TW201106816A - Copper foil for printed wiring boards - Google Patents
Copper foil for printed wiring boards Download PDFInfo
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- TW201106816A TW201106816A TW099121187A TW99121187A TW201106816A TW 201106816 A TW201106816 A TW 201106816A TW 099121187 A TW099121187 A TW 099121187A TW 99121187 A TW99121187 A TW 99121187A TW 201106816 A TW201106816 A TW 201106816A
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- H10W72/075—
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- H10W72/50—
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
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- H10W70/688—
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- H10W72/013—
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- H10W72/07331—
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- H10W72/30—
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Laminated Bodies (AREA)
- Physical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
201106816 六、發明說明： 【發明所屬之技術領域】 本务明係關於一種印刷配線板用銅箔，特別是關於一 種可撓性印刷配線板用銅箔。 【先前技術】 印刷配線板於這半個世紀以來發展快速，如今幾乎所 有電子設備中均有使用。隨著近年來電子設備之小型化、 f性能化需求之增大，搭載零件之高密度構裝化及訊號之 南頻化不斷發展，對於印刷配線板亦要求導體圖案之微細 化（細間距化）及高頻對應等。 印刷配線板通常係經過如下步驟來製造：將絕緣基板 接著於銅箱，製成覆銅積層板後’藉由蝕刻將導體圖^形 成於銅。因此’對於印刷配線板用㈣，係要求與絕 緣基板之接著性及蝕刻性β ' 提高與絕緣基板之接著性的技術，通f係實施稱為粗 处理之於銅箔表面形成凹凸的表面處理。例如且 古、、_±_ . F述 於電解銅箔之Μ面（粗面），使用硫酸鋼酸性鍍浴， 電’儿積複數個呈樹枝狀或小球狀之銅而形成微細之凹凸， ' j用疋準效應來改善接著性。於粗化處理後，為了、 步提兩接著特性’通常進行鉻酸處理或利 = 處理等。 /机堝合劑之 亦已知有於銅箔表面形成錫、鉻、銅、鐵' 鎳等之金屬層或合金層之方法。 、令、 然而，利用粗化處理提高接著性之方法’對形成細線 3 201106816 不利。即，若由於細間距化而使得導體間隔變窄，則存在 粗化處理部於利用蚀刻形成電路後殘留於絕緣基板上，引 起、、巴緣劣化之虞。為防止該情形而欲蝕刻整個粗化表面 時，需要較長之敍刻時間，且無法維持特定之配線寬度。 於銅落表面設置例如Ni層或Ni—cr合金層之方法 中，與絕緣基板之接著性之基本特性的改善餘地較大。於 銅洛表面設置例如〇層之方法雖可獲得較高之接著性，但 存在蝕刻性較差，易發生於進行用以形成導體圖案之蝕刻 處理後，〇殘留於絕緣基板面之「㈣殘留」的問題。 因此，近年來研究、開發有如下技術：於銅箱表面形 成止第I金屬層，並於該第！金屬層上，以㈣性良好之 程度較薄地形成與絕緣基板之接著性良好的&層來作為第 2金屬層’藉此同時獲得與絕緣基板之良好接著性及良好钱 刻性。 /此種技術，例如於專利歧丨巾記載有：⑨聚醯亞胺 系可撓性覆銅積層板用表面處理銅箔上，設置以沁量計含 有0.03〜3.0mg/dm2i Ni層或/及於Ni合金層上以二 量計含有0.03〜l.0mg//dm2^ Cr層或/及&合金層作為 表面處理層，藉此可獲得於與聚醯亞胺系樹脂層之間具有 較高剝離強度’且絕緣可靠性、配線圖案形成時之蝕刻特 性、f曲特性優異之聚醯亞胺系可·覆銅積層板用鋼箱。 [專利文獻1]日本特開2006- 2221 85號公報 【發明内容】 然而，如專利文獻1中所記載，藉由電鍍進行鋼箔表 4 201106816 無法以較高濃度形成與絕緣基板之 面之被覆層之情形時 ^合性良好之Cr層，因此雖姓刻性良好，但與絕緣基板之 密合性存在改善餘地。x，於利用濺錢而形成含較多川之 被覆層之情形時，亦存在由於Ni之磁性之影響而導致每片 靶之濺鍍效率下降，成本上不利之問題。 因此，本發明之課題在於提供一種與絕緣基板之接著 I·及敍亥丨H兩者自優異且製造成本廉價之印刷配線板用銅 4又本土明之另一課題在於提供一種此種印刷配線板 用銅箔之製造方法。 先前認為，藉由於銅箔基材表面依序以極薄之厚度設 置N!層及Cf層，可獲得與絕緣基板之良好之接著性同 時可獲得良好之姓刻性。對此，本發明人等為提供與絕緣 基板之接著性及飯刻性更高之印刷配線板用銅箱而反覆潛 心研究，結果發現，於銅羯基材表面依序以奈米級之極薄 之厚度均勻設置Ni-Sn合金層及Cr層的情形時，可獲得 具有更優異之與絕緣基板之密合性及更優異之姓刻性之銅 箔的被覆層。 又發現，該情形下’可耐長期使用之而才熱性變得良好。 進而’亦發現藉由調節Ni—Sn合金層t之各金屬元素 之成分，靶之使用效率提高，且製造成本變得廉價。 以上述見解為基礎而完成之本發明於一態樣中，係一 種印刷配線板用㈣，《具備銅謂基材與被覆該鋼羯基材 表面之至少-部分之被覆層，該被覆層係由自銅羯基材表 面依序積層之含有Ni與如之Ni_Sn合金層及^層所構 201106816 成，該Cr層中Cr以18〜180 " g/dm2之被覆量存在，該 Ni — Sn合金層中Ni及Sn以合計為1 8〜450 # g/ dm2之被 覆量存在》 本發明之印刷配線板用銅箔之一實施形態中，上述Cr 層中Cr以30〜150 # g/ dm2之被覆量存在，上述Ni- Sn 合金層中Ni及Sn以合計為3 6〜3 60 e g/dm2之被覆量存 在。 本發明之印刷配線板用銅箔之一實施形態中，上述Cr 層中Cr以30〜90 # g/ dm2之被覆量存在，上述Ni-Sn合 金層中Ni及Sn以合計為50〜360//g/dm2之被覆量存在。 本發明之印刷配線板用1銅箔之另一實施形態中，上述 Cr層中Cr以36〜75 // g/dm2之被覆量存在，上述Ni- Sn 合金層中Ni及Sn以合計為75〜270 # g/dm2之被覆量存 在。 本發明之印刷配線板用銅箱之再另一實施形態中，上 述Ni-Sn合金層中存在3〜70重量％之Sn。 本發明之印刷配線板用銅之再另一實施形態中，若 利用穿透式電子顯微鏡觀察被覆層之剖面時，最大厚度為 0.5〜7.5nm ’最小厚度為最大厚度之80%以上。 本發明之印刷配線板用銅箔之再另一實施形態中，若 將根據利用XPS之自表面起之深度方向分析所得的深度方 向（X :單位nm)之鉻之原子濃度（％)設為f(x) ’將金屬鉻之 原子濃度（％)設為f! (X)，將氧化物鉻（鉻氧化物中之鉻）之原 子濃度（％)設為將氧之原子濃度 201106816 (% )設為g(x)，將銅之原子濃度（％ )設為h(x)，將鎳之合計 原子濃度（％)設為i(x)，將錫之原子濃度（％)設為j(x)，將 碳之原子濃度（％ )設為k(x) ’將其他原子濃度之總和設為 1〇)，則於區間[0 ’ 1.0]内，$ f(x)dx/( S f(x)d)i+ $ g(x)dx + S h(x)dx+ S i(x)dx+ $ j(x)dx+ $ k(x)dx+ $ l(x)dx)滿 足 20〜50%，$ h(x)dx/( $ f(x)dx+ 丨 g(x)dx+ S h(x)dx+ $ i(x)dx+ $ j(x)dx+ S k(x)dx+ $ l(x)dx)為 1.0% 以下且滿足 OS S fKx^x/S f2(x)dx$ 1.0，於[1.〇，2.5]内，（S i(x)dx + S j(x)dx)/( S f(x)dx+ $ g(x)dx+ $ h(x)dx+ $ i(x)dx+ $ j(x)dx+ $ k(x)dx+ Sl(x)dx)為 l〇 〜70% 且 0.1$ $ fjx^x/ S f2(x)dx $ 1 _〇。 本發明之印刷配線板用銅箔之再另一實施形態中，當 進行相當聚醯亞胺硬化之熱處理時，若將根據利用XPS之 自表面起之深度方向分析所得的深度方向（x ••單位nm)之鉻 之原子濃度（％ )設為f(X)，將金屬鉻之原子濃度)設為 f|⑴，將氧化物鉻之原子濃度（％ )設為f2(x)(f⑴=fl⑴+ GO)) ’將氧之原子濃度（％ )設為g(x)，將銅之原子濃度) 設為h(x)，將鎳之合計原子濃度)設為i(x)，將錫之原子 漠度（％)設為j(x)，將碳之原子濃度設為k(x)，將其他 原子濃度之總和設為1(X)’則於區間[〇, 10]内，S f(x)dx/〇 f(x)dx + $ g(x)dx -t- $ h(x)dx + $ i(x)dx + $ j(x)dx + )； k(x)dx+ n(x)dx)滿足 20〜50%，$ h(x)dx/n f(x)dx+'$ g(x)dx + J h(x)dx+ $ i(x)dx + $ j(x)dx+ S k(x)dx + J l(x)dx)為 1.0% 以下且滿足 $ fi(x)dx/ 〗f2(x)dx$ 1〇，於 201106816 [1.0,2.5]W，（n(x)dx+n(x)dx)/(Sf(x)dx+Sg(x)dx + S h(x)dx+ $ i(x)dx+ $ j(x)dx+ $ k(x)dx+ $ i(x)dx)為 l〇 〜70% 且 0.1 $ S fJxWx/ $ f2(x)dx$ 1 .〇 〇201106816 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a copper foil for a printed wiring board, and more particularly to a copper foil for a flexible printed wiring board. [Prior Art] Printed wiring boards have developed rapidly in this half century and are now used in almost all electronic devices. With the increase in the demand for miniaturization and f-performance of electronic devices in recent years, the high-density mounting of mounted components and the southerly frequency of signals have been developed, and the printed wiring boards are required to be finer (fine pitch). ) and high frequency correspondence. The printed wiring board is usually manufactured by the following steps: after the insulating substrate is formed in a copper box to form a copper clad laminate, the conductor pattern is formed by etching. Therefore, 'For the printed wiring board (4), it is required to improve the adhesion to the insulating substrate and the etching property β ' to improve the adhesion to the insulating substrate, and to perform a surface treatment called rough processing to form irregularities on the surface of the copper foil. . For example, the ancient, _±_. F is described in the surface of the electrolytic copper foil (rough surface), using a sulfuric acid steel acid plating bath, electric 'children's multiple dendritic or small spherical copper to form fine bumps , ' j uses the quasi-effect to improve the adhesion. After the roughening treatment, in order to carry out the two-step property, 'the chromic acid treatment or the profit treatment is usually performed. A method of forming a metal layer or an alloy layer of tin, chromium, copper, iron 'nickel or the like on the surface of the copper foil is also known. However, the method of improving the adhesion by the roughening treatment is disadvantageous for forming the thin line 3 201106816. In other words, when the conductor spacing is narrowed by the fine pitch, the roughening treatment portion remains on the insulating substrate after the circuit is formed by etching, and the edge of the flange is deteriorated. In order to prevent this, when etching the entire roughened surface, a long scribe time is required, and a specific wiring width cannot be maintained. In the method of providing, for example, a Ni layer or a Ni-cr alloy layer on the surface of the copper drop, the improvement in the basic characteristics of the adhesion to the insulating substrate is large. Although a method of providing a ruthenium layer on a surface of a copper ruthenium, for example, a high adhesion property is obtained, but etching property is inferior, and it is easy to occur after the etching process for forming a conductor pattern, and "(4) residual" remains on the surface of the insulating substrate. The problem. Therefore, in recent years, research and development have been carried out to form a first metal layer on the surface of a copper box, and this is the first! On the metal layer, a layer having a good adhesion to the insulating substrate is formed to a good extent (4), and the second layer is formed as a second metal layer, thereby achieving good adhesion to the insulating substrate and good cost. / such a technique, for example, is disclosed on a surface-treated copper foil for a 9-polyimine-based flexible copper-clad laminate, which is provided with a 0.03 to 3.0 mg/dm2i Ni layer or And a layer of 0.03 to 1.0 mg//dm 2 ^ Cr layer or/and an alloy layer as a surface treatment layer on the Ni alloy layer, thereby being obtained between the layer and the polyimide layer A steel box for a polyylidene-based copper-clad laminate having a high peel strength, and an insulation reliability, an etching property at the time of formation of a wiring pattern, and a f-bending property. [Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A No. 2006-22218. SUMMARY OF THE INVENTION However, as described in Patent Document 1, steel foil is formed by electroplating. Table 4 201106816 cannot form a coating with a surface of an insulating substrate at a relatively high concentration. In the case of a layer, the Cr layer having good adhesion is good, and therefore, although the surname is good, there is room for improvement in adhesion to the insulating substrate. x When a coating containing a large amount of water is formed by splashing money, there is also a problem that the sputtering efficiency of each of the targets is lowered due to the influence of the magnetic properties of Ni, and the cost is unfavorable. Therefore, an object of the present invention is to provide a copper for a printed wiring board which is excellent in both the insulating substrate and the semiconductor substrate, and which is inexpensive in terms of manufacturing cost. Another object of the present invention is to provide such a printed wiring board. A method of manufacturing copper foil. It has been previously thought that since the surface of the copper foil substrate is sequentially provided with an extremely thin thickness of the N! layer and the Cf layer, good adhesion to the insulating substrate can be obtained at the same time, and good surname can be obtained. On the other hand, the inventors of the present invention have repeatedly studied the copper box for a printed wiring board which has higher adhesion to the insulating substrate and the engraving property, and found that the surface of the copper matte substrate is in the order of nanometers. When the thickness of the thin layer is