 10 °, and so on. Note that in the “crystal grains showing another four-fold symmetry” in the present embodiment, the above four diffraction peaks (β = 45 ± 10 °, 135 ± 10 °, 225 ± 10 °, 315 ± 10 °) It is sufficient that at least three of them are observed.

極点図測定のα角度＝40〜50°においてβ走査で得られる銅結晶の{２２０}Cu面回折が４回対称性を示すということは、該{２２０}Cu面と結晶幾何学的に45°の角度をなす{２００}Cu面が銅箔の圧延面（±５°の範囲の傾斜も含む）に存在し面内配向していることを意味する。また、第１の実施形態に係る４回対称性の結晶粒に加えて「別の４回対称性を示す結晶粒」が存在するということは、本実施の形態の圧延銅箔が第１の実施形態に係る圧延銅箔よりも{２００}Cu面配向の結晶粒（後述する「立方体組織の種結晶」）をより多く有することを意味する。これは、銅箔屈曲特性の更なる向上につながる。 That pole figure α angle = {220} of the copper crystals obtained by β scanning at 40 to 50 ° Cu surface diffraction measurements show a 4-fold symmetry, said {220} Cu plane and crystal geometrically 45 It means that the {200} Cu surface forming an angle of ° exists on the rolled surface of the copper foil (including the inclination in the range of ± 5 °) and is in-plane oriented. In addition to the four-fold symmetry crystal grains according to the first embodiment, the existence of “another crystal grain exhibiting four-fold symmetry” means that the rolled copper foil of the present embodiment is the first It means that it has more {200} Cu plane-oriented crystal grains (“cube seed crystal” described later) than the rolled copper foil according to the embodiment. This leads to further improvement of copper foil bending characteristics.

図４は、本発明に係る圧延銅箔において、最終冷間圧延工程の後かつ再結晶焼鈍前の状態で、圧延面に対して{２２０}Cu面のXRD極点図測定を行った結果（正極図）の１例である。銅箔の圧延方向をβ＝０°とした場合、図４から判るように、α角度＝40〜50°において第１の実施形態に係る４回対称性の回折（黒矢印）に加えて、別の４回対称性の回折（白抜き矢印）が確認できる。このような圧延銅箔は、再結晶焼鈍を施すことによって高い屈曲特性を有する（詳細は後述する）。 FIG. 4 shows the result of XRD pole figure measurement of {220} Cu plane with respect to the rolled surface in the rolled copper foil according to the present invention after the final cold rolling step and before recrystallization annealing (positive electrode) This is an example of FIG. When the rolling direction of the copper foil is β = 0 °, as can be seen from FIG. 4, in addition to the four-fold symmetry diffraction (black arrow) according to the first embodiment at an α angle = 40-50 °, Another fourfold symmetry diffraction (open arrow) can be confirmed. Such a rolled copper foil has high bending properties by performing recrystallization annealing (details will be described later).

〔本発明の第５の実施形態〕
（総合配向比率）
本実施の形態における圧延銅箔は、最終冷間圧延工程後に再結晶焼鈍を施した後の圧延銅箔であって、圧延面に対するＸ線回折２θ/θ測定から算出される立方体集合組織の比率[Ａ]と、当該立方体集合組織の結晶粒についてＸ線回折ロッキングカーブ測定から算出される面外配向比率[Ｂ]と、前記立方体集合組織の結晶粒について前記圧延面を基準としたＸ線回折極点図測定から算出される面内配向比率[Ｃ]との積が、「[Ａ]×[Ｂ]×[Ｃ] ≧ 0.5」であることを特徴とする。本発明においては、[Ａ]×[Ｂ]×[Ｃ]を総合配向比率と定義する。総合配向比率が0.5未満（[Ａ]×[Ｂ]×[Ｃ] ＜ 0.5）であると、高い屈曲特性が得られない。よって、総合配向比率を0.5以上とする。より望ましくは0.55以上であり、更に望ましくは0.6以上である。 [Fifth Embodiment of the Present Invention]
(Total orientation ratio)
The rolled copper foil in the present embodiment is a rolled copper foil after recrystallization annealing after the final cold rolling step, and the ratio of the cube texture calculated from the X-ray diffraction 2θ / θ measurement with respect to the rolled surface [A], the out-of-plane orientation ratio calculated from the X-ray diffraction rocking curve measurement for the crystal grains of the cubic texture, and the X-ray diffraction of the cubic texture crystals based on the rolling surface The product of the in-plane orientation ratio [C] calculated from the pole figure measurement is “[A] × [B] × [C] ≧ 0.5”. In the present invention, [A] × [B] × [C] is defined as the total orientation ratio. When the total orientation ratio is less than 0.5 ([A] × [B] × [C] <0.5), high bending characteristics cannot be obtained. Therefore, the overall orientation ratio is set to 0.5 or more. More desirably, it is 0.55 or more, and more desirably 0.6 or more.

次に、立方体集合組織の比率[Ａ]、立方体集合組織の面外配向比率[Ｂ]、立方体集合組織の面内配向比率[Ｃ]について説明する。   Next, the ratio [A] of the cube texture, the out-of-plane orientation ratio [B] of the cube texture, and the in-plane orientation ratio [C] of the cube texture will be described.

立方体集合組織の比率[Ａ]とは、最終冷間圧延工程の後に再結晶焼鈍を施した圧延銅箔の圧延面に対しＸ線回折２θ/θ測定を行い、立方体集合組織を現す{２００}Cu面回折ピークの全回折ピークに対する比率を次式により算出したものと定義する。
立方体集合組織の比率[Ａ] ＝ I{200}Cu / (I{111}Cu＋I{200}Cu＋I{220}Cu＋I{311}Cu)
ここで、
I{111}Cu：{１１１}Cu面の回折ピーク強度
I{200}Cu：{２００}Cu面の回折ピーク強度
I{220}Cu：{２２０}Cu面の回折ピーク強度
I{311}Cu：{３１１}Cu面の回折ピーク強度
である。 Cubic texture ratio [A] is the result of X-ray diffraction 2θ / θ measurement on the rolled surface of the rolled copper foil that has been recrystallized and annealed after the final cold rolling step to represent the cubic texture {200} The ratio of the Cu plane diffraction peak to the total diffraction peak is defined as calculated by the following formula.
Cubic texture ratio [A] = I {200} Cu / (I {111} Cu + I {200} Cu + I {220} Cu + I {311} Cu )
here,
I {111} Cu : Diffraction peak intensity of {111} Cu surface
I {200} Cu : {200} Diffraction peak intensity on Cu surface
I {220} Cu : {220} Diffraction peak intensity of Cu plane
I {311} Cu : {311} The diffraction peak intensity on the Cu surface.

立方体集合組織の面外配向比率[Ｂ]とは、最終冷間圧延工程の後に再結晶焼鈍を施した圧延銅箔の圧延面における{２００}Cu面のＸ線回折ロッキングカーブ測定を行い、その{２００}Cu面回折ピークの半価幅と積分幅の比率を次式により算出したものと定義する。
立方体集合組織の面外配向比率[Ｂ] ＝ ΔθFWHM / ΔθIW
なお、
ΔθFWHM：{２００}Cu面回折ピークの最大強度の半分の強度におけるピーク幅
ΔθIW：{２００}Cu面回折ピークの積分強度を該回折ピークの最大強度で除したもの
とする。 The out-of-plane orientation ratio [B] of the cube texture is measured by measuring the X-ray diffraction rocking curve of the {200} Cu surface on the rolled surface of the rolled copper foil subjected to recrystallization annealing after the final cold rolling step. {200} The ratio of the half-value width and the integral width of the Cu plane diffraction peak is defined as calculated by the following equation.
Out-of-plane orientation ratio of cubic texture [B] = Δθ FWHM / Δθ IW
In addition,
Δθ FWHM : {200} Peak width at half the maximum intensity of the Cu plane diffraction peak Δθ IW : {200} The integrated intensity of the Cu plane diffraction peak is divided by the maximum intensity of the diffraction peak.

立方体集合組織の面内配向比率[Ｃ]とは、最終冷間圧延工程の後に再結晶焼鈍を施した圧延銅箔に対し圧延面を基準としてα角度＝45°における{２２０}Cu面のＸ線回折極点図測定を行い、β走査で得られる４回対称の{２２０}Cu面回折ピークのうち、いずれか１つの回折ピークの半価幅と積分幅の比率を次式により算出したものと定義する。
立方体集合組織の面外配向比率[Ｃ] ＝ ΔβFWHM / ΔβIW
なお、
ΔβFWHM：{２２０}Cu面回折ピークの最大強度の半分の強度におけるピーク幅
ΔβIW：{２２０}Cu面回折ピークの積分強度を該回折ピークの最大強度で除したもの
とする。 The in-plane orientation ratio [C] of the cubic texture is the X of the {220} Cu surface at an α angle = 45 ° with respect to the rolled surface of the rolled copper foil subjected to recrystallization annealing after the final cold rolling step. A line diffraction pole figure measurement was performed, and the ratio of the half width and the integral width of any one of the four-fold symmetrical {220} Cu surface diffraction peaks obtained by β scanning was calculated by the following equation: Define.
Out-of-plane orientation ratio of cubic texture [C] = Δβ FWHM / Δβ IW
In addition,
Δβ FWHM : {220} Peak width at half the maximum intensity of the Cu- plane diffraction peak Δβ IW : {220} The integrated intensity of the Cu- plane diffraction peak is divided by the maximum intensity of the diffraction peak.

ここで、面外配向比率[Ｂ]および面内配向比率[Ｃ]において、回折ピークの半価幅と積分幅の比をとる意味について説明する。図５は、結晶配向性の良否と回折ピークの半価幅・積分幅との関係を示す模式図である。結晶配向性の低い圧延銅箔においてロッキングカーブ測定や面内配向測定を行うと、図５の(ａ)に示すように、ピーク中心近傍は比較的シャープであるがテール部分が大きい（裾野の広い）回折ピーク形状が得られやすい。一方、結晶配向性の高い圧延銅箔に対してロッキングカーブ測定や面内配向測定を行うと、図５の(ｂ)に示すようなピーク中心近傍に集中した回折ピーク形状が得られる。   Here, the meaning of taking the ratio of the half width of the diffraction peak to the integral width in the out-of-plane orientation ratio [B] and the in-plane orientation ratio [C] will be described. FIG. 5 is a schematic diagram showing the relationship between the quality of crystal orientation and the half-value width / integral width of a diffraction peak. When rocking curve measurement or in-plane orientation measurement is performed on a rolled copper foil with low crystal orientation, as shown in FIG. 5A, the vicinity of the peak center is relatively sharp but the tail portion is large (wide base). ) A diffraction peak shape is easily obtained. On the other hand, when rocking curve measurement or in-plane orientation measurement is performed on a rolled copper foil with high crystal orientation, a diffraction peak shape concentrated near the peak center as shown in FIG. 5B is obtained.

