201124269 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種使用於例如撓性印刷配線板（FPC : Flexible Printed Circuit)中之銅箔、及將該銅箔積層於樹 脂層之至少單面之覆銅積層板。 【先前技術】201124269 VI. Description of the Invention: [Technical Field] The present invention relates to a copper foil used in, for example, a flexible printed wiring board (FPC), and at least a single layer of the copper foil laminated on the resin layer Copper-clad laminate. [Prior Art]
作為驅動數位相機或行動電話等電子機器之電路，使 用有撓性印刷配線板（FPC : Flexible Printed Circuit)或覆 晶軟板（COF ’ chip of flexible circuit)。該 fpc 或 c〇F 係使用於樹脂層之單面或雙面積層有銅箔之覆銅積層板 (CCL，copper-clad laminate )，且於銅箔上形成電路圖案 而成。 並且’為使此種電子機器小型化及高功能化，採用有 將FPC摺疊收納至殼體内之狹小空間之方法。又，於用於 液晶顯示器周邊之C0F之情形時，為使鑲框（所謂之「邊 框」）變細，而將COF之銅配線折回至液晶基板之内側。 然而，摺疊FPC或COF時，存在銅箔部分受到較大之 變形負載而易造成斷裂之問題。 因此’揭示有由包含柱狀之銅晶粒且25°C夕仙才& u之伸長率為 5%以上之電解銅猪構成FPC，藉此獲得配線圖案不易斷裂 之FPC (專利文獻1 )。 專利文獻1 :曰本特開2007-3 3 5 541號公報 【發明内容】 先刖，認為C C L·之銅箔之彎曲性與銅^ e > …9〈伸長存在關 201124269 聯’因此如上述專利文獻i令所揭示般，使用伸長較大之 電解銅箔。 ^然而，本發明者等人發現：即便使用伸長較大之壓延 銅泊，亦存在CCL之彎曲性並未提高之情形。 即，本發明係為解決上述課題研究而成者，其目的在 於提供一種用於覆銅積層板時蠻曲性優異之銅^使料 之覆銅積層板。 〃 本發明者等人經種種研討後，發現作為提高ccl之 因素’重要的並非㈣之伸長而是加工硬化指數“ 為達成上述目的，本發明之銅箔為厚度5〜3 壓延平行方向之表面粗縫度Ra=<〜m， ：行 〇·5小時退火後之加工硬化指數為〇·3以上。.45以下订 本發明之銅箱之半軟化溫度較佳為15代以下。 無二：發明之銅箱較佳為由無氧铜或精銅構成，或者 組成計5°”量一下之“…η 二用積層㈣層且合計厚度為5。 落之露出面為外侧進行180度密合广上迷鋼 裂為止之彎曲次數較佳為4次以上。4曲時’至上述銅箱斷 最後冷壓延時之總加卫㈠抓以上 述最後冷壓延中之最後3道次 且將上 壓延而成。其中，將……” ^里設為以下條件 其中#最後道次之前2 4 201124269 為25000以下，將最後道次之前1道次之油膜當量設為 30000以下，將最後道次之油膜當量設為35000以下。此處， 將鑄錠熱壓延後，經冷壓延製造銅箔時，於冷壓延中交替 地進行冷壓延及退火。並且，將最後退火後最後進行之冷 壓延設為「最後冷壓延」。 本發明之覆銅積層板係將上述銅箔積層於樹脂層之至 少單面而成。 根據本發明，可獲得用於覆銅積層板時彎曲性優異之 銅箔。 【實施方式】 以下，針對本發明之實施形態之銅箔進行說明。再者， 本發明中之％，只要未特別預先說明，則表示質量 本發明之實施形態之銅落為厚度5〜30 #m，壓延平 行方向之表面粗糙度_，且以35〇t進行〇5小 時退火後之加工硬化指數為〇3以上〇·45以下。 加工硬化指數（ 應力與應變之關係由 的指數η表示。 η值）係由降伏點 下式 1 ( Holl〇mo 以上之塑性變形域之 n式）近似之情形時 加工硬化指數越大，舳雜款丄 （1) 越難發生局部變形，變形砗㈣ 斷裂。又，加工硬化指數較高之材料拉^ 時越莫 1 合於厂堅製加工。並且，於將銅落積=中力:工性優異4 而製造覆鋼積層板，且評估該覆鋼積“曰層之至少單S 時，認為加工硬化指數為〇 3以 之彎曲性之情^ •上之銅箔不易發生局部變 201124269 形，並且由彎曲部位整體承受變形，故銅箔難以斷裂。然 而，加工硬化指數超過0.45之材料退火後之強度較低且操 作性劣化，故不適宜用作覆銅積層板。 此處，將以350t進行0.5小時退火後之加工硬化指數 加以界定之理由，係因為製造覆銅積層板時之加熱條件為 。亥私度。再者，於覆銅積層板之樹脂層為將樹脂組成物塗 佈於銅箔並硬化而得之情形（樹脂層及銅箔之間未夾有接 者層之2 ^ CCL之情形）時’於上述加熱條件下進行樹脂 之硬化。 再者，作為提昇銅箔之彎曲性之因素，認為重要的並 非銅羯之伸長而是加工硬化指數（11值）之理由如下。 首先，加工硬化指數係表示材料之加工硬化行為的值 之，忒值越大，材料具有越容易加工硬化之性質。此處， 材料又到拉伸變形時’將局部地發生收縮而斷裂，然而加 更化係數較大之材料，將發生收縮之部分加工硬化，收 縮部變得不易變形。因&，其以外之部分便代替了不易變 形之收縮。p ’開始發生變形。藉由重複該步驟，而使材料 整體均句地變形。另-方面，伸長係在不考慮此種狀況之 、△觀地把握之指標，故即便伸長較大者亦未必加工硬 化指數較大。 ^先則’作為此種材料整體之均勻變形容易程度之指 ^〗如於具有厚度之材料的拉伸加工中，使用加工硬化 二曰:’然而薄如鋼箔之材料不會進行拉伸加工等加工，故 攻今尚未有將加工硬化指數作為指標者。因此，本發明中， 6 201124269 考慮若使銅箱之加工硬化指數增大，則即便於CCL之i8〇 度密合彎曲中’彎曲部整體亦會因均勻地變形而不於發生 斷裂之下彎曲。 進而，以20(TC進行〇.5小時退火後之加工硬化指數亦 較佳為0.3以上0.45以下。其原因在於，製造使用膜作為 樹脂層且膜與銅羯經由接著層而積層之3層CCL時的層壓 度度為200 C左右。加工硬化指數由於銅箔因加熱發生再結 晶而增大，因此若較3 5 〇 t低溫之2 〇 〇 t之加工硬化指數為 〇·3以上，則於35(TC亦可獲得〇·3以上之加工硬化指數。 又，為於上述退火中充分地獲得再結晶組織，銅猪之半軟 化溫度較佳為1 5 0 °C以下。 &作為將以35(TC進行〇·5小時退火後之銅猪之加工硬化 指數控制在0.3以上之方法，可舉出將最後冷壓延時之總加 工度設為85%以上。又’因必須獲得再結晶組織，故較佳 為將銅羯之半軟化溫度控制在⑽以下。通常再結晶溫卢 係依鋼落之組成及加工度決定、然而為使加工 0.3以上，可採用任一種方法。 為 若最後冷壓延時之總加工度未滿85%，則加工度會降 低且銅之軟化溫度會升高，故存在製造CCL時之加熱所 引起的鋼之再結晶變得不充分，殘留有加工應變且弯曲 會降低之傾向。 為提向將銅箔用於覆銅積層板時之彎曲性， 防上迷加 工石化指數之外，還必須考慮表面粗糙度之影響。此處， 針對加工硬化指數之大小’重要之要素為「材料最終可加 201124269 工:更化至何種程度」。因此’為使加工硬化指數為較大值， 又中材料必須為未加工硬化之狀態、即已除去加工 ^之狀態。對於CCL用銅落而言，必須係藉由ccl製造 步驟中之熱處理而使銅箔再結晶。 並且，CCL製造步驟中之熱處理條件係取決於樹脂之 ’丨質，故銅箱之再結晶溫度必須符合熱處理條件。銅箱之 再結晶溫度受組成及加工度影響，對於大量包含添加元素 之組成而言軟化溫度變得過高。又，即便銅猪之組成適當， 若加工度過高則會導致常溫軟化’若加工度過低則軟化溫 度變得過高。 除此種因素外，表面粗縫度係因與加工硬化指數不同 之原因而影響彎曲。若表面粗糙度較大，且於銅馆之材 料表面存在缺口狀之心，則進行彎曲時應力集中於缺口 前端，成為斷裂之原因。 根據此種事由，本發明之實施形態之銅箔的壓延平行 方向之表面⑽度R4(M 以下。其理由在於，若表 面粗糙度Ra超過(M ，則於彎曲銅箔時，容易以表面 之凹ώ為起點產生破裂（斷裂）。由壓延而形成於銅落表 面之被稱作油坑之凹陷係於壓延直角方向上形成伸長之槽 狀，故表面粗糙度係於壓延平行方向上進行測定。Ra係依 照 JIS( japanese Industrial Standards，日本工業標準 而經測定之算術平均粗糙度。 作為將銅箔之壓延平行方向之表面粗糙度Ra調整至 0.1 以下之方法，可舉出對最後冷壓延之最後3道次中 8 201124269 之^膜f量進行調整者。具體而言，將最後冷壓延之最後 C之4 2道人之油膜當量設為25000以下，將最後道次 之⑴1逼-人之’由膜當量設為3〇〇〇〇以下將最後道次之油 膜當量設為35000以下。 〜再者，右材料厚度變薄則油膜當量有增大之傾向，故 最後3道人之油膜當量之值逐漸增大。因此，針對各個厚 度不同，最後3道次’必須設定適當之油膜當量。 於最後冷壓延中，若使壓延油黏度及材料降伏應力於 所有道次中為相等’則油獏當量係與（壓延速度）/(咬入 角）旧成比例。若材料厚度變薄則咬入角變小’故存在越接 近取後道次則油膜當量越增大之傾向。又，為確保生產性， 越接近材料長度較長之最後道次越有必要提高壓延速度， 由此亦存在越接近最後道次則油膜當量越增大之傾向。 並且’若於最後冷壓延之中間道次中之材料表面粗糙 ^較高，㈣便於最後道次中將油膜當量抑制至較低亦益 法使材料表面充分地平滑。根據此種事由，而對最後冷壓 延之最後3道次中之油膜當量進行管理。 另-方面’於最後冷壓延中之最《3道次中，若未全 部滿足最後道次之前2道次之油膜當量為25_以下、最 後道次之W道次之油膜當量為3_以下、最後道次之 油膜當量為35_以下於最後3道次之任—道次中油 :當量超過上述值）’則鋼箱之表面變粗輪且壓延平行方 向之表面粗…超過。.〜，會產生以下之不良狀況。 為降低油膜當量，使最後道次之壓延加工度為洲以 201124269 上即可。 再者’上述油膜當量以下式表示。 (油膜當量）={(壓延油黏度、4(rc之動黏度；m) x(壓延速度；m/分）} /{(材料之降伏應力=kg/mm2) 乂 (輥咬入角；rad ) } 可設壓延油黏度為4.0〜8〇 cSt左右，壓延速度為 〜6〇〇 m/分，輥之咬入角為例如0.0005〜0.005 rad，較佳為 0.001 〜0.04 rad 〇 本發明之實施形態之銅箔中，將銅箔以35(rc幼」小時 進行大氣退火後’進㈣延面之X射線繞射時，各個（22〇〕 面及（200)面之強度的積分值（1)之比1(22〇) /1(2〇〇) 較佳為0.H以下。