uniformly provided with the Ni-Sn alloy layer and the Cr layer, a coating layer having a copper foil which is more excellent in adhesion to the insulating substrate and more excellent in the surname can be obtained. It has also been found that in this case, it is resistant to long-term use and the heat becomes good. Further, it has been found that by adjusting the components of the respective metal elements of the Ni-Sn alloy layer t, the use efficiency of the target is improved, and the manufacturing cost becomes inexpensive. The invention completed on the basis of the above findings is a printed wiring board (4), "a coating layer having a copper substrate and at least a portion covering the surface of the steel substrate, the coating layer From the surface of the copper-ruthenium substrate, Ni is mixed with the Ni_Sn alloy layer and the layer 201106816, and the Cr layer is present in the coating amount of 18~180 " g/dm2, the Ni-Sn In the alloy layer, Ni and Sn are present in a total amount of 18 to 450 #g/dm2. In one embodiment of the copper foil for a printed wiring board of the present invention, Cr in the Cr layer is 30 to 150 #g/dm2 The coating amount is present, and Ni and Sn in the Ni-Sn alloy layer are present in a total amount of 3 6 to 3 60 eg/dm 2 . In one embodiment of the copper foil for a printed wiring board according to the present invention, Cr is present in the Cr layer in an amount of 30 to 90 #g/dm2, and Ni and Sn in the Ni-Sn alloy layer are 50 to 360/in total. The amount of coating of /g/dm2 exists. In another embodiment of the copper foil for a printed wiring board according to the present invention, Cr is present in the Cr layer in an amount of 36 to 75 // g/dm 2 , and Ni and Sn in the Ni—Sn alloy layer are 75 in total. The amount of ~270 #g/dm2 is present. In still another embodiment of the copper box for a printed wiring board of the present invention, 3 to 70% by weight of Sn is present in the Ni-Sn alloy layer. In still another embodiment of the copper for a printed wiring board of the present invention, when the cross section of the coating layer is observed by a transmission electron microscope, the maximum thickness is 0.5 to 7.5 nm and the minimum thickness is 80% or more of the maximum thickness. In still another embodiment of the copper foil for a printed wiring board of the present invention, the atomic concentration (%) of chromium in the depth direction (X: unit nm) obtained by analyzing the depth direction from the surface by XPS is set to f(x) 'Set the atomic concentration (%) of the metal chromium to f! (X), and set the atomic concentration (%) of the oxide chromium (chromium in the chromium oxide) to the atomic concentration of oxygen 201106816 (%) ) is g(x), the atomic concentration (%) of copper is h(x), the total atomic concentration (%) of nickel is i(x), and the atomic concentration (%) of tin is set to j. (x), by setting the carbon atom concentration (%) to k(x) 'to set the sum of other atomic concentrations to 1〇), then within the interval [0 '1.0], $f(x)dx/(S f(x)d)i+ $ g(x)dx + S h(x)dx+ S i(x)dx+ $ j(x)dx+ $ k(x)dx+ $ l(x)dx) meets 20~50% , $ h(x)dx/( $ f(x)dx+ 丨g(x)dx+ S h(x)dx+ $ i(x)dx+ $ j(x)dx+ S k(x)dx+ $ l(x) Dx) is 1.0% or less and satisfies OS S fKx^x/S f2(x)dx$ 1.0, within [1.〇, 2.5], (S i(x)dx + S j(x)dx)/( S f(x)dx+ $ g(x)dx+ $ h(x)dx+ $ i(x)dx+ $ j(x)dx+ $ k(x)dx+ Sl(x)dx) is l〇~70% and 0.1 $ $ Fjx^x/ S f2(x)dx $ 1 _〇. In still another embodiment of the copper foil for a printed wiring board of the present invention, when performing heat treatment for hardening of the polyimide, if the depth direction is analyzed according to the depth direction from the surface by XPS (x • The atomic concentration (%) of chromium per unit nm is f(X), the atomic concentration of metal chromium is set to f|(1), and the atomic concentration (%) of chromium oxide is set to f2(x)(f(1)= Fl(1)+ GO)) 'Set the atomic concentration of oxygen (%) to g(x), the atomic concentration of copper to h(x), and the total atomic concentration of nickel) to i(x), and tin The atomic indifference (%) is set to j(x), the atomic concentration of carbon is set to k(x), and the sum of other atomic concentrations is set to 1 (X)' in the interval [〇, 10], S f(x)dx/〇f(x)dx + $ g(x)dx -t- $ h(x)dx + $ i(x)dx + $ j(x)dx + ); k(x)dx+ n(x)dx) satisfies 20~50%, $h(x)dx/nf(x)dx+'$ g(x)dx + J h(x)dx+ $ i(x)dx + $ j(x) Dx+ S k(x)dx + J l(x)dx) is 1.0% or less and satisfies $ fi(x)dx/ 〗 f2(x)dx$ 1〇, at 201106816 [1.0,2.5]W, (n( x)dx+n(x)dx)/(Sf(x)dx+Sg(x)dx + S h(x)dx+ $ i(x)dx+ $ j(x)dx+ $ k(x)dx+ $ i (x)dx) is l ~ 70% and 0.1 $ S fJxWx / $ f2 (x) dx $ 1 billion .〇
本發明之印刷配線板用銅箔之再另一實施形態中，係 經進行相當聚醯亞胺硬化之熱處理之銅箔，若將根據利用 XPS之自表面起之深度方向分析所得的深度方向（χ :單位 nm)之鉻之原子濃度（％ )設為f(x)，將金屬鉻之原子濃度（％ ) 設為f,(x)’將氧化物鉻之原子濃度（％ )設為fi(x) + f2(X))，將氧之原子濃度（％ )設為g(x)，將銅之原子濃度（％ ) 設為h(x)，將鎳之合計原子濃度（％ )設為i(x)，將錫之原子 濃度（％ )設為j(x)，將碳之原子濃度（％ )設為k(x)，將其他 原子濃度之總和設為l(x)，則於區間[0，1.0]内，$ f(x)dx/( $ f(x)dx + $ g(x)dx + $ h(x)dx + J i(x)dx + $ j(x)dx + $ k(x)dx+ $ l(x)dx)滿足 20〜50%，$ h(x)dx/(J f(x)dx+ SIn still another embodiment of the copper foil for a printed wiring board according to the present invention, the copper foil subjected to heat treatment which is hardened by polyimine is formed in a depth direction obtained by analyzing the depth direction from the surface by XPS ( χ : The atomic concentration (%) of chromium in unit nm is f(x), the atomic concentration (%) of metallic chromium is set to f, and (x)' is set to the atomic concentration (%) of chromium oxide. (x) + f2(X)), the atomic concentration (%) of oxygen is set to g(x), the atomic concentration (%) of copper is h(x), and the atomic concentration (%) of total nickel is set. For i(x), the atomic concentration (%) of tin is set to j(x), the atomic concentration (%) of carbon is k(x), and the sum of other atomic concentrations is set to l(x). Within the interval [0,1.0], $ f(x)dx/( $ f(x)dx + $ g(x)dx + $ h(x)dx + J i(x)dx + $ j(x) Dx + $ k(x)dx+ $ l(x)dx) satisfies 20~50%, $ h(x)dx/(J f(x)dx+ S
g(x)dx + S h(x)dx + $ i(x)dx + S j(x)d>c + S k(x)dx + S l(x)dx)為 1.0% 以下且滿足 0$ 丨 fJxWx/S f2(x)dx$1.0，於 [1·0，2.5]内，（$ i(x)dx+ S j(x)dx)/( $ f(x)dx+ S g(x)dx + S h(x)dx + S i(x)dx + $ j(x)dx + $ k(x)dx + $ l(x)dx)為 10 〜70% 且 0.1$ $ f丨（x)dx/$ f2(x)dx$1.0。 本發明之印刷配線板用銅箔之再另一實施形態中，對 於在絕緣基板上接著有被覆層之印刷配線板用銅箔，分析 將'絕緣基板自被覆層剝離後之被覆層之表面時，若將根據 利用XPS之自表面起之深度方向分析所得的深度方向（X : 單位nm)之鉻之原子濃度（％)設為f(x)，將金屬鉻之原子濃 8 201106816 度（％)設為fjx)’將氧化物鉻之原子濃度（％)設為f2(x)(f(x) fi(x)+ ί*2(χ))，將氧之原子濃度)設為g(x)，將銅之原 子濃度（％)設為h(x) ’將鎳之合計原子濃度（％)設為i(x)， 將錫之原子濃度（％ )設為j(x)，將碳之原子濃度)設為 k(x)，將其他原子濃度之總和設為1(χ)，且若將金屬鉻之濃 度取大之自表層起之距離設為Fi，則於區間[〇，Fi]内，$g(x)dx + S h(x)dx + $ i(x)dx + S j(x)d>c + S k(x)dx + S l(x)dx) is 1.0% or less and satisfies 0 $ 丨fJxWx/S f2(x)dx$1.0, in [1·0,2.5], ($ i(x)dx+ S j(x)dx)/( $ f(x)dx+ S g(x)dx + S h(x)dx + S i(x)dx + $ j(x)dx + $ k(x)dx + $ l(x)dx) is 10 to 70% and 0.1$ $ f丨(x) Dx/$ f2(x)dx$1.0. In still another embodiment of the copper foil for a printed wiring board of the present invention, the surface of the coating layer after the insulating substrate is peeled off from the coating layer is analyzed for the copper foil for a printed wiring board having a coating layer on the insulating substrate. If the atomic concentration (%) of chromium in the depth direction (X: unit nm) obtained by analyzing the depth direction from the surface using XPS is f(x), the atomic concentration of the metal chromium is 8 201106816 degrees (%) ) set to fjx) 'set the atomic concentration (%) of the oxide chromium to f2(x)(f(x) fi(x)+ ί*2(χ)), and set the atomic concentration of oxygen to g ( x), the atomic concentration (%) of copper is h(x) 'The total atomic concentration (%) of nickel is i(x), and the atomic concentration (%) of tin is set to j(x). The atomic concentration of carbon is set to k(x), and the sum of the other atomic concentrations is set to 1 (χ), and if the concentration of the metal chromium is large, the distance from the surface layer is set to Fi, then the interval [〇, Fi], $
h(X)dX/(丨 f(X)dx + S g(x)dx + 丨 h⑴dx + 丨 i(x)dx + S j(x)dx + $ k(x)dx + Sl(x)dx)為 5·〇% 以下且滿足 〇」$ ^ fi〇)dx/ $ f2(x)dxg l.o。 本發明之印刷配線板用銅箔之再另一實施形態中，銅 箔基材為壓延銅箔。 本發明之印刷配線板用銅箔之再另一實施形態中，印 刷配線板為可撓性印刷配線板。 本發明於另一態樣中，係一種印刷配線板用銅箔之製 k方法，其包含如下步驟：利用錢鍍法，以厚度為〇 2 5〜 5.0 nm之Ni-Sn合金層及厚度為〇25〜2 5 11〇1之Cr層依 序被覆銅羯基材表面之至少一部分。 本發明於進而另一態樣中，係一種覆銅積層板，其具 備本發明之銅箔。 本發明之覆鋼積層板之一實施形態中，具有銅箱接著 於聚醯亞胺之結構。 本發明於進而另一態樣中，係一種印刷配線板，其將 本發明之覆銅積層板作為材料。 可獲得與絕緣基板之接著性及姓刻性兩者皆優異、適 201106816 合於細節距化、且製造成本廉價之印刷配線板用銅箔。又， 本發明亦可應用於電磁屏蔽、高頻屏蔽、及向金屬條積層 聚酿亞胺或聚醯胺等樹脂以進行絕緣之技術。 【實施方式】 (銅箔基材） 可用於本發明之銅箔基材之形態並無特別限制，典型 的是能夠以壓延銅箔或電解銅箔之形態加以使用。通常， 電解銅ϋ係將銅自硫酸銅鐘浴電解析出至欽或不鑛鋼之滾 筒上而製造，壓延銅落係重複進行利用虔延報之塑性加工 與熱處理而製造。多將廢延銅落用於要求彎曲性之用途。 作為銅羯基材之材料，除通常用作印刷配線板之導體 圖案之款煉銅或無氧銅等高純度之鋼以外，例如亦可使用 如摻雜Sn之銅、摻雜Ag之銅、添加有等之 ::金、添加有沁及以等之卡遜系銅合金之類的銅合金。 =。’本說明書中’單獨使用術語「鋼箱」時亦包括銅合 要、尚本發明之銅箱基材之厚度亦並無特別限制，只 、田3周即為適合於印刷配線板用之厚声即可 〜左右。政由 7子度即可。例如可為.5 為⑽m以下，:^成精細圖案為目的之情形時 左右。 4佳為2—以下，典型的是5〜20“ m 對於用於本發明之銅猪基材， 佳。先前，通當 進仃粗化處理較 級之凹凸而實"為：下情況:利用特殊鑛敷於表面附上^ 而“表面粗化處理，利用物理性之定準效應而 10 201106816 使其具有與樹脂之接著性。然而，另一方面’就細節距及 高頻電氣特性而言，平滑之箔較良好，而粗化箔會朝不利 之方向發展。又，因省略粗化處理步驟，故亦存在提高經 濟性、生產性之效果。因此，本發明中所使用之羯為不特 別進行粗化處理之箱。 (被覆層） 則泊丞柯之表面之至少一部分由Ni_Sn合金層及^ 層依序被覆。Ni-Sn合金層及Cr層構成被覆層。被覆之部 位並無特別限制，通常為預定與絕緣基板接著之部位。: 2被覆層之存在，與絕緣基板之接著性提高…般認為， 若置於高溫環境下，銅箱與絕緣基板之間之接著力存在下 :=，：其係由於銅熱擴散至表面，並與絕緣基板反 ；:引起。本發明中’預先將銅之擴散防止優異之Nl_Sn δ金層設置於㈣基材上，藉此可防止銅之 緣,之接著性較Nl，合金層更優異之^層設 著故1s“金層上，藉此可進-步提高與絕緣基板之接 者性。由於Cr層之厚度因N1— 土扳之接 因此可減少對㈣性之不良影 者曰之存在而可較薄， 著性.，除指常態下之接著性以;卜本發明中所謂接 接著性(耐熱性)及置於高 Μ曰置於高溫下之後之 於太恭Β 下之後之接著性（耐渴性）。 於本發明之印刷配線板 …往） 均勻，並且完全覆蓋銅箱基材表面。二=薄且厚度 與絕緣基板之接著性提高之原因推測為藉由成為此種構成而 膜上形成與樹脂之接著性非 、Nl—Sn合金被 良-之Cr單層被膜作為最表 201106816 面藉此於g亞胺化時之高溫熱歷程後（約下3〇分鐘 〜數小時左右）亦保持具有高接著性之單層被膜結構β又認 為’藉由使被覆層成為極薄並且作為Ni_Sn合金與心之 雙層結構來減少cr之使用量，而蝕刻性提高。 具體而言，本發明之被覆層具有以下構成。 (1) Cr、Ni — Sn合金被覆層之鑑定 本發明中，銅箔素材之表面之至少一部分係以Ni— Sn 合金層及Cr層之順序進行被覆。該等被覆層之鑑定，可利 用XPS或AES等表面分析裝置’自表層進行紐鍍’進行 冰度方向之化學分析，由各檢測峰值之存在而鑑定Ni — Sn 合金層及Cr層。又，可根據各檢測峰值之位置來確認被覆 之順序。 (2) 附著量 另一方面，由於該等Ni — Sn合金層及Cr層非常薄， 因此利用XPS、AES不易進行準確之厚度之評估。因此， 本申請發明中，Ni—Sn合金層及（^層之厚度係以每單位面 積之被覆金屬之重置來加以評估。