201231179 六、發明說明： 【發明所屬之技術領域】 本發明關於一種可較佳地使用於要求撓曲性之Fpc之 壓延銅箔。 【先前技術】 用於撓曲用FPC(可撓性印刷電路基板）之銅箔，要求 較高之撓曲性。用以對銅箔賦予撓曲性之方法，眾所周知 有提高銅fg之（200 )面之晶向（crystal 〇dentati〇n )之定 向度之技術（專利文獻1 )、使銅箔之板厚方向上貫通之晶 粒之比例增多之技術（專利文獻2 )、將銅箔之相當於油坑 (oil pit)深度之表面粗糙度Ry (最大高度）降低至2〇μιη 以下之技術（專利文獻3 )。 通常之FPC製造步驟係如以下所示者。首先，將銅络 與樹脂膜接合。接合方法有藉由對塗佈於銅箔上之清漆施 加熱處理而醯亞胺化之方法、或使附有接著劑之樹脂膜與 銅箔疊合進行層壓之方法。藉由該等步驟而接合之附有樹 脂膜之銅箔稱作CCL (覆銅積層板_ ) ^藉由該CCL製造步 驟中之熱處理，而使銅箔進行再結晶。 然而，於使用銅箔製造FPC時，若為了使與覆蓋膜之 达合性知：尚而姓刻銅箔表面，則存在於表面產生直徑數 1 Ομηι左右之凹陷（碟型下陷（down))之問題。可認 為其原因在於，若於再結晶退火後，以立方體組織成長之 方式將晶向控制為（2 0 〇 )面，則於均一之組織中單獨地存 在不同晶向之晶粒。而且，由於因蝕刻之結晶面而導致蝕 201231179 刻速度不同，故而該單獨晶粒較周圍蝕刻深而成為凹陷。 該凹陷成為使電路之蝕刻性下降，或者於外觀檢查十判定 為不良導致良率下降之原因。 減少如此之凹陷之方法，報告有如下之技術：於壓延 前或壓延後，對銅箔之表面進行機械研磨， 變質層之變形後，進行再結晶（專利文獻^根據= 術， 藉由加工變質層而於再結晶後使表面突發不均一之晶粒， 則得晶向不同之晶粒便不會單獨存在。 專利文獻1 :曰本特許第3009383號公報 專利文獻2 .日本特開2 〇 〇 6 — 1 1 7 9 7 7號公報 專利文獻3 .日本特開2 〇 〇 1 — 〇 5 8 2 0 3號公報 專利文獻4 ·日本特開2 〇〇9 — 28〇8 5 5號公報 【發明内容】 然而，於專利文獻4記載之技術之情形時，存在不均 -之晶粒較多，銅结表面之結晶未定向於（2〇〇)面，故而 撓曲性降低之問題。 另方面可判月，雖然為確保銅箱於製造時與親之 合性’或者使銅箔製品之操作轡 壓延時之輥_增大，=:二:::行將最終冷 优則冶表面變付粗糙之處理 若使銅荡表面變得粗輪’則銅落表面之結晶之定向度降 低，導致撓曲性變差或者容易產生碟型下陷。 降 本發明係為解決上述問題而成者，其目的在 仏一種適度地使㈣表面變得高操作性，進= 曲性優異，並且表面触刻特性良好之壓延㈣。 201231179 本發明人等進行各種研究， 夕爭欲，*心 &果發現：於最終冷壓延 之敢終道次之前，不使錮笔 m 、 ' 表面變得粗糙，而於最終冷 塾k之最終道次中，使銅箔之矣而· 队 ^ 之表面變得粗糙，藉此，使最 、，·；之銅箔之表面變得粗糙，並 且使剪切變形帶變少，使撓 曲性k咼，碟型下陷變少。 為達成上述目的，本發明之厭μ^ 赞月之壓延鋼箔係於壓延平行方 向測得之表面之根據JIS—Ζ8741 δ/41之60度光澤度G60RD為 100以上300以下、200〇c加埶3 …υ刀鐘調質為再結晶組織之 狀態下’壓延面之由X射線績射书 艰現射衣侍之（2〇0 )面之強度（I ) 相對於由微粉末銅之X射線繞射求得之（2⑷面之強度（】。） 為I/IA50’在銅荡表面於壓延平行方向長度為175叫且 於壓延直角方向分別相隔5()叫以上之3條直線上相當於 油坑最大深度之各直線之厚度方向之最大高度與最小高度 之差的平均值d與上述銅落之厚度t之比率d/t為^以 下，且於壓延付方向測得之表面之光澤《G6〇Rd與於壓 延直角方向測得之表面之根據JIS 一Z8741之6〇度光澤度 G60TD 之比率 G60RD/ G60TD 未達 〇·8。 上述200°C x30分鐘熱處理後之銅箔表面於電解研磨後 利用EBSD進行觀察時，較佳為自[1〇〇]方位之角度差為 度以上之晶粒之面積率為20%以下。 將鑄塊於熱壓延後’反覆進行冷壓延與退火，最後進 行最終冷壓延而製造，且於該最終冷壓延步驟中，較佳為 於最終道次之前1道次之階段，於壓延平行方向測得之表 面之60度光澤度G60RD超過300。 201231179 根據本發明’可獲得使銅落表面適度 南操作性，進而撓曲性優異，並且表 ：广提 延銅箔。 』特性良好之壓 【實施方式】 以下，對本發明之實施形態之屋延銅落進 :本發明中所謂％只要未特別說明則均表示質量％ 最延t照圖對本發明之技術思想進行說明。若使 雖然銅治之操作性提高，但撓曲性變低等，或者容易^ 碟型下陷（圖1之先前例υ 生 J ”心馬具原因在於，获 終冷壓延中較粗糙之輥，而: 剐冶之厚度方向產生剪切變 進而壓延繼續，剪切變形帶成長。 粗二方面：為獲：銅箱之撓曲性而提高光澤度（表面 “又之方法自先别已為眾所周知。可認為此方法在於 f由利用粗輪度較低之親進行最終冷塵延，而使㈣之厚 度方向不易產生剪切變并 ^刀隻开/帶0然而，若提高銅羯之光澤度 (使表面粗縫度轡小），目f & & }則銅洎之操作性降低（圖1之先前 例2 )。 與此相對，本|明/欢 = 月人發現可藉由於最終冷壓延之接近 最終道次之前不使銅落之表面變得粗糙（例如，利用粗糙 度&低之報it仃壓延且於最終冷壓延之最終道次使銅笛 & ©皮;^粗^：(例如’利用較粗縫之棍進行壓延），而使 之銅4之表面變得粗糙，並且減少剪切變形帶，且使 撓曲性提高’碟型下陷減少（圖i之本發明例）。201231179 VI. Description of the Invention: [Technical Field] The present invention relates to a rolled copper foil which can be preferably used for Fpc requiring flexibility. [Prior Art] Copper foil for FPC (Flexible Printed Circuit Board) for flexing requires high flexibility. A technique for imparting flexibility to a copper foil is known as a technique for increasing the orientation of a crystal orientation of a (200) plane of copper fg (Patent Document 1), and a thickness direction of a copper foil. (Technical Document 2), a technique of reducing the surface roughness Ry (maximum height) of the copper foil corresponding to the depth of the oil pit to 2 〇μηη or less (Patent Document 3) ). The usual FPC manufacturing steps are as follows. First, the copper network is bonded to the resin film. The joining method is a method in which a varnish coated on a copper foil is heat-treated, or a method in which a resin film with an adhesive is laminated on a copper foil. The copper foil with a resin film joined by these steps is called CCL (Copper Clad Laminate). The copper foil is recrystallized by the heat treatment in the CCL manufacturing step. However, when FPC is produced using a copper foil, in order to make the contact with the cover film known: the surface of the copper foil is still surnamed, and a depression having a diameter of about 1 Ομηι is generated on the surface (disc type down). The problem. It is considered that the reason is that if the crystal orientation is controlled to the (20 〇) plane by the growth of the cubic structure after the recrystallization annealing, the crystal grains of different crystal orientations exist separately in the uniform structure. Further, since the etching speed is different due to the etching of the crystal face, the individual crystal grains are deeper than the surrounding and become concave. This recess causes the etching property of the circuit to be lowered, or the appearance inspection 10 is judged to be defective, resulting in a decrease in yield. In order to reduce such a depression, the following techniques have been reported: mechanically grinding the surface of the copper foil before or after calendering, and recrystallizing after deformation of the metamorphic layer (patent document ^ according to = surgery, by processing deterioration) In the case of recrystallization, the crystal grains having a non-uniform surface are suddenly formed, and the crystal grains having different crystal orientations do not exist alone. Patent Document 1: Japanese Patent No. 3009383 Patent Document 2. Japanese Patent Laid-Open No. 2 〇6 — 1 1 7 9 7 7 pp. Patent Document 3. Japanese Patent Publication No. 2 〇〇 1 — 〇 5 8 2 0 3 