これらの回折ピークに対しそれぞれ半価幅と積分幅を評価すると、結晶配向性の低い(ａ)の場合には半価幅と積分幅とで大きな差が生じ、結晶配向性の高い(ｂ)の場合には半価幅と積分幅の差が小さくなることが判る。そして、このような差異は、回折ピーク形状におけるテール部分の大小（回折ピーク形状に占めるテール部分の大きさ）に起因すると考えられる。そこで回折ピークの半価幅と積分幅の比をとることにより、半価幅や積分幅を個々に比較するよりも、圧延銅箔の結晶配向性の優劣をより明確に判定することができるようになる。   When the half width and the integral width are evaluated for these diffraction peaks, respectively, when the crystal orientation is low (a), a large difference occurs between the half width and the integral width, and the crystal orientation is high (b). In the case of, it can be seen that the difference between the half width and the integral width becomes small. Such a difference is considered to be caused by the size of the tail portion in the diffraction peak shape (the size of the tail portion in the diffraction peak shape). Therefore, by taking the ratio of the half width and integral width of the diffraction peak, it is possible to more clearly determine the superiority or inferiority of the crystal orientation of the rolled copper foil than comparing the half width and integral width individually. become.

〔圧延銅箔の製造方法〕
次に、図６を参照しながら、本発明に係る圧延銅箔の製造方法を説明する。図６は、本発明に係る圧延銅箔の製造工程の１例を示すフロー図である。 [Method for producing rolled copper foil]
Next, the manufacturing method of the rolled copper foil which concerns on this invention is demonstrated, referring FIG. FIG. 6 is a flowchart showing an example of a process for producing a rolled copper foil according to the present invention.

はじめに、原材料となるタフピッチ銅（例えばJIS H3100 C1100）や無酸素銅（例えばJIS H3100 C1020）や銅純度が99.9％以上である銅合金などのインゴット（鋳塊）を用意する（工程ａ）。次に、熱間圧延を行う熱間圧延工程（工程ｂ）を行う。熱間圧延工程の後、冷間圧延を行う冷間圧延工程（工程ｃ）と冷間圧延による加工硬化を緩和する中間焼鈍工程（工程ｄ）とを適宜繰り返し行うことにより「生地」と呼ばれる銅条が製造される。次に、生地焼鈍工程（工程ｄ’）が行われる。生地焼鈍工程においては、それ以前の加工歪が十分に緩和されること（例えば、略完全焼鈍）が望ましい。   First, an ingot (ingot) such as tough pitch copper (for example, JIS H3100 C1100), oxygen-free copper (for example, JIS H3100 C1020) or a copper alloy having a copper purity of 99.9% or more as a raw material is prepared (step a). Next, the hot rolling process (process b) which performs hot rolling is performed. After the hot rolling process, a copper called “dough” is obtained by appropriately repeating a cold rolling process (process c) for performing cold rolling and an intermediate annealing process (process d) for relaxing work hardening by cold rolling. Articles are manufactured. Next, a dough annealing step (step d ') is performed. In the dough annealing process, it is desirable that the previous processing strain is sufficiently relaxed (for example, substantially complete annealing).

その後、焼鈍した「生地」（「焼鈍生地」と称す）に対して最終冷間圧延工程（工程ｅ、「仕上げ圧延工程」と称される場合もある）を施して、所定厚さの圧延銅箔が製造される。最終冷間圧延工程後の圧延銅箔は、必要に応じて表面処理等が施され（工程ｆ）、FPC製造工程（工程ｇ）に供給される。前述したように、再結晶焼鈍（工程ｇ’）は工程ｇの中（例えば、CCL工程）で為されることが多い。本発明において、「最終冷間圧延工程」とは工程ｅを意味し、「再結晶焼鈍」工程とは工程ｅよりも後で実施される工程を意味するものとする。   Thereafter, the annealed “fabric” (referred to as “annealed fabric”) is subjected to a final cold rolling step (sometimes referred to as “step e” or “finish rolling step”), and rolled copper having a predetermined thickness. A foil is produced. The rolled copper foil after the final cold rolling process is subjected to surface treatment or the like as necessary (process f) and supplied to the FPC manufacturing process (process g). As described above, the recrystallization annealing (step g ′) is often performed in the step g (for example, the CCL step). In the present invention, the “final cold rolling step” means the step e, and the “recrystallization annealing” step means a step performed after the step e.

ここにおいて、本発明に係る圧延銅箔の製造方法の１つは、前記最終冷間圧延工程における２パス目以降の圧延パスにおいて、直前の圧延パスの加工度よりも1.1倍以上大きい加工度を有する圧延パスが１パス以上含まれることを特徴とする。これにより、該冷間圧延工程の最終段階で{２２０}Cu面配向の圧延集合組織形成を強め、さらに該圧延集合組織中に立方体組織の種結晶を積極的に形成することができる。そして、この立方体組織の種結晶が、再結晶焼鈍による立方体集合組織の高配向成長に寄与しているものと考えられる（詳細は後述する）。 Here, one of the methods for producing a rolled copper foil according to the present invention has a degree of processing that is 1.1 times greater than the degree of processing of the immediately preceding rolling pass in the second and subsequent passes in the final cold rolling step. One or more rolling passes are included. Thereby, in the final stage of the cold rolling process, the formation of {220} Cu plane-oriented rolling texture can be strengthened, and a cubic structure seed crystal can be actively formed in the rolling texture. And it is thought that the seed crystal of this cube structure has contributed to the high orientation growth of the cube texture by recrystallization annealing (details are mentioned later).

より好ましくは「直前の圧延パスの加工度よりも1.15倍以上大きい加工度を有する圧延パスが１パス以上含まれること」であり、さらに好ましくは「直前の圧延パスの加工度よりも1.2倍以上大きい加工度を有する圧延パスが１パス以上含まれること」である。上記規定から外れる「1.1倍より小さい加工度を有する圧延パス」では、圧延集合組織中に立方体組織の種結晶を形成することが困難である。   More preferably, “a rolling pass having a processing degree 1.15 times or more larger than the processing degree of the immediately preceding rolling pass is included”, and more preferably “1.2 times or more the processing degree of the immediately preceding rolling pass” “One or more rolling passes having a large degree of work are included”. In a “rolling pass having a degree of work smaller than 1.1 times” deviating from the above definition, it is difficult to form a cubic structure seed crystal in the rolling texture.

また、最終冷間圧延工程のうちの最終パスまたは最終直前のパスが、２パス目以降の圧延パスで最も大きい１パスあたりの加工度を有していることが望ましい。これにより、圧延集合組織中に形成した立方体組織の種結晶が、圧延工程の進行に伴って他方位に回転してしまうことを抑制することができる（詳細は後述する）。また、最終冷間圧延工程における総加工度を80％以上90％未満とすることにより、圧延工程の総パス数を低減することができるのに加えて、過度の加工硬化による圧延加工制御の困難性を回避でき、製造の低コスト化に寄与できる。上記のような特徴を有する本発明の製造方法によって、圧延銅箔における高屈曲特性化と低コスト化を両立することができる。   In addition, it is desirable that the final pass or the pass immediately before the final pass in the final cold rolling process has the highest degree of processing per pass in the second and subsequent passes. Thereby, it can suppress that the seed crystal of the cube structure | tissue formed in the rolling texture rotates to the other position with progress of a rolling process (details are mentioned later). In addition to reducing the total number of passes in the rolling process by making the total workability in the final cold rolling process 80% or more and less than 90%, it is difficult to control the rolling process due to excessive work hardening. This can contribute to a reduction in manufacturing costs. By the manufacturing method of the present invention having the above-described features, it is possible to achieve both high bending characteristics and low cost in the rolled copper foil.

また、上記の製造方法に換わる本発明に係る圧延銅箔の他の製造方法は、少なくとも生地焼鈍工程（工程ｄ’）を制御することによって、焼鈍生地を以下のように調整する製造方法である。生地焼鈍（工程ｄ’）の後で最終冷間圧延工程（工程ｅ）前の圧延銅箔（焼鈍生地）において、圧延面を基準としたＸ線回折極点図測定により得られる結果で、極点図測定のα角度を横軸とし各α角度におけるβ走査で得られる銅結晶の{２２０}Cu面回折ピークの規格化強度を縦軸としてグラフ表記した際に、α＝40〜50°の間に規格化強度の極大値Ｑが存在し、α＝20〜40°の間に規格化強度の極小値Ｓが存在し、前記極大値Ｑと前記極小値Ｓとの比が「２≦ Ｑ/Ｓ ≦３」である圧延銅箔を最終冷間圧延工程への焼鈍生地として用いることを特徴とする。さらに、そのような焼鈍生地に対して、総加工度が80％以上93％未満となるような最終冷間圧延工程（工程ｅ）を施すことを特徴とする。なお、生地焼鈍条件としては、例えば、600℃以上700℃未満（銅箔の実態温度）で１〜30分間保持する条件が好ましい。より好ましい温度は650℃以上700℃未満である。 Moreover, the other manufacturing method of the rolled copper foil which concerns on this invention replaced with said manufacturing method is a manufacturing method which adjusts an annealing material | dough as follows by controlling a material | dough annealing process (process d ') at least. . In the rolled copper foil (annealed dough) after the dough annealing (step d ′) and before the final cold rolling step (step e), the results are obtained by X-ray diffraction pole figure measurement based on the rolling surface. The graph shows the normalized intensity of the {220} Cu plane diffraction peak of the copper crystal obtained by β scanning at each α angle as the abscissa and α = 40 to 50 °. There is a maximum value Q of standardized strength, there is a minimum value S of standardized strength between α = 20 to 40 °, and the ratio of the maximum value Q to the minimum value S is “2 ≦ Q / S It is characterized by using a rolled copper foil of ≦ 3 ”as an annealed material for the final cold rolling process. Furthermore, the final cold rolling step (step e) is performed on such an annealed material so that the total degree of processing becomes 80% or more and less than 93%. In addition, as material | dough annealing conditions, the conditions hold | maintained for 1 to 30 minutes at 600 degreeC or more and less than 700 degreeC (actual temperature of copper foil) are preferable, for example. A more preferable temperature is 650 ° C. or higher and lower than 700 ° C.