該情形時，㈣中之（22〇)面之比例增 多’且35(TC Χ〇·5小時之退火時銅猪之再結晶會進行，加工 應變會減少而彎曲性提高。 進π使用於本發明之實施形態之銅箔之單面積層樹 脂層’合計厚度為50 Am以下’且寬度為3_以上5 _ 以下之試料’並以銅箱之露出面為外側進彳180度密合贊 曲時’至銅转裂為止曲次數較佳為4次以上。 於銅箱之單面積層樹脂層，合計厚度為5()心以下之 試料係模擬覆銅積層板者，且其⑽度密合變曲之青曲次 數用於對覆銅積層板之彎曲性進行評估。 樹脂層可使用聚醯…聚對苯二甲酸乙二醋 〇卟咖丨_如_加丨价，叩丁）；環氧樹脂、§分酿樹脂 等熱固性樹脂；及飽和聚醋樹脂等之熱塑性樹脂，但並不 10 201124269 二Γ # x ’亦可將溶劑+溶解有該等樹脂層成分而 成之清漆（例如雙酿J5 +此 * 之則驅物即聚醯胺酸溶液）塗佈 於銅泊之早面並加埶，藉 ^ ^ , … 除去洛劑而使得反應（例如醯 亞胺化反應）進行而使其硬化。 18 0度达、合彎曲係以折痕平行於自身之寬度 式折回試料，丨以手Μ機反覆壓扁而進行。並且，: 顯微鏡觀察彎曲邱夕立，丨工a μ %干 H ip之剖面之銅猪部分有無斷裂。若 裂，則打開密合彎曲接夕4 Μ + ’’’、斯 叙_，且使用手壓機使其伸展為 -於同-部位再次折回並以手壓機壓扁。如此， 求出直至銅箔斷裂為止之彎曲次數。 本發明之實施形態之銅箔之組成較佳 鋼（均由JIS-H3l〇〇m 銅或精 ““ ）構成。又’亦可於上述無氧銅或 精銅中含有合計500質量 一 負罝PPm以下之由Ag及Sn組成之群 卩上。於本發明之實施形態之㈣中，#添加 及仏組成之群之1種以上超過合計_質量PPm ’則存在 再結晶溫度過度升高’ I CCL製造步驟之熱處 變得不充分之情形。 丫丹、，口日日 本發明之覆銅積層板係將上述之銅箱積層於 層之至”面而成。本發明之實施形態之銅箱之靑曲，二 異，故採用其之覆銅積層板之彎曲性亦優異。例如， 明之覆銅積層板可適宜地使用於以半徑5 _以 ， 〜180度之用途。 T % 實施例 熔解無氧鋼或精銅（Jis H3100)，且視需要以表i中 11 201124269 所不之量添加Ag、Sn而進行鑄造，從而製作鑄錠。對鑄錠 進行熱壓延後，適當地重複冷壓延及退火而製作銅箔。為 调整軟化溫度’使最後冷壓延時之總加工度為8 5 %以上， 且為降低表面粗糙度，使用表面平滑（輥軸方向上Ra$ 〇. i V m)之輥進行最後冷壓延，而製造銅箔。於壓延油黏度為 4.0 8.0 cSt左右、壓延速度2〇〇〜600 m/分、輥之咬入角 0.003〜〇.〇3 rad之範圍内進行調整，使最後冷壓延之最後3 道-人中之油膜當量之任一者均為35000以下。 <加工硬化指數> 將所獲得之銅箔分別以2〇(TCx〇.5小時及35(TCx0.5小 時進打大氣退火後’進行拉伸試驗（依照ns_Z2241 )，求 出加工硬化指數。再者’必須使用材料經降伏後之均勻伸 長及應力來求出加工硬化指數，故使用自伸長2%至最大應 力點為止之值。而且，以最小平方法使根據所測定之伸長 及應力求出之真應變與真應力的雙對數曲線近似，根據曲 線之斜率而求出加工硬化指數。真應變與真應力係藉由以 下之式而求出。 [真應變]=In ( 1 + [應變]) [真應力]=(1 + [真應變χ[應力] <半軟化溫度> 將所獲得之銅箔分別以1 〇〇〜4〇〇〇c χ〇 5小時進行大氣 退火後進行拉伸拭驗’求出對應於熱處理條件之強度（拉 伸強度）。將退火後之強度TSh為壓延完成時（退火前） 之強度TSasroll與已完全軟化之狀態之強度TSanneal之平 12 201124269 均值的退火溫度設為半軟化溫度。 • <覆銅積層板之彎折次數> 其次，於所獲得之銅猪之單面，以鑄膜法將厚度約2〇 之聚醯亞胺層製膜，而製作單面ccl。具體而言對 所獲得之銅箱之單面進行化學處理（電鑛），且於該面以 厚j成為20 之方式塗佈聚醯亞胺樹脂之前驅物清漆 (于。卩興產製U-清漆A)。其後，於設定為13(Γ(：之熱風循 環式高溫槽巾乾们〇分鐘’且經2_秒時間逐漸升溫至 35〇°C為止使其硬化（醯亞胺化）而形成樹脂層（聚醯亞胺 層）’從而製作單面CCL。 180度密合彎曲係按照以下順序進行。首先，將該單面 CCL以寬度3.2麵，長度3Qmm且使試驗片之長度方向與 壓延方向平行之方式切出而作為試驗片，以樹脂層面為内 側並使其呈環狀，且以手壓機壓扁後進行i 8〇度密合彎曲。 然後，藉自光學顯微鏡觀察彎曲部之剖面之銅羯部分有無 斷裂。若無斷裂，則打開密合彎曲後之試料，使用手壓機 使其伸展為平坦之後，於同一部位再次折回並以手壓機壓 扁。如此，求出至銅箔斷裂為止之彎曲次數。 <銅箔之滑動彎曲次數> 其次，將所獲得之銅猪以寬度12·7 _、長度麵 且使試驗片之長度方向與壓延方向平行之方式切出而作為 试驗片，且以·。C進行30分鐘加熱而使其再結晶。藉由 圖1所示之IPC (美國印刷電路工業協會，Theinstitute〇fAs a circuit for driving an electronic device such as a digital camera or a mobile phone, a flexible printed wiring board (FPC: Flexible Printed Circuit) or a COF 'chip of flexible circuit is used. The fpc or c〇F is used for a copper-clad copper-clad laminate (CCL) on a single-sided or double-area layer of a resin layer, and a circuit pattern is formed on the copper foil. Further, in order to reduce the size and function of such an electronic device, a method of folding and storing the FPC into a narrow space in the casing is employed. Further, in the case of the COF for the periphery of the liquid crystal display, in order to make the bezel (so-called "edge") thin, the copper wiring of the COF is folded back to the inside of the liquid crystal substrate. However, when the FPC or the COF is folded, there is a problem that the copper foil portion is subjected to a large deformation load and is liable to cause cracking. Therefore, it is revealed that an FPC is formed by an electrolytic copper pig having a columnar copper crystal grain and an elongation of 25 ° C and an elongation of 5% or more, thereby obtaining an FPC in which the wiring pattern is not easily broken (Patent Document 1). . Patent Document 1: 曰本特开2007-3 3 5 541 SUMMARY OF THE INVENTION [Summary of the Invention] First, it is considered that the bending property of the copper foil of CCL· is related to the presence of copper in the 201124269. As disclosed in the patent document i, an electrolytic copper foil having a large elongation is used. However, the inventors of the present invention have found that even if a calendered copper having a large elongation is used, there is a case where the bendability of the CCL is not improved. In other words, the present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a copper-clad laminate which is excellent in the use of a copper-clad laminate. 