201242762 六、發明說明： 【發明所屬之技術領域】 本發明係關於_猫、* + 人1 Λ 羯及其製造方法刻而形成電路之複合銅 【先前技術】 ρ刷電路用銅落廣泛使用於電子•電氣設備，但 刷電路用銅箱诵堂她山社# Λ ρ “ 接者劑、或者不使用接著劑於高溫 :下接㈣合成樹脂板或膜等基材，以製造 其後為形成所要的電路，係藉由抗層佈及曝光步層:來 印刷電路，再經過去除不需要㈣之部分隸刻處理，又， 進而焊接各種元件而形成電子裝置用印刷電路。 '近年來，印刷配線板之配線密度變高，且電子零 連接端子之間隔戀」 變丨從而必然要求使覆銅積層板之銅荡 之厚度變薄。X ’積層板之多層構造化亦隨時代之潮流， 而對銅落要求如厚銅落/阻障層/薄銅落之複合銅络。當然， '為製作八有此種構造之覆銅積層板時之^始材料的銅落 必須具備重要之功能。 具有厚銅结/錄層/薄銅落之3層構造之㈣，使用厚質 之壓延㈣或電解則作為基底（載持體）之材料，並於 "上形成薄鎳被膜’進而於該鎳被膜上形成薄銅層。作為 具有此種構成之複合鋼笛’已知有具有載持體之㈣（參 照專利文獻卜專利文獻2、專利文獻3、專利文獻5)。 八有載持體之銅vg由於為薄銅層經触刻而形成電路之 201242762 才料故為壓延銅箔或電解銅箔之基底之銅層最後會 ^ J而被去除，鎳層亦會被去除。而且，於薄銅層側 多、電路°亥清形時之成為壓延銅箔或電解銅箔之基底銅 層係發揮有助於電路構成用薄銅馆之處理的作用，且鎳層 係發揮中間層之作用，故於電路形成時會被去除。 此對於具有戎等目的之厚銅箔/鎳層/薄銅箔之3層 構la的複α銅4，鎳層與薄銅箔間之密合性只要是於處理 中不會剝離即可的程度就好，並不十分重要。 另一方面，亦具有著重於鋼層與鎳層之密合性之文 獻。於專利文獻6,為此提出有將與錦層接觸之銅層之表面 粗糙度作為特定條件而使耐剝離性提高。 於錄層上略微形成有氧化膜，故於在該錄層上鑛敷有 銅之情形時’就鎳層與形成於其上之銅層的密合性而言， 即便使表面變粗糙’因該氧化膜而亦不會大幅提高剝離容 易度。 進而，提出有於鎳層上，較薄地形成例如鋼層作為密 合性提兩層，並將該鋼層與厚質之銅箔壓接（參照專利文 獻4)。 除此之外，提出有中間夾持有鎳之銅壓延而成的被覆 材料（clad material)(參照專利文獻7、專利文獻8 )。然而， 於組合不同種步驟之鍍敷步驟與壓延步驟時，會使製造成 本變大，又’此種機械性之方法，會有難以獲得均勻厚度 且儘可能溥之銅之積層構造的問題。 又’為了藉由壓延而與壓延輥相接之銅箔表面變平 4 201242762 滑，於需要與樹脂之密合時，需要實施粗化處理。 總而言之’認為目前並未解決如下等課題：如今，印 刷配線板之配線密度變高，被要求將電子零件之連接端子 之間隔縮小，進而 專利文獻1 : 專利文獻2 專利文獻3 專利文獻4 專利文獻5 專利文獻6 專利文獻7 專利文獻8 以低成本製作該等。 曰本特開昭58-108785號公報 曰本專利第3680321號公報 曰本專利第3543348號公報 曰本特開2005-72425號公報+ 曰本專利第4191977號公報 曰本特開平8-18 1432號公報 國際公開WO00-05934號公報 曰本專利第4195 162號公報 【發明内容】 〜本發明之課題在於獲得一種於製造由銅/鎳/銅構成之 複合銅箔時，提高鎳與銅、或銅與銅之層間的接合強度， 進而銅層之板厚精度優異且適於藉由蝕刻形成電路之複合 鋼箔及其製造方法。 ° ^本發明人等獲得如下知識見解：藉由對鍍銅與鍍鎳之步 驟進行没計來改善先前複合銅箔之缺點即鎳與銅之接合強 度不足，藉此可解決先前問題。進而，獲得可形成板厚精 度優異之銅層之知識見解。 月 本發明係基於該知識見解而提供一種： (1)複合銅箔，係由厚度為10〜15〇em之壓延銅箔 201242762 或電解銅箔、及形成於其兩面或單面 乙厚度〇.5〜3以m之 錦層、厚度5.一以上之銅層構成，上述銅層之 未達±5%，且剝離強度為〇·5 kg/crn以上。 又 又，本發明提供一種： 上述銅層由薄 (2)如上述（1)之複合銅箔，其中， 銅層（C)與厚銅層（D)之兩層構成。 又，本發明提供一種： 係由鋼/鎳/薄鋼/厚銅構 5/Zm，進而厚銅層（D) (3 )如上述（2 )之複合銅箔， 成’其中薄銅層（C)之厚度為〇.1〜 之厚度為5/^πι以上。 又’本發明提供一種： (4)如上述（2) & (3)之複合鋼落，係於上述薄銅 層（C)及/或厚銅層（0)上具備Cr含量為 里钓 10〜50/z g/dm2 之防銹層。 又’本發明提供一種： (5) 複合銅箔之製造方法，係於厚度為ι〇〜ι5〇以⑺ 之壓延mi或電解(A)之兩面或單面，藉由電鑛形成 厚度0.5〜3/zm之鎳層（B)，於鍍敷該鎳層（b)之後，立 即藉由電鍍連續地形成薄銅層（C )，進而於非連續步驟中， 藉由電鍍於該薄銅層（C)上形成厚銅層（D)。 又，本發明提供一種： (6) 複合銅箔之製造方法，係於厚度為1〇〜15〇以爪 之壓延銅箔或電解銅箔（A)之兩面或單面，藉由電鍍形成 厚度〇_5〜3/im之鎳層（B)，於鍍敷該鎳層（B)之後，立 6 201242762 即藉由電鍍連續地形成厚度o.l〜之薄銅層（c)，進 而於非連續步驟中，藉由電鍍於該薄銅層（C)上形成5// m以上之厚銅層（D)。 又，本發明提供一種： (7) 如上述（5)或（6)之複合銅箔之製造方法，其 中’於上述薄銅層（C)及/或厚銅層（〇)上形成Cr含量 為10〜5〇eg/dm2之防銹層。 又’本發明提供一種： (8) 如上述（5)至（7)中任一項之複合銅箔之製造 方法，其中，於上述薄銅層（C)上預先形成Cr含量為1〇 〜50 μ g/dm2之防銹層後，形成厚銅層（D )。 又’本發明提供一種： (9)如上述（5)至（7)中任一項之複合銅箔之製造 方法，其中，於上述厚銅層層上形成Cr含量為〜 50 // g/dm2之防銹層。 又，本發明提供一種： (1 〇 )如上述（5 )至 至（9 )中任一 造方法，其中 一項之複合銅落之製 (D) 〇 使用滾筒型電極以電鍍形成上述薄厚銅層 再者，本發明之特徵在於，在薄銅層201242762 VI. Description of the Invention: [Technical Field] The present invention relates to a composite copper in which a circuit is formed by _cat, *+ human 1 Λ 羯 and its manufacturing method. [Prior Art] Copper drop for ρ brush circuit is widely used in Electronic and electrical equipment, but copper box for brush circuit 诵堂山山社# Λ ρ " 接 接 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The required circuit is to print the circuit by the anti-layer cloth and the exposure step layer, and then remove the unnecessary part (4), and then solder various components to form a printed circuit for the electronic device. 'In recent years, printing The wiring density of the wiring board becomes high, and the gap between the electronic zero-connecting terminals is changed, which inevitably requires the thickness of the copper slab of the copper-clad laminate to be thin. The multi-layer structure of the X' laminate is also the trend of the times, and the copper is required to be a composite copper such as a thick copper/barrier/thin copper. Of course, 'the copper drop of the material used to make the copper-clad laminate with such a structure must have an important function. (4) having a thick copper clad/recording layer/thin copper falling three-layer structure, using thick calendering (four) or electrolysis as a material of the substrate (carrier), and forming a thin nickel film on the " A thin copper layer is formed on the nickel film. As the composite steel flute having such a configuration, (4) having a carrier is known (refer to Patent Document 2, Patent Document 3, and Patent Document 5). The copper vg of the eight-supported body is removed because the thin copper layer is formed by the engraving to form the circuit. Therefore, the copper layer of the base of the rolled copper foil or the electrolytic copper foil is finally removed, and the nickel layer is also removed. Remove. In addition, when the copper layer is on the side of the thin copper layer and the circuit is in the clear state, the base copper layer of the rolled copper foil or the electrolytic copper foil serves to facilitate the treatment of the thin copper chamber for circuit formation, and the nickel layer functions in the middle. The role of the layer is removed when the circuit is formed. For the complex α copper 4 having a thick copper foil/nickel layer/thin copper foil having a thickness of 戎, etc., the adhesion between the nickel layer and the thin copper foil is not to be peeled off during the treatment. The degree is good and not very important. On the other hand, it also has a focus on the adhesion between the steel layer and the nickel layer. Patent Document 6 proposes to improve the peeling resistance by setting the surface roughness of the copper layer in contact with the brocade layer as a specific condition. An oxide film is slightly formed on the recording layer, so that when the copper layer is deposited on the recording layer, 'the surface is roughened in terms of the adhesion of the nickel layer to the copper layer formed thereon. This oxide film does not greatly improve the ease of peeling. Further, it has been proposed to form a steel layer as a steel layer on the nickel layer as a thin layer, and to bond the steel layer to a thick copper foil (see Patent Document 4). In addition, a clad material in which copper of nickel is sandwiched is proposed (see Patent Document 7 and Patent Document 8). However, when the plating step and the calendering step of different steps are combined, the manufacturing cost becomes large, and the method of such mechanical properties has a problem that it is difficult to obtain a laminated structure of copper having a uniform thickness and being as thin as possible. Further, in order to flatten the surface of the copper foil which is brought into contact with the calender roll by rolling, the coating is required to be roughened when it is required to adhere to the resin. In short, it is considered that the following problems have not been solved: the wiring density of the printed wiring board is now high, and the interval between the connection terminals of the electronic components is required to be reduced. Patent Document 1: Patent Document 2 Patent Document 3 Patent Document 4 Patent Literature 5 Patent Document 6 Patent Document 7 Patent Document 8 These are produced at low cost. Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION The object of the present invention is to improve nickel and copper or copper when manufacturing a composite copper foil composed of copper/nickel/copper. The composite steel foil which is excellent in the bonding strength between the copper layers and the copper layer, and which is suitable for forming a circuit by etching and a method for producing the same. The inventors of the present invention have obtained the knowledge that the disadvantages of the prior composite copper foil, that is, the insufficient bonding strength of nickel and copper, can be solved by the steps of copper plating and nickel plating, whereby the previous problem can be solved. Further, knowledge of the copper layer excellent in sheet thickness accuracy is obtained. The present invention provides a kind of composite copper foil based on the knowledge and knowledge: (1) composite copper foil, which is made of rolled copper foil 201242762 or electrolytic copper foil with a thickness of 10~15 〇em, and formed on both sides or one side of the thickness 〇. 5 to 3 is composed of a gold layer of m and a copper layer having a thickness of 5. or more, and the copper layer is less than ±5%, and the peel strength is 〇·5 kg/crn or more. Furthermore, the present invention provides the copper layer (2) of the composite copper foil of the above (1), wherein the copper layer (C) and the thick copper layer (D) are composed of two layers. Moreover, the present invention provides: a composite copper foil of steel/nickel/thin steel/thick copper structure 5/Zm, and further a thick copper layer (D) (3), as in the above (2), into a thin copper layer ( The thickness of C) is 〇.1~ and the thickness is 5/^πι or more. Further, the present invention provides: (4) The composite steel falling piece according to (2) & (3) above, which has a Cr content for the above-mentioned thin copper layer (C) and/or thick copper layer (0). 10~50/zg/dm2 rustproof layer. Further, the present invention provides: (5) A method for producing a composite copper foil, which is formed on the two sides or one side of a calendered mi or an electrolysis (A) having a thickness of ι 〇 to ι 5 ( (7), and a thickness of 0.5 by electroforming. a nickel layer (B) of 3/zm, after plating the nickel layer (b), a thin copper layer (C) is continuously formed by electroplating, and in a discontinuous step, by plating on the thin copper layer A thick copper layer (D) is formed on (C). Moreover, the present invention provides a method for producing a composite copper foil by forming a thickness by plating on both sides or a single side of a rolled copper foil or an electrolytic copper foil (A) having a thickness of 1 to 15 inches.镍_5~3/im of the nickel layer (B), after plating the nickel layer (B), the vertical 6 201242762 is continuously formed by plating to form a thin copper layer (c) having a thickness ol~, and then discontinuous In the step, a thick copper layer (D) of 5//m or more is formed by plating on the thin copper layer (C). Further, the present invention provides: (7) The method for producing a composite copper foil according to the above (5) or (6), wherein 'the Cr content is formed on the thin copper layer (C) and/or the thick copper layer (〇) It is a rust-proof layer of 10~5〇eg/dm2. The method for producing a composite copper foil according to any one of the above (5) to (7), wherein the Cr content is previously formed on the thin copper layer (C) to be 1 〇 〜 After a rust-proof layer of 50 μg/dm 2 , a thick copper layer (D ) is formed. The present invention provides a method of producing a composite copper foil according to any one of the above (5) to (7), wherein a Cr content of the thick copper layer is formed to be ～50 // g/ Rm layer of dm2. Further, the present invention provides: (1) The method of any one of the above (5) to (9), wherein the composite copper drop (D) 〇 is formed by electroplating using the roll type electrode to form the thin copper Further, the present invention is characterized in that a thin copper layer
銅/鎳/銅構成之複合銅箔時， 於’在薄銅層上形成略厚於薄 層 表示為「薄銅 厚鋼層（D)」。 一種於製造由 可提高鎳與銅之接合強度且適 201242762 於藉由蚀刻形成電路 之複合銅箱及其製造方法。 【實施方式】 於装ie本發月之由銅/鎳/鋼構成之複合銅箔時，可使用 如圖1所tf之曲折式鍵敷裝置。成為起始材料之銅箱，使 用厚度為l〇〜150"m之壓延㈣或電解銅fg (Α)β對該落 (Α)之兩面或單面實施電鍍鎳。 於圖1中，自圖1之左側起進入鍍敷層，向右移動形 成特定厚度之鍍鎳層’即形成厚度〇 5〜3"爪之鎳層⑻。 -原因在於，H隋形時，若未達錦層之下限值即〇 ^⑺， 則易於產生針孔（pinh。丨e)，又，若超過上限值即3_， 則最終對錄層進行剝離或溶解時之貞擔會變大，而使生產 效率變差。 '如圖1所示’於鍍敷該錄層（B)之後，立即藉由電鍍 連續地形成厚度〇1〜5// , 5/zm之4銅層（（：）。首先形成該薄 銅層為其特徵，且該薄銅層具有重要之功能。 因為該薄銅層（C)擔負了抑制之前鎳層⑻之氧化、 使密。陡良好之重大功能。該銅層本身係耐氧化性豐富。 用以產生該效果之所需最低限之厚度。一。若薄銅層(c) 之厚度超過5卜則表面凹凸會變大，膜厚之均句性下降， 故最佳係設為上述數值之膜厚。 於上述薄銅層（C) ’可進一步形成。含量為ι〇〜 5〇“g/dm2之防銹層。其通常被稱為鉻層或者鉻酸鹽層。 於圖卜亦圖示有形成該防銹層之步驟，但該步驟曰並非 8 201242762 必需。…就抑制鍵銅層之稍微之氧化、或預防腐钮性 物質之附者之意圖而言有效。因&，該防錄步驟為較佳之 形態。 若=含量未達…g/dm2，則防錄層之控制會變困難， 因此设為該以上。又，甚fV八曰丄 又右Cr含蕙超過50"g/dm2,則效果 飽和’且由於步驟增加產生之負擔變A，因此較理想的是 將上限值設為如上所述。 經過該等步驟之銅㈣幾乎不會發生表面之氧化。此 後，，、形成厚銅層（D)。即，於非連續步驟中，藉由電鑛於 述（）（B)、（c)上形成5/^m以上之厚銅層（D)。即， 薄銅層（C)與厚銅層（D)均為鋼層，但成為各自獨立之 鍵銅層。 將其示於圖2。該圖2所示之步驟係使用滚筒型電極， ，銅泊環繞該電極之，進行電鍵者，因此與上述曲折 式鍍銅方法相比，厚度之精度極高。具體而言’於圓：實 把1次鍍敷，但並不限制於該步驟，可設為卜欠或]次以 曰相層（D)係藉由蝕刻形成電路之銅部分，故重要的 二其之控制’具體而言，較理想為使板厚精度未達+ 。。「，者，本說明書中之「板厚精度」無特別記载時，意 禾者因此’對於薄銅層（c)，需要形成5心以上。 亡：並不受到限定，但就為形成電路之層而言，較理想的 疋2 u a m以下。 再者，於本發明，重要的是厚銅層（D)之厚度精度， 201242762 ί = 與薄銅層(C)較薄，故對不均之影響度較小， 且壓I鋼箔或電解銅箔（A )係 品化去甘』 了幻/白進仃壓延或電解而製 ，者’其板厚精度未彡5%，故將壓延㈣或電解銅羯 ()、錦層⑻、薄銅層（C)、厚銅層（D)之合計之板 旱作為複合㈣之板厚，若能確保複合銅羯之板厚精度未 達5% ’則厚銅層（D)之板厚精度評估為未達±5%。 以上，如上述，於鎳層（B)上、薄鋼層（c)上，與 薄銅層（C)不同地使用板厚精度較高之電解電鍍方法來形 成厚度經過控制的厚銅層（D)，進而，成為於鎳層（B)、 薄銅層（C)、厚鋼層（D)間完全未發現剝離之複合銅箔。 此係本案發明之一大特徵。 於上述（D)層上，亦可進一步形成防銹層。其為任意 且雖為較佳之條件，但並非必需。再者，防銹層之形成條 件與上述相同。於該情形時，會有對圖案蝕刻液產生蝕刻 速度之差異的可能性，但可藉由適當選擇該量而進一步抑 制厚銅層（D )之表面之氧化，因此可實現保持電路寬度之 圖案之形成。 下述表示代表性且較佳之鍍敷條件之例。 (鑛銅（曲折式 銅：10〜5〇 g/i 硫酸：50〜1 〇〇 g/i 溫度：40〜6〇。0 電流密度：1〜5 A/dm2 (锻銅（滚筒式 10 201242762When a composite copper foil composed of copper/nickel/copper is formed on the thin copper layer to be slightly thicker than the thin layer, it is referred to as "thin copper thick steel layer (D)". One is to manufacture a composite copper box which can improve the bonding strength between nickel and copper and is suitable for forming a circuit by etching and a method of manufacturing the same. [Embodiment] When a composite copper foil composed of copper/nickel/steel is used for the present month, a zigzag keying device as shown in Fig. 1 can be used. As the copper material of the starting material, nickel plating is performed on both sides or one side of the falling (Α) using a thickness of 10 〇 150 150 (m) or electrolytic copper fg (Α) β. In Fig. 1, a plating layer is introduced from the left side of Fig. 1, and a nickel plating layer of a specific thickness is formed to the right, i.e., a nickel layer (8) having a thickness of 〇 5 to 3 " claws is formed. - The reason is that in the case of H隋, if the lower limit of the layer is not reached, ie, 〇^(7), pinholes (pinh.丨e) are likely to occur, and if the upper limit is exceeded, that is, 3_, the final recording layer When the peeling or dissolution is carried out, the burden becomes large, and the production efficiency is deteriorated. 'As shown in FIG. 1 ' Immediately after plating the recording layer (B), a copper layer ((:)) having a thickness of 〇1 to 5//, 5/zm is continuously formed by electroplating. The thin copper is first formed. The layer is characterized by the fact that the thin copper layer has an important function. Because the thin copper layer (C) is responsible for suppressing the oxidation of the nickel layer (8) and making it dense and steep, the copper layer itself is resistant to oxidation. The thickness of the minimum required to produce this effect. 1. If the thickness of the thin copper layer (c) exceeds 5, the surface roughness will become larger, and the uniformity of the film thickness will decrease. The film thickness of the above value may be further formed in the above-mentioned thin copper layer (C)'. The content is ι 〇 5 〇 "g/dm 2 of the rustproof layer. It is generally referred to as a chrome layer or a chromate layer. The step of forming the rustproof layer is also illustrated, but this step is not necessary for the 201242762. It is effective in suppressing the slight oxidation of the copper layer of the bond or preventing the intention of the attached material. The anti-recording step is a preferred form. If the content is less than ... g/dm2, the control of the anti-recording layer becomes difficult, so In addition, even if the fV gossip and the right Cr contain more than 50 "g/dm2, the effect is saturated' and the burden due to the increase of the step becomes A, so it is desirable to set the upper limit as described above. The copper (4) passing through the steps hardly undergoes oxidation of the surface. Thereafter, a thick copper layer (D) is formed. That is, in a non-continuous step, by electrowinning (), (B), (c) A thick copper layer (D) of 5/^m or more is formed on the surface. That is, both the thin copper layer (C) and the thick copper layer (D) are steel layers, but they are independent key copper layers. 2. The step shown in Fig. 2 uses a roller-type electrode, and copper is placed around the electrode to perform a key bond. Therefore, the thickness is extremely high in accuracy compared with the above-described zigzag copper plating method. : The plating is performed once, but it is not limited to this step. It can be set as the 欠 或 or the 曰 phase layer (D) is formed by etching to form the copper portion of the circuit, so the important control is 'specific In general, it is preferable that the plate thickness accuracy is less than +. "When the "thickness accuracy" in this specification is not specifically described, 'For the thin copper layer (c), it is necessary to form more than 5 cores. Death: It is not limited, but it is preferably less than 2 uam for forming a circuit layer. Further, in the present invention, it is important Thickness accuracy of thick copper layer (D), 201242762 ί = thinner with thin copper layer (C), so the degree of influence on unevenness is small, and pressure I steel foil or electrolytic copper foil (A) is refined 』The illusion/white 仃 仃 calendering or electrolysis system, the 'thickness accuracy is less than 5%, so it will be calendered (four) or electrolytic copper enamel (), gold layer (8), thin copper layer (C), thick copper layer ( D) The total plate thickness is the thickness of the composite (4). If the plate thickness accuracy of the composite copper enamel is less than 5%, the plate thickness accuracy of the thick copper layer (D) is less than ±5%. As described above, as described above, on the nickel layer (B) and the thin steel layer (c), a thick copper layer having a controlled thickness is formed by using an electrolytic plating method having a higher plate thickness precision than the thin copper layer (C). D) Further, a composite copper foil in which no peeling was observed between the nickel layer (B), the thin copper layer (C), and the thick steel layer (D) was observed. This is one of the major features of the invention. On the layer (D) above, a rustproof layer may be further formed. It is arbitrary and although preferred, it is not required. Further, the formation conditions of the rustproof layer are the same as described above. In this case, there is a possibility that a difference in etching speed is generated for the pattern etching liquid, but the oxidation of the surface of the thick copper layer (D) can be further suppressed by appropriately selecting the amount, so that a pattern for maintaining the circuit width can be realized. Formation. The following are examples of representative and preferred plating conditions. (Mineral copper (Zigzag type copper: 10~5〇 g/i Sulfuric acid: 50~1 〇〇 g/i Temperature: 40~6〇.0 Current density: 1~5 A/dm2 (wrought copper (drum type 10 201242762
Cu ： 90 g/L H2S04 ： 80 g/L Cl : 60 ppm 液溫：55〜57°C 添加劑：二硫雙（3-績丙基）二鈉（bis(3 — sulfopropyl) disulfide disodium) ( RASCH1G 公司製造 CPS) 50 ppm 添加劑：二苄胺（dibenzylamine)改質物50ppm (鑛鎳） 硫酸鎳：250〜300 g/L 氯化鎳：35〜45 g/L 乙酸鎳：10〜20 g/L 檸檬酸三鈉：15〜30 g/L 光澤劑：糖精、丁炔二醇等 十二基硫酸納：30〜100 ppm pH : 4 〜6 浴溫：50〜70°C (鉻酸鹽處理之條件） 浸潰鉻酸鹽處理 K2Cr207 ( Na2Cr207 或者 Cr03) : 0.1 〜5 g/升 pH ： 2〜13 溫度：常溫〜60°C 時間：5〜3 0秒 (鹼蝕刻之條件） NH4OH : 6莫耳/升 201242762Cu : 90 g/L H2S04 : 80 g/L Cl : 60 ppm Liquid temperature: 55 to 57 ° C Additive: bis(3 - sulfopropyl) disulfide disodium ( RASCH1G The company manufactures CPS) 50 ppm Additive: Dibenzylamine modified product 50ppm (mineral nickel) Nickel sulfate: 250~300 g/L Nickel chloride: 35~45 g/L Nickel acetate: 10~20 g/L Lemon Trisodium sulphate: 15~30 g/L Luster: Sodium sulphate, butanediol, etc. Dodecyl sulphate: 30~100 ppm pH: 4 ～6 Bath temperature: 50~70°C (Chromate treatment conditions) ) Impregnated chromate treatment K2Cr207 ( Na2Cr207 or Cr03) : 0.1 ~ 5 g / l pH : 2~13 Temperature: normal temperature ~ 60 ° C Time: 5 ~ 3 0 seconds (alkaline etching conditions) NH4OH : 6 mol /Leng 201242762
NH4C1 : 5莫耳/升 CuCl2 : 2莫耳/升 液溫：50°C (鎳及鉻之附著量分析方法 利用濃度3G /。之確酸，至少使樣品溶解至錄層溶解， 適當稀釋燒杯中之溶解液，以原子吸光分析進行錄及絡之 定量分析。 於使用上述複合鋼落製作覆銅積層板，並形成使用有 該覆銅積層板之電路時，於厚銅層（D)上形成電路形成用 抗蝕圖案’進而使用蝕刻液，將附有上述抗蝕圖案之部分 外之上述厚銅層⑼及薄銅層（c)積層部不需要部分加 以去除至鎳層（B )表面為止。或者，於樹脂側形成通孔而 形成多層電路。 另一方面，於壓延銅箔或電解銅箔（A)側，在（a) 上形成凸塊形成用抗蝕圖案，並藉由蝕刻將抗蝕圖案部以 外（A)之不要的部分去除直至鎳層（B )表面。此後，視 需要去除（B)之不要的部分。自該抗蝕圖案之形成起至不 要的銅箔去除係通常進行之方法，因此無需多作說明，故 省略。 再者，本發明之特徵在於，於壓延銅箔或電解銅箱 (A)、鎳層（B)、薄銅層（C)、厚銅層（D)間，完全未 發現剝離，故可同時實現（A )為凸塊形成層，（D ) + ( c、 為電路形成層之活用，但亦可用作如下之先前之用途：於 (D )表面上形成樹脂層後去除（a )、視狀況去除（B )、 12 201242762 且亦包含（c)而於（D)形成電路。 又，不進行用以提其士奎 ° 專利文獻7、8之密合性之壓接 加工，故⑼表面，可直接活用（D)形成時之電鑛粒， 可不實施粗化處理，且與樹脂之密合性優異。再者，亦可 實施粗化處理。 於使用銅羯之情形時，亦可相同地應用於電解銅揭之 粗化面（M面）或光澤面（s面），但㈣之面係通常使用 光澤面側或者與光澤面同等級以上平滑之銅箔之Μ面。於 使用壓延銅羯之情形時，亦可使用高純度壓延㈣或已提 高強度之壓延合金銅箱。本案發明包含所有該等㈣。 又，於實施本案發明時，只要不與本案發明發生矛盾， 則可利用所有上述敍述之公知技術。 實施例 接著，對本發明之實施例及比較例進行說明。再者， 本實施例係用以使理解變得容易，並不限制於上述例。即， 本發明於本說明書中記載之技術思想之範圍内，包含所有 除上述所示之實施例外之態樣或者變形。 (實施例1 ) 作為基底箔，使用70 # m厚之電解銅箔（Α八使用圖 斤示之鍍敷裝置，並使用上述鍍敷條件，對該電解銅箔施 以〇.7之鍍鎳（B)。其次’於該鍍鎳層（B)上，連續 也死^成〇.2/zrn之中間電鍛銅層（C)。 進而，使用圖2所示之裝置（滾筒型電極），形成⑺ Am之電鍍鋼層。藉此，製造由鋼/鎳/薄銅/厚銅構成之複合 13 201242762 銅箱。 由薄銅/厚銅構成之鋼層 杆 層之厚度之測疋係如下所述般進 仃。將由4銅/厚銅構成之 樹脂加壓並進行遮蔽。以」(基“側）向FR·4NH4C1 : 5 mol / liter CuCl2 : 2 mol / liter liquid temperature: 50 ° C (nickel and chromium adhesion analysis method using a concentration of 3G /. Acid, at least dissolve the sample to the recording layer, properly dilute the beaker The solution in the solution is quantitatively analyzed by atomic absorption spectrometry. When a copper clad laminate is produced by using the above composite steel, and a circuit using the copper clad laminate is formed, the thick copper layer (D) is used. Forming a resist pattern for circuit formation' and further using an etching solution to remove unnecessary portions of the thick copper layer (9) and the thin copper layer (c) laminated portion outside the portion of the resist pattern to the surface of the nickel layer (B) Alternatively, a via hole is formed on the resin side to form a multilayer circuit. On the other hand, a resist pattern for bump formation is formed on (a) on the side of the rolled copper foil or the electrodeposited copper foil (A), and is etched by etching. The unnecessary portion other than the resist pattern portion (A) is removed to the surface of the nickel layer (B). Thereafter, the unnecessary portion of (B) is removed as needed. From the formation of the resist pattern to the unnecessary copper foil removal system Usually done, so there is no need to explain more Further, the present invention is characterized in that no peeling is observed between the rolled copper foil or the electrolytic copper box (A), the nickel layer (B), the thin copper layer (C), and the thick copper layer (D). Therefore, (A) can be simultaneously realized as a bump forming layer, and (D) + (c, which is used for the circuit forming layer, but can also be used for the following purposes: after the resin layer is formed on the surface of (D) ( a), depending on the condition (B), 12 201242762, and also includes (c) and (D) to form a circuit. Further, the crimping process for improving the adhesion of the patent documents 7 and 8 is not performed. Therefore, the surface of (9) can directly utilize the electric ore particles at the time of (D) formation, and the roughening treatment can be omitted, and the adhesion to the resin is excellent. Further, the roughening treatment can be performed. It can also be applied to the roughened surface (M surface) or the shiny surface (s surface) of electrolytic copper, but the surface of (4) is usually the surface of the copper surface which is smooth on the shiny side or smoother than the shiny surface. In the case of using a rolled copper beryllium, it is also possible to use a high-purity calendering (four) or a rolled alloy copper box having an increased strength. The invention includes all of the above (4). Further, in the practice of the present invention, all of the above-described well-known techniques can be utilized as long as they do not contradict the present invention. Embodiments Next, embodiments and comparative examples of the present invention will be described. The present embodiment is intended to facilitate the understanding, and is not limited to the above examples. That is, the present invention includes all aspects or modifications other than the above-described implementation exceptions within the scope of the technical idea described in the present specification. (Example 1) As a base foil, a 70 #m thick electrolytic copper foil was used (the plating apparatus shown in Fig. 8 was used, and the electrolytic copper foil was plated with 〇.7 using the above plating conditions. Nickel (B). Secondly, on the nickel-plated layer (B), the copper layer (C) in the middle of the 2/zrn is continuously killed. Further, using the apparatus (drum type electrode) shown in Fig. 2, an electroplated steel layer of (7) Am was formed. In this way, a composite 13 201242762 copper box made of steel/nickel/thin copper/thick copper is manufactured. The thickness of the steel layer consisting of thin copper/thick copper is measured as follows. The resin composed of 4 copper/thick copper was pressed and shielded. "(base "side" to FR·4
“以鹼蝕刻使該樣品溶解直至由薄銅/ 厚銅構成之銅層溶解，廿拍4办.a A „ 並根據洛解前後之重量變化，對每 :位面積之銅之重量厚度進行測定。㉟而，若除以銅之比 8.93g/(m2· "m)’則可算出厚度（”）。 為了精度良好地求出厚度’較理想的是對2〇 W以上 之面積進行測定。測定係求出1〇處之板厚，而算出平均值, 且不均係設為（最大值—平均值）/平均值χ丨〇〇、或（平均 值：最小值）/平均值中較大者。評估係將未達观 〇j將5 以上且未達1 〇%設為「△」，將丨〇%以上設 為「X 0 關於密合性，於極薄銅箔側以150〇c以上對基材進行積 層，對剝離強度進行測定。於可產生剝離且在剝離強度未 達0.5 kg/cm而剝離時設為「X y於不會剝離或者剝離強度 為0.5 kg/cm以上之情形時設為「〇」。 以上之結果，板厚精度未達5%為良好，又，剝離強度 為0.5 kg/cm以上使密合性良好。將該結果相同地示於表1。 201242762 s 〇 〇 〇 〇 〇 〇 X X 〇 〇 楔 結果 / (板厚: 〇 〇 〇 〇 〇 〇 〇 〇 X < 3 u ：D) fim Ο 〇 〇 〇 〇 〇 〇 〇 fS B t-ι Ό u a ο ο 〇 m >rj 〇 〇 〇 〇 u 〇 H (Ν Ο 1*4 Ο CN 寸 CN (Ν 〇 〇 ο 5s 夺 z ¥ 〇 〇 〇 〇 〇 〇 X X 〇 〇 isf /~N 0D ^ B 卜 VO r- ο ο ΓΟ m ο • 一 璨 ^ isj： ε 硪a ο (Ν 〇〇 m 00 oo 〇 〇 (N CN r~N < 總 狹 狭 總 總 塚 塚 塚 毖 辆3 哟 竣1 lA'ftil •ζίβΓ 哟 辆1 r—Η 苳 4.¾) ¥5* CN m 寸 CN m 寸 磁 銻 ^3 jJ jJ -Ο 201242762 (實施例2) 作為基底箱，使用12/zm厚之壓延銅箔（A)。使用圖 1所示之鍍敷裝置，並使用上述鍍敷條件，對該壓延鋼箔施 以〇·6以m之鍍鎳（B )。其次，於該鍍鎳層（b )上，連續 地形成o.iwm之中間電鍍銅層（C)。 進而，使用圆2所示之裝置（滾筒型電極），形成5 " 電鍍銅層。藉此，製造由銅/錄/薄銅/厚銅構成之複合銅 V备。其他試驗條件係與實施例1相同。 以上之結果’板厚精度未達5%為良好，又，剝離強度 為〇.5 kg/cm以上使密合性良好。將該結果相同地示於表卜 (實施例3) 作為基底箔，使用1 8 // m厚之壓延銅箔（a )。使用圖 1所示之鍍敷裝置’並使用上述鍍敷條件，對該壓延銅箔施 以lym之鍍鎳（b)。其次，於該鍍鎳層（b)上，連續地 形成2#m之中間電鍍銅層（c)。 進而’使用圖2所示之裝置（滾筒型電極），形成10 之電鍍銅層。藉此，製造由銅/鎳/薄銅/厚銅構成之複合 銅馆。其他試驗條件係與實施例1相同。 以上之結果，板厚精度未達5%為良好，又，剝離強度 為〇·5 kg/cm以上使密合性良好。將該結果相同地示於表i。 (實施例4) 作為基底箔’使用3 5 // m厚之壓延銅箔（A )。使用圖 1所示之鍍敷裝置’並使用上述鍍敷條件，對該壓延銅箔施 以之鍍鎳（b)。其次，於該鍍鎳層（b)上，連續地 201242762 形成4"m之中間電鍍銅層（c)。 進而’使用上述浸潰條件進行鉻酸鹽處理後，使用圖2 所示之裝置（滾琦型電極），形成20“]^之電鐘銅層。再者， 鍵銅層（C)與電鍍層（d)之間Cr量為15// g/dm2。藉此， 製造由銅/鎳/薄銅/防銹層/厚銅構成之複合銅箔。其他試驗 條件係與實施例1相同。 以上之結果’板厚精度未達5%為良好，又，剝離強度 為0.5 kg/cm以上使密合性良好。將該結果相同地示於表卜 (實施例5) 作為基底箱，使用厚之壓延銅箔（A)。使用圖 1所示之鍍敷裝置，並使用上述鍍敷條件，對該壓延銅箔施 以lym之鑛鎳（B)。其次，於該鍍鎳層（b)上，連續地 形成之中間電鍍銅層（c)。 進而’於使用上述浸潰條件而進行鉻酸鹽處理後，使 用圖2所示之裝置（滾筒型電極），形成1〇ym之電鍍銅層。 再者’鍵銅層（C)與電鍍層（d)之間Cr量為45/z g/dm2。 藉此’製造由銅/鎳/薄銅/防銹層/厚銅構成之複合銅箔。其 他試驗條件係與實施例1相同。 以上之結果，板厚精度未達5%為良好，又，剝離強度 為0.5 kg/cm以上使密合性良好。將該結果相同地示於表卜 (實施例6) 作為基底羯’使用18/zm厚之電解銅箔（A)。使用圖 1所示之鍍敷裝置，並使用上述鍍敷條件，對該壓延銅箔施 以l"m之鍍鎳（B)。其次，於該鍍鎳層（b)上，連續地 201242762 形成2#m之中間電鍍銅層（c)。 進而’於使用圖2所示之裝置（滾筒型電極），形成10 ”之電錢層（D)後，使用上述浸潰條件進行鉻酸鹽處 理。再者’電鍍層⑼上之Cr量為3〇"/dm2。藉此，製 造由銅/鎳/薄銅/厚銅/防銹層構成之複合㈣。其他試驗條 件係與實施例1相同。 以上之結果’板厚精度未達5%為良好，又，剝離強度 為0.5 kg/cm以上使密合性良好。將該結果相同地示於表卜 (比較例1 ) 作為基底治，使用70 " m厚之電解銅馆（A )。使用圖 、斤示之鍍敷裝，並使用±述鍍敷條彳，對該電解銅箔施 以U m之鍍鎳（B )。使用圖2所示之裝置（滾筒型電極）， 於该（B)上形成10"m之電鍍銅層。藉此，製造由銅/鎳/ 厚鋼構成之複合鋼箔。其他試驗條件係與實施例丨相同。 以上之結果，板厚精度未達5%為良好，但剝離強度未 達〇.5 kg/cm使密合性不足。將該結果相同地示於表ι ^ (比較例2) 作為基底箔，使用70" m厚之壓延銅箔（Α)β使用圖 1所不之鍍敷裝置，並使用上述鍍敷條件，對該壓延銅箔施 U 3Am之鍍鎳（Β)β其次，於該鍍鎳層（β)上，連續地 形成0.01//m之中間電鍍鋼層（c)。 進而，使用圖2所示之裝置（滾筒型電極），於該層（〇 上形成10/z m之電鍍銅層。藉此’製造由銅/鎳/薄銅/厚銅 構成之複合銅箔。其他試驗條件係與實施例1相同。 18 201242762 以上之結果，板厚精度未達5%為良好，又，剝離強度 未達0.5kg/cm使密合性不足。可認為其原因在於，中間電 鑛銅層（C )之厚度不充分。將該結果相同地示於表卜 (比較例3) 使用12"m厚之電解銅落（a)。使用圖 ，並使用上述鍍敷條件，胃該電解銅结施 作為基底箔， 1所示之鍍敷裝置 以lym之鍍鎳（B)。其次， 形成20#m之電鍍銅層（c) 此，製造由銅/鎳/厚銅構成之 實施例1相同。 於該鍍鎳層（B )上，連續地 。形成10#m之電鍍銅層。藉 複合銅落。其他試驗條件係與 以上之結果’於步驟中’完全未發現錄層與銅層之間 之剝離，但板厚精度為1G%以上。可認為其原因在於，於 板厚精度差之ffl i的鐘敷裝置，未產生厚鍍敷。將該結果 相同地示於表1。 (比較例4) 作為基底羯’使用12#m厚之壓延鋼箱（A)。使用圖 1、所示之㈣裝置，並使用上賴敷條件，對該壓延㈣施 以之鍍鎳（Β)β其次，於該鍍鎳層上連續 地形成一之中間電鍍銅層⑻。進而，使用圖2所示之 裝置（滾筒型電極形成1〇"m之電鍍銅層。藉此，製造 由銅/錄/薄鋼/厚銅構成之複合銅_。其他試驗條㈣與實施 例1相同。 、之結果，剝離強度為Θ.5 kg/cm以上使密合性良 好’但板厚精度為5%以上且未達⑽。可認為其原因°在於^ 19 201242762 使板厚精度差之薄銅層變厚’而板厚精度變差。將該錄果 相同地示於表1 β [產生上之可利用性] 本發明具有如下等明顯之效果：可獲得一種於製造由 銅/鎳/銅構成之複合銅绪時’可提高鎳與銅之接合強度，真 適於藉由蝕刻形成電路之複合銅箔及其製造方法。 【圖式簡單說明】 圖1係表示於製造由銅/鎳/銅構成之複合銅箔時使用之 曲折式鍍敷裝置的例子。 技圖2係表示使用有於形成略厚於薄銅層（C)之銅層（D) 、使用之滾筒型電極裝置之例。"The sample is dissolved by alkali etching until the copper layer consisting of thin copper/thick copper is dissolved. The weight of the copper is determined by the weight change before and after the release. . 35. The thickness (") can be calculated by dividing the ratio of copper by 8.93 g/(m2· "m)'. It is preferable to measure the area of 2 〇W or more in order to accurately obtain the thickness. The measurement system calculates the plate thickness at 1 ,, and calculates the average value, and the unevenness is set to (maximum value - average value) / average value 或, or (average value: minimum value) / average value The evaluation system will set 5 or more and less than 1 〇% to "△", and 丨〇% or more to "X 0 for adhesion, 150 侧 on the ultra-thin copper foil side. When the substrate is laminated with c or more, the peeling strength is measured. When the peeling strength is less than 0.5 kg/cm and the peeling strength is less than 0.5 kg/cm, the peeling strength is set to "X y is not peeled off or the peeling strength is 0.5 kg/cm or more. In the case of the situation, set to "〇". As a result of the above, the sheet thickness accuracy was less than 5%, and the peel strength was 0.5 kg/cm or more to make the adhesion good. The results are shown in Table 1 in the same manner. 201242762 s 〇〇〇〇〇〇 XX 〇〇 wedge result / (plate thickness: 〇〇〇〇〇〇〇〇X < 3 u :D) fim Ο 〇〇〇〇〇〇〇fS B t-ι Ό ua ο ο 〇m >rj 〇〇〇〇u 〇H (Ν Ο 1*4 Ο CN 寸CN (Ν 〇〇ο 5s 夺z ¥ 〇〇〇〇〇〇 XX 〇〇isf /~N 0D ^ B VO r- ο ο ΓΟ m ο • 一璨^ isj: ε 硪a ο (Ν m 00 oo 〇〇 (N CN r~N < total narrow total vehicle 3 哟竣 1 lA 'ftil •ζίβΓ 11 r—Η 苳4.3⁄4) ¥5* CN m inch CN m inch magnetic 锑^3 jJ jJ -Ο 201242762 (Example 2) As a base box, 12/zm thick rolled copper is used Foil (A). Use the plating device shown in Figure 1 and use Under the plating conditions, the rolled steel foil was subjected to nickel plating (B) of 6 m. Next, an intermediate electroplated copper layer (C) of o.iwm was continuously formed on the nickel plating layer (b). Further, a device (drum-type electrode) shown by the circle 2 was used to form a 5 " electroplated copper layer. Thereby, a composite copper V made of copper/recorded/thin copper/thick copper was produced. Other test conditions were implemented The same results were obtained in Example 1. The above results were as good as the sheet thickness accuracy of less than 5%, and the peel strength was 〇5 kg/cm or more to make the adhesion good. The results are shown in the same table (Example 3). As the base foil, a rolled copper foil (a) having a thickness of 1 8 // m was used. The rolled copper foil was subjected to lym nickel plating (b) using the plating apparatus shown in Fig. 1 and using the above plating conditions. . Next, on the nickel plating layer (b), an intermediate plating copper layer (c) of 2 #m was continuously formed. Further, using the apparatus (drum type electrode) shown in Fig. 2, an electroplated copper layer of 10 was formed. In this way, a composite copper pavilion made of copper/nickel/thin copper/thick copper is produced. The other test conditions were the same as in Example 1. As a result of the above, the sheet thickness accuracy was less than 5%, and the peel strength was 〇·5 kg/cm or more to make the adhesion good. The results are shown in Table i in the same manner. (Example 4) As the base foil ', a rolled copper foil (A) having a thickness of 3 5 // m was used. The rolled copper foil was plated with nickel (b) using the plating apparatus shown in Fig. 1 and using the above plating conditions. Next, on the nickel plating layer (b), a 4"m intermediate electroplated copper layer (c) is formed continuously at 201242762. Further, after performing the chromate treatment using the above-described impregnation conditions, the device shown in Fig. 2 (rolling-type electrode) is used to form a copper layer of 20"]. Further, the key copper layer (C) and plating The amount of Cr between the layers (d) was 15 / / g / dm 2 , whereby a composite copper foil composed of copper / nickel / thin copper / rust preventive layer / thick copper was produced. Other test conditions were the same as in the first embodiment. As a result of the above, the sheet thickness accuracy was less than 5%, and the peel strength was 0.5 kg/cm or more, and the adhesion was good. The results are shown in the same table (Example 5). Rolled copper foil (A). The rolled copper foil is subjected to lym ore nickel (B) using the plating apparatus shown in Fig. 1. Secondly, the nickel plating layer (b) is used. The intermediate copper plating layer (c) is continuously formed. Further, after performing the chromate treatment using the above-described impregnation conditions, the apparatus shown in FIG. 2 (drum type electrode) is used to form an electroplated copper of 1 μm. Further, the amount of Cr between the 'bond copper layer (C) and the plating layer (d) is 45/zg/dm2. By this, the manufacturing is made of copper/nickel/thin copper/rust-proof layer/thick copper. The other test conditions were the same as in Example 1. As a result of the above, the sheet thickness accuracy was less than 5%, and the peel strength was 0.5 kg/cm or more to make the adhesion good. In the table (Example 6), an 18/zm thick electrolytic copper foil (A) was used as the substrate 羯'. Using the plating apparatus shown in Fig. 1, and using the above plating conditions, the rolled copper foil was subjected to l" Nickel plating (B) of the m. Next, on the nickel plating layer (b), a 2#m intermediate electroplated copper layer (c) is continuously formed at 201242762. Further, the device shown in Fig. 2 is used (drum type) Electrode), after forming a 10" electric money layer (D), chromate treatment was carried out using the above impregnation conditions. Further, the amount of Cr on the plating layer (9) was 3 〇 "/dm2. Thereby, a composite (four) composed of copper/nickel/thin copper/thick copper/rust-proof layer is produced. The other test conditions were the same as in Example 1. As a result of the above, the sheet thickness accuracy was less than 5%, and the peel strength was 0.5 kg/cm or more to make the adhesion good. The results are shown in the same table (Comparative Example 1). As a base treatment, a 70 "m thick electrolytic copper museum (A) was used. The electroplated copper foil was subjected to nickel plating (B) of U m using a plating apparatus of the figure and the scale, and using a plating strip of ±. An electroplated copper layer of 10 " m was formed on (B) using the apparatus shown in Fig. 2 (drum type electrode). Thereby, a composite steel foil composed of copper/nickel/thick steel is produced. The other test conditions are the same as in the examples. As a result of the above, the sheet thickness accuracy of less than 5% was good, but the peel strength was less than kg5 kg/cm, and the adhesion was insufficient. The results are shown in the same manner in Table ι ^ (Comparative Example 2) as a base foil, and a plating apparatus of the thickness shown in Fig. 1 is used using a 70"m thick rolled copper foil (Α) β, and the above plating conditions are used, The rolled copper foil was subjected to nickel plating (U) β of U 3 Am , and secondly, an intermediate plating steel layer (c) of 0.01 / / m was continuously formed on the nickel plating layer (β). Further, using the apparatus (drum type electrode) shown in Fig. 2, a 10/zm plated copper layer was formed on the layer (by this, a composite copper foil composed of copper/nickel/thin copper/thick copper was fabricated). The other test conditions are the same as those in the first embodiment. 18 201242762 The above results show that the sheet thickness accuracy is less than 5%, and the peel strength is less than 0.5 kg/cm, so that the adhesion is insufficient. The reason is that the intermediate electricity is The thickness of the ore layer (C) was insufficient. The results are shown in the same table (Comparative Example 3) using 12"m thick electrolytic copper (a). Using the above-mentioned plating conditions, the stomach should be used. Electrolytic copper is applied as a base foil, and the plating apparatus shown in 1 is nickel-plated (B) by lym. Secondly, an electroplated copper layer of 20#m is formed (c). Thus, the implementation of copper/nickel/thick copper is performed. In the same manner as in Example 1. On the nickel plating layer (B), a 10#m electroplated copper layer was formed continuously. The composite copper was dropped. Other test conditions were the same as the above results in the step: Peeling between copper layers, but the plate thickness accuracy is 1G% or more. It can be considered that the reason is that the plate thickness accuracy is poor. The bell coating apparatus of i did not produce thick plating. The results are shown in Table 1. (Comparative Example 4) A rolled steel box (A) having a thickness of 12 #m was used as the base 羯'. And (4) the device, and using the upper plating condition, the nickel (Β) β applied to the rolling (four) is followed by forming an intermediate copper plating layer (8) continuously on the nickel plating layer. Further, using FIG. The device (the roller-type electrode forms an electroplated copper layer of 1 〇" m. Thereby, a composite copper consisting of copper/recorded/thin steel/thick copper is produced. The other test strips (4) are the same as in the first embodiment. The peel strength is Θ.5 kg/cm or more to make the adhesion good. 'But the plate thickness accuracy is 5% or more and less than (10). It can be considered that the reason is that ^ 19 201242762 thickens the thin copper layer with poor plate thickness accuracy. 'The thickness accuracy of the plate is deteriorated. The results are shown in Table 1 in the same manner. [[Ease of use] The present invention has the following remarkable effects: a composite of copper/nickel/copper can be obtained. The copper thread can improve the bonding strength between nickel and copper, and is suitable for a composite copper foil which is formed by etching and a manufacturing method thereof. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an example of a meander type plating apparatus used for producing a composite copper foil composed of copper/nickel/copper. Fig. 2 shows that the use is formed to be slightly thicker than a thin copper layer ( C) Copper layer (D), an example of a roller type electrode device used.