これにより、最終冷間圧延工程（工程ｅ）の後で再結晶焼鈍（工程ｇ’）前の圧延銅箔における圧延面を基準としたＸ線回折極点図測定により得られる結果で、極点図測定のα角度＝45°におけるβ走査で得られる銅結晶の{２２０}Cu面回折ピークがβ角度の少なくとも90±５°毎に存在して４回対称性を示す結晶粒が存在し、加えて、極点図測定のα角度を横軸としβ走査で得られる銅結晶の{２２０}Cu面回折ピークの規格化強度を縦軸としてグラフ表記した際に、α＝25〜35°の間に規格化強度の極大値Ｐが存在し、α＝40〜50°の間に規格化強度の極大値Ｑが残存し、α＝85〜90°の間は規格化強度が単調増加しており、極大値Ｐと極大値Ｑとα＝90°における規格化強度の値Ｒとが「Ｑ≦Ｐ≦Ｒ」となる本発明に係る圧延銅箔が得られる。 As a result, the pole figure measurement is a result obtained by the X-ray diffraction pole figure measurement based on the rolling surface in the rolled copper foil after the final cold rolling process (process e) and before the recrystallization annealing (process g ′). {220} Cu plane diffraction peak of copper crystal obtained by β scan at α angle = 45 ° of the crystal exists at least every 90 ± 5 ° of β angle, and there is a crystal grain showing 4-fold symmetry. When the graph shows the normalized intensity of the {220} Cu plane diffraction peak of copper crystals obtained by β-scanning with the α angle of the pole figure measurement as the horizontal axis, the standard is between α = 25 to 35 °. There is a maximum value P of normalized strength, the maximum value Q of standardized strength remains between α = 40-50 °, and the normalized strength monotonically increases between α = 85-90 °. The rolled copper foil according to the present invention in which the value P, the maximum value Q, and the normalized strength value R at α = 90 ° are “Q ≦ P ≦ R” is obtained.

前述したように、銅結晶の{２２０}Cu面と{２００}Cu面とは、幾何学的に45°（両結晶面のなす角が45°）の関係にある。よって、α＝40〜50°の間にある規格化強度の極大値Ｑは、圧延銅箔の圧延面において{２００}Cu面の結晶粒が面内配向している程度に関係していると考えられる。言い換えると、生地焼鈍（工程ｄ’）の後で最終冷間圧延工程（工程ｅ）前の生地において圧延面に存在した{２００}Cu面配向かつ面内配向の結晶粒が、最終冷間圧延工程（工程ｅ）を経て「Ｑ≦Ｐ≦Ｒ」の関係となる程度に残存しているところに本発明の特徴がある。 As described above, the {220} Cu plane and the {200} Cu plane of the copper crystal have a geometrical relationship of 45 ° (the angle between both crystal planes is 45 °). Therefore, the maximum value Q of the normalized strength between α = 40 and 50 ° is related to the degree to which the crystal grains of the {200} Cu plane are in-plane oriented on the rolled surface of the rolled copper foil. Conceivable. In other words, the {200} Cu- plane-oriented and in-plane-oriented crystals present on the rolling surface in the dough after the dough annealing (step d ′) and before the final cold rolling step (step e) are finally cold rolled. The feature of the present invention resides in that it remains after the process (process e) to the extent that “Q ≦ P ≦ R” is satisfied.

また、最終冷間圧延工程における総加工度を80％以上93％未満とすることにより、従来の高加工度圧延銅箔に比して圧延工程の総パス数を低減することができるのに加えて、過度の加工硬化による圧延加工制御の困難性を回避でき、製造設備への負荷低減および製造の低コスト化に寄与できる。このような特徴を有する本発明の製造方法によって、圧延銅箔における高屈曲特性化と低コスト化を両立することができる。   In addition, by setting the total workability in the final cold rolling process to 80% or more and less than 93%, the total number of passes in the rolling process can be reduced compared to conventional high-workability rolled copper foil. Thus, difficulty in controlling the rolling process due to excessive work hardening can be avoided, and the load on the manufacturing facility can be reduced and the manufacturing cost can be reduced. With the production method of the present invention having such characteristics, it is possible to achieve both high bending characteristics and low cost in the rolled copper foil.

（高屈曲特性化のメカニズムの考察）
つぎに、本発明の実施の形態に係る圧延銅箔の高屈曲特性化のメカニズムについて説明する。 (Consideration of mechanism for high bending characteristics)
Below, the mechanism of the high bending characteristic of the rolled copper foil which concerns on embodiment of this invention is demonstrated.

金属結晶に応力が掛かると、結晶中の転位の移動は結晶のすべり面に沿って生じやすい。しかしながら、結晶粒界は一般的に転位の移動に対する障害物となる。多結晶体である圧延銅箔において、屈曲運動により転位が結晶粒界等に集積すると、集積箇所でクラックが生じやすくなり、いわゆる金属疲労を起こすと考えられる。言い換えると、金属多結晶体において転位が集積することを抑制できれば、屈曲特性が向上することが期待される。   When stress is applied to the metal crystal, the movement of dislocations in the crystal tends to occur along the slip plane of the crystal. However, crystal grain boundaries are generally an obstacle to dislocation movement. In a rolled copper foil that is a polycrystalline body, when dislocations accumulate at a grain boundary or the like due to a bending motion, cracks are likely to occur at the accumulation location, which is considered to cause so-called metal fatigue. In other words, if it is possible to suppress the accumulation of dislocations in the metal polycrystal, it is expected that the bending characteristics will be improved.

本発明の実施の形態に係る圧延銅箔は、焼鈍生地および/または最終冷間圧延工程後における結晶粒配向状態を制御することにより再結晶焼鈍後の立方体集合組織を制御することが可能であることを示している。再結晶によって、銅結晶の面心立方構造特有のすべり面である{１１１}Cu面の配向（すなわち、すべり方向を揃えること）が結晶粒界を跨いで良く制御された立方体集合組織を得ることができれば、それにより屈曲運動の際に転位が交差すべりを起こす確率が高くなり、その結果、高い屈曲特性が得られるものと考えられる。すなわち、結晶粒同士が３次元的に配向した（総合配向比率の高い）立方体集合組織をどのようにして形成するかがポイントとなる。 The rolled copper foil according to the embodiment of the present invention can control the cubic texture after the recrystallization annealing by controlling the annealing dough and / or the crystal grain orientation state after the final cold rolling process. It is shown that. Recrystallized to obtain a cubic texture in which the orientation of the {111} Cu plane (that is, aligning the slip direction), which is the slip plane peculiar to the face-centered cubic structure of copper crystals, is well controlled across the grain boundaries. If it is possible, the probability that the dislocations will cross and slip during the bending motion increases, and as a result, it is considered that high bending characteristics can be obtained. That is, the key point is how to form a cubic texture in which crystal grains are three-dimensionally oriented (having a high overall orientation ratio).

一方、圧延加工時に対象物に掛かる応力は、対象物に対して「圧縮応力成分」と「引張応力成分」に分けて考えることができる。また、銅箔に対する冷間圧延加工において、銅箔中の銅結晶は、圧延加工時の応力により回転現象を起こし、加工の進展とともに圧延集合組織を形成する。このとき、応力方向による結晶の回転方位（圧延面に配向する方位）は、一般的に、圧縮応力の場合が{２２０}Cu面、引張応力の場合が{３１１}Cu面や{２１１}Cu面である。これら回転現象に伴う加工ひずみの蓄積が、再結晶時における立方体集合組織形成の駆動力になると考えられてきた。 On the other hand, the stress applied to the object at the time of rolling can be divided into “compressive stress component” and “tensile stress component” for the object. Moreover, in the cold rolling process with respect to copper foil, the copper crystal in copper foil raise | generates a rotation phenomenon with the stress at the time of a rolling process, and forms a rolling texture with progress of a process. At this time, the rotation direction of the crystal depending on the stress direction (orientation oriented on the rolling surface) is generally {220} Cu surface in the case of compressive stress and {311} Cu surface or {211} Cu in the case of tensile stress. Surface. It has been considered that the accumulation of processing strains accompanying these rotational phenomena becomes the driving force for forming the cube texture during recrystallization.

従来の圧延銅箔においては、上記の観点から、最終冷間圧延工程における総加工度を高め（例えば、93％以上）に設定し、圧縮応力を高めることで{２２０}Cu面配向（圧延集合組織）と加工ひずみの蓄積を高めることを意図していた。なお、前述したように、立方体集合組織としては、圧延面において{２００}Cu面の占有率が高くなること（圧延面に垂直方向の１次元配向）のみに着目し、圧延面内での配向状態（すなわち、結晶粒同士の３次元配向）には特段の考慮がなされていなかった。また、最終冷間圧延工程における総加工度のみに着目し、１パスあたりの加工度には特段の考慮がなされていなかった。ただし、圧延加工が進行するほど加工硬化によって材料（銅箔）が硬くなることから、圧延加工の進行に伴って１パスあたりの加工度は小さくなるのが一般的と思われる。 In the conventional rolled copper foil, from the above viewpoint, the total workability in the final cold rolling process is set high (for example, 93% or more), and the {220} Cu plane orientation (rolling assembly) is set by increasing the compressive stress. It was intended to increase the accumulation of processing strains. In addition, as mentioned above, the cubic texture is focused on only the fact that the {200} Cu plane occupancy is high on the rolled surface (one-dimensional orientation in the direction perpendicular to the rolled surface). No particular consideration has been given to the state (that is, the three-dimensional orientation between crystal grains). Moreover, paying attention only to the total workability in the final cold rolling process, no special consideration has been given to the workability per pass. However, since the material (copper foil) becomes harder due to work hardening as the rolling process progresses, it seems that the degree of processing per pass decreases as the rolling process progresses.

