201200606 六、發明說明： 【發明所屬之技術領域】 本發明_於-種適μ各種電子零件之析出硬 銅s金即Cu~Co—Si系合金板，Β 勻附荖柯“ 域纟其疋關於-種鍍敷之均 勾附者’生優異之Cu-C〇-Si系合金板。 【先前技術】 等各開關、繼電器、接腳，、引線框架 …強： 使用之電子材料用鋼合金而言，要求 ^強度及高導電性（或導熱性）作為基本特性。近年 此對應I零件之南積體化及小型化、薄壁化急速發展，斑 漸提:'，對用於電子機器零件之銅合金之要求水準亦逐 合金，:t度及呵導電性之觀點而言，作為電子材料用銅 :磷主枘硬化型之銅合金的使用量逐漸増加，而代替以 型二Γ黄鋼等所代表之固溶強化型銅合金。析出硬化 處理、微料由對經固溶處理之過飽和固溶體進行時效 減少銅中之固田、Γ斤出物均句分散，讓合金強度變高，同時 彈性等機械性=量，提升導電性。因此，可獲得強度、 I優異，且導電性、導熱性良好之材料。 金之硬化型鋼合金之中’通常被稱作卡遜（corson)系合 系銅合金係兼具較高之導電性、強度及臂曲加 ϋί Τ生 >/JU ^ _ 鋼σ金，且係業界如今積極開發之合金之 。该鋼合今， 4 屬間化合物粒子由使銅基質中析出微細之N1—S1系金 于’而謀求強度與導電率之提高。 201200606 為了進一步提高卡遜合金之特性，正在進行下述各種 技術開發：添加除了 Ni及Si以外之合金成分 '排除對特性 造成不良影響之成分、結晶組織之最佳化、析出粒子之最 佳化等。例如，已知有藉由添加Co或控制母相中析出之第 二相粒子而提高特性，可列舉如下者來作為Ni _ si _ 系 銅合金之最近之改良技術。 於曰本特表2005 — 5 32477號公報（專利文獻丨）中， 為了得到彎曲加工性、導電率、強度及抗應力鬆弛性優異 之Nl—Si—C〇系銅合金’亦記載有控制Ni、Si、Co量及 其相互關係’及關於20 μ m以下之平均結晶粒徑。而且， 於其製造步驟中，特徵在於第一時效退火溫度高於第2時 效退火溫度（段落0045〜0047 )。 於曰本特開2007- 169765號公報（專利文獻2)中， 為了 k冋Ni ~ si — C〇系銅合金之彎曲加工性，而控制第2 相粒子之分佈狀態，抑制晶粒之粗大化。於該專利文獻中， 對於於卡遜合金中添加了鈷之銅合金，可明瞭具有抑制高 溫熱處理中之晶粒之粗大化之效果的析出物及其分佈狀態 之關係’且藉由控制結晶粒徑而提高強度、導電性、應力 緩和特性、彎曲加工性（段落0 0 1 6 )。結晶粒徑越小越佳， 藉由使結晶粒徑為1 〇以m以下而提高彎曲加工性（段落 0021 )。 曰本特開2008 — 248333號公報（專利文獻3)中揭示 有一種抑制Ni — Si — Co系銅合金中之粗大之第二相粒子之 產生的電子材料用銅合金。於該專利文獻中認為若藉由於 201200606 特定之條件下進杆也 ,、'、產延及固溶化處理，而抑制_ & $第 二相粒子之產生 仰制粗大之第 現目標之優異之特性（段落0012)。 專利文獻1 :曰士 4士 ± 日本特表2005- 532477號公報 專利文獻2 .日本特開2007- 169765號公報 專利文獻3 .日本特開2008- 248333號公報 【發明内容】 ":二連接器、開_ '繼電器、接腳、端子、引線框 …種電子零件中所使用之電子材料用鋼合金板多實施 鍍 Au，於此情形時，一 ^ ^ ^ ^ ^ 奴貫鈀鍍Νι作為基底。該Ni基底 錄敷«料年來零件之輕量化、薄壁化㈣㈣薄。 於疋&7未成為問題之鑛…之不良’具體而言為明 顯化鍍Ni局部不均勻地附著之不良。 "述專利文獻1〜3中記載之銅合金雖皆有記載其結晶 ，徑’但完全未意識到深度方向之結晶粒徑之木均，尤其 是形成於表面之粗大結晶與鍍敷之附著性之關係。 本發明之課題在於提供一種基底鍍敷、盆 附著錢NkCu - Co—Sl系合金板。 本發明人為了解決上述課題而反覆進行研究，結果可 知於Cu —Ni—si系合金板中’藉由將Ni替換為c〇而形成 Cu — Co—Sl系合金，可追求進一步之改善與基底鍍敷之密 接性。進而，發現該Cu _ c〇 _ Si系合金板之表層之結晶粒 徑比内部（板厚中心）之結晶粒徑易局部性粗大化，且由 於表面存在粗大化結晶，故即便整體之平均結晶粒徑較 小’亦導致鍍敷（均勻附著）性降低。本發明具有下述構 201200606 成0 ⑴-種電子材料用鋼合金板，其係含有c〇.〇5〜 3.0 質量％、Si : ^ 0,5 .U質量％，以及剩餘部分由Cu及不 可避免之雜質所構成，其柘甩士 肷*板厚中心之平均結晶粒徑為2 —201200606 VI. Description of the Invention: [Technical Fields of the Invention] The present invention is a Cu~Co-Si alloy plate which is deposited on various electronic components, and is uniformly coated with a Cu~Co-Si alloy plate. About Cu-C〇-Si alloy plate which is excellent in the plating of all kinds of plating. [Prior Art] Switches, relays, pins, lead frames, etc. Strong: Steel alloy for electronic materials used In addition, in recent years, the strength and high electrical conductivity (or thermal conductivity) are required as basic characteristics. In recent years, the south of the I-parts has been developed, and the miniaturization and thin-walled development have been rapidly developed. The required level of copper alloy of the parts is also alloy-by-alloy: from the viewpoint of t-degree and conductivity, the use of copper as a copper material for the electronic material is gradually increased, instead of the type II A solid solution-strengthened copper alloy represented by steel, etc. The precipitation hardening treatment and the micro-material are caused by the aging treatment of the solution-treated supersaturated solid solution, and the solidification of the solid and the powder in the copper are dispersed to make the alloy strength change. High, at the same time elastic and other mechanical = amount, lifting guide Therefore, a material having excellent strength and I and excellent electrical conductivity and thermal conductivity can be obtained. Among the hardened steel alloys of gold, 'usually called a corson-based copper alloy, which has a high electrical conductivity. Sex, strength and buckling ϋ Τ & & / / / / / / / / / / / / / / / / / / / 钢 钢 钢 钢 钢 钢 钢 钢 , 钢 钢 , , 钢 钢 钢 钢 , , , 钢 钢 钢 钢 钢 钢 钢 钢 钢 钢 钢 钢In order to further improve the characteristics of the Caston alloy, the following various technologies are being developed: adding alloy components other than Ni and Si to eliminate components that adversely affect characteristics. The optimization of the crystal structure, the optimization of the precipitated particles, etc. For example, it is known to increase the characteristics by adding Co or controlling the second phase particles precipitated in the matrix phase, and the following can be cited as Ni _ si _ A recent improvement technique of copper alloys. In order to obtain Nl-Si excellent in bending workability, electrical conductivity, strength, and stress relaxation resistance, U.S. Patent No. 2005-5382 (Patent Document No.) -C-based copper alloys are also described as controlling the amount of Ni, Si, Co and their relationship' and the average crystal grain size below 20 μm. Moreover, in the manufacturing step, it is characterized by a high first aging annealing temperature. In the second aging annealing temperature (paragraph 0045 to 0047), in the Japanese Patent Publication No. 2007-169765 (Patent Document 2), the bending processability of the k冋Ni ~ si - C〇 copper alloy is controlled. The distribution of the two-phase particles suppresses the coarsening of the crystal grains. In this patent document, it is known that the copper alloy to which cobalt is added to the Carson alloy has the effect of suppressing the coarsening of crystal grains in