〃 After inventors of the present inventors, it has been found that, as a factor for improving ccl, 'the important thing is not the elongation of (4) but the work hardening index. To achieve the above object, the copper foil of the present invention has a thickness of 5 to 3 and is rolled in a parallel direction. The rough work degree Ra = <~m, : The work hardening index after annealing for 5 hours is 〇·3 or more. The half softening temperature of the copper box of the present invention is preferably 15 or less. The copper case of the invention is preferably composed of oxygen-free copper or fine copper, or a layer of "4" layered with a thickness of 5 °" and a total thickness of 5. The exposed surface of the falling surface is 180 degrees dense. The number of bends until the steel crack is better than 4 times. In the case of 4 songs, the total cooling force of the last cold press delay to the above copper box is broken. (1) Grab the last 3 passes of the last cold rolling mentioned above and Calendering. Among them, ..." ^ is set to the following conditions. Among them, #4 201124269 is 25000 or less before the last pass, and the oil film equivalent of 1 pass before the last pass is set to 30,000 or less. The oil film equivalent is set to 35,000 or less. Here, after the ingot is subjected to hot rolling, and the copper foil is produced by cold rolling, cold rolling and annealing are alternately performed in cold rolling. Further, the final cold rolling after the final annealing is set to "final cold rolling". In the copper clad laminate of the present invention, the copper foil is laminated on at least one side of the resin layer. According to the present invention, a copper foil excellent in flexibility when used for a copper clad laminate can be obtained. [Embodiment] Hereinafter, a copper foil according to an embodiment of the present invention will be described. Further, the % in the present invention means that the copper of the embodiment of the present invention has a thickness of 5 to 30 #m, and the surface roughness _ of the rolling parallel direction is 未, and is 35 〇t, unless otherwise specified. The work hardening index after annealing for 5 hours is 〇3 or more and 4545 or less. The work hardening index (the relationship between stress and strain is represented by the index η. η value) is approximated by the following equation 1 (n-form of the plastic deformation domain above Holl〇mo). The more difficult it is to have local deformation, the deformation (砗) is broken. In addition, when the material with a high work hardening index is pulled, the more it is processed in the factory. In addition, when a steel-clad laminate is produced by copper drop = medium force: excellent workability 4, and the at least one S of the tantalum layer is evaluated, the work hardening index is considered to be the bendability of 〇3. ^ • The copper foil on the upper part is not easily deformed in the shape of 201124269, and the entire bending part is subjected to deformation, so the copper foil is difficult to be broken. However, the material with a work hardening index exceeding 0.45 is low in strength after annealing and the workability is deteriorated, so it is not suitable. It is used as a copper-clad laminate. Here, the reason why the work hardening index after annealing at 350t for 0.5 hours is defined is because the heating condition when manufacturing the copper-clad laminate is as follows. The resin layer of the laminate is obtained by applying a resin composition to a copper foil and curing it (in the case where the 2 ^ CCL of the carrier layer is not sandwiched between the resin layer and the copper foil). Hardening of the resin. Further, as a factor for improving the bendability of the copper foil, it is considered that the reason why the elongation of the copper enamel is not the elongation of the work hardening index (11 value) is as follows. First, the work hardening index indicates the addition of the material. The value of the hardening behavior, the larger the enthalpy value, the more easily the material has the property of work hardening. Here, when the material is stretched and deformed, it will locally shrink and break, but a material with a larger conversion coefficient will be added. Part of the shrinkage occurs, and the shrinkage portion becomes less deformable. The other part replaces the shrinkage that is not easily deformed. p ' begins to deform. By repeating this step, the material is deformed uniformly. On the other hand, the elongation is an index that does not take into account such a situation, and it is not necessarily a work hardening index. Therefore, the degree of uniform deformation of the material as a whole is not easy. For example, in the drawing process of a material having a thickness, a work hardening is used: 'However, a material such as a thin steel foil is not subjected to a drawing process or the like, so that the work hardening index has not been used as an indicator. Therefore, in the present invention, 6 201124269, considering that if the work hardening index of the copper box is increased, even if the C8 is in the tightness of the bending of the i8 degree, the entire curved portion will be uniformly The deformation is not bent under the occurrence of the fracture. Further, the work hardening index after annealing for 5 hours at TC is preferably 0.3 or more and 0.45 or less. The reason is that the film is used as a resin layer and the film and copper are used. The degree of lamination in the case of three layers of CCL laminated via the subsequent layer is about 200 C. The work hardening index increases due to recrystallization of the copper foil due to heating, so if it is 3 〇t lower than 2 〇〇t When the work hardening index is 〇·3 or more, the work hardening index of 〇·3 or more can be obtained at 35. Further, in order to sufficiently obtain the recrystallized structure in the above annealing, the half softening temperature of the copper pig is preferably 1 50 ° C or less. & As a method of controlling the work hardening index of copper pigs after 35 hours of refracturing for 5 hours, the total processing degree of the final cold press delay is set to 85. %the above. Further, since it is necessary to obtain a recrystallized structure, it is preferable to control the half softening temperature of the copper enamel to be (10) or less. Usually, the recrystallization temperament is determined by the composition and degree of processing of the steel. However, in order to process 0.3 or more, either method can be employed. If the total processing degree of the final cold pressing delay is less than 85%, the degree of processing will decrease and the softening temperature of copper will increase. Therefore, the recrystallization of steel caused by the heating in the production of CCL becomes insufficient, and remains. The tendency to process strain and bend will decrease. In order to improve the flexibility of the copper foil used in the copper clad laminate, in addition to the processing of the petrochemical index, the influence of the surface roughness must also be considered. Here, the important factor for the size of the work hardening index is "the material can eventually be added to 201124269: to what extent." Therefore, in order to make the work hardening index a large value, the material must be in a state of being unprocessed and hardened, that is, a state in which the processing has been removed. For copper drop for CCL, the copper foil must be recrystallized by heat treatment in the ccl manufacturing step. Further, the heat treatment conditions in the CCL manufacturing step depend on the resin's enamel, so the recrystallization temperature of the copper box must conform to the heat treatment conditions. The recrystallization temperature of the copper box is affected by the composition and the degree of workability, and the softening temperature becomes too high for a large amount of the composition containing the added element. Further, even if the composition of the copper pig is appropriate, if the degree of processing is too high, the room temperature softens. If the degree of processing is too low, the softening temperature becomes too high. In addition to this factor, the surface roughness is affected by bending due to the difference in work hardening index. If the surface roughness is large and there is a notch-like center on the surface of the material of the copper pavilion, the stress concentrates on the front end of the notch when bending, which is the cause of the fracture. According to such a case, the surface of the copper foil according to the embodiment of the present invention has a surface roughness (10) of R4 (M or less). The reason is that when the surface roughness Ra exceeds (M, the surface is easily formed when the copper foil is bent. The concave ridge is a rupture (fracture) from the starting point. The depression called the oil sump formed on the surface of the copper drop by calendering forms an elongated groove shape in the direction perpendicular to the rolling direction, so the surface roughness is measured in the parallel direction of the rolling. Ra is an arithmetic mean roughness measured according to JIS (Japanese Industrial Standards, Japanese Industrial Standards.) As a method of adjusting the surface roughness Ra of the rolling direction of the copper foil in the parallel direction to 0.1 or less, the final cold rolling may be mentioned. In the last 3 passes, the amount of film f is adjusted for 8 201124269. Specifically, the oil film equivalent of the last C of the final cold rolling is set to 25000 or less, and the last pass (1) 1 is forced to be human. When the film equivalent is 3 〇〇〇〇 or less, the oil film equivalent of the last pass is set to 35,000 or less. 〜 Furthermore, when the thickness of the right material is thin, the oil film equivalent tends to increase, so the last three people The value of the oil film equivalent is gradually increased. Therefore, for each thickness difference, the last 3 passes 'must set the appropriate oil film equivalent. In the final cold rolling, if the rolling oil viscosity and material lodging stress are equal in all passes 'The oil 貘 equivalent system is proportional to the (calendering speed) / (biting angle). If the material thickness is thin, the bite angle becomes small. Therefore, the oil film equivalent tends to increase as it approaches the subsequent pass. Further, in order to ensure productivity, the closer to the last pass of the material length, the more it is necessary to increase the rolling speed, so that the oil film equivalent tends to increase as it approaches the last pass. And if it is finally cold rolled The surface of the material in the middle pass is rougher and higher. (4) It is convenient to suppress the oil film equivalent to a lower level in the last pass, and the surface of the material is sufficiently smoothed. According to this reason, the last 3 passes of the final cold rolling are performed. In the middle of the last cold rolling, the oil film equivalent of 25 times or less, the last pass of the last pass. The oil film equivalent is 3_ or less, the last pass oil film equivalent is 35_ or less in the last 3 passes - the pass oil: the equivalent exceeds the above value) 'the surface of the steel box becomes coarse and the surface is rolled in parallel direction If the thickness is more than .., the following defects will occur. In order to reduce the oil film equivalent, the final rolling degree can be determined by the state of 201124269. The above oil film equivalent is expressed by the following formula: (oil film equivalent) = {(calendering oil viscosity, 4 (rc dynamic viscosity; m) x (calendering speed; m/min)} /{(material undulating stress = kg/mm2) 乂 (roll biting angle; rad ) } calendering can be set The oil viscosity is about 4.0 to 8 〇 cSt, the rolling speed is ～6 〇〇m/min, and the occlusion angle of the roller is, for example, 0.0005 to 0.005 rad, preferably 0.001 to 0.04 rad, in the copper foil of the embodiment of the present invention. When the copper foil is subjected to atmospheric annealing at 35 (rc) hours, the X-ray diffraction of the (four) extension surface is the ratio of the integral value (1) of each (22) plane and (200) plane (1) 22〇) /1(2〇〇) is preferably 0.H or less. In this case, the ratio of the (22〇) plane in (4) is increased and 35 (the recrystallization of the copper pig is performed during the annealing of TC Χ〇·5 hours, the processing strain is reduced and the bending property is improved. The single-layer resin layer of the copper foil of the embodiment of the invention has a total thickness of 50 Am or less and a sample having a width of 3 mm or more and 5 _ or less, and the outer surface of the copper box is 180 degrees. The number of times of the copper to the copper is preferably 4 or more. In the single-layer resin layer of the copper box, the sample having a total thickness of 5 () or less is a simulated copper-clad laminate, and the (10) degree is tight. The number of changes in the number of bucklings is used to evaluate the bendability of the copper-clad laminate. The resin layer can be used as a polyphthalate...polyethylene terephthalate 〇卟 如 _ _ _ 丨 叩 叩 ; ; ; ; ; ; A thermosetting resin such as an oxygen resin or a styrene resin; and a thermoplastic resin such as a saturated polyester resin, but not 10 201124269 Γ # x ' can also be a solvent + a varnish in which the resin layer components are dissolved (for example, double Brewed J5 + this * is the product of the polyamine acid solution) coated on the copper surface and Shame, by ^ ^, ... Los removed such that the reaction agent (e.g. acyl imidization) proceeds cured. At 18 degrees, the bending system folds back the sample with the crease parallel to the width of the body, and the crepe is repeatedly pressed and crushed by the handcuff machine. Also,: Microscopic observation of the curved Qiu Xili, completed a μ% dry H ip section of the copper pig section with or without fracture. If it is cracked, it is opened and closed, and the hand press is used to stretch it to - and the same