541347 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（！） 本發明之背景 本發明係關於一種抗摺曲性極佳的輥軋銅箔，適合應 用在諸如可撓性印刷電路之可撓性印刷線路元件上；亦關 係其製造方法。 以有機物爲主的印刷電路板大致分爲兩種：硬式印_ 電路板係一堅硬之覆銅層積物，其由玻璃-環氧樹脂基板和! 紙-酚基板所構成；而可撓性印刷電路板係一可撓之覆銅[胃 積物，其由聚醯亞胺基板和聚酯基板所構成。銅箔主要g 來做爲印刷電路板的導電材料。此銅箔產品視其製造方& ，可分爲電沈積箔和輥軋箔。 在印刷電路板中，可撓性印刷電路(爾後簡稱FPC)的 製造，係將銅箔層積於樹脂基板，並利用黏著劑將各層接 合’或以熱壓接合成一整合板。近年來，熟知爲累積板 (built-up boards)的多層板，已廣泛應用爲高密度封裝及安 置的有效方式。而用來製造FPC元件的銅箔大多爲輥軋銅 箔。 FPC被大量運用在印表機列表頭、硬碟機及其他需要 連線至可移動元件的地方。它們在使用時受到超過百萬次 的彎褶。這要求形成FPC元件的輥軋銅箔元件要有很好的 抗摺曲性。由於目前裝置走向迷你化、高性能，因此在抗 摺曲方面的要求更甚於以往。 至於用在FPC上的銅箔材料，係採用韌煉銅(tough一 pitch copper)或無氧銅。箔的製造係熱輥乳此類材料的銘塊 ，再重覆性地交互冷輥軋和退火，直到達到預定要的厚度 _ 3 本紙張尺度過用中國國豕fe準（CNS)A4規格（210 X 297公釐 -------------------訂—I------ (請先閱讀背面之注意事項再填寫本頁) 541347 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（V ) 。此輥軋過的銅箔再進行電鍍，以增加表面粗糙度，以增 進與樹脂基板的黏著。粗糙化電鍍之後，將銅箔切片並層 積至樹脂基板。爲能進行層積，採用了一種熱固型樹脂黏 著劑（如環氧樹脂）。將此黏著劑加熱至13(M70°C間1-24 小時使之硬化。然後將銅箔蝕刻，形成各種線路圖案。此 FPC中之銅箔有時可以折疊，或者可以與裝置做點接觸式 運作。 而銅箔的抗摺曲性經由再結晶退火而顯著改善，勝過 剛輥軋過的性質。因此，FPC元件所採用的箔是經過退火 的。此退火在運用上，可於粗糙化電鍍和切片後做熱處理 ;或者可利用黏著於樹脂基板時加熱來進行。 若要銅箔經熱處理而至再結晶的結構，其退火條{牛_ 在130-250°C進行15分鐘至24小時，始發揮作用，而典型 爲200°C、30分鐘。 本發明之目的 如前文所述，用於FPC材料之輥軋銅箔須具備高 摺曲性。而近來，裝置又走向迷你化、高階化，揺曲 的需求就更爲嚴謹。 本發明即針對改善傳統輥軋飼箔的抗摺曲性， 犧牲其伸長性和其他性質。 本發明之槪要 已提出一種改進輥軋銅箔抗摺曲性之製造方法 其增 (請先閱讀背面之注意事項再填寫本頁) .1 訂·！：------ K紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 541347 A7 經濟部智慧財產局員工消費合作社印製 B7 五、發明說明（>1 ) 加最終冷輥軋的減少率（日本專利公開號4-228553)。 爲驗証此參考發明之效果，本發明之作者群使銅箔之 最終減少率爲90至97%，並測試其抗摺曲性。發現它們並 未總是展現穩定且滿意的抗摺曲性。 爲此，本發明者鑽硏了使輥軋銅箔具備極佳且穩定的 抗摺曲性之方法。結果發現不只該調整最終冷輥軋的減少 率，且須調整在最終冷輥軋前的退火條件；意即’使因退 火處理而得之再結晶晶粒的平均晶粒大小範圍在5-2〇 ，再進行最終冷輥軋，且其減少率不低於90%。 依此製造出的銅箔，展現了穩定卓越的抗摺曲性；而 且可淸楚定義出一種立方體組織，此經過200°C、30分鐘 的熱處理而產生的再結晶結構，其輥軋表面經X射線繞射 測得的面200之積分強度(I)爲1/1〇>20，此Ιο爲細微銅粉 經X射線繞射測得的面200之積分強度。本發明之輥軋銅 箔具有極佳的抗摺曲性，在摺曲試驗中（於下文討論），其 摺曲疲勞壽命超過30,000回。 基於上述之發現，本發明提供： (1) —種具有極佳抗摺曲性之輥軋銅箔，其特徵在於立 方體組織，係經過200°C、30分鐘的熱處理而產生再結晶 結構’其輥軋表面經X射線繞射測得的面200之強度⑴爲 1/1〇>20，此1〇爲細微銅粉經X射線繞射測得的面2〇〇之 強度。 (2) —種製造輥軋銅箔（1)的方法，其係熱輥軋韌煉銅或 無氧銅的錠塊，再重覆性地交互冷輥軋和退火，最終冷輥 _ 5 本紙張尺度適用中國國豕4示準（CNS)A4規格（210 X 297公釐 —：----------------訂—^------ (請先閱讀背面之注意事項再填寫本頁) 541347 A7 B7 五、發明說明（斗） 軋使工件厚度不超過50#m°其特徵在於退火後立即進行 最終冷輥軋，此退火的條件爲使得退火再結晶之平均晶粒 大小在5-20/zm之間；而且確保最終冷輥軋的減少率不低 於 90%。 圖式之簡略說明 圖1爲一種摺曲測試儀之圖例，用來測知箔的摺曲疲 勞壽命。 圖2呈現最終輥軋之減少率、最終輥軋前經退火之晶 粒大小、I/Io三者間之關係。 圖3呈現Ι/Ιο和疲勞壽命(摺曲回數)間之關係。 本發明之具體實施例說明 本發明所採用的輥軋銅箔材料主要爲韌煉銅或者無氧 銅。此輥乳銅箔的製造，基本上係將韌煉銅或者無氧銅之 銅錠熱輥軋，再重覆輪流冷輥軋及退火，而以最終冷輥軋 而得完成品’其厚度以不超過50//m。依本發明，在最終 冷輥軋之前先立即退火，此退火的條件爲使得退火再結晶 之晶粒具有5-20//m間之平均晶粒大小；而且確保最終冷 輥軋的減少率不低於90%。 例如，退火的條件可在連續式退火爐中，溫度可在 500-80(TC之間，時間則視溫度高低而定，可在5-600秒間 ;或是以批次方式爲之，溫度在130-500°C間，時間則爲 1-24小時。 6 ^1 ·ϋ ϋ· ϋ n ·ϋ 1^1 ·ϋ I 1 i^i n· Hi-_、 mMmmg ϋ ϋ ·ϋ «1 I (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 541347 A7 B7 五、發明說明（<) 此退火條件能對成品的抗摺曲性有顯著的影響，其原 因說明於下： (請先閱讀背面之注意事項再填寫本頁) 當純銅經退火再結晶，其立方體組織（面（100)、方向 <〇〇1>、且面（100)與面(200)相等)會成長。而眾所週知地， 若退火前的減少率增加，立方體組織的成長會變明顯。本 發明係依據如下之發現爲基礎：輥軋前的晶粒大小對於立 方體組織的生成也有實質的影響；晶粒愈小，立方體組織 長的愈多，而立方體組織愈多，則抗摺曲性愈佳。推定其 係歸因於減低變形方向的楊氏係數的關係，如日本專利公 開號55-54554中所述，藉立方體組織的生長做爲改進銅疲 勞特性的根據。 經濟部智慧財產局員工消費合作社印製 從前文可了解到，如果單單只是增加輥軋的減少率， 是不足以穩定地達到極佳的抗摺曲性，仍須要將之前的退 火處理最適化才有辦法。因此，若將銅箔經過退火處理， 使得再結晶晶粒不大於20//m，再以不低於90%的減少率 來做最終冷輥軋，即可穩定地獲得高度抗摺曲性。結果所 得的立方體組織，其輥軋表面經X射線繞射測得的面200 之強度(I)爲1/1〇>20，此1〇爲細微銅粉經X射線繞射測得 的面200之強度。 以此細微銅粉的X射線繞射測得的面200之強度値 (1〇)爲參考値，此處其晶體係隨機指向的(其面200並未成 長）。 