Patent Document 4 · Japanese Special Report 2 〇〇 9 — 28〇 8 5 5 SUMMARY OF THE INVENTION However, in the case of the technique described in Patent Document 4, there are many problems in that there are many crystal grains having unevenness, and crystals on the surface of the copper junction are not oriented on the (2 〇〇) plane, so that the flexibility is lowered. On the other hand, it is possible to judge the moon, although to ensure the compatibility of the copper box at the time of manufacture or to make the operation of the copper foil product rolling delay _ increase, =: two::: will eventually cool the surface If the treatment of the rough surface becomes a thick wheel, then the copper surface is The degree of orientation of the crystal is lowered, resulting in poor flexibility or dishing of the dish. The present invention has been made to solve the above problems, and the object thereof is to moderately make the surface of the (4) high operability. Calendering with excellent surface and good surface engraving characteristics (4) 201231179 The inventors conducted various studies, eager for the future, *heart & fruit found: before the final cold rolling, the end of the road, do not make the pen m, 'The surface becomes rough, and in the final pass of the final cold k, the surface of the copper foil is roughened, and the surface of the copper foil is roughened. And the shear deformation zone is reduced, the flexibility is k咼, and the dish type is reduced. To achieve the above object, the rolled steel foil of the present invention is coated on the surface measured in the parallel direction of the calendering. According to JIS—Ζ8741 δ/41 60 degree gloss G60RD is 100 or more and 300 or less, 200〇c plus υ3 ... The boring clock is tempered to recrystallize the structure. The strength of the coat (2〇0) surface (I) relative to the micropowder The X-ray diffraction of copper is obtained (the intensity of the 2 (4) plane ().) The length of the I/IA50' on the copper-plated surface in the parallel direction of the rolling is 175, and the direction of the right-angle of the rolling is 5 () The ratio d/t of the average value d of the difference between the maximum height and the minimum height in the thickness direction of each straight line corresponding to the maximum depth of the oil sump on the straight line is equal to or less than the thickness t of the copper drop, and is measured in the direction of the rolling direction. The gloss of the surface "G6〇Rd and the ratio of the surface measured in the direction perpendicular to the calendering direction according to JIS-Z8741 6 G gloss degree G60TD G60RD/G60TD did not reach 〇·8. When the surface of the copper foil after the heat treatment at 200 ° C for 30 minutes is observed by EBSD after electrolytic polishing, it is preferable that the area ratio of the crystal grains having an angle difference of more than or equal to [1〇〇] is 20% or less. After the ingot is subjected to hot rolling, 'cold rolling and annealing are repeated, and finally final cold rolling is performed, and in the final cold rolling step, preferably in the first pass before the final pass, in the rolling parallel The 60 degree gloss G60RD of the surface measured in the direction exceeds 300. According to the present invention, it is possible to obtain a moderately aptitude of the surface of the copper drop, and further excellent flexibility, and a wide-angle copper foil can be obtained. EMBODIMENT OF THE INVENTION In the present invention, the term "%" is used to describe the technical idea of the present invention as long as it is not particularly described. If the operability of the copper rule is improved, the flexibility is lowered, or the dish is easily collapsed (the previous example of Fig. 1 is a J). The reason is that the rough roll is obtained by the final cold rolling, and: In the thickness direction of the smelting, the shearing is changed and the rolling is continued, and the shearing deformation zone is grown. The coarseness is two aspects: in order to obtain the flexibility of the copper box, the gloss is improved (the surface is again known as a method). It is considered that this method consists in that the final cold dust extension is performed by the parent with a lower coarse rotation, and the shear direction of the thickness direction of (4) is less likely to occur and the knife is only opened/banded. However, if the gloss of the copper enamel is increased, The rough surface of the surface is small, and the operation of the copper cymbal is reduced (previous example 2 of Fig. 1). In contrast, this is the result of the final cold rolling. The surface of the copper drop is not roughed until it is close to the final pass (for example, using the roughness & low, it is calendered and the final pass of the final cold rolling makes the copper flute & (eg 'calendering with a thicker stick'), making the surface of the copper 4 thick And reducing shear deformation band, and so to improve flexibility 'to reduce sagging dish (i FIG embodiment of the present invention).