しかしながら、そのようなパススケジュールは、高加工度パス（１パスあたりの加工度が大きい圧延パス）によって一旦{２２０}Cu面配向させられた結晶粒の一部が、その後の低加工度パスによって{３１１}Cu面配向や{２１１}Cu面配向に回転し始めることにつながると考えられる。これは、１パスあたりの加工度が大きい圧延パスは「圧縮応力成分」が優勢となり、１パスあたりの加工度が小さい圧延パスでは「引張応力成分」が優勢になると考えられるためである。 However, in such a pass schedule, a part of the crystal grains once {220} Cu- plane oriented by a high workability pass (rolling pass having a high workability per pass) is obtained by a subsequent low workability pass. It is thought that this leads to rotation to {311} Cu plane orientation or {211} Cu plane orientation. This is because the “compressive stress component” predominates in a rolling pass with a high degree of work per pass, and the “tensile stress component” predominates in a roll pass with a low degree of work per pass.

これに対し、本発明に係る圧延銅箔の製造方法の１つは、最終冷間圧延工程における２パス目以降の圧延パスにおいて、直前の圧延パスの加工度よりも1.1倍以上大きい加工度を有する圧延パスが１パス以上含まれるようなパススケジュールを採用している。具体的には、例えば、２パス目以降の圧延パスで最も大きい１パスあたりの加工度を有する圧延パスが圧延パススケジュールの後半に実行される構成や、１パスあたりの加工度が２パス目以降で徐々に大きくなるような構成が挙げられる。このような圧延加工方法は、従来の方法とはパススケジュールが逆の構成になっている。また、最終冷間圧延工程の２パス目以降（特に、圧延パススケジュールの後半）に、１パスあたりの加工度が高い圧延パスを実行することにより、圧延加工途中で部分的な再結晶現象等が生じ、圧延集合組織中に立方体組織の種結晶（{２００}Cu面配向の結晶粒）が形成されることが判明した。そして、この立方体組織の種結晶が、再結晶焼鈍における立方体集合組織の高配向成長に寄与しているものと考えられる。 In contrast, one of the methods for producing a rolled copper foil according to the present invention has a degree of processing that is 1.1 times greater than the degree of processing of the immediately preceding rolling pass in the second and subsequent passes in the final cold rolling step. A pass schedule is adopted in which one or more rolling passes are included. Specifically, for example, a configuration in which a rolling pass having the largest degree of processing per pass in the second and subsequent passes is executed in the second half of the rolling pass schedule, or the degree of processing per pass is the second pass. The structure which becomes large gradually after that is mentioned. Such a rolling method has a configuration in which the pass schedule is opposite to that of the conventional method. In addition, by executing a rolling pass with a high degree of processing per pass after the second pass of the final cold rolling process (particularly in the second half of the rolling pass schedule), a partial recrystallization phenomenon during the rolling process, etc. It was found that a seed crystal having a cubic structure ({200} Cu plane oriented crystal grains) was formed in the rolling texture. And it is thought that the seed crystal of this cube structure is contributing to the high orientation growth of the cube texture in recrystallization annealing.

一方、本発明に係る圧延銅箔の他の製造方法は、最終冷間圧延工程（工程ｅ）に供する焼鈍生地を制御し、最終冷間圧延工程（工程ｅ）における圧延集合組織（{２２０}Cu面配向）の形成過程において、該圧延集合組織中に適度な量（「Ｑ≦Ｐ≦Ｒ」の関係となる程度）の立方体組織（{２００}Cu面配向）の結晶粒を残存させることにポイントがある。そして、加工ひずみを蓄積した圧延集合組織中に分散して残存させた立方体組織を有する結晶粒が、再結晶焼鈍における立方体集合組織形成の種結晶として機能することで、高配向成長（特に３次元配向）に寄与しているものと考えられる。 On the other hand, the other manufacturing method of the rolled copper foil which concerns on this invention controls the annealing dough used for a final cold rolling process (process e), and the rolling texture ({220} in a final cold rolling process (process e)) In the formation process of ( Cu plane orientation), an appropriate amount (about the degree of relation of “Q ≦ P ≦ R”) of cubic grains ({200} Cu plane orientation) remains in the rolled texture. There is a point. Then, the crystal grains having a cubic structure dispersed and left in the rolled texture in which the working strain is accumulated function as a seed crystal for forming the cubic texture in the recrystallization annealing, thereby achieving highly oriented growth (especially three-dimensional growth). It is thought that it contributes to (orientation).

さらに、圧延銅箔の当該製造方法は、最終冷間圧延工程における総加工度が80％以上93％未満であり、上述した立方体組織の結晶粒（結晶面の回転現象が生じていない結晶粒）の残存と併せて、銅箔への加工ひずみの蓄積が従来技術の圧延銅箔（例えば、93％以上の総加工度）に比して十分少ないと考えられる。これは、再結晶焼鈍時における原子再配列の駆動力が小さいことにつながり、再結晶粒の粒成長（結晶粒の粗大化）を抑制することができる。再結晶粒の過剰粒成長の抑制は、FPC製造工程で最近問題になっている「Dish Down現象」を解決できることにつながる。なお、「Dish Down現象」とは、FPC製造工程中において銅箔をハーフエッチングする際、結晶粒単位でエッチングされる傾向があるために粒径の大きい結晶粒が優先的にエッチングされ、銅箔表面がクレーター状になってしまう現象をいう。   Further, in the manufacturing method of the rolled copper foil, the total degree of work in the final cold rolling process is 80% or more and less than 93%, and the above-mentioned cubic structure crystal grains (crystal grains in which the rotation phenomenon of the crystal plane does not occur) It is considered that the accumulation of processing strain on the copper foil is sufficiently small as compared with the remaining copper foil (for example, the total processing degree of 93% or more). This leads to a small driving force of atomic rearrangement during recrystallization annealing, and can suppress the growth of recrystallized grains (grain coarsening). Suppressing the excessive growth of recrystallized grains leads to the solution of the “Dish Down phenomenon”, which has recently become a problem in the FPC manufacturing process. The “Dish Down Phenomenon” means that when a copper foil is half-etched during the FPC manufacturing process, it tends to be etched in units of crystal grains. A phenomenon in which the surface becomes crater-like.

〔他の実施の形態〕
工程ａにおいて、溶解・鋳造方法に制限はなく、また、材料の寸法にも制限はない。工程ｂ、工程ｃおよび工程ｄにおいても、特段の制限はなく、通常の方法・条件でよい。また、FPCに用いる圧延銅箔の厚みは一般的に50μm以下であり、本発明の圧延銅箔の厚みも、50μm以下であれば制限はないが、20μm以下が特に好ましい。 [Other Embodiments]
In step a, the melting / casting method is not limited, and the material dimensions are not limited. There are no particular restrictions on step b, step c, and step d, and ordinary methods and conditions may be used. Moreover, the thickness of the rolled copper foil used for FPC is generally 50 μm or less, and the thickness of the rolled copper foil of the present invention is not limited as long as it is 50 μm or less, but 20 μm or less is particularly preferable.

〔フレキシブルプリント配線板の製造〕
上記実施の形態の圧延銅箔を用いて、通常行われている製造方法により、フレキシブルプリント配線板を得ることができる。また、圧延銅箔に対する再結晶焼鈍は、通常のCCL工程で行われる熱処理でもよいし、別工程で行われてもよい。 [Manufacture of flexible printed wiring boards]
A flexible printed wiring board can be obtained by the manufacturing method currently performed normally using the rolled copper foil of the said embodiment. Moreover, the recrystallization annealing for the rolled copper foil may be a heat treatment performed in a normal CCL process or may be performed in a separate process.

〔実施の形態の効果〕
上記の本発明の実施の形態によれば、下記の効果を奏する。
（１）従来よりも優れた屈曲特性を有する圧延銅箔を得ることができる。
（２）従来よりも優れた屈曲特性を有する圧延銅箔を安定して効率良く（すなわち、低コストで）製造することができる。
（３）従来よりも優れた屈曲特性を有するフレキシブルプリント配線板（FPC）等の可撓性配線を得ることができる。
（４）フレキシブルプリント配線板（FPC）のみに留まらず、高い屈曲特性（屈曲寿命）が要求される他の導電部材（例えば、耐振動性が必要な自動車用リチウムイオン電池の負極材料など）にも適用できる。 [Effect of the embodiment]
According to the above embodiment of the present invention, the following effects can be obtained.
(1) A rolled copper foil having bending properties superior to those of the conventional art can be obtained.
(2) A rolled copper foil having bending properties superior to those of conventional ones can be produced stably and efficiently (that is, at a low cost).
(3) A flexible wiring such as a flexible printed wiring board (FPC) having bending characteristics superior to those of the conventional one can be obtained.
(4) Not only flexible printed wiring boards (FPC) but also other conductive members that require high bending characteristics (flexion life) (for example, negative electrode materials for automotive lithium-ion batteries that require vibration resistance) Is also applicable.

以下、本発明を実施例に基づいて更に詳しく説明するが、本発明はこれらに限定されるものではない。   EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is not limited to these.

〔実施例１〜５および比較例１〜３〕
（作製手順）
はじめに、原料素材としてタフピッチ銅（酸素含有量150ppm）を作製し、厚さ200 mm、幅650 mmの鋳塊を製造した。その後、図６記載のフローにしたがって、10 mmの厚さまで熱間圧延を行った後、冷間圧延および中間焼鈍（生地焼鈍を含む）を適宜繰り返して、0.2 mmと0.1 mmの厚みを有する焼鈍生地を製造した。生地焼鈍としては、約700℃の温度で約１分間保持する熱処理（実施例１および比較例１）、約650℃の温度で約２分間保持する熱処理（実施例２，４）、約690℃の温度で約１分間保持する熱処理（実施例３，５）、約550℃の温度で約２分間保持する熱処理（比較例２）、約800℃の温度で１分間保持する熱処理（比較例３）を行った。なお、生地焼鈍の温度は、焼鈍炉の設定温度ではなく銅箔の実態温度である。 [Examples 1 to 5 and Comparative Examples 1 to 3]
(Production procedure)
First, tough pitch copper (oxygen content 150 ppm) was produced as a raw material, and an ingot having a thickness of 200 mm and a width of 650 mm was produced. Then, according to the flow shown in FIG. 6, after hot rolling to a thickness of 10 mm, cold rolling and intermediate annealing (including dough annealing) are repeated as appropriate, and annealing having thicknesses of 0.2 mm and 0.1 mm A dough was produced. As the dough annealing, heat treatment (Example 1 and Comparative Example 1) held at a temperature of about 700 ° C. for about 1 minute, heat treatment held at a temperature of about 650 ° C. for about 2 minutes (Examples 2 and 4), about 690 ° C. Heat treatment held at a temperature of about 1 minute (Examples 3 and 5), heat treatment held at a temperature of about 550 ° C. for about 2 minutes (Comparative Example 2), heat treatment held at a temperature of about 800 ° C. for 1 minute (Comparative Example 3) ) The temperature of the fabric annealing is not the set temperature of the annealing furnace but the actual temperature of the copper foil.