銅箔的再結晶結構及其製造方法之根據，依本發明之 說明槪述於下： 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 541347 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（) (1) 經過200°c、30分鐘的熱處理，其輥軋表面的X射 線繞射測得的面200之強度⑴特定爲1/1〇>2〇，因爲當立方 體組織的成長程度(I/Io)大於20時，令人滿意的抗摺曲性 便可達到。 (2) 再結晶晶粒的平均晶粒大小定在5_2〇//ιη間，因爲 當晶粒不大於20//m時，會使1/1〇>2〇，可得很好的抗摺曲 性；另一方面，如果晶粒小於5//m，其伸長率會降低，且 造成彎曲時會裂的問題。因此，很重要地，晶粒大小須適 度調整’使之不小於5 // m。 (3) 其減少率須不低於90%，因爲當減少率低於90%時 ，儘管之前的退火條件已加以調整，仍不會達到1/1〇>20 之狀況，且不會達到所要的抗摺曲性。 如是所得之銅范具有極佳的抗摺曲性，在摺曲試驗中（ .於下說明)會展現超過30,000回的摺曲疲勞壽命。 範例 本發明之範例與比較範例會詳細在此說明。 採用切煉銅（氧含量:250ppm)和無氧銅（氧含量:2ppm) 之銅錠，各200mm厚、600mm寬；經過熱輥軋後變成 10mm厚。重覆性地進行退火及冷輥軋後，得一已知厚度(t mm)之剛輥軋片。如表1所列，此片在加熱烘箱中經過預 定的時間退火，溫度的使用範圍在300-900°C。在去除氧化 物外垢後，再冷輥軋成厚度〇.〇35mm。最終冷輥軋的減少 率R以下列公式計算： 8 -----------裝--------訂—^------ (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 541347 A7 B7 五、發明說明（7) R = (t-0.035)/tX 100 (%) 最終退火之後，此退火晶粒大小依JIS G0551之切割 方法，垂直於輥軋方向的剖面測知。 r^PA.r>v ^^1 ^^1 ϋ a^i n an ^ ^1- i^i Hi I— I i (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 47 3 IX 54 五 A7 —___B7 發明說明（^) 表1試片的加工歷程與性質 本發明的範例 比較性範例 N〇. 銅材 最終退火f 1件 最終輥 壓減少 率（％) 200°C加熱30分鐘後 爐溫（ °〇 加熱時 間（秒） 晶粒大 小（//m) 1/1〇 摺曲壽 命（回數） 伸長 率（％) 1 韌煉銅 800 20 [8 95 50.7 64500 13.3 2 // 800 30 15 95 37.2 51100 15.6 3 // 800 40 18 95 31.4 42800 16.4 4 // 700 40 10 93 39.1 40700 15.2 5 // 700 50 13 93 33.4 48700 16.2 6 // 700 60 17 93 25.7 39200 17.6 7 // 600 90 7 98 64.2 82800 12.0 8 // 600 150 15 98 48.8 72300 13.6 9 // 500 300 8 92 39.1 49300 15.2 10 無氧銅 500 600 11 92 33.4 32800 16.3 11 11 800 30 15 95 37.2 68000 15.3 12 11 700 60 17 93 25.7 45300 17.6 13 11 600 90 7 98 64.2 93200 11.6 14 // 500 600 11 92 33.4 59200 16.1 」 韌煉銅 800 10 3 95 60.3 85400 6.2 2 無氧銅 800 60 27 95 14.1 19700 19.4 3 // 700 20 3 94 Π 56.5 91600 7.7 4 韌煉銅 350 1200 4 93 50.7 72700 8.4 5 無氧銅 800 30 15 88 Π 10.3 17600 1 20.1 6 韌煉銅 700 60 17 85 6.2 7300 23.9 7 // 800 10 3 98 73.7 92500 7.1 (請先閱讀背面之注意事項再填寫本頁) 訂—：------· 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 541347 A7 B7 五、發明說明（？） 不同的退火條件和不同的最終輥軋減少率所得之銅箔 試片，評估如下之性質： (1) 立方體組織 每一試片皆加熱至200°c、30分鐘，測其輥軋表面的 面200之X射線繞射強度積分値I。將此I値除以1〇，此 1〇爲細微銅粉(325目）的面200之X射線繞射強度積分値 ，來計算1/1〇値。 (2) 抗摺曲性 每一試片皆加熱至200°C、30分鐘，使之再結晶，然 後以如圖1之摺曲試驗儀測其摺曲疲勞壽命。此試驗儀有 一振動驅使單元4和一振動傳輸元件3連接驅使單元。將 一測試銅箔固定在總共4個點，如箭頭所指之處：即螺絲 2端點處及元件3底端。當振動元件3上下振動，銅箔1 的中段部分以已知的曲率半徑r，如髮簪插入般彎曲。於 觀察下，一直以底下條件重覆此彎曲動作，計算疲勞失能 前的摺曲回數。 經濟部智慧財產局員工消費合作社印制衣 (請先閱讀背面之注意事項再填寫本頁)541347 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs 5. Description of the invention (!) Background of the invention The invention relates to a rolled copper foil with excellent bending resistance, suitable for applications such as flexible printed circuits Flexible printed circuit components; also related to its manufacturing method. Organic printed circuit boards are mainly divided into two types: hard printed circuit boards are a hard copper-clad laminate, which is composed of a glass-epoxy substrate and a paper-phenol substrate; and it is flexible The printed circuit board is a flexible copper-clad gastric product consisting of a polyimide substrate and a polyester substrate. Copper foil is mainly used as a conductive material for printed circuit boards. This copper foil product can be divided into electrodeposited foil and rolled foil depending on its manufacturer &. Among the printed circuit boards, flexible printed circuits (hereinafter