TW574441B - Electrolytic copper foil for copper-clad laminate, and manufacturing method thereof - Google Patents
Electrolytic copper foil for copper-clad laminate, and manufacturing method thereof Download PDFInfo
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- TW574441B TW574441B TW90122570A TW90122570A TW574441B TW 574441 B TW574441 B TW 574441B TW 90122570 A TW90122570 A TW 90122570A TW 90122570 A TW90122570 A TW 90122570A TW 574441 B TW574441 B TW 574441B
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A7 574441 ___Β7_ 五、發明說明(1 ) [技術領域] 本發明係關於一種可精密地形成微細間距之配線圖案 的銅面積層板用電解銅箔及其製造方法。 [背景技術] 作爲於印刷配線(電路)板所使用之銅面積層板用銅箔 ,多使用著電解銅箔。一般’此電解銅箔係在旋轉之筒上 進行銅之電沉積,然後將該筒上所析出之銅析出物加以剝 離來連續地製造,惟所剝離之銅箔’與筒相接之面成爲平 坦的光澤面(S面),相反的面(電解液側)則成爲粗糙面(M 面)。又,粗糙面通常具備多數之高低變動大之凹凸。 此電解銅箔析出於筒上之初期階段的結構’其結晶粒 徑小而方向不規則,但隨著析出的進行結晶結構沿著析出 方向產生方向性,同時結晶粒徑也變得粗大。再者,以往 之電解銅箔係利用此種粗糙面的凹凸來獲致與樹脂基板間 的接著強度,而要進一步提升接著強度,則必須對上述凹 凸進一步可附著銅的微粒子的粗化處理。 將該電解銅箔使用於銅面積層板之情形,通常是對於 玻璃•環氧樹脂基板等之單面或雙面,讓前述電解銅箔之 .粗面側面向樹脂基板,進行熱壓接或透過接著劑來熱壓接 而使用之。所得之銅面積層板之銅箔係進行蝕刻來形成配 線圖案。 近年來,係要求在銅面積層板形成細微間距之配線圖 案。以蝕刻來形成此種細微間距之配線圖案的情況下,則 3 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) ' (請先閱讀背面之注意事項再填寫本頁)A7 574441 ___ Β7_ V. Description of the Invention (1) [Technical Field] The present invention relates to an electrolytic copper foil for a copper area laminate that can precisely form a fine-pitch wiring pattern and a method for manufacturing the same. [Background Art] As copper foil for copper area laminates used in printed wiring (circuit) boards, electrolytic copper foil is often used. Generally, "this electrolytic copper foil is produced by electrodeposition of copper on a rotating drum, and then the copper precipitates deposited on the drum are peeled off to be continuously manufactured, but the surface of the peeled copper foil" that is in contact with the drum becomes The flat glossy surface (S surface), and the opposite surface (electrolyte side) becomes the rough surface (M surface). In addition, the rough surface usually has a large number of irregularities with large fluctuations. This electrolytic copper foil precipitates out of the structure at the initial stage on the tube. The crystal grain diameter is small and the direction is irregular, but as the precipitation progresses, the crystal structure becomes directional along the precipitation direction, and the crystal grain size also becomes coarse. In addition, the conventional electrolytic copper foil uses such rough surface irregularities to obtain the bonding strength with the resin substrate. To further improve the bonding strength, it is necessary to roughen the fine particles to which copper can be attached. When this electrolytic copper foil is used for a copper area laminate, usually one side or both sides of a glass or epoxy substrate is used, so that the rough side of the aforementioned electrolytic copper foil faces the resin substrate, and is thermocompression bonded or It is used by thermocompression bonding through an adhesive. The copper foil of the obtained copper area laminate is etched to form a wiring pattern. In recent years, fine-pitch wiring patterns have been required to be formed on copper area laminates. In the case of forming such a fine-pitch wiring pattern by etching, 3 paper sizes apply the Chinese National Standard (CNS) A4 specification (210 X 297 public love) '(Please read the precautions on the back before filling this page)
574441 A7 ___B7___ 五、發明說明(V ) 利用以往之電解銅箱之銅面積層板,其蝕刻之配線圖案截 面係如圖1所示般,發生了蝕刻成爲上底1狹窄而下底2 寬廣之梯形狀的現象。在同圖1中,符號3係表示銅箔、 符號4係表示樹脂基板。 爲了防止梯形狀之導電圖案的短路,其間隔必須更寬 ,所以有無法形成微細圖案之問題存在。原本,理想上係 圖2所示般之上底5與下底6整列成爲大致垂直乃爲所希 望的蝕刻圖案形狀。 上述般之梯形的配線圖案,其底切差無法形成細微間 距之配線圖案。若進一步硏究此蝕刻不良的原因,乃在於 電解銅箔之粗糙面,當粗糙面之凹凸愈爲顯著則蝕刻時殘 存之圖案部的下部會被拉寬,於是相較於樹脂基板側在上 面的部分受到程度較大的蝕刻。 若將其以蝕刻因子來表示則會成爲以下之結果。亦即 ,如圖3所示般,關於銅箔之厚度a與下部寬度受到過度 蝕刻之部位的寬度b,當a/b(蝕刻因子)愈大,則細微間距 之配線圖案的蝕刻性愈佳。 惟,上述以往之電解銅箔的粗糙面之凹凸,係於製程 中必然形成的,又基於提升與樹脂基板之接著強度的考量 ,,此做法也是爲人所建議的。是以,以往並無在電解銅箔 之製程中減少銅箔之粗糙面的凹凸,或是使其細微化的想 法。 惟,基於在上述之銅面積層板形成細微間距之配線圖 案的要求上,乃必須在電解銅箔之製程中進行凹凸程度顯 4 本紙張尺度適]中國國家標準(CNS)A4規格(21G X 297公餐) (請先閱讀背面之注意事項再填寫本頁)574441 A7 ___B7___ V. Description of the Invention (V) Using the copper area laminates of the conventional electrolytic copper box, the etched wiring pattern cross-section is as shown in Figure 1. Etching has occurred to make the upper bottom 1 narrow and the lower bottom 2 wide. Ladder-shaped phenomenon. In FIG. 1, reference numeral 3 denotes a copper foil, and reference numeral 4 denotes a resin substrate. In order to prevent a short circuit of the ladder-shaped conductive pattern, the interval must be wider, so there is a problem that a fine pattern cannot be formed. Originally, it is desirable that the upper base 5 and the lower base 6 are aligned substantially vertically as a whole, as shown in FIG. The trapezoidal wiring pattern described above cannot form a fine-pitch wiring pattern due to the undercut difference. If the cause of this poor etching is further investigated, it is the rough surface of the electrolytic copper foil. When the unevenness of the rough surface becomes more prominent, the lower part of the pattern portion remaining during etching will be widened, so it is on the upper side compared to the resin substrate The part is subject to a greater degree of etching. When expressed in terms of an etching factor, the following results are obtained. That is, as shown in FIG. 3, regarding the thickness a of the copper foil and the width b of the portion where the lower width is over-etched, the larger the a / b (etching factor), the better the etching performance of the fine-pitch wiring pattern. . However, the above-mentioned unevenness of the rough surface of the conventional electrolytic copper foil is inevitable formed in the manufacturing process, and based on the consideration of improving the bonding strength with the resin substrate, this method is also recommended. Therefore, conventionally, there has been no idea of reducing the unevenness of the rough surface of the copper foil or making it finer in the electrolytic copper foil manufacturing process. However, based on the above requirements for forming fine-pitch wiring patterns on the copper area laminates, the degree of unevenness must be shown in the process of electrolytic copper foil. 4 This paper is appropriate.] Chinese National Standard (CNS) A4 Specification (21G X (297 meals) (Please read the notes on the back before filling out this page)
574441 A7 ____B7__ 五、發明說明(h ) 著之粗糙面的改良。 [發明之揭示] 本發明有鑒於上述問題,其目的在於提供一種銅面積 層板用電解銅箔,在對利用到電解銅箔之銅面積層板進行 蝕刻來形成細微間距之配線圖案之際,可防止因蝕刻時下 底被拉寬造成相較於樹脂基板側上底受到較顯著之蝕刻, 結果蝕刻成爲配線圖案之截面形狀呈現上底窄而下底寬之 梯形狀的現象,而可得到大致垂直之蝕刻面。 爲達到上述目的,本發明乃提供: 1 一種銅面積層板用電解銅箔,係使用有電解銅箔者 ;其特徵在於,該電解銅箔之粗糙面之表面粗糙度RZ爲 1.5〜4.0 // m ; 2如上述1之銅面積層板用電解銅箔,其中,電解銅 箔之粗糙面之表面粗糙度Rz爲1.5〜2.5/zm ; 3如上述1或2之銅面積層板用電解銅箔,其中,前 述電解銅箔之粗糙面係電解硏磨面或是化學硏磨面; 4.如上述3項之銅面積層板用電解銅箔,係使用有電 解銅箔者,其中,將該電解銅箔之粗糙面加以電解硏磨或 .化學硏磨,然後進一步對該電解硏磨面或化學硏磨面施以 粗化處理,使粗化處理面之粗糙度Rz成爲1.5〜4.0//m ; 5如上述4之銅面積層板用電解銅箔,其中,經粗化 處理之面之粗糙度Rz爲1.5〜2.5//m ; 6如上述4或5之銅面積層板用電解銅箔,其中,粗 5 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) ϋ n n ϋ n 一一口、I I ϋ n ϋ n I I ·_1 n n I ϋ n I I ϋ n n ϋ ϋ I ϋ n ϋ n n -ϋ 1 574441 A7 B7 五、發明說明(今 化處理之粒子大小爲1.5/zm以下; 7 —種銅面積層板用電解銅箔之製造方法’係將電解 銅箔之粗糙面加以電解硏磨或化學硏磨,使該電解銅箱之 粗糙面之表面粗糙度Rz成爲1.5〜4.0//m ; 8如上述7之銅面積層板用電解銅箔之製造方法,係 將電解銅箔之粗糙面加以電解硏磨或化學硏磨’使該電解 銅箔之粗糙面之表面粗糙度Rz成爲1.5〜; 9如上述8之銅面積層板用電解銅箔之製造方法’係 將電解銅箔之粗糙面加以電解硏磨或化學硏磨’然後進〜 步對該電解硏磨面或化學硏磨面施以粗化處理’使粗化處 理面之粗糙度Rz成爲1.5〜4.0//m ; 10如上述9之銅面積層板用電解銅箔之製造方法, 係將粗化處理面之粗糙度Rz設爲1·5〜2.5//m ; 11如上述9或10之銅面積層板用電解銅箔之製造方 法,其中,粗化處理之粒子大小爲以下; 12如上述9〜11之銅面積層板用電解銅箔之製造方法 ,係使用氯化物離子濃度在2mg/l以下之硫酸酸性硫酸_ 溶液來製造電解銅箔。 [圖式之簡單說明] 圖1係利用習知之電解銅箔之銅面積層板之蝕刻所形 成之配線圖案的截面說明圖,圖2係理想的銅面積層板之 蝕刻所形成之配線圖案的截面說明圖’圖3係蝕刻因子之 槪略說明圖。 6 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ί靖先閱讀背面之>i意事項再填寫本頁) IAW--------^訂—------_ 線 I 泰 574441 A7 __B7___ 五、發明說明(< ) [發明之實施形態] 電解銅箔係在旋轉之筒上進行銅之電沉積,然後將該 筒上所析出之銅析出物加以剝離來連續地製造者,惟如上 述所說明般,與筒相接之側面成爲平坦的光澤面,相反的 面(電解液側)則成爲凹凸顯著之粗糙面。 此電解銅箔在析出初期階段的結構,其結晶粒徑小而 方向不規則,但隨著析出的進行結晶結構會沿著析出方向 產生方向性,同時結晶粒徑有變大的傾向。 於本發明中,基於必須對上述之電解所形成之結晶結 構加以改善的見解,乃在電解銅箔之製程中,將上述凹凸 程度顯著之電解銅箱的粗糙面加以電解硏磨或是化學硏磨 ,使該電解銅箔之粗糙面的表面粗糙度Rz成爲1.5〜4.0// m ° 將電解銅箔之粗糙面加以電解硏磨或化學硏磨之後, 進一步對硏磨面進行粗化處理,使得該粗化處理面之粗糙 度Rz成爲1.5/zm〜4.0/zm乃爲所希望的。藉此,不僅能 獲致良好之蝕刻因子,也可提升剝離強度。 此時,經電解硏磨或化學硏磨後之粗化處理粒子之大 小以1.5/zm以下爲佳。 若Rz超過4.0//m,則無法充分地獲得本發明之效果( 亦即在銅面積層板之蝕刻之際,高精度地形成細微間距之 配線圖案的效果),又當Rz未滿1.5//m,則與樹脂基板之 接著強度會變低,所以Rz係設定成1.5/zm以上。較佳的 7 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) -IAV--------^________I IAV---I------------------ 574441 A7 ___B7__ 五、發明說明(b ) 情況爲將該電解銅箔之粗糙面或粗化面之表面粗糙度設定 在 1.5〜2.5 // m。 藉此,可緩和在以往之電解銅箔之製程中所必然形成 之粗糙面之顯著的凹凸,可有效地防止在對利用到電解銅 箔之銅面積層板進行蝕刻來形成配線圖案之際,出現上底 窄而下底寬之梯形狀的蝕刻現象,可得到大致垂直之蝕刻 面。 對電解銅箔之粗糙面進行硏磨之時,可例如在電解銅 箔之表面粗化等之連續、複數之電化學表面處理當中設置 電解硏磨製程,於該製程之電解液中配置與銅箔相對之用 以自銅箔集電之陰極板(直接連接於電極),利用液中集電 法來進行電解硏磨。藉此,可有效地實施連續性之銅箔的 電解硏磨。 本發明如上所述,其目的雖在減低電解銅箔之粗糙面 的表面粗糙度,但也毫無疑問地可依必要性倂用電解銅箔 之粗糙面的粗化處理或是光澤面的各種電化學表面處理, 本發明也包含這些處理方式。 又,即便是取代上述之電解硏磨改實施化學硏磨也可 得到同樣的效果。 , 作爲電解硏磨之一例係如下所示。 (硏磨液) H3P〇3 : 70vol% 水:30vol〇/〇 (硏磨條件) ’ 8 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 一 "~ (請先閱讀背面之注意事項再填寫本頁) IAW--------訂---------線· 574441 A7 ______ B7 _ 五、發明說明(,])574441 A7 ____B7__ 5. Description of the invention (h) Improvement of rough surface. [Disclosure of the Invention] The present invention has been made in view of the above problems, and an object thereof is to provide an electrolytic copper foil for a copper area laminate, in which a fine-pitch wiring pattern is formed by etching a copper area laminate using the electrolytic copper foil, It can prevent the upper bottom from being significantly etched compared to the resin substrate side due to the lower bottom being widened during etching. As a result, the cross-sectional shape of the wiring pattern shows a trapezoidal shape with a narrow upper bottom and a wide bottom bottom. Roughly vertical etched surface. In order to achieve the above object, the present invention provides: 1 An electrolytic copper foil for copper area laminates, which uses electrolytic copper foil; characterized in that the surface roughness RZ of the rough surface of the electrolytic copper foil is 1.5 ~ 4.0 / / m; 2 The electrolytic copper foil for copper area laminates according to 1 above, wherein the surface roughness Rz of the rough surface of the electrolytic copper foil is 1.5 to 2.5 / zm; 3 The electrolytic for copper area laminates according to 1 or 2 above Copper foil, wherein the rough surface of the aforementioned electrolytic copper foil is an electrolytic honing surface or a chemical honing surface; 4. The electrolytic copper foil for copper area laminates according to the above 3 items is one using electrolytic copper foil, of which, The rough surface of the electrolytic copper foil is subjected to electrolytic honing or chemical honing, and then the electrolytic honing or chemical honing is further subjected to a roughening treatment so that the roughness Rz of the roughened surface becomes 1.5 to 4.0. // m; 5 The electrolytic copper foil for copper area laminates according to the above 4, wherein the roughness Rz of the roughened surface is 1.5 to 2.5 // m; 6 For the copper area laminates according to 4 or 5 above Electrolytic copper foil, of which 5 paper sizes are applicable to China National Standard (CNS) A4 (210 X 297 mm) (please Read the notes on the back and fill in this page) ϋ nn ϋ n One-by-one, II ϋ n ϋ n II · _1 nn I ϋ n II ϋ nn ϋ ϋ I ϋ n ϋ nn -ϋ 1 574441 A7 B7 V. Description of the invention (The particle size of this chemical treatment is below 1.5 / zm; 7—A kind of manufacturing method of electrolytic copper foil for copper area laminates' is to roughen the electrolytic copper foil by electrolytic honing or chemical honing to make the electrolytic copper box The surface roughness Rz of the rough surface is 1.5 to 4.0 // m; 8 As described in the above 7 method of manufacturing the electrolytic copper foil for copper area laminates, the rough surface of the electrolytic copper foil is electrolytically honing or chemically honing. The surface roughness Rz of the rough surface of the electrolytic copper foil is 1.5 to 9; 9 The manufacturing method of the electrolytic copper foil for the copper area laminate of the above 8 is the electrolytic honing or chemical honing of the rough surface of the electrolytic copper foil 'Then proceed to roughen the electrolytic honing surface or the chemical honing surface' so that the roughness Rz of the roughened surface is 1.5 to 4.0 // m; 10 The electrolysis of the copper area laminate according to 9 above The manufacturing method of the copper foil is to set the roughness Rz of the roughened surface to 1.5 to 2.5 // m; 11 as above The method of manufacturing electrolytic copper foil for copper area laminates of 9 or 10, wherein the size of the roughened particles is the following; 12 As described above for the method of manufacturing electrolytic copper foil for copper area laminates of 9 to 11, the use of chloride Sulfuric acid acidic sulfuric acid solution with ion concentration below 2mg / l to produce electrolytic copper foil. [Simplified description of the figure] Figure 1 is a cross-sectional illustration of a wiring pattern formed by etching a copper area laminate of a conventional electrolytic copper foil FIG. 2 is a cross-sectional explanatory diagram of a wiring pattern formed by etching of an ideal copper area laminate. FIG. 3 is a schematic explanatory diagram of an etching factor. 6 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm). 靖 Jing first read the > I matter on the back and then fill out this page) IAW -------- ^ Order --- ----_ Line I Thai 574441 A7 __B7___ 5. Explanation of the invention (<) [Embodiments of the invention] The electrolytic copper foil is electrodeposited with copper on a rotating drum, and then the copper deposited on the drum is precipitated. However, as described above, the side that is in contact with the cylinder becomes a flat glossy surface, and the opposite side (the electrolyte side) becomes a rough surface with significant unevenness, as described above. The structure of this electrolytic copper foil at the initial stage of precipitation has a small crystal grain size and an irregular direction. However, as the precipitation progresses, the crystal structure will have directivity along the precipitation direction, and the crystal grain size tends to increase. In the present invention, based on the insight that the crystalline structure formed by the above-mentioned electrolysis must be improved, the rough surface of the electrolytic copper box with significant unevenness as described above is electrolytically polished or chemically polished in the electrolytic copper foil manufacturing process. Grinding, so that the surface roughness Rz of the rough surface of the electrolytic copper foil becomes 1.5 to 4.0 // m ° After roughening the rough surface of the electrolytic copper foil by electrolytic honing or chemical honing, further roughening the honing surface, It is desirable that the roughness Rz of the roughened surface be 1.5 / zm to 4.0 / zm. Thereby, not only a good etching factor can be obtained, but also peeling strength can be improved. At this time, the size of the roughened particles after electrolytic honing or chemical honing is preferably 1.5 / zm or less. If Rz exceeds 4.0 // m, the effect of the present invention (that is, the effect of forming a fine-pitch wiring pattern with high accuracy during the etching of a copper area laminate) cannot be obtained sufficiently, and when Rz is less than 1.5 / / m, the bonding strength with the resin substrate will be low, so Rz is set to 1.5 / zm or more. Better 7 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling this page) -IAV -------- ^ ________ I IAV- --I ------------------ 574441 A7 ___B7__ 5. Description of the invention (b) The situation is to set the surface roughness of the rough surface or roughened surface of the electrolytic copper foil 1.5 ~ 2.5 // m. This can alleviate the significant unevenness of the rough surface inevitably formed in the conventional electrolytic copper foil manufacturing process, and can effectively prevent the formation of wiring patterns when etching the copper area laminates using electrolytic copper foil. An etching phenomenon of a trapezoidal shape with a narrow upper bottom and a wide lower bottom appears, and an approximately vertical etching surface can be obtained. When honing the rough surface of the electrolytic copper foil, for example, an electrolytic honing process can be set in continuous and plural electrochemical surface treatments such as roughening the surface of the electrolytic copper foil, and copper is disposed in the electrolytic solution of the process. In contrast to a cathode plate (directly connected to an electrode) for collecting electricity from a copper foil, the foil is electrolytically honed by a liquid-collecting method. This makes it possible to effectively perform continuous honing of the copper foil. As described above, the present invention aims to reduce the surface roughness of the rough surface of the electrolytic copper foil, but it is also possible to use various types of roughening treatment of the rough surface of the electrolytic copper foil or various kinds of glossy surfaces as necessary. For electrochemical surface treatment, the present invention also includes these treatment methods. The same effect can be obtained even if the chemical honing is performed instead of the electrolytic honing. An example of electrolytic honing is shown below. (Honing fluid) H3P〇3: 70vol% Water: 30vol〇 / 〇 (Honing conditions) '8 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm). Read the notes on the back and fill in this page) IAW -------- Order --------- line · 574441 A7 ______ B7 _ 5. Description of the invention (,))
電流密度(Dk) : 10〜20A/dm2 時間:30〜60秒 電壓:3V 又,在對於已經過電解硏磨或化學硏磨之面所進行之 粗化處理,可施行以往眾知之(例如日本專利第1927340號 所記載者)細微之粗化處理。 作爲具體之粗化處理的例子,可舉出以下所述之Cu— Co—Ni三元系合金鍍敷。惟,本發明之粗化處理可使用上 述以外之處理,只要適合本發明之條件,並無特別的限制 〇 .(鍍浴組成與鍍敷條件)Current density (Dk): 10 ~ 20A / dm2 Time: 30 ~ 60 seconds Voltage: 3V In addition, the roughening treatment on the surface that has been electrolytically or chemically honed can be performed in the past (for example, Japan) (Patent No. 1927340) Subtle roughening treatment. Specific examples of the roughening treatment include Cu-Co-Ni ternary alloy plating described below. However, the roughening treatment of the present invention may use treatments other than the above, as long as it is suitable for the conditions of the present invention, there is no particular limitation. (Plating bath composition and plating conditions)
Cu : 10〜20g/lCu: 10 ~ 20g / l
Co : 1〜10g/lCo: 1 ~ 10g / l
Ni ·· 1 〜10g/l pH : 1 〜4Ni ·· 1 to 10 g / l pH: 1 to 4
溫度:40〜50°C 電流密度Dk : 20〜30A/dm2 時間:1〜5秒 再者’本發明除了前述電解銅箔之電解硏磨以外,尙 ,可倂用:以氯化物離子濃度設定在2mg/l以下之硫酸酸性 硫酸銅溶液來製造電解銅箔之技術,此將可獲致進一層之 效果。 藉由限制該氯化物離子濃度,則電解銅箔之結晶結構 變得微細,不會朝特定方向生長結晶,可得到凹凸少之結 9 本紙張^度適用中國國家標準(CNS)A4規格(21〇 X 297公釐) 一 "" (請先閱讀背面之注意事項再填寫本頁)Temperature: 40 ~ 50 ° C, Current density Dk: 20 ~ 30A / dm2, Time: 1 ~ 5 seconds, or 'The present invention can be used in addition to the above-mentioned electrolytic honing of electrolytic copper foil. It can be used: set by chloride ion concentration The technology of making electrolytic copper foil with acidic copper sulfate solution of sulfuric acid below 2mg / l will get the effect of one layer. By limiting the chloride ion concentration, the crystalline structure of the electrolytic copper foil becomes fine, and crystals will not grow in a specific direction, and a knot with less unevenness can be obtained. 9 This paper is compliant with China National Standard (CNS) A4 specifications (21 〇X 297mm) One " " (Please read the notes on the back before filling this page)
I - ·11111111 I — — — — — —— — — — —— I — — — — — I I I I I 574441 A7 ____B7___ 五、發明說明(S ) 構。 藉此,可適宜調整電解硏磨之量,可防止蝕刻成爲上 底窄而下底寬之梯形狀的現象,可有效地形成細微間距之 配線圖案。 此時之氯化物離子濃度若超過2mg/l,則幾乎無法期 待限制氯化物離子濃度之效果。是以,氯化物離子濃度必 須在2mg/l以下。較佳之氯化物離子濃度爲〇.5mgn。 又,將銅箔製造時通常使用之膠的添加量設定在 0.5mg/l以下、較佳爲().2mgA以下,貝[j在抑制前述特定方 向之結晶生長、得到凹凸少之電解銅箔的效果上更爲顯著 〇 若膠的添加量超過〇.5mg/l,則幾乎無法期待添加該膠 之效果。是以,必須在〇.5mg/l以下。 藉由將上述氯化物離子濃度與膠之量減少之電解銅箱 之製程所得之銅箔,其耐彎曲性優異,又經由加熱處理之 再結晶性也良好,此爲可確認之效果。 以下係顯示在電解銅箔之製程中較佳之電解液組成與 電解條件的一例。 (電解液組成)I-· 11111111 I — — — — — — — — — — — I — — — — — I I I I I 574441 A7 ____B7___ 5. Description of the invention (S) structure. Thereby, the amount of electrolytic honing can be appropriately adjusted, the etching can be prevented from becoming a trapezoidal shape with a narrow top and a bottom, and a fine-pitch wiring pattern can be effectively formed. If the chloride ion concentration at this time exceeds 2 mg / l, the effect of limiting the chloride ion concentration can hardly be expected. Therefore, the chloride ion concentration must be below 2 mg / l. A preferred chloride ion concentration is 0.5 mgn. In addition, the amount of the glue usually used in the production of copper foil is set to 0.5 mg / l or less, and preferably (). 2 mg A or less. In order to suppress the crystalline growth in the specific direction, an electrolytic copper foil with less unevenness is obtained. The effect is even more significant. If the amount of gum added exceeds 0.5 mg / l, the effect of adding the gum can hardly be expected. Therefore, it must be 0.5 mg / l or less. The copper foil obtained by the electrolytic copper box manufacturing process in which the chloride ion concentration and the amount of the glue is reduced as described above is excellent in bending resistance and good in recrystallization after heat treatment. This is a confirmable effect. The following shows an example of a preferable electrolyte composition and electrolytic conditions in the electrolytic copper foil manufacturing process. (Composition of electrolyte)
硫酸銅(CuS04 · 5H20) : 200〜600ge 硫酸(H2S04) : 20〜200gA 氯化物離子(Cl_) : 2mg/l以下、較佳爲〇.5mg/l以下 膠:不添加。又添加之情況則爲0.5mg/l以下(較佳爲 0.2mg/l 以下) 10 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) .· a — — — — — — —— — — — — — — — — — — — —— — — — — — — — — — 574441 A7 ___B7 ___ 五、發明說明(气) (電解條件) 電解液溫度:20〜70°C 電流密度:50〜200A/dm2 電解時間:1〇〜3〇〇秒 陽極:鉛(Pb) 實施例 其次,依據實施例來說明。又,本實施例僅爲適切之 一例,本發明並不限定於此實施例。是以,包含於本發明 之技術思想之變形、其他之實施例或是態樣,全都包含於 本發明中。 (實施例1) 利用筒型陰極來連續地製造厚度18〜12//m之電解銅 箔。電解液組成爲硫酸銅(CuS04 · 5H20) : 500g/l、硫酸 (H2S04) : 100g/l、氯化物離子(C〇 : 〇.45mg/l、膠: 0.5mgy^l 〇 以電解液溫度:60°C、電流密度:ΙΟΟΑ/dm2的條件來 電解。藉此所得之電解銅箔之粗糙面的表面粗糙度RZ爲 4·4〜4.8/zm。又,光澤面之表面粗糙度匕爲u/zm。 將此試料進一步分爲5個,作爲硏磨液使用H3P〇3 : 70vol%、水:30vol%,讓硏磨條件在電流密度: 10〜20A/dm2、時間:30〜60秒、電壓:3V之範圍做變化, 對於前述5個試料分別實施電解銅箔之粗糙面的電解硏磨 ’進一步於該等之處理面施以上述微細之粗化處理,使得 11 本紙張尺度適用中國S家標準(CNS)A4規格(210 X 297公一 一 ' (請先閱讀背面之注意事項再填寫本頁) ·--------訂丨 線丨-- 574441 A7 _____B7 ______ 五、發明說明(「0 ) 該粗糙面之最終表面粗糙度分別成爲Rz4.0//m、Rd.S/zm 、Rz2.5 // m、Rz2.0// m、Rzl.5 // m,將其分別稱爲試料 1 、試料2、試料3、試料4、試料5 〇 讓上述所得之試料1、試料2、試料3、試料4、試料 5之電解銅箔之粗糙面側加壓接著於玻璃環氧樹脂基板之 單面,製作各銅面積層板。進一步對該銅面積層板層合乾 式薄膜,然後使用光阻寬度100# m、電路間隔100# m之 圖案薄膜以UV曝光來製作電路圖案。 其次,利用氯化銅蝕刻液將之蝕刻。其結果,所得之 配線圖案的上底與下底之長度分別如表1所示。同樣地, 蝕刻因子(a/b)也顯示於同表。又,該等數値係針對各試料 做10個之測試結果之平均値。 (比較例1) 使用以相同於實施例.1之條件所製作之電解銅箔(粗糙 面的表面粗糙度Rz爲4.5//m。光澤面之表面粗糙度RZ爲 1.2// m) ’將該試料進一步分爲2個,使用與實施例1同樣 之硏磨液(H3P〇3 : 70vol%、水:30vol%),讓硏磨條件在電 流密度:10〜20A/dm2、時間:30〜60秒、電壓:3V之範圍 做變化,對於前述2個試料分別實施電解銅范之粗糖面的 •電解硏磨,進一步於該等之處理面施以與實施例同樣之微 細之粗化處理,製作出該粗糙面之最終表面粗糙度分別爲 Rz4.2 // m、Rzl.O // m 之試料 6、試料 7。 讓上述所得之試料6、試料7之電解銅箔之粗糙面側 加壓接著於玻璃環氧樹脂基板之單面,製作各銅面積層板 12 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) ---I-----------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 574441 A7 B7 五、發明說明(U ) 。進一步對該銅面積層板層合乾式薄膜,然後使用光卩且寬 度100// m、電路間隔100// m之圖案薄膜以UV曝光來製 (請先閱讀背面之注意事項再填寫本頁) 作電路圖案。 其次,利用氯化銅蝕刻液將之蝕刻。其結果,所:得$ 配線圖案的上底與下底之長度分別如袠i所示。同樣地, 蝕刻因子(a/b)也顯75於同表。又,該等數値係針對各試料 做10個之測試結果之平均値。Copper sulfate (CuS04 · 5H20): 200 ~ 600ge Sulfuric acid (H2S04): 20 ~ 200gA Chloride ion (Cl_): 2 mg / l or less, preferably 0.5 mg / l or less Gel: Do not add. If it is added, it is less than 0.5mg / l (preferably less than 0.2mg / l). 10 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm). (Please read the precautions on the back before (Fill this page). · A — — — — — — — — — — — — — — — — — — — — — — — — 574441 A7 ___B7 ___ V. Description of the Invention (Gas) (Electrolysis Conditions) Electrolyte temperature: 20 ~ 70 ° C Current density: 50 ~ 200A / dm2 Electrolysis time: 10 ~ 300 seconds Anode: Lead (Pb) Examples Next, it will be explained based on the examples. This embodiment is only an appropriate example, and the present invention is not limited to this embodiment. Therefore, the modifications, other embodiments, and aspects included in the technical idea of the present invention are all included in the present invention. (Example 1) An electrolytic copper foil having a thickness of 18 to 12 // m was continuously produced using a cylindrical cathode. The composition of the electrolytic solution is copper sulfate (CuS04 · 5H20): 500g / l, sulfuric acid (H2S04): 100g / l, chloride ion (C0: 0.45mg / l, gum: 0.5mgy ^ l), and the temperature of the electrolyte: Electrolysis at 60 ° C, current density: 100A / dm2. The surface roughness RZ of the rough surface of the electrolytic copper foil obtained was 4 · 4 ~ 4.8 / zm. The surface roughness of the glossy surface was u. This sample is further divided into five, and as a honing fluid, H3P03: 70vol%, water: 30vol%, and the honing conditions are set at a current density of 10 to 20A / dm2, and a time of 30 to 60 seconds, Voltage: The range of 3V is changed. For the aforementioned five samples, the electrolytic honing of the rough surface of the electrolytic copper foil is performed, and the above-mentioned fine roughening treatment is further applied to the treated surfaces, so that 11 paper sizes are suitable for China S. Home Standard (CNS) A4 Specification (210 X 297 Male One One) (Please read the precautions on the back before filling this page) · -------- Order 丨 Line 丨-574441 A7 _____B7 ______ V. Invention Explanation ("0") The final surface roughness of the rough surface becomes Rz4.0 // m, Rd.S / zm, Rz2.5 // m, Rz2.0 // m, Rzl.5 // m, which are referred to as sample 1, sample 2, sample 3, sample 4, sample 5 〇 press the rough surface side of the electrolytic copper foil obtained above the sample 1, sample 2, sample 3, sample 4, and sample 5 Next, each copper area laminate was made on one side of the glass epoxy substrate. Dry laminate films were further laminated on the copper area laminate, and then a pattern film with a photoresistance width of 100 # m and a circuit interval of 100 # m was exposed to UV. A circuit pattern is made. Next, it is etched with a copper chloride etchant. As a result, the lengths of the upper and lower bottoms of the obtained wiring pattern are shown in Table 1. Similarly, the etching factor (a / b) is also It is shown in the same table. In addition, these numbers are the average of the test results of 10 samples. (Comparative Example 1) An electrolytic copper foil (rough-faced) produced under the same conditions as in Example 1. The surface roughness Rz was 4.5 // m. The surface roughness RZ of the glossy surface was 1.2 // m) 'This sample was further divided into two samples, and the same honing liquid (H3P〇3: 70vol%) as in Example 1 was used. , Water: 30vol%), let honing conditions be at current density: 10 ~ 20A / dm2, time: 30 ~ 6 0 seconds, voltage: 3V. The range is changed. For the above two samples, the electrolytic sugar honing of the coarse sugar surface of the electrolytic copper fan is performed, and the processing surface is subjected to the same fine roughening treatment as in the example. Samples 6 and 7 with final surface roughnesses of Rz4.2 // m and Rzl.O // m were produced. The rough surface side of the electrolytic copper foil of samples 6 and 7 obtained above was pressed on one side of the glass epoxy substrate to produce copper laminates of 12 areas. The paper size is applicable to Chinese National Standard (CNS) A4 specifications ( 210 X 297 public love) --- I ----------------- Order --------- line (Please read the precautions on the back before filling this page ) 574441 A7 B7 V. Description of the invention (U). A dry film is further laminated on the copper area laminate, and then a patterned film with a width of 100 // m and a circuit interval of 100 // m is used for UV exposure (please read the precautions on the back before filling this page) Make a circuit pattern. Next, it is etched with a copper chloride etchant. As a result, the lengths of the upper and lower bases of the $ wiring pattern are shown as 袠 i, respectively. Similarly, the etching factor (a / b) is also shown in the same table. In addition, these numbers are the average of the test results of 10 samples for each sample.
No. 表面粗糙度 (Rz)(/m) a (/m) b (/m) ^刻因子 剝離強度 (kg/cm) 總合評價 1 4.0 12 1.90 0.97 A 實施例1 2 3.5 12 1.76 6.8 0.92 A 3 2.5 12 1.69 Ti 0.89 A 4 2.0 12 1.64 7.3 0.86 A 5 1.5 12 1.52 7.9 0.81 A 比較例1 6 4.2 12 2.03 5.9 1.09 B 7 1.0 12 1.45 8.3 0.50 B A :良好,B :不良 由上述表1可明顯看出,本發明之實施例(試料 No.1〜5)中之蝕刻因子(a/b)在6.3〜7.9屬良好,且隨著表面 粗糖度(Rz)之減小而變大。相反地剝離強度變小,但 0.97〜0.81kg/cm之範圍仍爲良好的。 在總合的評價方面,在剝離強度與蝕刻因子方面屬優 異,將銅面積層板以蝕刻來形成配線圖案之際,可有效地 抑制於配線截面之梯形狀的蝕刻現象,可得到大致垂直之 13 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) - 574441 A7 _B7__ 五、發明說明) 蝕刻面,可得到適於形成細微間距之配線圖案的銅面積層 板用電解銅箔。 相對於此,比較例之試料Νο·6之表面粗糙度Rz4.2// m,其蝕刻因子爲5.9屬不良情形,在配線截面會發生梯形 狀之蝕刻現象。 比較例之試料Νο·7之表面粗糙度Rzl_0//m,其蝕刻 因子雖良好,但有剝離強度低達〇.50(kg/cm)之問題發生。 是以,該試料Νο·7者並不適於作爲銅面積層板用電解銅箔 〇 於上述中,雖舉出實施電解銅箔之粗糙面的電解硏磨 ’進一步對該等處理面施以微細之粗化處理的例子,惟即 使不施以粗化處理之情況,電解銅箔之粗糙面之表面粗糙 度Rz爲1.5〜4.0//m者仍皆顯示優異之剝離強度與蝕刻因 子。 [發明之效果] 本發明之銅面積層板用電解銅箔,可有效地抑制對該 銅面積層板進行蝕刻來形成配線圖案之際,於配線截面出 現上底窄而下底寬之以往之銅面積層板所會見到之梯形狀 .的蝕刻現象,可得到大致垂直之蝕刻面,可得到在細微間 距之配線圖案的形成上爲適切的銅面積層板用電解銅箔。 [符號說明] 1,5 上底 14 本紙張尺度適用中關家標準(CNS)A4規格(21G X 297公餐) " (請先閱讀背面之注音?事項再填寫本頁) · I丨丨丨丨丨丨訂—丨---1111 · 574441 A7 _ B7 五、發明說明() 2?6 下底 3 銅箔 4 樹脂基板 (請先閱讀背面之注意事項再填寫本頁) 15 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)No. Surface roughness (Rz) (/ m) a (/ m) b (/ m) ^ Factor peel strength (kg / cm) Total evaluation 1 4.0 12 1.90 0.97 A Example 1 2 3.5 12 1.76 6.8 0.92 A 3 2.5 12 1.69 Ti 0.89 A 4 2.0 12 1.64 7.3 0.86 A 5 1.5 12 1.52 7.9 0.81 A Comparative Example 1 6 4.2 12 2.03 5.9 1.09 B 7 1.0 12 1.45 8.3 0.50 BA: Good, B: Defective according to Table 1 above It is obvious that the etching factor (a / b) in the examples (samples Nos. 1 to 5) of the present invention is good at 6.3 to 7.9, and becomes larger as the surface coarse sugar content (Rz) decreases. On the contrary, the peel strength is small, but the range of 0.97 to 0.81 kg / cm is still good. In terms of overall evaluation, it is excellent in peeling strength and etching factor. When a copper area laminate is etched to form a wiring pattern, it can effectively suppress the ladder-shaped etching phenomenon of the wiring cross section, and can obtain a substantially vertical 13 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love)-574441 A7 _B7__ V. Description of the invention) Etching surface can obtain electrolytic copper for copper area laminates suitable for forming fine-pitch wiring patterns Foil. On the other hand, the surface roughness Rz4.2 // m of the sample No. 6 of the comparative example has an etching factor of 5.9, which is a bad situation, and a trapezoidal etching phenomenon occurs on the wiring cross section. The surface roughness Rzl_0 // m of the sample No. 7 of the comparative example had a good etching factor, but had a problem that the peel strength was as low as 0.50 (kg / cm). Therefore, this sample No. 7 is not suitable as an electrolytic copper foil for copper area laminates. In the above, although the electrolytic honing of the rough surface of the electrolytic copper foil is mentioned, the processed surfaces are further finely divided. As an example of roughening treatment, even if the roughening treatment is not applied, even if the surface roughness Rz of the rough surface of the electrolytic copper foil is 1.5 to 4.0 // m, it still shows excellent peel strength and etching factor. [Effect of the Invention] The electrolytic copper foil for a copper area laminate of the present invention can effectively suppress the formation of a wiring pattern when the copper area laminate is etched to form a narrow and wide bottom cross section of the wiring cross section. The etching phenomenon of the ladder shape seen in the copper area laminate can obtain a substantially vertical etched surface, and an electrolytic copper foil for a copper area laminate suitable for the formation of a fine-pitch wiring pattern can be obtained. [Symbols] 1, 5 Top and 14 This paper size is applicable to Zhongguanjia Standard (CNS) A4 (21G X 297 meals) " (Please read the note on the back? Matters before filling out this page) · I 丨 丨丨 丨 丨 丨 Order—— 丨 -11-11 · 574441 A7 _ B7 V. Description of the invention () 2? 6 Bottom 3 Copper foil 4 Resin substrate (Please read the precautions on the back before filling this page) 15 Paper size Applicable to China National Standard (CNS) A4 (210 X 297 mm)
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JP5506497B2 (en) * | 2010-03-30 | 2014-05-28 | Jx日鉱日石金属株式会社 | Copper foil for printed wiring board for forming circuit with excellent electric transmission characteristics and laminate using the same |
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US5431803A (en) * | 1990-05-30 | 1995-07-11 | Gould Electronics Inc. | Electrodeposited copper foil and process for making same |
JP2754157B2 (en) * | 1994-03-31 | 1998-05-20 | 三井金属鉱業株式会社 | Manufacturing method of electrolytic copper foil for printed wiring board |
JP3155920B2 (en) * | 1996-01-16 | 2001-04-16 | 三井金属鉱業株式会社 | Electrolytic copper foil for printed wiring board and method for producing the same |
JPH09272994A (en) * | 1996-04-05 | 1997-10-21 | Furukawa Electric Co Ltd:The | Electrolytic copper foil for fine pattern |
JPH1036992A (en) * | 1996-07-19 | 1998-02-10 | Japan Energy Corp | Electrolytic copper foil and its production |
JPH11340596A (en) * | 1998-05-21 | 1999-12-10 | Furukawa Electric Co Ltd:The | Copper foil for printed circuit board and copper foil attached with resin |
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