本發明之Cr層中Cr以 18〜180/zg/dm2之被覆量存在，Ni—Sn合金層中％及Sn 以合計為18〜450 // g/dm2之被覆量存在。若Cr小於18 /zg/dm2,則無法獲得充分之剝離強度，若Cr超過18〇#g / dm2 ’則存在蝕刻性明顯下降之傾向。若Ni及&之合叶 小於18 y g / dm，則無法獲得充分之剝離強度，若Ni及 Sn之合計超過450 /zg/dm2，則存在蝕刻性明顯下降之傾 向。Cr之被覆量較佳為30〜ISOyg/dm2，更佳為3〇〜9〇 12 201106816 A g/dm2，進而較佳為36〜75" g/dm2，沁及如之合計 被f量較佳為36〜360 #g/dm2,更佳為5〇〜36〇Mg/ dm2，進而較佳為75〜27〇# g/dm2。 於焱鍍純Νι層之情形時，使用純Ni作為靶，但該純 Νι靶之磁性較強’於以磁控濺鍍等進行濺鍍之情形時’每 片靶之使用效率變低，成本上不利。相對於此，本發明之 Ni Sn合金層含有3〜7〇重量％之如。若犯―如合金層 中之Sn小於3重量％，則磁性較強，因此錢鍍效率較差。 若沁-Sn合金層中之Sn超過7〇重量％，則基材之銅之擴 政防止效果優異之Nl量變少，無法獲得與樹脂之充分之密 合性。Ni-Sn合金層中之Sn較佳為5〜3〇重量％ ^ (3)利用穿透式電子顯微鏡（TEM)之觀察 當利用穿透式電子顯微鏡觀察本發明之被覆層之剖面 時’為如下被覆層：最大厚度為〇 5〜7 5nm，較佳為〇 8〜 6.0ΓΠΠ，最小厚度為最大厚度之鄕以上，較佳為⑽以 上且不均非吊少。因為若被覆層厚度小於Μ譲，則於耐 熱試驗、耐濕試驗中，剝離強度之劣化較大，若厚度超過 7.5麵’則触刻性下降。於厚度之最小值為最大值之鄕以 上之情形時’該被覆層之厚度非常穩定，於耐熱試驗後亦 幾乎不發生變化。於利用而之觀察中，不易發現被覆層 :之Nl—〜合金層ACr層之明確之邊界，看起來為單層（參 知圖1及2)。根據本發明人等之研究結果，認為於麗觀 察中所發現之被覆層係以Cr為主體之層，亦認為 合金層存在於該銅箔基材側。因此，本發明中，將觀觀 13 201106816 察時之被覆層之厚度定義為看起來為單層之被覆層之厚 度。然而，因觀察部位之不同，亦會存在被覆層之邊界不 明確之處，而將此種部位自厚度之測定部位t排除。 根據本發明之構成，由於Cu之擴散受到抑制，因此認 為具有穩定之厚度。本發明之銅箔係與聚醯亞胺膜接著， 經過耐熱試驗（於溫度150tT且於空氣環境下之高溫環境 下放置1 68小時）後剝離樹脂之後，被覆層之厚度亦幾乎不 發生變化’最大厚度為〇.5〜8 Qnm ’最小厚度亦可維持為 最大厚度之60%以上 '較佳為7〇%。 (4)成膜後之被膜結構 就提高接著強度而言，較,·理想為内部之銅不擴散至被 覆層最表面（自表面起〇〜1_0nm之範圍卜因此，於本發明 之印刷配線板用銅箔中，較理想為：若將根據利用xps之 自表面起之深度方向分析所得的深度方向（χ:單位nm)之鉻 之原子濃度（％)設為f(X)，將金屬鉻之原子濃度設為 fi(x) ’將氧化鉻之原子濃度（％)設為f2(x)(f(x)=fi(x) + G(x))，將氧之原子濃度（％)設為g(x)，將銅之原子濃度（％) 設為h(x)，將鎳之合計原子濃度（％ )設為ί(χ)，將錫之原子 濃度（％ )設為j(x) ’將碳之原子濃度（％ )設為k(x)，將其他 原子濃度之總和設為l(x)，則於區間[〇, 1〇]内，$ h(x)dx/( $ f(x)dx+ s g(x)dx+ s h(x)dx+ s i(x)dx+ 5 j(x)dx+ 5 k(x)dx+ $ i(x)dx)為 i.o%以下。 又，較理想為於成膜後之被覆層最表面（自表面起〇〜 l.Onm之範圍）’以較高濃度存在與絕緣基板之密合性優異 201106816 之Cr層。較理想為於被膜層之内部（自表面起^〜厶“爪 之範圍），以較南 >辰度存在銅之擴散防止優異之Ni 一 gn合金 層。然而，右任一層之濃度過高，皆會成為蝕刻性變差之 原因。因此，本發明之印刷配線板用銅箔中，較佳為：於 根據利用XPS之自表面起之深度方向分析所得之深度方向 (X·單位 nm)的區間[〇, lo]内，$ f(x)dx/( $ f(x)dx+ $ + S h(x)dx+ $ $ j(x)dx+ $ k(x)dx+ $ 滿 足 20 〜50%，Π·0,2.5]内，⑴⑴$ j(x)dx)/(s f(x)dx + S g(x)dx+ S h(x)dx+ S i(x)dx+ S j(x)dx+ S k(x)dx+ $ l(x)dx)為 l〇〜70%。 又，於被覆層最表面（自表面起〇〜1〇nm之範圍），鉻 存在金屬鉻與鉻氧化物兩者，但就防止内部之銅之擴散且 確保接著力的觀點而言’理想的是金屬鉻，而就獲得良好 之蝕刻I·生而5，較理想為鉻氧化物。較理想為於被覆層最 表面下之深度1.0〜2.5nm内，氧濃度較小，鉻以金屬狀態 存在。其原因在於’與氧化之狀態相tb，鉻之金屬狀態的 防止内部之銅之擴散之能力更高，且可提高财熱性。因此， 就謀求兼具_性與接著力Μ，㈣為：若將根據利用 之自表面起之深度方向分析所得的金屬絡及氧化絡之 深度方向（X :單位㈣之原子濃度（％ )分別設為fl⑴、f2⑷’ 則於區間[〇, ！·_，滿；^ Sfi(x)dx/Sf2⑴心1〇,於 區間[1‘Q 2_5]内 ’ G·1 $ S fi(x)dxM f2(x)dxS 1.0。 當聚醯亞胺硬化之熱處理後之被膜結構 就提高接著強度而·r ’較理想為：於相當聚醯亞胺硬 15 201106816 化之熱處理後（於氮氣環境、35〇 t下加熱3〇分鐘〜數小 %)於被覆層最表面（自表面起0〜l.〇nm之範圍），内部之 銅不會由於熱歷程而擴散至表面。因此，本發明之印刷配 線板用銅箔中，較理想為：於相當聚醯亞胺硬化之熱處理 後，若將根據利用XPS之自表面起之深度方向分析所得的 深度方向（X :單位nm)之鉻之原子濃度（％)設為f(x)，將金 屬鉻之原子濃度（％ )設為fl (χ)，將氧化物鉻之原子濃度（％ ) 設為f2(X)(f(X)=广⑴+匕⑴）’將氧之原子濃度（％)設為 g(x)，將銅之原子濃度（％)設為h(x)，將鎳之合計原子濃度 (%)設為i⑴，將錫之原子濃度（％)設為〗⑴，將碳之原子 濃度（％ )設為k(X)，將其他原子濃度之總和設為1(χ)，則於 區間[〇 ’ 1.0]内 M h(x)dx/n f(x)dx+ 丨 g(x)dx+ S h(x)dx + S i(x)dx+ $ j(x)dx+ S k(x)dx+ n(x)dx)為 1_0% 以下。 又’較理想為·於相當聚酿亞胺硬化之熱處理後（於氮 氣環境、3501下加熱30分鐘〜數小時）之被覆層最表面（自 表面起0〜l.〇nm之範圍），以較高濃度存在與絕緣基板之密 合性優異之Cr層。較理想為於被膜層之内部（自表面起i .〇 〜2.5nm之範圍），以較高濃度存在銅之擴散防止優異之犯 —Sn合金層。然而，若任一層之濃度過高，皆會成為蝕刻 性變差之原因。因此’本發明之印刷配線板用銅箔中較 佳為：於相當聚醯亞胺硬化之熱處理後，在根據利用xps 之自表面起之深度方向分析所得之深度方向:單位nm) 的區間[0，1.0]内，$ f(x)dx/( 5 f(x)dx+ S g(x)dx+ $ h(x)dx + S i⑷dx+ $j(x)dx+ S k(x)dx+ Π ⑴dx)滿足 20 〜5〇 16 201106816 /6 ’ 於[1.0 ’ 2·5]内，（5 i(x)dx+ $ j(x)dx)/( $ f(x)dx+ $ g(x)dx + $ h(x)dx + 5 i(x)dx + S j(x)dx + S k(x)dx + $ l〇)dx)為 i〇〜7〇%。 又’較佳為：於相當聚醯亞胺硬化之熱處理後（於氮氣 壞境、350°C下加熱30分鐘〜數小時）之被覆層最表面（自表 面起0〜1.0 nm之範圍），若將根據利用XPS之自表面起之 深度方向分析所得的金屬鉻及氧化鉻之深度方向（χ :單位 nm)之原子濃度（％)分別設為f!(x)、f2(x)，則於區間[0，1.0] 内’滿尾0$ $心⑴心/ $ f2(x)dx$ 1.0，於區間μ 〇，2.5]内， 〇·1 $ $ fi(x)dx/ $ f2(x)dx$ 1.〇。 (絕緣基板剝離面之被膜結構） 就提高接著強度而言，較理想為：對於經由被覆層而 貼附於絕緣基板上之印刷配線板用銅箔，分析將絕緣基板 自被覆層剝離後之被覆層之表面時，内部之銅不會擴散至 被覆層最表面（自表面起〇〜丨.0nm之範圍）。較理想為：若 將根據利用XPS之自表面起之深度方向分析所得的鉻之原 子濃度（％)設為f(x)，將氧之原子濃度（％)設為g〇〇,將銅 之原子濃度（％)設為h(x),將鎳之原子濃度（％)設為i(x)， 將錫之原子濃度（％)設為j(x)，將碳之原子濃度設為 k(x)，將其他原子濃度之總和設為ι(χ)，將金屬鉻之濃度最 大之自表層起之距離設為F〗，則於區間[〇，I]内，χ h(x)dx/( 5 f(x)dx + 5 g(x)dx + s h(x)dx + s i(x)dx + s j(x)dx+ $ k(x)dx+ n(x)dx)為 5.0%以下。 又，較理想為：對於經由被覆層而貼附於絕緣基板上 17 201106816 之印刷配線板用銅箔，八 被覆声之类而《主 刀析將絕緣基板自被覆層剝離後之 向八:/曰.，若將根據利用之自表面起之深度方 子:得的金屬鉻之原子濃度（％)設為fl(x)，將氧化物鉻 設為f2(x)，將金屬鉻之濃度最大之自表層起 以〇離认為F|，則於區間[〇，F|]内，〇1qf|(x)dx/if2⑷dx 1鉻濃度及氧濃度分別係根據由利用XPS之自表面起之 听又方向刀析所得的Cr2p轨域及Ols轨域之峰值強度而算 出又’深度方向（X ··單位nm)之距離係根據Si〇2換算之 :鑛速率而算出之距離。絡漠度為絡氧化物濃度與金屬絡 艰度之合汁值’可分離為鉻氧化物濃度與金屬鉻濃度而加 以分析。 (本發明之銅箔之製法） 本發明之印刷配線板用銅箔可藉由濺鍍法而形成。 即，可藉由濺鍍法，以厚度為〇.25〜5 〇nm、較佳為〇 5〜 4.0nm、更佳為丨.0〜3.0nm2Nl—如合金層及厚度為〇25 〜2.5nm、較佳為〇·3〜2.〇nm、更佳為〇 5〜丨如爪之心層 依序被覆銅箔基材表面之至少一部分而製造。若以電鍍積 層此種極薄之被膜’則厚度產生不均，於耐熱、耐濕試驗 後剝離強度易下降。 此處所謂厚度，並非上述藉由XPS或TEM而決定之厚 度，而係根據錢鐘之成膜速度所導出之厚度。某種濺鍍條 件下之成膜速度》可進行0.1/i m(l 〇〇 nm)以上之濺鍵，根 據漱链時間與錢鍍厚度之關係進行計測。計測完該激鍍條 18 201106816 件下之成膜速度，則根據所期望 ^ + . 之厚度來設定濺鍍時問。 再者’濺鑛可連續或分批次進行， 且能夠以如本發明中指 疋之厚度均勻積層被覆層。濺鍍法 j幻舉直流磁控濺鍍法。 (印刷配線板之製造） 又戍 可使用本發明之銅箔，依攄舍 rpwm , 锞节用方法製造印刷配線板 (PWB)。以下，表不印刷配線板之製造例。 首先，貼合銅箱與絕緣基板而 衣1^•復銅積層板。積層 有銅箔之絕緣基板只要具有可適用 z 迥用於印刷配線板之特性， 則不受特別限制’例如用於剛性Pw _ t β可’可使用紙基材酚 树月曰、紙基材環氧樹脂、合成纖維布基材環氧樹脂、玻璃 布-紙複合基材環氧樹脂、玻璃布·破璃不織布複合基材環氧 樹脂及玻璃布基材環氧樹脂等，用 A ML岭’可使用聚酯 膜或聚醯亞胺膜等。 關於貼合之方法，於剛性PWB用之情形時，準備以下 之預浸體：將樹脂含浸於玻璃布等基材中，且使樹脂硬化 至半硬化狀態為止。可藉由將預浸體與銅箱之具有被覆層 之面疊合並進行加熱加壓而進行。 於可撓性印刷配線板（FPC)用之情形時，可使用環氧系 或丙烯酸系之接著劑，將聚醯亞胺膜或聚酯膜與銅箔之具 有被覆層之面接著（3層結構）。又，不使用接著劑之方法（2 層、構）T列舉：藉由將作為聚醯亞胺之前驅物之聚酿亞 胺清漆（聚醯胺酸（Polyamic acid)清漆）塗佈於銅箔之具有被 覆層之面，並進行加熱而醯亞胺化的澆鑄法；或於聚醯亞 胺膜上塗佈熱塑性之聚醯亞胺，於其上疊合銅箔之具有被 19 201106816 覆層之面’並進行加熱加壓的積層法。濟鑄法中，於冷佈 聚醯亞胺清漆之前預先塗佈熱塑性聚酿亞胺等錦… (anchor coat)材料亦有效。 曰 本發明之銅㈣之效果係、於採㈣鑄法製造Fpc時顯著 表現# s欲不使用接著劑而使銅箔與樹脂貼合時，特 別要求銅荡之盘樹脂夕姑贫, 树知之接者性，由於本發明之銅箔之與樹 脂、特別是聚醯亞胺之垃这& 7S w 妝之接者性優異，因此可以說適合於利 用澆鑄法之覆銅積層板之製造。 本發明之覆銅精 檟層板可用於各種之印刷配線板 (PWB) ’並無特別限制，例 川如就導體圖案之層數之觀點.而 言，可適用於單面PWB、雙面PWR ^ a 又曲PWB、多層pwb(3層以上）， 就絕緣基板材料之種類之觀點而言，可適用於剛性_、 可撓性PWB(FPC)、剛性-可撓性pWB。 由覆銅積層板製造印刷配線板之步驟採用本從業者所 周知之方法即可，例如可將阻㈣⑷此叫⑽堂佈於 覆銅積層板之銅羯面之作為道辨 ， <忭馮導體圖案的必要部分，並將蝕 刻液喷射於鋼箱面，藉此吟·} <处力η从 稽此除去多餘銅箔而形成導體圖案， 然後剝離、除去阻蝕劑而露出導體圖案。h(X)dX/(丨f(X)dx + S g(x)dx + 丨h(1)dx + 丨i(x)dx + S j(x)dx + $ k(x)dx + Sl(x)dx ) is 5·〇% or less and satisfies 〇"$^fi〇)dx/ $f2(x)dxg lo. In still another embodiment of the copper foil for a printed wiring board of the present invention, the copper foil substrate is a rolled copper foil. In still another embodiment of the copper foil for a printed wiring board of the present invention, the printed wiring board is a flexible printed wiring board. In another aspect, the present invention provides a method for producing a copper foil for a printed wiring board, comprising the steps of: using a money plating method, a Ni-Sn alloy layer having a thickness of 〇25 to 5.0 nm, and a thickness of The Cr layer of 〇25~2 5 11〇1 is sequentially coated on at least a part of the surface of the copper matte substrate. In still another aspect of the invention, there is provided a copper clad laminate comprising the copper foil of the invention. An embodiment of the steel-clad laminate according to the present invention has a structure in which a copper box is followed by a polyimide. In still another aspect of the invention, there is provided a printed wiring board comprising the copper clad laminate of the invention as a material. It is possible to obtain a copper foil for a printed wiring board which is excellent in both adhesiveness and surname of an insulating substrate, and is suitable for a fine pitch and has a low manufacturing cost. Further, the present invention can also be applied to electromagnetic shielding, high-frequency shielding, and a technique of laminating a resin such as a polyimide or a polyamide to a metal strip for insulation. [Embodiment] (Copper foil base material) The form of the copper foil base material which can be used in the present invention is not particularly limited, and it can be typically used in the form of a rolled copper foil or an electrolytic copper foil. Usually, an electrolytic copper bismuth system is produced by analyzing copper from a copper sulfate clock bath to a cylinder of a chin or a non-mineral steel, and the rolled copper is repeatedly produced by plastic working and heat treatment. More use of the copper is used for the purpose of bending. As the material of the matte base material, in addition to high-purity steel such as copper-clad or oxygen-free copper which is generally used as a conductor pattern of a printed wiring board, for example, copper doped with Sn, copper doped with Ag, or the like may be used. Add a copper alloy such as gold, a ruthenium or a ruthenium-based copper alloy. =. 'In this specification', the term "steel box" is used separately, and the thickness of the copper box substrate of the present invention is also not particularly limited. Only 3 weeks is suitable for printing wiring boards. Sound can be ~ left and right. The political power can be 7 sub-degrees. For example, the case where .5 is (10) m or less, and the case where the fine pattern is used for the purpose is about right and left. 4 is preferably 2 or less, typically 5 to 20" m. For the copper pig substrate used in the present invention, it is preferred. Previously, the roughening of the coarser processing was performed. Use a special mineral deposit on the surface to attach ^ and "surface roughening treatment, using the physical quasi-effects 10 201106816 to make it with the resin. However, on the other hand, smooth foils are better in terms of fine pitch and high frequency electrical characteristics, and roughened foils tend to develop in an unfavorable direction. Further, since the roughening treatment step is omitted, there is an effect of improving economy and productivity. Therefore, the crucible used in the present invention is a tank which is not particularly subjected to roughening treatment. (Coating layer) At least a part of the surface of the beryl is coated sequentially by the Ni_Sn alloy layer and the layer. The Ni-Sn alloy layer and the Cr layer constitute a coating layer. The portion to be covered is not particularly limited, and is usually a portion to be placed next to the insulating substrate. : 2 The existence of the coating layer and the adhesion to the insulating substrate are improved. It is considered that if placed under a high temperature environment, the adhesion between the