referred to as FPC) are manufactured by laminating a copper foil on a resin substrate and bonding the layers with an adhesive 'or by thermocompression bonding to form an integrated board. In recent years, multi-layer boards, known as built-up boards, have been widely used as an effective method for high-density packaging and placement. Most of the copper foils used to make FPC elements are rolled copper foils. FPCs are used extensively in printer heads, hard drives, and other places where you need to connect to removable components. They are crimped more than a million times during use. This requires the rolled copper foil element forming the FPC element to have good bending resistance. Since the current devices are miniaturized and high-performance, the requirements for anti-buckling are more than ever. As for the copper foil material used in FPC, tough-pitch copper or oxygen-free copper is used. The manufacturing of foil is the ingot of such materials as hot roll milk, and then repeatedly cold rolled and annealed repeatedly until it reaches the predetermined thickness _ 3 This paper has been used in China National Standard (CNS) A4 ( 210 X 297 mm -------- Order—I ------ (Please read the notes on the back before filling this page) 541347 A7 B7 Economy Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau. V. Invention Description (V). The rolled copper foil is then electroplated to increase the surface roughness and adhesion to the resin substrate. After roughening the electroplating, the copper foil Slice and laminate to the resin substrate. To enable lamination, a thermosetting resin adhesive (such as epoxy resin) is used. This adhesive is heated to 13 (1 to 24 hours at M70 ° C to harden it). The copper foil is then etched to form various circuit patterns. The copper foil in this FPC can sometimes be folded or operated in point contact with the device. The bending resistance of the copper foil is significantly improved by recrystallization annealing, which is better than Just rolled nature. Therefore, the foil used in FPC components is annealed. This annealing is used in applications It can be heat-treated after roughening electroplating and slicing; or it can be performed by heating when it is adhered to the resin substrate. If the copper foil is heat-treated to recrystallize the structure, its annealing strip {ox__ at 130-250 ° C It takes 15 minutes to 24 hours to start functioning, but it is typically 200 ° C and 30 minutes. The purpose of the present invention is as described above. The rolled copper foil used for FPC materials must have high bending properties. Recently, the device has Toward miniaturization and higher order, the demand for curling is even more rigorous. The present invention aims at improving the bending resistance of traditional rolled feeding foil, sacrificing its elongation and other properties. One of the present invention has proposed an improved roller The manufacturing method of the anti-buckling resistance of rolled copper foil is increased (please read the precautions on the back before filling this page) .1 Order · !: ------ K paper size applies Chinese National Standard (CNS) A4 specification ( (210 X 297 mm) 541347 A7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs B7 V. Description