portion is folded back again and crushed by a hand press. Thus, the number of times of bending until the copper foil was broken was obtained. The copper foil of the embodiment of the present invention is preferably composed of steel (all of which is composed of JIS-H3l〇〇m copper or fine ""). Further, the above-mentioned oxygen-free copper or refined copper may be contained in a group consisting of Ag and Sn in a total of 500 masses of a minus 罝 PPm. In (4) of the embodiment of the present invention, one or more of the group of #addition and yttrium composition exceeds the total _ mass PPm', and the recrystallization temperature is excessively increased. The heat of the I CCL manufacturing step is insufficient.丫丹,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The laminate is also excellent in flexibility. For example, the copper-clad laminate can be suitably used for a radius of 5 _ to 180 degrees. T % Example of melting oxygen-free steel or refined copper (Jis H3100), and It is necessary to add Ag and Sn in the amount of 11 201124269 in Table i to carry out casting, thereby producing an ingot. After the ingot is hot rolled, the cold rolling and annealing are appropriately repeated to prepare a copper foil. The total workability of the final cold press delay was 85 % or more, and in order to reduce the surface roughness, a copper foil was produced by performing a final cold rolling using a roll having a smooth surface (Ra$ 〇. i V m in the roll direction). Adjust the viscosity of the rolling oil to about 4.0 8.0 cSt, the rolling speed of 2〇〇~600 m/min, and the bite angle of the roll to 0.003~〇.〇3 rad to make the last 3 passes of the final cold rolling. Any of the oil film equivalents is 35,000 or less. <Process Hardening Index ≫ The obtained copper foil was subjected to a tensile test (in accordance with ns_Z2241) at 2 〇 (TCx〇.5 hours and 35 (TCx 0.5 hour after atmospheric annealing), and the work hardening index was determined. The work hardening index is obtained by using the uniform elongation and stress after the material is lowered, so the value from the elongation of 2% to the maximum stress point is used. Moreover, the true strain obtained from the measured elongation and stress is determined by the least square method. Approximate to the double logarithmic curve of true stress, the work hardening exponent is obtained from the slope of the curve. The true strain and the true stress are obtained by the following equation: [true strain] = In ( 1 + [strain]) [true Stress]=(1 + [true strain χ [stress] <semi-softening temperature> The obtained copper foil was subjected to atmospheric annealing at 1 〇〇 to 4 〇〇〇 c χ〇 for 5 hours, and then subjected to tensile inspection. 'Evaluate the strength (tensile strength) corresponding to the heat treatment conditions. The strength TSH after annealing is the strength of the TSasroll at the completion of calendering (before annealing) and the strength of the fully softened state TSanneal flat 12 201124269 Mean annealing temperature setting Is a semi-softening temperature. • < Bending Times of Copper Laminates> Next, on the single side of the obtained copper pig, a polytheneimine layer having a thickness of about 2 Å was formed by a cast film method to produce a single-sided ccl. One side of the obtained copper box was subjected to chemical treatment (electrical ore), and the surface of the obtained copper box was coated with a polyimide varnish (U-varnish A). Thereafter, the resin layer was formed by setting it to 13 (Γ(:), the hot air circulation type high-temperature sump was smashed for a few minutes, and gradually heated to 35 〇 ° C for 2 sec to harden it. (Polyimide layer) 'to make a single-sided CCL. The 180 degree close bending system was carried out in the following order. First, the one-side CCL was cut out as a test piece with a width of 3.2 mm and a length of 3 mm and the longitudinal direction of the test piece was parallel to the rolling direction, and the inside of the resin layer was formed into a ring shape and pressed by hand. After the machine is flattened, it is subjected to i 8 twist tight bending. Then, the portion of the copper beak of the section of the curved portion was observed by an optical microscope for the presence or absence of breakage. If there is no break, the sample after the close bending is opened, and after being flattened by a hand press, it is folded back again at the same portion and flattened by a hand press. Thus, the number of times of bending until the copper foil was broken was obtained. <Number of sliding bending of copper foil> Next, the obtained copper pig was cut out as a test piece with a width of 12·7 _ and a length surface so that the longitudinal direction of the test piece was parallel to the rolling direction, and ·. C was heated for 30 minutes to recrystallize. By the IPC shown in Figure 1 (American Institute of Printed Circuit Industry, The Institute 〇f