つぎに、上記の焼鈍生地に対し、表１または表２に示す条件で最終冷間圧延工程を行うことにより、厚さ16μmの圧延銅箔（実施例１〜５および比較例１〜３）を作製した。なお、実施例２，３および比較例２，３のグループと実施例４，５のグループとは最終冷間圧延工程における圧延速度を変えることで作り分けた。具体的には、実施例４，５のグループにおける圧延速度（最終冷間圧延工程での銅箔の供給速度）を、実施例２，３および比較例２，３のグループのそれよりも遅くした。   Next, by performing a final cold rolling process on the above-mentioned annealed dough under the conditions shown in Table 1 or Table 2, a rolled copper foil (Examples 1 to 5 and Comparative Examples 1 to 3) having a thickness of 16 μm is obtained. Produced. In addition, the groups of Examples 2 and 3 and Comparative Examples 2 and 3 and the groups of Examples 4 and 5 were separately formed by changing the rolling speed in the final cold rolling process. Specifically, the rolling speed in the groups of Examples 4 and 5 (feeding speed of copper foil in the final cold rolling process) was made slower than that of the groups of Examples 2 and 3 and Comparative Examples 2 and 3. .

Figure 0005390852
Figure 0005390852

Figure 0005390852
Figure 0005390852

（圧延銅箔に対するXRD評価）
圧延銅箔（生地焼鈍後、最終冷間圧延工程途中、最終冷間圧延工程後、再結晶焼鈍後）に対するXRD評価は次のように行った。なお、各種XRD測定（２θ/θ測定、ロッキングカーブ測定、極点図測定、面内配向測定）には、Ｘ線回折装置（株式会社リガク製、型式：RAD−B）を用いた。対陰極（ターゲット）はCuを用い、管電圧および管電流はそれぞれ40 kV、30 mAとした。また、XRD測定に供する試料の大きさは、約15×約15 mm2とした。 (XRD evaluation for rolled copper foil)
XRD evaluation for rolled copper foil (after dough annealing, during the final cold rolling process, after the final cold rolling process, and after recrystallization annealing) was performed as follows. An X-ray diffractometer (manufactured by Rigaku Corporation, model: RAD-B) was used for various XRD measurements (2θ / θ measurement, rocking curve measurement, pole figure measurement, in-plane orientation measurement). The counter cathode (target) was Cu, and the tube voltage and tube current were 40 kV and 30 mA, respectively. The size of the sample used for XRD measurement was about 15 × about 15 mm 2 .

XRD２θ/θ測定の条件は、一般的な広角ゴニオメータを用い、２θ＝40〜100°の範囲で測定した。２θ/θ測定におけるスリット条件は、発散スリットが１°、受光スリットが0.15 mm、散乱スリットが１°とした。また、XRDロッキングカーブ測定は、２θ/θ測定により得られた{２００}Cu面回折ピークの２θ値に検出器を固定し、試料をθ＝15〜35°まで走査して測定した。なお、ロッキングカーブ測定におけるスリット条件は２θ/θ測定と同じとした。 The XRD 2θ / θ measurement was performed using a general wide-angle goniometer in the range of 2θ = 40 to 100 °. The slit conditions in the 2θ / θ measurement were 1 ° for the divergent slit, 0.15 mm for the light receiving slit, and 1 ° for the scattering slit. The XRD rocking curve was measured by fixing the detector to the 2θ value of the {200} Cu plane diffraction peak obtained by 2θ / θ measurement, and scanning the sample to θ = 15 to 35 °. Note that the slit conditions in the rocking curve measurement were the same as in the 2θ / θ measurement.

XRD極点図測定および面内配向測定の条件は、一般的なシュルツ反射法を用い、α＝15〜90°（圧延面に垂直方向がα＝90°）の範囲でβ角度を０〜360°まで走査（自転）しながら、{２２０}Cu面の回折強度を測定した（２θ≒74°で、２θ値は試料毎に予備測定した結果を用いた）。このときのスリット条件は、発散スリット＝１°、散乱スリット＝７mm、受光スリット＝７mmおよびシュルツスリット（スリット高さ１mm）を用いた。なお、面内配向測定はα＝45°に固定して行った。 The conditions for XRD pole figure measurement and in-plane orientation measurement are the general Schulz reflection method, and the β angle is 0 to 360 ° within the range of α = 15 to 90 ° (α = 90 ° perpendicular to the rolling surface). The diffraction intensity of the {220} Cu surface was measured while scanning (spinning) until 2θ was about 74 ° (2θ value was obtained by using the result of preliminary measurement for each sample). The slit conditions at this time were diverging slit = 1 °, scattering slit = 7 mm, light receiving slit = 7 mm, and Schulz slit (slit height 1 mm). The in-plane orientation measurement was performed with α = 45 ° fixed.

〔実施例１および比較例１〕
（最終冷間圧延工程上がりの圧延銅箔）
上記のようにして作製した実施例１および比較例１の圧延加工上がりの状態（最終冷間圧延工程の後で再結晶焼鈍前）の各圧延銅箔（厚さ16μm）に対し、XRD測定を行った。図７は、最終冷間圧延工程上がりの圧延銅箔に対して面内配向測定（α＝45°における{２２０}Cu面の測定）を行った結果の1例である。図７(ａ)は実施例１、図７(ｂ)は比較例１である。 [Example 1 and Comparative Example 1]
(Rolled copper foil after the final cold rolling process)
XRD measurement was performed on each rolled copper foil (thickness: 16 μm) in the state after rolling of Example 1 and Comparative Example 1 manufactured as described above (after the final cold rolling step and before recrystallization annealing). went. FIG. 7 shows an example of the result of in-plane orientation measurement (measurement of {220} Cu plane at α = 45 °) for the rolled copper foil after the final cold rolling process. FIG. 7A shows Example 1 and FIG. 7B shows Comparative Example 1.

図７から判るように、実施例１の圧延銅箔は90±５°毎に存在する４回対称性の回折ピーク（黒矢印で示す）が認められる。また、該回折ピークはβ走査で得られる{２２０}Cu面回折の最小強度に対して1.5倍以上の回折強度を有している。これは、銅箔の圧延面で{２００}Cu面が良好な面内配向性を有していることを意味している。これに対し、比較例１の圧延銅箔では、β≒０°(360°)，180°に弱い回折ピークが見られるものの、β≒90°，270°には回折ピークがほとんど認められない。 As can be seen from FIG. 7, the rolled copper foil of Example 1 has four-fold symmetry diffraction peaks (indicated by black arrows) that exist every 90 ± 5 °. The diffraction peak has a diffraction intensity of 1.5 times or more with respect to the minimum intensity of {220} Cu plane diffraction obtained by β scanning. This means that the {200} Cu surface has a good in-plane orientation on the rolled surface of the copper foil. In contrast, the rolled copper foil of Comparative Example 1 shows weak diffraction peaks at β≈0 ° (360 °) and 180 °, but hardly shows diffraction peaks at β≈90 ° and 270 °.

図８は、比較例１における最終冷間圧延工程上がりの圧延銅箔に対して２θ/θ測定を行った結果の１例である。また、図３は、実施例１における２θ/θ測定結果の１例である。前述したように、図３に示す実施例１の圧延銅箔は、{２００}Cu面配向した結晶粒が圧延面で多く存在していることを示している。図３における{２００}Cu面の回折ピーク強度I{200}Cuを100とした場合、{２２０}Cu面の回折ピーク強度I{220}Cuは48であった。なお、銅結晶粉末における{２００}Cu面と{２２０}Cu面とのＸ線回折強度比がおよそ２：１であることを考慮すると、図３の圧延銅箔は、その圧延面において{２００}Cu面配向の結晶粒と{２２０}Cu面配向の結晶粒が面積比で略同程度に存在していると考えられる。 FIG. 8 is an example of a result of 2θ / θ measurement performed on the rolled copper foil after the final cold rolling process in Comparative Example 1. FIG. 3 is an example of 2θ / θ measurement results in Example 1. As described above, the rolled copper foil of Example 1 shown in FIG. 3 shows that many {200} Cu face-oriented crystal grains exist on the rolled face. If the {200} 100 diffraction peak intensity I {200} Cu of Cu surface in FIG. 3, the diffraction peak intensity I {220} Cu of {220} Cu plane was 48. In consideration of the X-ray diffraction intensity ratio between the {200} Cu plane and the {220} Cu plane in the copper crystal powder being about 2: 1, the rolled copper foil of FIG. } It is considered that the crystal grains of Cu plane orientation and the grains of {220} Cu plane orientation exist in substantially the same area ratio.

一方、図８に示す比較例１の圧延銅箔は、{２２０}Cu面の回折ピーク強度I{220}Cuを100とした場合、{２００}Cu面の回折ピーク強度I{200}Cuは76であり、{２２０}Cu面配向の結晶粒の方が銅箔の圧延面で圧倒的に優勢である。言い換えると、種結晶となる{２００}Cu面配向の結晶粒が非常に少ないことを意味している。 On the other hand, the rolled copper foil of Comparative Example 1 shown in FIG. 8, {220} is 100 diffraction peak intensity I {220} Cu of Cu plane, {200} diffraction peak intensity I {200} Cu of Cu surface 76, and {220} Cu -oriented crystal grains are overwhelmingly dominant on the rolled surface of the copper foil. In other words, it means that there are very few {200} Cu plane-oriented crystal grains to be seed crystals.

上記の面内配向測定および２θ/θ測定の結果を考え合わせると、実施例１の圧延銅箔には、立方体集合組織形成の種結晶となる３次元配向した銅結晶が確実に存在していることが判る。これに対し、比較例１の圧延銅箔では、圧延面に対して{２００}Cu面配向している結晶粒が存在するものの、それらは面内配向性に乏しく、３次元配向した種結晶がほとんど存在していないことが示唆される。 Considering the results of the in-plane orientation measurement and 2θ / θ measurement described above, the rolled copper foil of Example 1 surely has a three-dimensionally oriented copper crystal serving as a seed crystal for forming a cube texture. I understand that. In contrast, in the rolled copper foil of Comparative Example 1, although {200} Cu plane-oriented crystal grains exist with respect to the rolled surface, they are poor in in-plane orientation and three-dimensionally oriented seed crystals are formed. It is suggested that there is hardly any.

〔実施例２〜５および比較例２〜３〕
（焼鈍生地）
上記のようにして作製した実施例２〜５および比較例２〜３の焼鈍生地（生地焼鈍の後で最終冷間圧延工程前、厚さ0.2 mmと0.1 mm）に対し、XRD極点図測定を行った。図９は、焼鈍生地の圧延面に対して{２２０}Cu面のXRD極点図測定を行った結果の1例である。図９(ａ)は実施例２、図９(ｂ)は実施例３、図９(ｃ)は比較例２、図９(ｄ)は比較例３である。 [Examples 2-5 and Comparative Examples 2-3]
(Annealed fabric)
XRD pole figure measurement was performed on the annealed fabrics of Examples 2 to 5 and Comparative Examples 2 to 3 (thickness 0.2 mm and 0.1 mm after the fabric annealing and before the final cold rolling process) produced as described above. went. FIG. 9 is an example of the result of XRD pole figure measurement of {220} Cu surface with respect to the rolled surface of the annealed material. 9A shows Example 2, FIG. 9B shows Example 3, FIG. 9C shows Comparative Example 2, and FIG. 9D shows Comparative Example 3. FIG.

図９から判るように、全ての試料においてα＝40〜50°の間に規格化強度の極大値Ｑが存在し、α＝20〜40°の間に規格化強度の極小値Ｓが存在している。ここで、極大値Ｑと極小値Ｓとの比Ｑ/Ｓを取ると、実施例２および実施例３がそれぞれ2.2、2.6となり「２≦ Ｑ/Ｓ ≦３」の範囲であるのに対し、比較例２および比較例３のそれは、それぞれ3.1、1.5となり前記範囲から外れているのが判る。また、実施例４および実施例５は、それぞれ実施例２および実施例３と同様の傾向であった。   As can be seen from FIG. 9, the standardized strength maximum value Q exists between α = 40 to 50 ° and the standardized strength minimum value S exists between α = 20 to 40 ° in all samples. ing. Here, when the ratio Q / S between the maximum value Q and the minimum value S is taken, Example 2 and Example 3 are 2.2 and 2.6, respectively, whereas in the range of “2 ≦ Q / S ≦ 3”, The values of Comparative Example 2 and Comparative Example 3 are 3.1 and 1.5, respectively. Moreover, Example 4 and Example 5 were the same tendency as Example 2 and Example 3, respectively.

（最終冷間圧延工程途中の圧延銅箔）
上記４種類の生地を用いた最終冷間圧延工程途中の圧延銅箔に対し、XRD極点図測定を行った。図９は、最終冷間圧延工程途中の圧延銅箔の圧延面に対して{２２０}Cu面のXRD極点図測定を行った結果の1例である。図10(ａ)は実施例２、図10(ｂ)は実施例３、図10(ｃ)は比較例２、図10(ｄ)は比較例３である。 (Rolled copper foil during final cold rolling process)
The XRD pole figure measurement was performed with respect to the rolled copper foil in the middle of the final cold rolling process using the above four types of dough. FIG. 9 is an example of the result of XRD pole figure measurement of {220} Cu surface with respect to the rolled surface of the rolled copper foil during the final cold rolling process. 10 (a) is Example 2, FIG. 10 (b) is Example 3, FIG. 10 (c) is Comparative Example 2, and FIG. 10 (d) is Comparative Example 3.

図10から判るように、各試料においてα＝25〜35°の間に規格化強度の極大値Ｐが存在し（またはその兆候が見られ）、α＝40〜50°の間に規格化強度の極大値Ｑが存在し、α＝85〜90°の間は前記規格化強度が単調増加している。また、それに伴ってそれぞれ図９(ａ)〜(ｄ)と比較して、極大値Ｑの規格化強度が減少していることが判る。このような変化は、前述した圧延加工時の応力による銅結晶の回転現象に起因するものと考えられる。   As can be seen from FIG. 10, there is a maximum value P of the normalized strength between α = 25 to 35 ° in each sample (or a sign thereof), and the normalized strength between α = 40 to 50 °. And the normalized strength monotonously increases between α = 85 and 90 °. In addition, it can be seen that the normalized strength of the maximum value Q is reduced as compared with FIGS. 9 (a) to 9 (d). Such a change is considered to be caused by the rotation phenomenon of the copper crystal due to the stress during the rolling process described above.

（最終冷間圧延工程上がりの圧延銅箔）
上記のようにして作製した圧延加工上がりの状態（最終冷間圧延工程の後で再結晶焼鈍前）の圧延銅箔（厚さ16μm）に対し、XRD測定を行った。図11は、最終冷間圧延工程上がりの圧延銅箔に対して{２２０}Cu面のXRD極点図測定を行った結果の1例である。図11(ａ)は実施例２、図11(ｂ)は実施例３、図11(ｃ)は比較例２、図11(ｄ)は比較例３である。 (Rolled copper foil after the final cold rolling process)
XRD measurement was performed on the rolled copper foil (thickness 16 μm) in the state after rolling (prepared after the final cold rolling step and before recrystallization annealing) produced as described above. FIG. 11 is an example of the result of XRD pole figure measurement of {220} Cu surface on the rolled copper foil after the final cold rolling process. 11 (a) is Example 2, FIG. 11 (b) is Example 3, FIG. 11 (c) is Comparative Example 2, and FIG. 11 (d) is Comparative Example 3.

図11から判るように、実施例２と実施例３の圧延銅箔は「Ｑ≦Ｐ≦Ｒ」の関係になっているが、比較例２の圧延銅箔は「Ｑ＞Ｐ，Ｑ＞Ｒ」となっており、比較例３の圧延銅箔では極大値Ｑがほとんど検出されない。「Ｑ≦Ｐ≦Ｒ」の関係とは、面内配向した立方体組織の種結晶が適度な量で存在し、加工ひずみを蓄積した圧延集合組織が必要十分な量で存在していることを意味していると考えられる。これに対し、極大値Ｑがほとんど検出されなかった比較例３は、面内配向した立方体組織の種結晶がほとんど無いことを示唆している。また、「Ｑ＞Ｐ，Ｑ＞Ｒ」である比較例２では、面内配向した立方体組織の銅結晶が存在すると考えられるが、加工ひずみを蓄積した圧延集合組織の形成が不十分であることを示唆している。また、実施例４および実施例５は、それぞれ実施例２および実施例３と同様の傾向であった。   As can be seen from FIG. 11, the rolled copper foils of Example 2 and Example 3 have a relationship of “Q ≦ P ≦ R”, but the rolled copper foil of Comparative Example 2 has “Q> P, Q> R”. In the rolled copper foil of Comparative Example 3, the maximum value Q is hardly detected. The relationship of “Q ≦ P ≦ R” means that an in-plane oriented cubic structure seed crystal is present in an appropriate amount, and a rolling texture in which processing strain is accumulated is present in a necessary and sufficient amount. it seems to do. On the other hand, Comparative Example 3 in which almost no maximum value Q was detected suggests that there are almost no in-plane oriented seed crystals of the cubic structure. Further, in Comparative Example 2 where “Q> P, Q> R”, it is considered that in-plane oriented copper crystals of a cubic structure exist, but the formation of a rolling texture with accumulated work strain is insufficient. It suggests. Moreover, Example 4 and Example 5 were the same tendency as Example 2 and Example 3, respectively.

図12は、上記最終冷間圧延工程上がりの圧延銅箔に対して２θ/θ測定を行った結果の１例である。図12(ａ)は実施例２、図12(ｂ)は実施例３、図12(ｃ)は比較例２である。図12から判るように、実施例２と実施例３の圧延銅箔は、{２００}Cu面配向した結晶粒が圧延面で多く存在していることを示している。これに対し、比較例２の圧延銅箔は、{２００}Cu面配向した結晶粒が圧延面で多く存在する一方で、{１１１}Cu面配向した結晶粒も多く存在し、{２２０}Cu面配向した結晶粒が少なくなっている。なお、比較例３は図８と略同じ結果が得られ、種結晶となる{２００}Cu面配向の結晶粒が非常に少なく、{２２０}Cu面配向の結晶粒の方が優勢であった。また、実施例４および実施例５は、それぞれ実施例２および実施例３と同様の傾向であった。 FIG. 12 shows an example of the result of 2θ / θ measurement performed on the rolled copper foil after the final cold rolling process. 12A shows the second embodiment, FIG. 12B shows the third embodiment, and FIG. 12C shows the second comparative example. As can be seen from FIG. 12, the rolled copper foils of Example 2 and Example 3 show that many {200} Cu face-oriented crystal grains exist on the rolled surface. In contrast, the rolled copper foil of Comparative Example 2 has many {200} Cu face-oriented crystal grains on the rolled face, while many {111} Cu face-oriented crystal grains exist, and {220} Cu The number of plane-oriented crystal grains is reduced. In Comparative Example 3, substantially the same results as in FIG. 8 were obtained, and there were very few {200} Cu plane oriented crystal grains serving as seed crystals, and {220} Cu plane oriented crystal grains were dominant. . Moreover, Example 4 and Example 5 were the same tendency as Example 2 and Example 3, respectively.

図４は、実施例４における正極図の１例である。前述したように、α角度＝40〜50°において第１の実施形態に係る４回対称性の回折（黒矢印）に加えて、別の４回対称性の回折（白抜き矢印）が確認できる。実施例５における正極図は、別の４回対称性の回折がやや弱く３箇所しか確認できなかったが、実施例４のそれ（図４）と同様の傾向が確認された。一方、実施例２，３における正極図は、α角度＝40〜50°において第１の実施形態に係る４回対称性の回折が確認されたが、別の４回対称性の回折は確認されなかった。また、比較例２，３における正極図では、第１の実施形態に係る４回対称性の回折も第４の実施形態に係る別の４回対称性の回折も確認されなかった。   FIG. 4 is an example of a positive electrode diagram in Example 4. As described above, in addition to the four-fold symmetry diffraction (black arrow) according to the first embodiment at the α angle = 40 to 50 °, another four-fold symmetry diffraction (open arrow) can be confirmed. . In the positive electrode diagram in Example 5, another four-fold symmetry diffraction was slightly weak and could be confirmed only in three places, but the same tendency as that in Example 4 (FIG. 4) was confirmed. On the other hand, in the positive electrode diagrams in Examples 2 and 3, the four-fold symmetry diffraction according to the first embodiment was confirmed at α angle = 40 to 50 °, but another four-fold symmetry diffraction was confirmed. There wasn't. Further, in the positive electrode diagrams in Comparative Examples 2 and 3, neither the four-fold symmetry diffraction according to the first embodiment nor another four-fold symmetry diffraction according to the fourth embodiment was confirmed.