of the invention (> 1) plus the reduction rate of the final cold rolling (Japanese Patent Publication No. 4-228553). To verify this reference Effect of the invention The final reduction of copper foil was 90 to 97%, and its bending resistance was tested. It was found that they did not always exhibit stable and satisfactory resistance to bending. To this end, the inventors drilled and rolled the copper foil A method with excellent and stable resistance to bending. As a result, it was found that not only the reduction rate of the final cold rolling should be adjusted, but also the annealing conditions before the final cold rolling; The average grain size of the crystal grains is in the range of 5-20, and then the final cold rolling is performed, and the reduction rate is not less than 90%. The copper foil manufactured thereby exhibits stable and excellent resistance to bending; Moreover, a cubic structure can be defined clearly. The recrystallized structure produced by heat treatment at 200 ° C for 30 minutes has an integrated intensity (I) of the surface 200 of the rolled surface measured by X-ray diffraction of 1 / 10 > 20, which is the integrated intensity of the surface 200 measured by X-ray diffraction of fine copper powder. The rolled copper foil of the present invention has excellent bending resistance. In a bending test (discussed below), its bending fatigue life exceeds 30,000 cycles. Based on the above findings, the present invention provides: (1) a rolled copper foil with excellent bending resistance, which is characterized by a cubic structure and undergoes a heat treatment at 200 ° C for 30 minutes to produce a recrystallized structure. The strength 面 of the surface 200 measured by X-ray diffraction on the rolled surface is 1/1 10> 20, and 10 is the strength of the surface 200 measured by X-ray diffraction of fine copper powder. (2) — A method for manufacturing rolled copper foil (1), which is hot rolling of ingots of toughened copper or oxygen-free copper, and then repeatedly cold rolling and annealing, and finally cold rolling Paper size applies to China National Standard 4 (CNS) A4 (210 X 297 mm —: ---------------- Order — ^ ------ (Please read first Note on the back page, please fill in this page again) 541347 A7 B7 V. Description of the invention (bucket) Rolling so that the thickness of the workpiece does not exceed 50 # m °. It is characterized by final cold rolling immediately after annealing. The annealing conditions are such that annealing recrystallizes The average grain size is between 5-20 / zm; and ensure that the reduction rate of the final cold rolling is not less than 90%. Brief description of the figure Figure 1 is a legend of a bending tester used to determine the foil Fig. 2 shows the relationship between the reduction rate of the final rolling, the grain size annealed before the final rolling, and I / Io. Fig. 3 shows the I / I and the fatigue life (bending times) ). The specific embodiments of the present invention illustrate that the rolled copper foil material used in the present invention is mainly toughened copper or oxygen-free copper. The manufacture of this rolled milky copper foil is basically The rolled ingots of toughened copper or oxygen-free copper are hot-rolled, followed