copper box and the insulating substrate exists: =,: because the copper is thermally diffused to the surface, And opposite to the insulating substrate;: caused. In the present invention, the N1_Sn δ gold layer which is excellent in diffusion prevention of copper is provided on the (4) substrate in advance, whereby the edge of copper can be prevented, and the adhesion is better than that of N1, and the alloy layer is set so that 1 s "gold" On the layer, the contact with the insulating substrate can be further improved. Since the thickness of the Cr layer is reduced by the N1 - soil pull, the existence of the (4) bad shadow can be reduced and the thickness can be thin. In addition, it refers to the adhesiveness under normal conditions; the adhesion (heat resistance) in the present invention and the adhesion (thirstyness) after being placed under high temperature after being placed under high temperature. The printed wiring board of the present invention is uniform and completely covers the surface of the copper case substrate. The reason why the thickness is thin and the adhesion between the thickness and the insulating substrate is increased is presumed to be formed on the film by the resin. Subsequent non-Nl-Sn alloy is a good---Cr single-layer film as the most recent 201106816 surface, which is also maintained after the high temperature thermal history of g imidization (about 3 minutes to several hours) The subsequent single-layered film structure β is considered to be 'by making the coating layer extremely thin and Further, as the two-layer structure of the Ni_Sn alloy and the core, the amount of use of Cr is reduced, and the etching property is improved. Specifically, the coating layer of the present invention has the following constitution. (1) Identification of Cr, Ni-Sn alloy coating layer The present invention At least a part of the surface of the copper foil material is coated in the order of the Ni—Sn alloy layer and the Cr layer. The coating layer can be identified by a surface analysis device such as XPS or AES. In the chemical analysis in the direction, the Ni-Sn alloy layer and the Cr layer are identified by the presence of each detection peak. Further, the order of the coating can be confirmed based on the position of each detection peak. (2) The amount of adhesion, on the other hand, Since the Ni—Sn alloy layer and the Cr layer are very thin, it is difficult to perform accurate thickness evaluation using XPS and AES. Therefore, in the present invention, the Ni—Sn alloy layer and the thickness of the layer are coated metal per unit area. In the Cr layer of the present invention, Cr is present in an amount of 18 to 180/zg/dm 2 , and % and Sn in the Ni—Sn alloy layer are in a total amount of 18 to 450 // g/dm 2 . Exist. If Cr is less than 18 /zg/dm2, A sufficient peel strength cannot be obtained, and if Cr exceeds 18 〇 #g / dm2 ', the etching property tends to be remarkably lowered. If the joint of Ni and & is less than 18 yg / dm, sufficient peel strength cannot be obtained, if Ni When the total amount of Sn and the total amount of Sn exceeds 450 /zg/dm2, the etching property tends to be remarkably lowered. The coating amount of Cr is preferably 30 to ISOyg/dm2, more preferably 3〇~9〇12 201106816 A g/dm2, and further Preferably, the amount of f is preferably 36 to 360 #g/dm2, more preferably 5〇~36〇Mg/dm2, and further preferably 75~27〇# g/dm2. In the case of plating pure Ν layer, pure Ni is used as the target, but the magnetic properties of the pure Ν target are stronger. 'When sputtering is performed by magnetron sputtering, the efficiency of use of each target is low, and the cost is low. Unfavorable. On the other hand, the Ni Sn alloy layer of the present invention contains 3 to 7 % by weight. If the Sn in the alloy layer is less than 3% by weight, the magnetic properties are strong, so the money plating efficiency is poor. When the amount of Sn in the bismuth-Sn alloy layer exceeds 7% by weight, the amount of N1 which is excellent in the effect of preventing the expansion of copper of the substrate is small, and sufficient adhesion to the resin cannot be obtained. Sn in the Ni-Sn alloy layer is preferably 5 to 3 % by weight ^ (3) Observation by a transmission electron microscope (TEM) when observing the cross section of the coating layer of the present invention by a transmission electron microscope The coating layer has a maximum thickness of 〇5 to 7.5 nm, preferably 〇8 to 6.0 Å, and a minimum thickness of 最大 or more, preferably (10) or more, and unevenness. When the thickness of the coating layer is less than Μ譲, the deterioration of the peel strength is large in the heat resistance test and the moisture resistance test, and if the thickness exceeds 7.5 faces, the etchability is lowered. When the minimum value of the thickness is the maximum value or more, the thickness of the coating layer is very stable, and it hardly changes after the heat resistance test. In the observation of use, it is difficult to find the boundary of the coating layer: the Nr-~ alloy layer ACr layer, which appears to be a single layer (see Figs. 1 and 2). According to the findings of the present inventors, it is considered that the coating layer found in the observation is a layer mainly composed of Cr, and it is considered that the alloy layer exists on the side of the copper foil substrate. Therefore, in the present invention, the thickness of the coating layer at the time of observation 13 201106816 is defined as the thickness of the coating layer which appears to be a single layer. However, depending on the observation site, there is also a ambiguity in the boundary of the coating layer, and such a portion is excluded from the measurement site t of the thickness. According to the constitution of the present invention, since the diffusion of Cu is suppressed, it is considered to have a stable thickness. The copper foil of the present invention and the polyimide film are then subjected to a heat resistance test (after standing at a temperature of 150 tT and placed in a high temperature environment for 1 to 68 hours), and the thickness of the coating layer hardly changes after peeling off the resin. The maximum thickness is 〇.5~8 Qnm 'the minimum thickness can also be maintained at 60% or more of the maximum thickness', preferably 7〇%. (4) The film structure after film formation improves the adhesion strength, and it is preferable that the inner copper does not diffuse to the outermost surface of the coating layer (from the surface to the range of 1 to 10 nm). Therefore, the printed wiring board of the present invention is used. In the case of the copper foil, it is preferable to set the atomic concentration (%) of chromium in the depth direction (χ: unit nm) obtained by the depth direction analysis from the surface by xps to f(X). The atomic concentration is set to fi(x) 'The atomic concentration (%) of chromium oxide is f2(x)(f(x)=fi(x) + G(x)), and the atomic concentration of oxygen (%) Let g(x), set the atomic concentration (%) of copper to h(x), set the total atomic concentration (%) of nickel to ί(χ), and set the atomic concentration (%) of tin to j ( x) 'Set the atomic concentration (%) of carbon to k(x), and set the sum of other atomic concentrations to l(x), then within the interval [〇, 1〇], $ h(x)dx/( $ f(x)dx+ sg(x)dx+ sh(x)dx+ si(x)dx+ 5 j(x)dx+ 5 k(x)dx+ $ i(x)dx) is io% or less. The surface of the coating layer after film formation (from the surface 〇 l l. Onm range) 'has a higher concentration and adhesion to the insulating substrate Excellent Cr layer of 201106816. It is preferable to have a Ni-gn alloy layer which is excellent in the diffusion of copper at a southerly degree from the surface of the film layer (from the surface to the "claw range"). However, right When the concentration of any of the layers is too high, the etching property is deteriorated. Therefore, in the copper foil for a printed wiring board of the present invention, it is preferable to use a depth direction obtained by analyzing the depth direction from the surface using XPS. In the interval [〇, lo] of (X·unit nm), $ f(x)dx/( $ f(x)dx+ $ + S h(x)dx+ $ $ j(x)dx+ $ k(x)dx+ $ satisfies 20 ～50%, Π·0,2.5], (1)(1)$ j(x)dx)/(sf(x)dx + S g(x)dx+ S h(x)dx+ S i(x)dx+ S j(x)dx+ S k(x)dx+ $ l(x)dx) is l〇~70%. Also, in the outermost surface of the coating layer (from the surface 〇~1〇nm range), chromium exists in metallic chromium and Both chrome oxides, but in terms of preventing the diffusion of copper inside and ensuring the adhesion force, 'ideal is metallic chromium, and good etching is obtained, and 5 is preferable, and chromium oxide is preferable. For the depth of the bottom surface of the coating layer is 1.0~2.5nm, the oxygen concentration is small, and the chromium is The genus state exists. The reason is that 'the state of oxidation is tb, and the metal state of chrome has a higher ability to prevent the diffusion of copper inside, and it can improve the heat. Therefore, it is desirable to have both _ sex and adhesion. (4) In the depth direction (X: atomic concentration (%) of unit (4) is set to fl(1), f2(4)' respectively according to the depth direction of the metal layer and the oxide network obtained from the depth direction of the surface to be used, in the interval [〇, ! · _, full; ^ Sfi(x)dx/Sf2(1) heart 1〇, within the interval [1 'Q 2_5] ′ G·1 $ S fi(x)dxM f2(x)dxS 1.0. When the heat treatment of the polyimide is hardened, the structure of the film is increased. The strength of the film is preferably: after the heat treatment of the equivalent polyimine hard 15 201106816 (heating for 3 minutes in a nitrogen atmosphere at 35 〇t) ~ a small percentage) on the outermost surface of the coating layer (from 0 to 1. 