上記の極点図測定および２θ/θ測定の結果を考え合わせると、実施例２〜５の圧延銅箔には、立方体集合組織形成の種結晶となる３次元配向した銅結晶が適度な量で残存していることが判る。これに対し、比較例３の圧延銅箔では、圧延面に対して{２００}Cu面配向している結晶粒が存在するものの、それらは面内配向性に乏しく、３次元配向した種結晶がほとんど存在していないことが示唆される。また、比較例２においては、立方体組織の{２００}Cu面配向の結晶粒が確かに残存するものの、立方体集合組織形成の駆動力となる「加工ひずみを蓄積した圧延集合組織」の形成が不十分であると考えられる。 Considering the results of the above pole figure measurement and 2θ / θ measurement in combination, the rolled copper foils of Examples 2 to 5 have an appropriate amount of three-dimensionally oriented copper crystals that serve as seed crystals for forming the cube texture. You can see that On the other hand, in the rolled copper foil of Comparative Example 3, although there are crystal grains with {200} Cu plane orientation with respect to the rolling surface, they are poor in in-plane orientation and three-dimensionally oriented seed crystals are formed. It is suggested that there is hardly any. Further, in Comparative Example 2, although {200} Cu plane oriented crystal grains in the cubic structure remain, the formation of the “rolling texture with accumulated work strain” that serves as the driving force for the formation of the cubic texture is not possible. It is considered sufficient.

〔実施例１〜５および比較例１〜３〕
（再結晶焼鈍後の圧延銅箔）
上記のようにして作製した各圧延銅箔（厚さ16μm、最終冷間圧延工程上がり）に対し、温度180℃で60分間保持する再結晶焼鈍を施した後にXRD測定を行い、総合配向比率[Ａ]×[Ｂ]×[Ｃ]を評価した。立方体集合組織の比率[Ａ]の結果を表３に示し、面外配向比率[Ｂ]および面内配向比率[Ｃ]の結果を表４に示し、総合配向比率[Ａ]×[Ｂ]×[Ｃ]の結果を表５に示す。 [Examples 1 to 5 and Comparative Examples 1 to 3]
(Rolled copper foil after recrystallization annealing)
Each rolled copper foil (thickness 16μm, final cold rolling process completed) produced as described above is subjected to recrystallization annealing that is held at a temperature of 180 ° C. for 60 minutes, and then XRD measurement is performed. A] × [B] × [C] was evaluated. The results of the cubic texture ratio [A] are shown in Table 3, the results of out-of-plane orientation ratio [B] and in-plane orientation ratio [C] are shown in Table 4, and the total orientation ratio [A] × [B] × The results of [C] are shown in Table 5.

なお、前述したように、[Ａ], [Ｂ], [Ｃ]はそれぞれ次のような式で算出した。
立方体集合組織の比率[Ａ] ＝ I{200}Cu / (I{111}Cu＋I{200}Cu＋I{220}Cu＋I{311}Cu)
立方体集合組織の面外配向比率[Ｂ] ＝ ΔθFWHM / ΔθIW
立方体集合組織の面外配向比率[Ｃ] ＝ ΔβFWHM / ΔβIW As described above, [A], [B], and [C] were calculated by the following equations, respectively.
Cubic texture ratio [A] = I {200} Cu / (I {111} Cu + I {200} Cu + I {220} Cu + I {311} Cu )
Out-of-plane orientation ratio of cubic texture [B] = Δθ FWHM / Δθ IW
Out-of-plane orientation ratio of cubic texture [C] = Δβ FWHM / Δβ IW

Figure 0005390852
Figure 0005390852

Figure 0005390852
Figure 0005390852

Figure 0005390852
Figure 0005390852

表５の結果から明らかなように、実施例１〜５の圧延銅箔は総合配向比率[Ａ]×[Ｂ]×[Ｃ]が0.5を十分に上回っているが、比較例１〜３の圧延銅箔は総合配向比率が0.5を下回った。これは、最終冷間圧延工程上がりの圧延銅箔において、立方体集合組織形成の種結晶となる３次元配向した銅結晶が存在するか否か、および/または加工ひずみを蓄積した圧延集合組織の形成の程度に起因するものと考えられる。   As is clear from the results in Table 5, the rolled copper foils of Examples 1 to 5 have a total orientation ratio [A] × [B] × [C] sufficiently higher than 0.5. The rolled copper foil had an overall orientation ratio of less than 0.5. This is because, in the rolled copper foil after the final cold rolling process, whether or not there is a three-dimensionally oriented copper crystal serving as a seed crystal for the formation of a cubic texture and / or formation of a rolled texture that accumulates processing strain. This is thought to be due to the degree of the above.

（再結晶焼鈍後の圧延銅箔の屈曲特性）
上記のようにして作製した各圧延銅箔（実施例１〜５および比較例１〜３、厚さ16μm、再結晶焼鈍後）に対する屈曲特性の評価は、次のように行った。図13は、屈曲特性評価（摺動屈曲試験）の概略を表した模式図である。摺動屈曲試験装置は信越エンジニアリング株式会社製、型式：SEK−31B2Sを用い、Ｒ＝2.5 mm、振幅ストローク＝10 mm、周波数＝25 Hz（振幅速度＝1500回/分）、試料幅＝12.5 mm、試料長さ＝220 mm、試料片の長手方向が圧延方向となる条件で測定した。測定は10試料ずつ行った。結果を表６に示す。 (Bending characteristics of rolled copper foil after recrystallization annealing)
Evaluation of the bending characteristic with respect to each rolled copper foil (Examples 1-5 and Comparative Examples 1-3, thickness 16 micrometers, after recrystallization annealing) produced as mentioned above was performed as follows. FIG. 13 is a schematic diagram showing an outline of bending characteristic evaluation (sliding bending test). Sliding and bending test equipment manufactured by Shin-Etsu Engineering Co., Ltd., model: SEK-31B2S, R = 2.5 mm, amplitude stroke = 10 mm, frequency = 25 Hz (amplitude velocity = 1500 times / min), sample width = 12.5 mm The sample length was 220 mm, and the measurement was performed under the condition that the longitudinal direction of the sample piece was the rolling direction. Measurement was performed for 10 samples. The results are shown in Table 6.

Figure 0005390852
Figure 0005390852

表６の結果から明らかなように、実施例１〜５の圧延銅箔は、比較例１〜３に比して２倍以上の屈曲寿命回数（高い屈曲特性）を有していることが判る。この結果は、実施例１〜５における立方体集合組織の高い総合配向比率（表５参照）に起因しているものと考えられる。   As is clear from the results in Table 6, it can be seen that the rolled copper foils of Examples 1 to 5 have a bending life frequency (high bending characteristics) that is twice or more that of Comparative Examples 1 to 3. . This result is considered to originate in the high comprehensive orientation ratio (refer Table 5) of the cube texture in Examples 1-5.

本発明に関係する銅結晶の主な結晶面を示す模式図である。It is a schematic diagram which shows the main crystal planes of the copper crystal relevant to this invention. Ｘ線回折における入射Ｘ線・検出器・試料・走査軸の関係を示す概略図である。It is the schematic which shows the relationship of the incident X-ray in X-ray diffraction, a detector, a sample, and a scanning axis. 本発明に係る圧延銅箔において、最終冷間圧延工程の後かつ再結晶焼鈍前の状態で、圧延面に対してＸ線回折２θ/θ測定を行った結果の１例である。In the rolled copper foil which concerns on this invention, it is an example of the result of having performed X-ray diffraction 2 (theta) / (theta) measurement with respect to the rolling surface in the state after a final cold rolling process and before recrystallization annealing. 本発明に係る圧延銅箔において、最終冷間圧延工程の後かつ再結晶焼鈍前の状態で、圧延面に対して{２２０}Cu面のXRD極点図測定を行った結果（正極図）の１例である。In the rolled copper foil according to the present invention, in the state after the final cold rolling step and before the recrystallization annealing, the result of XRD pole figure measurement of the {220} Cu surface with respect to the rolled surface (positive electrode diagram) 1 It is an example. 結晶配向性の良否と回折ピークの半価幅・積分幅との関係を示す模式図である。It is a schematic diagram which shows the relationship between the quality of crystal orientation, and the half-value width and integral width of a diffraction peak. 本発明に係る圧延銅箔の製造工程の１例を示すフロー図である。It is a flowchart which shows one example of the manufacturing process of the rolled copper foil which concerns on this invention. 最終冷間圧延工程上がりの圧延銅箔に対して面内配向測定（α＝45°における{２２０}Cu面の測定）を行った結果の1例であり、図７(ａ)は実施例１、図７(ｂ)は比較例１である。FIG. 7A is an example of the result of in-plane orientation measurement (measurement of {220} Cu surface at α = 45 °) performed on the rolled copper foil after the final cold rolling process. FIG. 7B is Comparative Example 1. 比較例１における最終冷間圧延工程上がりの圧延銅箔に対して２θ/θ測定を行った結果の１例である。It is an example of the result of having performed 2 (theta) / (theta) measurement with respect to the rolled copper foil after the last cold rolling process in the comparative example 1. FIG. 焼鈍生地の圧延面に対して{２２０}Cu面のXRD極点図測定を行った結果の1例であり、図９(ａ)は実施例２、図９(ｂ)は実施例３、図９(ｃ)は比較例２、図９(ｄ)は比較例３である。FIG. 9A is an example of the result of XRD pole figure measurement of {220} Cu surface with respect to the rolled surface of the annealed material, FIG. 9A is Example 2, FIG. 9B is Example 3, and FIG. (c) is Comparative Example 2, and FIG. 最終冷間圧延工程途中の圧延銅箔の圧延面に対して{２２０}Cu面のXRD極点図測定を行った結果の1例であり、図10(ａ)は実施例２、図10(ｂ)は実施例３、図10(ｃ)は比較例２、図10(ｄ)は比較例３である。FIG. 10 (a) is an example of the result of XRD pole figure measurement of {220} Cu surface with respect to the rolled surface of the rolled copper foil during the final cold rolling process. ) Is Example 3, FIG. 10 (c) is Comparative Example 2, and FIG. 10 (d) is Comparative Example 3. 最終冷間圧延工程上がりの圧延銅箔に対して{２２０}Cu面のXRD極点図測定を行った結果の1例であり、図11(ａ)は実施例２、図11(ｂ)は実施例３、図11(ｃ)は比較例２、図11(ｄ)は比較例３である。Fig. 11 (a) shows Example 2 and Fig. 11 (b) shows the result of XRD pole figure measurement of {220} Cu surface on the rolled copper foil after the final cold rolling process. Example 3 and FIG. 11C are Comparative Example 2, and FIG. 最終冷間圧延工程上がりの圧延銅箔に対して２θ/θ測定を行った結果の１例であり、図12(ａ)は実施例２、図12(ｂ)は実施例３、図12(ｃ)は比較例２である。FIG. 12A is an example of the result of 2θ / θ measurement performed on the rolled copper foil after the final cold rolling process. FIG. 12A shows Example 2, FIG. 12B shows Example 3, and FIG. c) is Comparative Example 2. 屈曲特性評価（摺動屈曲試験）の概略を表した模式図である。It is a schematic diagram showing the outline of bending characteristic evaluation (sliding bending test).