by alternate cold-rolling and annealing, and the final cold-rolling is used to obtain the finished product, whose thickness does not exceed 50 // m. Anneal immediately before the final cold rolling. The conditions of this annealing are such that the annealed and recrystallized grains have an average grain size between 5-20 // m; and that the reduction rate of the final cold rolling is not less than 90. %. For example, the annealing conditions can be in a continuous annealing furnace, the temperature can be between 500-80 (TC, the time depends on the temperature, it can be between 5-600 seconds; or batch mode, The temperature is between 130-500 ° C, and the time is 1-24 hours. 6 ^ 1 · ϋ ϋ · ϋ n · ϋ 1 ^ 1 · ϋ I 1 i ^ in · Hi-_, mMmmg ϋ ϋ · ϋ «1 I (Please read the notes on the back before filling this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is printed in accordance with China National Standard (CNS) A4 (210 X 297 mm) 541347 A7 B7 V. Description of the invention (≪) This annealing condition can have a significant effect on the bending resistance of the finished product. The reason is as follows: (Please read the notes on the back first Fill in this page again) When pure copper is annealed and recrystallized, its cubic structure (face (100), direction < 〇〇1 >, and face (100) and face (200)) will grow. As is well known, if annealing The increase of the previous reduction rate will make the growth of the cube structure obvious. The present invention is based on the following findings: the grain size before rolling has a substantial effect on the generation of the cube structure; the smaller the grain, the longer the cube structure The more and more cubic structure, the better the resistance to bending. It is presumed that this is due to the Young's coefficient that reduces the deformation direction. As described in Japanese Patent Laid-Open No. 55-54554, the growth of the cubic structure is used as a basis for improving the fatigue characteristics of copper. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. It can be understood from the foregoing that if only the reduction rate of rolling is increased, it is not enough to stably achieve excellent resistance to bending. The previous annealing treatment must still be optimized. There is a way. Therefore, if the copper foil is annealed so that the recrystallized grains are not more than 20 // m, and then the final cold rolling is performed with a reduction rate of not less than 90%, a high degree of bending resistance can be stably obtained. As a result, the intensity (I) of the surface 200 of the cubic structure measured by X-ray diffraction on the rolled surface was 1/1 0> 20, and 10 was the surface of fine copper powder measured by X-ray diffraction. 200 strength. The intensity 値 (10) of the surface 200 measured by the X-ray diffraction of the fine copper powder is used as a reference 値, where the crystal system thereof is randomly oriented (the surface 200 is not grown). The basis of the recrystallized structure of copper foil and its manufacturing method is described below according to the description of the present invention: 7 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 541347 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative A7 B7 V. Description