the high-temperature heat treatment. The relationship between the substance and its distribution state', and by controlling the crystal grain size, the strength, conductivity, stress relaxation property, and bending workability are improved (paragraph 0 0 16). The smaller the crystal grain size, the better, and the bending workability is improved by setting the crystal grain size to 1 〇 or less (paragraph 0021). Japanese Laid-Open Patent Publication No. 2008-248333 (Patent Document 3) discloses a copper alloy for an electronic material which suppresses generation of coarse second phase particles in a Ni—Si—Co-based copper alloy. In this patent document, it is considered that if the rod is also subjected to the specific conditions of 201200606, the 'production delay and the solution treatment, the suppression of the generation of the second phase particles is superior to the coarse target. Characteristics (paragraph 0012). [Patent Document 1] 曰 4 ± 日本 日本 日本 日本 日本 日本 日本 2005 2005 2005 2005 2005 2005 2005 2005 : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : , _ 'relay, pin, terminal, lead frame...The electronic material used in the electronic parts is mostly plated with Au. In this case, a ^ ^ ^ ^ ^ is used as a palladium-plated Ν Substrate. The Ni substrate is recorded as "lightweight and thin-walled (4) (four) thin parts. The defect that Yu Yu & 7 has not become a problem is specifically a defect in which the Ni plating is unevenly adhered. "The copper alloys described in Patent Documents 1 to 3 have crystals whose diameter is 'but are not recognized at all in the depth direction, especially the coarse crystals formed on the surface and the adhesion of plating. The relationship between sex. An object of the present invention is to provide a base plating and a pot-attachment NkCu-Co-Sl alloy sheet. In order to solve the above problems, the present inventors have conducted research on the above-mentioned problems, and as a result, it has been found that in the Cu—Ni—Si-based alloy sheet, a Cu—Co—Sl-based alloy is formed by replacing Ni with c〇, and further improvement and substrate can be pursued. Plating adhesion. Further, it has been found that the crystal grain size of the surface layer of the Cu_c〇_Si-based alloy sheet is more locally coarser than the crystal grain size of the inside (thickness center), and since the surface has coarsened crystals, even the overall average crystallizes. A smaller particle size also results in a decrease in plating (uniform adhesion). The present invention has the following structure 201200606 into 0 (1) - a steel alloy plate for electronic materials, which contains c〇.〇5~3.0% by mass, Si: ^0,5.U% by mass, and the remainder is Cu and not The impurities are avoided, and the average crystal grain size of the center of the gentleman's plate is 2
以下，接觸於表面且長徑A 瓦L马45 y m U上之晶粒相對於壓延 方向長度1 mm為5個以下。 ⑺如（1)之電子材料用銅合金板，其進而含有最 多0.5質量％之Cr。 ((1)或（2)之電子材料用銅合金板，其進而 含有總計最多2.0質量％之選自由Mg、p ' As、^、^、B、Hereinafter, the crystal grains which are in contact with the surface and have a long diameter of A watts of 45 y m U are 5 or less with respect to the length of the rolling direction of 1 mm. (7) The copper alloy sheet for an electronic material according to (1), which further contains at most 0.5% by mass of Cr. (1) or (2) a copper alloy plate for an electronic material, which further contains a total of at most 2.0% by mass selected from the group consisting of Mg, p'As, ^, ^, B,
Sn Τι ' Zr、A卜Fe ' Zn及Ag所組成之群中之i種 或2種以上。 (4) 一種電子材料用銅合金板之製造方法係製造如 (1)至（3)中任一項之電子材料用銅合金板，其包含依 序進行如下步驟： 溶解鎮造鎮鍵之步驟； 將材料溫度設為950。(：以上且105(TC以下並加熱1小 時以上後，進行熱壓延，熱壓延結束溫度為7〇(rc以上之步 驟； 以8%以上之加工度進行最終道次之固溶化前之中間壓 延步驟； 將材料溫度設為850°C以上且1050°C以下並加熱0.5分 知〜1小時之中間固溶化步驟； 以4001以上且600°C以下進行加熱之時效步驟；及 6 201200606 加工度為10〜50%之最終壓延步驟。 【實施方式】 (1 ) Co及Si之添加量 所添加之Co及Si係藉由實施適當之熱處理而於銅合 金内形成金屬間化合物，且即便存在除銅以外之添加元素 亦不會使導電率劣化’藉由析出強化效果而實現高強度化。 於Co及Sl之添加量分別為& :未達〇 5質量％、Si : 未達〇·ι質量％時，無法獲得所期望之強度。相反，於c〇: 超過3.0質量％、si :超過1〇質量％時，雖然可實現高強 度化仁導電率顯著下降，進而熱加工性劣化。因此，將 Co及Si之添加量設為c〇: 〇 5〜3 〇質量％、si : 〇 Η 〇 質量％。Co及Sl之添加量較佳為c〇 : 〇 5〜2 〇質量％、s(: 0 · 1〜0.5質量％。 、Cr之添加量 二係於溶解鎮造時之冷卻過程中優先析出於結晶 .^ , 热加工時不易產生裂痕，而 抑制1k時之產率降低。 M w ㈣固〜化處理等對炼解 拉界析出之Cr進行再固溶，於接下來之時效析 作為主成分之bcc結構之析出粒子或… “勿（矽化物）。於通常之Ni—Si系 、 量中，無助於時效析出之s y中’所添加之 存，從而成為導電車降供〉谷於母相中之狀態而 化物形成元素之使無助於時效析出之加作為 進-步析出’可降低固溶 纟為石夕化物 從而可在不損害強度下 201200606 止導電率下降。然而，若Cr濃度超過〇5質量％，則由於 易形成粗大之第二相粒子，故而損害製品特性。因此，於 本發明之CU-CO - Sl系合金令，最多可添加〇5質量％之Any one or two or more of the group consisting of Sn Τι ' Zr, A, Fe ' Zn and Ag. (4) A method for producing a copper alloy sheet for an electronic material, which comprises the step of producing the copper alloy sheet for an electronic material according to any one of (1) to (3), comprising the steps of: dissolving the town bond; ; Set the material temperature to 950. (: above and above 105 (TC below and heating for 1 hour or more, hot rolling, hot rolling end temperature is 7 〇 (rc or more; before the final pass of solid solution with a processing degree of 8% or more) Intermediate calendering step; an intermediate solutionizing step of setting the material temperature to 850 ° C or higher and 1050 ° C or lower and heating 0.5 to 1 hour; aging step of heating