Panted Circuits )滑動變曲裝置對其進行π滑動靑曲次數 13 201124269 之測定。該裝置係將振動傳遞構# 3結合於振盈驅動體4 之構造，且試驗片1係於箭頭所示之螺釘2之部分與3之Panted Circuits) The sliding buckling device measures the number of π sliding distortions 13 201124269. The device is configured to couple the vibration transmission structure #3 to the vibration drive body 4, and the test piece 1 is attached to the portion of the screw 2 and the arrow 3 shown by the arrow.
前端部之共計4點處固定於^ . A 处口疋於裝置。若振動部3上下驅動， 則s式驗片1之中間部以；^ 1 + ^ 預疋之曲率半徑r彎曲為髮夾狀。本 試驗中，求出按照以下條件 你1干更複，考曲時之直至斷裂為止之 次數。 二===動行程:2一振動速度 < I ( 220 ) /1 ( 200 ) > 將所獲得之銅落以35『C XG.5小時進行大氣退火後，進 行壓延面之X射線繞射’分別求出（22〇)面及（2〇〇)面 之繞射峰值強度之積分值（I)。 1表示所獲得之結果。再者，於表1之組成中，OFC 及TPC分別矣-aA total of 4 points at the front end are fixed at ^. A is at the device. When the vibrating portion 3 is driven up and down, the intermediate portion of the s-type test piece 1 is bent into a hairpin shape by the curvature radius r of the ^1 + ^ pre-twist. In this test, the number of times you have completed the test and the time until the break is detected according to the following conditions. Two ===moving stroke: 2 - vibration speed < I ( 220 ) /1 ( 200 ) > After the obtained copper is subjected to atmospheric annealing at 35 "C XG. 5 hours, X-ray winding of the calendering surface is performed. The integral value (I) of the diffraction peak intensity of the (22 〇) plane and the (2 〇〇) plane is obtained by respectively. 1 indicates the result obtained. Furthermore, in the composition of Table 1, OFC and TPC are respectively 矣-a
, 不無氧銅及精銅（JISH3100)，Agl00ppmTPC 係表不於精鋼中添力口 100質量ppm之Ag者。 14 彎折 次數 寸 00 Ο 寸 寸 卜 〇 (N 一 (N <Ν — — 滑動彎 曲次數 35000 60000 : 85000 65000 50000 45000 40000 40000 1 88000 30000 45000 80000 80000 80000 50000 35000 斷裂伸長 (%) 18.2 (Ν οο 00 14.5 16.6 — 27.5 19.4 寸 〇〇 21.0 12.3 1(220)/1(200) 0.06 0.00 0.00 0.00 0.01 0.11 0.06 0.00 0.38 0.06 0.13 0.00 0.00 0.01 11.67 0.20 半軟化溫度 (°C) _ί 3 5 Ό § 丨322 〇〇 (N 卜 <N 油膜當量 最後 道次； 34000 24000 20000 22000 25000 13000 24000 20000 18000 1 38000 33000 34000 34000 22000 23000 18000 最後道次 之前丨道次i 30000 28000 29000 28000 27000 10000 17000 15000 00 35000 30000 32000 29000 28000 27000 14000 ^ 靶_ π 23000 12000 12000 13000 14000 15000 15000 13000 12000 26000 22000 15000 28000 15000 17000 10000 最後冷壓延 靶Η 29.0 29.0 27.0 27.0 27.0 27.0 27.0 27.0 25.0 21.0 27.0 27.0 27.0 29.0 27.0 27.0 總加工度 (%) 88.7 98.9 98.9 99.4 99.4 96.7 98.9 96.7 91.0 92.0 83.0 99.4 99.4 83.0 83.0 83.0 Ra (βτη) 0.07 0.08 0.08 0.08 0.07 0.07 0.09 0.06 0.05 0.14 0.07 0.15 0.11 0.08 0.08 0.07 η值 200°C -0.5h ； 1 0.30 0.31 0.33 0.44 0.30 1 0.25 1 1 0.32 0.27 0.33 0.32 0.25 1 0.17 350〇C -0.5h 0.31 0.32 0.34 0.42 0.32 0.30 0.30 0.32 0.17 0.32 0.28 0.31 1 0.30 0.27 0.21 0.28 組成 TPC u α. Η Ε α a ο υ α. Η ε α α 〇\ U α. Η ε α § Ό\ "οό Ο 〇Η ε α ο m U IX Ο £ α α ο *3 U u. 〇 ε a 1 i 屋 〇 U U, 〇 ε 屋 , i TPC TPC U CL Η Ε α σ\ "ci U 1 U a. E a a Q\ u a. 〇 E a ^Q. o to 00 U u. 〇 E 屋 o 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 I實施例7 實施例8 1比較例ί 比較例2 |比較例3 比較例4 |比較例5 比較例6 比較例7 比較例8 201124269 可明確，於半軟化溫度為15(TC以下，壓延平 根據表 1 β m，且以350°C進行〇.5小 0.3以上之實施例1〜8之情形 行方向之表面粗糙度Ra 時退火後之加工硬化指數為 時，進行180度密合彎曲時1曲次數為4次以上，蠻曲 性優異。 另-方面’最後冷壓延時之總加工度未滿85%之比較 例3、6、7 ' 8之情形時’以35(rc進行〇 5小時退火後之 加工硬化指數未滿0.3，進行18〇度密合彎曲時之彎曲次數 未滿4人，聲曲性劣化。再者，於比較例1之情形時，因 銅箔中Sn之添加量超過5〇〇質量ppm，故半軟化溫度超過 150°C，且加工硬化指數未滿〇 3。 又，於半軟化溫度超過15〇。(：之比較例1、7、8之情形 時，以350t進行0.5小時退火後之加工硬化指數未滿〇 3， 進行1 80度密合彎曲時之彎曲次數未滿4次，彎曲性劣化。 於作為最後冷壓延之最後3道次中之油膜當量，最後 道次之前2道次之油膜當量超過25〇〇〇，最後道次之前}道 -人之油膜當量超過30000，且最後道次之油膜當量超過 3 5000之比較例2之情形時，壓延平行方向之表面粗糖度, non-oxygen-free copper and refined copper (JISH3100), Agl00ppmTPC is not added to the 100% by mass of Ag in the steel. 14 Bending times 00 Ο Inch inch dip (N one (N < Ν - Sliding bending times 35000 60000 : 85000 65000 50000 45000 40000 40000 1 88000 30000 45000 80000 80000 80000 50000 35000 Elongation at break (%) 18.2 (Ν οο 00 14.5 16.6 — 27.5 19.4 inch 〇〇 21.0 12.3 1(220)/1(200) 0.06 0.00 0.00 0.00 0.01 0.11 0.06 0.00 0.38 0.06 0.13 0.00 0.00 0.01 11.67 0.20 Semi-softening temperature (°C) _ί 3 5 Ό § 丨322 〇〇(N 卜<N oil film equivalent last pass; 34000 24000 20000 22000 25000 13000 24000 20000 18000 1 38000 33000 34000 34000 22000 23000 18000 Last pass before ramp i 30000 28000 29000 28000 27000 10000 17000 15000 00 35000 30000 32000 29000 28000 27000 14000 ^ Target _ π 23000 12000 12000 13000 14000 15000 15000 13000 12000 26000 22000 15000 28000 15000 17000 10000 Final cold rolling target Η 29.0 29.0 27.0 27.0 27.0 27.0 27.0 27.0 25.0 21.0 27.0 27.0 27.0 29.0 27.0 27.0 Total processing ( %) 88.7 98.9 98.9 99.4 99.4 96.7 98.9 96.7 91.0 92.0 83.0 99.4 99.4 83.0 83.0 83.0 Ra (βτη) 0.07 0.08 0.08 0.08 0.07 0.07 0.09 0.06 0.05 0.14 0.07 0.15 0.11 0.08 0.08 0.07 η value 200°C -0.5h ; 1 0.30 0.31 0.33 0.44 0.30 1 0.25 1 1 0.32 0.27 0.33 0.32 0.25 1 0.17 350〇C -0.5h 0.31 0.32 0.34 0.42 0.32 0.30 0.30 0.32 0.17 0.32 0.28 0.31 1 0.30 0.27 0.21 0.28 Composition TPC u α. Η Ε α a ο υ α. Η ε α α 〇 \ U α. Η ε α § Ό\ " Οό Ο 〇Η ε α ο m U IX Ο £ α α ο *3 U u. 〇ε a 1 i 〇 UU, 〇ε屋, i TPC TPC U CL Η Ε α σ\ "ci U 1 U a E aa Q\ u a. 〇E a ^Q. o to 00 U u. 〇E house o Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 I Example 7 Example 8 1 Comparative Example ί Comparative Example 2 | Comparative Example 3 Comparative Example 4 | Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 8 201124269 It is clear that the semi-softening temperature is 15 (TC or less, and the rolling is flat according to Table 1 β m, and When the surface roughness Ra of the row direction is 0.5 at a temperature of 350 ° C, the surface hardness of the row direction is Ra, and the work hardening index after annealing is 180 degrees. Number 4 or more times, quite excellent music. On the other hand, in the case of Comparative Example 3, 6, and 7 '8, the total processing degree of the final cold-pressing delay is less than 85%, and the work hardening index after annealing for 5 hours at rc is less than 0.3, and 18 is performed. In the case of Comparative Example 1, the amount of Sn added in the copper foil exceeds 5 〇〇 mass ppm, so the semi-softening temperature exceeds 150 ° C, and the work hardening index is less than 。 3. Also, the semi-softening temperature exceeds 15 〇. (: In the case of Comparative Examples 1, 7, and 8, the work hardening index after annealing at 350 t for 0.5 hours is not full. 〇3, the bending time is less than 4 times when the 1 80-degree close bending is performed, and the bendability is deteriorated. The oil film equivalent of the last 3 passes as the last cold rolling, the oil film equivalent of 2 passes before the last pass exceeds 25 〇〇〇, before the last pass, when the oil film equivalent of the human-to-human is more than 30,000, and the oil film equivalent of the last pass exceeds 35,000, the surface roughness of the surface in the parallel direction is calendered.
Ra超過〇. 1以m’進行1 8〇度密合彎曲時之彎曲次數未滿4 次，彎曲性劣化》 於最後冷壓延之最後3道次中之油膜當量之中，最後 道次之前1道次之油膜當量超過30000之比較例4之情形 時’壓延平行方向之表面粗糙度Ra超過〇.1 μ m，進行18〇 度密合彎曲時之彎曲次數未滿4次，彎曲性劣化。 16 201124269 於最後冷壓延之最後3道次中之油膜當量之中’最後 道次之前2道次之油膜當量超過25000之比較例5之情形 時，亦為壓延平行方向之表面粗糙度Ra超過0.1 "m，進 行1 80度密合彎曲時之彎曲次數未滿4次，彎曲性劣化。 再者，可知於比較例1〜8之情形時，先前之彎曲性之 sf·估即ipc滑動彎曲次數亦與各實施例相同’於滑動膏曲 試驗中無法評估覆銅積層板之彎曲性。 【圖式簡單說明】 圖1係表示採用IPC滑動―曲裝置之滑動彎曲方法之 圖。 【主要元件符號說明】 1 試驗片 2 螺釘 3 振動傳遞構件 4 振盪驅動體 Γ 曲率半徑Ra exceeds 〇. 1 The number of bends in the case of 18's tight bending is less than 4 times, and the bending property is deteriorated. Among the oil film equivalents in the last 3 passes of the last cold rolling, before the last pass 1 In the case of Comparative Example 4 in which the oil film equivalent of the pass exceeds 30,000, the surface roughness Ra in the rolling parallel direction exceeds 〇1 μm, and the number of bendings when the 18-degree tight bending is performed is less than four times, and the bendability is deteriorated. 16 201124269 In the case of the comparative example 5 of the oil film equivalent of the last 3 passes of the last cold rolling 'the oil film equivalent of 25000 before the last pass, the surface roughness Ra of the rolling parallel direction is more than 0.1. "m, the bending time is less than 4 times when the 180-degree tight bending is performed, and the bending property is deteriorated. Further, it is understood that in the case of Comparative Examples 1 to 8, the sf of the previous bendability is estimated to be the same as that of the respective embodiments. The bendability of the copper clad laminate cannot be evaluated in the sliding paste test. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a sliding bending method using an IPC sliding-curve device. [Explanation of main component symbols] 1 Test piece 2 Screw 3 Vibration transmission member 4 Oscillating drive body 曲率 Radius of curvature
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