of the invention () (1) After 200 ° c, 30 minutes of heat treatment, the strength of the surface 200 measured by X-ray diffraction on the rolled surface is specified as 1/1 0> 20, because when the degree of growth (I / Io) of the cubic structure is greater than 20, satisfactory bending resistance can be achieved. (2) The average grain size of the recrystallized grains is set between 5_2〇 // ιη, because when the grains are not larger than 20 // m, it will make 1 / 1〇> 2〇, and it can obtain good resistance. Flexibility; on the other hand, if the grain size is less than 5 // m, its elongation will be reduced, and it will cause a problem of cracking during bending. Therefore, it is important that the grain size is adjusted appropriately 'so that it is not less than 5 // m. (3) The reduction rate must not be less than 90%, because when the reduction rate is less than 90%, although the previous annealing conditions have been adjusted, it will still not reach the condition of 1 / 1〇> 20, and will not reach Desired buckling resistance. If the obtained copper sample has excellent bending resistance, it will show a bending fatigue life of more than 30,000 times in the bending test (described below). Examples The examples and comparative examples of the present invention will be described in detail here. Copper ingots of cut copper (oxygen content: 250 ppm) and oxygen-free copper (oxygen content: 2 ppm) are each 200 mm thick and 600 mm wide; after hot rolling, they become 10 mm thick. After repeated annealing and cold rolling, a rigid rolled sheet having a known thickness (t mm) was obtained. As shown in Table 1, this sheet is annealed in a heating oven for a predetermined time, and the temperature range of use is 300-900 ° C. After removing the oxide scale, it was cold rolled to a thickness of 0.035 mm. The final cold rolling reduction rate R is calculated by the following formula: 8 ----------- installation -------- order-^ ------ (Please read the note on the back first Please fill in this page again for this matter) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 541347 A7 B7 V. Description of the invention (7) R = (t-0.035) / tX 100 (%) Final annealing Thereafter, the size of the annealed grains was measured according to the cutting method of JIS G0551, and the cross section perpendicular to the rolling direction was measured. r ^ PA.r > v ^^ 1 ^^ 1 ϋ a ^ in an ^ ^ 1- i ^ i Hi I— I i (Please read the precautions on the back before filling out this page) Staff Consumption of Intellectual Property Bureau of the Ministry of Economic Affairs The paper size printed by the cooperative applies the Chinese National Standard (CNS) A4 (210 X 297 mm) 47 3 IX 54 Five A7 — ___B7 Description of the invention (^) Table 1 Processing history and properties of test pieces Example No. Copper final annealing f 1 Final roll reduction rate (%) Furnace temperature after heating at 200 ° C for 30 minutes (° 〇 Heating time (seconds) Grain size (// m) 1/110 flex Life (times) Elongation (%) 1 Toughened copper 800 20 [8 95 50.7 64500 13.3 2 // 800 30 15 95 37.2 51100 15.6 3 // 800 40 18 95 31.4 42800 16.4 4 // 700 40 10 93 39.1 40700 15.2 5 // 700 50 13 93 33.4 48700 16.2 6 // 700 60 17 93 25.7 39200 17.6 7 // 600 90 7 98 64.2 82800 12.0 8 // 600 150 