〇nm from the surface), the internal copper does not diffuse to the surface due to thermal history. Therefore, in the copper foil for a printed wiring board of the present invention, it is preferable to use a depth direction (X: unit nm) obtained by analysis in the depth direction from the surface by XPS after heat treatment in which the polyimide is hardened. The atomic concentration (%) of chromium is set to f(x), the atomic concentration (%) of metallic chromium is set to fl (χ), and the atomic concentration (%) of chromium oxide is set to f2(X) (f) (X) = wide (1) + 匕 (1)) 'The atomic concentration (%) of oxygen is set to g (x), the atomic concentration (%) of copper is h (x), and the atomic concentration (%) of total nickel is used. When i(1) is set, the atomic concentration (%) of tin is set to (1), the atomic concentration (%) of carbon is set to k(X), and the sum of other atomic concentrations is set to 1 (χ), and the interval is [〇]. ' 1.0]M h(x)dx/nf(x)dx+ 丨g(x)dx+ S h(x)dx + S i(x)dx+ $ j(x)dx+ S k(x)dx+ n(x ) dx) is 1_0% or less. Further, it is more preferable to be the outermost surface of the coating layer (in the range of 0 to 1. 〇nm from the surface) after the heat treatment of the hardening of the polyacrylonitrile (heating in a nitrogen atmosphere at 3501 for several minutes to several hours) A Cr layer having excellent adhesion to an insulating substrate exists at a relatively high concentration. It is preferable that the inside of the coating layer (in the range of i. 〜 to 2.5 nm from the surface), the diffusion of copper at a high concentration is excellent in preventing the Sn alloy layer. However, if the concentration of any of the layers is too high, it will cause etchability to deteriorate. Therefore, it is preferable that the copper foil for a printed wiring board of the present invention has a range of depth direction (unit: nm) obtained by analysis in the depth direction from the surface by xps after heat treatment of the polyimine hardening [ Within 0,1.0], $ f(x)dx/( 5 f(x)dx+ S g(x)dx+ $ h(x)dx + S i(4)dx+ $j(x)dx+ S k(x)dx+ Π (1)dx) Meet 20 ～5〇16 201106816 /6 ' Within [1.0 ' 2·5], (5 i(x)dx+ $ j(x)dx)/( $ f(x)dx+ $ g(x)dx + $ h(x)dx + 5 i(x)dx + S j(x)dx + S k(x)dx + $ l〇)dx) is i〇~7〇%. Further, it is preferably: the outermost surface of the coating layer (from 0 to 1.0 nm from the surface) after heat treatment of hardening of the polyimine (in a nitrogen atmosphere, heating at 350 ° C for 30 minutes to several hours), When the atomic concentration (%) of the depth direction (χ: unit nm) of the metal chromium and chromium oxide obtained by analyzing the depth direction from the surface by XPS is f!(x), f2(x), respectively, Within the interval [0,1.0] 'full tail 0$ $ heart (1) heart / $ f2(x)dx$ 1.0, within the interval μ 〇, 2.5], 〇·1 $ $ fi(x)dx/ $ f2( x)dx$ 1.〇. (The structure of the film of the insulating substrate peeling surface) In order to improve the adhesive strength, it is preferable to analyze the coating of the insulating substrate from the coating layer after the copper foil for the printed wiring board attached to the insulating substrate via the coating layer is analyzed. When the surface of the layer is used, the inner copper does not diffuse to the outermost surface of the coating layer (from the surface 〇~丨.0 nm). Preferably, if the atomic concentration (%) of chromium obtained by analysis in the depth direction from the surface by XPS is f(x), the atomic concentration (%) of oxygen is set to g〇〇, and copper is used. The atomic concentration (%) is h(x), the atomic concentration (%) of nickel is i(x), the atomic concentration (%) of tin is j(x), and the atomic concentration of carbon is k. (x), the sum of the other atomic concentrations is set to ι(χ), and the distance from the surface layer where the concentration of the metal chromium is the largest is F, then 区间 h(x)dx in the interval [〇, I] /( 5 f(x)dx + 5 g(x)dx + sh(x)dx + si(x)dx + sj(x)dx+ $ k(x)dx+ n(x)dx) is 5.0% or less. Further, it is preferable that the copper foil for a printed wiring board which is attached to the insulating substrate via the coating layer 17 201106816, the sound of eight coatings, and the like, "the main knife peels off the insulating substrate from the coating layer to the eighth: /曰If the atomic concentration (%) of the metal chrome obtained from the surface is: fl(x), the oxide chrome is set to f2(x), and the concentration of the metal chrome is maximized. Since the surface layer is considered to be F|, then in the interval [〇, F|], 铬1qf|(x)dx/if2(4)dx 1 chromium concentration and oxygen concentration are respectively based on the listening from the surface using XPS. The distance between the Cr2p orbital field and the Ols orbital field obtained by the direction of the blade is calculated and the distance in the 'depth direction (X··unit nm) is the distance calculated from the Si矿2 conversion: the ore rate. The cohesiveness of the complex oxide concentration and the metal complexity can be separated into chromium oxide concentration and metal chromium concentration for analysis. (Method for Producing Copper Foil of the Present Invention) The copper foil for a printed wiring board of the present invention can be formed by a sputtering method. That is, by sputtering, the thickness is 〇25~5 〇nm, preferably 〇5~4.0nm, more preferably 丨.0~3.0nm2Nl—such as alloy layer and thickness 〇25 ～2.5nm Preferably, it is 〇3~2. 〇nm, more preferably 〇5~丨, such as the core layer of the claw is sequentially coated on at least a part of the surface of the copper foil substrate. If such an extremely thin film is laminated by plating, the thickness is uneven, and the peel strength is liable to be lowered after the heat resistance and moisture resistance test. The thickness herein is not the thickness determined by XPS or TEM described above, but is the thickness derived from the film formation speed of the clock. The film formation rate under a certain sputtering condition can be performed with a sputtering key of 0.1/i m (l 〇〇 nm) or more, and is measured based on the relationship between the enthalpy chain time and the thickness of the stencil. After measuring the film formation speed under the 2011-0816 piece, the sputtering time is set according to the thickness of the desired ^ + . Further, 'splashing can be carried out continuously or in batches, and the coating layer can be uniformly laminated with the thickness of the finger as in the present invention. Sputtering method j magic DC magnetron sputtering method. (Manufacturing of Printed Wiring Board) Further, a printed wiring board (PWB) can be manufactured by using the copper foil of the present invention in accordance with the method of rpwrpm and 锞. Hereinafter, a manufacturing example of a printed wiring board will be described. First, the copper box and the insulating substrate are bonded to each other to form a composite copper laminate. The insulating substrate with the copper foil laminated is not particularly limited as long as it has the characteristics of being applicable to the printed wiring board. For example, for the rigid Pw _ t β can be used, the paper substrate phenol tree ruthenium, paper substrate can be used. Epoxy resin, synthetic fiber cloth substrate epoxy resin, glass cloth-paper composite substrate epoxy resin, glass cloth, broken glass non-woven fabric composite substrate epoxy resin and glass cloth substrate epoxy resin, etc., with A ML Ridge 'A polyester film or a polyimide film can be used. Regarding the bonding method, in the case of rigid PWB, the following prepreg is prepared: the resin is impregnated into a substrate such as glass cloth, and the resin is cured to a semi-hardened state. This can be carried out by laminating the prepreg and the surface of the copper box having the coating layer by heating and pressurizing. In the case of a flexible printed wiring board (FPC), an epoxy-based or acrylic-based adhesive may be used to bond the polyimide film or the polyester film to the surface of the copper foil having the coating layer (3 layers). structure). Further, a method in which no adhesive is used (two layers, structure) T is exemplified by applying a polyaniline varnish (polyamic acid varnish) as a precursor of polyimine to a copper foil. a casting method having a surface of the coating layer and heating to iodide; or coating a thermoplastic polyimide on the polyimide film, and laminating the copper foil thereon to have a coating of 19 201106816 The layered method of 'heating and pressing'. In the casting method, the thermoplastic coater and the like are pre-coated with the cold cloth polyimide varnish. The (anchor coat) material is also effective. The effect of the copper (4) of the present invention is remarkable when the Fpc is produced by the casting method. The sb is required to adhere to the resin without using an adhesive, and the resin of the copper plate is particularly required to be poor. In the case of the copper foil of the present invention, it is excellent in the connection with the resin, in particular, the polyimide, and it is suitable for the production of a copper-clad laminate using a casting method. The copper-clad laminate of the present invention can be used for various printed wiring boards (PWB)', and is not particularly limited. For example, in terms of the number of layers of the conductor pattern, the method can be applied to a single-sided PWB or a double-sided PWR. ^ a PWB and multi-layered pwb (three or more layers) are applicable to rigid_flexible PWB (FPC) and rigid-flexible pWB from the viewpoint of the type of insulating substrate material. The step of manufacturing a printed wiring board from a copper-clad laminate can be carried out by a method known to a person skilled in the art. For example, the resistance of (4) (4) is called (10) on the copper-faced surface of the copper-clad laminate, and A necessary portion of the conductor pattern is sprayed on the surface of the steel box, whereby the excess force is removed from the excess copper foil to form a conductor pattern, and then the resist is removed and removed to expose the conductor pattern.