at 4001 or more and 600 ° C or less; and 6 201200606 processing The final calendering step is 10 to 50%. [Embodiment] (1) Co and Si added by the addition amount of Co and Si are formed into an intermetallic compound in a copper alloy by performing appropriate heat treatment, and even if present The addition of elements other than copper does not deteriorate the conductivity. The strength is increased by the precipitation strengthening effect. The addition amount of Co and Sl is &: not more than 5 mass%, Si: not up to When it is 1% by mass, the desired strength cannot be obtained. Conversely, when c〇: more than 3.0% by mass and si: more than 1% by mass, the electrical conductivity of the high-strength temper is remarkably lowered, and the hot workability is deteriorated. Therefore, adding Co and Si The amount is set to c〇: 〇5~3 〇 mass%, si: 〇Η 〇 mass%. The addition amount of Co and Sl is preferably c〇: 〇5~2 〇 mass%, s(: 0 · 1~0.5 The mass %. and the addition amount of Cr are preferentially precipitated in the cooling process during the cooling process. The crack is less likely to be generated during hot working, and the yield is reduced when the temperature is suppressed by 1 k. M w (4) solidification treatment The Cr precipitated in the refining and unwinding is re-dissolved, and then the precipitated particles of the bcc structure as the main component are analyzed as follows: "Do not (deuteride). In the usual Ni-Si system, the amount is not helpful. In the sy precipitated in the sy, the added matter, so that the conductive car drop supply is in the state of the mother phase and the formation of the element does not contribute to the precipitation of the aging as a step-by-step precipitation to reduce the solid solution In the case of the Lixi compound, the electrical conductivity can be lowered without breaking the strength of 201200606. However, if the Cr concentration exceeds 〇5 mass%, the coarse second phase particles are easily formed, thereby impairing the product characteristics. CU-CO - Sl alloy, up to 5% by mass
Cr。然而，於Cr未達〇.〇1質量％時，其效果較小，因 佳為添加讀〜G.5 f量％，更佳為添加0.09〜〇_3質量 (3)第3元素之添加量 °° a) Mg、Mn、Ag及Ρ之添加量 若添加微量之及Ρ，則會改善強度、廣 力緩和特性等之製品特性而不損害導電率。主: 上述Mg、Mn、Ag及Ρ固溶於母相 吏 於母相而發揮添加之效果，伯 亦可藉由使第二相粒子中含右 仁 而㈣、… 有上通MnAg及p固溶 而發揮進-步之效果 '然而，若Mg、Mn、Ag 度超過2.0質量％，則特性 〜遘 改善效果飽和且有損製造性。因 w < HSi系合金板中’較佳為最多添加 總sf 2.0質量〇/0之選自Λ/ί 〜 上。然而，於未達二=:g及”之1種或2種以 、 質里/〇時，其效果較小’因此更佳 為總計添加〇. 〇 1〜2 〇暂 文佳 0.5質吾。/，也， 進而更佳為總計添加〇.02〜 〇八！的是總計添加〇.〇4〜0_2質量％。 b) Sn及Zn之添加量 藉由添加微詈n。 铲敷性耸制。 亦可改善強度、應力緩和特性、 鑛敷性專製品待性Cr. However, when Cr is less than 质量1〇%, the effect is small, because it is better to add ~G.5 f%, more preferably 0.09~〇_3 quality (3) addition of the third element Amount °° a) When a small amount of cerium is added to the amounts of Mg, Mn, Ag, and cerium added, the properties of the product such as strength and broad-running properties are improved without impairing the electrical conductivity. Main: The above Mg, Mn, Ag and sputum are dissolved in the parent phase and exerted the effect of adding to the parent phase. The second phase particles may also contain the right kernel (4), ... and the upper MnAg and p solid In the case where the Mg, Mn, and Ag degrees exceed 2.0% by mass, the characteristic-遘 improvement effect is saturated and the manufacturability is impaired. In the w < HSi-based alloy sheet, it is preferable to add a total of sf 2.0 mass 〇 / 0 which is selected from Λ / ί 〜 . However, when one or two of the two types are used, and the quality is small, the effect is small. Therefore, it is better to add 〇. 〇1~2 〇 文文佳0.5质吾. Further, it is more preferable to add 〇.02~ 〇8 to the total amount of 〇.〇4~0_2% by mass. b) The addition amount of Sn and Zn is added by adding micro 詈n. It can also improve strength, stress relaxation characteristics, and mineralization properties.
Zn固溶於母相 ㈣羊主要藉由使上述Sn及 計超過2.0質量％ 效果。然而，若〜及Zn之總 此，於本發明之：則特性改善效果飽和且有損製造性。因 C〇 Sl系合金板中，最多可添加總計 8 201200606 2.0質二/。之選“n & Zn中之丨種或2種。然而，於未 〇.〇=。質量％時，其效果較小，因此較佳為總計添加_〜2 〇 質1 %，更佳為總計添加〇5〜丨〇質量％。 〇 As、Sb、Be、B、Tl、Zr、A1/Fww 對於AS、Sb、Be、B、Ti、Zr、八丨及以而言，亦藉 根據所要求之製品特性來調整添加量，而改善導電率：強 度、應力緩和特性、鍍敷性等製品特性。主要藉由使 As、Sb、Be、B、Ti、7r、δ 1 b c 迷 A1及Fe固溶於母相而發揮添加 之效果’但亦可藉由使第二相粒子中含有上述AH〜、 B、Ti、Zr、A1及Fe，或形成新組成之第二相粒子而發揮進 -步之效果。然而，若該等元素之總計超過2 〇質量％，則 特性改善效果飽和且有損製造性。因此，於本發明之 C〇—Si系合金板中，最多可添加總計2 〇質量％之選自A。 Sb、Be ' B、Ti、Zr、Ai及Fe中之i種或2種以上。然而S， 於未達0.001質量％時，其效果較小，因此較佳為總計添加 0.001〜2.0質量％，更佳為總計添加心㈦〜丨〇質量％。 〇 若上述 Mg、P、As、Sb、Be、b、Mn、Sn、Ti、 A卜Fe、Zn及Ag之添加量合計超過2.0質量％，則易於損 害製造性’因此較佳為將該等元素之合計設為2 〇質量％以 下’更佳為設為1.5質量％以下，進而更佳為設為i 〇質量 %以下。 (4 )結晶粒徑 先前公知若結晶粒徑較小則可獲得高強度，於本發曰月 中’壓延方向剖面之板厚中心之平均結晶粒徑亦為2〇 V爪 201200606 以下此處，板厚中心之平均結晶粒徑係根據JIS H 05〇 j (斷法）而測疋。本發明之銅合金板之板厚中心之平均 、。日曰粒徑於加工度冑10〜5〇%之最終壓延之前後不發生顯 者之相對變化。因此’若於最終壓延前A 20" m以下之平 句、σ 粒徑則於最終壓延後亦維持較平均結晶粒徑為2〇 ^ 衆本銅5金更微細之結晶構造。因此，即便結晶構造 過於微細而使最線遞证治# & & /丄 成取、、铿延後之平均結晶粒徑於數值上無法正 確地測疋出’亦可藉由將於相同條件下對最終壓延前平均 結晶粒徑為2(^m之樣本進行最終壓延者作為標準並進行 比較，而判斷是否平均結晶粒經超㉟、m。再者，本發明 之「於板厚中心處平均結晶粒徑為…m以下」係用以確 定與先前技術相同之高強度之規定，「板厚中心」係用以表 示測定位置之用語。 於先前技術中，結晶粒徑之不均、尤其是表面之粗大 化結晶並不特別醒目，令缺x 4 士 王然不知表面中之粗大化晶粒會 鑛敷之均句附著性造成不良影響。然而，表層於壓延步驟 中最易積存應變能，且.於通常之製造條件下與内部（板厚 中心）相比，其結晶易局部性粗大化。又，於熱處理步驟 中存在表層與内。p之熱歷程不同之情形，亦存在與内部 (板厚中心）相比結晶局部性袓大化之情形。再。 情形時，此處所謂之「表層」係指距離表面25心圍此 本發明人等發現藉由使Cu〜c〇—以系合金板圍 粗大化之晶粒變少，可獲得錢數均句地附著之電子材钭用 銅合金板。 