15 98 48.8 72300 13.6 9 // 500 300 8 92 39.1 49 300 15.2 10 Oxygen-free copper 500 600 11 92 33.4 32 800 16.3 11 11 800 30 15 95 37.2 68000 15.3 12 11 700 60 17 93 25.7 45 300 17.6 13 11 600 90 7 98 64.2 93200 11.6 14 // 500 600 11 92 33.4 59 200 16.1 `` Toughened copper 800 10 3 95 60.3 85 400 6.2 2 Oxygen-free copper 800 60 27 95 14.1 19700 19.4 3 // 700 20 3 94 Π 56.5 91600 7.7 4 tough Copper smelting 350 1200 4 93 50.7 72700 8.4 5 Oxygen-free copper 800 30 15 88 Π 10.3 17600 1 20.1 6 Tough copper smelting 700 60 17 85 6.2 7300 23.9 7 // 800 10 3 98 73.7 92500 7.1 (Please read the notes on the back first Please fill in this page for matters) Order —: ------ · Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economy The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 541347 A7 B7 V. Invention description (? ) The copper foil test pieces obtained under different annealing conditions and different final rolling reduction rates were evaluated for the following properties: (1) Each test piece of a cube structure was heated to 200 ° c for 30 minutes, and the rolling surface of the test piece was measured. The X-ray diffraction intensity integral 値 I of the surface 200. This I 値 is divided by 10, which is the X-ray diffraction intensity integral 値 of the surface 200 of the fine copper powder (325 mesh) to calculate 1/1 値. (2) Bending resistance Each test piece was heated to 200 ° C for 30 minutes to recrystallize it, and then its bending fatigue life was measured by a bending tester as shown in FIG. This tester has a vibration driving unit 4 and a vibration transmission element 3 connected to the driving unit. Fix a test copper foil at a total of 4 points, as indicated by the arrows: the end of the screw 2 and the bottom of the component 3. When the vibrating element 3 vibrates up and down, the middle portion of the copper foil 1 is bent with a known radius of curvature r like a bun inserted. Under observation, this bending action has been repeated under the following conditions, and the number of bending cycles before fatigue disability is calculated. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (Please read the precautions on the back before filling this page)
其測試條件爲：試片寬度==12.7mm、試片長度=200mm 、取樣方向=每一試片之長度皆平行於輥軋方向而切下、曲 率半徑r=2.5mm、振動衝程=25mm、振動速度= 1500次/分 鐘。 若試片的摺曲疲勞壽命超過30,〇〇〇回，則視此試片具 有極佳的抗摺曲性。此種測試係一加速測試方式，其試片 之摺曲測試條件比實際情況更爲嚴格。 (3) 伸長率 氏張尺度適用中關家標準（CNS)A4規格（210 X 297 541347 A7 B7 五、發明說明（丨0 ) 每一試片皆經加熱至200°c、30分鐘而再結晶，再以 抗拉測試機測試，其拉力方向與輥軋方向平行。試片寬 12.7mm ' 長 150mm、標距 50mm 〇 表1列出了試片的加工歷程與性質。依本發明之輥軋 銅箔，其I/IO大於20，摺曲壽命極佳，超過30,000回’ 伸長率亦不錯，超過10%。 另一方面，比較範例1、3、4和7，其伸長率低於 10%，因其最終退火後之晶粒小於5//m。比較範例2退火 後之晶粒大於20um，而比較範例5、6之最終輥軋減少率 低於90%，因此這些試片雖經20(TC、30分鐘之加熱，仍 呈現出未成長的(200)結構，因而其摺曲壽命皆低於20,000 回。 圖2即根據表1之數據繪成，呈現出最終輥軋減少率 、最終輥軋前退火晶粒大小、I/Io，三者間之關係。其再結 晶結構的成長，明顯地隨減少率的增加和晶粒的變小而增 加。圖3則展現出1/1〇和摺曲疲勞壽命(摺曲回數)間的關 係。此圖扼要總結了最終輥軋前之退火條件和減少率的數 據間的關係，並指出再結晶結構的成長可加強抗摺曲性。 而比較起始材料爲韌煉銅和爲無氧銅之不同，後者的 摺曲壽命稍長。此差異乃解釋爲它們各有不同的Cu2〇夾 雜物。韌煉銅有較多的Cu20夾雜物，促進裂隙的成長與 散播，而無氧銅則只有很少的Cu20夾雜物。 