符号の説明Explanation of symbols

１…銅箔、２…試料固定板、２ａ…ねじ、３…振動伝達部、４…発振駆動体、
Ｒ…曲率。 DESCRIPTION OF SYMBOLS 1 ... Copper foil, 2 ... Sample fixing plate, 2a ... Screw, 3 ... Vibration transmission part, 4 ... Oscillation drive body,
R: Curvature.

Claims (4)

最終冷間圧延工程の後で再結晶焼鈍前の圧延銅箔であって、
圧延面を基準としたＸ線回折極点図測定による銅結晶の{２２０}Cu面回折の正極点図結果で、α角度が40〜50°の範囲において、β角度の少なくとも90±５°毎に存在して４回対称性を示す結晶粒群に起因する回折ピークが存在し、さらに、前記β角度の90±10°毎に存在して４回対称性を示す別の結晶粒群に起因する回折ピークが存在することを特徴とする圧延銅箔。 A rolled copper foil after the final cold rolling process and before recrystallization annealing,
The result of positive pole figure of {220} Cu face diffraction of copper crystal by X-ray diffraction pole figure measurement with reference to the rolling surface. When the α angle is in the range of 40-50 °, the β angle is at least every 90 ± 5 °. There is a diffraction peak due to a crystal grain group that exists and exhibits 4-fold symmetry, and further, due to another crystal grain group that exists every 90 ± 10 ° of the β angle and exhibits 4-fold symmetry. A rolled copper foil characterized by the presence of diffraction peaks. 請求項１に記載の圧延銅箔において、
前記圧延面を基準としたＸ線回折極点図測定により得られる結果で、極点図測定のα角度を横軸とし各α角度におけるβ走査で得られる銅結晶の{２２０}Cu面回折ピークの規格化強度を縦軸としてグラフ表記した際に、
α＝25〜35°の間に前記規格化強度の極大値Ｐが存在し、α＝40〜50°の間に前記規格化強度の極大値Ｑが存在し、α＝85〜90°の間は前記規格化強度が単調増加しており、
前記極大値Ｐと前記極大値Ｑと前記α＝90°における前記規格化強度の値Ｒとが「Ｑ≦Ｐ≦Ｒ」であることを特徴とする圧延銅箔。 In the rolled copper foil according to claim 1,
The result obtained by X-ray diffraction pole figure measurement based on the rolling surface, and the standard of {220} Cu plane diffraction peak of copper crystal obtained by β scanning at each α angle with the α angle of the pole figure measurement as the horizontal axis When the graphed strength is plotted on the vertical axis,
The maximum value P of the normalized strength exists between α = 25 to 35 °, the maximum value Q of the normalized strength exists between α = 40 to 50 °, and between α = 85 to 90 ° The normalized strength is monotonically increasing,
The rolled copper foil, wherein the maximum value P, the maximum value Q, and the normalized strength value R at α = 90 ° are “Q ≦ P ≦ R”. 請求項１または請求項２に記載の圧延銅箔において、
前記圧延面に対するＸ線回折２θ/θ測定により得られる結果で、銅結晶の回折ピークの強度が「I{200}Cu ≧ I{220}Cu」であることを特徴とする圧延銅箔。 In the rolled copper foil of Claim 1 or Claim 2,
A rolled copper foil characterized in that the intensity of a diffraction peak of a copper crystal is “I {200} Cu ≧ I {220} Cu ” as a result obtained by X-ray diffraction 2θ / θ measurement on the rolled surface. 請求項１乃至請求項３のいずれか１項に記載の圧延銅箔に対して再結晶焼鈍を施した後の圧延銅箔であって、
前記圧延面に対するＸ線回折２θ/θ測定から算出される立方体集合組織の比率[Ａ]と、当該立方体集合組織の結晶粒についてＸ線回折ロッキングカーブ測定から算出される面外配向比率[Ｂ]と、前記立方体集合組織の結晶粒について前記圧延面を基準としたＸ線回折極点図測定から算出される面内配向比率[Ｃ]との積が、「[Ａ]×[Ｂ]×[Ｃ] ≧ 0.5」であることを特徴とする圧延銅箔。 A rolled copper foil after subjecting the rolled copper foil according to any one of claims 1 to 3 to recrystallization annealing,
The ratio [A] of the cube texture calculated from the X-ray diffraction 2θ / θ measurement with respect to the rolled surface, and the out-of-plane orientation ratio [B] calculated from the X-ray diffraction rocking curve measurement for the crystal grains of the cube texture And the in-plane orientation ratio [C] calculated from the X-ray diffraction pole figure measurement based on the rolling surface for the crystal grains of the cubic texture is “[A] × [B] × [C ] ≧ 0.5 ”. A rolled copper foil, characterized in that
JP2008327610A 2008-12-24 2008-12-24 Rolled copper foil Expired - Fee Related JP5390852B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008327610A JP5390852B2 (en) 2008-12-24 2008-12-24 Rolled copper foil

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2008327610A JP5390852B2 (en) 2008-12-24 2008-12-24 Rolled copper foil

Publications (2)

Publication Number Publication Date
JP2010150578A JP2010150578A (en) 2010-07-08
JP5390852B2 true JP5390852B2 (en) 2014-01-15

Family

ID=42569976

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2008327610A Expired - Fee Related JP5390852B2 (en) 2008-12-24 2008-12-24 Rolled copper foil

Country Status (1)

Country Link
JP (1) JP5390852B2 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5752536B2 (en) * 2011-08-23 2015-07-22 Jx日鉱日石金属株式会社 Rolled copper foil
EP2765215B1 (en) 2011-11-11 2017-05-03 Furukawa Electric Co., Ltd. Rolled copper foil
JP5201431B1 (en) * 2012-05-17 2013-06-05 日立電線株式会社 Rolled copper foil
JP5201432B1 (en) * 2012-05-17 2013-06-05 日立電線株式会社 Rolled copper foil
JP5373940B1 (en) * 2012-07-17 2013-12-18 株式会社Ｓｈカッパープロダクツ Rolled copper foil
JP5373941B1 (en) * 2012-07-17 2013-12-18 株式会社Ｓｈカッパープロダクツ Rolled copper foil

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02170951A (en) * 1988-12-22 1990-07-02 Nippon Mining Co Ltd Production of copper or copper alloy foil having improved heat resistance
JP3514180B2 (en) * 1999-08-24 2004-03-31 日立電線株式会社 Method for producing rolled copper foil
JP5320638B2 (en) * 2008-01-08 2013-10-23 株式会社Ｓｈカッパープロダクツ Rolled copper foil and method for producing the same

Also Published As

Publication number Publication date
JP2010150578A (en) 2010-07-08

Similar Documents

Publication Publication Date Title
JP5320638B2 (en) Rolled copper foil and method for producing the same
JP4466688B2 (en) Rolled copper foil
JP4285526B2 (en) Rolled copper foil and method for producing the same
JP4215093B2 (en) Rolled copper foil and method for producing the same
JP5245813B2 (en) Rolled copper foil
US7789977B2 (en) Rolled copper foil and manufacturing method thereof
JP3856582B2 (en) Rolled copper foil for flexible printed circuit board and method for producing the same
JP4992940B2 (en) Rolled copper foil
JP5752536B2 (en) Rolled copper foil
JP5390852B2 (en) Rolled copper foil
JPH11286760A (en) Rolled copper foil and its production
JP2000212660A (en) Rolled copper foil for flexible printed circuit board and its production
KR101893280B1 (en) Rolled copper foil, method for producing rolled copper foil, flexible flat cable, and method for producing flexible flat cable
JP2010150597A (en) Rolled copper foil
JP2009111203A (en) Rolled copper foil, and flexible printed wiring board
JP2007107038A (en) Copper or copper alloy foil for circuit
JP6294257B2 (en) Copper alloy foil for flexible printed circuit board, copper-clad laminate using the same, flexible printed circuit board, and electronic device
US20090173414A1 (en) Rolled Copper Foil and Manufacturing Method of Rolled Copper Foil
JP3709109B2 (en) Rolled copper foil for printed circuit board excellent in overhang processability and method for producing the same
JP2008038170A (en) Rolled copper foil
JP5562218B2 (en) Rolled copper foil
JP3830680B2 (en) Rolled copper foil for flexible printed circuit board and method for producing the same
JP3986707B2 (en) Rolled copper foil for flexible printed circuit board and method for producing the same
JP5562217B2 (en) Rolled copper foil
JP2002167632A (en) Rolled copper foil for flexible printed circuit board and its production method

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20110121

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20121011

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20121023

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20130507

A711 Notification of change in applicant

Free format text: JAPANESE INTERMEDIATE CODE: A712

Effective date: 20130628

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20131002

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20131011

R150 Certificate of patent or registration of utility model

Ref document number: 5390852

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

Free format text: JAPANESE INTERMEDIATE CODE: R150

S111 Request for change of ownership or part of ownership

Free format text: JAPANESE INTERMEDIATE CODE: R313113

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

LAPS Cancellation because of no payment of annual fees