201231179 即’先刖係認為銅箔之定向性單純依存於銅箔表面之 粗縫度，但實際可知材料内部之剪切變形帶之規模會對定 向度（及碟型下陷）產生影響。而且，於最終冷壓延中， 若於最終道次以前之道次中可充分地抑制剪切帶之成長， 則即便於最終道次中將銅箔表面精加工成較為粗糙，亦可 獲得較高之定向性。 …然而，上述剪切帶之成長度無法僅由先前一直使用之 光澤度值明確地捕獲。即，可認為若一面如圖1之「本發 明例」所示使最終銅羯之表面變得粗糙，—面減少剪切變 形帶，則油坑較淺且具有某種程度之寬度，進而油坑之產 生頻率憂）（參照圖2(a))，其係於與油坑方向垂直之壓 延平行方向RD之光澤度中不易表現。另一方面，若自壓延 直角方向TD觀察’則油坑具有某程度之寬度，故而，相較 平行方向，易捕獲油坑之形狀或頻率之變化。 參照圖2說明如此之油坑與光澤度之關係。圖2 (心、201231179 That is, the sputum system considers that the orientation of the copper foil depends solely on the rough seam of the surface of the copper foil. However, it is actually known that the scale of the shear deformation zone inside the material affects the orientation (and the dish sinking). Moreover, in the final cold rolling, if the growth of the shear band can be sufficiently suppressed in the pass before the final pass, even if the surface of the copper foil is finished to be rough in the final pass, it can be obtained higher. Orientation. ... However, the length of the above shear band cannot be clearly captured only by the gloss value that has been used before. That is, it can be considered that if the surface of the final copper enamel is roughened as shown in the "Example of the invention" of Fig. 1, the surface is reduced in shear deformation, the oil sump is shallow and has a certain width, and thus the oil The frequency of occurrence of the pits (see Fig. 2(a)) is not easily expressed in the gloss in the rolling parallel direction RD perpendicular to the sump direction. On the other hand, if the crater is observed from the TD in the right angle direction, the sump has a certain width, so that the shape or frequency of the sump is easily caught in the parallel direction. The relationship between such oil pits and gloss is explained with reference to FIG. Figure 2 (heart,
Jb)、（0係分別對應於圖！之「本發明例」、「先前例丨」、 「先前例2」之銅箔表面。 ^首先，於圖2 (a)之「本發明例」之情形時，若沿著 壓延平行方向RD，測定光澤度grd，則於油坑中反射光之 方向產生變化而未能檢測到，光澤度降低。另一方面，沿 著左延直角方向TD，測定光澤度gtd之情形時，油坑沿著 TD延伸，故而於油坑中即便反射光之方向橫向（向RD方 向）偏離亦可檢測到’光澤度升高。即，與Gw相比，Gtd 相對變高，若對後述之60度光澤度進行測定，則滿足G6〇rd 201231179 /G60TD< 〇·8 之關係。 接著’於圖2 (b)之「先前例丨」之情形時，銅箱表 面變得過於粗糙，油坑之深度及長度（產生頻率）增加， 即便沿著壓延平行方向RD及壓延直角方向TD之任一方向 測定光澤度，於油坑中亦因反射光之方向產生變化而未能 檢測到，光澤度降低。於此情形時，與Grd相比，Gw相^ 變低，若對後述60度光澤度進行測定，則滿足G6〇rd/ G60td> 1之關係。 另-方面’於圖2(c)之「先前例2」之情形時，由於 銅羯表面變得過於平滑，油坑變得過淺，故即便沿著壓延 平行方向RD測定光澤度Grd，於油坑_亦因反射光之方向 不易改變’光澤度提高。即’與、相比，Grd相對變$， 故若對後述60度光澤度進行敎，則G6w 係接近】（即，RD與TD之異向性變小）。然而’如== ::。」所示，由於㈣表面並不粗輪，故而成為g6Wg6〇td 接著，對本發明之壓延㈣之規定及組成進行說明。 (1 )光澤度G60rd 使於壓延平行方向RD測得夕志二 為刚以上则以下。若⑽^面之6〇。光澤度⑽心 、Ά n RD超過300 ’則銅箔表面變得 過於平滑而銅箔之製造時之盥 σ ^ 之密S性降低’或者銅箔 I。口之才呆作具有難度。另一方面 ^ 箔表面變得過於粗糙 RD 100，則銅 落表面之社曰之^ / 内部，剪切變形帶成長而銅 …日之U度降低’撓曲性變差，或者易產生碟 201231179 型下陷。 (2 ) G60rd/ G60td 如上所述’藉由於最終冷壓延之最終道次之前，不使 銅之表面變得粗縫’且於最終冷壓延之最終道次中使銅 /备之表面變得粗糙，而使最終銅箔之表面變粗，並且減少 剪切變形帶，使撓曲性提高，碟型下陷減少。而且，藉由 本發明人等之實驗（後述之實施例）而獲悉如此之剪切變 形帶較少之表面達到G60rd/G6〇td<〇 8。因此，將於壓延 平打方向測得之表面之60。光澤度G6〇rd與於壓延直角方向 測得之表面之60。光澤度G6〇td之比率G6〇rd/G6〇td規定 為未達0.8。再者，採用比率係為了抵消整體之光澤度之影 響。 右達到G60RD/G60TDg 0.8，則如上述之圖2( b)所述， 銅fl表面變得過於平滑，導致銅落之製造時與親之密合性 降低，或者鋼落製品之操作有困難。又，若如上述之圖2 (c)所述，G60rd/G6〇td>丨，則銅箔表面變得過於粗糙， 導致剪切變形帶成長，使撓曲性降低等，或者易產生碟型 下陷。 再者’達到G60RD/G60TD<〇.8之方法係於上述之最終 冷壓延中，於最終道次以前之道次抑制剪切帶之成長，即 於最終冷壓延之最終道次以前之道次中，使用粗糙度（表 面粗趟度Ra例如為〇 〇5μηι以下）較小之輥進行壓延即可。 另一方面，於最終冷壓延之最終道次中，使用粗糙度（表 面粗糙度Ra例如為0.06μιη以上）較大之輥進行壓延’使 9 201231179 最終獲得之銅箔表面變得粗糙即可。 此處，於最終冷塵延中，若使在最終道次之前i道次 之p “又於壓延平行方向測得之表面之光澤&⑽ 則最終冷壓延之最終道次以前之道次中，㈣表面變 侍相對千滑，剪切變形帶不易被導入，故而較佳。 (3 ) d/ t 之厚度t變薄，則即便相同之表面⑽度，㈣ = 之表面凹凸之比例變大’故存在上述之g60rd 八6‘之_表面之評價無法充分進行之情形。因此，於 本發明中，可藉由規定/ 心/ t=山1，而不依靠銅箔之厚度來 進行銅羯表面之評價。Jb) and (0) correspond to the surface of the copper foil of the "inventive example", "previous example", and "previous example 2" of Fig. 2. First, in the "invention example" of Fig. 2 (a) In the case where the gloss grd is measured along the rolling parallel direction RD, the direction of the reflected light in the oil pit changes and is not detected, and the gloss is lowered. On the other hand, the measurement is performed along the left direction orthogonal direction TD. In the case of the gloss gtd, the oil pit extends along the TD, so that even if the direction of the reflected light is shifted laterally (in the RD direction) in the oil pit, the glossiness can be detected. That is, compared with Gw, Gtd is relatively When the height is 60 degrees, the relationship of G6〇rd 201231179 /G60TD< 〇·8 is satisfied. Then, in the case of the "previous example" in Fig. 2 (b), the copper box surface It becomes too rough, and the depth and length (production frequency) of the oil pit increase, and the gloss is measured in either direction along the rolling parallel direction RD and the rolling orthogonal direction TD, and the direction of the reflected light changes in the oil pit. Undetected, the gloss is reduced. In this case, Compared with Grd, the Gw phase is low, and if the 60-degree gloss is measured later, the relationship of G6〇rd/G60td>1 is satisfied. The other aspect is the case of "previous example 2" in Fig. 2(c). At this time, since the surface of the matte is too smooth and the oil sump becomes too shallow, even if the gloss Grd is measured along the rolling parallel direction