何衧用 10 201200606 言’接觸於表面且最終壓延後之長徑為^ 上之日日粒相對於壓延方向之長度lmm為5個以下，較佳 為4個以下，更佳為2個 +, . 超過5個，則鍍敷無法 句勻地附者，成為當以肉眼觀窣 態之不良品。 冑察鍍敷表面時產生模糊之狀 又，晶粒個數係於顯微鏡照片（倍率：m〇〇)中 :壓延方向之剖面之表面接觸的45心以上之晶粒之個 數’將晶粒個數除以複數（1〇次）測定視野中之表面之長 度2_㈣之範圍的合計長度而料‘單位。 本發明之銅合金板由於表面中長徑…⑺以上之晶粒 為5個以下，故而鑛敷之均句附著性優異。本發明之銅合 金板可使用各種鍍敷材料’例如可列舉通常用於鍍Au之基 底之A基底鍍敷、或Cu基底鍍敷、鍍以。 關於本發明之鍍敷 自不用說，即便為0.5〜 附著性。 厚度，通常使用之2〜5//m之厚度 2.〇ym之厚度亦表現出充分之均勻 製造方法使用銅合金板中一般的 熱壓延—中間冷壓延—中間固溶 但於其步驟内調整下述條件而製 ，中間壓延、中間固溶化亦可視 (5 )製造方法 本發明之銅合金板之 製造製程（熔解、鑄造〜 化—最終冷壓延—時效）， 造目標之銅合金板。再者 需要重複進行複數次。 〜肌也把I ?工·丨，;|⑺心、〒間广 延、中間固溶化處理之條件。其原因在於，本發明 11 201200606 而第二相粒子之 冷卻速度較大地 於熔解、鑄造步驟中， 得到所期望之組成之溶液。繼而電:銅t、sl、c。等她 於其後之熱麗延中必須進二將此熔液鑄造成鑄錠。 除铸造中產… 的熱處理，且儘可能地去Zn is solid-solubilized in the mother phase. (4) The sheep mainly has an effect of exceeding 2.0% by mass of the above Sn. However, if the total of ～ and Zn is in the present invention, the effect of improving the properties is saturated and the manufacturability is impaired. A maximum of 8 201200606 2.0 quality II can be added to the C〇 Sl alloy plate. The choice of "n & Zn in the genus or two species. However, in the case of 〇.〇 =. mass%, the effect is small, so it is better to add _~2 〇 1%, more preferably A total of 〇5~丨〇% by mass is added. 〇As, Sb, Be, B, Tl, Zr, A1/Fww For AS, Sb, Be, B, Ti, Zr, gossip and The required product characteristics are adjusted to adjust the amount of addition, and the conductivity is improved: strength, stress relaxation characteristics, plating properties, etc., mainly by making As, Sb, Be, B, Ti, 7r, δ 1 bc A1 and Fe It is dissolved in the matrix phase to exert the effect of addition. However, it can also be achieved by including the above-mentioned AH~, B, Ti, Zr, A1 and Fe in the second phase particles or forming the second phase particles of the new composition. However, if the total of the elements exceeds 2 〇 mass%, the characteristic improvement effect is saturated and the manufacturability is impaired. Therefore, in the C 〇-Si alloy plate of the present invention, a total of 2 〇 can be added in total. The mass % is selected from A. Sb, Be 'B, Ti, Zr, Ai, and Fe, or two or more. However, when S is less than 0.001% by mass, the effect is small. Therefore, it is preferable to add 0.001 to 2.0% by mass in total, and it is more preferable to add a total of (7) to 丨〇% by mass. 〇If the above Mg, P, As, Sb, Be, b, Mn, Sn, Ti, A, Fe, When the total amount of addition of Zn and Ag is more than 2.0% by mass, the productivity is easily impaired. Therefore, it is preferable to set the total of these elements to 2% by mass or less, more preferably 1.5% by mass or less, and still more preferably It is assumed that i 〇 mass% or less. (4) Crystal grain size previously known, if the crystal grain size is small, high strength can be obtained, and the average crystal grain size of the center of the plate thickness in the section of the calendering direction is also 2 in the present month. 〇V-claw 201200606 Hereinafter, the average crystal grain size of the center of the plate thickness is measured according to JIS H 05〇j (breaking method). The average thickness of the plate thickness center of the copper alloy plate of the present invention. The degree of processing 胄10~5〇% does not change significantly after the final calendering. Therefore, if the A 20" m before the final rolling, the sigma and σ particle size will maintain the average crystallization after the final calendering. The particle size is 2〇^ The copper 5 gold is more finely crystallized. Therefore, even the knot The crystal structure is too fine, so that the average line of the treatment is #&&/amp; /丄, the average crystal grain size after the delay is not correctly measured by the value of The sample having an average crystal grain size of 2 (m) before final rolling is subjected to final calendering as a standard and compared, and it is judged whether or not the average crystal grain is over 35, m. Further, the average crystallizing at the center of the plate thickness of the present invention The particle size is ...m or less" is used to determine the same high strength as the prior art, and the "thickness center" is a term used to indicate the position of the measurement. In the prior art, the unevenness of the crystal grain size, especially the coarse crystallized surface of the surface, is not particularly conspicuous, so that the lack of coarse grains in the surface may adversely affect the adhesion of the uniformity of the ore. . However, the surface layer is most likely to accumulate strain energy in the calendering step, and the crystal is easily localized coarser than the inside (thickness center) under normal manufacturing conditions. Further, the surface layer and the inner layer are present in the heat treatment step. In the case where the thermal history of p is different, there is also a case where the crystal is locally enlarged compared with the inside (thickness center). again. In this case, the term "surface layer" as used herein refers to the distance from the surface of the surface of the surface of the surface of the surface of the surface of the surface of the surface of the core. A copper alloy plate is used for the grounding of the electronic material.衧 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 If there are more than 5, the plating will not be attached to the sentence, and it will become a defective product when it is naked. Observing the surface of the plated surface, the number of grains is in the micrograph (magnification: m〇〇): the number of grains above 45 cores in contact with the surface of the profile in the rolling direction The number is divided by the complex number (1 〇) to determine the total length of the range of the length 2_(4) of the surface in the field of view and the unit is 'unit. In the copper alloy sheet of the present invention, since the crystal grains having a long diameter (...) or more in the surface are five or less, the uniformity of the mineral deposit is excellent. The copper alloy sheet of the present invention can use various plating materials. For example, A-base plating, Cu-based plating, or plating, which is usually used for Au-plated substrates, can be cited. Regarding the plating of the present invention, it is needless to say that it is 0.5 to adhesion. Thickness, usually used 2~5//m thickness 2. 〇ym thickness also shows sufficient uniform manufacturing method using copper alloy sheet in general hot calendering - intermediate cold calendering - intermediate solid solution but within its steps The following conditions can be adjusted, and intermediate calendering and intermediate solution melting can also be considered as follows. (5) Manufacturing method The copper alloy sheet manufacturing process (melting, casting, finalizing, final cold rolling, aging) of the present invention, the target copper alloy sheet. Furthermore, it needs to be repeated several times. ~Muscle also puts the conditions of I, 丨, |,; (7) heart, daytime, and intermediate solution treatment. The reason for this is that the present invention 11 201200606 and the cooling rate of the second phase particles are large in the melting and casting steps, and a solution having a desired composition is obtained. Then electricity: copper t, sl, c. Wait for her to cast the melt into an ingot in the subsequent heat. In addition to the heat treatment of casting,... and go as far as possible
。,、 0 Sl等結晶化物。例如，於950°c〜105C 、寺。“寺以上後進行熱壓延。於熱壓延前之保持溫 又95〇C時，固溶不充分，另一方面，若超過1〇5〇。(： 則存在材料溶解之可能性。 又於熱壓延結束時之溫度未達7〇〇〇c之情形時，表示 熱壓延之最終道次或包含最終道次之數道次之加工係於未 達700 C下進行。於熱壓延結束時之溫度未達7〇〇〇c之情形 時，内部為再結晶狀態，相對於此，纟層以受到加工應變 之狀態結束《若於此狀態下經過冷壓延，且於通常之條件 下進行固〉谷化，則内部為正常之再結晶組織，相對於此， 表層形成粗大化之晶粒。因此，為了防止表層之粗大化結 晶之形成，理想的是以7〇(rc以上、較佳為850〇c以上結束 熱壓延，且理想的是熱壓延結束後進行急冷。急冷可藉由 水冷而達成。 於熱壓延後，於目標範圍内適當選擇次數及順序而進 行中間壓延及中間固溶化。若中間壓延之最終道次之加工 度未達5% ’則僅材料表面積蓄加工應變能，因此導致於表 層產生粗大之晶粒。尤其是將最終道次之中間壓延加工度 12 201200606 设為8 %以上較佳。7 控制用於中間壓延之麼延油之黏度 及中間屢延之速度亦 』有效地均勻施加加工應變能。 充分地進行中門m + 曰J LJ >谷化’以使熔解鑄造時之結晶化粒 子或熱壓延後之析屮# a 祈出粒子固溶，而儘可能地去除粗大之Co -Si等析出物。例如，若固溶化處理溫度未達赋，則固 :不充分，無法獲得所期望之強度。另一方面若固溶化 處理溫度超過105(rc，則存在材料熔解之可能性。因此， 車父佳為進行使材料溫度力°熱i 8501〜職。C之固溶化處 理。固溶化處理之時間較佳為〇_5分鐘〜i小時。 再者，溫度與時間之關係，為了獲得相同之熱處理效 果（例如相同之結晶粒徑），赍 )常識上必須於兩溫之情形時縮 於低溫之情形時增加時間。例如，於本發明中， 理想的是於950°C之情开彡b本盔,，、g 時為o.H分鐘。為2/刀知，於1〇〇『C之情形 關^溶化處理後之冷卻速度，Μ為了防止已固溶 之第—相粒子析出而進行急冷。 繼而，於鐵以上且6〇〇t以下之溫度條件下 …里，使微細之第二相粒子均勻地析出。其原因、 右時效溫度未達戰，則有第二相粒子之析 ，、’ 法獲得所期望之強度與導電率之問題，若超過6〇吖：而無 析出之第二相粒子粗大化，❿無法獲得所期望之強則有 題。時效溫度較佳為450t以上且55〇t以下。 之問 最終壓延之加工度較佳為〖。〜5〇%，更佳為扣〜⑽。 未達10。/。，則無法獲得所期望之強度。— 万面，若超 13 201200606 過5 0°/。，則彎曲加工性劣化。 由於本發明之銅合金板於表面不存在粗大晶粒，故而 鑛敷之均句附著性優異’可適用於引線框架、連接器、接 腳、端子、繼電器、聞M、二次電池用箔材等電子零件。 [實施例] 以下表示本發明之實施例及比較例，該等實施例係為 了更加理解本發明及其優點而提供者並不意圖限定發明.、: (1 )測定方法 (a )板厚中心之結晶粒徑：於固溶化處理後製造最終 壓延則之塵延方向之板厚中心、之平均結晶粒徑$ 2q "①的 ‘準樣本（Co :丨〇質量％、Si : 〇 66質量％、剩餘部分為 銅）。平均結晶粒徑係根據JIS H 〇5〇1 (切斷法）而測定。 對‘準樣本進行最終冷壓延（加工度丨5% )，拍攝壓延方向 4面之板厚中心之光學顯微鏡照片（倍率：χ4〇〇 )並作為 基準。然後，以目測比較各實施例（發明例及比較例）之 最終冷壓延後之板厚中心之光學顯微鏡照片（與基準相同 倍率）與基準的大小，於大於基準之情形時，於結晶粒捏 較大的情形係結晶粒徑大於20 /ζ m (> 20仁m )，於與基準 相同或小於基準之情形時，將結晶粒徑作為2〇 "爪以下 2〇/zm)〇 = (b )表層附近之晶粒之觀察 關於表層，使用壓延方向表層剖面之顯微鏡照片於 自表層起深度10 # m之位置繪製平行於表面之線，以1〇個 予求出線之長度’同時藉由線段法求出一部分接觸於表 14 201200606 面之45 v m以上之結晶粒徑之個數， 粒徑之個數的合計除以線段之合計， m以上之結晶粒徑之個數。 將45以m以上之結晶 而求出每1mm之45 /z (c )鍍敷附著之均勻性 (電解脫脂順序） 於鹼性水溶液中將試料作. 寸忭為陰極進行電解脫脂。 使用10質量％硫酸水溶液進行酸洗。 (Ni基底鍍敷條件） 删酸. , 0 Sl and other crystallized materials. For example, at 950 ° c ~ 105 C, the temple. "There is hot rolling after the temple is over. When the temperature is maintained at 95 °C before hot rolling, the solid solution is insufficient. On the other hand, if it exceeds 1〇5〇. (: There is a possibility that the material dissolves. When the temperature at the end of hot rolling is less than 7〇〇〇c, the final pass of hot rolling or the number of passes containing the final pass is performed at less than 700 C. When the temperature at the end of the delay is less than 7 〇〇〇c, the inside is in a recrystallized state. On the other hand, the ruthenium layer is finished in a state of being subjected to the processing strain. "If it is subjected to cold rolling in this state, and under normal conditions When the solidification is carried out, the inside is a normal recrystallized structure, and the surface layer is formed into coarsened crystal grains. Therefore, in order to prevent the formation of coarsened crystals of the surface layer, it is preferable to use 7 〇 or more. Preferably, the hot rolling is completed at 850 〇c or more, and it is desirable to perform rapid cooling after the end of the hot rolling. The quenching can be achieved by water cooling. After the hot rolling, the number of times and the order are appropriately selected within the target range. Calendering and intermediate solution melting. If the middle is the most calendered If the processing degree of the final pass is less than 5%, only the surface area of the material can be processed and strained, so that coarse grains are formed on the surface layer. Especially, the intermediate rolling processing degree of the final pass 12 201200606 is preferably 8 % or more. 7. Control the viscosity of the oil used for the intermediate calendering and the speed of the intermediate extension. "Efficiently apply the processing strain energy evenly. Fully carry out the middle door m + 曰J LJ > gluten' to make the casting The crystallized particles or the precipitation after hot rolling # a pray out that the particles are solid-dissolved, and remove coarse precipitates such as Co-Si as much as possible. For example, if the solution treatment temperature is not up to the equilibrium, the solid is insufficient. On the other hand, if the solution treatment temperature exceeds 105 (rc, there is a possibility that the material is melted. Therefore, the car owner performs the solution to heat the temperature of the material. The time of the solution treatment is preferably 〇5 minutes to i hours. Furthermore, the relationship between temperature and time, in order to obtain the same heat treatment effect (for example, the same crystal grain size), 赍) common sense must be at two temperatures Time shrink In the case of low temperature, the time is increased. For example, in the present invention, it is desirable to open the helmet at 950 ° C, and o is oH minutes at g. It is 2 / knife, at 1 〇〇 "C In the case of the cooling rate after the melting treatment, Μ is quenched in order to prevent precipitation of the solid phase-phase particles. Then, under the temperature conditions of iron and below 6 〇〇t, the second is fine. The phase particles are uniformly deposited. The reason is that the right aging temperature does not reach the war, then there is the analysis of the second phase particles, and the 'method obtains the desired strength and conductivity. If it exceeds 6〇吖: no precipitation The two-phase particle is coarsened, and the enthalpy is not able to obtain the desired strength. The aging temperature is preferably 450 t or more and 55 〇 t or less. The final calendering degree is preferably 〖. ~5〇%, better for deduction~(10). Not up to 10. /. , the desired strength cannot be obtained. — 万面, if the super 13 201200606 over 5 0 ° /. Then, the bending workability is deteriorated. Since the copper alloy sheet of the present invention does not have coarse crystal grains on the surface, the uniformity of the mineral deposit is excellent, and it can be applied to a lead frame, a connector, a pin, a terminal, a relay, a smell M, and a foil for a secondary battery. Electronic parts. [Examples] The following are examples and comparative examples of the present invention, which are intended to provide a better understanding of the present invention and its advantages, and are not intended to limit the invention. (1) Measurement method (a) Thickness center Crystal grain size: the quasi-sample (Co: 丨〇 mass%, Si: 〇66 mass) of the average crystal grain size of the 2nd < 2q "1 after the solution treatment is performed to obtain the final calendering direction %, the remaining part is copper). The average crystal grain size is measured in accordance with JIS H 〇 5〇1 (cutting method). For the final quenching of the quasi-sample (processing degree 丨 5%), an optical microscope photograph (magnification: χ4〇〇) of the center of the thickness of the four sides in the rolling direction was taken as a reference. Then, the optical micrographs (the same magnification as the reference) and the reference size of the center of the plate thickness after the final cold rolling of each of the examples (inventive examples and comparative examples) were visually compared, and when the ratio was larger than the reference, the crystal grains were pinched. In the larger case, the crystal grain size is larger than 20 / ζ m (> 20 ren m). When the ratio is the same as or lower than the standard, the crystal grain size is taken as 2 〇 " 2 〇 / zm below the claw 〇 = (b) Observation of crystal grains in the vicinity of the surface layer Regarding the surface layer, a microscope photograph of the surface layer profile of the rolling direction is used to draw a line parallel to the surface at a depth of 10 # m from the surface layer, and the length of the line is obtained by one ' The number of crystal grains of 45 vm or more which are in contact with a surface of Table 14 201200606 is determined by the line segment method, and the total number of particle diameters is divided by the total of the line segments, and the number of crystal grains of m or more. For 45 or more crystals of m or more, 45/z (c) per 1 mm of plating adhesion uniformity (electrolytic degreasing order) was determined. The sample was subjected to electrolytic degreasing in an alkaline aqueous solution. Acid washing was carried out using a 10% by mass aqueous sulfuric acid solution. (Ni substrate plating conditions)
.鍍敷浴組成：硫酸鎳25〇g八、氣化鎳45g八、 30g/L •鍍敷浴溫度：5 0。(： .電流密度：5A/dm2 .鑛Ni厚度係藉由電鍍時間進行調整，設為ι 〇心。 鍵敷厚度測定係❹CT-丨型電解式膜厚計（電測股份有 限公司製造）’並使用Kocour公司製造之電解液r—54來 進行。 • . (錄敷附著均勻性評價） 拍攝鍍敷表面之光學顯微鏡照片（倍率：χ2〇〇,規衧 面積為0W)，測定觀察島狀鍍敷之個數及分佈狀態。評 價如下述所示。 s :無， A :島狀鍍敷之個數為5〇個/ mm2以下， B :島狀鍍敷之個數為1 〇〇個〆mm2以下， C :島狀鍍敷之個數超過100個/ mm2。 15 201200606 再者’圖1係本發明例1之鍍敷表面之光學顯微鏡照 片’相當於「S」等級，圖2係比較例11之鍍敷表面之光 學顯微鏡照片，相當於「C」等級。又，圖3係於鍍敷表面 所觀察到之「島狀鍍敷」之放大照片（倍率：X2500 )，將 此種島形狀作為1個而測定視野中之島狀鍍敷之個數。 (d )強度 進行壓延平行方向之拉伸試驗而測定〇 2%安全限應力 (YS : MPa)。 (e) 導電率（ec ; %IACS) 藉由利用雙電橋之體積電阻率測定而求出。 (f) 彎曲加工性 依據JIS Η 3 1 30進行Bad way (彎曲軸為與壓延方向相 同之方向）之W彎曲試驗，測定不產生裂痕之最小半徑 (MBR)相對於板厚⑴之比即MBR/1值。彎曲加工性 係利用以下之基準而進行評價。 MBR/tS 2·〇 良好 2-0<MBR/t 不良 (2 )製造方法 藉由高頻熔解爐於13〇〇t：下熔化表丨中記載之各成 組成之銅合金’而鑄造成厚度3Qmm之鑄銳。然後，將此 鍵於表i中記載之條件下加熱.3小時後，以熱壓延結束 度（最終溫度）進行熱壓延直至板厚$ 1〇職為止，埶壓 結束後迅速地進行水冷直至室溫為止。繼而，為了去除 面之鏽皮’實施平面切削直至厚度為9麵為止後，適當 16 201200606 行最終道次之加 下之0.5分鐘~ 0.1 5 mm之板。固 至室溫為止。繼A 之時效處理。繼· 製造各言式驗片。 l度為5〜15%之冷壓延、材料溫度900°C 1小時之中間固溶化步驟，而製成厚度 溶化處理結率後以水冷迅速地進行冷卻直 |，於惰性環境中且於52(TC下進行3小時 而’進行加工度為15%之最終冷壓延，而 各成驗片之測定結果示於表1。 17 201200606 r-1 鍍敷均 勻性 〇0 < CQ on < PQ C/3 00 on U U u U U U U U U U 彎曲加 工度 索 •ttCd -mv^ 索 Όώί 衆 索 索 ^ΰά 泶 Όώί -αβί /Γί^ 導電性 ο Ό S <N v〇 <N v〇 m VO oo VO in Os s 〇\ § δ 00 IT) in g ν〇 〇 00 VO o 00 VO 〇 卜 Ο 卜 o VO tr> o o ir> 00 VO iTi VO o OS iT) ON VO 00 Ό ο ο »r> Ο 〇 卜 Ο Ό i〇 o 個數 Ο 〇\ d 00 <N o VO o 00 <N o ο o o On uS 00 卜: o U^) 〇\ Os CN ο r-H 00 〇{ ν〇 cK 00 αί 平均結晶 粒徑 1 ^20//m 1 ^20//m j ^20/zm | 1 ^20//m | | $20//111 I | ^20/im | | $20"m I $20//m $20"m 1 ^20/zm I | ^20/zm | 1^20^m I ^20//m | ‘20//m | $20 "m 1 $20"m 1 1 ^20^m 1 ^20μτη | ^20βτη j ^20βΐΏ I 最終壓延 加工度 (%) in ΙΤΪ in yr\ in ♦—1 in ^Τ) τ—^ l〇 r—^ 時效處 理rc) ο CN o (N o CN o CN wo o (N IT) o CN iTi o CN o (N i〇 o (N 〇 (N *T) o cs iTi o CN ID ί〇 ο CN •ο Ο <Ν Ο (Ν ο CN m o <N i〇 中間固溶 化時間 (min) tr> υο i〇 ΙΤΪ in ί〇 ι〇 un iTi 中間固溶 化溫度 rc) 〇 ON o 〇\ 〇 〇 Os 〇 o o o 〇 o § o ON O σ> 〇 ο Ch ο § ο Ο g 〇 § ο 冢 o 冢 最終道次 加工度 o in o in tn in ΙΤΪ ιη in 熱壓延條件 最終 溫度 O JO o IQ o o o JO o UQ o o o JO o JO o JO o JQ o ^T) Ο JO O ο 沄 ο JO ο 沄 ο 沄 Ο ο 沄 O 沄 開始 溫度 o o On o o U^i On 〇 trj ON o On o irv 〇\ o o On o in ON o ο o g ο 00 ο σ\ ο οο ο g ο 00 ο g o oo 其他 O.lMg | 0.5Sn I O.lMg 0.5Sn j ώ d o 〇 o ο ο ο t—Η Ο o 寸 c5 寸 d 对 o 寸 o 寸 o 寸 o 寸 o ro c5 o 寸 o o 寸 o 寸 ο 寸 ο 寸 ο 寸 ο 寸 ο m d v〇 o Ο υ ON Ch ON f—H O) O) G\ O) d ·/> (N O) O) a\ Ο) CS α\ τ—Η Ο) Ο) o (N 6 CN m 寸 yr\ 卜 00 C\ o CN m 二 ιη ν〇 卜 00 Os 〇〇 201200606 發明例1之最終道次中之中間壓延之加工度為ι5%， 相對於此’相同組成之發明合"中加工度較低為⑽，因 此於表面產生粗大粒子而鍍敷均勻附著性稍差。發明例4 與5之關係亦相同。 發明例1之最終溫度（熱壓延結束時之溫度）為 °C，相對於此，相同組成之發明例3中最終溫度較低為7⑻ c ’因此鍍敷均勻附著性更差。發㈣^ 4與6之關係亦相 同。 發明例1之熱壓延開始溫度為95〇〇c，最終溫度為 °c，相對於此，相同組成之比較例n中分別較低為8〇〇。〇 及500X：，因此於表面產生粗大粒子而鍍敷均勻附著性較 差。再者，若於比較例11之銅合金表面以3〇 #爪之厚度 實施鍍Νι，則鍍敷後之表面之島狀鍍敷變得不明顯，而成 為接近「S」專級之狀態。 發明例4與比較例丨4之關係亦相同。 比較例11之最終道次中之中間壓延之加工度為15%， 相對於此，相同組成之比較例12中加卫度較低為5%，因 此於表面進一步產生粗大粒子而鍍敷均勻附著性更差。 發明例7之熱壓延開始溫度為95〇t，最終溫度為75〇 °c ’最終道次中之中間壓延之加工度為15%，相對於此’ 相同組成之比較例17中均較低為8〇〇t、5〇〇t：、5%，因 此於表面產生粗大粒子而鍍敷均勻附著性較差。發明例8 與比較例1 8之關係亦相同。 【圖式簡單說明】 19 201200606 圖1 ’係實施鍍Ni之太欢 只 之本發明之銅合金板 之錢敷表面之顯微鏡照4 (倍率：x200)。 圖2，係實施鍍Νι之比較例之銅合金板（ 之鐘敷表面之顯微鏡照片（倍率·· χ200 )。 圖3 ’係圖2之鍍敷表面之放大顯微鏡照 χ2500 ) 〇 【主要元件符號說明】 無 (發明例1 ) 比較例I 1 ) 片（倍率： 20The composition of the plating bath: nickel sulfate 25 〇 g VIII, vaporized nickel 45 g 八, 30 g / L • plating bath temperature: 50. (: . Current density: 5A/dm2. The thickness of the mineral Ni is adjusted by the plating time, and is set to ι 〇. Key thickness measurement system ❹ CT-丨 electrolytic type film thickness meter (manufactured by Electric Co., Ltd.)' And using the electrolyte r-54 manufactured by Kocour Co., Ltd.. (Evaluation of adhesion uniformity) Photograph of the photomicrograph of the plated surface (magnification: χ2〇〇, gauge area: 0W), and the observation island shape The number of platings and the distribution state are as follows: s : none, A : the number of island plating is 5 / / mm 2 or less, B : the number of island plating is 1 〇〇 〆mm2 or less, C: The number of island plating is more than 100/mm2. 15 201200606 Further, 'Fig. 1 is an optical microscope photograph of the plated surface of the first embodiment of the present invention' corresponding to the "S" grade, and FIG. 2 is The optical micrograph of the plated surface of Comparative Example 11 corresponds to the "C" grade. Further, Fig. 3 is an enlarged photograph of the "island plating" observed on the plated surface (magnification: X2500). The number of islands in the field of view is measured as one island shape. (d) The strength is rolled flat. The 〇2% safety limit stress (YS: MPa) was measured by the tensile test in the row direction. (e) The conductivity (ec; % IACS) was determined by measuring the volume resistivity of the double bridge. (f) Bending The W bend test of the Bad way (the bending axis is the same direction as the rolling direction) was carried out in accordance with JIS Η 3 1 30, and the ratio of the minimum radius (MBR) to the thickness (1) which is not cracked, that is, the MBR/1 value was measured. The bending workability was evaluated by the following criteria: MBR/tS 2·〇Good 2-0<MBR/t Poor (2) Manufacturing method is described in the high-frequency melting furnace at 13〇〇t: melting table Each of the formed copper alloys was cast into a thickness of 3Qmm. Then, the bond was heated under the conditions described in Table i. After 3 hours, hot rolling was performed at the end of hot rolling (final temperature). Until the thickness of the plate is $1, the water is rapidly cooled to room temperature after the completion of the pressing. Then, in order to remove the surface of the scale, the surface is cut until the thickness is 9 faces, and the final pass is made. Add 0.5 minutes to 0.1 5 mm plate. Fix to room temperature. Following A After the treatment, each sentence is made. The degree is 5~15% cold rolling, the material temperature is 900 °C for 1 hour, and the intermediate solution treatment step is made to melt the treatment and the temperature is rapidly cooled by water cooling. Cooling straight |, in an inert environment and at 52 (TC for 3 hours and 'the processing degree is 15% of the final cold rolling, and the measurement results of each test piece are shown in Table 1. 17 201200606 r-1 plating Uniformity 〇0 < CQ on < PQ C/3 00 on UU u UUUUUUU Bending processing degree ttCd -mv^ 索Όώί 众索索 ^ΰά 泶Όώί -αβί /Γί^ Conductivity ο Ό S <N v 〇 N N N δ δ δ 00 00 00 VO 00 Ό ο ο »r> 〇 〇 Ο Ό 〇 i〇o number 〇 d \ d 00 <N o VO o 00 <N o ο oo On uS 00 Bu: o U^) 〇\ Os CN ο rH 00 〇{ ν〇cK 00 αί average crystal grain size 1 ^20//m 1 ^20//mj ^20/zm | 1 ^20//m | | $20//111 I | ^20/im | $20"m I $20//m $20"m 1 ^20/zm I ^20/zm | 1^20^m I ^20//m | '20//m | $20 "m 1 $20"m 1 1 ^20^m 1 ^20μτη | ^20βτη j ^20βΐΏ I Finally Calendering degree (%) in ΙΤΪ in yr\ in ♦—1 in ^Τ) τ—^ l〇r—^ aging treatment rc) ο CN o (N o CN o CN wo o (N IT) o CN iTi o CN o (N i ( ( ( ( ( ( ( ( ( ; υο i〇ΙΤΪ in ί〇ι〇un iTi intermediate solution temperature rc) 〇ON o 〇\ 〇〇Os 〇ooo 〇o § o ON O σ> 〇ο Ch ο § ο Ο g 〇§ ο 冢o 冢The final pass processing degree o in o in tn in ΙΤΪ ιη in hot rolling condition final temperature O JO o IQ ooo JO o UQ ooo JO o JO o JO o JQ o ^T) Ο JO O ο 沄ο JO ο 沄ο ο ο 沄O 沄Starting temperature oo On oo U^i On 〇trj ON o On o irv 〇\ oo On o in ON o ο og ο 00 ο σ\ ο οο ο g ο 00 ο go oo Other O.lMg | 0.5Sn I O.lMg 0.5Sn j ώ do 〇o ο ο t—Η Ο o inch c5 inch d to o inch o inch o inch o inch o ro c5 o inch oo inch o inch ο inch ο inch ο inch ο inch ο mdv〇o Ο υ ON Ch ON f—HO) O G\ O) d ·/> (NO) O) a\ Ο) CS α\ τ—Η Ο) Ο) o (N 6 CN m inch yr\ 00 00 C\ o CN m 二ιη ν〇卜00 Os 〇〇 201200606 The degree of intermediate rolling in the final pass of Invention Example 1 is ι 5%, and the degree of processing is lower than (10) in the invention of the same composition, so that coarse particles are formed on the surface and plated. The uniform adhesion is slightly poor. The relationship between the inventive examples 4 and 5 is also the same. The final temperature (temperature at the end of hot rolling) of Inventive Example 1 was ° C. On the other hand, in Example 3 of the same composition, the final temperature was as low as 7 (8) c ', so that the plating uniform adhesion was worse. The relationship between (4) and 4 is the same. The hot rolling start temperature of Inventive Example 1 was 95 〇〇c, and the final temperature was °c. On the other hand, Comparative Example n of the same composition was lower than 8 分别. 〇 and 500X:, therefore, coarse particles are formed on the surface and the plating is poorly adhered. Further, when the surface of the copper alloy of Comparative Example 11 was plated with a thickness of 3 〇 #爪, the island-like plating on the surface after plating became inconspicuous, and it became a state close to the "S" level. The relationship between the inventive example 4 and the comparative example 丨4 is also the same. The degree of intermediate rolling in the final pass of Comparative Example 11 was 15%. On the other hand, in Comparative Example 12 of the same composition, the degree of addition was as low as 5%, so that coarse particles were further formed on the surface and plating was uniformly adhered. Sex is worse. Inventive Example 7 has a hot calendering start temperature of 95 〇t and a final temperature of 75 〇 °c. The degree of intermediate calendering in the final pass is 15%, which is lower than Comparative Example 17 of the same composition. It is 8〇〇t, 5〇〇t:, 5%, so coarse particles are formed on the surface and the plating is poorly adhered. The relationship between the inventive example 8 and the comparative example 18 is also the same. [Simple description of the drawing] 19 201200606 Fig. 1 ′ is a photomicrograph of the surface of the copper alloy plate of the present invention (magnification: x200). Fig. 2 is a photomicrograph (magnification · χ200) of a copper alloy plate of a comparative example of plating Ν ι. Fig. 3 'Amplified microscope photograph of the plated surface of Fig. 2 χ 2500 〇 主要 [main component symbol Explanation] None (Inventive Example 1) Comparative Example I 1) Sheet (magnification: 20