[實施例J 以下，表示本發明之實施例，但該等係為了更好地理 解而提供者，並非意圖限定本發明者。 (例1 :實施例No.l〜11) 準備厚度18“m之壓延銅箔(日礦金屬製cu〇〇)及電解 銅箱之無粗化處理箱作為銅箱基材。壓延鋼搭與電解銅箱 20 201106816 之表面粗糖度（Rz)分別為〇 7 # m、1 5从m。 變化 對於該銅羯之單面，於以下條件下利用逆向賤錢，預 先除去附著於銅箱基材表面之較薄之氧化膜’依序成膜沁 ―如合金層及^層。被覆層之厚度係藉由調整成膜時間而 裝置：批次式濺鍍裝置（ULVAC公司， 6000) 型號MNS — 極限真空（ultimate vacuum) : i.〇xi〇-5 pa •濺鍍壓：0.2 Pa .逆向濺錢功率：RF1 〇〇 w •乾： 所示之各種靶組成及合金[Example J] The examples of the present invention are shown below, but are provided for the purpose of better understanding, and are not intended to limit the inventors. (Example 1: Examples No. 1 to 11) A rolled copper foil (manufactured by Nippon Mining & Metal Co., Ltd.) having a thickness of 18 m and a non-roughening treatment box of an electrolytic copper box were prepared as a copper box base material. The surface roughness (Rz) of the electrolytic copper box 20 201106816 is 〇7 #m, and 15 from m. The change is for the single side of the copper enamel, and the reverse 贱 money is used to remove the adhesion to the copper box substrate under the following conditions. The thinner oxide film on the surface 'sequentially forms a film—such as an alloy layer and a layer. The thickness of the coating layer is adjusted by filming time. Device: Batch Sputtering Device (ULVAC, 6000) Model MNS — Ultimate vacuum: i.〇xi〇-5 pa • Sputtering pressure: 0.2 Pa. Reverse splashing power: RF1 〇〇w • Dry: Various target compositions and alloys as shown
Ni—Sn合金層用=下述表 組成之Ni — Sn合金 再者’由於濺鍍速度因構成 舟战兀京而異，故靶組成及被 、口金組成並不一定為彼此相同。The Ni-Sn alloy layer is made of the Ni-Sn alloy which is composed of the following table. Since the sputtering rate varies depending on the composition of the boat, the composition of the target and the composition of the gold and the gold are not necessarily the same.
Cr層用=Cr(純度為3 N)Cr layer = Cr (purity is 3 N)
•濺鍍功率：5 0 W •成膜速度：對於各靶，於輸出功率2 5w/c々 約〇·2 # m，利用三維測定 成膜 盗測定厚度，算出每單位時間之 濺鍍速率。 對於設置有被覆層之鋼續 J /白’根據以下順序接著 胺膜 聚醯亞 (1)對於7cmx7cm之銅汔 ^ ^ ^ ^ /自，使用塗佈器，塗佈乾燥體狀 心之于部興產製uvarnish〜 醯亞胺清漆）至25" m。 21 201106816 (2) 於空氣下利用乾燥機以12(rc將（1)中所得之附有 脂之銅箔乾燥3 〇分鐘。 (3) 於氮流量設定為l〇L/min之高溫加熱爐中以 。(：加熱30分鐘，進行樹脂硬化。 <附著量之測定> 將50mmx50mm之銅结表面之被覆層溶解於混合有 HNCM2重量％)與Ηα(5重量％)之溶液中，利用^光 分光分析裝置（SII NanoTechnology股份有限公司製，SFC -糊，對該溶液中之各金屬濃度進行定量，算出每單位 面積之金屬量㈧g/dm2)。對於各試料測定5次’將其平均 值作為附著量。 〃 〈利用XPS之測定> 將製作被覆層之縱深分析時之XPS之運轉條件示於以 下。 .裝置：XPS測定裝置（ULVAC ~ PHI公司’型號 5600MC) .極限真空：3.8xHT7pa X射線·單色Α1Κ α，X射線輸出功率為300 W，檢 測面積為試料與檢測器所叙角度為γ 離子束.離子種類為Ar+，加速電壓為3 ，拂掠 (_ep)面積為3_x3_，_速率為Μ·〆 必換 算） .於XPS之測定結果中’鉻氧化物與金屬絡之分離係使 用ULVAC公司製分析軟體Multi m 1來進行。 22 201106816 ’則疋係對如下被膜進行分析，即，於利用濺鍍之成膜 後，實施較測定接著強度時之聚醯亞胺硬化條件（35(rCx3〇 ^鐘）更嚴苛之條件之熱處理⑽。CX120分），在此狀態下接 著剝離絕緣基板後之被膜。 〈利用TEM之測定> 將利用TEM觀察被覆層時之TEM之測定條件示於以 下。表中所示之厚度係對於觀察視野中所拍攝之被覆層整 體之厚度，針對1個視野測定5 〇nm間之厚度之最大值、最 小值，求出任意選擇之3個視野之最大值與最小值，以百 分率求出最大值及相對於最大值之最小值之比例。又，表 中，「耐熱試驗後」之TEM觀察結果係根據上述順序，於 試驗片之被覆層上接著聚醯亞胺膜之後，將試驗片置於下 述高溫環境下，依照90。剝離法（JIS C 6471 8.1)，自所得之 試驗片剝離聚醯亞胺膜後的TEM像。圖1及2中，例示地 表示利用TEM之剛濺鍍後及相當聚醯亞胺清漆硬化之熱處 理後的各觀察照片。 •裝置：TEM(日立製作所公司，型號H9000NAR) •加速電壓：300 kV •倍率：300000倍 •觀察視野：60nmx60nm <接著性評估> 對於以上述方式積層有聚醯亞胺之銅箔，於剛積層後 (常態）、於溫度150°C之空氣環境下之高溫環境下放置ι68 小時後（耐熱性）、於溫度40°C且相對濕度95%之空氣環境 23 201106816 下之高濕環境下放置96小時後（耐濕性）3種條件下測定剝 離強度。剝離強度係依據9〇。剝離法（JIS c 647i 8 U而測 定。 <餘刻性評估> 於《玄被覆層上貼附白膠帶’使用蚀刻液（二水合氣化 銅、氣化錢、氨水、液溫50〇c )進行蝕刻處理。其後，利用 ICP發光分光分析裝置’對附著於處理後之膠帶上之蝕刻殘 邊的金屬成分進行定量，以下述基準進行評估。 X :蝕刻殘渣為140 " g/ dm2以上 △:蝕刻殘渣為70以上且小於140 // g/dm2 〇：蝕刻殘.渣小於70# g/dm2 (例2 :比較例No.a〜j) 於例1中所使用之壓延銅箔基材之單面，改變濺鍍時 間而形成表2之厚度之被膜。又，於No.b(濕式鍍敷/鉻酸鹽） 中’於以下條件下依序實施電鍍Ni及鉻酸處理。 ⑴鍍Ni •鍍浴：胺磺酸鎳（以Ni2 +計為li〇g/L)、H3BO3(40g/ L)• Sputtering power: 50 W • Film formation rate: For each target, the output power was 2 5 w/c 々 about 〇·2 # m, and the thickness was measured by three-dimensional measurement. The sputtering rate per unit time was calculated. For the steel provided with the coating layer, continue to J/white' according to the following sequence: followed by the amine film poly(Asian) (1) for 7cmx7cm of copper 汔^^^^ /, using an applicator, coating the dry body of the heart Hing production uvarnish ~ 醯 imine varnish) to 25 " m. 21 201106816 (2) Dry the grease-attached copper foil obtained in (1) with air for 12 minutes using a dryer (3). (3) High-temperature heating furnace with a nitrogen flow rate of l〇L/min. (:: heating for 30 minutes, resin hardening. <Measurement of adhesion amount> A coating layer of a 50 mm x 50 mm copper junction surface was dissolved in a mixture of HNCM 2% by weight) and Ηα (5% by weight) was used. ^ Optical spectroscopic analyzer (SFC-paste, manufactured by SII NanoTechnology Co., Ltd., quantifies the concentration of each metal in the solution, and calculates the amount of metal per unit area (eight) g/dm2). The sample is measured five times for each sample. The value is the amount of adhesion. 〈 <Measurement by XPS> The operating conditions of XPS in the depth analysis of the coating layer are shown below. Device: XPS measuring device (ULVAC ~ PHI's model 5600MC). Ultimate vacuum: 3.8 xHT7pa X-ray · Monochrome Α 1 Κ α, X-ray output power is 300 W, the detection area is γ ion beam for the sample and detector. The ion type is Ar+, the acceleration voltage is 3, and the 拂 ( (_ep) area is 3_x3_ , _ rate is Μ·〆 must be changed ). The results of the XPS measurement in the "separation factor of a chromium oxide and a metal complex to make an analysis software manufactured by ULVAC Multi m. 22 201106816 'The 疋 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对 对Heat treatment (10). CX 120 minutes), in this state, the film after peeling off the insulating substrate. <Measurement by TEM> The measurement conditions of the TEM when the coating layer was observed by TEM are shown below. The thickness shown in the table is the maximum and minimum values of the thickness between 5 〇 nm for one field of view for the thickness of the entire coating layer captured in the observation field, and the maximum value of the arbitrarily selected three fields of view is obtained. The minimum value is the ratio of the maximum value to the minimum value of the maximum value in percentage. Further, in the table, the results of the TEM observation after the "heat-resistant test" were carried out in the above-described order, and then the polyimide film was placed on the coating layer of the test piece, and then the test piece was placed in a high-temperature environment as described above, in accordance with 90. The peeling method (JIS C 6471 8.1), the TEM image after peeling the polyimide film from the obtained test piece. In Figs. 1 and 2, each observation photograph after heat treatment by TEM immediately after sputtering and hardening of a considerable polyimide varnish is shown. • Device: TEM (Hitachi, Ltd., model H9000NAR) • Accelerating voltage: 300 kV • Magnification: 300,000 times • Observation field of view: 60 nm x 60 nm <Adhesion evaluation > For the copper foil laminated with polyimine in the above manner, Immediately after laminating (normal), placed in a high temperature environment at a temperature of 150 ° C in a high-temperature environment, after eta for 68 hours (heat resistance), at a temperature of 40 ° C and a relative humidity of 95% in an air environment 23 201106816 under high humidity environment The peel strength was measured under three conditions of leaving after 96 hours (moisture resistance). Peel strength is based on 9〇. Peeling method (measured in JIS c 647i 8 U. <Residuality evaluation> Using an etching solution on the "white tape attached to the mysterious coating layer" (dihydrate vaporized copper, vaporized money, ammonia water, liquid temperature 50 〇) c) etching treatment. Thereafter, the metal component of the etching residual adhered to the treated tape was quantified by an ICP emission spectroscopic analyzer, and evaluated according to the following criteria: X: etching residue was 140 " g/ Dm2 or more Δ: The etching residue is 70 or more and less than 140 // g/dm2 〇: etching residual. The slag is less than 70# g/dm2 (Example 2: Comparative Examples No. a to j) The rolled copper used in Example 1 On one side of the foil substrate, the sputtering time was changed to form the film of the thickness of Table 2. Further, in No. b (wet plating/chromate), electroplating of Ni and chromic acid was sequentially performed under the following conditions. (1) Ni plating • Plating bath: nickel sulfonate (li〇g/L in terms of Ni2+), H3BO3 (40g/L)