RD, it is difficult to change the direction of the reflected light in the oil pit_the glossiness is improved. Compared with , Grd is relatively $, so if the 60-degree gloss is described later, G6w is close to (that is, the anisotropy of RD and TD becomes smaller). However, 'such as == ::. It is shown that since (4) the surface is not rough, it is g6Wg6〇td. Next, the specification and composition of the rolling (four) of the present invention will be described. (1) Gloss G60rd is measured in the parallel direction of the rolling RD. In the following, if the (10) surface is 6 〇. Gloss (10), Ά n RD exceeds 300 Å, the surface of the copper foil becomes too smooth, and the density of 铜 ^ of the copper foil is reduced, or the copper foil I. It’s difficult to stay in the mouth. On the other hand, the surface of the foil becomes too rough RD 100, and the surface of the copper drop surface ^ / Internal, the shear deformation zone grows and the copper...the U degree of the day decreases, the deflection becomes worse, or the dish 201231179 is trapped. (2) G60rd/ G60td as described above 'by the final cold rolling Before the pass, the surface of the copper is not roughed and the surface of the copper/preparation is roughened in the final pass of the final cold rolling, so that the surface of the final copper foil becomes thicker and the shear deformation zone is reduced. In the experiment of the present inventors (the later-described embodiment), it was found that the surface having such a small shear deformation band reached G60rd/G6〇td<〇8. Therefore, 60 of the surface measured in the direction of the flattening will be rolled. The gloss G6 〇rd is 60 of the surface measured in the direction perpendicular to the rolling. The ratio of gloss G6〇td to G6〇rd/G6〇td is set to be less than 0.8. Furthermore, the ratio is used to offset the overall glossiness. When the G60RD/G60TDg 0.8 is reached to the right, as described in Fig. 2(b) above, the surface of the copper fl becomes too smooth, resulting in a decrease in adhesion to the copper during the manufacture of the copper drop, or difficulty in handling the steel product. Further, as described in Fig. 2(c) above, G60rd/G6〇td>丨, the surface of the copper foil becomes too rough, resulting in growth of the shear deformation zone, deterioration of flexibility, etc., or easy generation of a dish type. Sink. Furthermore, the method of achieving G60RD/G60TD < 〇.8 is in the final cold rolling mentioned above, and inhibits the growth of the shear band before the final pass, that is, before the final pass of the final cold rolling. In the meantime, rolling may be performed using a roll having a small roughness (the surface roughness Ra is, for example, 〇〇5 μηι or less). On the other hand, in the final pass of the final cold rolling, the roll having a large roughness (the surface roughness Ra is, for example, 0.06 μm or more) is rolled, and the surface of the copper foil finally obtained by 9 201231179 is roughened. Here, in the final cold dust extension, if the i-pass of the i-pass before the final pass is again "the gloss of the surface measured in the parallel direction of the calendering & (10), the final pass of the final cold-rolling is in the pass. (4) The surface becomes relatively slippery, and the shear deformation zone is not easily introduced, so it is preferable. (3) If the thickness t of d/t becomes thin, even if the same surface (10) degree, (4) = the ratio of the surface unevenness becomes large. Therefore, there is a case where the evaluation of the surface of the above-mentioned g60rd 八6' cannot be sufficiently performed. Therefore, in the present invention, the ruthenium can be made by specifying the thickness / t = mountain 1, without relying on the thickness of the copper foil. Evaluation of the surface.
冑d係如圖3所不在銅箔表面於壓延平行方向RD 175叫，且於壓延直角方向TD分別相隔5〇降以上 之3條直線L 1 ^ L 3上，：fcn Α μ、| 3上相虽於油坑之最大深度之各直線Li 〜L3之厚度方向之最女古 琅大同度HM與最小高度Hs之差di之 均值。具體而言，利用姐雜斗 刊用接觸式粗糙度，測定L1〜L3上之 度方向之分佈，求得最央古痒 大间度Hm與最小高度Hs，且將各 直線L,〜L〇之di加以平均即可。 銅羯（或銅合金箱）之厚度並不無特別限制 較佳地使用5〜50Hm者。 (4) 1/1〇 以200〇C加熱3〇分鐘裥暂& s从 里調質為再結晶組織之狀態下，由 壓延面之X射線繞射哫俨+ ^ 侍之（200 )面之強度（I)，規定為 相對於由微粉末銅之父Mώ丄 射線、，堯射求得之（200)面之強度（1〇) 10 201231179 為I/IG50。藉此，撓曲性優異之（200)面之定向度提高。 若為1/1〇<50 ’則撓曲性下降。上述2〇(rc3〇分鐘之^ 係模仿CCL製造步驟中賦予銅箔之溫度歷程。 (5 ) EBSD之方位差 於200 C加熱3G分鐘調f為再結晶組織之狀態下，對 銅猪表面進行電解研磨後利肖EBSD觀察之情形時，較佳 為，自剛方位之角度差為15度以上之晶粒之面積率為 20%以下。上述·。C3Q分鐘之退火係模仿饥製造步 中賦予㈣之溫度歷程。再者，對已接受熱歷程而成為CCL 之銅落，可於20(TC加熱3〇分鐘 '經熱處理直至暫時再社 晶為止之銅箱之組織，即便再次加熱亦幾乎不會變化，故 於EBSD之觀察時，並不區別接受熱歷程之㈣與未接受熱 歷程之銅箔，而均於2〇〇<t加熱3〇分鐘。 於利用EBSD進行觀察之情形日寺，若±述面積率未達 2〇 /。則銅箔表面之晶粒彼此之方位差較小均一之組織中 晶向不同之晶粒單獨存在之比例較少，故而，蝕刻造成之 凹陷（碟型下陷）減少。再者，於制EBSD進行觀察之情 形時，如上所述可藉由於最終冷壓延中，在最終道次以前 之道-人中抑制剪切帶之成長而使上述面積率未達20。/。，即， 於最、ς冷壓延之最終道次以前之道次中使用粗糙度（表面 又Ra例如為〇 〇5μηι以下）相對較小之輥壓延即可。 (6 )組成 銅洎，可使用純度99.9 wt°/〇以上之精銅（tough pitch pper )無氧銅’又，可視需求之強度或導電性使用公知 11 201231179 之銅合金。無氧銅係規格設為JIS _ h35丨〇 (合金編號 C1011)、JIS—Η3100 (合金編號ci〇20)，且精銅係規格設 為 JIS — H3 100 (合金編號 C1100 )。 公知之銅合金’例如可列舉〇 〇丨〜〇 3 wt%之摻錫銅合 金（更佳為0.001〜〇.〇2 wt%之摻錫銅合金）；〇 〇1〜〇 〇5 wt〇/〇 之摻銀銅合金，0.005〜0.02 wt°/〇之摻銦銅合金；0.005〜0.02 wt%之摻鉻銅合金；包含合計為〇 〇5 wt%以下之選自由錫、 銀、銦及鉻構成之群中之一種以上之銅合金；其中，性之 優異者’多使用Cu — 〇.