本發明之優點 12 本紙張尺度適用中國國豕標準（CNS)A4規格（21〇 X 297公爱） (請先閱讀背面之注意事項再填寫本頁) -裝--------訂---^------The test conditions are: test piece width == 12.7mm, test piece length = 200mm, sampling direction = the length of each test piece is cut parallel to the rolling direction, the radius of curvature r = 2.5mm, vibration stroke = 25mm, Vibration speed = 1500 times / minute. If the bending fatigue life of the test piece exceeds 30, 000 times, the test piece is considered to have excellent bending resistance. This test is an accelerated test method, and the bending test conditions of the test piece are more stringent than the actual situation. (3) The elongation scale is applicable to the Zhongguanjia Standard (CNS) A4 specification (210 X 297 541347 A7 B7) 5. Description of the invention (丨 0) Each test piece is recrystallized after being heated to 200 ° c for 30 minutes The tensile direction is parallel to the rolling direction. The test piece is 12.7mm wide, 150mm long, and the gauge distance is 50mm. Table 1 lists the processing history and properties of the test piece. Rolling according to the present invention Copper foil, whose I / IO is greater than 20, has a good bending life, more than 30,000 cycles, and the elongation is also good, exceeding 10%. On the other hand, in Comparative Examples 1, 3, 4, and 7, the elongation is less than 10%. Because the grain size after final annealing is less than 5 // m. The grain size after annealing of Comparative Example 2 is greater than 20um, and the final rolling reduction rate of Comparative Examples 5 and 6 is less than 90%. (TC, heating for 30 minutes, still exhibits an ungrown (200) structure, so its bending life is less than 20,000 cycles. Figure 2 is drawn based on the data in Table 1, showing the final rolling reduction rate, the final The relationship between the grain size, I / Io, and the annealing annealing before rolling. The growth of the recrystallization structure obviously increases with the decrease rate. Addition and grain size increase and decrease. Figure 3 shows the relationship between 1/10 and flexural fatigue life (bending times). This figure summarizes the annealing conditions and reduction rates before final rolling. The relationship between the data and pointed out that the growth of the recrystallized structure can enhance the resistance to bending. Compared to the difference between the starting material being toughened copper and oxygen-free copper, the latter has a slightly longer bending life. This difference is explained by them Each has different Cu20 inclusions. Toughened copper has more Cu20 inclusions, which promotes the growth and spread of cracks, while oxygen-free copper has very few Cu20 inclusions. Advantages of the invention 12 This paper scale is applicable to China National Standard (CNS) A4 (21〇X 297 public love) (Please read the precautions on the back before filling out this page) -Install -------- Order --- ^ ------
經濟部智慧財產局員工消費合作社印製 541347 A7 _B7 五、發明說明（ll ) 本發明提供了一種輥乳銅箔，其具備了極佳的抗摺曲 性，最適用在可撓性印刷電路和類似者的可撓性線材，而 且提供了一種有效的製造方法。 (請先閱讀背面之注意事項再填寫本頁) 【裝----Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 541347 A7 _B7 V. Description of the Invention (ll) The present invention provides a roll-milk copper foil, which has excellent anti-buckling properties, and is most suitable for flexible printed circuits and flexible printed circuits. A similar flexible wire, but also provides an efficient manufacturing method. (Please read the precautions on the back before filling this page)
經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm)