201035390 四、指定代表圖： (二 )本代表圖之元件符號簡單說明： 卜具有載體箔之電解銅箔； 3〜接合界面層（有機劑層）； 5〜耐熱金屬層。 2〜載體箔； 4〜電解銅箔層 五、本案若有化學式時， Ml 〇 請揭示最能顯示翻_的化學式 六、發明說明： 【發明所屬之技術領域】 本發明係關於具有截許$ 节戰體泊之電解銅箔、 之電解銅箔之製造方法 便用该具有载體箔 獲致之銅覆層積板。 該具有載體箔 之電解銅箔所 【先前技術】 具有載體箔之電解鉬炫 ty ^ ,，係做為在電氣、電子產孝的 分野被廣泛使用之印刷雷肷i 杲的 刎電路板製造用材料而被使用至今。 一般而言，電解銅箔係與破 ^ ^ 坂增—銥虱基材、苯酚基材、聚 酰亞胺薄膜等高分子猫绪 、、緣基材貼合做為銅覆層積板，而用 於印刷電路板之製造。 化 特別是’近年來的電子機 低消費電力化之要求_年 器’隨著輕薄短小化之小型 比一年嚴格。其結果，要求 201035390 組入這些電子機器之印 € 路板之配線回路的導體厚度 ^ _ g . ^ 電路板之設計。具體 而吕，具有導體厚度2"m~i〇"m，電 ^ a：, λ4 ^ 軍路見約10 // m的細間 距配線電路之印刷電路板也已經 Φ ,. β i 貫用化了。然後，為達到 这二要求，具有載體羯電 冤解銅泊之使用廣泛地普及。 此具有载體箔之電解銅落， ,甘呈s 有刀為可剝離式與可腐蝕 Ο Ο ,^ ^ ^ 為加工成銅覆層積板後，可剝離 式係將載體珀剝離而除去 /式，可腐蝕式係將載體箔腐 蝕而除去的形式。不管是哪— ^ μ i ^ - 種八有载體箔之電解銅箔， 係藉由載體，泊之存在， 防止對於薄銅箔層之皺摺之發 生，而使銅箔表面之里 衣曲之異物附者及污染防止為可能。因此， 使具有載體箔之電解銅箔 質❸…… 乍，做為銅覆層積板之品 貝維持也變的容易。 近年來之傾向為，由於不需要特殊之設 載體箔剝離而除去之可剝離 π，' 剝離式之具有載體箱 ：：逮增加。做為此可 被供給於市場。 括各種剥離層之製品 例如，專利女龄·！ 79fiR1 v 獻1 (日本國專利申請特開昭57 — 72851唬公報）所開示之 笮r. ^ 了亲離式之具有載體箔之電解銅 治，係在銘载體上，設 电解幻 剝離層，在此剝離層 苒成之 θ上併用濺鍍等乾式 來形成銅箔層。秋而，—收 左/、钔電鍍法 3 ^ 右將如此之無機氧化物做為可剝離 式之具有载體箔之電解鉬# j到離 然耐熱性優良，但載卜_ ，雖 栽體治之剝離強度的安定化被認為是有 3 201035390 困難的。 利申請特開2:::二請者們，提倡專利文件2(曰本國專 載敝電解銅心：號公報)所開示之可剝離式具有 表面上，形成❹ 利文獻2中，開示了在載體落之 在該接合界面層上來形成之有機系接合界面層’ 載體箱之電㈣ 層析出形成之可剝離式具有 二亦即，此可剝離式具有_之電解 層構成之物太治/有機系接合界面層/電解鋼箱層之3 ，使、中壓 於以往之可剝離式具有载體落之電解銅 並且/❹後之載制之剝離強度之安定化為可能， 並且’可以小力量來剝離載體落’品質飛越地提升。其結 σ彔J離式具有載體箔之電解銅箔的使用變的隨手可 而廣泛被市場接受。 -而，近年來’銅箔與絕緣樹脂基材貼合時的負荷溫 度有上升的傾向。其結果，若將以有機劑製成接合界面： 之專利文獻2所開示的具有載體箔之電解銅箔，在超過別〇 C之冲壓成形温度之銅覆層積板製造條件下使用的情況， :於有機系接合界面層會劣化消I，因此載體菌與電解銅 治層燒結黏合在-起’而難以剝離除去載體@。為解決此 問題，本發明之申請者們，提倡專利文件3(曰本國專利申 請特開2001 — 688〇4號公報）以及專利文件4(日本國專利 申请特開2003 — 328178號公報）所開示之可剝離式具有 载體箱之電解銅箔 在此專利文獻3中，開示以提供··可解決可剝離式具 201035390 有載體箔之電解銅箔在超過30(rc的高溫沖壓成形後之載 體'每剝離強度的不安定性，且以小力量即可安定地剝離載 體羯之具有載體荡之電解銅猪為目的，在載體猪之表面 上开^成使用知l氰尿酸來形成之接合界面層，在該接合界 面層上使電解銅箔層析出形成之可剝離式具有載體箔之電 解銅箔。 然後，在此專利文獻4中，開示以提供：即使在2〇〇 ◎ c以上之溫度沖壓加工，載體箔之剝離也很容易之高溫耐 熱用具有載體箔之電解銅箔之製造方法為目的，對於載體 箔表面之有機接合界面的形成，其特徵在於：係使用含有 接合界面層形成時所使用之有機劑50Ppm〜2000Ppm之酸洗 溶液，一邊將載體箱之表面酸洗溶解，並藉由同時使有機 劑吸附來做為酸洗吸附有機覆膜而形成之高溫耐熱用具有 載體箔之電解銅箔之製造方法。 ‘二而專利文獻3及專利文獻4所開示之可剝離式具 ❹有載體々之電解銅猪，雖然可提升在超3 0 01之高溫沖 壓成形後之載體箔剝離強度的安定化，但在近年來變的更 夕樣化之進行了各種高溫負荷之銅覆層積板的製造中，也 被要求更進一步之高溫負荷後的載體箱剝離強度之 化° 特別是’在近年來之高溫沖壓成形中，也有在4〇〇t： 、、' 、门/JIIL進行加工的狀況，即使是專利文獻3及專利文 獻4所開不之具有載體箔之電解銅箔，都得到載體箔無法 剝離的纟士 I m 因此，在市場上，期望即使負荷了 4 〇 〇 °c附 5 201035390 剝離式具有載體 近的溫度’也可容易地將載體箔剝離之。 j 箔之電解銅猪的供給。 【發明内容】 【發明所欲解決之課題】 因此，本發明者們，經過精 ^研究的結果，以專利文 獻2、專利文獻3、專利文獻4所開示 > 找 ^ ^ 网不之發明為基礎，想到 若是以下的技術思想之具有载體箔 、 ，白艾電解銅箔，即使受到 將近4 0 0 C的鬲溫負荷，也可使费許々斤 ^ 文戰體泊之剥離強度低，且 文定化至可說是容易進行剝離作業的程芦。 具有載體箔之電解銅箔：盥太旅nnj_ /、本發明有關之具有載體箔 之電解銅猪’其特徵在於：若在包括栽體羯，接合界面層/ :熱金屬層/電解㈣層之層構成之具有載體箱之電解銅 Ό二使用GDS分析襄置’纟常態下從該具有載體羯之電 解鋼落之電解銅羯層側向載體荡側測定該耐熱金屬成分之 深j方向的輪料之常態峰值的半高寬為ψ卜將該具有載 冶之電解銅泊在3GG°C的大氣氣氛中加熱i 2Q分後，從 電解鋼H層侧向載體㈣，測定該耐熱金屬成份之深度方 向輪廟時之同峰值之半高寬為W2時，滿足 ([w2；H；W1])/[wl]s〇.3 之關係。 又與本發明有關之具有載體箔之電解銅箔，若使用 GDS/:析裝置，纟常態下從該具有載體箱《電解銅箱之電 、層側向載體m測定前述耐熱金屬成分之深度方向 、輪廓時之常態峰值的峰頂位置為P1，將該具有載體箔之 201035390 電解編在縦c的大氣氣氛中加熱3〇分後 層側向載體落側，測定該耐熱金屬成 ：：銅治 之同牵值之蜂頂位置為P2時，…向輪廊時 rγρ?ι-γρι Ίλ ^ λ ，、 2之峰頂位置差 (][Ρ1])在0· 2〇a m以内為佳。 更且，使用電解銅箔做為與本發明 ::::::前述_，設置 有鋅/I:界面層為有機劑層，在此接合界面層上以具 〇為佳。 一金層之任—種耐熱金屬層 況，在與本發明有關之具有載體箱之電解銅箱之情 為則述载體箔來使用之電 粗度，包括.矣电鮮則泊之析出面，其表面 為·ls)未滿、光澤度[Gs(60 7 上、以η太咖—丄 動方向測定之MD光澤声 定之TD光澤度與在流 為〇 9丨 ，X之比為[TD光澤度]/[MD光澤度] υ· 9〜1. 1之特性為佳。 〇…二]，前述載體箱’以使用包括析出面側之光澤度 光澤度[GS(6Q。）]之關係之電解銅箱為佳。 具有栽^體箱之電解銅箱之製造方法：與本發明有關之 面層：::::銅荡之製造方法，係包括㈣ 解鋼nu 電解飼落層之層構成之具有載體箱之電 < 造方法，盆胜與士 μ 含有3-疏基叫該載體箱，係使用電解 所選樓 丙院續酸或是雙（3—績丙基）二硫化物 〜杯之至少—種、且女咖 之硫萨$ ^ 、/、有環狀構造之4級銨鹽聚合物、氯 …電解液來得到之電解銅落，在此電解銅箱之析 201035390 出面側，依序設置做為接合界面層之有機劑層、耐熱金屬 層’在該耐熱金屬層上設置電解銅箔層。 銅覆層積板：與本發明有關之銅覆層積板，其特徵在 於：係使用上述具有載體箔之電解銅箔而獲致。 【發明效果】 與本發明有關之具有載體箔之電解銅箔，即使受到將 近400 C之高溫負荷，載體箔之剝離強度仍然低，且安定 化。因此，為即使在進行各種高溫負荷之銅覆層積板之製 造中也可使用之可剝離式具有載體箔之電解銅箔。又，做 為載體落，藉由使用電解含有3—巯基—丨一丙烷磺酸（以 下，僅稱為「MPS」）或是雙（3—續丙基）二硫化物（以下， 僅稱為「sps」）所選擇之至少一種、具有環狀構造之4級 銨鹽聚合物、氣之硫酸系銅電解液來得到之電解銅羯，而 可得到品質安定之具有載體箔之電解銅箔製品。 【實施方式】 * 、下f十於與本發明有關之具有載體箱之電解銅羯之 形態，及與本發明有關之銅覆層積板之形態，依序說明。 A.與本發明有關之具有載體笛之電解铜箱之形態 與本發明有關之具有載體荡之電解銅箱ι，係包括載 體箱2/接合界面層3/耐熱金屬層5/電解銅箱層4之層構 成，其層構成之概”模式地示於第1圖。在此第i圖中， 係由做為接合界㈣3之有機劑層與耐熱金屬層5所形 成。又，在此第i圖中，係為了把握各層之層積狀態而記 201035390 載對於各層之厚度並沒有反應現實製品 以構成與本發明有關之具有劃之電解銅：：：’ 箔」、「桩人^ 载體 之順序來說:層」、「耐熱金屬層」、「電解㈣層」 包括第！圖所示層構成之與本發明有關之具 之，箱，係包括載體請合界面暦/耐熱金屬 ： ❹ 〇 銅治層之層構成之具有載體箔之電解銅箔，使用GDS八 裝置a H態下從該具有載體箱之電解銅箱之 層側向載體箱側測定該耐熱金屬成分之深 ： ::常態峰值的半高寬…，「將該具有载體落 二在30JC的大氣氣氛中加熱12。分後，從電解鋼201035390 IV. Designation of representative drawings: (2) Brief description of the symbol of the representative figure: Electrolytic copper foil with carrier foil; 3~ joint interface layer (organic agent layer); 5~ heat resistant metal layer. 2~ Carrier foil; 4~ Electrolytic copper foil layer 5. If there is a chemical formula in this case, Ml 揭示Please reveal the chemical formula which can best show the turning _. Description of the invention: [Technical field of invention] The present invention relates to having a cut-off $ The copper clad laminate obtained by the carrier foil is used in the method for producing an electrolytic copper foil and an electrolytic copper foil. Electrolytic copper foil with a carrier foil [Prior Art] Electrolytic molybdenum ty ty ty ty ty ty ty ty ty ty y y y y y y y y y y y y y y y y y y y y y y y y y y y y y The material has been used to this day. In general, the electrolytic copper foil is bonded to a polymer such as a ruthenium-ruthenium substrate, a phenol base material, or a polyimide film, and a rim substrate is used as a copper-clad laminate. Used in the manufacture of printed circuit boards. In particular, the demand for low-consumption electric power in recent years has become stricter than that of a year. As a result, 201035390 is required to be incorporated into these electronic machines. The conductor thickness of the wiring circuit of the circuit board ^ _ g . ^ The design of the circuit board. Specifically, Lu, has a conductor thickness of 2 "m~i〇" m, electric ^ a:, λ4 ^ military road sees about 10 / m m fine-pitch wiring circuit printed circuit board has also been Φ,. β i melted. Then, in order to meet these two requirements, the use of the carrier 羯 冤 铜 铜 广泛 广泛 广泛 广泛 is widely used. The electrolytic copper having the carrier foil has a knives which are peelable and corrodible, and ^ ^ ^ is processed into a copper-clad laminate, and the peelable type peels off the carrier and removes / The erosive form is a form in which the carrier foil is etched away. No matter which - ^ μ i ^ - a kind of electrolytic copper foil with a carrier foil, by the presence of a carrier, to prevent the occurrence of wrinkles on the thin copper foil layer, and to make the surface of the copper foil It is possible to attach foreign objects and prevent pollution. Therefore, the electrolytic copper foil having the carrier foil is ❸ 乍, and it is easy to maintain the product as a copper clad laminate. In recent years, there has been a tendency to peel off π which is removed without special carrier foil peeling, and the peeling type has a carrier case :: catch increase. To do this, it can be supplied to the market. Products including various peeling layers For example, patent female age! 79fiR1 v 献 1 (Japanese Patent Application Laid-Open No. 57-72851唬), 笮r. ^ The isolated electrolytic copper with carrier foil is attached to the carrier, and the electrolytic detachable layer is provided. The copper foil layer is formed by dry-drying such as θ on the peeling layer. Autumn, - close left /, 钔 plating method 3 ^ right will be such an inorganic oxide as a peelable type of electrolytic foil with carrier foil # j to the excellent heat resistance, but the carrier _, although the carrier The stability of the peel strength of the treatment is considered to be difficult for 3 201035390. The application for special opening 2::: Two applicants, the patent document 2 (曰 national special 敝 敝 铜 : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : The carrier is formed on the bonding interface layer to form an organic bonding interface layer. The carrier box is electrically (4). The strippable type formed by chromatography is two, that is, the strippable type has the electrolytic layer formed by the chemical layer. The organic bonding interface layer/electrolytic steel box layer 3 makes it possible to pressurize the peeling strength of the conventionally peelable electrolytic copper with the carrier and the carrier after the crucible, and it can be small. The strength to strip the carrier falls' quality is improved. The use of the electrolytic copper foil having the carrier foil of the carrier σ彔J is widely accepted by the market. - In recent years, the load temperature when the copper foil and the insulating resin substrate are bonded together tends to increase. As a result, in the case where the electrodeposited copper foil having the carrier foil disclosed in Patent Document 2 in which the organic solvent is used as the joint interface is used under the conditions of the copper-clad laminate production of the press-forming temperature of the other C, : The organic bonding interface layer deteriorates, so the carrier bacteria and the electrolytic copper layer are sintered and bonded to each other, and it is difficult to peel off the carrier@. In order to solve this problem, the applicant of the present invention has proposed the disclosure of Patent Document 3 (Japanese Patent Application Laid-Open No. 2001-688-4) and Patent Document 4 (Japanese Patent Application Laid-Open No. 2003-328178). The peelable type electrolytic copper foil having a carrier case is disclosed in Patent Document 3 to provide a carrier capable of solving the peelable type of 201035390 electrolytic copper foil having a carrier foil after more than 30 (r high temperature press forming) 'Establishing interface layer formed by using known cyanuric acid on the surface of the carrier pig for the purpose of the instability of the peel strength and the stable removal of the carrier 羯 of the electrolytic copper pig with a small force A peelable type electrolytic copper foil having a carrier foil formed by chromatography of the electrolytic copper foil on the joint interface layer. Then, in Patent Document 4, it is disclosed to provide a temperature of at least 2 〇〇 ◎ c or more. Stamping processing, peeling of the carrier foil is also easy. High-temperature heat-resistant. For the purpose of manufacturing a copper foil with a carrier foil, the formation of an organic bonding interface on the surface of the carrier foil is characterized by : using a pickling solution containing an organic agent 50Ppm to 2000Ppm used for forming the interface layer, pickling and dissolving the surface of the carrier tank, and simultaneously adsorbing the organic agent to pickle the organic film. A method for producing an electrolytic copper foil having a carrier foil formed by high-temperature heat resistance. The second and the peelable type of electrolytic copper pig having a carrier 开, which is disclosed in Patent Document 3 and Patent Document 4, can be improved in Super 3 0 01 After the high-temperature press forming, the peeling strength of the carrier foil is stabilized. However, in the production of copper-clad laminates in which various high-temperature loads have been carried out in recent years, further high-temperature load is required. The peeling strength of the carrier case is particularly high. In the case of the high-temperature press forming in recent years, there is a case where the processing is performed at 4〇〇t:, ,, and JIIL, even if it is not disclosed in Patent Document 3 and Patent Document 4. The electrolytic copper foil with the carrier foil is obtained from the gentleman I m which cannot be peeled off by the carrier foil. Therefore, on the market, it is expected that even if the load is 4 〇〇°c attached 5 201035390, the peeling type has a near temperature of the carrier. In the present invention, the inventors of the present invention have studied the results of the research and development of In the patent document 3 and the patent document 4, it is based on the invention of the invention, and it is thought that the following technical idea has the carrier foil, and the white aluminum electrolytic copper foil, even if it is nearly 4,000 C. The temperature load can also be used to reduce the peeling strength of the Wenshi body mooring, and the text can be said to be easy to carry out the peeling operation of the process. Electrolytic copper foil with carrier foil: 盥太旅nnj_ /, The electrolytic copper pig having a carrier foil according to the present invention is characterized in that: in the case of an electrolytic copper crucible having a carrier tank composed of a layer of a carrier layer, a bonding interface layer/: a hot metal layer/electrolyte (four) layer, GDS analysis is used. The half-height width of the normal peak of the rod in the deep j direction of the heat-resistant metal component is measured from the lateral side of the electrolytic copper layer of the electrolytic steel having the carrier 羯. Electrolytic copper plating for loading and smelting at 3GG After heating the i 2Q fraction in the atmospheric atmosphere of °C, from the side of the electrolytic steel H layer to the carrier (4), when the half-height width of the same peak of the heat-resistant metal component is measured as W2, it satisfies ([w2;H ;W1])/[wl]s〇.3 relationship. Further, in the electrolytic copper foil having a carrier foil according to the present invention, if a GDS/:precipitation device is used, the depth direction of the heat-resistant metal component is measured from the electric carrier of the electrolytic copper box and the lateral carrier m by the carrier box. The peak position of the normal peak at the time of the contour is P1, and the 201035390 with the carrier foil is electrolyzed in the atmosphere of 縦c, and the side of the lateral carrier is heated by 3 〇, and the heat-resistant metal is determined to be: When the position of the bee top of the same value is P2, it is better that the position of the peak top position (][Ρ1]) of rγρ?ι-γρι Ίλ ^ λ , 2 is better than 0·2〇am. Further, an electrolytic copper foil is used as the organic solvent layer provided with the zinc/I:interfacial layer as the organic layer of the present invention, and the bonding interface layer is preferably used. A gold layer of any kind of heat-resistant metal layer, in the case of an electrolytic copper box with a carrier box according to the present invention, the electrical thickness of the carrier foil is used, including the precipitation surface of the 矣 矣 鲜, the surface is · ls) under full, gloss [Gs (60 7 on, η too coffee - 丄 方向 测定 MD MD MD MD MD MD MD MD MD MD MD MD MD MD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD Gloss]/[MD gloss] υ·9~1. 1 is preferable. 〇...2], the carrier case 'is used in relation to the glossiness [GS(6Q.)] including the side of the deposition surface. The electrolytic copper box is preferred. The manufacturing method of the electrolytic copper box with the body box: the surface layer related to the invention: :::: The manufacturing method of the copper slab, including (4) the layer of the steel nu electrolytic feeding layer The electric storage method with the carrier box is constructed. The method of basin-winning and sinking contains 3-salt-based carrier box, which is the use of electrolysis to select a building or a double (3-propyl) disulfide. ~ At least one of the cups, and the female sulphur sulphur $ ^, /, a ring-structured 4-stage ammonium salt polymer, chlorine ... electrolyte to obtain electrolytic copper, where copper is electrolyzed On the exit side of the box 201035390, an organic agent layer and a heat resistant metal layer as the joint interface layer are disposed in sequence, and an electrolytic copper foil layer is disposed on the heat resistant metal layer. Copper clad laminate: copper clad layer related to the present invention The laminated sheet is obtained by using the above-mentioned electrolytic copper foil having a carrier foil. [Effect of the Invention] The electrolytic copper foil having a carrier foil according to the present invention is peeled off by a carrier foil even if subjected to a high temperature load of approximately 400 C. The strength is still low and stable. Therefore, it is a peelable type electrolytic copper foil having a carrier foil which can be used even in the manufacture of a copper-clad laminate which is subjected to various high-temperature loads. At least one selected from the group consisting of 3-mercapto-indenyl propane sulfonic acid (hereinafter, simply referred to as "MPS") or bis(3-propyl) disulfide (hereinafter, simply referred to as "sps") is used. An electrolytic copper crucible having a carrier foil having a ring-shaped structure of a 4-stage ammonium salt polymer and a sulfuric acid-based copper electrolyte obtained in a gas phase can be obtained, and an electrolytic copper foil product having a carrier foil having a stable quality can be obtained. ten The form of the electrolytic copper crucible having the carrier case according to the present invention and the form of the copper clad laminate according to the present invention are described in order. A. The form of the electrolytic copper box with the carrier flute related to the present invention The electrolytic copper box ι having the carrier sway according to the present invention comprises a layer of a carrier case 2 / a bonding interface layer 3 / a refractory metal layer 5 / an electrolytic copper box layer 4, and the layer constitution thereof is schematically shown in the Figure 1, in this figure i, is formed by the organic agent layer and the heat-resistant metal layer 5 as the bonding boundary (4) 3. In this figure, in order to grasp the layering state of each layer, it is recorded in 201035390. The thickness of each layer does not reflect the actual product to constitute the electrolytic copper of the present invention: :: 'Foil", "Pile of the carrier": layer, "heat resistant metal layer", "electrolysis (four) layer" including the first! The layer shown in the figure is related to the present invention, and the box comprises a carrier 请/heat-resistant metal: 电解 电解 治 治 layer of electrolytic layer of electrolytic copper foil with carrier foil, using GDS eight device a H The depth of the heat-resistant metal component is measured from the side of the layer of the electrolytic copper box having the carrier box to the side of the carrier box: :: the full width at half maximum of the normal peak..., "the carrier is placed in an atmosphere of 30 JC. After heating 12 minutes, from electrolytic steel
二載體則，測定該耐熱金屬成份之深度方向輪廓時之 Ρ值之半高寬」為W2時’滿足（[W2]_[W1])/[W1]S 之關係為特徵。關於設置如此參數的理由，說明如下一。· :2圖，係使用：使用以往之電解銅羯做為载體箱， 表面上形成構成接合界面層之有機劑層，在1表面上 屬層，在該舰屬層之表面上形成電解㈣ 載體箱之電解銅落，藉由堀場製作所製的高頻輝 先放電为光表面分析裝置(GDS(GD—_分析裝置”，表― :ί:向(從電解銅箱層側向载體荡側之以氯機射探測； -度方向)之耐熱金屬成分的輪摩。然後，在第3圖中， 係使用與本發明有闕之具有載體箱之電解銅箱，表干同樣 以㈣成分之輪廊。在此，第2圖⑷及第 圈⑷，係在常態之耐熱金屬成分之錄的深度方向輪廊。 9 201035390 =2圖⑻及第3圖（b)’係在⑽。⑽分之加教處理 二t分之深度方向輪廓。更且’第2圖⑷及第3圖⑹， J 20分之加熱處理後同成分之深度方向輪廊。 在此，從第略)及第3圖(c)之錄的峰值形狀來看， 於第2圖(C)之錄峰值形狀’可明顯知道第3圖(c)之 錦峰值形狀變的寬廣。然而， 性的侧標。因此，考慮如下差亦:無=括客觀 與第2圖（c)之關係，以及第3 圖（a) 去磨 圃以）及第3圖（c)之關係來 :慮宫-開始，著眼於料值之形狀，比較該檢出峰值之 首先，以以往之電解㈣做為載體落來使用之具 值之電解銅箱的情況來看，第2圖⑷之常態的錄峰 值的半南寬W1為〇.42/im。然後， 八 交弟2圖（c)之300t： xl20 刀=熱處理後的料值半高寬W2$ Q 6i”。亦即， ([W2]-[WlD/[wl]=〇.45。相對於此， 有載體4明有關之具 半 弟3 ®(a)之常態的鎳峰值的 ^ 第 3 圖（C)之獄χ12〇 分 ;;、，、處理後的錄峰值半高寬W2為Ο.”"。亦即， ([W2]-[W1])/[W1] = 〇. 〇4。 做為2些情況來看’可理解到相較於以以往之電解㈣ 關：=、泊來使用之具有載體揭之電解銅落，與本發明有 於載體/體备之電解銅荡即使受到長時間的加熱，錄對 之ΐ Γ則的擴散也很少，而可防止電解鋼结層與載體羯 二黏合。根據本發明者們的研究，若上述之 Wl])/[Wl]$〇.3,即使受到 4〇(Γς：χ3(^~ΐ2〇 分之 10 201035390In the case of the second carrier, the half-height width of the Ρ value when the depth-direction profile of the heat-resistant metal component is measured is W2, and the relationship of ([W2]_[W1])/[W1]S is satisfied. The reason for setting such parameters is as follows. · : 2, used: using the conventional electrolytic copper crucible as a carrier box, forming an organic agent layer constituting the joint interface layer on the surface, forming a layer on the surface of 1 and forming electrolysis on the surface of the ship layer (4) Electrolytic copper drop of the carrier box, the high-frequency glow first discharge produced by the market is a light surface analysis device (GDS (GD-_analytical device), table - : ί: direction (from the side of the electrolytic copper box side to the side of the carrier) The wheel of the heat-resistant metal component is detected by a chlorine machine; and in the third figure, an electrolytic copper box having a carrier box which is the same as the present invention is used, and the surface is also made of the wheel of the (four) component. Here, Fig. 2 (4) and circle (4) are in the depth direction of the normal heat-resistant metal component. 9 201035390 = 2 (8) and 3 (b) '(10). (10) The teaching process is to deal with the depth direction contour of the two t points. Moreover, the second direction (4) and the third figure (6), J 20, the heat treatment of the same direction of the depth direction of the corridor. Here, from the first and third figures (c) In the peak shape of the record, the peak shape of the record in Fig. 2(C) is clearly known as the peak shape of the picture (c). The broadness of the sexual side, however, considers the following differences: no = the objective relationship with the second figure (c), and the third figure (a) to remove the wear and tear) and the third figure (c) The relationship: the consideration of the palace - the beginning, focusing on the shape of the value of the material, compare the peak of the detection first, the previous electrolytic (four) as a carrier to use the value of the electrolytic copper box, Figure 2 (4) The semi-south width W1 of the normal recorded peak value is 〇.42/im. Then, the octagonal brother 2 figure (c) 300t: xl20 knife = the half value width W2$ Q 6i after heat treatment. That is, ([W2]-[WlD/[wl]=〇.45. In contrast, there is a carrier 4 that is related to the normal nickel peak of the third half (3). The prison is 12 points;;,, after processing, the peak height and width W2 is Ο."". That is, ([W2]-[W1])/[W1] = 〇. 〇4. In some cases, it can be understood that it is compared with the electrolyzed copper which has the carrier uncovered in the previous electrolysis (4):=, mooring, and the electrolysis copper which is in the carrier/body preparation of the present invention is subjected to a long time. The heating, the recording of the ΐ 的 的 的 的 的 的 的 的 的 的 的 的 的 的 的 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解Even if you receive 4 〇 (Γς:χ3(^~ΐ2〇10 of 10, 2010,390,390
加熱，也可出盔-^ A 成為可各易地剝離載體之具有載㈣之 ^ ，在此採用30(TCxl20分之加熱條件，係 比第2圖及第3菌b 係如同對 變化之故。理解，可顯著地觀察錄峰值形狀的 位詈的值，处第2圖（a)來看之第2圖（b)的鎳峰值峰頂 、移，與從第3圖（a)來看之第3圖化）的 頂位置的偏移。從笛9固，、 ㈣峰值峰 Ο Ο 常態之具有载體：Γ 第3圖(a)來看，可知「從 測定耐敖全屬成Γ ^電解㈣層側向載體落側 位置叫=之深度方向的輪料之常態峰值的蜂頂 「將具有載#:從弟2圖⑻及第3圖(b)來看，可知 鐘後，從雷：之電解銅箱在300。。之大氣氣氛加熱30分 鐘谩’從電解銅绾 71 層側向載體箔側測定耐熱金屬成分之深 度方向的輪廓時 衣 峰值的峰頂位置（P2)」。此時，在 以在之電解鋼箔做 在 箱的产、兄，η為載體泪來使用之具有_之電解銅 值峰頂位晋“仗第2圖(a)來看之第2圖⑻的鎳峰 離(第咖 電解㈣的情Πλ在與本發明有關之具有載體猪之 圖⑻之a的距離)。，、“(第3 因此，相較於倕用 裁體、〃之電解銅箔做為載體箔之具有 戟體治之電解鋼箔， 落，即使受到加熱，在深=有關之具有載體箱之電解銅 變化氺作，丨、 又方向輪廓的鎳峰值峰頂的位置 很^而可理解到錄對於載體羯侧的擴散少，電解 201035390 銅羯層與载體羯層之燒結黏合的防止效果高。根據本發明 研九右（[Ρ2]-[ρι ]) ^ 〇· 2〇 a m，即使受到 4〇〇。匸 刀120刀之加熱’也為可更確實且容易地將載體猪剝離之 具有載體箱之電解銅落。又，在此採用3〇〇tx3〇分之加熱 條件，係如同對比笛9国Β @ 0 π J對比弟2圖及弟3圖即可理解，力口熱後之峰 頂位置之偏差（第2圖⑻及第3圖⑻之a距離），較300 ⑶分之加，後的峰頂位置之偏差（第2圖⑷及第W c之距離）容易捕捉到明顯的差異。 有’關於為得到包括上述參數之與本發明有關之具 有載體…解銅箱之適當的構成材料，說明如下。 明有關之具有_之電解銅 係使用電解含有從MPS或是SPS所選 一 、具有環狀構造之4級銨^ 、 解液而得到之電解銅二 =二之硫酸銅系銅電 解液，適人做A& θ ， 〇之硫®夂鋼系銅電 載p 發明有關之具有載體@之電解銅箱之 戰體治之雷紐Λ·/Τ >也,丨 ’白 曰4电解銅泊之製造為可 酸系銅電解液」之其太έ人 所說之「硫 12〇g/1 ,, 基本 '、且。，以採用銅濃度為4〇g/1〜 由硫酸濃度為60以〗〜220g/：l為佳。妒 佳的情況為，銅濃'，，）後，更 g 8°g/卜自由硫酸濃以 〜15〇g/1之範圍。 i辰度為 藉由選擇性使用以如此製 做為載體笮,± &万/去木侍到之電解銅箔 巧載體㈣較於使用以往 〜 設置於其析出而夕雄々从 日7障况’可推測 冓成接合界面層的有機層之形An 異。亦即，可相刭蕤άH s之形成形態相 使用上述之電解鋼箱做為載體箱， 12 201035390 即使受到加埶，★可 ''也可错由抑制構成接合界面@ + 構成成分之分解而使有機劑層的消失量受:二：有機劑的 到使構成接合界面層的成分往載體㈣之擴=且可得 (以下’將這些效果稱為「擴散防止 之效果 防止載體箱與電解銅箱層之燒結黏合，載體二果’可 層之燒結黏合變的不容…b載體治與電解銅箱 的低且安定化。易發生，可推測載體箱剝離強度變 構成前述栽體箔之電解銅Heating, can also be helmeted - ^ A becomes a carrier that can easily peel off the carrier (4) ^, here using 30 (TCxl20 heating conditions, compared to the second figure and the third bacteria b as the change Understand, the value of the position of the peak shape can be significantly observed, and the peak of the nickel peak and the shift of the second graph (b) in Fig. 2(a) and the view from Fig. 3(a) The offset of the top position of the third graph). From the flute 9 solid, (4) peak peak Ο Ο Normal carrier: Γ Figure 3 (a), it can be seen that "from the determination of sputum resistance to all Γ ^ electrolysis (four) layer lateral carrier side position = = The top of the normal peak of the wheel material in the depth direction "will have the load #: from the brothers 2 (8) and 3 (b), it can be seen that after the clock, from the mine: the electrolytic copper box is 300. After heating for 30 minutes, the peak top position (P2) of the peak of the heat-resistant metal component in the depth direction of the heat-resistant metal component was measured from the side of the electrolytic copper crucible 71 to the side of the carrier foil. At this time, in the case where the electrolytic steel foil is used in the production of the box, the brother, η is used as the carrier tear, and the electrolytic copper value peak position of the _ is shown in Fig. 2 (a) (Fig. 2) The nickel peak is separated (the distance λ of the electrolysis (4) is in the distance of the carrier of the carrier (8) associated with the present invention), and "(3, therefore, compared to the electrolytic copper of the 裁, 〃 The foil is used as a carrier foil for the electrolytic steel foil with a ruthenium treatment. Even if it is heated, the position of the peak of the nickel peak of the 轮廓 and the direction profile is very high in the depth = the change of the electrolytic copper with the carrier box. It can be understood that the diffusion of the carrier side of the carrier is small, and the effect of preventing the sintering adhesion of the electrolytic layer 201035390 between the copper layer and the carrier layer is high. According to the invention, the research is nine ([Ρ2]-[ρι ]) ^ 〇· 2〇 Am, even if it is subjected to 4 〇〇. The heating of the trowel 120 knives is also an electrolytic copper drop with a carrier box which can peel the carrier pig more reliably and easily. Moreover, the heating condition of 3 〇〇tx3 〇 is used here. , as the contrast flute 9 country Β @ 0 π J contrast brother 2 map and brother 3 map can be understood, after the hot mouth peak position The deviation (a distance between Fig. 2 (8) and Fig. 3 (8)) is more than 300 (3) points, and the deviation of the rear peak position (the distance between Fig. 2 (4) and the W c) is easy to capture a significant difference. 'About obtaining a suitable constituent material having a carrier-resolved copper box according to the present invention including the above parameters, the following is a description of the electrolytic copper-based electrolysis containing electrolysis containing one selected from MPS or SPS. A 4-layer ammonium compound in a ring structure, an electrolytic copper obtained from the liquid solution, and a copper sulphate-based copper electrolyte, which is suitable for A& θ, sulphur sulphur® bismuth steel-based copper electric carrier p. @之 electrolytic copper box battle body treatment of the Λ Λ Τ Τ Τ 也 也 也 也 也 也 也 也 也 曰 曰 曰 曰 曰 曰 曰 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解/1,, Basic ', and., to use copper concentration of 4〇g/1~ from sulfuric acid concentration of 60 to 〗 〖220g/:l. In the case of 妒佳, after copper thick ',,), More g 8 °g / Bu free sulfuric acid concentration of ~ 15 〇 g / 1 range. i Chen degree by selective use to make this carrier as a carrier, ± & Wan / go wood The electrolytic copper foil carrier (4) of the waiter is different from the use of the conventional ~ set in the precipitation of the Xia Xiong from the 7th fault condition 'the organic layer of the joint interface layer can be presumed to be different. That is, it can be compared with H The formation phase of s uses the above-mentioned electrolytic steel box as a carrier box, 12 201035390 Even if it is subjected to twisting, it can be mistaken by inhibiting the decomposition of the constituent components of the joint interface @ + and causing the disappearance of the organic agent layer. : 2: The organic agent is added to the carrier (4) to form the bonding interface layer (the following is 'the effect of the diffusion prevention effect to prevent the sintering of the carrier case and the electrolytic copper box layer, the carrier 2 The result is that the sintering bond of the layer can not be changed... The b carrier treatment is low and stable with the electrolytic copper box. It is easy to occur, it can be inferred that the peeling strength of the carrier box becomes the electrolytic copper of the aforementioned carrier foil.
ΟΟ
一 ’，-相·<>啊出面，包衽A :面粗度（邮S)未滿光澤度[Gs(6G。）]為二 以及在寬度方向测定之TD光澤度與在流動方向測定之 MD光澤度之比⑽光澤度]/W光澤度])為之特 者為佳。包括如此之物理表面狀態之電解銅箔的析出 面，可使有機劑吸附時以均一的厚度之高密度且密著性優 良，有機皮膜之形成為可能，防止熱擴散造成之有機劑層 的消失。X ’包括如此之物理表面狀態之電解銅箔的析出 面，可使「有機劑層之均一厚度的形成能」、「載體落與 接合界面層之密著性」、「透過接合界面層與耐熱金屬層 來接著之與電解銅箔層的密著性」安定化。 在此析出面側之表面粗度（Rzj i S)之下限值沒有限 定。然而，根據不同測定器的感度，經驗上該表面粗度的 下限值為0. 1 # m程度。但是，在實際的測定中，可見到差 異，因此做為可保證之測定值之下限被認為是〇. 2 # m程 度。從以往，為評價電解銅箔之析出面的平滑性，使用表 面粗度Rzjis之值至今。但是，只能到高度方向的 13 201035390 四凸情報，無法得到 〇 止 >里ώ〆 寺情報。相對仇 此先澤度係反映兩者情報的參數，藉由 }於 而可综合判斷表面粗度周期、起 ZJ1S的併用 性等各種參數。 Λ 別之面内的均一 因此’與本發明有關之電解銅羯之 澤度_。)]為40。以上之特性為佳 ’心括光 [Gs⑽]]為6〇()以上更佳。 _ 4’以先澤度 疋在上述表面粗度 内，且光澤度[Gs(60。）]為400以上， 圍 ，-Φ ^ ^ J 〇兄疋表面起伏極 〇 ^電解對於有機劑層之均-厚度的形成為有利， 且可为別使载體笛與接合界面層之密著性 層與耐熱金屬層來接著之與電解 1面 ^ 电解銅咱層的密著性安定化。 又，若該光澤度[Gs(6〇。）]為6〇〇以上 _ _ ⑴ 有機劑層之的 :厚度的形成能」、「載體箱與接合界面層之密著性」、 ❹ ^過接合界面層與财熱金屬層來接著之與電解銅羯層的 -者性」之各特性的安定化效果也飛躍性的提升。在此， 光澤度的上限值並沒有規定，但以經驗來判斷&⑽ 以900程度為上限。 在此，[⑽〇。他光澤度，係對於電解銅猪表面以入 射角6。的測定光來照射’而測定以反射角6〇。所反射回來 的光強度。在此所說之入射角，係以對於光的照射面之垂 直方向為。。。然後’根據Jlszmi—1997,記載入射角 相異之5種鏡面光澤度測定方法，應根據試料的光澤度來 «最適當之入射角。其中，又以入射角6〇。為可廣泛測 疋低光澤度的試料至高光澤度的試料。因此，與本發明有 14 201035390 關之電解銅箱之光澤度測定，係主要採用6〇。。又，盥本 發明有關之光澤度’係使用曰本電色工業股份公司製：澤 計P G — 1Μ型，根播本、、黑由 嚴先澤度之測定方法之JIS Ζ 8741 — 1997 來測定。 以上所述表面粗度與光澤度，由於具有—^的關連 [生所以考慮同時管理兩者，係表示低輪麻銅箱之低輪A ', - phase · < > ah, package A: surface roughness (mail S) less than gloss [Gs (6G.)] is two and measured in the width direction of the TD gloss and in the flow direction The ratio of the measured MD gloss (10) gloss / W gloss] is preferred. The deposition surface of the electrolytic copper foil including such a physical surface state can make the organic agent have a high density and excellent adhesion with uniform thickness, and it is possible to form an organic film to prevent the disappearance of the organic agent layer due to thermal diffusion. . X' includes the deposition surface of the electrolytic copper foil in such a physical surface state, and enables "the formation of a uniform thickness of the organic agent layer", "the adhesion between the carrier and the interface layer", and "the transmission interface layer and the heat resistance". The adhesion of the metal layer to the electrolytic copper foil layer is then stabilized. The lower limit of the surface roughness (Rzj i S) on the side of the deposition surface is not limited. However, the lower limit of the surface roughness is empirically 0.11 m degree according to the sensitivity of the different measuring devices. However, in the actual measurement, a difference is observed, so the lower limit of the measured value as a guarantee is considered to be 〇. 2 # m degree. In the past, in order to evaluate the smoothness of the deposition surface of the electrolytic copper foil, the value of the surface roughness Rzjis has been used up to now. However, it is only possible to get to the height of the 13 201035390 four convex information, can not get the information of the gt & > Relative vengeance This is the parameter that reflects the intelligence of both, and can be used to comprehensively judge the surface roughness cycle and the compatibility of ZJ1S.均 Uniformity in the other side Therefore, the degree of the electrolytic copper enamel associated with the present invention is _. )] is 40. The above characteristics are better. ‘Including light [Gs(10)]] is better than 6〇(). _ 4' is in the above surface roughness, and the gloss [Gs(60.)] is 400 or more, and the circumference of -Φ ^ ^ J 〇 〇 疋 疋 疋 电解 电解 电解 电解 电解 电解The formation of the uniform thickness is advantageous, and the adhesion between the carrier flute and the adhesive layer of the interface layer and the heat resistant metal layer may be followed by adhesion to the electrolytic copper layer. Further, if the gloss [Gs (6 〇.)] is 6 〇〇 or more _ _ (1) the organic agent layer: the thickness formation ability", "the carrier case and the bonding interface layer adhesion", ❹ ^ The stability effect of the characteristics of the interface layer and the heat metal layer followed by the electrolytic copper layer is also greatly improved. Here, the upper limit of the gloss is not specified, but it is judged empirically that & (10) is an upper limit of 900 degrees. Here, [(10) 〇. His gloss is based on the angle of incidence of the electrolytic copper pig. The measurement light was irradiated' and measured at a reflection angle of 6 〇. The intensity of the light reflected back. The incident angle referred to here is the vertical direction of the irradiation surface with respect to light. . . Then, according to Jlszmi-1997, the five methods for measuring the specular gloss of incident angles are based on the gloss of the sample «the most appropriate angle of incidence. Among them, the incident angle is 6〇. It is widely used to measure low gloss samples to high gloss samples. Therefore, the gloss measurement of the electrolytic copper box with the invention of 14 201035390 is mainly carried out by using 6 〇. . In addition, the glossiness of the invention is measured by JIS Ζ 8741-1997, which is manufactured by Sakamoto Denshoku Industries Co., Ltd.: Zeji P G-1 type, root broadcast, and black by Yan Xianze's measurement method. The surface roughness and gloss mentioned above have a correlation of -^. Therefore, it is considered to manage both at the same time, which means the low wheel of the low-waist copper box.
品質，對於使「有機,泡丨思—L 機劑層之均一厚度的形成能」、「载體 Ο ’;#與接合界面層之密菩袖 「、 屬層來接著之與電解銅過接。界面層與财熱金 %钔泊層的密著性」安定化是有用的。 又’本發明之做為 出面側的光澤度[Gs=自「來使用之電解㈣，前述析 )]之在寬度方向測定之TD光澤 度」與在流動方向測定 光澤度]的值為在0 9]^ 光澤度]^ 為佳。亦即，寬二1之乾圍，變化幅度以在職内 TD . , ^ °及流動方向的光澤度的差很小，意 味著TD方向與肋方向之 用如此之電解㈣來做異小。因此，若使 厚度的形成能、「• 從使「有機劑層之均- b」 载體箔與接合界面層之密著性 「.悉 過接合界面層與耐敎金屬…卩面層之…」、「透 性 '、、、金屬層來接著之與電解銅羯層的密著 」*3C疋化的勸點枣4 沒有差異，因w 於以方向與MD方向之密著性 又 冑體箱剝離時’不需要在意剝離方向。 況，以使用11月中做為載體箔來使用之電解銅箔的情 [_。心係=:==°。)]>光澤度 與[Gs(6(ru，1宙 做為先澤度，藉由使用[GS(20。）] 〇明顯地捕捉與以往之做為载體箔來使用 15 201035390 之電解銅名之差異。在本發明中所使用之電解鋼羯，前述 析出面側’係包括光澤度[Gs(2(r)]>光澤度[Gs(6〇。)]之 關係攸驗來看’在高光澤且低表面粗度之電解銅箔的 情況，會成立光澤度[Gs(2(r)]>光澤度[Gs(6(r)]>光澤 度[Gs(85 )]之關係。然後，在低光澤且低表面粗度之電解 銅議況，會成立光澤度[Gs⑽。 >光澤度[Gs⑻。）]之關係。更且，在無光澤且低表面粗度 之電解銅箱的情況，會成立光澤度[Gs(85。)]〉光澤度 光澤度[Gs(2〇。)]之關係。因此，可判斷除； -定的入射角之光澤度的值以外，根據與其他*同入射角 之先澤度之值，做為電解銅箱的平滑性的指標是有用的。 如以上所述之做為載體箱來使用之電解銅羯，並沒有 特別限制厚度，但若考量到操作性，以厚 ^ 又有 ㈣為佳。特別是，本發明所使用之做為載' 箔，若在使用後述製造方法 2 A之電解銅 造的愈厚，有該析出面的粗声：電解銅箱的厚度製 接合界面層=:，光澤度也上升… 位於攸第丨圖可理解之位置之 層，係採用所謂有機劑層為佳 ° 金屬氧化物等無機材來構成之接合界m屬或是 離特性*定化之故。以下，依序說明。 在此所說的「接合界面層（有機 機化合物内，使用具有置換基之三唾化物二在含氮有 笨并三唾(以下，稱為「βτΑ」）、 二 2’3- 為「〜、Ν，，Ν，—雙竣基：开三。坐(以下，稱 又v本开二唑曱基）脲（以下，稱 16 201035390 為「BTD — U|)、l 氮一1 ? A ^ An r J ; a ’ 2, 4—二唾（以下，稱為「TA ) …一胺基-1氮-1，2,卜三唾(以下，稱為「A二 等來形成之層為佳。此「接合界面層(有機劑 ： -Jtr '4- 4- Ail 」成* 方法’在製造形態中會敘述。 耐熱金屬層：然後’ 「耐熱金屬層」，係由鎳、錄— 磷、鎳一鉻、鎳一鉬、鎳—鉬—鈷、 ” ΛΒ ^ ^ ，、，古鎳一鎢、鎳 -錫，錄合金n — n銦、銘—鶴、始— Ο Ο 銅：钻—鎳—鱗、鈷—踢-磷等録合金之任-種來構成。 ^耐熱金屬層」之形成方法，會在製造形態中敘述。 藉由此耐熱金屬層之存在，與本發明有關 治之電解銅箱，即使受到如沖壓加 有載體 。〜上之熱履歷，_也可容易度在30° 甚播出拉人 也了令易地攸電解銅箱層剝離。 右構成接合界面層之有機 離下，6 ^ 4 、电解钔泊層在直接接觸的狀 :構成雷 3°〇t之溫度’則構成有機劑層之有機劑 散==二"發生-定― 存在耐熱金屬層做:屏::之 而可防止在高溫沖壓侔件下夕“ 相互擴散 輯件下之有機劑層的消失。 二》後’耐熱金屬層 圍。此時之厚声 X ’為〇. 001^〜〇· 05/Z m之範 時之異種金屬之平均备少王的平面上形成耐熱金屬層 從此耐熱金屬層的厚度：：面積之覆膜量來計算的厚度。 屬層的厚度若未滿〇二，可知為非常薄的層。耐熱金 應達成之功能Φ . θ況，在上述耐熱金屬層之 、中，無法達到做為屏障層之功能而有損耐熱 17 201035390 =性則Si二若耐熱金屬層的厚度超過°.°5… 中l加工後之具有載體箔之電解銅落 離強度差異會變大。 ㈣體 > 自剝 ㈣銅μ:在此所說之電解銅羯層’係設置於上述 八”、、層上之銅層，與銅覆層積板的基材樹脂直接貼 口而用於回路形成用之銅層。關於此電解銅箔層之厚度'， 並沒有特別限定。然而’若考慮為具有載體箱之電解銅笛 之電解銅箱層，可想料10"以下之厚度。這是由於若 :解銅箱層之厚度若料1〇"，則失去了做為具有載體 泊之電解鋼泊的意義之故。然後，在電解銅箔 施以下各種表面處理也為可能。 面實 表面處理：在此所說之表面處王里，係在該電解銅落層 之表面，根據用途適當組合實施防鏽處ί里、粗化處理、密 著性提升之處理等。例如，將與本發明有關之具有載體落 ，銅箱與印刷電路板用之聚酰亞胺樹脂、聚酰胺樹脂、或 氟树月曰基材、液晶聚合物等熱可塑性樹脂貼合之情況時， 為得到固定效果而也可附加粗化處理。這是由於相較於不 在銅箱表面施以粗化處理之情況，可得到高接著強度、而 耐熱性等的要求特性提升之故。 β.具有载體箔之電解銅箔之製造形態 與本發明有關之具有載體笛之電解銅箱之製造方法， 做為載體箔，使用電解含有3一巯基—丙烷磺酸（以下， 僅稱為「MPS」）或是雙（3—磺丙基）二硫化物（以下，僅稱 為SPS」）所選擇之至少一種 '具有環狀構造之4級銨鹽 18 201035390 聚合物、氣之硫酸系銅電解液來得到之電解銅箔。 載體羯之製造形態：簡單敘述關於載體羯之製造方 法。用於載體箱之製造之硫酸系銅電解液，係使用含有_ 或sps之至少丄種、具有環狀構造之4級銨鹽聚合物、氯Quality, for the "organic, bubble — - L layer layer formation of uniform thickness", "carrier Ο '; # and the interface layer of the dense puppet", the genus layer followed by electrolytic copper The adhesion between the interface layer and the financial charge layer is safe. "Stabilization is useful. Further, the glossiness of the surface of the present invention (Gs = TEM gloss measured in the width direction and the gloss measured in the flow direction) is 0. 9]^ Gloss]^ is better. That is to say, the width of the width of the width of the gap is 1 TD. The difference between the gloss of the flow direction and the flow direction is small, which means that the TD direction and the rib direction are so electrolyzed (4). Therefore, if the thickness can be formed, "• from the "organic agent layer - b" carrier foil and the bonding interface layer" "to understand the bonding interface layer and the yttrium-resistant metal... "Transparency,", and the metal layer followed by the adhesion of the electrolytic copper layer" *3C 疋化 advised jujube 4 no difference, because w is in the direction of the MD and the adhesion and corpus callosum When the box is peeled off, it is not necessary to care about the direction of peeling. In the case of the use of electrolytic copper foil used as a carrier foil in November [_. Heart system =:==°. )]> Gloss and [Gs(6, ru, 1 as the first Zee, by using [GS(20.)] 〇 Obviously capture and use as a carrier foil to use 15 201035390 The difference in the name of the copper. In the electrolytic steel crucible used in the present invention, the side of the precipitation surface includes the relationship of gloss [Gs (2 (r)] > gloss [Gs (6 〇.)]