〇2 wt%Ag。 接著，對本發明之壓延銅箔之製造方法之一例進行說 月首先，將由銅及必要之合金元素且更包含不可避免之 雜質構成之鑄塊熱壓延後，反覆進行冷壓延與退火，最後 於最終冷壓延精加工成特定厚度。 此處，如上所述，藉由於最終冷壓延之最終道次之前， 不使銅笛之表面變得較粗糙，且於最終冷壓延之最終道次 中使銅4之表面變得較粗輪，而使最終之銅结之表面變得 粗糙，並且使剪切變形帶變少，使撓曲性提高，碟型下陷 減少。而且，如此之剪切變形帶較少之表面成為g6〇rd/ G6〇td < 0.8 〇 因此，於最終冷壓延之最終道次之前，以使銅箔之表 面不變付粗糙之方式，使用粗糙度（表面粗糙度Ra例如為 0.0 5 μπι以下）相對較小之輥進行壓延’或者將最終冷壓延 中之1道次加工度變大進行壓延即可。另一方面，於最終 冷壓延之最終道次中，使用粗糙度（表面粗糙度Ra例如為胄d is not in the rolling parallel direction RD 175 as shown in Fig. 3, and is on the three straight lines L 1 ^ L 3 which are separated by more than 5 于 in the direction perpendicular to the rolling TD, : fcn Α μ, | 3 The average value of the difference di of the most female 琅 琅 HM and the minimum height Hs in the thickness direction of each of the straight lines Li to L3 at the maximum depth of the sump. Specifically, the contact roughness is measured by the sister magazine, and the distribution in the direction of the degree of L1 to L3 is measured, and the most common itching degree Hm and the minimum height Hs are obtained, and the respective lines L, LL are 〇 Di is averaged. The thickness of the copper matte (or copper alloy case) is not particularly limited. It is preferably used in the range of 5 to 50 Hm. (4) 1/1〇heated at 200〇C for 3 minutes, temporarily adjusted to the recrystallized structure, and X-ray diffraction from the calendering surface + ^ servant (200) surface The intensity (I) is defined as the I/IG50 of the (200) plane strength (1〇) 10 201231179 obtained from the parent M ray of the fine powder copper. Thereby, the degree of orientation of the (200) surface excellent in flexibility is improved. If it is 1/1 〇 < 50 ’, the flexibility is lowered. The above 2 〇 (rc3 〇 minutes ^ mimics the temperature history of the copper foil imparted in the CCL manufacturing step. (5) The orientation of the EBSD is 200 C heated for 3 G minutes and the f is recrystallized. In the case of the EBSD observation after the electrolytic polishing, it is preferable that the area ratio of the crystal grains having an angle difference of 15 degrees or more from the rigid orientation is 20% or less. The above-mentioned C3Q minute annealing is given in the immature manufacturing step. (4) The temperature history. In addition, for the copper that has been subjected to the thermal history and becomes CCL, it can be heated at 20 (TC is heated for 3 minutes) until it is temporarily re-crystallized, even if it is heated again. It will change. Therefore, when observing EBSD, it does not distinguish between the four (4) and the copper foil that have not been subjected to the thermal history, and both are heated at 2 〇〇<t for 3 〇 minutes. If the area ratio of the surface of the copper foil is less than 2 〇 /, the difference in the orientation of the crystal grains on the surface of the copper foil is small, and the proportion of crystal grains having different crystal orientations in the structure is small, so that the etching is caused by the depression (disc) Type subsidence) reduction. Furthermore, in the production of EBSD In the case of observation, as described above, by the final cold rolling, the growth of the shear band is suppressed in the way before the final pass, and the area ratio is less than 20%, that is, at the most In the previous pass of cold rolling, the roll having a relatively small roughness (the surface Ra is, for example, 〇〇5μηι or less) is used in the previous pass. (6) The composition of the copper ruthenium can be used with a purity of 99.9 wt°/〇 or more. Tough pitch pper (Oxygen-free copper) In addition, the copper alloy of the well-known 11 201231179 can be used depending on the strength or conductivity required. The oxygen-free copper specification is JIS _ h35 丨〇 (alloy number C1011), JIS Η 3100 (alloy number ci〇20), and the fine copper type specification is JIS - H3 100 (alloy No. C1100). The known copper alloy 'for example, 〇〇丨~〇3 wt% of tin-doped copper alloy (more preferably 0.001~〇.〇2 wt% tin-doped copper alloy); 〇〇1~〇〇5 wt〇/〇 silver-doped copper alloy, 0.005~0.02 wt°/〇 indium-doped copper alloy; 0.005~0.02 wt% a chromium-doped copper alloy; comprising a total of 〇〇5 wt% or less selected from the group consisting of tin, silver, indium and chromium One or more of the copper alloys of the group; wherein the superiority of the property is 'usually more than Cu-〇.〇2 wt% Ag. Next, an example of the method for producing the rolled copper foil of the present invention will be described first. After the necessary alloying elements and more inconsistent impurities, the ingot is hot rolled, then subjected to cold rolling and annealing, and finally finished to a specific thickness by final cold rolling. Here, as described above, by the final cold rolling Before the final pass, the surface of the copper flute is not roughened, and the surface of the copper 4 becomes thicker in the final pass of the final cold rolling, and the surface of the final copper joint becomes rough. Further, the shear deformation zone is reduced, the flexibility is improved, and the dish type is reduced. Moreover, the surface with such a small shear deformation band becomes g6〇rd/G6〇td < 0.8 〇 Therefore, before the final pass of the final cold rolling, the surface of the copper foil is not roughened, and the surface is used. The roll having a roughness (the surface roughness Ra is, for example, 0.05 μm or less) may be rolled, or the first degree of the final cold rolling may be increased to be rolled. On the other hand, in the final pass of the final cold rolling, roughness is used (the surface roughness Ra is, for example,
12 201231179 0.06μιη以上）相對較大之輥進行壓延，或者使用黏度較高 之壓延油進行壓延’使最終所得之銅箔表面變得粗糙。 再者，為使最終之銅箱之表面變得粗糙，並且使剪切 變形帶變少，而必需於最終冷壓延之最終2道次、或最終 道次中’使用上述之較粗糙輥，或者使用黏度較高之壓延 油進行壓延，但就便於調整之方面而言，較佳為調整最終 道次中之壓延條件。另一方面，若自最終冷壓延之最終3 道次之則將親之粗糙度變得粗糙，則剪切變形帶成長。 再者，以使利用最終冷壓延之前之退火所得之再結晶 粒之平均粒！成為5〜2 〇 μπι之方式，調整退火條件即可。 又’使最終冷壓延中之壓延加工度為90%以上即可。 實施例 將添加有表1所示之組成之元素之精銅或無氧銅作為 原料鑄造成鑄錠，且於8〇〇〇c以上進行熱壓延直至厚度達到 10mm為止，對表面之氧化皮進行平面切削後，反覆進行冷 壓延與退火，最後利用最終冷壓延精加工成厚度0.012mm (實施例1〜9、比較例1〜7 )。其中，實施例1 〇中使精加 工厚度為0.0l8mm，且實施例u中使精加工厚度為 0.006mm。使最終冷壓延中之壓延加工度達到”,2〇/。。 再者，最終冷壓延進行10〜15道次，且如表丨所示， 改變最終道次之前之輥之表面粗糙度、及最終道次之輥之 ^面粗糙度進行壓延。自最終道次之第1道次直至最終道 -人之剛之輥之表面粗糙度全部相同。 再者，表1之組成欄之「添加〇 〇2%Ag之TPC」係才t 13 201231179 對J1S — H3100 (合金編號C1100)之精銅（TPC)中添加 0.02質量％之Ag。又，表1之組成欄之「添加0.007 % Sn之 OFC」係指對jIS—H3100(合金編號C1020 )之無氧銅（0Fc) 中添加0.007質量％之Sn。其中’僅於實施例6中，使用規 格設為JIS — H3510(合金編號C1011)之無氧銅（〇fc)作 為無氧銅’而於實施例4、5、7、9、10、比較例7中，使 用規格設為JIS—H3100(合金編號C1020)之無氧銅（〇fc) 作為無氧銅。 對以此方式獲得之各銅箔試樣，進行各特性之評價。 (1)光澤度 分別沿著壓延平行方向RD、及壓延直角方向TD，依 據JIS—Z8741，測定銅箔表面之光澤度G6〇rd' g6〇td。 (2 )立方體集合組織 將試樣於20CTC加熱30分鐘後，求出由壓延面之χ射 線繞射求得之（200)面強度之積分值（小將該值除以預 先測得之微粉末銅（ 325mesh，於氫氣流中在3〇〇。(：加熱i 小時後使用）之（ 200 )面強度之積分值（ι。），算出！八 值0 使用接觸式粗糙度計（小阪研究所製造SE—3_，如 圖3所示，分別求得在銅落表面於屋延平行方向長度 ⑺㈣’且於歷延直角方向TD分別求得相隔5〇_以上之 3根直線Ll〜L3上之最大高度Hm與最小高仏之差以。 將各直線L丨〜Ιο之di加以平均作為d。 。再者’設為d ( mm )12 201231179 0.06μιη or more) The relatively large roll is calendered, or calendered with a higher viscosity calendering oil to make the surface of the resulting copper foil rough. Furthermore, in order to roughen the surface of the final copper box and reduce the shear deformation zone, it is necessary to use the above-mentioned rougher roll in the final 2 passes of the final cold rolling, or in the final pass, or The calendering oil having a higher viscosity is used for calendering, but in terms of ease of adjustment, it is preferred to adjust the calendering conditions in the final pass. On the other hand, if the roughness of the parent is roughened from the final three passes of the final cold rolling, the shear deformation zone grows. Furthermore, the average grain of recrystallized grains obtained by annealing before final cold rolling is used! To become 5~2 〇 μπι, adjust the annealing conditions. Further, the degree of calendering in the final cold rolling may be 90% or more. In the examples, the refined copper or oxygen-free copper to which the elements of the composition shown in Table 1 are added is cast as an ingot, and hot rolled at a temperature of 8 〇〇〇c or more until the thickness reaches 10 mm, and the scale of the surface is After planar cutting, cold rolling and annealing were repeated, and finally, the final cold rolling was performed to a thickness of 0.012 mm (Examples 1 to 9 and Comparative Examples 1 to 7). Among them, in Example 1, the finishing thickness was made to be 0.018 mm, and in Example u, the finishing thickness was 0.006 mm. The degree of calendering in the final cold rolling is ", 2 〇 /.. Further, the final cold rolling is carried out 10 to 15 times, and as shown in the table, the surface roughness of the roll before the final pass is changed, and The surface roughness of the roll of the final pass is rolled. The surface roughness of the roll from the first pass of the final pass to the final pass of the final pass is the same. 2% Ag TPC" t 13 201231179 Add 0.02% by mass of Ag to J1S - H3100 (alloy No. C1100) refined copper (TPC). Further, "the addition of 0.007 % of Sn of OFC" in the composition column of Table 1 means that 0.007 mass% of Sn is added to the oxygen-free copper (0Fc) of jIS-H3100 (alloy No. C1020). In the example 6, only the oxygen-free copper (〇fc) having the specification JIS-H3510 (alloy No. C1011) was used as the oxygen-free copper', and in the examples 4, 5, 7, 9, 10, and the comparative examples. In 7, the oxygen-free copper (〇fc) having the specification JIS-H3100 (alloy No. C1020) was used as the oxygen-free copper. Each of the copper foil samples obtained in this manner was evaluated for each characteristic. (1) Gloss The gloss G6〇rd' g6〇td of the surface of the copper foil was measured in accordance with JIS-Z8741 along the rolling parallel direction RD and the rolling orthogonal direction TD, respectively. (2) Cube assembly structure After heating the sample at 20 CTC for 30 minutes, the integral value of the (200) plane intensity obtained by the radiant diffraction of the calendering surface is obtained (small value is divided by the previously measured micro powder copper) ( 325mesh, in the hydrogen flow at 3 〇〇. (: used after heating for 1 hour) (200) surface intensity integral value (ι.), calculated! Eight value 0 using contact roughness meter (made by Kosaka Research Institute) SE-3_, as shown in Fig. 3, find the maximum of the three straight lines L1 to L3 separated by 5 〇 _ above the length of the copper drop surface in the parallel direction (7) (four)' and the TD in the right angle direction. The difference between the height Hm and the minimum height is equal to the d of each straight line L丨~Ιο. In addition, 'set to d (mm)
14 201231179 /t ( mm) 〇 (4) EBSD之方位差 對於（2 )中於200°C加熱30分鐘後之試樣表面進行電 解研磨後利用EBSD (電子背散射繞射裝置，曰本電子股份 有限公司JXA8500F、加速電壓2〇kV、電流2e—8A、測定 範圍ΙΟΟΟμπίχΙΟΟΟμπι、階寬5μιη)觀察。利用影像分析求得 自[1〇〇]方位之角度差為15度以上之晶粒之面積率。進而， 以目視計量試樣表面lmm見方之觀察範圍内晶粒徑超過 20μηι者之個數。接著，對包含該觀察範圍之試樣，使用 ADEKATEC CL — 8 ( ADEKA股份有限公司製造）2〇%溶液， 於常溫進行2分鐘蝕刻，並利用光學顯微鏡拍攝蝕刻後之 表面所付之影像明暗一值化，將超過短徑5 〇 μηι之暗部作為 碟型下陷進行計量。再者，蝕刻後之銅箔表面變為反映晶 向之形狀，且具有[100]方位之組織成為與銅箔表面平行之 面，相對於此，具有其他之晶向之部分出現因晶向引起之 凹凸。因此，碟型下陷之部分在光學顯微鏡中顯得較暗。 再者’圖4係表示實施例丨之光學顯微鏡像，圖5係 表示比較例3之光學顯微鏡像。又，圖6係表示實施例1 之EBSD測定結果’圖7係表示比較例1之EBSD測定結果。 於圖6圖7中，灰色或黑色之區域係表示自[丨〇〇]方位之 角度差為1 5度以上之晶粒。 (5 )表面之傷痕 對各試樣之表面進行目測觀察，且將於壓延方向具有 10mm以上之長度之傷痕以5部位/以2以上存在之情形作 15 201231179 為 (6)撓曲性 將試樣於200°C加熱30分鐘倕甘 _ _ ^ 使其再結晶後，藉由圖8 試驗裝置，進行撓曲疲勞壽命之測定。該裝置 驅動體4結合有振動傳遞構件3之構造而成，被 係於箭線表示之螺釘2之部分…前端部之 =4處固定於裝置。若將振㈣3進行上下驅動，則銅 :山之間部以特定之曲率半徑Γ撓曲為迴管狀。本試驗係 求出以下之條件下反覆撓曲時直至斷裂為止之次數。 再者，於板厚為〇.〇12mm之情形時，試驗條件為以下 所述.試驗 又· l2.7mm，試驗片長度：200mm，試驗 片採取方向：以試聪 . 、驗片之長度方向成為與壓延方向平行之 方式採取，曲率丰你 · 丁k Γ · 2.5mm，振動衝程：25rnm，振動速 度· 1 5 0 〇次/分許 /刀《里。再者，於撓曲疲勞壽命為3萬次以上 之清形時：判：為具有優異撓曲性。 ;板马'刀別為0.018mm、0.006mm之情形時，以 使彎曲應變盥板厘故λ 、低厚為〇.012mm時之撓曲試驗相同之方式， 將曲率半徑r分_ 良更為4mm、1 ·3mm ’而其他試驗條件相 同。14 201231179 /t ( mm) 〇(4) EBSD azimuth difference For the surface of the sample after heating at 200 ° C for 30 minutes in (2), EBSD (Electronic Backscatter Diffraction Device, Sakamoto Electronics Co., Ltd.) Co., Ltd. JXA8500F, acceleration voltage 2〇kV, current 2e-8A, measurement range ΙΟΟΟμπίχΙΟΟΟμπι, step width 5μιη). The area ratio of the crystal grains having an angular difference of 15 degrees or more from the [1〇〇] orientation was obtained by image analysis. Further, the number of crystal grains having a crystal grain size exceeding 20 μm in the observation range of 1 mm square on the surface of the sample was visually measured. Next, a sample containing the observation range was etched using a 2% by weight solution of ADEKATEC CL-8 (manufactured by ADEKA Co., Ltd.) at room temperature for 2 minutes, and an image of the surface after etching was photographed by an optical microscope. For the value, the dark portion exceeding the short diameter of 5 〇μηι is measured as a dish type sag. Further, the surface of the copper foil after etching becomes a shape reflecting the crystal orientation, and the structure having the orientation of [100] becomes a surface parallel to the surface of the copper foil, whereas the other crystal orientation portion is caused by the crystal orientation. Bump. Therefore, the dished portion is darker in the optical microscope. Further, Fig. 4 shows an optical microscope image of Example ,, and Fig. 5 shows an optical microscope image of Comparative Example 3. 6 shows the EBSD measurement result of Example 1. FIG. 7 shows the EBSD measurement result of Comparative Example 1. In Fig. 6 and Fig. 7, the gray or black region indicates crystal grains having an angular difference of more than 15 degrees from the [丨〇〇] orientation. (5) The surface of the sample is visually observed on the surface of each sample, and the flaw having a length of 10 mm or more in the rolling direction is used in the case of 5 parts/two or more. 15 201231179 (6) Flexibility test The sample was heated at 200 ° C for 30 minutes to recrystallize it, and then the flexural fatigue life was measured by the test apparatus of Fig. 8. The device driving body 4 is coupled to the structure of the vibration transmitting member 3, and is attached to the device at a portion of the front end portion of the screw 2 indicated by the arrow line. When the vibration (four) 3 is driven up and down, the copper: the mountain portion is deflected by a specific radius of curvature 为 into a tubular shape. This test is to determine the number of times from the time of repeated deflection to the time of fracture under the following conditions. Furthermore, when the thickness of the plate is 〇.〇12mm, the test conditions are as follows. The test is again · l2.7mm, the length of the test piece is 200mm, and the test piece takes the direction: to test the length of the test piece. It is taken in a way parallel to the direction of rolling, the curvature is rich, you · □ k Γ · 2.5mm, the vibration stroke: 25rnm, the vibration speed · 1 5 0 〇 / min / knife "Li. In addition, when the flexural fatigue life is 30,000 times or more, it is judged to have excellent flexibility. When the plate horse 'knife is 0.018mm or 0.006mm, the radius of curvature r is better than the bending test when the bending strain is reduced by λ and the thickness is 〇.012mm. 4mm, 1 · 3mm ' and other test conditions are the same.
所付結果示於表1 CThe results paid are shown in Table 1 C.
16 201231179 r·—π16 201231179 r·—π
卜 s 201231179 由表1可知，於G6〇rd為1〇〇以上3〇〇以下且I/】> 5〇，且 d/t 為（Μ 以下，G6〇rd/G6〇td 未達 〇 8 之 例之情形時，EBSD之自[⑽]方位之角度差& ^以上之 :曰粒之面積率未達20% ’碟型下陷之個數較少，：而銅落 表面無傷痕’撓曲性亦優異。 另一方面，於最終冷壓延中，直至最終道次之前之輥 之表面粗糙度，及最終道次之輥之表面粗糙度均為Ra = 0_05_以下之比較例卜5、7之情形時，㈣表面之⑽⑽ 超過300，銅箔表面劃有傷痕，操作性變差。再者，於比較 例5之情形時，由於最終冷壓延之壓延加工度降低為％%， 故1/1〇<50,即便提高光澤度，自[1〇〇]方位之角度差為b 度以上之晶粒之面積率亦超過2〇%，較多地產生碟型下陷。 於最終冷壓延中，使直至最終道次之前之輥之表面粗 縫度變粗達到Ra=0 〇6μπι以上，且使最終道次之輕之表面 粗糙度達至,j Ra= 〇 05μπι以下之比較例2之情形時上述面 積率超過20%，碟型下陷之個數增加。又，銅箔表面之g60rd 超過300 ’銅箔表面劃有傷痕，操作性變差。 於最終冷壓延中，使直至最終道次之前之輥之表面粗 縫度、及最終道次之輥之表面粗糙度均變粗達到Ra = 〇.06μηι以上之比較例3、4、6之情形時，上述面積率超過 2〇%，碟型下陷之個數增加》 再者，於比較例3、4之情形時，由於使最終冷壓延之 所有道-欠之輥表面粗縫度變粗，故於材料内部，剪切變形 帶成長’鋼箔表面之結晶之定向度下降，達到1/ IQ < 50。 201231179 另一方面，於比較例6之情形時，由於使直至最終道次之 前之輥之粗糙度相較比較例3、4平滑，故光澤度及ι/ι〇 成為高於比較例3、4之值，但剪切帶之抑制依然不充分， 上述面積率㈣2〇%，碟型下陷之個數增加。再者，可認 為於使直至接近最終道次之前之較㈣度為g g7㈣之狀態 下，存在使通板速度下降，以抑制剪切帶等之方法，但於 此情形時:¾澤度超過300，故表面傷判定為χ。 【圖式簡單說明】 圖1係表示銅羯表面之粗縫度與剪切變形帶之關係之 之圖 圖2係表示油坑與光澤度之關係之圖。 圖3係表示相當於油坑最大深度之平均 值d之測定法 圖 圖 圖 圖 圖 方法之 I 1 2 3 4 4係表示實施例1之光學顯微鏡像之圖。 5係表示比較例3之光學顯微鏡像之圖。 6係表示實施例1之EBSC^^定結果之圖。 7係表示比較例1之EBSD測定結果之圖 8係表示藉由挽曲試驗裝置來測定撓曲疲勞壽命之 圖 主要元件符號說明 銅箔 螺釘 振動傳遞構件 振盈驅動體 201231179 RD 壓延平行方向 TD 壓延直角方向 Grd ' Gjd ' G60RD、G60TD 光澤度 l,〜l3 直線 Hm 最大面度 Hs 最小高度 Ry、Ra 表面粗縫度 d 平均值 di 最大高度與最小高度之差 I ' I〇 強度 t 厚度 r 曲率半徑 20卜s 201231179 It can be seen from Table 1 that G6〇rd is 1〇〇 or more and 3〇〇 or less and I/]> 5〇, and d/t is (Μ below, G6〇rd/G6〇td is less than 8 In the case of the case, the angle difference between the [(10)] orientation of EBSD is higher than that of the above: the area ratio of the granules is less than 20%. The number of dish sag is small, and the surface of the copper is not scratched. On the other hand, in the final cold rolling, the surface roughness of the roll before the final pass, and the surface roughness of the roll of the final pass are all Ra = 0_05_ below. In the case of 7 (4), the surface (10) (10) exceeds 300, and the surface of the copper foil is scratched, and the workability is deteriorated. Further, in the case of Comparative Example 5, since the degree of calendering of the final cold rolling is reduced to %%, 1 /1〇<50, even if the gloss is increased, the area ratio of the crystal grains having an angle difference of more than b degrees from the [1〇〇] orientation is more than 2%, and the dish type sinks more frequently. In the middle, the rough surface of the roll before the final pass is thickened to Ra=0 〇6μπι or more, and the surface roughness of the final pass is light. In the case of Comparative Example 2 in which j Ra = 〇05μπι or less, the area ratio exceeds 20%, and the number of dish-shaped sinks increases. Further, the surface of the copper foil exceeds 300', and the surface of the copper foil is scratched, and the operation becomes variable. In the final cold rolling, the surface roughness of the roll before the final pass, and the surface roughness of the roll of the final pass are all coarsened to Comparative Examples 3, 4, and 6 of Ra = 〇.06μηι or more. In the case of the above, the area ratio exceeds 2%, and the number of dishings increases. Further, in the case of Comparative Examples 3 and 4, the rough surface of all the rolls of the final cold rolling is changed. Thick, so inside the material, the shear deformation zone grows. The orientation of the crystal on the surface of the steel foil decreases, reaching 1/ IQ < 50. 201231179 On the other hand, in the case of Comparative Example 6, since the final pass The roughness of the previous roll was smoother than that of Comparative Examples 3 and 4, so the gloss and ι/ι〇 were higher than those of Comparative Examples 3 and 4, but the suppression of the shear band was still insufficient, and the above area ratio (4) 2〇% The number of disc-shaped sags increases. Furthermore, it can be considered to be close to In the state in which the (four) degree before the final pass is g g7 (four), there is a method of lowering the speed of the pass plate to suppress the shear band, etc., but in this case, the degree of the film exceeds 300, so the surface damage is judged to be χ. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing the relationship between the rough seam of the matte surface and the shear deformation zone. Fig. 2 is a graph showing the relationship between the oil pit and the gloss. Fig. 3 is a graph showing the relationship between the oil pit and the gloss. The measurement method of the average value d of the depths is shown in Fig. 1 to Fig. 1 shows the optical microscope image of the first embodiment. The fifth embodiment shows the optical microscope image of the comparative example 3. 6 is a diagram showing the results of the EBSC determination of Example 1. 7 shows the result of the EBSD measurement of Comparative Example 1. FIG. 8 shows the measurement of the flexural fatigue life by the bending test device. Main component Symbol Description Copper foil screw vibration transmission member vibration drive body 201231179 RD Calender parallel direction TD calender Right angle Grd ' Gjd ' G60RD, G60TD Gloss l, ~l3 Straight line Hm Maximum face Hs Minimum height Ry, Ra Surface roughness d Average value di Difference between maximum height and minimum height I ' I〇 Strength t Thickness r Curvature Radius 20