TWI420991B - A copper-clad laminate, a surface-treated copper foil for manufacturing the copper-clad laminate, and a printed circuit board manufactured using the copper-clad laminate - Google Patents
A copper-clad laminate, a surface-treated copper foil for manufacturing the copper-clad laminate, and a printed circuit board manufactured using the copper-clad laminate Download PDFInfo
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- TWI420991B TWI420991B TW098116835A TW98116835A TWI420991B TW I420991 B TWI420991 B TW I420991B TW 098116835 A TW098116835 A TW 098116835A TW 98116835 A TW98116835 A TW 98116835A TW I420991 B TWI420991 B TW I420991B
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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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
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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
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
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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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
- ing And Chemical Polishing (AREA)
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Description
本發明係關於覆銅層積板、使用於製造該覆銅層積板之表面處理銅箔以及使用該覆銅層積板製造的印刷電路板。特別是關於使用於製造印刷電路板的覆銅層積板，且此印刷電路板包括在含硫酸與過氧化氫之蝕刻液中調製電路線路製程。The present invention relates to a copper clad laminate, a surface treated copper foil used for producing the copper clad laminate, and a printed circuit board produced using the copper clad laminate. In particular, it relates to a copper clad laminate for use in the manufacture of printed circuit boards, and the printed circuit board includes a modulation circuit circuit process in an etching solution containing sulfuric acid and hydrogen peroxide.
近年來，不只產業用電子及電子機器，甚至民生用電子及電子機器等，附加資料處理功能之情形越來越多，前述產品中當然有中央處理器(CPU)、大規模積體電路(LSI)等積體電路(IC)元件的搭載。作為具前述資料處理功能機器的代表，行動電話、行動音樂播放器等追求小型且高功能。此結果組裝於搭載大規模積體電路等封裝基板之前述機器的印刷電路板，對輕薄短小化的要求變強。因此，關於印刷電路板的製造，提出有採用各種各樣加工工法的方案，而開發出適用各種工法的覆銅層積板，特別是作為朝輕薄短小化對應的印刷電路板，電路板彎曲性致容易收納至有限且狹窄框體內的可彎折印刷電路板(Flexible Printed Circuit；以下簡稱「FPC」)被大多數的機器採用。In recent years, there have been more and more data processing functions, not only industrial electronic and electronic equipment, but also electronic and electronic equipment for people's livelihood. Of course, there are central processing units (CPUs) and large-scale integrated circuits (LSIs). ) The mounting of integrated circuit (IC) components. As a representative of the above-mentioned data processing function machine, mobile phones, mobile music players and the like pursue small size and high functionality. As a result, the printed circuit board of the above-described device equipped with a package substrate such as a large-scale integrated circuit is assembled, and the demand for lightness and thickness is increased. Therefore, regarding the manufacture of printed circuit boards, various methods of processing methods have been proposed, and copper clad laminates suitable for various methods have been developed, particularly as printed circuit boards corresponding to thinness and thinness, and circuit board bendability. A Flexible Printed Circuit (FPC) that is easily stored in a limited and narrow frame is used by most machines.
然而，以進一步輕薄短小化為目的時，因印刷電路板被小型化、多層化以及印刷電路間距狹小化，無電解電鍍(無電解銅電鍍、無電解金電鍍等)會析出在電路線路間，而發生人稱所謂之「銅遺漏」或「金遺漏」的「電鍍遺漏現象」。而且，印刷電路板電路線路間距變得越狹窄，越易發生此種電鍍遺漏現象，甚至移除電路線路間金屬成分的修理作業變困難。特別是在帶式包裝電路(Tape Carrier Package，TCP)等印刷電路板製造中，雖然可以在可彎折印刷電路板(FPC)中使用不設置接著劑層的2層可彎折覆銅印刷電路板(Flexible Copper Clad Laminate；以下簡稱「FCCL」)，但因使用薄絕緣層，致使修理作業大體上是不可能。在前述中，不能進行修補作業的產品，因成為當作不良品廢棄對象的機率很高，進而構成資源的浪費，而為不佳。作為防止此「電路遺漏現象」發生的對策，在電路線路形成後的電路間使不殘留金屬成分或離子性無機成分，過去被認為有效。However, in order to further reduce the size and thickness of the printed circuit board, electroless plating (electroless copper plating, electroless gold plating, etc.) is deposited between the circuit lines due to miniaturization, multilayering, and narrowing of the printed circuit pitch. The "electroplating omission phenomenon" that the so-called "copper omission" or "golden omission" is called. Moreover, the narrower the line pitch of the printed circuit board becomes, the more likely such a plating omission occurs, and even the repair work for removing the metal component between the circuit lines becomes difficult. In particular, in the manufacture of printed circuit boards such as Tape Carrier Package (TCP), it is possible to use a two-layer bendable copper-clad printed circuit in which a laminate layer is not provided in a bendable printed circuit board (FPC). Flexible Copper Clad Laminate (hereinafter referred to as "FCCL"), but due to the use of a thin insulating layer, repair work is generally impossible. In the above-mentioned products, the product that cannot be repaired has a high probability of being discarded as a defective product, and further constitutes a waste of resources, which is not preferable. In order to prevent this "circuit leakage phenomenon" from occurring, it is considered to be effective in that no metal component or ionic inorganic component remains between the circuits after the formation of the circuit line.
還有，也可以使用前述2層FCCL，製造具有多個電路線路層的多層FPC。在此多層FPC製造程序中，在使用聚亞醯胺等絕緣樹脂基材的FCCL上形成電路線路，經由結合薄板組合成多層化，再形成介層窗等層間導通方式，以使多個電路線路層間電連接。然而，構成FPC絕緣樹脂層的聚亞醯胺樹脂、芳香族聚醯胺樹脂等，一般而言耐熱性佳，但因缺乏耐藥品性特別是對鹼性藥品之耐藥品性，而致印刷電路板加工製程受到限制。為此，在用以多層化層積的前處理或介層窗形成前的軟蝕刻中，大多使用包含硫酸或過氧化氫且不含氯等強酸離子的水溶液。Further, it is also possible to manufacture a multilayer FPC having a plurality of circuit wiring layers by using the above two-layer FCCL. In the multilayer FPC manufacturing process, a circuit line is formed on the FCCL using an insulating resin substrate such as polyamidene, and the multilayer wiring is combined by a bonding thin plate, and an interlayer conduction manner such as a via window is formed to make a plurality of circuit lines. Inter-layer electrical connection. However, a polyimide resin, an aromatic polyamide resin or the like constituting the FPC insulating resin layer is generally excellent in heat resistance, but is printed circuit because of lack of chemical resistance, particularly chemical resistance to alkaline chemicals. The board processing process is limited. For this reason, an aqueous solution containing sulfuric acid or hydrogen peroxide and containing no strong acid ions such as chlorine is often used in the soft etching before the formation of the multilayer lamination or the formation of the via.
為此，用以解決上述FPC問題的方式是從作為構成材料之銅箔、絕緣樹脂層構成材料的雙方向上，必須提出有用以解決前述問題的進路。從銅箔領域來看，欲使金屬成分等不殘留，需對蝕刻特性的改善、絕緣樹脂層貼合面的低稜線化、粗化處理粒子的微細化、防銹成分等進行研究。Therefore, in order to solve the above-mentioned FPC problem, it is necessary to propose an approach to solve the above problems from both the copper foil and the insulating resin layer constituting material. In the field of the copper foil, in order to prevent the metal component or the like from remaining, it is necessary to improve the etching characteristics, the low ridge line of the insulating resin layer bonding surface, the miniaturization of the roughened particles, and the rust preventing component.
例如，專利文獻1(日本專利申請：特開平10-138394號公報)中，將上述FPC製造引入視野，而揭示關於銅箔的技術。亦即，前述技術之目的是提供一種銅箔，以在銅箔被接著面層積樹脂基材作為覆銅層積板時，可以在保持高銅箔與樹脂基材間剝離強度之同時，具有較佳之耐熱性、耐化學藥品性、耐濕性，且在無電解電鍍時，藉由蝕刻進行去除時銅箔上不會引起朝樹脂基材面之電鍍金屬析出，而有較佳之無電解電鍍處理性。此技術是揭示了在銅箔被接著面上具有由矽烷耦合劑、矽酸鹽及硫撐二乙酸所構成混合物披覆層的印刷電路板用銅箔製造方法。還有，依據專利文獻1所揭示之銅箔製造方法，是揭示被接著面設置粗化處理層及防銹層之同時，防銹層是由鎳-鉬-鈷合金層或銦-鋅合金層與鉻酸鹽層所構成之層形成。For example, in the patent document 1 (Japanese Patent Application Laid-Open No. Hei 10-138394), the above-mentioned FPC manufacturing is introduced into a field of view, and a technique relating to a copper foil is disclosed. That is, the object of the foregoing technology is to provide a copper foil which can maintain the peeling strength between the high copper foil and the resin substrate while the copper foil is laminated on the back surface of the resin substrate as the copper clad laminate. Preferably, heat resistance, chemical resistance, moisture resistance, and electroless plating, when removed by etching, the copper foil does not cause plating metal deposition on the surface of the resin substrate, and preferably electroless plating Handling. This technique discloses a method for producing a copper foil for a printed circuit board having a coating layer of a mixture of a decane coupling agent, a ceric acid salt and a sulfuric acid diacetic acid on a copper foil-attached surface. Further, according to the copper foil manufacturing method disclosed in Patent Document 1, it is disclosed that the roughening treatment layer and the rustproof layer are provided on the adhesive surface, and the rustproof layer is composed of a nickel-molybdenum-cobalt alloy layer or an indium-zinc alloy layer. Formed with a layer of chromate layer.
然而，使用貼合此專利文獻1揭示技術所製造之「經防銹層中含鉬等複合金屬層形成粗化處理粒子的銅箔」的FCCL時，也會如第2圖所示，有發生異常底切現象(符號2箭頭所指處為底切部)的傾向。此現象發生時，即使外觀上為良好線路寬度的電路線路，也會因此電路線路與樹脂絕緣層間密著性大幅劣化，而容易引起線路剝離，並易因反覆彎曲應力而增加線路脫離之危險性。However, when the FCCL of the "copper foil containing the composite metal layer containing molybdenum or the like in the rust-preventing layer to form the roughened particles" is bonded, as shown in Fig. 2, it may occur as shown in Fig. 2 Abnormal undercut phenomenon (the symbol 2 arrow points to the undercut). When this phenomenon occurs, even if the circuit line has a good line width, the adhesion between the circuit line and the resin insulating layer is greatly deteriorated, and the line peeling is likely to occur, and the risk of line detachment is easily increased by the repeated bending stress. .
由上述可知，在FPC業界，為了有在含硫酸及過氧化氫之蝕刻液處理下，不會在電路線路底部發生底切現象的FCCL，而要求有對可防止前述現象發生之銅箔。As described above, in the FPC industry, in order to have an FCCL which does not cause undercut at the bottom of a circuit line under the treatment of an etching solution containing sulfuric acid and hydrogen peroxide, a copper foil which can prevent the occurrence of the above phenomenon is required.
為此，本發明者深入研究的結果，想到使用具有下述特性覆銅層積板作成印刷電路板，不僅可以使微細線路形成變可能，還可以在被含硫酸及過氧化氫蝕刻液處理時，不會在電路線路底部發生底切現象。For this reason, the inventors have intensively studied the results, and it is conceivable to use a copper-clad laminate having the following characteristics to form a printed circuit board, which can not only make the formation of fine lines, but also can be treated by a sulfuric acid-containing and hydrogen peroxide etching solution. , there will be no undercut at the bottom of the circuit line.
本發明覆銅層積板：本發明覆銅層積板是使用於包括在含硫酸與過氧化氫之蝕刻液中調製電路線路製程之印刷電路板製造的覆銅層積板，此覆銅層積板不僅銅層與絕緣樹脂層為相互貼合之結構，甚至在此銅層與此絕緣樹脂層間界面上具有包括鋅成分與取得3種類以下離子價數之鋅以外過渡金屬成分的表面處理層，且此銅層與此絕緣樹脂層間界面表面粗度(Rzjis)在2.5微米以下。The copper-clad laminate of the present invention: the copper-clad laminate of the present invention is a copper-clad laminate for use in a printed circuit board comprising a process for modulating a circuit line in an etching solution containing sulfuric acid and hydrogen peroxide, the copper-clad layer In addition, the copper layer and the insulating resin layer are bonded to each other, and even a surface treatment layer including a zinc component and a transition metal component other than zinc having a valence of three or less kinds is obtained at the interface between the copper layer and the insulating resin layer. And the interface surface roughness (Rzjis) between the copper layer and the insulating resin layer is 2.5 micrometers or less.
本發明覆銅層積板中，前述表面處理層之鋅與前述過渡金屬成分合計質量厚度較佳為40毫克/平方公尺(mg/m2 )以上。In the copper-clad laminate of the present invention, the total thickness of the zinc of the surface-treated layer and the transition metal component is preferably 40 mg/m 2 or more.
本發明覆銅層積板中，前述銅層之與絕緣樹脂基材的貼合面上較佳是設有粗化處理。In the copper clad laminate of the present invention, it is preferable that the bonding surface of the copper layer and the insulating resin substrate is provided with a roughening treatment.
本發明覆銅層積板較佳是使用在前述絕緣樹脂基材上具可撓性樹脂膜而成之可彎折覆銅層積板。The copper clad laminate of the present invention is preferably a bendable copper clad laminate obtained by using a flexible resin film on the insulating resin substrate.
本發明表面處理銅箔：本發明表面處理銅箔為使用於上述覆銅層積板製造的表面處理銅箔，在與絕緣樹脂基材間貼合面上具有包括鋅成分與取得3種類以下離子價數之鋅以外過渡金屬成分的表面處理層，且與此絕緣樹脂基材間貼合面表面粗度(Rzjis)在2.5微米以下。The surface-treated copper foil of the present invention is a surface-treated copper foil produced by using the above-mentioned copper-clad laminate, and has a zinc component and an ion of three or less types on a bonding surface with an insulating resin substrate. The surface treatment layer of the transition metal component other than the valence of zinc, and the surface roughness (Rzjis) of the bonding surface with the insulating resin substrate is 2.5 μm or less.
本發明表面處理銅箔中，前述表面處理銅箔之與絕緣樹脂基材的貼合面上較佳是設有粗化處理。In the surface-treated copper foil of the present invention, the surface of the surface-treated copper foil and the insulating resin substrate are preferably provided with a roughening treatment.
本發明印刷電路板：本發明印刷電路板是使用上述覆銅層積板進行蝕刻加工等而得。In the printed circuit board of the present invention, the printed circuit board of the present invention is obtained by etching or the like using the above copper clad laminate.
還有，本發明印刷電路板中，將前述電路線路浸漬於硫酸濃度10%至30%、過氧化氫濃度10%至20%之液溫攝氏30度水溶液中30秒後，於前述電路與前述絕緣樹脂基材間界面形成之底切深度為自前述電路端面起3.0微米(μm)以下的特性。Further, in the printed circuit board of the present invention, the circuit circuit is immersed in an aqueous solution having a sulfuric acid concentration of 10% to 30% and a hydrogen peroxide concentration of 10% to 20% at a liquid temperature of 30 degrees Celsius for 30 seconds, after the foregoing circuit and the foregoing The undercut depth formed by the interface between the insulating resin substrates is 3.0 micrometers (μm) or less from the end face of the above-mentioned circuit.
本發明覆銅層積板為用於在含硫酸與過氧化氫蝕刻液中調製電路線路製程的印刷電路板製造。此覆銅層積板在此銅層與此絕緣樹脂層間界面上具有包括鋅成分與取得3種類以下離子價數之鋅以外過渡金屬成分的表面處理層，且此銅層與此絕緣樹脂層間界面表面粗度(Rzjis)在2.5微米以下。此結果顯示，由於在於含硫酸與過氧化氫之蝕刻液中進行處理時不會發生底切現象，故可在印刷電路板製造程序所得電路線路與絕緣樹脂層間發揮良好的密著性。而且，由於前述銅層與前述絕緣樹脂層間界面表面粗度(Rzjis)較低，故FPC所要求之微細電路形成變容易。因此，可以得到較適於印刷電路板製造的覆銅層積板以及對前述覆銅層積板加工而得的印刷電路板。還有，本發明中覆銅層積板所具層結構可以使用本發明表面處理銅箔輕易製造得到。The copper clad laminate of the present invention is a printed circuit board for modulating a circuit line process in a sulfuric acid and hydrogen peroxide etching solution. The copper clad laminate has a surface treatment layer including a zinc component and a transition metal component other than zinc having a valence of three or less kinds at the interface between the copper layer and the insulating resin layer, and an interface between the copper layer and the insulating resin layer The surface roughness (Rzjis) is below 2.5 microns. As a result, since undercut occurs in the etching liquid containing sulfuric acid and hydrogen peroxide, it is possible to exhibit good adhesion between the circuit line obtained by the printed circuit board manufacturing process and the insulating resin layer. Further, since the interface surface roughness (Rzjis) between the copper layer and the insulating resin layer is low, the formation of a fine circuit required by the FPC becomes easy. Therefore, a copper clad laminate which is suitable for the manufacture of a printed circuit board and a printed circuit board obtained by processing the above copper clad laminate can be obtained. Further, the layered structure of the copper clad laminate in the present invention can be easily produced by using the surface treated copper foil of the present invention.
本發明覆銅層積板實施例：本發明覆銅層積板是使用於包括在含硫酸與過氧化氫之蝕刻液中調製電路線路製程之印刷電路板製造的覆銅層積板。本發明覆銅層積板基本上有銅層與絕緣樹脂層為相互貼合之層結構，且第1特徵是在此銅層與此絕緣樹脂層間界面上具有包括鋅成分與取得3種類以下離子價數之鋅以外過渡金屬成分的表面處理層。還有，本發明覆銅層積板第2特徵是此銅層與此絕緣樹脂層間界面表面粗度(Rzjis)在2.5微米以下。Copper-clad laminate according to the present invention: The copper-clad laminate of the present invention is a copper-clad laminate produced by using a printed circuit board comprising a process for modulating a circuit line in an etching solution containing sulfuric acid and hydrogen peroxide. The copper-clad laminate of the present invention basically has a layer structure in which a copper layer and an insulating resin layer are bonded to each other, and the first feature is that the interface between the copper layer and the insulating resin layer includes a zinc component and three or less kinds of ions are obtained. A surface treatment layer of a transition metal component other than the valence of zinc. Further, a second feature of the copper clad laminate of the present invention is that the interface surface roughness (Rzjis) between the copper layer and the insulating resin layer is 2.5 μm or less.
首先對第1特徵進行說明。第1特徵是在此銅層與此絕緣樹脂層間界面上，具有包括「鋅成分」與「取得3種類以下離子價數之鋅以外過渡金屬成分」的表面處理層。在此，表面處理層中「鋅成分」為必須成分。此外，例如有鋅以外其他金屬成分是「取得3種類以下離子價數之鋅以外過渡金屬成分」，即使係與銅的合金化為困難的金屬成分，具有易使鋅與銅合金化的性質，因此在包括有含「鋅成分」與「取得3種類以下離子價數之鋅以外過渡金屬成分」的表面處理層與銅層間得到良好密著性。而且，鋅成分因可以提升作為印刷電路板之耐熱特性，而成為必要成分。First, the first feature will be described. The first feature is that a surface treatment layer including a "zinc component" and a "transition metal component other than zinc having three or more kinds of ion valences" is provided at the interface between the copper layer and the insulating resin layer. Here, the "zinc component" in the surface treatment layer is an essential component. In addition, for example, a metal component other than zinc is a transition metal component other than zinc having three or more kinds of ion valences, and even if it is a metal component which is difficult to alloy with copper, it has a property of easily alloying zinc with copper. Therefore, good adhesion is obtained between the surface treatment layer including the "zinc component" and the "transition metal component other than zinc having three types of ion valence" and the copper layer. Further, the zinc component is an essential component because it can be improved as a heat-resistant property of a printed circuit board.
而且，鋅以外成分是「取得3種類以下離子價數之鋅以外過渡金屬成分」。一般而言，在水溶液中金屬與金屬離子間的舉動，從離子化傾向可以有特定推測。然而，將覆銅層積板加工成印刷電路板之際所接觸之各種溶液，大多具有溶解金屬成分的氧化力。覆銅層積板接觸前述溶液(稀硫酸、稀鹽酸等)接觸之際，金屬銅會一邊被氧化，一邊被溶解成銅離子。In addition, the component other than zinc is a "transition metal component other than zinc having three or less kinds of ion valences". In general, the behavior between metal and metal ions in an aqueous solution can be specifically estimated from the ionization tendency. However, most of the solutions that are contacted when the copper clad laminate is processed into a printed circuit board have an oxidizing power that dissolves the metal component. When the copper clad laminate is in contact with the solution (dilute sulfuric acid, dilute hydrochloric acid, etc.), the metallic copper is dissolved into copper ions while being oxidized.
對前述溶解反應模型而言，表面處理層包括「可取得超過3種類離子價數之鋅以外過渡金屬成分(以下簡稱為「多價金屬」)」，對此使用含硫酸與過氧化氫之蝕刻液時，因存在有作為氧供給源之過氧化氫水，故在多價金屬本身及其多個氧化物之間，容易引起伴隨著離子價數變化的不可逆反應。此結果是對應使用於電路線路處理的蝕刻液氧化還原電位變化，不僅表面處理層內多價金屬成分之氧化還原狀態會變化，甚至鋅或銅溶解析出前氧化狀態也會受到影響。此結果，表面處理層與銅層間電位差變動變大，會產生銅層優先溶解的現象，而可能出現底切現象。In the above dissolution reaction model, the surface treatment layer includes "a transition metal component other than zinc which can obtain more than three kinds of ion valences (hereinafter referred to as "polyvalent metal"), and an etching using sulfuric acid and hydrogen peroxide is used for this. In the case of a liquid, since hydrogen peroxide water is provided as an oxygen supply source, an irreversible reaction accompanying a change in the valence of ions is likely to occur between the polyvalent metal itself and a plurality of oxides thereof. This result corresponds to a change in the oxidation-reduction potential of the etching liquid used for the circuit line treatment, and not only the redox state of the polyvalent metal component in the surface treatment layer changes, but also the oxidation state before the dissolution of zinc or copper is affected. As a result, the fluctuation of the potential difference between the surface treatment layer and the copper layer becomes large, and the copper layer is preferentially dissolved, and undercutting may occur.
對此，只要表面處理層所含金屬可取得離子價數是3種類以內(例如溶解析出之金屬離子為1價、2價、3價任一之情形)，即使使用含硫酸與過氧化氫之蝕刻液時，也不易引起伴隨著此金屬成分與其氧化物間離子價數變化的不可逆反應，不呈現上述現象，而顯現為與使用氯化鐵(III)銅蝕刻液或氯化銅(III)蝕刻液等之一般銅蝕刻之際相同的舉動，故可以在得到穩定電路線路形狀之同時，不會引起底切現象。在此所謂之「可取得3種類以下離子價數之鋅以外過渡金屬成分」是指鎳、鉻、鐵、鉑、錳、銅等。前述中較佳是使用「可取得2種類以下離子價數之鋅以外過渡金屬成分」。此取得2種類以下離子價數之鋅以外過渡金屬成分具體而言是形成1價離子或2價離子的銅、形成2價離子或3價離子的鐵、僅形成2價離子的鎳。還有，以上所述之「取得3種類以下離子價數之鋅以外過渡金屬成分」即使以溶解析出方式共存於蝕刻液中，對形成電路線路時的銅蝕刻也沒有不良影響。On the other hand, as long as the metal contained in the surface treatment layer can obtain an ion valence of three or less (for example, when the metal ion dissolved and precipitated is one of monovalent, divalent, or trivalent), even if sulfuric acid and hydrogen peroxide are used, In the case of an etchant, it is not easy to cause an irreversible reaction accompanied by a change in the valence of the ion between the metal component and its oxide, and does not exhibit the above phenomenon, but appears to be in contact with the copper (III) chloride etching solution or copper (III) chloride. When the etching solution or the like is generally the same as the copper etching, it is possible to obtain a stable circuit line shape without causing undercut. Here, the "transition metal component other than zinc having three or more kinds of ion valences" means nickel, chromium, iron, platinum, manganese, copper, or the like. In the above, it is preferred to use "a transition metal component other than zinc which can obtain two or more kinds of ion valences". The transition metal component other than zinc having two or more kinds of ion valences is specifically copper which forms a monovalent ion or a divalent ion, iron which forms a divalent ion or a trivalent ion, and nickel which forms only a divalent ion. In addition, the above-mentioned "transition metal component other than zinc having three or more kinds of ion valences" does not adversely affect copper etching in forming a circuit line even if it is coexisted in the etching liquid by dissolution and precipitation.
在此，第1圖所示為在以下所述本發明製造使用於表面處理銅箔的覆銅層積板及使用前述覆銅層積板之印刷電路板製造中，於電路線路形成後使用含硫酸與過氧化氫之蝕刻液進行微蝕刻的結果。此結果是電路線路底部沒有發生底切現象時，從銅層2、表面處理層3、絕緣樹脂基材5剖面所得之層結構。前述情形是使用本發明表面處理銅箔製造覆銅層積板及使用前述覆銅層積板之印刷電路板製造。還有，第2圖所示為使用含硫酸與過氧化氫之蝕刻液進行微蝕刻的結果。此結果是從電路線路(銅層2)底部發生底切現象時之剖面所得之底切部6樣子。此是使用具含鉬表面處理層的表面處理銅箔製造覆銅層積板，且使用此覆銅層積板進行印刷電路板製造之情況，鉬是取得超過3種類離子價數之過渡金屬成分。比對第1圖與第2圖可知，表面處理層所含金屬取得離子價數在3種類以內(例如溶解析出之金屬離子為1價、2價、3價任一情形)時，使用含硫酸與過氧化氫之蝕刻液進行微蝕刻之情形下，不會發生底切現象。Here, FIG. 1 is a view showing the production of a copper-clad laminate for use in a surface-treated copper foil and a printed circuit board using the copper-clad laminate according to the present invention described below. The result of microetching of an etching solution of sulfuric acid and hydrogen peroxide. As a result, when the undercut phenomenon occurs at the bottom of the circuit line, the layer structure obtained from the copper layer 2, the surface treatment layer 3, and the insulating resin substrate 5 is obtained. The foregoing is a case where a copper-clad laminate is produced using the surface-treated copper foil of the present invention and a printed circuit board using the copper-clad laminate. Further, Fig. 2 shows the results of microetching using an etching solution containing sulfuric acid and hydrogen peroxide. This result is the undercut portion 6 obtained from the cross section when the undercut phenomenon occurs at the bottom of the circuit line (copper layer 2). This is a case where a copper-clad laminate is produced using a surface-treated copper foil having a molybdenum-containing surface treatment layer, and a printed circuit board is produced using the copper-clad laminate. Molybdenum is a transition metal component that obtains more than three kinds of ion valences. . In comparison with the first and second figures, it is understood that when the metal contained in the surface treatment layer has an ion valence of three or less (for example, when the metal ions dissolved and precipitated are monovalent, divalent or trivalent), sulfuric acid is used. In the case of micro-etching with an etching solution of hydrogen peroxide, undercutting does not occur.
以上所述本發明覆銅層積板之表面處理層之「鋅成分」與「可取得3種類以下離子價數之鋅以外過渡金屬成分」合計質量厚度較佳為40毫克/平方公尺(mg/m2 )以上。此質量厚度不足40毫克/平方公尺時，依據前述表面處理層界面披覆存在不完全部分之傾向變強，且銅層與絕緣樹脂基材間的密著性、耐熱性、耐藥品性會依場所產生變化而為不佳。在此，對質量厚度下限值為40毫克/平方公尺的理由進行說明。此質量厚度是完全平的理想平面上披覆成厚度為40埃之前述表面處理層的量。而且，在40埃厚度下覆蓋理想平面的合金成分量是以理想平面表面積為基準，在幾乎平滑表面上存在有形狀變化小且微細之粗化處理粒子而成的粗化處理面，前述的表面積比只要在2前後，包括具有粗化處理粒子的突出的懸崖部分，都有充足的量進行幾乎無遺漏地覆蓋。The "zinc component" of the surface treatment layer of the copper-clad laminate of the present invention described above and the "transition metal component other than zinc having three or more kinds of ion valences" have a total mass thickness of preferably 40 mg/m 2 (mg). /m 2 ) Above. When the mass thickness is less than 40 mg/m 2 , the tendency of the surface layer to be incompletely formed is increased according to the surface treatment layer, and the adhesion between the copper layer and the insulating resin substrate, heat resistance, and chemical resistance are It is not good depending on the changes in the place. Here, the reason why the lower limit of the mass thickness is 40 mg/m 2 will be described. This mass thickness is the amount of the aforementioned surface treatment layer which is completely flat and ideally coated with a thickness of 40 angstroms. Further, the amount of the alloy component covering the ideal plane at a thickness of 40 angstroms is a roughened surface having a small shape change and finely roughened particles on an almost smooth surface based on an ideal planar surface area, and the aforementioned surface area. There is a sufficient amount for almost complete coverage as long as it is around 2, including the protruding cliff portion with roughened particles.
還有，在此並未設定此質量厚度上限，不過有些構成表面處理層的金屬種類，因前述金屬成分存在大量時，在蝕刻下形成電路線路之際，會有難以溶解的成分。在上述結構中，為了不使所使用合金成分有蝕刻殘留等情形，表面處理層質量厚度較佳是80毫克/平方公尺以下。Further, although the upper limit of the mass thickness is not set here, there are some types of metals constituting the surface treatment layer. When the metal component is present in a large amount, when a circuit line is formed by etching, a component which is difficult to dissolve may be formed. In the above structure, the thickness of the surface treatment layer is preferably 80 mg/m 2 or less in order not to cause etching residues or the like of the alloy component to be used.
接著，對本發明覆銅層積板第2特徵「此銅層與此絕緣樹脂層間界面表面粗度(Rzjis)在2.5微米以下」進行說明。此界面表面粗度(Rzjis)超過2.5微米時，製造多層FPC時，層間絕緣可靠性及微細電路線路形成會變困難。相對於此，界面表面粗度(Rzjis)在2.5微米以下時，不僅局部形成過大粗化處理粒子之可能性會消失，甚至使用於絕緣樹脂層薄的多層FPC製造也可以維持層間絕緣可靠性。還有，FPC的線/空間為25微米/25微米之微細電路形成變容易。Next, the second feature of the copper-clad laminate of the present invention, "the interface surface roughness (Rzjis) between the copper layer and the insulating resin layer is 2.5 μm or less" will be described. When the interface surface roughness (Rzjis) exceeds 2.5 μm, the interlayer insulation reliability and the formation of fine circuit lines become difficult when a multilayer FPC is manufactured. On the other hand, when the interface surface roughness (Rzjis) is 2.5 μm or less, the possibility of not only partially forming excessively roughened particles is lost, and even the multilayer FPC manufactured by using a thin insulating resin layer can maintain interlayer insulation reliability. Also, it is easy to form a fine circuit of a line/space of FPC of 25 μm / 25 μm.
還有，本發明覆銅層積板的銅層與絕緣樹脂基材的貼合面上較佳是設有粗化處理，以提高銅層與絕緣樹脂層間密著性。因此，本發明覆銅層積板之設於銅層與絕緣樹脂基材的粗化處理層是在測量此覆銅層積板剖面展開阻抗時，附著微細銅粒等所形成之粗化處理層的粗化處理層阻抗值(RB1 )與銅層之塊狀銅層塊狀層阻抗值(RB2 )相異，較佳是具有RB1 ＜RB2 的關係。具有前述關係時，對防止底切現象而言為較佳的。Further, it is preferable that the bonding surface of the copper layer of the copper-clad laminate of the present invention and the insulating resin substrate is provided with a roughening treatment to improve the adhesion between the copper layer and the insulating resin layer. Therefore, the roughened layer provided on the copper layer and the insulating resin substrate of the copper-clad laminate of the present invention is a roughened layer formed by attaching fine copper particles or the like when measuring the strain of the copper-clad laminate. The roughened layer resistance value (R B1 ) is different from the bulk copper layer bulk layer resistance value (R B2 ) of the copper layer, and preferably has a relationship of R B1 <R B2 . When the above relationship is present, it is preferable to prevent the undercut phenomenon.
第3圖係繪示電路線路底部沒有發生底切現象時，使用之覆銅層積板之剖面的展開阻抗測量結果。第4圖係繪示電路線路底部發生底切現象時，使用之覆銅層積板之剖面的展開阻抗測量結果。在前述圖面中，顏色越暗表示展開阻抗測量值越高的部分，各圖的a)是剖面展開阻抗影像，b)則是以塊狀銅部平均值(約為2千歐姆(kΩ))為基準所得之展開阻抗影像。還有，前述圖面上部是銅層與絕緣樹脂層構成材料間貼合界面，且表層有經粗化處理的粗化處理層。在此，比對第3圖與第4圖可以得知，在第3圖之情形下，銅層之絕緣樹脂層構成材料貼合面附近(粗化處理層)色調較明亮，其他塊狀銅層色調則較暗。相對於此，第4圖之情形下，銅層之絕緣樹脂層構成材料貼合面附近的粗化處理層色調與其他塊狀銅層色調間的差異呈無法明顯確認之狀態。還有，僅看此第3圖與第4圖之覆銅層積板銅層與絕緣樹脂層構成材料間貼合界面最表層，比起第3圖，第4圖高阻抗區域會被顯著地觀察到。在此，處理千兆赫(GHz)命令高頻信號的電路線路中，鑑於依據表皮效果，也就是信號會流動於銅箔與絕緣樹脂基材間接著面側，故為改善高頻傳送特性，覆銅層積板的銅層絕緣樹脂層構成材料間貼合面阻抗越低越佳。因此，從前述觀點來看，本發明覆銅層積板較佳是具有粗化處理層阻抗值(RB1 )＜塊狀層阻抗值(RB2 )的關係。Fig. 3 is a graph showing the developed impedance measurement of the cross section of the copper clad laminate used when no undercut occurs at the bottom of the circuit. Fig. 4 is a graph showing the developed impedance measurement of the cross section of the copper clad laminate used when the undercut occurs at the bottom of the circuit. In the above figures, the darker the color, the higher the portion where the impedance measurement is developed. A) is the cross-sectional expansion impedance image, and b) is the average value of the bulk copper (approximately 2 kohm (kΩ)). ) The expanded impedance image obtained from the benchmark. Further, the upper surface portion is a bonding interface between the copper layer and the insulating resin layer constituent material, and the surface layer has a roughened treatment layer. Here, it can be seen from the comparison between FIG. 3 and FIG. 4 that in the case of FIG. 3, the insulating resin layer of the copper layer constitutes a bright color near the bonding surface of the material (roughening layer), and other bulk copper The layer tones are darker. On the other hand, in the case of Fig. 4, the difference between the color tone of the roughened layer in the vicinity of the bonding surface of the insulating resin layer of the copper layer and the color tone of the other bulk copper layer was not clearly confirmed. In addition, only the outermost layer of the bonding interface between the copper-clad laminate copper layer and the insulating resin layer constituting material of the third and fourth figures can be seen, and the high-impedance region of FIG. 4 is significantly higher than that of FIG. observed. Here, in the circuit circuit for processing the high-frequency signal of the gigahertz (GHz) command, in order to improve the high-frequency transmission characteristics, in view of the effect of the skin, that is, the signal flows on the interface side between the copper foil and the insulating resin substrate. The copper layer insulating resin layer of the copper laminated board preferably has a lower bonding surface resistance between the constituent materials. Therefore, from the foregoing point of view, the copper clad laminate of the present invention preferably has a relationship of a roughened layer resistance value (R B1 ) < a bulk layer resistance value (R B2 ).
本發明覆銅層積板較佳是使用在前述絕緣樹脂基材上具可撓性樹脂膜而成之可彎折覆銅層積板。在此所謂之具可撓性樹脂膜是聚亞醯胺樹脂膜、芳香族聚醯胺樹脂膜、聚對苯二甲酸乙二醇酯(PET)樹脂膜、液晶聚合物樹脂膜等，膜材質、膜厚度等並未特別限定。The copper clad laminate of the present invention is preferably a bendable copper clad laminate obtained by using a flexible resin film on the insulating resin substrate. The flexible resin film referred to herein is a polyimide resin film, an aromatic polyamide resin film, a polyethylene terephthalate (PET) resin film, a liquid crystal polymer resin film, or the like. The film thickness and the like are not particularly limited.
本發明表面處理銅箔：本發明表面處理銅箔為使用上述覆銅層積板製造的表面處理銅箔。因此，在與絕緣樹脂層間貼合面上具有包括鋅成分與可取得3種類以下離子價數之鋅以外過渡金屬成分的表面處理層，且與此絕緣樹脂層間貼合面表面粗度(Rzjis)在2.5微米以下。此表面處理銅箔貼合於絕緣樹脂層構成材料上，即得到上述本發明覆銅層積板。因此，對此表面處理銅箔之說明時，關於「表面處理層」及「貼合面表面粗度(Rzjis)在2.5微米以下」說明為了避免重複，而在此省略說明。此時本發明表面處理銅箔1係由銅箔(塊狀銅層)2、表面處理層3所構成，此層結構的模式剖面圖如第5圖所示。還有，本發明表面處理銅箔之情形下，進一步提高與絕緣樹脂層構成材料間密著性的方法是在表面處理層表面上進一步設置矽烷耦合劑處理層。The surface-treated copper foil of the present invention: the surface-treated copper foil of the present invention is a surface-treated copper foil produced by using the above copper-clad laminate. Therefore, a surface treatment layer including a zinc component and a transition metal component other than zinc having three or less kinds of ion valences is provided on the surface to be bonded to the insulating resin layer, and the surface roughness of the bonding surface between the insulating resin layers (Rzjis) Below 2.5 microns. The surface-treated copper foil is bonded to the insulating resin layer constituting material to obtain the above-described copper-clad laminate of the present invention. Therefore, in the description of the surface-treated copper foil, the description of the "surface-treated layer" and the "surface roughness of the surface of the bonding surface (Rzjis) of 2.5 μm or less" will be omitted in order to avoid redundancy. At this time, the surface-treated copper foil 1 of the present invention is composed of a copper foil (block copper layer) 2 and a surface treatment layer 3, and a schematic sectional view of this layer structure is shown in Fig. 5. Further, in the case of the surface-treated copper foil of the present invention, the method of further improving the adhesion to the insulating resin layer constituting material is to further provide a decane coupling agent treatment layer on the surface of the surface treatment layer.
而且，本發明表面處理銅箔的表面處理銅箔與絕緣樹脂基材的貼合面上較佳是設有粗化處理。本發明表面處理銅箔1之情形下，在銅箔2的貼合面上，形成施加粗化處理而得之粗化處理面4，再於此粗化處理面4上形成表面處理層3，通常是如第6圖所示之層結構。在此粗化處理面4之形成中，使用附著粗化處理粒子方法之情形下，使用金屬銅所構成之微細銅粒子，可以在形成電路線路之際的銅蝕刻下一併進行粗化處理粒子蝕刻去除，又因用以去除粗化處理粒子的過蝕刻時間不需增加，而仍可以維持良好的蝕刻因子。藉由覆銅層積板製造程序中所施加之熱履歷，在銅塊(銅箔側)與微細銅粒子(粗化處理粒子)間附著界面，關於所引起之銅相互擴散，更可以使對銅塊之粗化處理粒子密著性進一步強化固定。Further, it is preferable that the surface of the surface-treated copper foil of the surface-treated copper foil of the present invention and the insulating resin substrate are provided with a roughening treatment. In the case of the surface-treated copper foil 1 of the present invention, the roughened surface 4 obtained by applying a roughening treatment is formed on the bonding surface of the copper foil 2, and the surface treated layer 3 is formed on the roughened surface 4, It is usually a layer structure as shown in Fig. 6. In the formation of the roughening treatment surface 4, in the case of using the method of adhering the roughened particles, the fine copper particles composed of metallic copper can be used for roughening the particles under copper etching at the time of forming the circuit wiring. The etching is removed, and the overetching time for removing the roughened particles does not need to be increased, and a good etching factor can be maintained. By the thermal history applied in the copper clad laminate manufacturing process, an interface is adhered between the copper block (copper foil side) and the fine copper particles (roughened particles), and the copper interdiffusion is caused by the mutual diffusion. The roughening of the copper block is further enhanced by the particle adhesion.
本發明印刷電路板之形態：本發明印刷電路板是使用上述覆銅層積板進行蝕刻加工等而得。在前述中，於多層印刷電路板製造程序中，即使電路線路浸漬於各種藥品中，電路端面上也不會發生底切，而為電特性及連接可靠性俱佳的印刷電路板。In the form of the printed circuit board of the present invention, the printed circuit board of the present invention is obtained by etching or the like using the above copper clad laminate. In the above, in the multilayer printed circuit board manufacturing process, even if the circuit wiring is immersed in various chemicals, the undercut of the circuit end face does not occur, and the printed circuit board is excellent in electrical characteristics and connection reliability.
還有，本發明印刷電路板中，將前述電路線路浸漬於硫酸濃度10%至30%、過氧化氫濃度10%至20%之液溫攝氏30度水溶液中30秒後，於前述電路與前述絕緣樹脂基材間界面形成之底切深度為自前述電路端面起3.0微米(μm)以下的特性。亦即，溢料蝕刻、微蝕刻、銅線路蝕刻之際，即使用含硫酸與過氧化氫之蝕刻液也不會發生底切現象。因此，印刷電路板中也適於追求微細線路形成之可彎折印刷電路板用途。Further, in the printed circuit board of the present invention, the circuit circuit is immersed in an aqueous solution having a sulfuric acid concentration of 10% to 30% and a hydrogen peroxide concentration of 10% to 20% at a liquid temperature of 30 degrees Celsius for 30 seconds, after the foregoing circuit and the foregoing The undercut depth formed by the interface between the insulating resin substrates is 3.0 micrometers (μm) or less from the end face of the above-mentioned circuit. That is, during the flash etching, micro etching, and copper line etching, the undercut phenomenon does not occur even if an etching solution containing sulfuric acid and hydrogen peroxide is used. Therefore, printed circuit boards are also suitable for the use of bendable printed circuit boards for the formation of fine lines.
本發明覆銅層積板為用於在含硫酸與過氧化氫蝕刻液中調製電路線路製程的印刷電路板製造。使用此覆銅層積板在溢料蝕刻、微蝕刻、銅線路蝕刻中，即使用含硫酸與過氧化氫之蝕刻液也不會發生底切現象。而且，由於前述銅層與前述絕緣樹脂層間界面表面粗度(Rzjis)較低，故FPC所要求之微細電路形成變容易。特別是本發明覆銅層積板可以滿足可彎折印刷電路板所要求之要求特性。還有，本發明覆銅層積板使用本發明表面處理銅箔時，藉由構成絕緣樹脂層之樹脂薄板、預浸漬體等進行層積加工等可以容易製造。The copper clad laminate of the present invention is a printed circuit board for modulating a circuit line process in a sulfuric acid and hydrogen peroxide etching solution. The use of the copper clad laminate does not cause undercutting in the flash etching, microetching, or copper wiring etching, that is, using an etching solution containing sulfuric acid and hydrogen peroxide. Further, since the interface surface roughness (Rzjis) between the copper layer and the insulating resin layer is low, the formation of a fine circuit required by the FPC becomes easy. In particular, the copper clad laminate of the present invention can satisfy the required characteristics required for a bendable printed circuit board. In the copper-clad laminate of the present invention, when the surface-treated copper foil of the present invention is used, it can be easily produced by laminating a resin sheet or a prepreg which constitutes an insulating resin layer.
1．．．表面處理銅箔1. . . Surface treated copper foil
2．．．銅層2. . . Copper layer
3．．．表面處理層3. . . Surface treatment layer
4．．．粗化處理面4. . . Roughing surface
5．．．絕緣樹脂基材5. . . Insulating resin substrate
6．．．底切部6. . . Undercut
第1圖係繪示電路線路底部沒有發生底切現象時，從剖面所見樣子的光學顯微鏡觀察圖。Fig. 1 is an optical microscopic view showing the appearance of the cross section when no undercut occurs at the bottom of the circuit.
第2圖係繪示電路線路底部發生底切現象時，從剖面所見樣子的光學顯微鏡觀察圖。Fig. 2 is a photomicrograph showing the appearance of the undercut when the undercut occurs at the bottom of the circuit.
第3圖係繪示電路線路底部沒有發生底切現象時，使用作為表面處理銅箔塊狀銅層剖面的展開阻抗測量結果。Fig. 3 is a graph showing the results of the developed impedance measurement using a cross-section of a copper-clad copper layer as a surface-treated copper foil when no undercut occurs at the bottom of the circuit.
第4圖係繪示電路線路底部發生底切現象時，使用作為表面處理銅箔塊狀銅層剖面的展開阻抗測量結果。Fig. 4 is a graph showing the results of the developed impedance measurement using the cross section of the surface treated copper foil bulk copper layer when undercut occurs at the bottom of the circuit.
第5圖係繪示用以說明本發明表面處理銅箔層結構的模式剖面圖。Figure 5 is a schematic cross-sectional view showing the structure of the surface-treated copper foil layer of the present invention.
第6圖係繪示用以說明本發明含粗化處理層之表面處理銅箔層結構的模式剖面圖。Fig. 6 is a schematic cross-sectional view showing the structure of a surface-treated copper foil layer containing a roughened layer of the present invention.
1．．．表面處理銅箔1. . . Surface treated copper foil
2．．．銅層2. . . Copper layer
3．．．表面處理層3. . . Surface treatment layer
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| JP2008143599A JP5474316B2 (en) | 2008-05-30 | 2008-05-30 | Copper-clad laminate, surface-treated copper foil used for manufacturing the copper-clad laminate, and printed wiring board obtained using the copper-clad laminate |
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| TWI420991B true TWI420991B (en) | 2013-12-21 |
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| TWI627882B (en) * | 2014-01-17 | 2018-06-21 | Jx Nippon Mining & Metals Corp | Surface treatment copper foil, copper foil with carrier, printed wiring board, copper clad laminate, laminated body, and printed wiring board manufacturing method |
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| CN103002663B (en) * | 2011-09-09 | 2015-07-15 | 深南电路有限公司 | Printed circuit board processing method |
| JP5559288B2 (en) * | 2012-11-13 | 2014-07-23 | メック株式会社 | Printed wiring board manufacturing method and surface treatment apparatus |
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| JP3292774B2 (en) * | 1994-02-15 | 2002-06-17 | 三井金属鉱業株式会社 | Copper foil for printed wiring board and method for producing the same |
| JP3769084B2 (en) * | 1996-11-12 | 2006-04-19 | 日本電解株式会社 | Copper foil for printed wiring board and method for producing the same |
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| JP2007081214A (en) * | 2005-09-15 | 2007-03-29 | Mitsui Mining & Smelting Co Ltd | Method of manufacturing printed circuit board |
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| TW493366B (en) * | 1999-03-03 | 2002-07-01 | Daiwa Kk | Production method for multi-layer wiring board |
| TW200509761A (en) * | 2003-07-22 | 2005-03-01 | Mitsui Mining & Smelting Co | Copper foil with an extremely thin adhesive layer and the method thereof |
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| CN101594736B (en) | 2013-04-17 |
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| TW201010539A (en) | 2010-03-01 |
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