. See 'In the case of high-gloss and low-surface-thickness electrolytic copper foil, glossiness will be established [Gs(2(r)]> Gloss [Gs(6(r)]] Gloss [Gs(85) Then, in the case of low-gloss and low surface roughness of electrolytic copper, the relationship of gloss [Gs(10). >gloss [Gs(8).)] is established. Moreover, in matt and low surface roughness In the case of an electrolytic copper box, the relationship of gloss [Gs (85.)] > gloss gloss [Gs (2 〇.)] is established. Therefore, it can be judged that the value of the gloss of the incident angle is determined. In addition, it is useful as an index of the smoothness of the electrolytic copper box based on the value of the first incident angle with the other *. The electrolytic copper crucible used as the carrier case as described above is not particularly limited. Thickness, but if In order to measure the operability, it is preferable to use a thickness of (4). In particular, the present invention is used as a carrier foil, and if the electrolytic copper is used in the production method 2A described later, the thickness of the precipitation surface is thick. Acoustic: The thickness of the electrolytic copper box is the interface layer =:, the gloss is also increased. The layer located at a position understandable by the 攸 丨 , is a combination of a so-called organic agent layer and an inorganic material such as a metal oxide. The m is a genus or a property of the characterization. The following is a description of the following. In the "interfacial interface layer", the use of a tri-salt with a substituent in the organic compound is stupid in the nitrogen-containing Saliva (hereinafter, referred to as "βτΑ"), 2 2'3- is "~, Ν, Ν, - 竣 竣: Kaisan. Sit (hereinafter, referred to as v-open oxazolidine) urea (below , said 16 201035390 is "BTD — U|), l nitrogen -1 A ^ An r J ; a ' 2, 4 - disa (hereinafter, referred to as "TA" ... an amine-1 nitrogen-1, 2 , 卜三唾 (hereinafter, referred to as "A second layer to form the layer is better. This "joint interface layer (organic agent: -Jtr '4- 4- Ail" into * method' in the manufacturing form It will be described. Heat-resistant metal layer: then 'heat-resistant metal layer', is made of nickel, recorded-phosphorus, nickel-chromium, nickel-molybdenum, nickel-molybdenum-cobalt, ΛΒ ^ ^ , , , ancient nickel-tungsten, nickel - tin, recorded alloy n - n indium, Ming - crane, beginning - Ο Ο copper: drilling - nickel - scale, cobalt - kick - phosphorus, etc. of any kind of alloy. ^ Formation of heat-resistant metal layer, It will be described in the production form. By the presence of the heat-resistant metal layer, the electrolytic copper box which is related to the present invention is subjected to, for example, a stamping plus a carrier. ~ On the hot resume, _ can also be easily at 30 °, even broadcasted people also made the easy to 攸 electrolytic copper box layer peeling. The right part constitutes the joint interface layer of the organic separation, 6 ^ 4, the electrolytic mooring layer in the direct contact state: the temperature of the composition of the mine 3 ° 〇 t 'the organic agent layer of the organic agent layer == two " ― There is a heat-resistant metal layer: screen:: It can prevent the disappearance of the organic agent layer under the interdiffusion piece on the eve of the high-temperature stamping element. Second, after the 'heat-resistant metal layer. At this time, the thick sound X' 〇 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 05 If the thickness is less than 〇2, it can be known as a very thin layer. The heat-resistant gold should achieve the function Φ. θ, in the above-mentioned refractory metal layer, can not achieve the function as a barrier layer and damage heat resistance 17 201035390 = If the thickness of the heat-resistant metal layer exceeds °.°5... The difference in the drop strength of the electrolytic copper with the carrier foil after processing is increased. (4) Body > Self-stripping (4) Copper μ: Here, The electrolytic copper layer is provided on the above-mentioned eight", the copper layer on the layer, and the copper coating Directly attached to the base resin plate for opening the loop forming the copper layer. The thickness "of the electrolytic copper foil layer" is not particularly limited. However, if it is considered to be an electrolytic copper box layer of an electrolytic copper whistle having a carrier case, it is conceivable that the thickness is 10 " This is because if the thickness of the copper-clad layer is 1 〇", it loses the meaning of being an electrolytic steel pouch with a carrier. Then, various surface treatments are also possible in the electrolytic copper foil. Surface treatment: In the surface of the electrode, the surface of the electrode is placed on the surface of the electrolytic copper layer, and the rust-proof, roughening, and adhesion-improving treatments are appropriately combined according to the application. For example, in the case of a carrier having a carrier, a copper case, and a thermoplastic resin such as a polyimide resin, a polyamide resin, a fluorophyllin substrate, or a liquid crystal polymer for a printed circuit board, , roughing processing can also be added for a fixed effect. This is because the required characteristics such as high adhesion strength and heat resistance can be improved as compared with the case where the surface of the copper box is not roughened. .. A method for producing an electrolytic copper foil having a carrier foil and a method for producing an electrolytic copper box having a carrier flute according to the present invention, as a carrier foil, using electrolysis containing 3-mercapto-propanesulfonic acid (hereinafter, simply referred to as "MPS") or at least one selected from the group consisting of bis(3-sulfopropyl) disulfide (hereinafter, referred to as SPS only), a 4-stage ammonium salt having a cyclic structure 18 201035390 polymer, gas sulfuric acid system Electrolytic copper foil obtained by copper electrolyte. Manufacturing form of carrier :: A brief description of the manufacturing method of carrier 羯. The sulfuric acid-based copper electrolyte used for the production of the carrier tank is a quaternary ammonium salt polymer having a ring structure of at least 丄 or sps, and chlorine.
^。在此’「MPS3tSPS之至少1種」之濃度，係以硫酸 系銅電解液中之MPS及/或SPS之合算濃度來考慮即可。亦 即，此合算濃度，以0.5ppm〜1〇〇卿為佳，而以 〇. 5^ppm〜50ppm更佳，更以lppm〜3〇ppm更佳。此Mps或sps 之濃度若未滿0.5ppm之情況，則無法得到上述之擴散防止 效果’電解銅箱之析出面變粗，包括低輪廓析出面之電解 銅羯之製造變得困難。另-方面，㈣s及/或SPS之濃度 超過100PPm，所得到之電解銅羯之析出面之平滑化效果也 無法提昇，只是導致廢液處理之成本增加而已。又，本發 明所說之MPS及SPS,係分別包含其鹽類而使用，濃度之 記載值，係做為鈉鹽之3—巯基—丨一丙烷磺酸鈉之換算 值。然後，MPS，係藉由在銅電解液中二聚化而得到sps構 造。因此，MPS及SPS濃度，係除了 3—酼基一卜丙烷磺 酸單體或是MPS-Na等鹽類之外，也包含做為sps來添加之 物以及做為MPS來添加至電解液中以後聚合成sps等變性 物之濃度。 然後，與本發明有關之硫酸系銅電解液，以含有濃度 為1 ppm〜15 Oppm的範圍來含有具有環狀構造之4級銨鹽聚 合物為佳，而以1〇口口111〜12〇?0111較佳，更以151)1)111~4〇??111更 佳。在此’可使用各種具有環狀構造之4級敍鹽聚合物。 19 201035390 而•考慮开’成低輪廓之析出面的效果以使用二烯丙 基一甲基銨氣化物聚合物(以下，僅稱為「DMc聚合物」） 為最佳。DDAC聚合物’係在做為聚合物構造時成為環狀構 造之物，環狀構造的-部份係由4級銨之氣原子構成。然 後，DDAC聚合物之前述的環狀構造為4員環〜7員環之任二 種或是其混合物。 此DDAC聚合物之在硫酸系銅電解液中的濃产以 1PP計150卿為佳，而以1〇_〜12〇卿較佳，^以 1 5ΡΡΙΠ,卿更佳。在硫酸系銅電解液中眶聚合物的濃 度未滿1 ppm的情況，不論如何提高Mps及sps的濃度，也 無法得到上述擴散防止效果，電解銅箔之析出面變粗， 難以得到低輪廓電解銅荡。另_方面，若硫酸系銅 中的DDAC聚合物濃度鉬# 收 交過150卿，則銅的析出狀態變的 不安定，難以得到低輪廓之電解銅箔。 更且，前述硫酸系銅電解液中的氣濃度 5卿.卿為佳，更以1Q卿〜6Q卿更佳。在此氣濃户 未滿5刚之情況，電解銅箱之析出面變粗，無法維持低： 摩：另一方面，若氯濃度超過，電解銅箱之析心 :變粗’電解狀態不女定’⑥變的無法形成低輪廓之析出 如以上’在前述硫酸系鋼電解液中之_及/ DDAC聚合物與氣的成分平衡是最重要的1料量二 超過上述範圍’則結果為電解鋼箱之析出面變粗 2 持低輪廊’無法求得載體箱與「接合界面層及與接：界維 201035390 層鄰接的電解銅箔層」之密著性的安定化。 然後’使用前述 # ^ 麦系銅電解液，製造做為裁體箔來 使用之電解銅羯之情 ㈣冶來 圍之陰極與不溶性陽極來電解此'表面粗度調整在既定範 而以4(TC〜55t為佳 0’的“為2°C〜60°C ’ 為佳。^度為ΜΑ.2，.2,而以 Ο Ο 之析有機劑層)之形成形態__對於前述_ 敘过關… 合界面層，係由有機劑層構成。以下， 劑的種類係如j /成方法。又，關於所使用之有機 此有機劑層係直接與載體箱表面接觸的層 機劑層，如下述來形忐Α社 成為佳。關於對於載體荡表面之有機 Μ層的形成，以進行為 膜、污染物除去之酸洗處二之多餘的氧化覆 I光處理為佳，但在此酸洗溶液中，使 、含有用以形成有機劑層之有機劑，藉由將此含有有機劑 之酸洗溶液與載體箱接觸，可一邊將載體荡之表面溶解， -邊同時使有機劑的成分吸附於載體箱的表面為佳。如 此’若在酸洗溶液中混入使其吸附之有機劑，相較於不進 仃載體猪的溶解而使有機劑吸附之情況，對於載體落上之 有機劑的沉殿速度提高，且同時可得到均—之吸附狀態。 如此來形成之有機劑層，沉殿吸附而形成之有機_ 吸附組織很微細，且相較於僅與使有機劑分散之水溶液接 觸而使其沉殿吸附之情況’可使多量的有機劑均二地吸 附。在載體箱之溶解過程中產生金屬離子，該金屬離子與 21 201035390 有機劑形成配位化合物，該配位化合物會由於載體箔表面 附近之pH變化造成的濃度斜率等而產生沉澱促進作用，結 果為配位化之有機劑之對於載體保表面的吸附變的容易 因此’有機劑的吸附速度增加，且可形成緻密的有機覆膜。 又，在本發明所使用之有機劑層，由於為載體萡之構成金 屬成分做為金屬離子（在本發明中為「銅離子」）而溶出带 成在酸洗溶液中’而由於酸洗溶液中之金屬離子與有機叫 反應而進行配位形成，該配位化之金屬離子包含於有機叫 層之可能性很高，為含有一定量之金屬成分的狀態。 又，「酸洗溶液」，可根據載體羯之構成成分、可採 用之酸洗時間來適當選擇其種類即可，若考慮載體箔為電 解銅箔，則酸性溶液中又以使用硫酸系溶液為佳。 對於以上所述「酸洗溶液」之「有機劑」的添加，使 有機劑的濃度在50ppm〜20 00ppm之範圍來添加為佳。在未 滿50Ppm之濃度的情況，有機劑的吸附速度變慢，且所形 成之酸洗吸附有機覆膜之厚度有變的不均一的傾向。相對 於此’上限值為2_ppm之濃度’係由於雖然超過此濃度 實際上也可使有機劑溶解’但若考慮溶液的品質安定性： '際作業時之經濟性，沒有必要採用過剩的溶解量。 片盘二此時之「酸洗溶液」的溫度’係考慮酸洗處理速 有機劑層的形成速度來適當 定知丄 亚，又有特別限 ° —由於係使有機劑並存於酸洗溶液中 情7 4日仕提问/夜〉皿的 …同的有機劑的種類’需要留意應選擇不會造 成有機劑分解的溫度。 倖不會^ 22 201035390 -士以上所述，構成與本發明有關之具有載體箔之電解 銅箱之接合界面層之有機劑層，基本上係在此酸洗溶液中 使其含有既定的有機劑來形成。然而，作為此有機劑層之 形成方法’也可採用以下所述之各種方法。例如，如上述， 在酸洗溶液中使其含有為了形成有機劑層之有機劑而形成 有機劑層。也可反覆進行此有機劑層的形成，來調整有機 劑層的厚度。 Ο Ο 又，也可使用不同成分之有機劑來做成多層的有機劑 層。以下，敘述關於# 草錄…關於使用2種有機劑層之情況。藉由使用 某種有機劑，在載體箔卜^ 弟1有機劑層後，在此第1 有機劑層上，使用僅人女w 3有另一種類之有機劑的溶液，使有 機砌再吸附，來形成新的單 層為佳。此第2有機¥覆膜之第2有機劑 力伐齊丨j層，不同於篦 僅含右右祕亦,^、 、 有機劑層’係使用 ，夷而μ ’合液’將此溶液與第1有機劑層接觸，在 該表面上使有機劑吸田接碼在 /刀，相較於第！有機劑層，吸附量也 有金屬成 此筮9古拖a 荷溥的有機劑層。 U有機層的形成’係使與上述 或分散於溶劑之水等來 有機劑溶解 為；谷液，將此溶液虚截~ 成了第1有機劑層的面接觸。且體^ =載體治之形 潰包括第i有機劑層…糸在該溶液中浸 層之表面上噴浴法、噴2泊’或是可採用在第1有機劑 用於此第2有機劑屏+ / 、 ^ 度，在上述有機劑中，tl/形成之溶液中的有機劑的濃 °C〜6(TC之範圍為佳^濃度G.Glg/卜_卜液溫20 有機割的濃度並沒有特別限定，本來 201035390 的濃度南或低都沒有問題。然 o.〇lg/i還低之濃度，則難以得到對有機劑濃度若為較 -的吸附狀態，其結果 +於第1有機劑層之均 差異，而製品品質易發生差異。：：合界面層的厚度產生 的濃度超過1〇g/卜特別是有機’即使使有機劑 吸附速度也不會隨著添加量而增加，"有機劑層的 無法說是好的。 從生產成本面來看也 又，第2有機劑層之形成所 第1有機劑層之形成所使用的有 、劑，雖然是從 有必要選擇同於第丨有機 ,A k擇使用，但也沒 可從上述有機劑群中任意選擇使用。使用的有機劑’也 如此之包括以第！有機劑層 有機劑層的具有载體荡之電解銅笔，有機劑層來構成之 溶液中含有使有機劑層右/相較於僅包括在酸洗 具有載體箱之電解銅落f即使受^劑來形成之有機劑層的 履歷後’將载體箱從銅箱層剥： 造成之加熱 的情況。 之幻離強度也有更安定 如以上所述之構成人 之範圍為 口層的有機劑層’厚度以在 孕已囷马佳。有機劑層的 — 況，有機劑層的厚度會產生差昱，又，右未滿hni之情 其結果，無法得到加熱後之安；而無法成為均-之臈厚。 將載體箔剝離之情況。另一方、剝離強度，甚至有無法 一’則欲形成電解銅箱層機劑層的厚度若超過 的析出狀況不安定 、包狀態變的不安定，銅 而難以形成均-厚度之電解鋼落層。 201035390 耐熱金屬層的形成形態：接著，敘述關於耐熱金屬層 之开V成开7 I、。此耐熱金屬層，係將形成了有機劑層之載體 泊本身，在含有耐熱金屬成分之電解液中陰極化，使金屬 成刀析出於構成接合界面層之有機劑層的表面上而形成。 在此所說之金屬成分，係如上述，為鎳'鎳一磷、鎳一鉻、 Ο 〇 銦、鎳-鉬—鈷、鎳—鈷、鎳—鎢、鎳一錫—磷等鎳 合金；鈷、鈷-磷、鈷—鉬、鈷—鎢、鈷—銅、鈷—鎳— 秘、钻—錫—磷等銘合金之成分。然後，只要可將這些金 屬成分電解析出，使其厚度為（^謝㈣〜㈣⑽並沒有 特別的電解條件之限制。 電解銅羯之形成形態：此電解銅荡層，係將形成了耐 熱金屬層之載體箱本身，在銅電解液中陰極化，使銅成分 析出在耐熱金屬層上而形成。此時之銅電解液及電解條 件，係使用硫酸銅系溶液、焦磷酸銅系溶液等可做為銅離 :供給源之溶液’ i沒有特別限定。例如，也可使用載體 箱之製造所使用的銅電解液，或是可使用其他組合m 鋼系溶液、焦魏銅系溶液等。然後，也可在電解銅箱層 之表面上把以以下各種表面處理。 表面處理的形態：在此所說的各種表面處理，係根據 :要來任意進行的處理’在該銅猪層的表面上，可根據用 :來適當組合實施防鏽處理、粗化處理、密著性提高處理 等。又，根據表面處理的方法，也有在载體箱表面上施以 表面處理的情況，如此情況也沒有特別的問題，沒有特別 限定。關於此時之防鏽處理、粗化處理等手法，可轉用眾 25 201035390 所周知的技術，並不需要特別限定。 c.銅覆層積板之形態 以上所敘述之與本發明有關之具有載體羯之電解鋼 泊，不僅在負荷高溫熱履歷之沖壓製程，在通常最高到達 溫度為180°C前後之通常沖壓加工條件中使用，也可確保 非常優良之載體箱剝離強度的安定性，而可顯著提升作業 的信賴性。因此，與本發明有關之具有载體猪之電解銅箱^ 並不限定包含於銅覆層積板液晶聚合物基板、聚酰亞胺基 板、氟樹脂基板、低介電基板等，也可適當地使用於全部 的「丙階酚醛樹脂系基板」、「TAB、C0B等軟性基板」、 「混合基板」等之製造，而可提供高品質之銅覆層積板。 [實施例] 在此實施例中’係依照載體箔製造工程、接合界面層 形成工程、耐熱金屬層形成工程、電解銅箔層形成工程、 表面處理工程之順序來進行，最終水洗後使其乾燥而獲致 與本發明有關之具有載體箔之電解銅箱。以下，依照各工 程之順序來進行說明。 載體箔製造工程：在此工程中，係使用以下所表示的 組合之銅電解液’使用DSA為陽極’使用陰極（表面以2〇〇〇 號砂紙進行研磨，表面粗度為調整到rz j i s j為丨.5 # m之 鈥板電極），以液溫50°C，電流密度60A/dm2之條件來電解， 而得到1 8 // m厚之電解銅箔。 銅濃度：80g/l 自由硫酸濃度：140g/l 26 201035390 SPS 濃度：5mg/l DDAC聚合物濃度：30mg/l 氣濃度：25mg/l 此做為載體落來使用之電解銅羯，析出面的表面粗度 (Rzjis)為0. 6// m。又，此表面粗度的測定，係根據b 0601，以使用先端曲率半徑為2/zm之鑽石探針之觸針式表 Ο Ο 面粗度計來測定。然後’此做為載體箔來使用之電解銅箔 之析出面的光澤度[Gs(60。）]係如表1所示。 彳 接合界面層形成工程：在此工程中，在載體箱之析出 面側，形成接合界面層之有機劑層。藉由對於硫酸為 15〇g/卜銅濃度為10g/卜CBTA濃度為8〇〇卿、液溫為 C之含有有機劑之料酸水料，使㈣㈣製造工程中 :獲致之電解㈣浸潰3〇秒鐘後拉起，而將附著於電解銅 治之污染成份酸洗除去，且同時使咖吸附於表面， 電解銅載體幻之表面上形成了有機劑層。 耐熱金屬層形成工藉·並装 » . 戚权.接者，在此工程中，在接合界 面層上形成做為耐熱金屬層之錄層。此時做為錄電解液， 糸使用硫酸鎳（Nis〇4· 6H2〇)為3 一㈣為—之瓦::，： 。:=密一來電解，成― :解銅箱層形成工程：耐熱金屬層的形成結束後，在 =之:熱金屬層的表面上形成電解㈣層。此 ，自層之形成，係在銅電解槽内，注滿銅激度 27 201035390 酸濃度為150g/l、液溫45°C之硫酸銅溶液，以電流密度 1 5A/dm2來電解，形成厚之電解銅箔層，而獲致具有 載體羯之電解銅箔。 表面處理工程：在此工程中，係在電解銅析出工程所 得到之具有載體箔之銅箔的銅落面上，實施表面處理。在 此之表面處理，並非實施粗化處理，而是形成鋅_鎳合金 防鏽層，施以電解鉻化物處理，與氨基系#耦合劑處理。 測定與此實施例有關之具有載體落之電解銅羯之深产 方向輪扉時之測定結果係整理表示於I i。深度方向輪二 的：度，係以賤射率13Wsec之銅換算來算出之值。又， 疋在此貝施例所得到之具有載體箱之電解銅落之載體笛 層’、電解銅伯層之剝離強度。關於其結果，使其可與比較 列對比而整理表示於表2。 [比較例] 在此比較例中， 有實施粗化處理及防 所使用之做為載體箔 用。除了此點以外， 羯之電解銅箔。 係使用分類於等級3之18"m厚之沒 鏽處理的市售電解銅箱，取代實施例 所使用之電解銅箔，來做為载體箔使 其餘工程同於實施例而得到具有載體 深声方…得到之具有載體猪之電解銅箱 木度方向輪廓時之測定結 Ί 使其可與實施例對比而整 不於表1。又，測定載體箔屏 w ^ ^ ^ # ^ Β與電解銅、冶層之剝離強方 J於其結果，使其可與實施 J對比而整理表示於表2。 28 201035390 【表1】 試料 載體箔（電解銅箔）之析出面* 具有載體箔之雷解錮箔 光澤2 Gs 表面粗度 載體箔剝離強唐 Rzjis 常態 加熱後林 (20。） (60。） — 1 條件2 條件3 TD MD TD MD TD/MD (卵） (kef/cm) 實施例 1240 1255 787 795 0.99 0.60 4.0 「5. 0 9.0 16 0~ 比較例 >i〇鈸艚 1 / 结Γ雷 63 78 山 — 0.81 1.34 5. 0 6.0 35.0 94.0 **)加熱條件 試料 W1 W2 ([W2]-[W1])/[W1] [P2HP1 广 //m 實施例 0.52 0.55 0.05 0.08 比較例 0. 50 0.71 0.42 0. 27 【表2】^. The concentration of "at least one of the types of MPS3tSPS" may be considered as the total concentration of MPS and/or SPS in the sulfuric acid-based copper electrolyte. That is, the total concentration is preferably 0.5 ppm to 1 ,, and more preferably ^ 5 5 ppm to 50 ppm, more preferably 1 ppm to 3 〇 ppm. If the concentration of the Mps or sps is less than 0.5 ppm, the above-mentioned diffusion preventing effect cannot be obtained. The deposition surface of the electrolytic copper box becomes thick, and the production of the electrolytic copper crucible including the low profile deposition surface becomes difficult. On the other hand, if the concentration of (4) s and / or SPS exceeds 100 ppm, the smoothing effect of the precipitate of the obtained electrolytic copper ruthenium cannot be improved, but the cost of waste liquid treatment is increased. Further, the MPS and the SPS in the present invention are each used in the form of a salt thereof, and the measured value of the concentration is a conversion value of sodium 3-mercapto-sodium monopropane sulfonate of the sodium salt. Then, MPS was obtained by dimerization in a copper electrolyte to obtain a sps structure. Therefore, the concentrations of MPS and SPS are in addition to salts such as 3-mercapto-propanesulfonic acid monomer or MPS-Na, and are also added as sps and added to the electrolyte as MPS. It is later polymerized to the concentration of denatures such as sps. Then, the sulfuric acid-based copper electrolytic solution according to the present invention preferably contains a 4-stage ammonium salt polymer having a cyclic structure in a concentration range of 1 ppm to 15 Oppm, and is preferably 1 to 11 ports. ?0111 is better, and more preferably 151) 1) 111~4〇??111. Here, various four-stage salt-synthesis polymers having a cyclic structure can be used. 19 201035390 The effect of using a low-profile precipitation surface to use a diallyl-monomethylammonium vaporized polymer (hereinafter, simply referred to as "DMc polymer") is preferred. The DDAC polymer' is formed into a cyclic structure as a polymer structure, and the portion of the cyclic structure is composed of a gas atom of a 4-stage ammonium. Then, the aforementioned ring structure of the DDAC polymer is either a 4-membered ring or a 7-membered ring or a mixture thereof. The concentration of the DDAC polymer in the sulfuric acid-based copper electrolyte is preferably 150 psi in terms of 1 ppm, and preferably 1 〇 〜 12 〇 , ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 。 。 。 。 。 。 。 。 。 。. When the concentration of the ruthenium polymer in the sulfuric acid-based copper electrolytic solution is less than 1 ppm, the diffusion prevention effect cannot be obtained regardless of the concentration of Mps and sps, and the deposition surface of the electrolytic copper foil becomes thick, making it difficult to obtain low-profile electrolysis. Copper swings. On the other hand, if the DDAC polymer concentration molybdenum in the sulfuric acid-based copper is over 150, the precipitation state of copper becomes unstable, and it is difficult to obtain a low-profile electrolytic copper foil. Furthermore, the gas concentration in the above-mentioned sulfuric acid-based copper electrolyte is better than that of the Qingqing, and more preferably from 1Q to 6Q. In the case where the gas-rich household is less than 5, the precipitation surface of the electrolytic copper box becomes thick and cannot be kept low: Mo: On the other hand, if the chlorine concentration exceeds, the electrolytic copper box is analyzed: thickening 'electrolysis state is not female It is impossible to form a low profile precipitation as described above. 'In the above sulfuric acid steel electrolyte, the composition balance of DDAC and gas is the most important. 1 The amount of material 2 exceeds the above range'. The result is electrolysis. The precipitation surface of the steel box becomes thicker. 2 The low-wheeled porch cannot be used to ensure the stability of the adhesion between the carrier case and the "bonding interface layer and the electrodeposited copper foil layer adjacent to the layer 201035390." Then 'using the above # ^ wheat-based copper electrolyte to make the electrolytic copper enamel used as a cut-off foil (4) smelting the cathode and the insoluble anode to electrolyze the 'surface roughness adjustment in the established range to 4 ( TC~55t is good for 0's "for 2°C~60°C'. ^^ is ΜΑ.2,.2, and the formation of organic layer of Ο Ο _ _ _ The interface layer is composed of an organic agent layer. Hereinafter, the type of the agent is, for example, a j/forming method. Further, regarding the organic layer used, the layer of the organic agent layer directly contacts the surface of the carrier case, As described below, it is preferable to form an organic ruthenium layer on the surface of the carrier, and it is preferable to carry out an excess oxidized I light treatment for the pickling portion of the film and the contaminant removal, but the acid is preferably used here. In the washing solution, the organic agent for forming the organic agent layer is contained, and by contacting the acid washing solution containing the organic agent with the carrier, the surface of the carrier can be dissolved while the organic agent is simultaneously It is better to adsorb to the surface of the carrier box. So, if it is mixed in the pickling solution, it is sucked. With the organic agent, compared with the dissolution of the organic agent without the dissolution of the carrier pig, the speed of the sinking of the organic agent on the carrier is increased, and at the same time, the adsorption state of the uniform is obtained. The organic agent layer, the organic formed by the adsorption of the vestibule, is very fine, and the amount of the organic agent can be uniformly adsorbed in comparison with the case where it is adsorbed only by contact with the aqueous solution in which the organic agent is dispersed. During the dissolution of the carrier tank, metal ions are generated, and the metal ions form a coordination compound with the 21 201035390 organic agent, and the coordination compound causes a precipitation promotion effect due to a concentration gradient caused by a pH change near the surface of the carrier foil, and the result is The organic component of the ligand is easily adsorbed to the surface of the carrier, so that the adsorption rate of the organic agent is increased, and a dense organic film can be formed. Further, the organic agent layer used in the present invention is a carrier. The constituent metal component is used as a metal ion ("copper ion" in the present invention) and the elution band is formed in the pickling solution" because of the acid pickling solution Metal ions and an organic complexing called performed to form, the metal ion of the formulation of bits contained in the organic layer is called a high probability, the state containing a certain amount of the metal component. Further, the "acid pickling solution" may be appropriately selected depending on the constituent components of the carrier and the pickling time which can be used. When the carrier foil is an electrolytic copper foil, the sulfuric acid solution is used in the acidic solution. good. It is preferable to add the "organic agent" of the "acid washing solution" described above so that the concentration of the organic agent is in the range of 50 ppm to 200 ppm. In the case of a concentration of less than 50 Ppm, the adsorption rate of the organic agent becomes slow, and the thickness of the formed pickling-adsorbed organic film tends to be uneven. In contrast, the 'concentration value of the upper limit value is 2 _ppm' because the organic agent can be dissolved even if it exceeds this concentration. However, considering the quality stability of the solution: 'Economic efficiency at the time of operation, there is no need to use excess dissolution. the amount. The temperature of the "acid pickling solution" at the time of the sheet 2 is determined by considering the formation speed of the pickling treatment speed organic layer, and has a special limit - because the organic agent is present in the pickling solution. Love 7 4th Shi asked questions / night > dish ... the same type of organic agent 'need to pay attention to choose the temperature that will not cause decomposition of the organic agent. Fortunately, the organic agent layer constituting the joint interface layer of the electrolytic copper case with the carrier foil according to the present invention is basically contained in the pickling solution to contain a predetermined organic agent. To form. However, as the method of forming the organic agent layer, various methods described below can also be employed. For example, as described above, an organic agent layer is formed in the pickling solution to contain an organic agent for forming an organic agent layer. The formation of the organic agent layer can also be repeated to adjust the thickness of the organic agent layer. Ο Ο In addition, organic agents of different compositions can also be used to form a multilayer organic layer. Hereinafter, the case of using two kinds of organic agent layers will be described. By using an organic agent, after the carrier layer of the carrier foil 1 organic agent layer, a solution of only another type of organic agent is used on the first organic agent layer to re-adsorb the organic building. To form a new single layer is better. The second organic agent of the second organic film is the same as the right organic compound, and the organic layer is used, and the solution is used. The first organic agent layer is in contact, and the organic agent is sucked in the surface of the knife on the surface, compared to the first! The organic agent layer, the amount of adsorption also has a metal into this organic layer of 筮9 ancient drag a lotus. The formation of the U organic layer is such that the organic agent is dissolved in water or the like dispersed in the solvent; the solution is creased to form a surface contact of the first organic agent layer. And the body ^ = carrier treatment of the fracture includes the i-th organic agent layer ... 糸 in the solution of the surface of the leaching layer on the surface of the spray bath, spray 2 / ' can be used in the first organic agent for the second organic agent screen + / , ^ degree, in the above organic agent, the concentration of the organic agent in the solution formed by tl / ° ° ~ 6 (the range of TC is good ^ concentration G. Glg / Bu - liquid temperature 20 organic cut concentration and There is no particular limitation. Originally, the concentration of 201035390 is no problem at the south or low. However, if the concentration of 〇lg/i is still low, it is difficult to obtain the adsorption state of the organic agent concentration, and the result is + the first organic agent. The difference in the quality of the layers, and the quality of the products are prone to differences.: The thickness of the interface layer is more than 1 〇g / b, especially organic 'even if the adsorption rate of the organic agent does not increase with the amount of addition, " The organic agent layer cannot be said to be good. From the viewpoint of the production cost, the agent used for the formation of the first organic agent layer in the formation of the second organic agent layer is selected from the same丨Organic, A k is used, but it is not arbitrarily selected from the above organic agent group. The organic agent' also includes the organic layer of the organic agent layer having the organic layer of the organic agent layer, and the organic agent layer is formed in the solution containing the organic agent layer right/compared to only included in the pickling The electrolytic copper of the carrier box f is peeled off from the copper box layer after the history of the organic agent layer formed by the agent: the case where the heating is caused. The illusion intensity is also more stable as described above. The range of the human body is the thickness of the organic layer of the mouth layer. In the case of the organic agent layer, the thickness of the organic agent layer will be different, and the result of the right is not full. After the heating, it is not able to be uniform. The carrier foil is peeled off. The other side, the peeling strength, and even the failure to form the thickness of the electrolytic copper layer agent layer exceeds the precipitation state. The stability and the state of the package are unstable, and copper is difficult to form a uniform-thickness electrolytic steel falling layer. 201035390 Formation form of the heat-resistant metal layer: Next, the opening of the heat-resistant metal layer is described, and the heat-resistant metal layer is described. , the system will form The carrier of the organic agent layer itself is formed by being cathodized in an electrolytic solution containing a heat resistant metal component, and the metal is formed into a surface of the organic agent layer constituting the bonding interface layer. The metal component is referred to herein. The above are nickel alloys such as nickel 'nickel-phosphorus, nickel-chromium, antimony indium, nickel-molybdenum-cobalt, nickel-cobalt, nickel-tungsten, nickel-tin-phosphorus; cobalt, cobalt-phosphorus, cobalt-molybdenum, Cobalt-tungsten, cobalt-copper, cobalt-nickel--secret, drill-tin-phosphorus and other alloys. Then, as long as these metal components can be electrically resolved, the thickness is (^ Xie (4) ~ (4) (10) and there is no special Limitation of Electrolytic Conditions: Formation Form of Electrolytic Copper Beryllium: This electrolytic copper layer is formed by forming a heat-resistant metal layer carrier box itself, which is cathodized in a copper electrolyte to cause copper to be analyzed on a heat-resistant metal layer. form. In the case of the copper electrolyte and the electrolysis conditions, the copper sulfate-based solution, the copper pyrophosphate-based solution, or the like can be used as the copper ion-supplying source solution i is not particularly limited. For example, a copper electrolytic solution used for the production of a carrier case may be used, or other combinations of m steel system solutions, coke-based copper-based solutions, and the like may be used. Then, it is also possible to treat various surfaces as follows on the surface of the electrolytic copper tank layer. Form of surface treatment: The various surface treatments mentioned here are based on the treatment to be carried out arbitrarily. 'On the surface of the copper pig layer, rust-proof treatment, roughening treatment, and compactness can be appropriately combined according to the use: Improve the processing and so on. Further, depending on the method of the surface treatment, there is a case where a surface treatment is applied to the surface of the carrier case, and there is no particular problem in this case, and it is not particularly limited. Regarding the rust-preventing treatment and the roughening treatment at this time, it is possible to switch to the technique known to the public, and it is not particularly limited. c. Form of copper clad laminate The electrolyzed steel pouch with carrier crucible described above in connection with the present invention is not only in the stamping process of the high temperature heat history, but also in the usual stamping before and after the maximum reaching temperature of 180 ° C The use of the processing conditions also ensures the stability of the very good carrier box peel strength, and can significantly improve the reliability of the operation. Therefore, the electrolytic copper case having the carrier pig according to the present invention is not limited to be included in the copper-clad laminate liquid crystal polymer substrate, the polyimide substrate, the fluororesin substrate, the low dielectric substrate, etc., and may be appropriately It is used for the manufacture of all "Phenolic phenolic resin-based substrates", "soft substrates such as TAB and COB", and "mixed substrates", and provides high-quality copper-clad laminates. [Examples] In this embodiment, 'in accordance with the carrier foil manufacturing process, the joint interface layer forming process, the heat resistant metal layer forming process, the electrolytic copper foil layer forming process, and the surface treatment process, the process was carried out, and finally dried after washing with water. An electrolytic copper box having a carrier foil associated with the present invention is obtained. Hereinafter, the description will be made in accordance with the order of each project. Carrier foil manufacturing project: In this project, the copper electrolyte used in the following combination is used. The cathode is used as the anode using DSA (the surface is ground with 2 Å sandpaper, and the surface roughness is adjusted to rz jisj).丨.5 #m's 鈥 plate electrode) was electrolyzed at a liquid temperature of 50 ° C and a current density of 60 A/dm 2 to obtain an electrolytic copper foil of 1 8 // m thick. Copper concentration: 80g / l Free sulfuric acid concentration: 140g / l 26 201035390 SPS concentration: 5mg / l DDAC polymer concentration: 30mg / l gas concentration: 25mg / l This is used as a carrier to use the electrolytic copper crucible, the precipitation surface 6// m。 Surface roughness (Rzjis) is 0. 