.電流密度：1 .〇A/ dm2 •浴溫：5 5 °C •Ni 量：220#g/dm2(厚度約 l.lnm) (2)鉻酸處理 •鍍浴：Cr03(lg/L)、Zn(粉末 〇.4g)、Na2S〇4(l〇g/L) .電流密度：2.0A/ dm2 24 201106816Current density: 1 .〇A/ dm2 • Bath temperature: 5 5 °C • Ni amount: 220#g/dm2 (thickness about l.lnm) (2) Chromic acid treatment • Plating bath: Cr03 (lg/L) , Zn (powder 〇.4g), Na2S〇4 (l〇g/L). Current density: 2.0A/ dm2 24 201106816
•浴溫：5 5 °C •Cr 量：21〆 g/dm2(厚度約 〇 5nm) 接著’對於設置有被覆層之銅箔，根據與例1相同之 順序，接著聚醯亞胺膜。 將上述實施例No.l〜11及比較例n〇.a〜j之測定條件 及測定結果示於表1〜4。表中，SP/SP表示Ni~ Sn合金、 Cr均利用濺鍍而被覆。 [表1] 製膜法 厚度(nm) 附著量（Mg/dm ) TE^ 1¾¾--—| Ni — Sn合金層 剛濺鍍後 耐熱就私ίϊ No Ni - Sn 合 金/Cr Ni-Sn 合金 Cr Ni Sn Ni + Sn Sn組成 (wt%) Cr層 被覆層最 大厚度 (nm) 最小值/ 最大值 (%) 被 大厚度 最大值 1 SP/SP 0.25 0.25 18 4 22 18 18 0.5 85 2 SP/SP 0.25 0.5 19 3 22 14 35 0.8 88 3 SP/SP 0.5 o,s 4T 2 43 5 36 1.0 85 ............1.6 4 SP/SP 1.0 1.0 74 14 88 16 70 2.0 88 .2.2 8〇 5 SP/SP 5.0 1.0 422 19 441 4 72 6.0 87 83 82^* 6 SP/SP 1.0 2.0 34 44 78 56 144 3.0 88 ............3.Ϊ 7 SP/SP 5.0 2.0 222 182 404 45 143 7.0 86 ....7：2 .......... 8 SP/SP 5.0 0.25 364 66 430 15 18 5.3 88 ...........5：5 ............ 9 SP/SP 0.25 2.5 21 1 22 5 180 2.8 86 8〇 ·.··· ϊδ SP/SP 4.0 1.2 328 22 350 6 87 4.2 89 η SP/SP 1.0 1.0 74 14 88 16 72 2.0 88 25 201106816 -<〕 壓延銅箔 壓延銅箔 i壓延銅箔 壓延銅箔I 壓延銅箔 1壓延銅箔ι 壓延銅箔 壓延銅箔 壓延銅箔1 壓延銅箔 電解銅箔 Lji 一 Sn 靶 1使用效率 (%) ο ο Ο 蝕刻殘渣 ("g/dm2) <20(0) 36(〇) 1 40(0) 1 58(0) 62(〇) I 89(Δ) 1 1〇〇(Δ) <20(0) 139(Δ) 1 68(0) 1 55(0) 剝離強度 I (kN/m) 00 rn o ON wn ΓΛ Μ οο wn 0'S 5 OS (N oo ΓΛ fO Tf μ ¥ 〇 vq 00 § § NO 卜 ㈣ f I i 表面深度 x=(0~Fi)nm (Si02換算） δ (N — 寸 〇 <N (S Γ*Ί Ο <N 00 ΓΛ 寸 o CN fi(x)dx/ f2(x)dx ro 〇 (N d 〇 ΓΛ o CS Ο ΓΛ Ο ο 寸 Ο Γ〇 ο (N 〇 寸 d XPS表面分析(相當聚醖亞胺硬化之熱處理後） 表面深度 χ= 1·0 〜2.5nm (Si02換算） f!(x)dx/ f2(x)dx d CO d 寸 o ΓΛ d ο ΓΛ Ο 寸 ο V-) d CN Ο d d Ni + Sn (%) <N <N F—H 9 m m <Ν ν〇 (Ν in 00 CN E ^ 匈〇林 〇 ^ II 2, 6 〇〇 o r- o o m ο ο 寸· m o ΓΛ ο o o _g 13 〇 (N 〇 f-H o (Ν Ο ίΝ Ο CO o m ο (N 〇 o (N (N ΡΛ 芝 Ο m (N m ΓΛ XPS表面分析(剛濺鍍後） 1 表面深度 x= 1.0 〜2.5nm (Si02換算） f!(x)dx/ f2(x)dx r- d 〇\ d q C\ 〇 r- d 〇 ρ v〇 d Ον Ο 00 d 卜 d Ni + Sn(%) <N yn ο V〇 ΓΟ σ； v〇 fO E ^ ttSi 〇 Η *i>〇 < II ^ 00 d o (N O o ΓΛ Ο (Ν Ο ο 寸 o m ο CN 〇 ^-H d f,(x)dx/ f2(x)dx ΓΛ d CN 〇 d »r> 〇 (Ν Ο 寸 Ο Γ〇 Ο o 寸 ο (N d CN d Cr(%) 〇\ (N r^> Ο σ\ ν〇 Γ〇 Jn α； 〇 2 (N ΓΛ 寸 \〇 卜 00 Ον o 201106816• Bath temperature: 5 5 ° C • Cr amount: 21 〆 g/dm 2 (thickness: about 5 nm) Next, for the copper foil provided with the coating layer, the polyimide film was bonded in the same order as in Example 1. The measurement conditions and measurement results of the above Examples Nos. 1 to 11 and Comparative Examples n〇.a to j are shown in Tables 1 to 4. In the table, SP/SP indicates that the Ni-Sn alloy and Cr are all coated by sputtering. [Table 1] Film thickness (nm) Adhesion (Mg/dm) TE^ 13⁄43⁄4--—| Ni — Sn alloy layer is heat-resistant after sputtering. No Ni - Sn alloy / Cr Ni-Sn alloy Cr Ni Sn Ni + Sn Sn composition (wt%) Cr layer coating maximum thickness (nm) minimum / maximum (%) is the maximum thickness of 1 SP / SP 0.25 0.25 18 4 22 18 18 0.5 85 2 SP / SP 0.25 0.5 19 3 22 14 35 0.8 88 3 SP/SP 0.5 o,s 4T 2 43 5 36 1.0 85 ............1.6 4 SP/SP 1.0 1.0 74 14 88 16 70 2.0 88 .2.2 8〇5 SP/SP 5.0 1.0 422 19 441 4 72 6.0 87 83 82^* 6 SP/SP 1.0 2.0 34 44 78 56 144 3.0 88 ............3.Ϊ 7 SP/SP 5.0 2.0 222 182 404 45 143 7.0 86 ....7:2 .......... 8 SP/SP 5.0 0.25 364 66 430 15 18 5.3 88 ........ ...5:5 ............ 9 SP/SP 0.25 2.5 21 1 22 5 180 2.8 86 8〇····· ϊδ SP/SP 4.0 1.2 328 22 350 6 87 4.2 89 η SP/SP 1.0 1.0 74 14 88 16 72 2.0 88 25 201106816 -<] Calendered copper foil rolled copper foil i rolled copper foil rolled copper foil I rolled copper foil 1 rolled copper foil ι rolled copper foil rolled copper foil rolled copper Foil 1 rolled copper foil Copper foil Lji-Sn target 1 use efficiency (%) ο ο 蚀刻 Etch residue ("g/dm2) <20(0) 36(〇) 1 40(0) 1 58(0) 62(〇) I 89 (Δ) 1 1〇〇(Δ) <20(0) 139(Δ) 1 68(0) 1 55(0) Peel strength I (kN/m) 00 rn o ON wn ΓΛ Μ οο wn 0'S 5 OS (N oo ΓΛ fO Tf μ ¥ 〇vq 00 § § NO Bu (4) f I i Surface depth x=(0~Fi)nm (Si02 conversion) δ (N - inch 〇 <N (S Γ*Ί Ο < N 00 ΓΛ 寸 o CN fi(x)dx/ f2(x)dx ro 〇(N d 〇ΓΛ o CS Ο ΓΛ Ο ο Ο Ο (ο (N 〇 inch d XPS surface analysis (equivalent polyimine hardening) After heat treatment) Surface depth χ = 1·0 ～2.5nm (Si02 conversion) f!(x)dx/ f2(x)dx d CO d inch o ΓΛ d ο ΓΛ Ο inch ο V-) d CN Ο dd Ni + Sn (%) <N <NF-H 9 mm <Ν ν〇(Ν in 00 CN E ^ 〇林〇^ II 2, 6 〇〇o r- oom ο ο 寸 · mo ΓΛ ο oo _g 13 〇(N 〇fH o (Ν Ο Ν Ν Ο CO om ο (N 〇o (N (N N Ο Ο m (N m ΓΛ XPS surface analysis (just after sputtering) 1 Surface depth x = 1.0 ~ 2.5nm (Si02 conversion) f!(x)dx/ f2(x)dx r- d 〇\ dq C\ 〇r- d 〇ρ v〇d Ον Ο 00 d 卜d Ni + Sn(%) <N yn ο V〇ΓΟ σ ; v〇fO E ^ ttSi 〇Η *i>〇< II ^ 00 do (NO o ΓΛ Ο (Ν Ο ο om om ο CN 〇^-H df, (x) dx/ f2(x)dx ΓΛ d CN 〇d »r> 〇(Ν Ο Ο Ο o οο (N d CN d Cr(%) 〇\ (N r^> Ο σ\ ν〇Γ〇Jn α; 〇 2 (N ΓΛ寸\〇卜00 Ον o 201106816
【ε i TEM觀察 耐熱試驗後 最小值/最大值 {%) g o 00 § (N 00 被覆層最大厚度 (run) ! CN os o (N 00 p-H o — 寸 iri (N 寸 CN 剛濺鍍後 最小值/最大值 (%) ss ON 00 00 00 00 VO 00 ON 00 ss 00 00 被覆層最大厚度ί ㈣ o (N o o od 寸 o 00 ΓΛ 〇 W-I q o <N <N rO 1 Cr層 jn 1 1 215 360 (N 卜 144 Ni — Sn合金層 Sn組成 (wt%) j 1 Ό 卜 jrj 1 1 JO Ni + Sn j (>(ϊ Ni)89 | (僅 Ni)220 OS 00 690 00 (N 00 1 1 486 卜 1 1 s ΓΛ 1 1 |219 g Os 00 220 P 585 寸 1 1 1267 v〇 厚度(nm) i p I t 1 CN d o CO 〇 q p o CN Ni —Sn合金 (僅 Ni)1.0 1 P 1-H 〇 00 (N d o 1 1 o v〇 CN d 製膜法 Ni —Sn 合金/Cr SP/SP 濕式/絡酸鹽 SP/- SP/- SP/SP SP/SP CL, CO 1 -/SP SP/SP SP/SP o ：2i x> o <D CUO Λ • l-H LZ .nb 201106816 〔寸<〕 銅落 壓延銅箔 電解銅箔 壓延銅箔 壓延銅箔 壓延銅箔 壓延銅箔 壓延銅箔 壓延銅箔 壓延銅箔 壓延銅箔 C ^ CO 〇π 1 2說 1 (僅 Ni)5 1 1 ο t t ο 钱刻殘;'查 ("g/dm2) 1 40(〇) 1 1 <20(0) I \ 36(0) I 1 329(x) I 1 <20(0) 1 Ι80(χ) 276(χ) I 55(0) I 145(χ) 120(Δ) 剝離強度 (kN/m) 耐濕 vq 0.66 0.54 0.89 1 ψ-^ m o CS «ο 0.98 耐熱 (N vq (N Ό 〇 0.30 0.42 0.77 $ *"Η U-| 0.94 ΓΛ 00 00 ο 卜· w-> Ό 〇 CO Ό 〇 o 0.97 ν〇 w^i CM ir> σ\ ο f ^ <2 GO ^ 表面深度 x = (0〜F^nm (Si02換算） a妥 (N 〇 1 <N 00 vrl On ίΝ* Ο iN d 00 寸 Ο (Ν f,(x)dx/ f2( x)dx <N 〇 1 « 1 ψ^* d Ό ο O yn d ο 卜 Ο XPS表面分析(相當聚醯亞胺硬化之熱處理 後） 表面深度 x= 1.0 〜2.5nm (Si02換算） f,(x)dx/ f2( x)dx 〇 〇 1 1 卜 d ΓΟ ο o o m ο ir> Ο cS ^ n,*v/ VO in 口 On 卜 1 1 00 w ^^ u茗 d tJ- d fO d 00 v〇 ο rf d (N 〇 o od ο m in 表面深度 x = 0 〜l.Oiu (Si02換算: f,(x)dx/ f2 (x)dx d o 1 1 ο 呀 ο (N 〇 o Ο m d ΰ妥 Os (N <N 1 1 (Ν (SJ vn Os in 沄 00 r〇 ο XPS表面分析(剛濺鍍後） 表面深度 x= 1.0~2.5nm (Si02換算） f,(x)dx/ f2 (x)dx d o • 1 Ο 寸 ο d σ\ d ο ο Ni 十 Sn (%) 〇\ § P； <N 00 Cs μ « 1 JN 卜 表面深度 x = 0~1.0nm (Si02換算） ag 寸 o o ΓΛ d 寸 d Ο (Ν Ο 寸 d m d Ο q f,(x)dx/ f2(x )dx m d o 1 1 wn Ο <Ν Ο (N 〇 寸 d ο ΙΟ d 寸 o 1 t 00 Ό VO ο Z 〇 CQ 〇 T) V cm • «η ··—» 201106816 - (實施例之評估） 如表1及2所示，實施例Ν〇 ·丨〜丨丨均具有良好之剝離 強度及蝕刻性。將實施例No.4之銅箔之剛濺鍍後及相當聚 醯亞胺清漆硬化之熱處理後之利用xps所得的各縱深分析 示於圖3及4，以供參考用。進而，對於實施例N〇 4之銅 箔，將剛濺鍍後及相當聚醯亞胺清漆硬化之熱處理後之鉻 分離為金屬鉻與氧化鉻時的利用xps所得之各縱深分析示 於圖5及6。 又，實施例No.l〜11之任一 Ni_Sn靶之使用效率均 為30〜40%而良好。 (比較例之評估） 比較例No.a之靶之使用效率較實施例低。其原因在 於，因比較例No.a形成Ni層代替Ni_Sn合金層，故磁性 較強’對靶之使用效率出現不良影響。 比較例No.b係藉由濕式電鍍處理及鉻酸處理而形成沁 層及Cr層，但剝離強度不良。 比較例No.C係未形成Cr層者，剝離強度不良。 比較例No.d係未形成Cr層者，剝離強度不良。又’ Ni—Sn合金層中之Ni及Sn之合計超過45(^g/dm2，而 蝕刻性不良。 比較例No_e係Cr層之Cr小於丨8 # g/ dm2，而剥離強 度不良。 比較例No.f係Cr層之Cr超過18〇^g/dm2,而蝕刻 性不良。 29 201106816 比較例Ν ο. g及h係未形成N i — S η合金層者，敍刻性 或剝離強度不良。 比較例No.i係Ni — Sη合金層中之Ni及Sη之合計超過 45 0 " g/ dm2，而钱刻性不良。 比較例No.j係Ni — Sn合金層小於1 8 # g/ dm2，剝離 強度不良。 【圖式簡單說明】 圖1係實施例No.4之銅箔（剛濺鍍後）之TEM照片（剖 面）。 圖2係實施例No.4之銅箔（相當聚醯亞胺清漆硬化之熱 處理後）之TEM照片（剖面）。 圖3係實施例No.4之銅箔（剛濺鍍後）之利用XPS所得 之縱深分析》 圖4係實施例No.4之銅箔（相當聚醯亞胺清漆硬化之熱 處理後）之利用XPS所得之縱深分析。 圖5係將實施例Νο·4之銅箔（剛濺鍍後）之鉻分離為金 屬鉻與氧化絡時之利用X P S所得的縱深分析。 圖6係將實施例N0.4之鋼箔（相當聚醯亞胺清漆硬化之 熱處理後）之鉻分離為金屬鉻與氧化鉻時之利用xps所得的 縱深分析。 