TWI509111B - Surface treatment of electrolytic copper foil, laminated board, and printed wiring board, electronic equipment - Google Patents

Surface treatment of electrolytic copper foil, laminated board, and printed wiring board, electronic equipment Download PDF

Info

Publication number
TWI509111B
TWI509111B TW102143163A TW102143163A TWI509111B TW I509111 B TWI509111 B TW I509111B TW 102143163 A TW102143163 A TW 102143163A TW 102143163 A TW102143163 A TW 102143163A TW I509111 B TWI509111 B TW I509111B
Authority
TW
Taiwan
Prior art keywords
copper foil
roughness
treated
electrolytic copper
printed wiring
Prior art date
Application number
TW102143163A
Other languages
Chinese (zh)
Other versions
TW201428139A (en
Inventor
Michiya Kohiki
Kenji Inukai
Original Assignee
Jx Nippon Mining & Metals Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jx Nippon Mining & Metals Corp filed Critical Jx Nippon Mining & Metals Corp
Publication of TW201428139A publication Critical patent/TW201428139A/en
Application granted granted Critical
Publication of TWI509111B publication Critical patent/TWI509111B/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/38Electroplating: Baths therefor from solutions of copper
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/06Wires; Strips; Foils
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00Electroforming
    • C25D1/04Wires; Strips; Foils
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/56Electroplating: Baths therefor from solutions of alloys
    • C25D3/58Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/06Wires; Strips; Foils
    • C25D7/0614Strips or foils
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/09Use of materials for the conductive, e.g. metallic pattern
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/38Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03Conductive materials
    • H05K2201/0332Structure of the conductor
    • H05K2201/0335Layered conductors or foils
    • H05K2201/0355Metal foils

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Laminated Bodies (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Description

表面處理電解銅箔、積層板、及印刷配線板、電子機器Surface treatment of electrolytic copper foil, laminated board, and printed wiring board, electronic equipment

本發明係關於一種表面處理電解銅箔、積層板、及印刷配線板。The present invention relates to a surface treated electrolytic copper foil, a laminated board, and a printed wiring board.

印刷配線板自這半個世紀以來取得了較大之發展,如今甚至用於幾乎所有電子機器。伴隨近年之電子機器之小型化、高性能化需要之增大,搭載零件向高密度安裝化或信號向高頻化發展,對於印刷配線板要求導體圖案之微細化(微間距化)或應對高頻等。Printed wiring boards have made great strides since this half century and are now used in almost all electronic machines. With the increase in the miniaturization and high performance of the electronic equipment in recent years, the mounted components are being mounted at a high density or the signal is becoming high-frequency. The printed wiring board is required to be finer (fine pitch) or high in response to the conductor pattern. Frequency and so on.

銅箔粗糙化處理面之粗糙度越低,越良好地形成導體圖案相對於印刷配線板之微間距。因此,伴隨近年之導體圖案之微間距化,對銅箔粗糙化處理面之低粗糙度化之要求增大。The lower the roughness of the roughened surface of the copper foil, the better the fine pitch of the conductor pattern with respect to the printed wiring board is formed. Therefore, with the fine pitch of the conductor pattern in recent years, the demand for the low roughness of the roughened surface of the copper foil is increased.

另一方面,銅箔與樹脂接著而構成積層板,但就此時之與樹脂之密接可靠性而言,由於銅箔之粗糙面之粗糙度越大則於粗糙面產生之固定效果越高,因而密接可靠性越好。該密接可靠性於形成微間距之方面為一個重要之管理項目,且只要90°剝離強度為固定值(0.6kg/cm)以上即可。又,作為其他密接可靠性之評價方法,有使與樹脂基板之積層體浸漬於260℃之高溫浴中,測定於表面產生之突起數之方法,將該突起產生數為0~1個/m2 設為密接可靠性之基準。On the other hand, the copper foil and the resin are then laminated to form a laminated board. However, in terms of the reliability of the adhesion to the resin at this time, the greater the roughness of the rough surface of the copper foil, the higher the fixing effect on the rough surface. The better the connection reliability. This adhesion reliability is an important management item in terms of forming fine pitch, and it is only required that the 90° peel strength is a fixed value (0.6 kg/cm) or more. In addition, as a method for evaluating the adhesion reliability, there is a method of measuring the number of protrusions generated on the surface by immersing the laminate with the resin substrate in a high temperature bath at 260 ° C, and the number of projections is 0 to 1 / m. 2 is the benchmark for the reliability of the connection.

關於可實現微間距化且提高與樹脂之密接可靠性之銅 箔,開發有各種技術。例如,於專利文獻1中,揭示有一種表面處理銅箔,其特徵在於具備與絕緣樹脂基材之接著面,該接著面之表面粗糙度(Rzjis)為2.5μm以下,以利用雷射法測定表面積為6550μm2 之二維區域時之表面積(三維面積:Aμm2 )與二維區域面積之比〔(A)/(6550)〕所算出之表面積比(B)之值為1.25~2.50,二維區域之每單位面積之鉻之量為2.0mg/m2 以上。There are various techniques for developing a copper foil that can achieve fine pitch and improve adhesion to a resin. For example, Patent Document 1 discloses a surface-treated copper foil which is provided with a contact surface with an insulating resin substrate, and has a surface roughness (Rzjis) of 2.5 μm or less, which is measured by a laser method. surface area is the surface area (area D: Aμm 2) when the two-dimensional area of 6550μm 2 ratio of the two-dimensional area of [(A) / (6550)] was calculated as the ratio of surface area (B) value of 1.25 to 2.50, two The amount of chromium per unit area of the dimension region is 2.0 mg/m 2 or more.

[專利文獻1]日本特開2009-105286號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-105286

如專利文獻1中所揭示般,先前技術主要為如下技術,即為了提高與樹脂之密接可靠性,尤其著眼於銅箔之粗糙化面之Rz,並對其進行控制。然而,根據發明者等人之研究,獲得如下結果:即便以使銅箔之粗糙化面之Rz成為相同值之方式進行控制,且其他條件亦設為相同,上述之與樹脂基板之接著界面之突起產生數亦不同。因此,可明確若為僅對銅箔之粗糙化面之Rz進行控制之銅箔,則不足以獲得良好之密接可靠性。As disclosed in Patent Document 1, the prior art is mainly a technique of controlling the Rz of the roughened surface of the copper foil in order to improve the adhesion reliability with the resin, and to control it. However, according to the study by the inventors and the like, the following results were obtained: even if the Rz of the roughened surface of the copper foil was controlled to be the same value, and other conditions were also the same, the above-mentioned interface with the resin substrate was The number of protrusions is also different. Therefore, it can be understood that if it is a copper foil which controls only the Rz of the roughened surface of a copper foil, it is not enough to obtain favorable adhesion reliability.

本發明提供一種表面處理電解銅箔、積層板、及印刷配線板,該表面處理電解銅箔可實現微間距化且與樹脂之密接可靠性優異。The present invention provides a surface-treated electrodeposited copper foil, a laminated board, and a printed wiring board. The surface-treated electrodeposited copper foil is finely pitched and excellent in adhesion to a resin.

於降低粗糙化面之Rz以使銅箔之導體圖案微間距化之情形時,於銅箔表面與樹脂基板之接著界面,空氣積存於形成於銅箔表面之微細之凹凸。由於難以去除該空氣,故而若設為高溫狀態,則積存於微細之凹凸之空氣膨脹而產生突起。因此,本發明者等人反覆努力研究,結果 發現:藉由對銅箔表面賦予如即便使用微間距化用之低粗糙化銅箔而空氣亦不易積存於銅箔表面般之構造,從而可抑制上述突起之產生,藉此可獲得與樹脂基板之良好之密接可靠性。When the Rz of the roughened surface is lowered to make the conductor pattern of the copper foil finely pitched, air is accumulated in the fine unevenness formed on the surface of the copper foil at the interface between the surface of the copper foil and the resin substrate. Since it is difficult to remove the air, if it is set to a high temperature state, the air accumulated in the fine concavities and convexities expands to generate protrusions. Therefore, the inventors and the like have repeatedly worked hard to study and the results It has been found that the surface of the copper foil is provided with a structure in which air is less likely to accumulate on the surface of the copper foil even if a low-roughened copper foil for micro-pitching is used, whereby generation of the above-mentioned protrusions can be suppressed, whereby a resin substrate can be obtained. Good connection reliability.

基於以上之見解而完成之本發明之一個態樣係一種表面處理電解銅箔,其使用觸針式粗糙度計測定出之銅箔之粗糙面之粗糙度Rz為2.0μm以下,上述粗糙面之粗糙度曲線之峰度(kurtosis)數Sku為2~4。An aspect of the present invention which is completed based on the above findings is a surface-treated electrolytic copper foil having a roughness Rz of a roughness of a copper foil measured by a stylus type roughness meter of 2.0 μm or less, and the rough surface The kurtosis number Sku of the roughness curve is 2 to 4.

於本發明之表面處理電解銅箔之一實施形態中,上述粗糙度Rz為0.8~1.8μm。In an embodiment of the surface-treated electrodeposited copper foil of the present invention, the roughness Rz is 0.8 to 1.8 μm.

於本發明之表面處理電解銅箔之另一實施形態中,上述峰度數Sku為2.5~3.5。In another embodiment of the surface-treated electrodeposited copper foil of the present invention, the kurtosis number Sku is 2.5 to 3.5.

於本發明之表面處理電解銅箔之又一實施形態中,上述粗糙面之表面積A、與俯視上述粗糙面時所得之面積B之比A/B為1.2~2.0。In still another embodiment of the surface-treated electrodeposited copper foil of the present invention, the ratio A/B of the surface area A of the rough surface to the area B obtained by observing the rough surface is 1.2 to 2.0.

於本發明之表面處理電解銅箔之進而又一實施形態中,上述比A/B為1.3~1.9。In still another embodiment of the surface-treated electrodeposited copper foil of the present invention, the ratio A/B is from 1.3 to 1.9.

於本發明之表面處理電解銅箔之進而又一實施形態中,常態剝離強度為0.8kg/cm以上。In still another embodiment of the surface-treated electrodeposited copper foil of the present invention, the normal peel strength is 0.8 kg/cm or more.

本發明之另一態樣係一種積層板,其係積層本發明之表面處理電解銅箔與樹脂基板而構成。Another aspect of the present invention is a laminate comprising a surface-treated electrodeposited copper foil of the present invention and a resin substrate.

本發明之又一態樣係一種以本發明之積層體為材料之印刷配線板。Still another aspect of the present invention is a printed wiring board using the laminate of the present invention as a material.

根據本發明,可提供一種表面處理電解銅箔、積層板、及 印刷配線板,該表面處理電解銅箔可實現微間距化且與樹脂之密接可靠性優異。According to the present invention, a surface treated electrolytic copper foil, a laminate, and In the printed wiring board, the surface-treated electrolytic copper foil can be finely pitched and excellent in adhesion to a resin.

圖1係實施例1之試樣之粗糙化處理面之SEM觀察照片。Fig. 1 is a SEM observation photograph of the roughened surface of the sample of Example 1.

圖2係比較例1之試樣之粗糙化處理面之SEM觀察照片。Fig. 2 is a SEM observation photograph of the roughened surface of the sample of Comparative Example 1.

本發明中所使用之電解銅箔係對藉由與樹脂基板接著而製作積層體,並利用蝕刻將其去除而使用之電解銅箔較為有用。The electrolytic copper foil used in the present invention is useful for producing an electrolytic copper foil which is formed by laminating a resin substrate and then removing it by etching.

本發明中所使用之電解銅箔係以於銅箔之與樹脂基板接著之面、即粗糙化面提高積層後之銅箔之剝離強度(密接可靠性)為目的,而對預處理後之銅箔之表面實施進行疙瘩狀之電鍍之粗糙化處理。電解銅箔雖然於製造時間點具有凹凸,但藉由粗糙化處理而增強電解銅箔之凸部而使凹凸變得更大。The electrolytic copper foil used in the present invention is intended for the purpose of improving the peel strength (adhesion reliability) of the copper foil after the copper foil is bonded to the surface of the resin substrate, that is, the roughened surface, and the copper is pretreated. The surface of the foil is roughened by plating. Although the electrolytic copper foil has irregularities at the time of manufacture, the convex portion of the electrolytic copper foil is reinforced by the roughening treatment to make the unevenness larger.

[粗糙度Rz][roughness Rz]

本發明之表面處理電解銅箔依據JIS B0601-1994並使用觸針式粗糙度計測定出之銅箔之粗糙面之粗糙度Rz為2.0μm以下。若粗糙度Rz超過2.0μm,則於銅箔表面與樹脂基板之接著界面,空氣容易積存於形成於銅箔表面之微細之凹凸而難以去除該空氣。因此,若設為高溫狀態,則積層於微細之凹凸之空氣膨脹而產生突起。使用觸針式粗糙度計測定出之上述粗糙化面之粗糙度Rz較佳為0.8~1.8μm,更佳為1.0~1.7μm。該粗糙度Rz可藉由使銅箔之光澤面(S面)處理條件最佳化及使用兩面平滑生箔而 進行控制。The surface-treated electrolytic copper foil of the present invention has a roughness Rz of a rough surface of the copper foil measured by a stylus type roughness meter according to JIS B0601-1994 of 2.0 μm or less. When the roughness Rz exceeds 2.0 μm, air is likely to accumulate on the fine unevenness formed on the surface of the copper foil at the interface between the surface of the copper foil and the resin substrate, and it is difficult to remove the air. Therefore, when the temperature is set to a high temperature state, the air accumulated in the fine concavities and convexities expands to generate protrusions. The roughness Rz of the roughened surface measured by a stylus type roughness meter is preferably 0.8 to 1.8 μm, more preferably 1.0 to 1.7 μm. The roughness Rz can be optimized by processing the shiny surface (S surface) of the copper foil and using the smoothed foil on both sides. Take control.

[峰度數Sku][Hawness Sku]

對於本發明之表面處理電解銅箔之存在於粗糙面之凹凸,就其「峭度」對與樹脂基板之密接可靠性產生影響之觀點而言,將粗糙面之粗糙度曲線之峰度數Sku控制為2~4。粗糙度曲線之峰度數Sku表示銅箔粗糙面上之凹凸之尖峭狀況(圓滑狀況),峰度數Sku越小,凹凸越成為帶有弧度之曲線,峰度數Sku越大,凹凸成為越尖峭之曲線。粗糙度曲線之峰度數Sku係依據ISO25178繪圖之利用非接觸式粗糙度計之三維表面粗糙度測定中之凹凸之尖峭程度之指標,以下述式表示係三維表面粗糙度之Z軸方向之凹凸(凸起之)高度且於基準長度1 r之凸起之高度Z(x)之下述四次方根除以下述均方根粗糙度Rq之四次方而得者。In the surface-treated electrolytic copper foil of the present invention, the roughness of the rough surface is controlled, and the kurtosis of the rough surface is controlled by the kurtosis Sku of the roughness of the resin substrate. It is 2~4. The kurtosis number Sku of the roughness curve indicates the sharpness of the unevenness on the rough surface of the copper foil (smooth condition), and the smaller the kurtosis number Sku, the more the curvature becomes a curve with a curvature, the larger the kurtosis number Sku, the sharper the ridge The curve. The kurtosis of the roughness curve Sku is an index of the degree of sharpness of the unevenness in the measurement of the three-dimensional surface roughness by the non-contact type roughness meter according to ISO 25178, and the Z-axis direction of the three-dimensional surface roughness is expressed by the following formula The height of the (bump) is the following four roots of the height Z(x) of the protrusion of the reference length 1 r divided by the fourth power of the root mean square roughness Rq described below.

於基準長度1 r之凸起之高度之四次方根:{(1/1 r)×∫ Z4 (x)dx(其中,積分為0至1 r之累計值)}The fourth root of the height of the protrusion of the reference length 1 r: {(1/1 r) × ∫ Z 4 (x)dx (wherein the integral is the cumulative value of 0 to 1 r)}

均方根粗糙度Rq:Rq:√{(1/1 r)×∫ Z2 (x)dx(其中,積分為0至1 r之累計值)}Root mean square roughness Rq: Rq: √ {(1/1 r) × ∫ Z 2 (x) dx (where the integral is the cumulative value of 0 to 1 r)}

粗糙度曲線之峰度數Sku:Sku=(1/Rq4 )×{(1/1 r)×∫ Z4 (x)dx(其中,積分為0至1 r之累計值)}The kurtosis of the roughness curve Sku: Sku = (1/Rq 4 ) × {(1/1 r) × ∫ Z 4 (x) dx (wherein the integral is the cumulative value of 0 to 1 r)}

如上所述,於銅箔粗糙面之凹凸之尖峭程度、尖峭形式越陡峭,粗糙度曲線之峰度Sku越大。而且,凹凸之尖峭程度、尖峭形式越陡峭,存在於銅箔粗糙面之凹凸之大小之偏差變得越大。因此,若控制表示控制凹凸形狀之粗糙度曲線之峰度數Sku,則可進一步控制存在於銅箔粗 糙面之凹凸之大小之更大之偏差。藉由如此抑制存在於銅箔粗糙面之凹凸之大小之偏差,即便進行微間距化,空氣亦不易積存於銅箔表面。因此,抑制由高溫狀態下之積存於凹凸內之空氣之膨脹所引起之突起之產生,藉此可獲得與樹脂基板之良好之密接可靠性。若粗糙面之粗糙度曲線之峰度Sku未達2,則變得無法保持與樹脂之充分之密接力,若超過4,則如上所述,有加熱後產生突起之問題。又,粗糙度曲線之峰度數Sku較佳為2.5~3.7,更佳為2.5~3.5,更佳為2.4~3.4。峰度數Sku可藉由使銅箔之粗糙化處理條件最佳化而進行控制。As described above, the sharpness of the unevenness of the rough surface of the copper foil and the steeper the sharp form, the larger the kurtosis Sku of the roughness curve. Further, the sharpness of the unevenness and the steeper the sharp form, the greater the variation in the size of the unevenness of the rough surface of the copper foil. Therefore, if the kurtosis number Sku indicating the roughness curve of the control uneven shape is controlled, the copper foil thick can be further controlled. The larger the deviation of the roughness of the rough surface. By suppressing the variation in the size of the irregularities existing on the rough surface of the copper foil, even if the pitch is finely divided, air is less likely to accumulate on the surface of the copper foil. Therefore, generation of protrusions due to expansion of the air accumulated in the unevenness in a high temperature state is suppressed, whereby good adhesion reliability to the resin substrate can be obtained. If the kurtosis Sku of the roughness curve of the rough surface is less than 2, it becomes impossible to maintain sufficient adhesion with the resin, and if it exceeds 4, as described above, there is a problem that protrusions are generated after heating. Further, the kurtosis number Sku of the roughness curve is preferably from 2.5 to 3.7, more preferably from 2.5 to 3.5, still more preferably from 2.4 to 3.4. The kurtosis number Sku can be controlled by optimizing the roughening treatment conditions of the copper foil.

[表面積比A/B][surface area ratio A/B]

本發明之表面處理電解銅箔較佳為粗糙面(經粗糙化處理之面)之表面積A、與俯視粗糙面時所得之面積B之比A/B為1.2~2.0。此處,表面積A係利用雷射法測定規定範圍之二維區域時之表面積(三維面積),俯視粗糙面時所得之面積B表示該二維區域之面積。該等表面積比A/B係表面處理電解銅箔與樹脂基板之接觸面積之替代指標,若表面積比A/B未達1.2,則有無法充分確保與樹脂之密接力之虞,若超過2.0,則如上所述,有出現加熱後產生突起之問題之虞。表面積比A/B更佳為1.3~1.9。表面積比A/B可藉由使銅箔之粗糙化處理條件最佳化而進行控制。例如,若於銅粗糙化處理液添加W,則表面積比A/B變大。又,若於銅粗糙化處理中提高電流密度,則表面積比A/B變大,若降低電流密度,則表面積比變小。可以如此方式將表面積比A/B控制為1.2~2.0。The surface-treated electrodeposited copper foil of the present invention preferably has a surface area A of a rough surface (a roughened surface) and a ratio A/B of an area B obtained when the rough surface is viewed from a surface of 1.2 to 2.0. Here, the surface area A is a surface area (three-dimensional area) when a two-dimensional region of a predetermined range is measured by a laser method, and an area B obtained by looking at a rough surface is an area of the two-dimensional area. If the surface area ratio A/B is less than 1.2, the surface area ratio A/B is less than 1.2, and the adhesion to the resin cannot be sufficiently ensured. As described above, there is a problem that a protrusion is generated after heating. The surface area is preferably from 1.3 to 1.9 in comparison with A/B. The surface area ratio A/B can be controlled by optimizing the roughening treatment conditions of the copper foil. For example, when W is added to the copper roughening treatment liquid, the surface area ratio A/B becomes large. Moreover, when the current density is increased in the copper roughening treatment, the surface area ratio A/B becomes large, and when the current density is lowered, the surface area ratio becomes small. The surface area ratio A/B can be controlled to 1.2 to 2.0 in this manner.

[常態剝離強度][Normal peel strength]

本發明之表面處理電解銅箔如上所述具有良好之常態剝離強度。詳細 而言,本發明之表面處理電解銅箔較佳為依據JIS C5016測定出之常態剝離強度為0.8kg/cm以上。又,該常態剝離強度更佳為0.9kg/cm以上。The surface-treated electrodeposited copper foil of the present invention has a good normal peel strength as described above. detailed In the surface-treated electrodeposited copper foil of the present invention, the normal peel strength measured in accordance with JIS C5016 is preferably 0.8 kg/cm or more. Further, the normal peel strength is more preferably 0.9 kg/cm or more.

[高溫浴槽突起][High temperature bath protrusion]

本發明之表面處理電解銅箔可如上所述良好地抑制高溫浴突起。詳細而言,本發明之表面處理電解銅箔較佳為形成作為導體圖案之微間距電路後,於粗糙化面與樹脂基板接著時,於260℃之高溫浴槽浸漬1分鐘後之突起產生數為0~1個/m2The surface-treated electrodeposited copper foil of the present invention can satisfactorily suppress high-temperature bath protrusions as described above. Specifically, in the surface-treated electrodeposited copper foil of the present invention, after forming the micro-pitch circuit as a conductor pattern, when the roughened surface is followed by the resin substrate, the number of protrusions after immersion in a high-temperature bath at 260 ° C for 1 minute is 0~1/m 2 .

作為本發明之表面處理電解銅箔之製造方法,首先製作電解銅箔(生箔)。本發明中所使用之電解銅箔係具有作為生箔之較為有用之特性即抑制針孔之較高之高溫伸長量之電解銅箔。As a method of producing the surface-treated electrodeposited copper foil of the present invention, first, an electrolytic copper foil (raw foil) is produced. The electrolytic copper foil used in the present invention has an electrolytic copper foil which is a useful property of the green foil, that is, a high temperature elongation of the pinhole.

本發明中所使用之電解銅箔可藉由使用硫酸酸性硫酸銅電解液之電解進行製作。可藉由將該電解液中之膠液濃度調整為0.5ppm以下,較佳為調整為0.01~未達0.2ppm,又,較佳為藉由添加經調整之量之氯離子,又,亦一併調整電解液溫度、硫酸濃度之類之其他電解條件,而製造無針孔之產生、具有較高之高溫伸長量之電解銅箔。減少向使用該電解液所製造之電解銅箔中之膠液之添加量,於高溫處理時促進結晶之退火(再結晶),作為其結果,增大高溫之伸長率。The electrolytic copper foil used in the present invention can be produced by electrolysis using a sulfuric acid acidic copper sulfate electrolyte. By adjusting the concentration of the glue in the electrolyte to 0.5 ppm or less, preferably to 0.01 to less than 0.2 ppm, and preferably by adding a adjusted amount of chloride ions, Further, other electrolytic conditions such as electrolyte temperature and sulfuric acid concentration are adjusted to produce an electrolytic copper foil having no pinholes and having a high elongation at a high temperature. The amount of the glue added to the electrolytic copper foil produced by using the electrolytic solution is reduced, and annealing (recrystallization) of the crystal is promoted at the time of high temperature treatment, and as a result, the elongation at high temperature is increased.

添加氯離子之情形時之本發明中所使用之電解液之組成及電解條件如下所述。The composition and electrolytic conditions of the electrolytic solution used in the present invention in the case of adding chlorine ions are as follows.

(A)電解液組成:(A) electrolyte composition:

Cu:50~120g/lCu: 50~120g/l

H2 SO4 :20~200g/l,較佳為40~120g/lH 2 SO 4 : 20~200g/l, preferably 40~120g/l

氯離子(Cl- ):20~100ppm(mg/l)Chloride ion (Cl - ): 20~100ppm (mg/l)

膠液:0.5ppm(mg/l)以下,較佳為0.01~未達0.2ppm(mg/l)Glue: 0.5ppm (mg / l) or less, preferably 0.01 ~ less than 0.2ppm (mg / l)

(B)電解條件:(B) Electrolysis conditions:

電解液溫度:20~70℃,較佳為40~60℃Electrolyte temperature: 20~70°C, preferably 40~60°C

電流密度:20~150A/dm2 Current density: 20~150A/dm 2

陽極:PbAnode: Pb

若膠液濃度超過0.5ppm,則高溫之伸長率幾乎未提高。又,為了防止針孔等而必須添加最小限量之膠液。較佳為添加0.01~未達0.2ppm(mg/l)之量之膠液。If the concentration of the glue exceeds 0.5 ppm, the elongation at high temperature hardly increases. Further, in order to prevent pinholes and the like, it is necessary to add a minimum amount of glue. It is preferred to add 0.01 to a dose of less than 0.2 ppm (mg/l).

較理想為將硫酸濃度設為20~200g/l,較佳為40~120g/l。若未達20g/l,則電解液之電導率降低,電解槽電壓上升。若超過200g/l,則高溫伸長量高之銅箔之製造變得越來越困難,容易產生設備之腐蝕。It is preferred to set the sulfuric acid concentration to 20 to 200 g/l, preferably 40 to 120 g/l. If it is less than 20 g/l, the electrical conductivity of the electrolyte is lowered and the cell voltage is increased. If it exceeds 200 g/l, the production of a copper foil having a high elongation at high temperature becomes more and more difficult, and corrosion of equipment is likely to occur.

較佳為於氯離子為20~100ppm(mg/l)之量中添加。於該範圍外,電解銅箔之基本特性(抗拉強度、粗糙度等)無法成為固定。氯離子以鹽酸、食鹽、氯化鉀等形式添加。It is preferably added in an amount of from 20 to 100 ppm (mg/l) of chloride ions. Outside of this range, the basic characteristics (tensile strength, roughness, etc.) of the electrolytic copper foil cannot be fixed. Chloride ions are added in the form of hydrochloric acid, common salt, potassium chloride or the like.

較理想為電解液溫度設為20~70℃,較佳為40~60℃。若降低電解液溫度,則即便膠液濃度較高亦可製造高溫伸長量高之銅箔。若未達20℃,則電解液之電導率降低,電解槽電壓上升。若超過70℃,則高溫伸長量高之銅箔之製造越來越困難,能量成本亦增大。Preferably, the electrolyte temperature is set to 20 to 70 ° C, preferably 40 to 60 ° C. When the temperature of the electrolyte is lowered, a copper foil having a high elongation at a high temperature can be produced even if the concentration of the solution is high. If it is less than 20 ° C, the conductivity of the electrolyte is lowered and the cell voltage is increased. If it exceeds 70 ° C, the production of a copper foil having a high elongation at high temperature becomes more and more difficult, and the energy cost also increases.

為了穩定地且於實用上所容許之時間內製造電解銅箔,電流密度範圍為20~150A/dm2In order to produce an electrolytic copper foil stably and practically, the current density ranges from 20 to 150 A/dm 2 .

以下,表示生箔製箔中之峰度數Sku之控制方法之例:Hereinafter, an example of a method of controlling the kurtosis number Sku in the raw foil foil is shown:

<生箔製箔條件><raw foil foiling conditions>

於生箔製箔時之電解液中,將膠液濃度設為1~10ppm,SPS[聚二硫二丙烷磺酸鈉]設為1~50ppm,胺系化合物[三級胺化合物]設為1~50ppm,藉此使生箔表面變得平滑(凹凸變得不尖銳)。藉此,於其後之粗糙化處理中,覆銅鍍敷後之表面之粗糙化粒子之形狀變圓。以如此方式,可使峰度數Sku小於通常之電解銅箔(例如利用添加有銅、硫酸、Cl、膠液之電解液製造生箔之情形)。In the electrolyte solution for foil production, the concentration of the glue is set to 1 to 10 ppm, SPS [sodium polydithiodipropane sulfonate] is set to 1 to 50 ppm, and the amine compound [tribasic amine compound] is set to 1 ~50 ppm, whereby the surface of the green foil is smoothed (the unevenness becomes not sharp). Thereby, in the subsequent roughening treatment, the shape of the roughened particles on the surface after the copper plating is rounded. In this manner, the kurtosis number Sku can be made smaller than a conventional electrolytic copper foil (for example, a case where a green foil is produced by using an electrolyte containing copper, sulfuric acid, Cl, or a glue liquid).

再者,使用以下之化合物作為三級胺化合物。Further, the following compounds were used as the tertiary amine compound.

(上述化學式中,R1 及R2 係選自由羥烷基、醚基、芳基、取代芳香族之烷基、不飽和烴基、烷基所組成之群中者;於下述實施例中,R1 及R2 均設為甲基)(In the above chemical formula, R 1 and R 2 are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, a substituted aromatic alkyl group, an unsaturated hydrocarbon group, and an alkyl group; in the following examples, R 1 and R 2 are both set to methyl)

再者,下述實施例中所使用之上述化合物可藉由混合規定量之例如Nagase chemteX股份公司製造之Denacol Ex-314與二甲基胺,於60℃反應3小時而獲得。Further, the above-mentioned compound used in the following examples can be obtained by mixing a predetermined amount of, for example, Denacol Ex-314 manufactured by Nagase ChemteX Co., Ltd. with dimethylamine, and reacting at 60 ° C for 3 hours.

其次,對電解銅箔之表面進行粗糙化處理。作為粗糙化處理,例如可採用以下所示之條件。於本發明中,將電解銅箔之經粗糙化處理之側之面設為粗糙面。Next, the surface of the electrolytic copper foil is roughened. As the roughening treatment, for example, the conditions shown below can be employed. In the present invention, the roughened surface of the surface of the electrolytic copper foil which has been subjected to the roughening treatment is referred to as a rough surface.

生箔為通常之電解銅箔之情形(例如利用添加有銅、硫酸、Cl、膠液之電解液製造生箔之情形)When the raw foil is a normal electrolytic copper foil (for example, a raw foil is produced by using an electrolyte containing copper, sulfuric acid, Cl, or glue)

[銅粗糙化處理條件][Copper roughening treatment conditions]

Cu:5~50g/lCu: 5~50g/l

H2 SO4 :10~100g/lH 2 SO 4 : 10~100g/l

.其他添加元素(條件1~4中之任一者). Other added elements (any of conditions 1 to 4)

(條件1)(Condition 1)

As:0.01~20mg/l(ppm)且 W:0.01~10mg/l(ppm)As: 0.01~20mg/l (ppm) and W: 0.01~10mg/l (ppm)

(條件2)(Condition 2)

Mo:0.01~5mg/l(ppm)Mo: 0.01~5mg/l (ppm)

(條件3)(Condition 3)

Mo:0.01~5mg/l(ppm) 且 As:0.01~5mg/l(ppm)及/或W:0.01~5mg/l(ppm)及/或Co:0.01~0.5mg/l(ppm)Mo: 0.01~5mg/l (ppm) And As: 0.01~5mg/l (ppm) and/or W: 0.01~5mg/l (ppm) and/or Co: 0.01~0.5mg/l (ppm)

(條件4)(Condition 4)

As:0.01~20mg/l(ppm)且 W:0.01~10mg/l(ppm)且 Co:0.01~0.5mg/l(ppm)As: 0.01~20mg/l (ppm) and W: 0.01~10mg/l (ppm) and Co: 0.01~0.5mg/l (ppm)

液溫:室溫(20℃)~50℃Liquid temperature: room temperature (20 ° C) ~ 50 ° C

電流密度:5~120A/dm2 Current density: 5~120A/dm 2

時間:1~30秒Time: 1~30 seconds

生箔為兩面平滑(平坦)箔(由於將調平劑添加至電解液,故而為銅之析出面較通常之電解銅箔更平滑之箔)之情形(例如利用添加有銅、硫酸、Cl、膠液、SPS、胺化合物之電解液製造生箔之情形)The raw foil is a smooth (flat) foil on both sides (because the leveling agent is added to the electrolyte, so the copper precipitation surface is smoother than the usual electrolytic copper foil) (for example, by adding copper, sulfuric acid, Cl, The case of making a foil with an electrolyte of a glue, SPS or an amine compound)

[銅粗糙化處理條件][Copper roughening treatment conditions]

Cu:5~50g/lCu: 5~50g/l

H2 SO4 :10~100g/lH 2 SO 4 : 10~100g/l

.其他添加元素(條件1~4中之任一者). Other added elements (any of conditions 1 to 4)

(條件1)(Condition 1)

As:0.01~5mg/l(ppm)且 W:0.01~5mg/l(ppm)As: 0.01~5mg/l (ppm) and W: 0.01~5mg/l (ppm)

(條件2)(Condition 2)

Mo:0.01~3mg/l(ppm)Mo: 0.01~3mg/l (ppm)

(條件3)(Condition 3)

Mo:0.01~3mg/l(ppm) 且 As:0.01~5mg/l(ppm)及/或W:0.01~5mg/l(ppm)及/或Co:0.01~1mg/l(ppm)Mo: 0.01~3mg/l (ppm) And As: 0.01~5mg/l (ppm) and/or W: 0.01~5mg/l (ppm) and/or Co: 0.01~1mg/l (ppm)

(條件4)(Condition 4)

W:0.01~5mg/l(ppm)及/或Co:0.01~1mg/l(ppm)W: 0.01~5mg/l (ppm) and/or Co: 0.01~1mg/l (ppm)

液溫:室溫(20℃)~50℃Liquid temperature: room temperature (20 ° C) ~ 50 ° C

電流密度:5~130A/dm2 Current density: 5~130A/dm 2

時間:1~30秒Time: 1~30 seconds

以下,表示銅粗糙化處理中之峰度數Sku之控制方法之例:Hereinafter, an example of a method of controlling the kurtosis number Sku in the copper roughening treatment will be described:

<銅粗糙化處理條件><copper roughening treatment conditions>

藉由於銅粗糙化處理液中添加As及W這兩者、或添加Mo,而使粗糙化粒子之形狀變圓。以如此方式可使峰度數Sku變小。The shape of the roughened particles is rounded by adding both As and W or adding Mo to the copper roughening treatment liquid. In this way, the kurtosis number Sku can be made small.

又,藉由於銅粗糙化處理液中添加Co、或單獨添加W(無As),可使粗糙化粒子之形狀變尖(粒子之頂端尖銳)。以如此方式可使峰度數Sku變大。Further, by adding Co to the copper roughening treatment liquid or separately adding W (without As), the shape of the roughened particles can be sharpened (the tip of the particles is sharp). In this way, the kurtosis number Sku can be made larger.

進而,可藉由降低液溫(例如設為20℃以上低於25℃),而使粗糙化粒子之形狀變尖(粒子之頂端尖銳)。以如此方式可使峰度數Sku變大。Further, the shape of the roughened particles can be sharpened (the tip of the particles is sharp) by lowering the liquid temperature (for example, 20 ° C or more and less than 25 ° C). In this way, the kurtosis number Sku can be made larger.

粗糙化處理後,進行較薄之鍍銅作為用以防止粒子之脫落之覆層。例如可採用以下之條件。After the roughening treatment, a thin copper plating is performed as a coating for preventing the particles from falling off. For example, the following conditions can be employed.

[覆銅薄層鍍敷條件][Copper plating conditions]

Cu:30~100g/lCu: 30~100g/l

H2 SO4 :10~200g/lH 2 SO 4 : 10~200g/l

液溫:室溫~75℃Liquid temperature: room temperature ~ 75 ° C

電流密度:5~65A/dm2 Current density: 5~65A/dm 2

時間:1~30秒Time: 1~30 seconds

以下,表示覆銅鍍敷處理中之峰度數Sku之控制方法之例:Hereinafter, an example of a method of controlling the kurtosis number Sku in the copper plating process:

<覆銅鍍敷條件><Copper plating conditions>

可藉由使電流密度變高(例如設為大於60A/dm2 ),而使粗糙化粒子之形狀變尖(粒子之頂端尖銳)。以如此方式可使峰度數Sku變大。The shape of the roughened particles can be sharpened by making the current density high (for example, greater than 60 A/dm 2 ) (the tip of the particles is sharp). In this way, the kurtosis number Sku can be made larger.

較佳為對粗糙化面進行形成選自Cu、Cr、Ni、Fe、Co及 Zn中之1種或2種以上之單一金屬層或合金層之加工處理。作為合金鍍敷之例,可列舉Cu-Ni、Cu-Co、Cu-Ni-Co、Cu-Zn及其他。如此之加工處理發揮作為決定銅箔之最終特性之作用,又作為障壁之作用。Preferably, the roughened surface is formed to be selected from the group consisting of Cu, Cr, Ni, Fe, Co, and Processing of one or more single metal layers or alloy layers of Zn. Examples of the alloy plating include Cu-Ni, Cu-Co, Cu-Ni-Co, Cu-Zn, and others. Such processing functions as a function of determining the final characteristics of the copper foil and acting as a barrier.

又,亦可以鎳、鈷、銅、鋅之單體或合金等於粗糙化面形成耐熱層或防銹層,進而亦可對其表面實施鉻酸鹽處理、矽烷偶合處理等處理。或亦可不進行粗糙化處理,而以鎳、鈷、銅、鋅之單體或合金等形成耐熱層或防銹層,進而對其表面實施鉻酸鹽處理、矽烷偶合處理等處理。即,可於粗糙化處理層之表面(粗糙化面)形成選自由耐熱層、防銹層、鉻酸鹽處理層及矽烷偶合處理層所組成之群中之1種以上之層,亦可於電解銅箔之表面形成選自由耐熱層、防銹層、鉻酸鹽處理層及矽烷偶合處理層所組成之群中之1種以上之層。再者,上述耐熱層、防銹層、鉻酸鹽處理層、矽烷偶合處理層亦可分別由複數層形成(例如2層以上、3層以上等)。Further, a single layer or alloy of nickel, cobalt, copper or zinc may be used to form a heat-resistant layer or a rust-proof layer equal to the roughened surface, and the surface may be subjected to a treatment such as chromate treatment or decane coupling treatment. Alternatively, the heat-resistant layer or the rust-preventive layer may be formed of a monomer, an alloy or the like of nickel, cobalt, copper or zinc, and the surface may be subjected to a treatment such as chromate treatment or decane coupling treatment. In other words, one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer may be formed on the surface (roughened surface) of the roughened layer. The surface of the electrolytic copper foil is formed into one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer. Further, the heat-resistant layer, the rust-preventing layer, the chromate-treated layer, and the decane coupling treatment layer may be formed of a plurality of layers (for example, two or more layers, three or more layers, or the like).

可將本發明之表面處理電解銅箔自粗糙化處理面側貼合於樹脂基板而製造積層體。樹脂基板只要為具有可應用於印刷配線板等之特性者,則不受特別限制,例如可於剛性PWB(印刷配線板)用中使用紙基材酚樹脂、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-玻璃不織布複合基材環氧樹脂及玻璃布基材環氧樹脂等,於FPC(柔性配線板)用中使用聚酯膜或聚醯亞胺膜、液晶聚合物(LCP)膜等。The surface-treated electrodeposited copper foil of the present invention can be bonded to the resin substrate from the side of the roughened surface to produce a laminate. The resin substrate is not particularly limited as long as it has characteristics suitable for use in a printed wiring board or the like. For example, a paper substrate phenol resin, a paper substrate epoxy resin, or a synthetic fiber can be used for a rigid PWB (printed wiring board). Cloth substrate epoxy resin, glass cloth-paper composite substrate epoxy resin, glass cloth-glass non-woven composite substrate epoxy resin and glass cloth substrate epoxy resin, etc., used in FPC (flexible wiring board) An ester film or a polyimide film, a liquid crystal polymer (LCP) film, or the like.

關於貼合之方法,於剛性PWB用之情形時,準備使樹脂含浸於玻璃布等基材,並使樹脂硬化至成為半硬化狀態而成之預浸體。可藉由將銅箔自被覆層之相反側之面重疊於預浸體並進行加熱加壓而進行貼 合。於FPC之情形時,可藉由將聚醯亞胺膜等基材經由接著劑、或不使用接著劑而於高溫高壓下積層接著於銅箔,或塗佈、乾燥、硬化聚醯亞胺前驅物等而製造積層板。In the case of the rigid PWB, the method of bonding is prepared by impregnating a resin with a base material such as a glass cloth, and curing the resin to a semi-cured state. The copper foil can be attached by superimposing the surface of the copper foil on the opposite side of the coating layer on the prepreg and heating and pressing it. Hehe. In the case of FPC, a substrate such as a polyimide film can be laminated under high temperature and high pressure via an adhesive or without an adhesive, followed by coating on a copper foil, or coating, drying, and hardening the polyimide precursor. A laminate is produced by the object or the like.

本發明之積層體可用於各種印刷配線板(PWB),並無特別限制,例如,就導體圖案之層數之觀點而言,可應用於單面PWB、雙面PWB、多層PWB(3層以上),就絕緣基板材料之種類之觀點而言,可用於剛性PWB、柔性PWB(FPC)、剛性-柔性PWB。The laminate of the present invention can be used for various printed wiring boards (PWB), and is not particularly limited. For example, from the viewpoint of the number of layers of the conductor pattern, it can be applied to single-sided PWB, double-sided PWB, and multilayer PWB (three or more layers). From the viewpoint of the kind of the insulating substrate material, it can be used for rigid PWB, flexible PWB (FPC), and rigid-flexible PWB.

[實施例][Examples]

作為實施例1~6及比較例1~5,藉由表1所示之製造條件而製造生箔,繼而,藉由表2所示之製造條件而進行粗糙化處理,進而,藉由表3所示之製造條件而對粗糙化處理面進行覆銅鍍敷,而分別形成粗糙面。於表1~3中,處理面M表示無光澤面(銅之析出面),處理面S表示光澤面。As Examples 1 to 6 and Comparative Examples 1 to 5, raw foils were produced by the production conditions shown in Table 1, and then roughened by the production conditions shown in Table 2, and further, by Table 3 The roughened surface was subjected to copper plating plating to form rough surfaces, respectively, under the manufacturing conditions shown. In Tables 1-3, the treatment surface M represents a matte surface (precipitation surface of copper), and the treatment surface S represents a glossy surface.

對於如上所述般製造之實施例及比較例之各樣品,如下所述般進行各種評價。Each of the samples of the examples and the comparative examples produced as described above was subjected to various evaluations as described below.

觸針粗糙度; 使用小坂研究所股份公司製造之接觸粗糙度計Surfcorder SE-3C觸針式粗糙度計進行測定。Stylus roughness; The measurement was carried out using a contact roughness meter Surfcorder SE-3C stylus type roughness meter manufactured by Otaru Research Co., Ltd.

表面積比(A/B); 粗糙面之表面積係使用藉由雷射顯微鏡之測定法。藉由使用Olympus製造之LEXT OLS 4000,測定相當於粗糙化處理面之257.9×257.9μm之面積B(實際資料中為66524μm2 )之三維表面積A,並以三維表面積A÷二維表面積B=面積比(A/B)之形式之方法而進行設定。測定環境溫度設為23~25℃。Surface area ratio (A/B); The surface area of the rough surface is determined by a laser microscope. The three-dimensional surface area A corresponding to the area B of 257.9 × 257.9 μm (66524 μm 2 in the actual data) corresponding to the roughened surface was measured by using LEXT OLS 4000 manufactured by Olympus, and the three-dimensional surface area A ÷ two-dimensional surface area B = area Set according to the method of the form of (A/B). The measurement ambient temperature was set to 23 to 25 °C.

峰度數Sku; 使用Olympus製造之LEXT OLS 4000三維表面形狀測定裝置,以平面0.12μm、高度0.01μm之解析度測定試驗材料之粗糙化處理面之257.9×257.9μm之區域。將測定環境溫度設為23~25℃。Kurtosis number Sku; Using a LEXT OLS 4000 three-dimensional surface shape measuring apparatus manufactured by Olympus, a region of 257.9 × 257.9 μm of the roughened surface of the test material was measured at a resolution of 0.12 μm in plane and 0.01 μm in height. The measurement ambient temperature was set to 23 to 25 °C.

常態剝離強度; 依據JIS C5016(8.1.6測定(1)方法A(90°方向剝離方法)),利用拉伸試驗機Autograph100測定常態剝離強度。Normal peel strength The normal peel strength was measured by a tensile tester Autograph 100 in accordance with JIS C5016 (8.1.6 Measurement (1) Method A (90° direction peeling method)).

高溫浴槽突起; 將銅箔積層接著於玻璃布基材環氧樹脂板,藉由蝕刻(氯化鐵水溶液)而於銅箔形成微間距電路而製成積層體。繼而,將該積層體於260℃之高溫浴中浸漬1分鐘,測定於表面產生之突起數,並換算為每1m2 之個數。The high temperature bath is protruded; the copper foil is laminated on the glass cloth substrate epoxy resin sheet, and a micro-pitch circuit is formed on the copper foil by etching (aqueous solution of ferric chloride) to form a laminate. Then, the laminate was immersed in a high temperature bath at 260 ° C for 1 minute, and the number of protrusions generated on the surface was measured and converted into the number per 1 m 2 .

將評價結果示於表4。The evaluation results are shown in Table 4.

(評價結果)(Evaluation results)

實施例1~6均具有良好之密接可靠性,即便浸漬於高溫浴槽中亦未產生突起。Each of Examples 1 to 6 had good adhesion reliability, and no protrusion was generated even when immersed in a high-temperature bath.

比較例1~5雖然粗糙度Rz均為2.0μm以下,但由於粗糙面之粗糙度曲線之峰度數Sku為2~4之範圍外,故而密接可靠性不良,或浸漬於高溫浴槽中時產生大量突起。In Comparative Examples 1 to 5, although the roughness Rz is 2.0 μm or less, since the kurtosis number Sku of the roughness curve of the rough surface is outside the range of 2 to 4, the adhesion reliability is poor, or a large amount is generated when immersed in the high temperature bath. Protrusion.

圖1中表示實施例1之試樣之粗糙化處理面之SEM觀察照片。圖2中表示比較例1之試樣之粗糙化處理面之SEM觀察照片。Fig. 1 shows a SEM observation photograph of the roughened surface of the sample of Example 1. Fig. 2 shows an SEM observation photograph of the roughened surface of the sample of Comparative Example 1.

Claims (11)

一種表面處理電解銅箔,其使用觸針式粗糙度計測定出之銅箔之粗糙面之粗糙度Rz為2.0μm以下,上述粗糙面之粗糙度曲線之峰度數Sku為2~4。 A surface-treated electrodeposited copper foil having a roughness Rz of a roughness of a copper foil measured by a stylus type roughness meter of 2.0 μm or less, and a kurtosis number Sku of a roughness curve of the rough surface of 2 to 4. 如申請專利範圍第1項之表面處理電解銅箔,其中上述粗糙度Rz為0.8~1.8μm。 The surface-treated electrolytic copper foil according to claim 1, wherein the roughness Rz is 0.8 to 1.8 μm. 如申請專利範圍第1項之表面處理電解銅箔,其中上述峰度數Sku為2.5~3.5。 The surface treated electrolytic copper foil according to claim 1, wherein the kurtosis number Sku is 2.5 to 3.5. 如申請專利範圍第1項之表面處理電解銅箔,其中上述粗糙面之表面積A、與俯視上述粗糙面時所得之面積B之比A/B為1.2~2.0。 The surface-treated electrodeposited copper foil according to the first aspect of the invention, wherein the ratio A/B of the surface area A of the rough surface to the area B obtained by observing the rough surface is 1.2 to 2.0. 如申請專利範圍第3項之表面處理電解銅箔,其中上述粗糙面之表面積A、與俯視上述粗糙面時所得之面積B之比A/B為1.2~2.0。 The surface-treated electrodeposited copper foil according to claim 3, wherein a ratio A/B of the surface area A of the rough surface to the area B obtained when the rough surface is viewed from above is 1.2 to 2.0. 如申請專利範圍第4項之表面處理電解銅箔,其中上述比A/B為1.3~1.9。 The surface treated electrolytic copper foil of claim 4, wherein the ratio A/B is 1.3 to 1.9. 如申請專利範圍第5項之表面處理電解銅箔,其中上述比A/B為1.3~1.9。 The surface treated electrolytic copper foil according to claim 5, wherein the ratio A/B is 1.3 to 1.9. 如申請專利範圍第1項之表面處理電解銅箔,其常態剝離強度為0.8kg/cm以上。 The surface-treated electrolytic copper foil according to the first aspect of the patent application has a normal peel strength of 0.8 kg/cm or more. 一種積層板,其係積層申請專利範圍第1至8項中任一項之表面處理電解銅箔與樹脂基板而構成。 A laminated board comprising a surface-treated electrodeposited copper foil and a resin substrate according to any one of claims 1 to 8. 一種印刷配線板,其係以申請專利範圍第9項之積層體為材料者。 A printed wiring board which is made of a laminate of the ninth application patent. 一種電子機器,其使用有申請專利範圍第10項之印刷配線板。 An electronic machine using the printed wiring board of claim 10 of the patent application.
TW102143163A 2012-11-26 2013-11-26 Surface treatment of electrolytic copper foil, laminated board, and printed wiring board, electronic equipment TWI509111B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2012257896 2012-11-26

Publications (2)

Publication Number Publication Date
TW201428139A TW201428139A (en) 2014-07-16
TWI509111B true TWI509111B (en) 2015-11-21

Family

ID=50776215

Family Applications (1)

Application Number Title Priority Date Filing Date
TW102143163A TWI509111B (en) 2012-11-26 2013-11-26 Surface treatment of electrolytic copper foil, laminated board, and printed wiring board, electronic equipment

Country Status (7)

Country Link
JP (1) JP5710845B2 (en)
KR (2) KR102078897B1 (en)
CN (1) CN104812945B (en)
MY (1) MY176308A (en)
PH (1) PH12015501174A1 (en)
TW (1) TWI509111B (en)
WO (1) WO2014081041A1 (en)

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107614760B (en) * 2015-07-03 2018-07-13 三井金属矿业株式会社 Roughening treatment copper foil, copper-clad laminated board and printed circuit board
JP6342078B2 (en) * 2015-07-29 2018-06-13 三井金属鉱業株式会社 Roughening copper foil, copper clad laminate and printed wiring board
TWI732892B (en) * 2016-07-26 2021-07-11 日商松下知識產權經營股份有限公司 Laminate board for see-through electrode, see-through electrode material, component, and method for manufacturing laminate board for see-through electrode
WO2018047933A1 (en) * 2016-09-12 2018-03-15 古河電気工業株式会社 Copper foil and copper-clad laminate comprising same
KR101734840B1 (en) * 2016-11-11 2017-05-15 일진머티리얼즈 주식회사 Electrolytic copper foil of secondary battery enhanced for flexibility resistance and manufacturing method thereof
JP7492808B2 (en) 2017-03-31 2024-05-30 Jx金属株式会社 Surface-treated copper foil, surface-treated copper foil with resin layer, copper foil with carrier, laminate, method for manufacturing printed wiring board, and method for manufacturing electronic device
JP7356209B2 (en) * 2017-03-31 2023-10-04 Jx金属株式会社 Surface-treated copper foil, surface-treated copper foil with resin layer, copper foil with carrier, laminate, method for manufacturing printed wiring boards, and method for manufacturing electronic devices
WO2018198905A1 (en) * 2017-04-25 2018-11-01 古河電気工業株式会社 Surface-treated copper foil
US11950376B2 (en) 2018-03-30 2024-04-02 Mitsui Mining & Smelting Co., Ltd. Copper-clad laminate
WO2019198610A1 (en) * 2018-04-10 2019-10-17 Dic株式会社 Composite structure and manufacturing method therefor
JP6606317B1 (en) * 2018-04-25 2019-11-13 古河電気工業株式会社 Surface-treated copper foil, copper-clad laminate, and printed wiring board
JP7032239B2 (en) * 2018-05-28 2022-03-08 古河電気工業株式会社 Lead frame material and its manufacturing method and semiconductor package
JP6895936B2 (en) * 2018-09-28 2021-06-30 古河電気工業株式会社 Surface-treated copper foil, and copper-clad laminates and circuit boards using this
US10581081B1 (en) 2019-02-01 2020-03-03 Chang Chun Petrochemical Co., Ltd. Copper foil for negative electrode current collector of lithium ion secondary battery
CN113795615B (en) * 2019-06-07 2024-08-02 古河电气工业株式会社 Surface-treated copper foil, copper-clad laminate, and printed circuit board
JP7392996B2 (en) 2019-06-19 2023-12-06 金居開發股▲分▼有限公司 Advanced electrolytic copper foil and copper-clad laminates using it
TWM608774U (en) * 2019-06-19 2021-03-11 金居開發股份有限公司 Advanced reverse-treated electrodeposited copper foil and copper clad laminate using the same
TWI697574B (en) 2019-11-27 2020-07-01 長春石油化學股份有限公司 Electrolytic copper foil and electrode and lithium-ion battery comprising the same
CN115380633A (en) * 2020-03-30 2022-11-22 三菱综合材料株式会社 Joined body and insulated circuit board
CN114514798B (en) * 2020-06-11 2023-04-11 三井金属矿业株式会社 Double-sided copper-clad laminated board
WO2022153580A1 (en) * 2021-01-15 2022-07-21 Jx金属株式会社 Surface-treated copper foil, copper-clad laminate, and printed wiring board
WO2023281759A1 (en) * 2021-07-09 2023-01-12 Jx金属株式会社 Surface-treated copper foil, copper-clad laminate, and printed wiring board

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008285751A (en) * 2007-04-19 2008-11-27 Mitsui Mining & Smelting Co Ltd Surface treated copper foil, copper clad laminate obtainable using the surface treated copper foil, and printed circuit board obtainable using the copper clad laminate
TW201229322A (en) * 2010-10-06 2012-07-16 Furukawa Electric Co Ltd Copper foil and manufacturing method therefor, copper foil with carrier and manufacturing method therefor, printed circuit board, and multilayer printed circuit board
JP2012169598A (en) * 2011-01-26 2012-09-06 Sumitomo Bakelite Co Ltd Printed wiring board and manufacturing method therefor

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4567360B2 (en) * 2004-04-02 2010-10-20 三井金属鉱業株式会社 Copper foil manufacturing method and copper foil obtained by the manufacturing method
JP5215631B2 (en) * 2007-10-24 2013-06-19 三井金属鉱業株式会社 Surface treated copper foil
TWI434965B (en) * 2008-05-28 2014-04-21 Mitsui Mining & Smelting Co A roughening method for copper foil, and a copper foil for a printed wiring board which is obtained by the roughening method
US8524378B2 (en) * 2008-11-25 2013-09-03 Jx Nippon Mining & Metals Corporation Copper foil for printed circuit
JP5282675B2 (en) * 2009-06-23 2013-09-04 日立電線株式会社 Copper foil for printed wiring board and method for producing the same
JP5634103B2 (en) * 2010-04-06 2014-12-03 福田金属箔粉工業株式会社 A treated copper foil for a copper clad laminate, a copper clad laminate obtained by bonding the treated copper foil to an insulating resin substrate, and a printed wiring board using the copper clad laminate.
JP5885054B2 (en) * 2010-04-06 2016-03-15 福田金属箔粉工業株式会社 A treated copper foil for a copper clad laminate, a copper clad laminate obtained by bonding the treated copper foil to an insulating resin substrate, and a printed wiring board using the copper clad laminate.

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008285751A (en) * 2007-04-19 2008-11-27 Mitsui Mining & Smelting Co Ltd Surface treated copper foil, copper clad laminate obtainable using the surface treated copper foil, and printed circuit board obtainable using the copper clad laminate
TW201229322A (en) * 2010-10-06 2012-07-16 Furukawa Electric Co Ltd Copper foil and manufacturing method therefor, copper foil with carrier and manufacturing method therefor, printed circuit board, and multilayer printed circuit board
JP2012169598A (en) * 2011-01-26 2012-09-06 Sumitomo Bakelite Co Ltd Printed wiring board and manufacturing method therefor

Also Published As

Publication number Publication date
WO2014081041A1 (en) 2014-05-30
KR102078897B1 (en) 2020-02-19
MY176308A (en) 2020-07-28
JPWO2014081041A1 (en) 2017-01-05
CN104812945A (en) 2015-07-29
KR20140124402A (en) 2014-10-24
CN104812945B (en) 2018-08-28
TW201428139A (en) 2014-07-16
JP5710845B2 (en) 2015-04-30
PH12015501174B1 (en) 2015-08-10
KR20170002705A (en) 2017-01-06
PH12015501174A1 (en) 2015-08-10

Similar Documents

Publication Publication Date Title
TWI509111B (en) Surface treatment of electrolytic copper foil, laminated board, and printed wiring board, electronic equipment
JP6193534B2 (en) Roughening copper foil, copper clad laminate and printed wiring board
JP5634103B2 (en) A treated copper foil for a copper clad laminate, a copper clad laminate obtained by bonding the treated copper foil to an insulating resin substrate, and a printed wiring board using the copper clad laminate.
KR101803165B1 (en) Copper foil with carrier, printed circuit board, copper clad laminated sheet, electronic device, and printed circuit board fabrication method
KR20060041689A (en) Surface treatment copper foil and circuit board
WO2007105635A1 (en) Surface treated elctrolytic copper foil and process for producing the same
TW201800242A (en) Surface-treated copper foil and copper-clad laminate produced using same
CN104271813A (en) Surface-treated copper foil and laminate using same, copper foil, printed wiring board, electronic device, and process for producing printed wiring board
KR20160034915A (en) Surface-treated copper foil, copper foil with carrier, substrate, resin substrate, printed circuit board, copper-clad laminate, and method for manufacturing printed circuit board
TW202020233A (en) Surface-treated copper foil, carrier-attached copper foil, copper-clad laminate, and printed wiring board
KR101695236B1 (en) Copper foil, electric component and battery comprising the foil
JP2010180454A (en) Surface-treated copper foil, method for manufacturing the same and copper-clad laminate
JPH09217193A (en) Non-cyanide brass plating bath mixture, production of metallic foil having brass layer and method for using non-cyanide brass plating bath
CN105264123A (en) Copper foil, copper foil with carrier, copper-clad laminate, printed circuit board, circuit forming substrate for semiconductor package, semiconductor package, electronic device, resin substrate, circuit forming method, semiadditive method, and printed circuit board manufacturing method
CN113795615B (en) Surface-treated copper foil, copper-clad laminate, and printed circuit board
KR20090084517A (en) Copper foil for printed circuit improved in thermal resistance and chemical resistance property and fabrication method thereof
JP6353193B2 (en) Copper foil with carrier, method for producing a copper-clad laminate using the copper foil with carrier, method for producing a printed wiring board using the copper foil with carrier, and method for producing a printed wiring board
JP2020183565A (en) Electrolytic copper foil, surface-treated copper foil using electrolytic copper foil, copper-clad laminate using surface-treated copper foil, and printed circuit board
TWI805902B (en) Surface treated copper foil, copper clad laminate and printed circuit board
JP2014208481A (en) Copper foil with a carrier, printed wiring board, copper-clad laminate, electronic apparatus and method for producing printed wiring board
CN112004964B (en) Surface-treated copper foil, copper-clad plate and printed circuit board
JP2014208480A (en) Copper foil with a carrier, printed wiring board, printed circuit board, copper-clad laminate and method for producing printed wiring board
TWI808700B (en) Coarse treatment of copper foil, copper foil laminates and printed wiring boards
WO2022255422A1 (en) Roughened copper foil, copper-clad laminate board, and printed circuit board
JP2014208482A (en) Copper foil with a carrier, printed wiring board, copper-clad laminate, electronic apparatus and method for producing printed wiring board