6 / / m. Further, the measurement of the surface roughness was carried out according to b 0601 using a stylus type surface roughness gauge of a diamond probe having a tip radius of curvature of 2/zm. Then, the gloss [Gs (60.)] of the deposition surface of the electrolytic copper foil used as the carrier foil is as shown in Table 1.接合 Bonding interface layer forming process: In this process, an organic agent layer that joins the interface layer is formed on the side of the deposition surface of the carrier case. By (4) (4) in the manufacturing process for the sulfuric acid of 15〇g/b copper concentration of 10g/b CBTA concentration of 8〇〇qing, liquid temperature of C containing organic acid material, the obtained electrolysis (four) impregnation After pulling for 3 seconds, the contaminated components attached to the electrolytic copper treatment were pickled and removed, and at the same time, the coffee was adsorbed on the surface, and an organic agent layer was formed on the surface of the electrolytic copper carrier. Heat-resistant metal layer forming work and assembly » . In this project, a recording layer as a heat-resistant metal layer is formed on the joint interface layer. At this time, as the electrolyte is recorded, 硫酸 use nickel sulphate (Nis 〇 4· 6H2 〇) as 3 (four) as the watt::,: . :=Mining to electrolysis, into: - Copper layer formation process: After the formation of the heat-resistant metal layer is completed, an electrolytic (four) layer is formed on the surface of the hot metal layer. Therefore, the formation of the self-layer is in a copper electrolysis cell, and is filled with a copper sulfate solution having a copper concentration of 27 201035390 and an acid concentration of 150 g/l and a liquid temperature of 45 ° C, and is electrolyzed at a current density of 15 A/dm 2 to form a thick layer. The electrolytic copper foil layer is obtained to obtain an electrolytic copper foil having a carrier crucible. Surface treatment engineering: In this project, a surface treatment is carried out on a copper falling surface of a copper foil having a carrier foil obtained by electrolytic copper deposition. The surface treatment is not a roughening treatment, but a zinc-nickel alloy rust preventive layer is formed, which is treated with an electrolytic chromium compound and treated with an amino group # coupling agent. The measurement results when the deep-rolling direction rim of the electrolytic copper crucible having the carrier falling in relation to this example were measured are shown in I i. The depth direction wheel 2: degree is calculated from the copper conversion rate of 13 Wsec. Further, the peeling strength of the carrier flake layer of the electrolytic copper having the carrier case and the electroplated copper layer obtained by the present invention. The results are shown in Table 2 in comparison with the comparison column. [Comparative Example] In this comparative example, there was a roughening treatment and a use as a carrier foil. In addition to this, the electrolytic copper foil of 羯. A commercially available electrolytic copper box classified according to the grade 3 of 18 "m thick rust treatment is used instead of the electrolytic copper foil used in the embodiment as a carrier foil so that the remaining works are the same as the examples to obtain a carrier deep. The acoustic side...the measured knot with the wood-like direction profile of the electrolytic copper box of the carrier pig can be compared with the embodiment and is not in Table 1. Further, the peeling strength of the carrier foil screen w ^ ^ ^ # ^ Β and the electrolytic copper and the smelting layer was measured, and the result was shown in Table 2 in comparison with the embodiment J. 28 201035390 [Table 1] Precipitation surface of sample carrier foil (electrolytic copper foil) * Relief 锢 foil gloss with carrier foil 2 Gs Surface roughness Carrier foil peeling strong Tang Rzjis Normally heated forest (20.) (60.) — 1 Condition 2 Condition 3 TD MD TD MD TD/MD (egg) (kef/cm) Example 1240 1255 787 795 0.99 0.60 4.0 “5. 0 9.0 16 0~ Comparative Example> i〇钹艚1 / Crust雷63 78山—0.81 1.34 5. 0 6.0 35.0 94.0 **) Heating condition sample W1 W2 ([W2]-[W1])/[W1] [P2HP1 宽//m Example 0.52 0.55 0.05 0.08 Comparative Example 0. 50 0.71 0.42 0. 27 [Table 2]
條件 1 : 180°Cx60 分 條件 2 : 350°Cx60 分 條件 3 : 400°Cx60 分 [實施例與比較例的對比] 一邊參照表1，一邊進行實施例與比較例的對比。實 施例之(⑽-㈤)/間之值為〇.〇5,滿足〇3以内的條 件。又’實施例之（[P2] —[P1D之值為GG8，滿U.2Mm 以内之條件。相對於此’比較例之（⑽韻])/m]之值 為〇.42’（[P2HP1])之值為0.27㈣，沒有滿足本發明所 說的條件。此結果被認為做為表2所示之「載體㈣離強 度」的差異而表現出來。 ……，-透說明如下。首先，關於做為電解 銅羯層之形成面而使用之載體荡(電解銅羯)之析出面的特 性’對比實施例與比較例來說 凡a 在貫施例之情況，（1 ) 「表面粗度（Rzjis)未滿h 〇 # m」、（2)「光澤度[Gs(60。）] 201035390 為400以上」、（3)「在宮 I度方向測定之TD光澤度與在流 動方向測定之MD光澤廑> ^ Γ ^ 比[ΤΙ)光澤度]/[MD光澤度]為 0.9〜1.1」、（4)「fGsr?nc、i S(2〇 )]>光澤度[GS(60。）]」之各表 面特性（1)〜（4)全部滿足。相 & 相對方；此，比較例所使用之載體 V白（電解銅洎）之情況中，今 ^ (1)〜（4)之各表面特性皆沒有滿 足。 此載體箔（電解銅箔）之杯 j之析出面的表面特性差異，被認 為係做為具有載體箔之電解 ^ β 电解銅泊之载體箔剝離強度」的 差異而表現出來。甚丟表T i r 兄出木t看表i中「載體箱剝離強度」之值， ::】在吊態及條件1(18rcx6。分之加熱後)之「載體箔 剝離強度」’實施例與比較例之間並沒有產生很大的差異。 =而’在條件2⑽。Cx㈣之加熱後）及條件3(鮮Cx6〇 刀之加熱後）之「載體箱剝離強度」，實施例與比較例之間 TUm大的差異。相較於比較例之「載體錢離強度」 之值’、可以很明顯地理解到實施例之「載體箱剝離強度」 、-而且實施例即使負荷在條件3(4〇〇X： x60分之 :熱後）之嚴苛的加熱條件，也可以未滿的力來 去載體箱除去’因此可知以作業者的手作業即可容易地除 :體箱。又’在條件3(4，Cx6〇分之加熱後)中比較例 ^ 顯示94kgf/cm之剝離強度，以手作業來進行將载 心W時業者的負擔很大’且載體绪拉斷的可能性 也變高。 201035390 與本發明有關之古截_& 近·。c之高溫卜（、有载體/白之電解銅箱，即使受到將 因此_ 、何，其載體泊之剝離強度仍低且安定化， /&之_作業之作業效率飛躍地提升。因此，可 來=Γ在對於液晶聚合物基板、㈣表面以鑄造法 Α酰亞胺樹脂層、氟樹脂基板等進行g π負1 鋼覆層積板之製造。 ⑯寻進仃一負何之 ❹ 【圖式簡單說明】 之層表示與本發明有關之具有載體箱之電解鋼箱 構成的剖面模式圖。 以往士）係使用GDS(GD—GES)分㈣置，從以 鋼C做為載體羯來使用時之具有載體謂之電解 之電解鋼箔你丨A身Μ π ^ 方向 D載體洎側，以氬濺射來探測時之深度 的耐熱金屬成分之輪靡。 度 ο與本i2(awc0係使用GDS(GD—0ES)分析裳置，從以 體簿倒，有載體箱之電解銅箱之電解鋼箱側向栽 輪靡。鼠踐射來探測時之深度方向的耐熱金屬成分之 主要元件符號說明】 具有載體荡之電解鋼箔；2〜載體箔； 3〜接合界面層（有機劑層）；4〜電解銅荡層； 5〜耐熱金屬層。 31Condition 1 : 180 ° C x 60 minutes Condition 2 : 350 ° C x 60 minutes Condition 3 : 400 ° C x 60 minutes [Comparative Example vs. Comparative Example] The comparison between the examples and the comparative examples was carried out while referring to Table 1. The value of ((10)-(f))/between in the embodiment is 〇.〇5, which satisfies the conditions within 〇3. Further, the 'example ([P2] - [P1D value is GG8, which is within the range of U.2Mm. The value of ((10) rhyme))/m] relative to this 'comparative example' is 〇.42' ([P2HP1 The value of ]) is 0.27 (four), and the conditions described in the present invention are not satisfied. This result is considered to be expressed as the difference of "carrier (four) intensity" shown in Table 2. ......, - through the following description. The characteristics of the deposition surface of the carrier (electrolytic copper ruthenium) used as the formation surface of the electrolytic copper ruthenium layer. In the case of the comparative example and the comparative example, (a) "surface roughness" (Rzjis) under h 〇# m", (2) "gloss [Gs(60.)] 201035390 is 400 or more", (3) "TD gloss measured in the direction of the I degree and measured in the flow direction MD gloss 廑 > ^ Γ ^ ratio [ΤΙ] gloss] / [MD gloss] is 0.9~1.1", (4) "fGsr?nc, i S(2〇)]> Gloss [GS (60) The surface characteristics (1) to (4) of .)] are all satisfied. In the case of the carrier V white (electrolytic copper crucible) used in the comparative example, the surface characteristics of the present (1) to (4) are not satisfied. The difference in surface characteristics of the surface of the cup of the carrier foil (electrolytic copper foil) is considered to be the difference in the peeling strength of the carrier foil of the electrolytic β-electrolytic copper pouch having the carrier foil. The value of the "carrier peel strength" in Table i is checked, and the "carrier foil peel strength" in the suspension state and condition 1 (18rcx6.) There was no big difference between the comparative examples. = and 'in condition 2 (10). The "carrier peel strength" after the heating of Cx (4) and the condition 3 (after heating of the fresh Cx6 knife), the difference in TUm between the examples and the comparative examples was large. The "carrier peel strength" of the embodiment can be clearly understood from the value of the "carrier strength" of the comparative example, and the embodiment is even if the load is in the condition 3 (4〇〇X: x60) The harsh heating conditions after the heat can be removed from the carrier box with less force. Therefore, it can be seen that the operator can easily remove the body box. In addition, in the case of the condition 3 (4, after the heating of Cx6), the peeling strength of 94 kgf/cm was shown, and the burden on the carrier W was greatly increased by hand work, and the carrier was broken. Sex also becomes higher. 201035390 Ancient cuts related to the present invention _& The high temperature of c (the carrier/white electrolytic copper box, even if it is subject to _, and, the peel strength of the carrier is still low and stable, the work efficiency of /& Manufacture of g π negative 1 steel clad laminates on the liquid crystal polymer substrate, (4) surface, casting phthalimide resin layer, fluororesin substrate, etc. BRIEF DESCRIPTION OF THE DRAWINGS The layers are schematic cross-sectional views showing the construction of an electrolytic steel box having a carrier box according to the present invention. In the past, GDS (GD-GES) was used (four), and steel C was used as a carrier. When it is used, it has a carrier called electrolysis of electrolytic steel foil. You 丨A body π ^ direction D carrier 洎 side, argon sputtering to detect the depth of the hot metal component of the rim. Degree ο and this i2 (awc0 system uses GDS (GD-0ES) to analyze the skirting, from the body book, the electrolytic steel box with the electrolytic box of the carrier box is planted to the side of the wheel rim. The depth of the mouse is shot to detect the depth Explanation of main components of the heat-resistant metal component in the direction] Electrolytic steel foil with carrier smearing; 2~ carrier foil; 3~ joint interface layer (organic agent layer); 4~ electrolytic copper layer; 5~ heat resistant metal layer.