【主要元件符號說明】 1、2 TEM觀察時之被覆層之厚度 30[ε i TEM observation of the minimum/maximum value of the heat resistance test {%) go 00 § (N 00 maximum thickness of the coating (run)! CN os o (N 00 pH o - inch iri (N inch CN is the smallest after sputtering) Value/maximum value (%) ss ON 00 00 00 00 VO 00 ON 00 ss 00 00 Maximum thickness of the coating layer ί (4) o (N oo od inch o 00 ΓΛ 〇 WI qo < N < N rO 1 Cr layer jn 1 1 215 360 (N 144 Ni - Sn alloy layer Sn composition (wt%) j 1 Ό 卜 jrj 1 1 JO Ni + Sn j (>(ϊ Ni)89 | (Ni only) 220 OS 00 690 00 (N 00 1 1 486 1 1 s ΓΛ 1 1 |219 g Os 00 220 P 585 inch 1 1 1267 v〇 thickness (nm) ip I t 1 CN do CO 〇qpo CN Ni —Sn alloy (Ni only) 1.0 1 P 1-H 〇00 (N do 1 1 ov〇CN d film forming method Ni-Sn alloy/Cr SP/SP wet/all acid salt SP/- SP/- SP/SP SP/SP CL, CO 1 -/ SP SP/SP SP/SP o :2i x> o <D CUO Λ • lH LZ .nb 201106816 [inch <] copper drop rolled copper foil electrolytic copper foil rolled copper foil rolled copper foil rolled copper foil rolled copper foil rolling Copper foil rolled copper foil rolled copper foil rolled copper foil C ^ CO 〇π 1 2 says 1 (Ni only ) 5 1 1 ο tt ο Money is cruel; 'Check ("g/dm2) 1 40(〇) 1 1 <20(0) I \ 36(0) I 1 329(x) I 1 <20 (0) 1 Ι80(χ) 276(χ) I 55(0) I 145(χ) 120(Δ) Peel strength (kN/m) Moisture resistance vq 0.66 0.54 0.89 1 ψ-^ mo CS «ο 0.98 Heat resistance ( N vq (N Ό 〇0.30 0.42 0.77 $ *"Η U-| 0.94 ΓΛ 00 00 ο 卜 · w-> Ό 〇CO Ό 0.9o 0.97 ν〇w^i CM ir> σ\ ο f ^ < 2 GO ^ Surface depth x = (0~F^nm (Si02 conversion) a (N 〇1 <N 00 vrl On Ν* Ο iN d 00 inch Ο (Ν f,(x)dx/ f2( x) Dx <N 〇1 « 1 ψ^* d Ό ο O yn d ο Ο XPS surface analysis (after heat treatment of polyimine hardening) Surface depth x = 1.0 ~ 2.5nm (Si02 conversion) f, (x )dx/ f2( x)dx 〇〇1 1 卜d ΓΟ ο oom ο ir> Ο cS ^ n,*v/ VO in mouth On 1 1 00 w ^^ u茗d tJ- d fO d 00 v〇 ο rf d (N 〇o od ο m in surface depth x = 0 ~ l.Oiu (Si02 conversion: f, (x)dx/ f2 (x)dx do 1 1 ο 呀 ο (N 〇o Ο md ΰ Os (N <N 1 1 (Ν(SJ vn Os in 沄00 r〇ο XPS surface analysis (just after sputtering) table Surface depth x = 1.0~2.5nm (Si02 conversion) f, (x)dx/ f2 (x)dx do • 1 Ο inch ο d σ\ d ο ο Ni Ten Sn (%) 〇\ § P; <N 00 Cs μ « 1 JN Surface depth x = 0~1.0nm (Si02 conversion) ag inch oo ΓΛ d inch d Ο (Ν Ο inch dmd Ο qf, (x)dx/ f2(x )dx mdo 1 1 wn Ο <Ν Ο (N dd ο ΙΟ d inch o 1 t 00 Ό VO ο Z 〇CQ 〇T) V cm • «η ··—» 201106816 - (Evaluation of Examples) As shown in Tables 1 and 2 The examples Ν〇·丨~丨丨 all have good peel strength and etchability. Each of the depth analyses obtained by xps after the thermal spraying of the copper foil of Example No. 4 and after the heat treatment of the comparative polyimide varnish was shown in Figs. 3 and 4 for reference. Further, with respect to the copper foil of Example N〇4, the depth analysis obtained by using xps when the chromium after the heat treatment after the sputtering and the heat treatment of the polyimine varnish were separated into metal chromium and chromium oxide is shown in FIG. 5. And 6. Further, in any of Examples Nos. 1 to 11, the use efficiency of the Ni_Sn target was 30 to 40%, which was good. (Evaluation of Comparative Example) The use efficiency of the target of Comparative Example No. a was lower than that of the examples. The reason for this is that the comparative layer No. a forms a Ni layer instead of the Ni_Sn alloy layer, so that the magnetic property is strong, which adversely affects the use efficiency of the target. In Comparative Example No. b, a tantalum layer and a Cr layer were formed by wet plating treatment and chromic acid treatment, but the peel strength was poor. In Comparative Example No. C, the Cr layer was not formed, and the peel strength was poor. In Comparative Example No. d, the Cr layer was not formed, and the peel strength was poor. Further, the total of Ni and Sn in the Ni-Sn alloy layer exceeds 45 (^g/dm2), and the etching property is poor. The Cr of the Cr layer of the comparative example No_e is smaller than 丨8 #g/dm2, and the peel strength is poor. The Cr of the No.f-based Cr layer exceeds 18 〇^g/dm2, and the etching property is poor. 29 201106816 Comparative Example ο. g and h are those in which the N i — S η alloy layer is not formed, and the scratch or peel strength is poor. In the comparative example No. i, the total of Ni and Sη in the Ni—Sη alloy layer exceeds 45 0 " g/ dm 2 , and the hardness is poor. Comparative Example No. j is a Ni—Sn alloy layer of less than 18 # g / dm2, the peel strength is poor. [Simplified illustration of the drawings] Fig. 1 is a TEM photograph (cross section) of the copper foil of Example No. 4 (after sputtering). Fig. 2 is a copper foil of Example No. 4 (equivalent TEM photograph (cross section) of the heat treatment after curing of the polyimide varnish. Fig. 3 is a depth analysis by XPS of the copper foil of Example No. 4 (after sputtering). Fig. 4 is an example No. 4. The depth analysis by XPS of copper foil (after heat treatment of hardening of polyimine varnish). Figure 5 is the separation of chromium from the copper foil of the example 刚ο·4 (after sputtering) The depth analysis obtained by XPS when the metal chromium and the oxidized complex are used. Fig. 6 is the use of the chromium of the steel foil of Example N0.4 (after heat treatment of the hardened polyimide varnish) to be separated into metal chromium and chromium oxide. Depth analysis obtained by xps. [Explanation of main component symbols] 1. 2 Thickness of coating layer during TEM observation 30
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| TW200642553A (en) * | 2005-05-27 | 2006-12-01 | Kingtron Electronics Co Ltd | Embedded chip on film (COF) |
| JP4429979B2 (en) | 2005-06-29 | 2010-03-10 | 古河電気工業株式会社 | Ultra-thin copper foil with carrier and method for producing ultra-thin copper foil with carrier |
| JP5024930B2 (en) * | 2006-10-31 | 2012-09-12 | 三井金属鉱業株式会社 | Surface-treated copper foil, surface-treated copper foil with ultra-thin primer resin layer, method for producing the surface-treated copper foil, and method for producing surface-treated copper foil with an ultra-thin primer resin layer |
| JP2008279663A (en) * | 2007-05-10 | 2008-11-20 | Nikko Kinzoku Kk | Copper foil with al coating for copper clad laminate and copper clad laminate |
| JP5069051B2 (en) | 2007-07-13 | 2012-11-07 | Ｊｘ日鉱日石金属株式会社 | Nickel alloy sputtering target |
| CN101904228B (en) * | 2007-12-21 | 2014-01-01 | Jx日矿日石金属株式会社 | Copper foil for printed wiring board |
| JP2010109275A (en) * | 2008-10-31 | 2010-05-13 | Nippon Mining & Metals Co Ltd | Coiled copper foil for printed circuit board |
| JP2010258399A (en) * | 2009-03-31 | 2010-11-11 | Jx Nippon Mining & Metals Corp | Copper foil for printed wiring boards |
| JP5373453B2 (en) * | 2009-03-31 | 2013-12-18 | Ｊｘ日鉱日石金属株式会社 | Copper foil for printed wiring boards |
| JP2010239095A (en) * | 2009-03-31 | 2010-10-21 | Nippon Mining & Metals Co Ltd | Copper foil for printed wiring boards |
| JP2010258398A (en) * | 2009-03-31 | 2010-11-11 | Jx Nippon Mining & Metals Corp | Copper foil for printed wiring boards |
| JP2010238926A (en) * | 2009-03-31 | 2010-10-21 | Nippon Mining & Metals Co Ltd | Copper foil for printed wiring board and method for producing the same |
-
2009
- 2009-11-25 CN CN200980135019.4A patent/CN102150479B/en not_active Expired - Fee Related
- 2009-11-25 WO PCT/JP2009/069879 patent/WO2011001551A1/en not_active Ceased
- 2009-11-25 KR KR1020107017993A patent/KR101086656B1/en not_active Expired - Fee Related
- 2009-11-25 JP JP2010526088A patent/JP4659140B2/en not_active Expired - Fee Related
-
2010
- 2010-06-29 TW TW099121187A patent/TWI414215B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| WO2011001551A1 (en) | 2011-01-06 |
| CN102150479B (en) | 2013-03-27 |
| TWI414215B (en) | 2013-11-01 |
| JP4659140B2 (en) | 2011-03-30 |
| KR20110021707A (en) | 2011-03-04 |
| CN102150479A (en) | 2011-08-10 |
| KR101086656B1 (en) | 2011-11-24 |
| JPWO2011001551A1 (en) | 2012-12-10 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |