TWI749123B - Surface treatment copper foil and copper clad laminate - Google Patents

Surface treatment copper foil and copper clad laminate Download PDF

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TWI749123B
TWI749123B TW106143933A TW106143933A TWI749123B TW I749123 B TWI749123 B TW I749123B TW 106143933 A TW106143933 A TW 106143933A TW 106143933 A TW106143933 A TW 106143933A TW I749123 B TWI749123 B TW I749123B
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copper foil
layer
treatment layer
silane coupling
treated copper
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TW201839178A (en
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篠崎健作
奧野裕子
宇野岳夫
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日商古河電氣工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • 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
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern

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

Abstract

本發明係一種表面處理銅箔，其係於銅箔之至少單面，以前述銅箔為基準而依序積層有粗化處理層、防銹處理層及矽烷偶合層的表面處理銅箔，且作為自前述矽烷偶合層之表面測定的三維表面性狀之複合參數的界面之展開面積率Sdr之值為8~140%之範圍。The present invention is a surface-treated copper foil, which is on at least one side of the copper foil, and the surface-treated copper foil is laminated with a roughening treatment layer, an anti-rust treatment layer and a silane coupling layer in this order based on the aforementioned copper foil, and The value of the spread area ratio Sdr of the interface, which is a composite parameter of the three-dimensional surface properties measured from the surface of the aforementioned silane coupling layer, is in the range of 8 to 140%.

Description

表面處理銅箔及覆銅積層板Surface treatment copper foil and copper clad laminate

本發明係關於一種表面處理銅箔及覆銅積層板，尤其係關於一種適合用作構成印刷配線板之構件的表面處理銅箔及覆銅積層板，其中上述印刷配線板在超過幾千兆赫(GHz)之高頻帶使用時，高頻電氣訊號之傳輸損耗少，且具有優異之回焊耐熱性。The present invention relates to a surface-treated copper foil and a copper-clad laminate board, and more particularly to a surface-treated copper foil and a copper-clad laminate board suitable for use as a component constituting a printed wiring board, wherein the printed wiring board is above several gigahertz ( When used in the high frequency band of GHz), the transmission loss of high-frequency electrical signals is small, and it has excellent reflow heat resistance.

由於雲端服務(cloud service)之增加、通訊設備之發達等，資料之通訊量不斷增加。伴隨於此，為了提高通訊速度，作為路由器(router)、伺服器、行動電話之基地台之天線等設備，近年來正在開發應對超過20 GHz之高頻者。關於該等應對高頻之設備之印刷配線板，就高頻傳輸之觀點而言，使用具有低介電常數及低介電損耗正切之材料特性的改質聚苯醚樹脂或液晶聚合物等樹脂基材，另外，作為形成訊號流過之電路配線之材料，需求傳輸損耗較少之銅箔。Due to the increase of cloud services and the development of communication equipment, the amount of data communication continues to increase. Along with this, in order to increase the communication speed, devices such as routers, servers, and mobile phone base station antennas have been developed in recent years to cope with high frequencies exceeding 20 GHz. Regarding the printed wiring boards of such high-frequency equipment, from the viewpoint of high-frequency transmission, resins such as modified polyphenylene ether resins or liquid crystal polymers with material characteristics of low dielectric constant and low dielectric loss tangent are used The base material, in addition, as a material for forming the circuit wiring through which the signal flows, copper foil with less transmission loss is required.

於超過幾GHz之高頻帶下，電路配線中流動之電流因集膚效應而集中於導體表面，因此，為了提高與樹脂之密接性而使用單純增大了表面粗糙度之銅箔時，有銅箔表面之傳輸損耗增大之問題。為了減少傳輸損耗，通常想到的是以使用減小表面粗糙度之銅箔為佳。In the high frequency band exceeding a few GHz, the current flowing in the circuit wiring is concentrated on the surface of the conductor due to the skin effect. Therefore, in order to improve the adhesion to the resin and use the copper foil with a purely increased surface roughness, there is copper The problem of increased transmission loss on the foil surface. In order to reduce the transmission loss, it is usually better to use copper foil with reduced surface roughness.

對於高頻印刷配線板而言，伴隨高功能化而發展為多層化，大多情況下使用層數為30層以上之高多層印刷配線板。多層印刷配線板中，於熱負荷時容易產生層間之剝離現象。尤其是將電子零件安裝於印刷配線板之表面時進行的回流焊接步驟中，存在如下的傾向：印刷配線板於短時間內受到伴隨急遽溫度上升之高溫之熱負荷，因而樹脂中之水分或有機物一下子氣化而發生體積膨脹，由此容易發生起泡，結果產生層間剝離之不良的風險變高。因此，就可靠性之觀點而言，回流焊接時之密接性（以下稱為「回焊耐熱性」）良好受到重視。As for high-frequency printed wiring boards, multi-layers have been developed along with higher functionality. In most cases, high-multilayer printed wiring boards with more than 30 layers are used. In multilayer printed wiring boards, delamination between layers is prone to occur under thermal load. In particular, in the reflow soldering step performed when electronic parts are mounted on the surface of a printed wiring board, there is a tendency that the printed wiring board is exposed to a high temperature heat load accompanied by a rapid temperature rise in a short period of time, so moisture or organic matter in the resin It evaporates at once and expands in volume, so foaming is likely to occur, and as a result, the risk of defective interlayer peeling increases. Therefore, from the viewpoint of reliability, good adhesion during reflow soldering (hereinafter referred to as "reflow heat resistance") is valued.

作為用以提高銅箔對樹脂基材之剝落強度並且減少高頻帶之傳輸損耗的手段，例如，於專利文獻1中揭示有一種高頻印刷配線板用銅箔，其特徵在於：於銅箔之至少一個面具有由直徑為0.05~1.0 µm之球狀微細粗化粒子所構成之粗化處理層，且於前述粗化處理層上具有由鉬、鎳、鎢、磷、鈷、鍺中之至少一種以上所構成之耐熱-防銹層，並且於前述耐熱-防銹層上具有鉻酸鹽皮膜層，且於前述鉻酸鹽皮膜層上具有矽烷偶合劑層。另外，於專利文獻1中揭示：藉由減小形成於上述銅箔之粗化粒子，銅箔對樹脂基材之剝落強度較強，且銅箔之藉由蝕刻形成電路圖案後的電路底線(bottom line)之直線性較高，可減少傳輸損耗。然而，專利文獻1並未著眼於作為回流焊接時之密接性的回焊耐熱性，另外，關於具體之表面粗化形狀及集膚效應對傳輸特性降低之效果亦未作研究。As a means for improving the peeling strength of the copper foil to the resin substrate and reducing the transmission loss in the high frequency band, for example, Patent Document 1 discloses a copper foil for a high frequency printed wiring board, which is characterized by: At least one surface has a roughening treatment layer composed of spherical fine roughened particles with a diameter of 0.05~1.0 µm, and the roughening treatment layer has at least one of molybdenum, nickel, tungsten, phosphorus, cobalt, and germanium. A heat-resistant anti-rust layer composed of more than one type, and has a chromate film layer on the heat-resistant anti-rust layer, and a silane coupling agent layer on the chromate film layer. In addition, Patent Document 1 discloses that by reducing the roughening particles formed on the copper foil, the peeling strength of the copper foil to the resin substrate is stronger, and the circuit bottom line of the copper foil after the circuit pattern is formed by etching ( The bottom line) has high linearity, which can reduce transmission loss. However, Patent Document 1 does not focus on the reflow heat resistance as the adhesiveness during reflow soldering. In addition, it has not studied the effect of the specific surface roughening shape and the skin effect on the reduction of the transmission characteristics.

另外，於專利文獻2中揭示有一種表面處理銅箔，其特徵在於：與絕緣樹脂基材貼合之接著表面之表面粗糙度(Rzjis)為2.5 µm以下，且利用雷射法對二維表面積為6550 µm2 之區域進行測定時的三維表面積(A) µm2 與該二維表面積之比[(A)/(6550)]之值，即，表面積比(B)為1.2~2.5。另外，於專利文獻2中揭示：若使用該表面處理銅箔，則形成於印刷配線板之配線電路之邊緣可獲得良好之直線性，不僅與絕緣樹脂基材之密接性良好，耐化學品性、耐吸濕性等亦良好，關於GHz帶之高頻訊號之傳輸損耗或特性阻抗等，可實現接近設計值之電氣特性。然而，專利文獻2雖採用將表面粗糙度(Rzjis)及表面積比(B)分別限定於適當範圍之構成，但僅限定表面粗糙度及表面積比之情況下無法指定準確之表面性狀。例如，圖4(a)及圖4(b)中雖然概念性地示出了從幾何學上看表面積相同但具有不同表面粗糙度之兩個表面狀態，但由兩表面狀態之比較亦表明，山之高度或寬度之尺寸係兩者大不相同，難以視為傳輸特性或與樹脂之密接性相同。另外，專利文獻2並未著眼於回焊耐熱性，此外，關於具體之表面粗化形狀及集膚效應對傳輸特性降低之效果亦未作研究。In addition, Patent Document 2 discloses a surface-treated copper foil, which is characterized in that the surface roughness (Rzjis) of the bonding surface bonded to the insulating resin substrate is 2.5 µm or less, and the two-dimensional surface area is measured by the laser method. three-dimensional surface area (a) measured at an area of 6550 μm 2 μm 2 surface area of the two-dimensional ratio [(a) / (6550) ] of the value, i.e., the surface area ratio (B) is 1.2 to 2.5. In addition, Patent Document 2 discloses that if the surface-treated copper foil is used, the edge of the wiring circuit formed on the printed wiring board can obtain good linearity, not only has good adhesion with the insulating resin substrate, but also has chemical resistance. , Moisture resistance, etc. are also good. Regarding the transmission loss or characteristic impedance of high-frequency signals in the GHz band, electrical characteristics close to the design values can be achieved. However, although Patent Document 2 adopts a configuration in which the surface roughness (Rzjis) and the surface area ratio (B) are respectively limited to appropriate ranges, it is not possible to specify accurate surface properties when only the surface roughness and the surface area ratio are limited. For example, Figure 4(a) and Figure 4(b) conceptually show two surface states with the same surface area but different surface roughness from a geometrical point of view, but the comparison of the two surface states also shows that, The dimensions of the height or width of the mountain are very different, and it is difficult to be regarded as the same as the transmission characteristics or the adhesion with the resin. In addition, Patent Document 2 does not focus on the heat resistance of reflow, and has not studied the specific surface roughening shape and the effect of the skin effect on the reduction of transmission characteristics.

於專利文獻3中揭示有一種粗化處理銅箔，其於銅箔之表面具備使微細銅粒子析出形成之粗化處理面，且上述粗化處理銅箔之特徵在於：該粗化處理面包含頭頂部角度為85°以下之突起形狀之微細銅粒子。另外，於專利文獻3中揭示：該粗化處理銅箔對液晶聚合物、聚苯氧基樹脂(polyphenylene oxide resin, PPO)、聚苯醚樹脂(polyphenylene ether resin, PPE)、環烯烴聚合物(COP)等高耐熱性及高頻特性優異之樹脂具有充分之密接性，而且可降低傳輸特性。然而，專利文獻3僅規定構成粗化處理面之微細銅粒子之頭頂部角度，關於頭頂部以外之形狀未作任何限定。另外，專利文獻3雖然使用L*a*b*表色系統之L*值、a*值及b*值附帶地間接定量粗化之形狀，但L*、a*、b*為色度之參數。因此，在因Ni或Co、Cr等而於銅箔表面形成有色電鍍皮膜之情形、或銅箔之表面發生氧化變色之情形時，對該等值大幅度地造成影響，因此，準確地把握並管理粗化處理之表面形狀於技術上非常困難。Patent Document 3 discloses a roughening treatment copper foil, which has a roughening treatment surface formed by precipitating fine copper particles on the surface of the copper foil, and the roughening treatment copper foil is characterized in that the roughening treatment surface includes Fine copper particles in the shape of protrusions with a head angle of 85° or less. In addition, Patent Document 3 discloses that the roughening treatment of copper foil is effective for liquid crystal polymer, polyphenylene oxide resin (PPO), polyphenylene ether resin (PPE), cycloolefin polymer ( COP) and other resins with high heat resistance and excellent high frequency characteristics have sufficient adhesion and can reduce transmission characteristics. However, Patent Document 3 only specifies the angle of the crown of the fine copper particles constituting the roughened surface, and does not impose any limitation on the shape other than the crown. In addition, although Patent Document 3 uses the L* value, a* value, and b* value of the L*a*b* color system to indirectly quantitatively roughen the shape, but L*, a*, and b* are the chromaticity parameter. Therefore, when a colored electroplated film is formed on the surface of copper foil due to Ni, Co, Cr, etc., or when the surface of the copper foil is oxidized and discolored, it will greatly affect these values. Therefore, it is necessary to accurately grasp and It is technically very difficult to manage the surface shape of the roughening treatment.

另外，專利文獻4揭示有一種表面處理銅箔，其係於至少一個表面形成有表面處理層，並且前述表面處理層包含粗化處理層，前述表面處理層中之Co、Ni、Fe之合計附著量為300 µg/dm2 以下，前述表面處理層具有Zn金屬層或含有Zn之合金處理層，前述表面處理層表面之藉由雷射顯微鏡所測定之三維表面積相對於二維表面積之比為1.0~1.9，且至少一個表面之表面粗糙度Rzjis為2.2 µm以下。另外，於專利文獻4中揭示：該表面處理銅箔中，將表面處理層中之於常溫下顯示強磁性之金屬(Co、Ni、Fe)之合計附著量控制為預定量以下，且含有於常溫下不顯示強磁性之Zn，藉此減少高頻傳輸損耗，並且將表面粗糙度Rz及更準確地表示與樹脂（介電質）之接觸面積的二維表面積相對於三維表面積之比控制於適當範圍，藉此可改善傳輸特性。然而，專利文獻4中，如上述般藉由表面積比及Rz來指定表面處理銅箔之表面形狀或特性非常困難，無法明確定義對傳輸特性造成顯著影響之表面。另外，通常於製作印刷配線板之步驟中，需要用以形成電路之蝕刻步驟或回流焊接之步驟，從而要求耐化學品性、回焊耐熱性等。另一方面，如專利文獻4所記載之表面處理銅箔般，採用藉由減少表面處理層中之強磁性金屬而改善傳輸特性的構成時，含有Zn之表面處理層於蝕刻所使用之氯化銅、氯化鐵、硫酸-過氧化氫水等蝕刻液中容易溶解。因此，於蝕刻時容易產生過蝕刻，電路之直線性較差，最差之情形是有可能於製作電路圖案後，從樹脂剝離。另外，因進行加熱而使Zn容易擴散於Cu層中，因此，於後述之回焊耐熱試驗中，在銅-樹脂間容易發生剝離不良。即，傳輸特性優異，但容易產生印刷配線板之製造步驟中之不良狀況，亦有工業上無法穩定地製造之問題。 [先行技術文獻] [專利文獻]In addition, Patent Document 4 discloses a surface-treated copper foil in which a surface-treated layer is formed on at least one surface, the surface-treated layer includes a roughened layer, and the total amount of Co, Ni, and Fe in the surface-treated layer is adhered The amount is 300 µg/dm 2 or less, the surface treatment layer has a Zn metal layer or an alloy treatment layer containing Zn, and the ratio of the three-dimensional surface area to the two-dimensional surface area measured by a laser microscope on the surface of the surface treatment layer is 1.0 ~1.9, and the surface roughness Rzjis of at least one surface is below 2.2 µm. In addition, Patent Document 4 discloses that in the surface-treated copper foil, the total adhesion amount of the metal (Co, Ni, Fe) exhibiting ferromagnetism at room temperature in the surface-treated layer is controlled to a predetermined amount or less, and is contained in Zn, which does not exhibit ferromagnetism at room temperature, reduces high-frequency transmission loss, and controls the surface roughness Rz and the ratio of the two-dimensional surface area to the three-dimensional surface area that more accurately represents the contact area with the resin (dielectric) The proper range can improve the transmission characteristics. However, in Patent Document 4, it is very difficult to specify the surface shape or characteristics of the surface-treated copper foil by the surface area ratio and Rz as described above, and it is impossible to clearly define the surface that significantly affects the transmission characteristics. In addition, usually in the steps of making printed wiring boards, an etching step or a reflow soldering step for forming a circuit is required, which requires chemical resistance, reflow heat resistance, and the like. On the other hand, as in the surface-treated copper foil described in Patent Document 4, when the transmission characteristics are improved by reducing the ferromagnetic metal in the surface-treated layer, the surface-treated layer containing Zn is used in the chlorination of etching. Copper, ferric chloride, sulfuric acid-hydrogen peroxide water and other etching solutions are easily dissolved. Therefore, over-etching is likely to occur during etching, and the linearity of the circuit is poor. In the worst case, it may be peeled off from the resin after the circuit pattern is made. In addition, Zn is easily diffused in the Cu layer due to heating. Therefore, in the reflow heat resistance test described later, peeling failures easily occur between the copper and the resin. That is, the transmission characteristics are excellent, but defects in the manufacturing steps of the printed wiring board are prone to occur, and there is also a problem that it cannot be manufactured stably in the industry. [Prior technical literature] [Patent literature]

專利文獻1：日本專利特開2006-210689號公報 專利文獻2：日本專利特開2008-285751號公報 專利文獻3：日本專利特開2010-236058號公報 專利文獻4：日本專利特開2015-105440號公報Patent Document 1: Japanese Patent Laid-Open No. 2006-210689 Patent Document 2: Japanese Patent Laid-Open No. 2008-285751 Patent Document 3: Japanese Patent Laid-Open No. 2010-236058 Patent Document 4: Japanese Patent Laid-Open No. 2015-105440 Bulletin

[發明欲解決之課題][The problem to be solved by the invention]

如上所述，作為傳輸損耗較少之高頻印刷配線板用之銅箔，通常需求具有表面粗糙度較小之表面形狀之銅箔，但若銅箔變得平滑，則會產生與樹脂之密接性降低、回焊耐熱性降低等問題。另外，為了提高與樹脂之密接性，用矽烷偶合劑對銅箔表面進行處理，而提高與樹脂基材之化學密接力，但為了提高矽烷偶合劑與樹脂基材之化學密接性，需要使樹脂以某種程度具有極性大之取代基。As mentioned above, as a copper foil for high-frequency printed wiring boards with less transmission loss, copper foil with a surface shape with a smaller surface roughness is usually required. However, if the copper foil becomes smooth, it will adhere to the resin. Problems such as reduced performance and reduced heat resistance of reflow. In addition, in order to improve the adhesion to the resin, the surface of the copper foil is treated with a silane coupling agent to improve the chemical adhesion with the resin substrate. However, in order to improve the chemical adhesion between the silane coupling agent and the resin substrate, it is necessary to make the resin To a certain extent, it has a very polar substituent.

然而，介電常數或介電損耗正切較低之樹脂不具有極性大之取代基，或者，即便具有極性大之取代基，其含量亦少，因此與矽烷偶合劑之化學密接力降低，難以確保銅箔與樹脂基材之充分密接性。另一方面，若為了提高密接性或回焊耐熱性而增大銅箔之表面粗糙度，則會產生傳輸特性降低之問題。高頻基板中，需要兼具此種處於取捨(trade-off)關係之特性之銅箔，亦即，具有充分之密接強度及回焊耐熱性，並且傳輸特性亦優異之銅箔。However, resins with a low dielectric constant or dielectric loss tangent do not have a substituent with a large polarity, or even with a substituent with a large polarity, its content is small, so the chemical adhesion with the silane coupling agent is reduced, and it is difficult to ensure Adequate adhesion between copper foil and resin substrate. On the other hand, if the surface roughness of the copper foil is increased in order to improve adhesion or reflow heat resistance, the problem of reduced transmission characteristics will occur. High-frequency substrates require copper foils that have such trade-off characteristics, that is, copper foils that have sufficient adhesion strength and reflow heat resistance, and excellent transmission characteristics.

如上所述，當用作，例如，在超過幾GHz之高頻帶使用的高頻印刷配線板用之銅箔時，專利文獻1~4所記載之表面處理銅箔的任一者均難以提供以較高水準充分滿足傳輸特性與回焊耐熱性兩者之印刷配線板，需要表面處理銅箔之表面性狀等之進一步改善。As described above, when used as, for example, copper foil for high-frequency printed wiring boards used in high frequency bands exceeding several GHz, it is difficult to provide any of the surface-treated copper foils described in Patent Documents 1 to 4 A higher level of printed wiring boards that fully meets both transmission characteristics and reflow heat resistance requires further improvement of the surface properties of the surface-treated copper foil.

本發明之目的在於提供一種表面處理銅箔及覆銅積層板，上述表面處理銅箔即便用作，例如，在超過幾GHz之高頻帶使用的高頻印刷配線板用之銅箔，亦可製造高頻電氣訊號之傳輸損耗少，且具有優異之回焊耐熱性的印刷配線板。 [解決問題之技術手段]The object of the present invention is to provide a surface-treated copper foil and a copper-clad laminate. The surface-treated copper foil can be manufactured even if it is used as, for example, copper foil for high-frequency printed wiring boards used in high frequency bands exceeding several GHz. A printed wiring board with low transmission loss of high-frequency electrical signals and excellent reflow heat resistance. [Technical means to solve the problem]

本發明者等人針對具備優異之回焊耐熱性並且減少傳輸損耗的表面處理銅箔之表面形狀，利用與先前不同之方法來控制粗化處理層之表面性狀，藉此，即便用作，例如，在超過幾GHz之高頻帶使用的高頻印刷配線板用之銅箔，亦成功地提供以較高水準充分滿足傳輸特性與回焊耐熱性兩者的印刷配線板。具體而言，獲得了以下見解：為了適當地控制粗化處理層之表面性狀，藉由使用光干涉式顯微鏡嚴密地控制粗化處理層之表面性狀，並規定與先前之表面性狀之適當化不同的新穎的三維表面性狀之複合參數，可穩定地提供可表現出優異特性之表面處理銅箔。The inventors of the present invention aimed at the surface shape of surface-treated copper foil with excellent reflow heat resistance and reduced transmission loss, and used a method different from the previous method to control the surface shape of the roughened layer, thereby, even if used as, for example, , Copper foil for high-frequency printed wiring boards used in high frequency bands exceeding a few GHz has also successfully provided printed wiring boards that fully satisfy both transmission characteristics and reflow heat resistance at a high level. Specifically, the following knowledge was obtained: In order to appropriately control the surface properties of the roughened layer, the surface properties of the roughened layer were strictly controlled by using an optical interference microscope, and the appropriateness of the surface properties was different from the previous one. The complex parameters of the novel three-dimensional surface properties can stably provide surface-treated copper foils that exhibit excellent characteristics.

即，本發明的主要構成如下所示。 (1) 一種表面處理銅箔，其係於銅箔之至少單面，以前述銅箔為基準而依序積層有粗化處理層、防銹處理層及矽烷偶合層的表面處理銅箔，其特徵在於：作為自前述矽烷偶合層之表面測定的三維表面性狀之複合參數的界面之展開面積率Sdr之值為8~140%之範圍。 (2) 如上述(1)所記載之表面處理銅箔，其特徵在於：作為自前述矽烷偶合層之表面測定的三維表面性狀之複合參數的均方根表面梯度Sdq之值為25~70°之範圍。 (3) 如上述(1)或(2)所記載之表面處理銅箔，其中作為自前述矽烷偶合層之表面測定的三維表面性狀之空間參數的表面性狀之縱橫比Str之值為0.25~1。 (4) 如上述(1)至(3)中任一項所記載之表面處理銅箔，其特徵在於：自前述矽烷偶合層之表面測定的十點平均粗糙度Rzjis為0.9~1.5 µm之範圍。 (5) 如上述(1)至(4)中任一項所記載之表面處理銅箔，其特徵在於：前述粗化處理層及前述防銹處理層中的銅以外之金屬及該金屬之氧化物之合計含量換算成金屬元素而為0.15~0.50 mg/dm2 。 (6) 如上述(1)至(5)中任一項所記載之表面處理銅箔，其特徵在於：前述粗化處理層及前述防銹處理層中之Ni及Zn之含量分別為0.05~0.30 mg/dm2 。 (7) 如上述(1)至(6)中任一項所記載之表面處理銅箔，其特徵在於：前述銅箔為電解銅箔，僅於該電解銅箔之M面具有前述粗化處理層。 (8) 一種覆銅積層板，其特徵在於：具有如上述(1)至(7)中任一項所記載之表面處理銅箔、及積層於該表面處理銅箔之前述矽烷偶合層上的樹脂，該樹脂在頻率10 GHz下之介電常數為3.5以下且介電損耗正切為0.006以下。 [發明效果]That is, the main structure of the present invention is as follows. (1) A surface-treated copper foil, which is on at least one side of the copper foil, and the surface-treated copper foil is laminated with a roughening treatment layer, an anti-rust treatment layer, and a silane coupling layer in sequence based on the aforementioned copper foil, and It is characterized in that the value of the spread area ratio Sdr of the interface, which is a composite parameter of the three-dimensional surface properties measured from the surface of the aforementioned silane coupling layer, is in the range of 8 to 140%. (2) The surface-treated copper foil as described in (1) above, characterized in that the root mean square surface gradient Sdq, which is a composite parameter of the three-dimensional surface properties measured from the surface of the aforementioned silane coupling layer, has a value of 25 to 70° The scope. (3) The surface-treated copper foil as described in (1) or (2) above, wherein the value of the aspect ratio Str of the surface texture as the spatial parameter of the three-dimensional surface texture measured from the surface of the aforementioned silane coupling layer is 0.25~1 . (4) The surface-treated copper foil described in any one of (1) to (3) above, characterized in that: the ten-point average roughness Rzjis measured from the surface of the aforementioned silane coupling layer is in the range of 0.9 to 1.5 µm . (5) The surface-treated copper foil described in any one of (1) to (4) above, characterized in that the metal other than copper in the roughening treatment layer and the anti-rust treatment layer and the oxidation of the metal The total content of substances is 0.15~0.50 mg/dm 2 in terms of metal elements. (6) The surface-treated copper foil as described in any one of (1) to (5) above, characterized in that the contents of Ni and Zn in the roughening treatment layer and the antirust treatment layer are 0.05~ 0.30 mg/dm 2 . (7) The surface-treated copper foil described in any one of (1) to (6) above, characterized in that: the copper foil is an electrolytic copper foil, and only the M surface of the electrolytic copper foil has the roughening treatment Floor. (8) A copper-clad laminate, characterized by having the surface-treated copper foil described in any one of (1) to (7) above, and the silane coupling layer laminated on the surface-treated copper foil Resin, which has a dielectric constant of 3.5 or less and a dielectric loss tangent of 0.006 or less at a frequency of 10 GHz. [Effects of the invention]

根據本發明，提供一種表面處理銅箔及覆銅積層板，其中上述表面處理銅箔係一種於銅箔之至少單面以前述銅箔為基準而依序積層有粗化處理層、防銹處理層及矽烷偶合層之表面處理銅箔，藉由作為自前述矽烷偶合層之表面測定的三維表面性狀之複合參數的界面之展開面積率Sdr之值為8~140%之範圍，可穩定地製造具有藉由表面積或表面粗糙度等先前使用之指標（參數）難以控制的表面粗化形狀之表面處理銅箔，上述表面處理銅箔即便用作，例如，載超過幾GHz之高頻帶使用的高頻印刷配線板用之銅箔，亦可製造高頻電氣訊號之傳輸損耗少，且具有優異之回焊耐熱性的印刷配線板。另外，藉由使用三維光干涉式顯微鏡，可適當控制表面處理銅箔之表面的凹凸之尖銳程度（表面梯度）、展開面積等等。According to the present invention, there is provided a surface-treated copper foil and a copper-clad laminate, wherein the above-mentioned surface-treated copper foil is a type of copper foil having a roughening treatment layer and an anti-rust treatment layer sequentially laminated on at least one side of the copper foil based on the aforementioned copper foil The surface treatment copper foil of the silane coupling layer and the silane coupling layer can be manufactured stably by using the spread area ratio Sdr of the interface as the composite parameter of the three-dimensional surface properties measured from the surface of the silane coupling layer to be in the range of 8~140% Surface-treated copper foil with a roughened surface shape that is difficult to control by previously used indicators (parameters) such as surface area or surface roughness. Copper foil for high-frequency printed wiring boards can also be used to produce printed wiring boards with low transmission loss of high-frequency electrical signals and excellent reflow heat resistance. In addition, by using a three-dimensional light interference microscope, it is possible to appropriately control the sharpness (surface gradient), the development area, etc. of the unevenness of the surface of the surface-treated copper foil.

接著，以下對本發明之實施形態加以詳細說明。本發明之表面處理銅箔係於銅箔之至少單面，以銅箔為基準而依序積層有粗化處理層、防銹處理層及矽烷偶合層。即，於銅箔之至少單面形成有粗化處理層，於該粗化處理層上形成有防銹處理層，於該防銹處理層上形成有矽烷偶合層。另外，作為相當於此種積層構造之最外層的矽烷偶合層之表面性狀，將作為自矽烷偶合層之表面測定的三維表面性狀之複合參數的界面之展開面積率Sdr之值控制為8~140%之範圍。Next, the embodiments of the present invention will be described in detail below. The surface-treated copper foil of the present invention is on at least one side of the copper foil, and a roughening treatment layer, an anti-rust treatment layer and a silane coupling layer are sequentially laminated based on the copper foil. That is, a roughening treatment layer is formed on at least one side of the copper foil, an antirust treatment layer is formed on the roughening treatment layer, and a silane coupling layer is formed on the antirust treatment layer. In addition, as the surface properties of the silane coupling layer corresponding to the outermost layer of this layered structure, the value of the spread area ratio Sdr of the interface, which is a composite parameter of the three-dimensional surface properties measured from the surface of the silane coupling layer, is controlled to be 8~140 % Range.

於本發明之表面處理銅箔之表面性狀之分析時，可使用三維光干涉式顯微鏡。光之干涉為自對象物表面至某個點的光之距離（光路）產生差異時產生的現象。光干涉計是利用該現象而測量對象物表面之凹凸。作為三維光干涉式顯微鏡之特徵，可列舉：Z方向（高度方向）之解析度為0.1 nm左右而能以非常良好之靈敏度進行測定；即便改變測定倍率，Z方向之解析度亦不變化。另一方面，例如，先前以來廣泛地使用之共焦(confocal)方式之雷射顯微鏡係實施X、Y方向之雙軸掃描，故Z方向之解析度大至10 nm~300 nm，不適於辨識表面處理銅箔之非常微細之表面性狀。另外，該共焦方式中，Z方向之解析度視測定倍率而大幅度地變化，故不適於定量地表現粗化形狀。In the analysis of the surface properties of the surface-treated copper foil of the present invention, a three-dimensional light interference microscope can be used. Light interference is a phenomenon that occurs when there is a difference in the distance (optical path) of light from the surface of the object to a certain point. The optical interferometer uses this phenomenon to measure the unevenness of the surface of the object. As a characteristic of the three-dimensional light interference microscope, the resolution in the Z direction (height direction) is about 0.1 nm, which can be measured with very good sensitivity; even if the measurement magnification is changed, the resolution in the Z direction does not change. On the other hand, for example, the confocal laser microscope, which has been widely used before, implements biaxial scanning in the X and Y directions, so the resolution in the Z direction is as large as 10 nm~300 nm, which is not suitable for identification Surface treatment copper foil has very fine surface properties. In addition, in this confocal method, the resolution in the Z direction greatly changes depending on the measurement magnification, so it is not suitable for quantitatively expressing the roughened shape.

因此，本發明者等人為了獲得傳輸損耗少，且回焊耐熱性良好之銅箔，使用三維光干涉式顯微鏡進行了研究。其結果為，藉由嚴密地控制作為自矽烷偶合層之表面測定的三維表面性狀之複合參數的界面之展開面積率Sdr之值，可獲得傳輸損耗少，且回焊耐熱性亦良好之表面處理銅箔。Therefore, the inventors of the present invention conducted studies using a three-dimensional light interference microscope in order to obtain a copper foil with low transmission loss and good reflow heat resistance. As a result, by strictly controlling the value of the spread area ratio Sdr as a composite parameter of the three-dimensional surface properties measured from the surface of the silane coupling layer, a surface treatment with less transmission loss and good reflow heat resistance can be obtained. Copper foil.

Sdr表示粗化處理層之界面（表面）之展開面積率。再者，本發明中，Sdr之值是自作為表面處理銅箔之最表層的矽烷偶合層之表面進行測定，但確認到，構成表面處理銅箔之粗化處理層之表面形狀，與在該粗化處理層上進一步積層形成防銹處理層及矽烷偶合層後的矽烷偶合層之表面形狀相比，幾乎未變化。因此，本發明中，將自矽烷偶合層之表面測定的Sdr之值與自粗化處理層之表面測定的Sdr之值視為相同，而加以規定。Sdr represents the spread area ratio of the interface (surface) of the roughened layer. Furthermore, in the present invention, the value of Sdr is measured from the surface of the silane coupling layer which is the outermost layer of the surface-treated copper foil. The roughening treatment layer is further laminated to form an anti-rust treatment layer and the surface shape of the silane coupling layer after the silane coupling layer is almost unchanged. Therefore, in the present invention, the value of Sdr measured from the surface of the silane coupling layer and the value of Sdr measured from the surface of the roughening treatment layer are regarded as the same and specified.

此處，Sdr表示界面之展開面積率，係由下式表示。 [數式1]

Figure 02_image001
Here, Sdr represents the spread area ratio of the interface, which is expressed by the following formula. [Numerical formula 1]
Figure 02_image001

Sdr之特徵為可區分具有類似算術平均高度Sa之表面之形狀。算術平均高度Sa表示各點相對於表面之平均面的高度差之絕對值之平均值，故雖然適於判斷凹凸之平均高度之資訊，但無法判斷表面形狀之凹凸之複雜性。The characteristic of Sdr is that the shape of the surface with similar arithmetic mean height Sa can be distinguished. The arithmetic average height Sa represents the average value of the absolute value of the height difference of each point with respect to the average surface of the surface. Therefore, although it is suitable for judging the information of the average height of the concavity and convexity, it cannot judge the complexity of the concavity and convexity of the surface shape.

相對於此，Sdr之值受到表面形狀之凹凸之振幅與間隔兩者之影響，振幅愈大且間隔愈窄，則顯示愈高的值。通常，Sdr較低時，大多情況下Sa較低，於Sdr較大時，則有Sa增大之傾向，但Sa為表示高度之參數，因此不依存於凹凸之振幅或間隔。即，Sdr能辨識無法利用Sa表示的表面形狀之凹凸之複雜性。於Sdr之值較小時，具有接***坦之表面形狀，相對於此，若Sdr之值變大，則具有凹凸較多之表面形狀。In contrast, the value of Sdr is affected by both the amplitude and the interval of the unevenness of the surface shape. The larger the amplitude and the narrower the interval, the higher the value is displayed. Generally, when Sdr is low, Sa is usually low in most cases, and when Sdr is large, Sa tends to increase. However, Sa is a parameter representing height and therefore does not depend on the amplitude or interval of unevenness. That is, Sdr can recognize the complexity of the unevenness of the surface shape that cannot be represented by Sa. When the value of Sdr is small, it has a surface shape that is close to flat. On the other hand, when the value of Sdr is large, it has a surface shape with more unevenness.

本發明者等人嘗試製作了Sdr之值不同的多個表面處理銅箔，並針對與傳輸特性及回焊耐熱性之關係進行了潛心研究，藉由將Sdr之值限定於8~140%之範圍，而適當控制存在於粗化處理層之表面的粗化粒子之凹凸之複雜性，其結果為，傳輸特性及回焊耐熱性均優異。若Sdr之值小於8%，則可觀察到回焊耐熱性降低之傾向。推定其原因在於：粗化粒子之間隔較寬或不均勻地成長，因此與樹脂之密接不充分。另一方面，若Sdr之值大於140%，則可觀察到傳輸特性降低之傾向。推定其原因在於：因Sdr變大而粗化粒子之凹凸變大，傳輸損耗增大。再者，Sdr之值，以20~120%之範圍為佳，以40~100%之範圍為更佳。The inventors tried to produce multiple surface-treated copper foils with different values of Sdr, and conducted painstaking research on the relationship between transmission characteristics and reflow heat resistance. By limiting the value of Sdr to between 8 and 140% Range, and the complexity of the unevenness of the roughened particles existing on the surface of the roughened layer is appropriately controlled. As a result, the transmission characteristics and reflow heat resistance are excellent. If the value of Sdr is less than 8%, a tendency to reduce the heat resistance of reflow can be observed. It is presumed that the reason for this is that the distance between the roughened particles is wide or grows unevenly, and therefore the adhesion with the resin is insufficient. On the other hand, if the value of Sdr is greater than 140%, a tendency to decrease the transmission characteristics can be observed. It is presumed that the reason for this is that as the Sdr becomes larger, the unevenness of the roughened particles becomes larger, and the transmission loss increases. Furthermore, the value of Sdr is preferably in the range of 20 to 120%, and more preferably in the range of 40 to 100%.

再者，藉由控制粗化處理層之表面之展開面積率，而使傳輸特性及回焊耐熱性均變良好之原因雖不確定，但可認為，尤其是在電流因集膚效應而集中於導體表面之高頻帶中，有如下傾向：因為在粗化處理層之整個表面流動之電流變多，所以隨著展開面積率變高而傳輸損耗增加。此外，若粗化粒子成為微細至某種程度之表面形狀，則表面處理銅箔之粗化處理面之粗化粒子與樹脂基材之表面的物理密接力（錨固效應）有降低之傾向，但藉由使粗化粒子彼此之間隙變窄或使粗化粒子之高度不均勻，粗化粒子與樹脂基材之界面的密接性提高。其結果為，可認為於回流焊接時之加熱時不易發生起泡，而回焊耐熱性提升。Furthermore, the reason why the transmission characteristics and reflow heat resistance are improved by controlling the surface area ratio of the roughening treatment layer is uncertain, but it can be considered that, especially when the current is concentrated due to the skin effect In the high frequency band on the surface of the conductor, there is a tendency that the current flowing through the entire surface of the roughened layer increases, so as the spread area ratio becomes higher, the transmission loss increases. In addition, if the roughened particles become fine to a certain degree of surface shape, the physical adhesion (anchor effect) between the roughened particles on the roughened surface of the surface-treated copper foil and the surface of the resin substrate tends to decrease, but By narrowing the gap between the roughened particles or making the height of the roughened particles non-uniform, the adhesion of the interface between the roughened particles and the resin substrate is improved. As a result, it is considered that blistering is less likely to occur during heating during reflow soldering, and the reflow heat resistance is improved.

接著，對粗化處理層之表面之展開面積率對回焊耐熱性造成之影響加以說明。 對於藉由熱壓等方法將表面處理銅箔與樹脂基材貼合而成之覆銅積層板而言，於表面處理銅箔之粗化處理層與樹脂基材之界面，因熱壓時出現之缺陷等而存在微細之空隙（下文中，將此種空隙稱為「龜裂」）。若覆銅積層板於回流焊接時受到加熱，則樹脂基材中之低分子量之成分以氣體之形式揮發，蓄積於龜裂而產生膨脹力。此時，在展開面積率較低之情形，可認為：於鄰接之粗化粒子之間龜裂容易連結而擴展，龜裂逐漸傳播，因此發生界面之連續剝離而發生起泡。另一方面，若展開面積率高至某種程度，則粗化粒子與樹脂基材之接觸面積變大，作用於粗化處理層與樹脂基材之間的摩擦力增大。因此，可認為：相較於樹脂基材中之低分子量之成分以氣體之形式揮發時蓄積於龜裂而產生的膨脹力，作用於粗化處理層與樹脂基材之間的摩擦力更大，藉此發揮抑制龜裂之傳播的效果。其結果，可推測：龜裂之傳播不易進行，粗化處理層與樹脂基材之界面的連續剝離受到抑制，而不易發生起泡。Next, the influence of the spread area ratio of the surface of the roughened layer on the heat resistance of reflow will be explained. For the copper-clad laminated board formed by bonding the surface-treated copper foil and the resin substrate by hot pressing, the interface between the roughened layer of the surface-treated copper foil and the resin substrate appears due to the hot pressing There are fine voids such as defects (hereinafter, such voids are referred to as "cracks"). If the copper-clad laminate is heated during reflow soldering, the low-molecular-weight components in the resin base material volatilize in the form of gas and accumulate in the cracks to generate expansion force. At this time, when the spread area ratio is low, it can be considered that the cracks between adjacent coarse particles are easily connected and spread, and the cracks gradually propagate, so continuous peeling of the interface occurs and blistering occurs. On the other hand, if the spread area ratio is high to a certain level, the contact area between the roughened particles and the resin substrate increases, and the frictional force acting between the roughened layer and the resin substrate increases. Therefore, it can be considered that the frictional force acting between the roughening treatment layer and the resin substrate is greater than the expansion force generated by the cracks when the low molecular weight components in the resin substrate volatilize in the form of gas. , Thereby exerting the effect of restraining the propagation of cracks. As a result, it can be presumed that the propagation of cracks is not easy to proceed, the continuous peeling of the interface between the roughening treatment layer and the resin base material is suppressed, and blistering is unlikely to occur.

另外，本發明中，作為自矽烷偶合層之表面測定的三維表面性狀之複合參數的均方根表面梯度Sdq之值，以為25~70°之範圍為佳。另外，於本發明中確認到，Sdq之值亦與Sdr之值同樣地，構成表面處理銅箔的粗化處理層之表面形狀，與在該粗化處理層上進一步積層形成防銹處理層及矽烷偶合層後的矽烷偶合層之表面形狀相比，幾乎未變化。因此，關於Sdq，亦將自矽烷偶合層之表面測定的Sdq之值與自粗化處理層之表面測定的Sdq之值視為相同，而加以規定。In addition, in the present invention, the value of the root mean square surface gradient Sdq, which is the composite parameter of the three-dimensional surface properties measured from the surface of the silane coupling layer, is preferably in the range of 25 to 70°. In addition, it was confirmed in the present invention that the value of Sdq is also the same as the value of Sdr, and the surface shape of the roughened layer constituting the surface-treated copper foil is further laminated on the roughened layer to form an antirust treatment layer and Compared with the surface shape of the silane coupling layer after the silane coupling layer, there is almost no change. Therefore, regarding Sdq, the value of Sdq measured from the surface of the silane coupling layer and the value of Sdq measured from the surface of the roughening treatment layer are also regarded as the same and specified.

所謂Sdq，係指粗化處理層之表面梯度（斜率），具體而言，是在以所有方向進行評價之表面構成的均方根（rms）表面梯度，且為下式所表示之值。

Figure 02_image003
再者，式中之x、y為平面坐標，Z為高度方向之坐標。Z(x，y)表示某點之坐標，藉由將其進行微分而成為在該坐標之斜率。上式係將所有點（A個）之x方向斜率與y方向斜率之平方相加並求平方根而得。The so-called Sdq refers to the surface gradient (slope) of the roughened layer. Specifically, it is the root mean square (rms) surface gradient of the surface evaluated in all directions, and is the value represented by the following formula.
Figure 02_image003
Furthermore, the x and y in the formula are plane coordinates, and Z is the height coordinate. Z(x, y) represents the coordinate of a certain point, and it becomes the slope at that coordinate by differentiating it. The above formula is obtained by adding the square root of the slope in the x direction and the slope in the y direction of all points (A points).

Sdq之特徵為可區分具有類似算術平均高度Sa之表面之形狀。算術平均高度Sa表示各點相對於表面之平均面的高度差之絕對值之平均值，故雖然適於判斷凹凸之平均高度之資訊，但無法判斷表面形狀之尖銳程度（傾斜）。The characteristic of Sdq is that the shape of the surface with similar arithmetic mean height Sa can be distinguished. The arithmetic average height Sa represents the average value of the absolute value of the height difference of each point relative to the average surface of the surface, so although it is suitable for judging the information of the average height of the unevenness, it cannot judge the sharpness (tilt) of the surface shape.

相對於此，Sdq之值受到表面形狀之振幅與間隔兩者之影響。Sdq之值較小時，具有平緩之表面形狀，相對於此，若Sdq變大，則具有尖銳之表面形狀。本發明者等人嘗試製作了Sdq之值不同的多個表面處理銅箔，並針對與傳輸特性及回焊耐熱性之關係進行了潛心研究，藉由將Sdq之值限定於25~70°之範圍，而更適當地控制存在於粗化處理層之表面的粗化粒子之尖銳程度，其結果為，可獲得傳輸特性及回焊耐熱性均良好之表面處理銅箔。若Sdq之值小於25°，則有傳輸特性降低之傾向，若Sdq之值超過70°，則有回焊耐熱性降低之傾向，故Sdq之值以控制於25~70°之範圍為佳，以30~65°之範圍為更佳，以40~60°之範圍為進一步更佳。In contrast, the value of Sdq is affected by both the amplitude and interval of the surface shape. When the value of Sdq is small, it has a gentle surface shape. On the other hand, when Sdq becomes large, it has a sharp surface shape. The inventors tried to produce multiple surface-treated copper foils with different values of Sdq, and conducted painstaking research on the relationship with transmission characteristics and reflow heat resistance. By limiting the value of Sdq to 25-70° Range, and more appropriately control the sharpness of the roughened particles present on the surface of the roughened layer. As a result, it is possible to obtain a surface-treated copper foil with good transmission characteristics and reflow heat resistance. If the value of Sdq is less than 25°, the transmission characteristics will tend to decrease. If the value of Sdq exceeds 70°, the heat resistance of reflow will decrease. Therefore, the value of Sdq should be controlled within the range of 25~70°. The range of 30 to 65° is more preferable, and the range of 40 to 60° is further more preferable.

再者，藉由控制存在於粗化處理層之表面的粗化粒子之尖銳程度，而使傳輸特性及回焊耐熱性均變良好之原因雖不確定，但可認為：尤其是在電流因集膚效應而集中於導體表面之高頻帶中，若粗化粒子成為尖銳至某種程度之表面形狀，則電流無法到達粗化粒子之頂端，難以在通過該頂端之路徑中流動。另一方面，粗化粒子之尖銳較小的表面形狀時，可認為：在高頻帶下流動之電流流動於包括粗化粒子之頂端的整個表面，因而傳輸損耗增加。此外，若粗化粒子之尖銳變得過大，則粗化粒子彼此之間隙變窄，於表面處理銅箔與樹脂之積層時，難以將樹脂填充至表面處理銅箔之表面凹凸之底部（凹部）位置。其結果，可認為：在回流焊接時之加熱時容易發生起泡，而有回焊耐熱性劣化之傾向。Furthermore, by controlling the sharpness of the roughened particles present on the surface of the roughened layer, the reason why the transmission characteristics and reflow heat resistance are improved is uncertain, but it can be considered that: The skin effect is concentrated in the high frequency band on the surface of the conductor. If the roughened particles become sharp to a certain degree of surface shape, the current cannot reach the top of the roughened particle, and it is difficult to flow in the path through the top. On the other hand, in the case of the sharp and small surface shape of the roughened particle, it can be considered that the current flowing in the high frequency band flows on the entire surface including the tip of the roughened particle, thereby increasing the transmission loss. In addition, if the sharpness of the roughened particles becomes too large, the gap between the roughened particles will be narrowed. When the surface-treated copper foil and resin are laminated, it is difficult to fill the resin to the bottom of the surface of the surface-treated copper foil (recesses). Location. As a result, it is considered that blistering is likely to occur during heating during reflow soldering, and the heat resistance of reflow soldering tends to deteriorate.

接著，對構成粗化處理層之表面的粗化粒子之尖銳程度對傳輸特性造成之影響進行說明。圖1係於國際公開第2016/035876號中所揭示，其中將粗化粒子之高度設為h，將粗化粒子之h/2高度位置之寬度設為w時，以表皮深度d將粗化粒子之高度h及寬度w標準化，示出各表面粗化形狀之等價導電率之算出結果。具體而言，圖1中縱軸、橫軸分別是經過表皮深度d標準化之h/d、w/d，示出計算等價導電率之分佈的結果。在圖1中，可得知等價導電率自左下區域（等價導電率：(5.5~6.0)×107 S/m)向右上區域（等價導電率：(0~2.0)×107 S/m)變低。Next, the influence of the sharpness of the roughened particles constituting the surface of the roughened layer on the transmission characteristics will be explained. Figure 1 is disclosed in International Publication No. 2016/035876, in which the height of the coarsening particles is set to h, and the width of the h/2 height position of the coarsening particles is set to w, the skin depth d will be used to coarsen The height h and width w of the particles are standardized, and the calculation result of the equivalent conductivity of each roughened surface shape is shown. Specifically, the vertical axis and the horizontal axis in FIG. 1 are respectively h/d and w/d normalized by the skin depth d, and show the results of calculating the distribution of equivalent conductivity. In Figure 1, it can be seen that the equivalent conductivity is from the lower left area (equivalent conductivity: (5.5~6.0)×10 7 S/m) to the upper right area (equivalent conductivity: (0~2.0)×10 7 S/m) becomes lower.

此處對等價導電率之定義進行說明。若高頻電流於銅箔上流動，則電流分佈集中於距銅箔表面的表皮深度d之區域，在該集中部位因導體電阻而產生電流損耗。尤其若電流是流動於表面形成有突起（粗化粒子）作為粗化處理層之粗化導體中，而非流動於表面未形成粗化處理層之平滑導體中，則電流損耗增大。因存在於表面之粗化粒子所致的電流損耗增大，可替換為與因導電率之降低所致的損耗增大等價。即，能以表觀導電率評價表面粗化狀態之高頻特性之優劣。將此種表觀導電率定義為等價導電率。The definition of equivalent conductivity is explained here. If a high-frequency current flows on the copper foil, the current distribution is concentrated in the area of the skin depth d from the surface of the copper foil, and current loss occurs at the concentrated part due to the conductor resistance. In particular, if current flows in a roughened conductor with protrusions (roughened particles) formed on the surface as a roughening treatment layer, instead of flowing in a smooth conductor without a roughening treatment layer formed on the surface, the current loss will increase. The increase in current loss due to the roughened particles present on the surface can be replaced with an equivalent increase in the loss due to the decrease in conductivity. That is, it is possible to evaluate the quality of the high-frequency characteristics of the roughened surface by the apparent conductivity. This apparent conductivity is defined as equivalent conductivity.

通常已知等價導電率會隨著圖1之縱軸，即，h/d而變化。即，可認為粗化粒子之高度h愈小，愈不存在等價導電率之大幅降低，作為銅箔之傳輸特性是可容許的。先前以來，已知表面粗糙度愈小，則傳輸特性愈提高。因此，為了確保密接力而將粗化粒子之高度增大至表皮深度程度以上，會導致傳輸特性之降低，而並不理想，鑒於這一先前之想法，在與表皮深度相同或較其更高之粗化粒子高度，即，h/d≥1的區域中，傳輸特性開始劣化，因此，特別是為了獲得良好之傳輸特性，通常難以採用粗化粒子高度較高之表面形狀。It is generally known that the equivalent conductivity will vary with the vertical axis of FIG. 1, that is, h/d. That is, it can be considered that the smaller the height h of the roughened particles is, the less there is a significant decrease in the equivalent electrical conductivity, which is allowable as the transmission characteristic of the copper foil. Previously, it has been known that the smaller the surface roughness, the better the transmission characteristics. Therefore, increasing the height of the roughened particles above the depth of the skin in order to ensure the adhesion will result in a decrease in the transmission characteristics, which is not ideal. In view of this previous idea, it is the same or higher than the depth of the skin. In the region where the height of the roughened particles, that is, h/d≥1, the transmission characteristics begin to deteriorate. Therefore, especially in order to obtain good transmission characteristics, it is usually difficult to adopt a surface shape with a higher roughening particle height.

相對於此，於本發明中，在w/d為1以下之情況下，即便h/d≥1，亦確認到表觀導電率（等價導電率）不降低而h/d之範圍（區域）擴大之傾向，即，確認到以非線性變化之形式的等價導電率之改善效果，藉由進一步將w/d設為0.5以下，等價導電率保持在較高的狀態而幾乎不降低，可觀察到等價導電率之改善效果。尤其是在h/d≥1之粗化粒子高度h較高（表面粗糙度較粗）時，此種等價導電率之改善效果更為顯著。為了確保與樹脂基材之密接力而不得不增大粗化粒子高度h時，該見解特別有效。In contrast, in the present invention, when w/d is 1 or less, even if h/d≥1, it is confirmed that the apparent conductivity (equivalent conductivity) does not decrease but the h/d range (area ) The tendency to expand, that is, the effect of improving the equivalent conductivity in the form of non-linear change is confirmed. By further setting w/d to 0.5 or less, the equivalent conductivity is maintained at a high state and hardly decreases , The improvement effect of equivalent conductivity can be observed. Especially when the height h of the roughened particles with h/d≥1 is higher (the surface roughness is coarser), the improvement effect of this equivalent conductivity is more significant. This finding is particularly effective when it is necessary to increase the height h of the roughened particles in order to ensure the adhesion with the resin substrate.

此種等價導電率隨著經過表皮深度d標準化之粗化粒子之寬度w之變化，而非線性地急遽變化之現象，可認為係基於如下所述之原理。This phenomenon that the equivalent conductivity changes rapidly and non-linearly with the width w of the coarsened particles standardized by the skin depth d can be considered based on the principle described below.

（粗化粒子之寬度w與電流密度） 圖2(a)及(b)為於電磁場分析上於紙面水平方向施加高頻電場，並將此時流動之高頻傳導電流密度於銅箔剖面上示出之概念圖，圖中之虛線為等電流密度線。圖2(a)表示經標準化之寬度w/d之值相對較大的粗化粒子之情形，圖2(b)表示經標準化之粗化粒子之寬度w/d之值相對較小的情形。另外，於圖2(a)中，A點為電流密度較小之點，B點為電流密度較高之點。又，於圖2(b)中，E點為電流密度較小之點，F點為電流密度較高之點。(The width w and the current density of the roughened particles) Figure 2 (a) and (b) show the electromagnetic field analysis by applying a high-frequency electric field in the horizontal direction of the paper, and applying the high-frequency conduction current density flowing at this time on the copper foil section Shown in the conceptual diagram, the dotted line in the figure is the equal current density line. Fig. 2(a) shows a situation where the normalized width w/d value of coarse particles is relatively large, and Fig. 2(b) shows a situation where the normalized width w/d value of the coarse particles is relatively small. In addition, in Figure 2(a), point A is the point where the current density is small, and point B is the point where the current density is high. In addition, in Figure 2(b), point E is the point where the current density is relatively small, and point F is the point where the current density is relatively high.

通常，伴隨傳導電流之高頻化，集膚效應愈加顯著，這種現象可以解釋為電流更加集中於銅箔表面流動。此種現象係將銅箔為表面平滑構造作為前提，與該表面平滑之情形相比較，如本發明般表面具有粗化形狀之情形的電流之疏密狀況變得非常特殊。具體而言，於圖2(a)、圖2(b)中均確認到電流於可謂更表面側的粗化粒子之頂端側不易流動之狀況（A點、E點）。此時，於粗化粒子之頂端部分發生的是傳導電流之抵消。Generally, the skin effect becomes more pronounced with the higher frequency of the conduction current. This phenomenon can be explained by the fact that the current flows more concentrated on the surface of the copper foil. This phenomenon is based on the premise that the copper foil has a smooth surface structure. Compared with the case where the surface is smooth, the current density condition when the surface has a roughened shape like the present invention becomes very special. Specifically, in both Fig. 2(a) and Fig. 2(b), it was confirmed that the current did not easily flow on the tip side of the roughened particles on the more surface side (point A, point E). At this time, what happens at the top of the roughened particle is the cancellation of the conduction current.

可認為此種現象係起因於以下理由。電流之大部分集中於銅箔表面之表皮深度d以內，於該集中部分彼此流動之電流絲毫不干涉時成為傳導電流。另一方面，在如粗化粒子（突起）之頂端部般之成為表皮深度d以下之部分中，朝向不同方向的電流互相干涉（重疊）時，若於干涉部分電流朝向相反方向流動則被抵消，傳導電流不流動。例如，若朝向粗化粒子之頂端方向的電流、與自粗化粒子之頂端流向基部側之電流發生干涉，則於干涉部分電流被抵消而產生傳導電流不流動之現象，但可認為該現象自身不成為產生電流損耗之原因。It is considered that this phenomenon is due to the following reasons. Most of the current is concentrated within the skin depth d on the surface of the copper foil, and when the currents flowing in the concentrated part do not interfere with each other at all, it becomes a conduction current. On the other hand, in the part below the skin depth d like the tip of the roughened particle (protrusion), when the currents in different directions interfere with each other (overlap), if the current flows in the opposite direction in the interference part, it will be cancelled. , The conduction current does not flow. For example, if the current in the direction toward the tip of the roughened particle interferes with the current flowing from the tip of the roughened particle to the base side, the current in the interfering part is canceled and the conduction current does not flow. However, this phenomenon can be considered as it is. Does not become the cause of current loss.

更詳細而言，對圖2(a)及圖2(b)中分別示出之表面形狀之差異加以描述。於圖2(b)之情形時，粗化粒子之寬度w較圖2(a)更窄，粗化粒子內之電流密度相對較小。例如，於圖2(a)之情形，與粗化粒子的高度h的1/2高度位置相比，粗化粒子的表面位置（D點）更靠頂端側，此位置的電流密度與將粗化粒子之兩側基部連結的內部中央點（C點）之電流密度等價。即，粗化粒子之高度h的1/2高度位置之表面之電流密度與粗化粒子之內部中央點（C點）之電流密度等價。由此可認為，圖2(a)為電流容易流動至粗化粒子之靠近頂端之高度的狀態，因此，有於頂端側流動之電流變多，而於粗化粒子之基部側流動之電流變少的傾向。In more detail, the difference between the surface shapes shown in Fig. 2(a) and Fig. 2(b) will be described. In the case of Fig. 2(b), the width w of the roughened particles is narrower than that of Fig. 2(a), and the current density in the roughened particles is relatively small. For example, in the case of Figure 2(a), the surface position of the roughened particle (point D) is closer to the tip side than the position of 1/2 height of the height h of the roughened particle. The current density of the inner central point (point C) connected by the bases on both sides of the chemical particle is equivalent. That is, the current density of the surface at 1/2 height of the height h of the roughened particle is equivalent to the current density of the inner central point (point C) of the roughened particle. From this, it can be considered that Fig. 2(a) shows a state where the current easily flows to the height of the roughened particle close to the tip. Therefore, there is an increase in the current flowing on the tip side and the current flowing on the base side of the roughened particle. Less tendency.

相對於此，於圖2(b)之情形，與粗化粒子之高度h之1/2高度位置相比，粗化粒子的表面位置（I點）位於基部側，此位置的電流密度與將粗化粒子之兩側基部連結的內部中央點（G點）之電流密度等價。即，粗化粒子之高度h之1/2高度位置之表面的電流密度低於粗化粒子之內部中央點（G點）之電流密度。由此可認為，於圖2(b)中，有於粗化粒子之頂端側流動之電流變少，而於粗化粒子之基部側流動之電流變多的傾向。如此可認為，藉由選擇如下表面粗化構造可降低電流損耗，該表面粗化構造係相對於在粗化粒子之基部附近流動之電流，減少於粗化粒子之頂端側（尤其是較突起高度h/2更靠頂端側）流動之電流量。In contrast, in the case of Figure 2(b), the surface position (point I) of the roughened particle is located at the base side compared to the 1/2 height position of the height h of the roughened particle. The current density at this position is The current density of the inner central point (point G) connected by the bases on both sides of the roughened particle is equivalent. That is, the current density of the surface at 1/2 height of the height h of the roughened particle is lower than the current density of the inner central point (point G) of the roughened particle. From this, it can be considered that, in FIG. 2(b), there is a tendency that the current flowing on the tip side of the roughened particle decreases, and the current flowing on the base side of the roughened particle tends to increase. It can be considered that the current consumption can be reduced by selecting the roughened surface structure, which is reduced on the tip side of the roughened particle (especially higher than the height of the protrusion) relative to the current flowing near the base of the roughened particle h/2 is closer to the tip side) the amount of current flowing.

於本發明中，基於此種作用，藉由將Sdr之值設為8~140%之範圍而對銅箔表面實施具有適當粗化形狀之粗化，可減少傳輸損耗。In the present invention, based on this effect, by setting the value of Sdr in the range of 8 to 140%, the surface of the copper foil is roughened with an appropriate roughened shape to reduce transmission loss.

根據以上內容，於本發明中，將作為自矽烷偶合層之表面測定的三維表面性狀之複合參數的界面之展開面積率Sdr之值設為8~140%之範圍，較佳為進一步將均方根表面梯度Sdq之值設為25~70°之範圍。Based on the above content, in the present invention, the value of the spread area ratio Sdr of the interface, which is a composite parameter of the three-dimensional surface properties measured from the surface of the silane coupling layer, is set in the range of 8 to 140%, and it is preferable to further reduce the mean square The value of root surface gradient Sdq is set in the range of 25~70°.

此外，作為自矽烷偶合層之表面測定的三維表面性狀之空間參數的表面性狀之縱橫比(aspect ratio) Str之值，以0.25~1為佳，以0.30以上為更佳，以0.50以上為進一步更佳。Str為表示表面形狀之縱橫向之等向性的參數。Str之值最大為1，Str值為1之情形表示完全之等向性。通常，Str之值若為0.5以上，則顯示較強之等向性，反之，若小於0.30，則顯示非等向性。通常，印刷配線板之電路係於縱向、橫向、傾斜方向上隨意形成。因此，藉由粗化之形狀於銅箔面內顯示等向性，於銅箔面內之因測定位置、測定方向等之傳輸損耗之偏差變小。Str較佳為接近1，反之Str之值愈小，則銅箔面內之因測定位置、測定方向等所致的傳輸損耗之偏差愈變大，因而不佳。In addition, the value of the aspect ratio Str, which is the spatial parameter of the three-dimensional surface properties measured from the surface of the silane coupling layer, is preferably 0.25~1, more preferably 0.30 or more, more preferably 0.50 or more Better. Str is a parameter representing the isotropy of the surface shape in the vertical and horizontal directions. The maximum value of Str is 1, and the case where the value of Str is 1 indicates complete isotropy. Generally, if the value of Str is 0.5 or more, it shows strong isotropy, on the contrary, if it is less than 0.30, it shows anisotropy. Usually, the circuit of the printed wiring board is randomly formed in the vertical, horizontal, and oblique directions. Therefore, the roughened shape exhibits isotropy in the surface of the copper foil, and the deviation of the transmission loss due to the measurement position, the measurement direction, etc., in the surface of the copper foil becomes smaller. Str is preferably close to 1. On the contrary, the smaller the value of Str, the greater the deviation of the transmission loss due to the measurement position and the measurement direction in the copper foil surface, which is not good.

進而，較佳為自矽烷偶合層之表面測定的十點平均粗糙度Rzjis為0.9~1.5 µm之範圍。其原因在於：若前述十點平均粗糙度Rzjis小於0.9 µm，則有密接性、回焊耐熱性等變得不充分之虞，另外，若Rzjis超過1.5 µm，則有傳輸損耗增加之虞。另外，於本發明中確認到，Str及Rzjis之值亦與Sdr之值同樣地，構成表面處理銅箔的粗化處理層之表面形狀，與在該粗化處理層上進一步積層形成防銹處理層及矽烷偶合層後的矽烷偶合層之表面形狀相比，幾乎未變化。因此，關於Str及Rzjis，亦將自矽烷偶合層之表面測定的Str及Rzjis之值與自粗化處理層之表面測定的Str及Rzjis之值視為相同，而加以規定。Furthermore, it is preferable that the ten-point average roughness Rzjis measured from the surface of the silane coupling layer is in the range of 0.9 to 1.5 µm. The reason is that if the ten-point average roughness Rzjis is less than 0.9 µm, the adhesion, reflow heat resistance, etc. may become insufficient, and if the Rzjis exceeds 1.5 µm, the transmission loss may increase. In addition, it has been confirmed in the present invention that the values of Str and Rzjis are the same as the value of Sdr, which constitutes the surface shape of the roughened layer of the surface-treated copper foil, and the roughened layer is further laminated to form a rust preventive treatment. Compared with the surface shape of the silane coupling layer after the silane coupling layer, there is almost no change in the surface shape. Therefore, with regard to Str and Rzjis, the values of Str and Rzjis measured from the surface of the silane coupling layer and the values of Str and Rzjis measured from the surface of the roughening treatment layer are also regarded as the same and specified.

另外，於本發明中，較佳為粗化處理層及防銹處理層中的銅以外之金屬及該金屬之氧化物之合計含量換算成金屬元素而為0.15~0.50 mg/dm2 。藉由在形成粗化處理層之粗化電鍍液中添加銅以外之金屬，例如，Mo、Fe、Ni、Co、W等之金屬離子，可控制粗化處理層之表面形狀，這一情況已廣為人知。另一方面，該等金屬係電阻大於銅，並且容易形成氧化物，因此，若於粗化處理層中或防銹處理層中過剩地含有上述金屬，則有對傳輸特性造成不良影響之虞。因此，若粗化處理層及防銹處理層中的銅以外之金屬及該金屬之氧化物之合計含量換算成金屬元素而小於0.15 mg/dm2 ，則有難以有效地控制粗化處理層之表面形狀之虞，另外，若超過0.50 mg/dm2 ，則有電阻變大而傳輸特性劣化之傾向。因此，粗化處理層及防銹處理層中的銅以外之金屬及該金屬之氧化物之合計含量較佳為換算成金屬元素而為0.15~0.50 mg/dm2 。In addition, in the present invention, it is preferable that the total content of the metal other than copper and the oxide of the metal in the roughening treatment layer and the antirust treatment layer is 0.15 to 0.50 mg/dm 2 in terms of metal elements. The surface shape of the roughened layer can be controlled by adding metals other than copper, such as Mo, Fe, Ni, Co, W, etc., to the roughening electroplating solution for forming the roughened layer. Well known. On the other hand, these metals have higher resistance than copper, and oxides are easily formed. Therefore, if the above-mentioned metals are excessively contained in the roughening treatment layer or the rust prevention treatment layer, it may adversely affect the transmission characteristics. Therefore, if the total content of metals other than copper and oxides of the metal in the roughening treatment layer and the antirust treatment layer is less than 0.15 mg/dm 2 in terms of metal elements, it is difficult to effectively control the roughening treatment layer. Regarding the surface shape, if it exceeds 0.50 mg/dm 2 , the electrical resistance will increase and the transmission characteristics will tend to deteriorate. Therefore, the total content of the metal other than copper and the oxide of the metal in the roughening treatment layer and the antirust treatment layer is preferably 0.15 to 0.50 mg/dm 2 in terms of metal elements.

進而，較佳為前述粗化處理層及前述防銹處理層中之Ni及Zn之含量分別為0.05~0.30 mg/dm2 。其原因在於：若前述粗化處理層及前述防銹處理層中之Ni及Zn之含量分別小於0.05 mg/dm2 ，則有回焊耐熱性變得不充分之虞，另外，若分別超過0.30 mg/dm2 ，則Ni含量之增大會導致傳輸損耗之增加，Zn含量之增大會導致過蝕刻，其結果為，有可能導致銅箔與樹脂基材之界面的密接性降低，而回焊耐熱性降低。Furthermore, it is preferable that the contents of Ni and Zn in the roughening treatment layer and the antirust treatment layer are 0.05 to 0.30 mg/dm 2, respectively . The reason is that if the contents of Ni and Zn in the roughening treatment layer and the rust prevention treatment layer are less than 0.05 mg/dm 2 , respectively, the reflow heat resistance may become insufficient, and if the contents exceed 0.30, respectively mg/dm 2 , the increase of Ni content will lead to the increase of transmission loss, and the increase of Zn content will lead to over-etching. As a result, the adhesion of the interface between the copper foil and the resin substrate may decrease, and the reflow heat resistance Sexual decrease.

而且，構成本發明之表面處理銅箔的銅箔包含輥軋銅箔或電解銅箔。通常，電解銅箔係藉由電解電鍍使銅於製箔用之金屬製滾筒(drum)表面析出，將該滾筒表面側稱為S面，將其相反面側稱為M面。銅箔為電解銅箔時，就抑制傳輸損耗之增加而言，較佳為僅於該電解銅箔之M面具有前述粗化處理層。Furthermore, the copper foil constituting the surface-treated copper foil of the present invention includes rolled copper foil or electrolytic copper foil. Generally, electrolytic copper foil deposits copper on the surface of a metal drum for foil making by electrolytic plating. The surface of the drum is called the S surface, and the opposite side is called the M surface. When the copper foil is an electrolytic copper foil, in terms of suppressing an increase in transmission loss, it is preferable to have the aforementioned roughening treatment layer only on the M surface of the electrolytic copper foil.

進而，本發明製造覆銅積層板，此覆銅積層板具有上述表面處理銅箔、及積層於該表面處理銅箔之前述矽烷偶合層上的樹脂，其中該樹脂在頻率10 GHz下之介電常數為3.5以下且介電損耗正切為0.006以下，藉此可製造高頻電氣訊號之傳輸損耗少，且具有優異之回焊耐熱性的印刷配線板。再者，將構成前述覆銅積層板之樹脂限定為在頻率10 GHz下之介電常數為3.5以下且介電損耗正切為0.006以下之樹脂的原因在於：減少傳輸損耗之效果較大。Furthermore, the present invention manufactures a copper-clad laminate. The copper-clad laminate has the above-mentioned surface-treated copper foil and a resin laminated on the aforementioned silane coupling layer of the surface-treated copper foil, wherein the resin has a dielectric material at a frequency of 10 GHz. With a constant of 3.5 or less and a dielectric loss tangent of 0.006 or less, a printed wiring board with low transmission loss of high-frequency electrical signals and excellent reflow heat resistance can be manufactured. Furthermore, the reason why the resin constituting the aforementioned copper clad laminate is limited to a resin with a dielectric constant of 3.5 or less and a dielectric loss tangent of 0.006 or less at a frequency of 10 GHz is that the effect of reducing transmission loss is greater.

（表面處理銅箔之製造條件） 作為構成本發明之表面處理銅箔的銅箔（原箔），可使用表面平滑之銅箔、及於表面具有微小凹凸之銅箔之任一者。將原箔A之M面（於製箔時與電解液接觸之面）之表面形狀示於圖3(a)，另外，將原箔B之M面及S面（於製箔時與電解滾筒接觸之面）之表面性狀分別示於圖3(b)及圖3(c)。(Production conditions of surface-treated copper foil) As the copper foil (original foil) constituting the surface-treated copper foil of the present invention, any one of a copper foil with a smooth surface and a copper foil with minute irregularities on the surface can be used. The surface shape of the M surface of the original foil A (the surface in contact with the electrolyte during the foil making) is shown in Figure 3(a). In addition, the M surface and the S surface of the original foil B (which is in contact with the electrolytic drum during the foil making) The surface properties of the contact surface are shown in Figure 3(b) and Figure 3(c), respectively.

＜原箔A之電解條件＞

Figure 106143933-A0304-0001
＜Electrolysis condition of original foil A＞
Figure 106143933-A0304-0001

＜原箔B之電解條件＞

Figure 106143933-A0304-0002
＜Electrolysis condition of original foil B＞
Figure 106143933-A0304-0002

（粗化處理層之形成條件） 形成於銅箔表面之粗化處理層，係利用粗化電鍍步驟與膠囊電鍍步驟之二階段粗化處理來實施，上述粗化電鍍步驟用於形成微細之銅粒子，上述膠囊電鍍步驟用於防止該微細粒子之脫落。於粗化電鍍步驟中，將於銅-硫酸水溶液中添加有金屬離子者用作粗化電鍍液。作為一例，較佳電鍍條件如以下所述。(Formation conditions of the roughening treatment layer) The roughening treatment layer formed on the surface of the copper foil is implemented by a two-stage roughening treatment of a roughening electroplating step and a capsule electroplating step. The above-mentioned roughening electroplating step is used to form fine copper Particles, the above-mentioned capsule electroplating step is used to prevent the fine particles from falling off. In the roughening electroplating step, the copper-sulfuric acid aqueous solution added with metal ions is used as the roughening electroplating solution. As an example, preferable plating conditions are as follows.

＜粗化電鍍條件＞

Figure 106143933-A0304-0003
＜Roughening plating conditions＞
Figure 106143933-A0304-0003

於膠囊電鍍步驟中，將銅-硫酸水溶液用作膠囊電鍍液。作為一例，較佳電鍍條件如以下所述。In the capsule electroplating step, a copper-sulfuric acid aqueous solution is used as the capsule electroplating solution. As an example, preferable plating conditions are as follows.

＜膠囊電鍍條件＞

Figure 106143933-A0304-0004
＜Capsule plating conditions＞
Figure 106143933-A0304-0004

另外，上述粗化電鍍液及膠囊電鍍液中之氯化物離子濃度，以0.3質量ppm以下為佳。作為電解銅箔之原料，通常使用經粉碎之電線屑。該電線屑中含有油分，若直接使用則會產生針孔等電鍍不良。因此，為了自電鍍液（電解液）中去除油分而使用活性炭之技術已廣為人知，但活性炭係於再生步驟中進行利用鹽酸之處理，故吸附有氯化物離子。因此，於電解液中不可避免地混入氯化物離子，含有幾ppm左右。In addition, the chloride ion concentration in the roughening plating solution and the capsule plating solution is preferably 0.3 mass ppm or less. As the raw material of electrolytic copper foil, pulverized wire scraps are usually used. This wire scrap contains oil, and if it is used directly, plating defects such as pinholes may occur. Therefore, the technology of using activated carbon to remove oil from the electroplating solution (electrolyte) is widely known. However, the activated carbon is treated with hydrochloric acid in the regeneration step, so chloride ions are adsorbed. Therefore, chloride ions are inevitably mixed in the electrolyte, and contain about several ppm.

若含有氯化物離子濃度多於0.3質量ppm，則Mo、Fe、Ni、Co、W等之金屬離子之作用無法充分發揮，無法獲得均勻且微細之表面形狀。為了將氯化物離子濃度設為0.3質量ppm以下，較佳為將可捕獲氯化物離子且最終可自電鍍液中去除般之物質添加至電鍍液中，例如，於電鍍液中添加0.01~0.2質量ppm左右之Ag離子。藉由在電鍍液中添加Ag離子，Ag離子與氯化物離子反應成為氯化銀而沉澱，因此，可將氯化物離子自電鍍液中去除。沉澱之氯化銀係利用過濾器自電鍍液中去除，故不會對粗化之形狀造成影響。另外，氯化物離子之分析是使用離子層析法。If the chloride ion concentration is more than 0.3 mass ppm, the effects of metal ions such as Mo, Fe, Ni, Co, W, etc. cannot be fully exerted, and a uniform and fine surface shape cannot be obtained. In order to set the chloride ion concentration to 0.3 mass ppm or less, it is preferable to add a substance that can capture chloride ions and finally be removed from the electroplating solution into the electroplating solution, for example, add 0.01~0.2 mass to the electroplating solution Ag ion of about ppm. By adding Ag ions in the plating solution, Ag ions react with chloride ions to become silver chloride and precipitate. Therefore, the chloride ions can be removed from the plating solution. The precipitated silver chloride is removed from the electroplating bath with a filter, so it will not affect the roughened shape. In addition, the analysis of chloride ions uses ion chromatography.

另外，較佳為不在粗化電鍍液及膠囊電鍍液中積極地添加有機添加劑。其原因在於，若使用有機添加劑，則有以下傾向：難以管理有機添加劑向銅箔中之取入及因陽極處之氧化反應而產生的副產物，工業上難以穩定地製造。In addition, it is preferable not to actively add organic additives to the roughening plating solution and the capsule plating solution. The reason is that if an organic additive is used, it tends to be difficult to manage the intake of the organic additive into the copper foil and the by-products produced by the oxidation reaction at the anode, and it is difficult to industrially produce it stably.

進而，構成本發明之表面處理銅箔的粗化處理層之形成，較佳為相互取得條件之平衡而進行粗化電鍍條件與膠囊電鍍條件兩者，例如，可列舉：於粗化電鍍條件與膠囊電鍍條件中相互適當地設定電流密度及處理時間之情形。另外，除了電流密度及處理時間以外，為了發揮使粗化粒子微細且均勻之效果，較佳為也適當地選擇添加至粗化電鍍液中之金屬離子之種類及添加量。若加以具體例示，則於提高電流密度之情形，只要提高所添加之金屬離子之濃度即可。即，其原因在於：因提高電流密度，粗化粒子容易不均勻地成長，但藉由大量添加金屬離子，可獲得微細且均勻之粗化粒子。Furthermore, for the formation of the roughening treatment layer constituting the surface-treated copper foil of the present invention, it is preferable to balance the conditions to perform both roughening plating conditions and capsule plating conditions. For example, there may be mentioned: In the capsule plating conditions, the current density and processing time are mutually set appropriately. In addition, in addition to the current density and the treatment time, in order to exert the effect of making the roughened particles fine and uniform, it is preferable to appropriately select the type and amount of metal ions added to the roughening plating solution. If it is specifically exemplified, in the case of increasing the current density, it is only necessary to increase the concentration of the added metal ion. That is, the reason is that the roughened particles tend to grow unevenly by increasing the current density, but by adding a large amount of metal ions, fine and uniform roughened particles can be obtained.

接著，關於積層形成於銅箔之粗化處理層上的防銹處理層，以下對電鍍液組成及電鍍條件之較佳範圍進行說明。Next, regarding the anti-rust treatment layer formed on the roughening treatment layer of the copper foil, the preferable range of the electroplating solution composition and electroplating conditions will be described below.

作為防銹處理層，可列舉由一層或兩層以上的各種含金屬或含合金層所構成之情形，作為具體例，可列舉將Ni電鍍層、Zn電鍍層及鉻酸鹽處理層等三層依序積層而形成之情形。另外，亦可除了Ni電鍍層、Zn電鍍層及鉻酸鹽處理層以外，或代替該等層中之至少一層，而使用Ni-Zn、Zn-Cr、Ni-Cr等之合金電鍍層。以下示出用以形成Ni電鍍層、Zn電鍍層、Ni-Zn合金電鍍層及鉻酸鹽處理層之電鍍浴組成及電鍍條件之代表例。As the anti-rust treatment layer, one or more layers of various metal-containing or alloy-containing layers can be cited. As a specific example, three layers such as Ni plating layer, Zn plating layer, and chromate treatment layer can be cited. The situation is formed by layering in sequence. In addition, in addition to the Ni electroplating layer, Zn electroplating layer, and chromate treatment layer, or instead of at least one of these layers, an alloy electroplating layer of Ni-Zn, Zn-Cr, Ni-Cr, etc. can also be used. The following shows representative examples of electroplating bath compositions and electroplating conditions for forming Ni electroplated layers, Zn electroplated layers, Ni-Zn alloy electroplated layers, and chromate treated layers.

＜Ni電鍍浴組成及電鍍條件＞

Figure 106143933-A0304-0005
<Ni electroplating bath composition and electroplating conditions>
Figure 106143933-A0304-0005

＜Zn電鍍浴組成及電鍍條件＞

Figure 106143933-A0304-0006
＜Zn electroplating bath composition and electroplating conditions＞
Figure 106143933-A0304-0006

＜Ni-Zn合金電鍍浴組成及電鍍條件＞

Figure 106143933-A0304-0007
＜Ni-Zn alloy plating bath composition and plating conditions＞
Figure 106143933-A0304-0007

＜鉻酸鹽處理浴組成及處理條件＞

Figure 106143933-A0304-0008
＜Chromate treatment bath composition and treatment conditions＞
Figure 106143933-A0304-0008

接著，於上述防銹處理層上，為了提高與樹脂之密接性而基層形成矽烷偶合層。所使用之矽烷偶合劑之種類可列舉：具有環氧基、乙烯基、胺基、丙烯酸基、甲基丙烯酸基等之矽烷偶合劑。該等矽烷偶合劑藉由與樹脂中之具有反應性之官能基的作用而有不同的效果，故需要根據與樹脂之相容性而適當選定所使用之矽烷偶合劑。Next, on the rust-preventing treatment layer, a silane coupling layer is formed on the base layer in order to improve the adhesion with the resin. The types of silane coupling agents used include: silane coupling agents having epoxy groups, vinyl groups, amino groups, acrylic groups, methacrylic groups, and the like. These silane coupling agents have different effects due to the action of the reactive functional groups in the resin. Therefore, it is necessary to appropriately select the silane coupling agent used according to the compatibility with the resin.

作為上述矽烷偶合劑之具體例，可列舉：胺基烷基三甲氧基矽烷（例如，3-胺基丙基三甲氧基矽烷）、胺基烷基三乙氧基矽烷（例如，3-胺基丙基三乙氧基矽烷）、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、(3-(甲基)丙烯醯氧基丙基)三甲氧基矽烷、(3-(甲基)丙烯醯氧基丙基)三乙氧基矽烷、(甲基)丙烯醯基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-丙烯醯氧基丙基三乙氧基矽烷、苯乙烯基三甲氧基矽烷、苯乙烯基三乙氧基矽烷、苯乙烯基丙基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷等，即便為其他矽烷偶合劑，亦可適當選擇使用。Specific examples of the above-mentioned silane coupling agent include: aminoalkyltrimethoxysilane (for example, 3-aminopropyltrimethoxysilane), aminoalkyltriethoxysilane (for example, 3-amine Propyl triethoxy silane), vinyl trimethoxy silane, vinyl triethoxy silane, (3-(meth) propylene oxypropyl) trimethoxy silane, (3-(methyl) )Acrylicoxypropyl)triethoxysilane, (meth)acryloxypropyltriethoxysilane, 3-propenyloxypropyltrimethoxysilane, 3-propenyloxypropyl Triethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, styrylpropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane Silane, 3-glycidoxypropyltrimethoxysilane, etc., even if they are other silane coupling agents, they can be appropriately selected and used.

關於將上述矽烷偶合劑塗佈於金屬處理層表面時之上述矽烷偶合劑之溶液濃度，為了於防銹處理層之（最外）表面塗佈充分量之矽烷偶合劑。且實現更高之密接性，以設為0.01~15體積%為佳，以設為0.1~10體積%為更佳。作為該溶液之溶劑，以使用水為佳。Regarding the solution concentration of the silane coupling agent when the silane coupling agent is applied to the surface of the metal treatment layer, a sufficient amount of the silane coupling agent is applied to the (outermost) surface of the antirust treatment layer. And to achieve higher adhesion, it is better to set it as 0.01-15% by volume, and it is better to set it as 0.1-10% by volume. As the solvent of this solution, it is better to use water.

再者，上文所述僅表示本發明之實施形態之一例，可於申請專利範圍內加以各種變更。 [實施例]Furthermore, the above is only an example of the embodiment of the present invention, and various changes can be made within the scope of the patent application. [Example]

接著，嘗試製作本發明之表面處理銅箔，並評價性能，於下文中進行說明。 （實施例1~42以及比較例1~4） 關於銅箔（原箔），藉由上述兩種原箔之製造（電解）條件而分別獲得厚度18 µm之原箔A及原箔B。關於原箔A之表面粗糙度Rzjis，S面（於製箔時與電解滾筒接觸之面）為1.5 µm，M面（於製箔時與電解液接觸之面）為0.8 µm。關於原箔B之表面粗糙度Rzjis，S面為1.5 µm，M面為3.3 µm。Next, try to produce the surface-treated copper foil of the present invention, and evaluate the performance, which will be described below. (Examples 1 to 42 and Comparative Examples 1 to 4) Regarding the copper foil (original foil), the original foil A and the original foil B with a thickness of 18 µm were respectively obtained under the manufacturing (electrolysis) conditions of the above two kinds of original foils. Regarding the surface roughness Rzjis of the original foil A, the S surface (the surface in contact with the electrolytic drum during foil making) is 1.5 µm, and the M surface (the surface in contact with the electrolyte during foil making) is 0.8 µm. Regarding the surface roughness Rzjis of the original foil B, the S surface is 1.5 µm and the M surface is 3.3 µm.

接著，對原箔A或原箔B實施如表1所示之粗化處理I或II，實施粗化電鍍及膠囊電鍍。於表2中示出銅箔（原箔）之種類及處理面、以及粗化處理類型、粗化電鍍條件及膠囊電鍍條件。再者，粗化處理之條件中，極限電流密度、臨界電流密度等會依據電鍍液（浴）之組成或濃度、金屬離子添加物而大幅度地變化，因此，表2所示之粗化處理條件，係顯示作為上文所示之電鍍浴組成的情況下之一例。Next, roughening treatment I or II shown in Table 1 was performed on the original foil A or the original foil B, and roughening plating and capsule plating were performed. Table 2 shows the type of copper foil (original foil) and the surface to be treated, as well as the type of roughening treatment, roughening plating conditions, and capsule plating conditions. Furthermore, in the conditions of the roughening treatment, the limiting current density, critical current density, etc. will vary greatly depending on the composition or concentration of the plating solution (bath), and metal ion additives. Therefore, the roughening treatment shown in Table 2 The conditions are shown as an example of the composition of the electroplating bath shown above.

然後，於經過粗化處理之銅箔上，使用以下所示之電鍍液，形成依序積層鎳電鍍層、鋅電鍍層及鉻酸鹽層而構成之防銹處理層。將構成防銹處理層之各層之附著量示於表2中。 ＜鎳電鍍浴組成及電鍍條件＞

Figure 106143933-A0304-0009
Then, on the roughened copper foil, use the electroplating solution shown below to form an anti-rust treatment layer composed of a nickel electroplated layer, a zinc electroplated layer and a chromate layer in sequence. Table 2 shows the adhesion amount of each layer constituting the anti-rust treatment layer. <Nickel plating bath composition and plating conditions>
Figure 106143933-A0304-0009

＜Zn電鍍浴組成及電鍍條件＞

Figure 106143933-A0304-0010
＜Zn electroplating bath composition and electroplating conditions＞
Figure 106143933-A0304-0010

＜鉻酸鹽處理浴組成及處理條件＞

Figure 106143933-A0304-0011
＜Chromate treatment bath composition and treatment conditions＞
Figure 106143933-A0304-0011

接著，於銅箔之防銹處理層上，使用具有胺基之3-胺基丙基三乙氧基矽烷，以形成如表2所示之矽(Si)附著量之矽烷偶合層的方式實施矽烷偶合處理，製造表面處理銅箔。Then, on the anti-rust treatment layer of the copper foil, use 3-aminopropyltriethoxysilane with amino groups to form a silane coupling layer with the amount of silicon (Si) attached as shown in Table 2. Silane coupling treatment to manufacture surface-treated copper foil.

（比較例5及6） 除了利用表1所示之粗化處理II進行粗化處理層之形成以外，比較例5及6分別以與實施例1及12相同之條件進行處理而製造表面處理銅箔。再者，表1所示之粗化處理II中所用之粗化電鍍液及膠囊電鍍液中之氯化物離子濃度較高者係僅添加活性炭，且並未添加用以使氯化物離子以氯化銀之形式沉澱並去除的Ag離子者，表1所示之粗化處理I中所用之粗化電鍍液及膠囊電鍍液中之氯化物離子濃度較低者係添加活性炭並且添加Ag離子，使氯化物離子以氯化銀之形式沉澱並去除者。(Comparative Examples 5 and 6) Except that the roughening treatment II shown in Table 1 was used to form the roughening treatment layer, Comparative Examples 5 and 6 were treated under the same conditions as those of Examples 1 and 12 to produce surface-treated copper. Foil. Furthermore, the roughening electroplating solution and the capsule electroplating solution with higher chloride ion concentration used in the roughening treatment II shown in Table 1 only add activated carbon, and no addition is used to chlorinate the chloride ions. For the Ag ions that are precipitated and removed in the form of silver, the roughening plating solution used in the roughening treatment I shown in Table 1 and the lower chloride ion concentration in the capsule plating solution is to add activated carbon and add Ag ions to make chlorine The compound ion is precipitated and removed in the form of silver chloride.

（比較例7） 比較例7中，於原箔A之M面，利用與專利文獻1之實施例9相同之方法，以Cu 20 g/L（硫酸銅五水合物50 g/L）、3-巰基-1-丙磺酸鈉0.25 g/L、鈷離子5.2 g/L、鎳離子2.2 g/L、浴溫40℃、電流密度10 A/dm2 、電解時間10秒之條件形成粗化處理層之後，以硫酸鎳(II)六水合物30 g/L、鉬(VI)酸二鈉二水合物60 g/L、檸檬酸三鈉二水合物50 g/L、pH值10.5之溶液組成，以電流密度4 A/dm2 、電解時間6秒進行處理後，利用專利文獻1所揭示之方法積層鉻酸鹽處理層而形成防銹處理層。然後，使用胺基丙基三乙氧基矽烷進行矽烷偶合處理，製造表面處理銅箔。(Comparative Example 7) In Comparative Example 7, on the M side of the original foil A, using the same method as Example 9 of Patent Document 1, Cu 20 g/L (copper sulfate pentahydrate 50 g/L), 3 -Sodium mercapto-1-propanesulfonate 0.25 g/L, cobalt ion 5.2 g/L, nickel ion 2.2 g/L, bath temperature 40℃, current density 10 A/dm 2 , electrolysis time 10 seconds to form coarsening After treating the layer, use a solution of nickel (II) sulfate hexahydrate 30 g/L, molybdenum (VI) acid disodium dihydrate 60 g/L, trisodium citrate dihydrate 50 g/L, and pH 10.5. The composition is treated with a current density of 4 A/dm 2 and an electrolysis time of 6 seconds, and then a chromate treatment layer is laminated by the method disclosed in Patent Document 1 to form a rust prevention treatment layer. Then, a silane coupling treatment was performed using aminopropyltriethoxysilane to produce a surface-treated copper foil.

（覆銅積層板之製造） 為了進行高頻傳輸特性及特別是回焊耐熱性之評價，將上述所得到之各表面處理銅箔以粗化處理面側與樹脂基材對向之方式與厚度250 µm之市售之高頻應對絕緣樹脂基材（松下(Panasonic)股份有限公司製造之Megtron 6）重疊，作為一例，以壓製溫度：200℃、壓製壓力：3 MPa、壓製時間：120分之通常壓製條件，進行積層而製作覆銅積層板，視需要實施電路配線之加工等而準備測定基板。(Production of copper clad laminate) In order to evaluate the high frequency transmission characteristics and especially the heat resistance of reflow, the surface treated copper foils obtained above were made such that the roughened surface faces the resin substrate and the thickness The 250 µm commercially available high-frequency response insulating resin substrate (Megtron 6 manufactured by Panasonic Co., Ltd.) overlaps, as an example, the pressing temperature: 200℃, pressing pressure: 3 MPa, pressing time: 120 minutes Under normal pressing conditions, lamination is performed to produce a copper-clad laminate, and circuit wiring is processed as necessary to prepare a measurement substrate.

＜試片之特性評價＞ (1)金屬附著量之測定 關於粗化處理層及防銹處理層中之金屬附著量之測定，以塗料將試樣之未進行粗化處理之面遮蔽後，切成10 cm見方，利用經加溫至80℃之混合酸（硝酸1：鹽酸1（體積比））將銅箔之實施了粗化處理之面的表面溶解3~5 µm左右後，使用原子吸光光度計（日立高新技術股份有限公司製造之Z-2300）藉由原子吸光分析法對所得到的溶液中之金屬質量進行定量分析，求出所述金屬附著量。<Characteristic evaluation of the test piece> (1) Measurement of the amount of metal adhesion For the measurement of the amount of metal adhesion in the roughening treatment layer and the anti-rust treatment layer, the surface of the sample that has not been roughened is covered with paint, and then cut In a square of 10 cm, use a mixed acid (nitric acid 1: hydrochloric acid 1 (volume ratio)) heated to 80°C to dissolve the roughened surface of the copper foil for about 3 to 5 µm, then use atomic absorption The photometer (Z-2300 manufactured by Hitachi High-Tech Co., Ltd.) quantitatively analyzes the metal mass in the obtained solution by atomic absorption analysis to obtain the metal adhesion amount.

(2)表面粗糙度之測定 使用接觸式表面粗糙度測定機（小阪研究所股份有限公司製造之SE1700型），依據JIS B0601：2001測定十點平均粗糙度Rzjis。利用接觸式表面粗糙度測定機來測定表面粗糙度之原因在於：為了對本次實驗中所得到的銅箔之宏觀表面粗糙度進行評價，而以觀察微觀區域為目的之三維白色干涉型顯微鏡無法正確地測定宏觀表面粗糙度之差異。(2) Measurement of surface roughness A contact surface roughness measuring machine (SE1700 type manufactured by Kosaka Laboratory Co., Ltd.) was used to measure the ten-point average roughness Rzjis in accordance with JIS B0601:2001. The reason for measuring the surface roughness with a contact surface roughness measuring machine is that in order to evaluate the macroscopic surface roughness of the copper foil obtained in this experiment, the three-dimensional white interference microscope for the purpose of observing the microscopic area cannot Accurately measure the difference in macroscopic surface roughness.

(3)三維表面性狀之參數（S參數）之測定 關於Sdr、Sdq及Str之值，使用Bruker公司製造之三維白色干涉型顯微鏡Wyko（Contour GT-K高分辨率CCD（Charged Coupled Device；電荷耦合元件）規格：1280×960像素），以垂直掃描式白色干涉方式(VSI)以10倍之倍率，自構成表面處理銅箔之矽烷偶合層之表面於不同3處對477 µm×357 µm之面積進行測定，算出該等之平均值。再者，於測定時不進行濾光。(3) Measurement of the parameters (S parameters) of the three-dimensional surface properties Regarding the values of Sdr, Sdq, and Str, the three-dimensional white interference microscope Wyko (Contour GT-K High Resolution CCD (Charged Coupled Device; Charge Coupled Device) manufactured by Bruker is used Element) Specifications: 1280×960 pixels), using vertical scanning white interference method (VSI) with a magnification of 10 times, from the surface of the silane coupling layer of the surface-treated copper foil to an area of 477 µm×357 µm at 3 different locations Measure and calculate the average value of these. Furthermore, no filtering is performed during the measurement.

(4)回焊耐熱性之評價 回焊耐熱性之評價係依據IPC TM-650 2.4.24.1「使用TMA（Thermomechanical analysis；熱機械分析）之分層之時間測定」，使用由上述覆銅積層板所得到之回焊耐熱性測定用基板，以288℃下之直至發生起泡為止之時間（起泡時間）進行評價。回焊耐熱性，係將起泡時間為60分鐘以上之情形評價為「◎」，將45分鐘以上、小於60分鐘之情形評價為「○」，將30分鐘以上、小於45分鐘之情形評價為「Δ」，將小於30分鐘之情形評價為「×」，本發明中，將「◎」、「○」及「Δ」視為合格水準。(4) Evaluation of reflow heat resistance The evaluation of reflow heat resistance is based on IPC TM-650 2.4.24.1 "Determination of delamination time using TMA (Thermomechanical analysis)", using the above-mentioned copper clad laminate The obtained substrate for reflow heat resistance measurement was evaluated by the time until blistering occurred at 288°C (blistering time). For reflow heat resistance, the blistering time of 60 minutes or more is evaluated as "◎", the case of 45 minutes or more and less than 60 minutes is evaluated as "○", and the case of 30 minutes or more and less than 45 minutes is evaluated as "○" "Δ" is evaluated as "×" when it is less than 30 minutes. In the present invention, "◎", "○" and "Δ" are regarded as pass levels.

(5)傳輸特性之評價 關於傳輸特性，使用抗蝕劑寬度300 µm之圖案膜藉由UV曝光於上述覆銅積層板上形成圖案，進而實施蝕刻，形成帶線(strip line)長200 mm之微帶線而獲得傳輸特性測定用基板（尺寸：長度210 mm、寬度30 mm）。對該傳輸特性測定用基板使用網路分析儀(Keysight Technology N5247A)，以50 Ω之特性阻抗進行40 GHz之頻率下之通過特性S21之測定。傳輸特性，係將通過特性S21為-28 dB以上之情形評價為「◎」，將通過特性S21為-30 dB以上、小於-28 dB之情形評價為「○」，將-33 dB以上、小於-30 dB之情形評價為「Δ」，將小於-33 dB之情形評價為「×」，於本發明中，將「◎」、「○」及「Δ」視為合格水準。(5) Evaluation of transmission characteristics Regarding the transmission characteristics, a patterned film with a resist width of 300 µm was patterned on the above-mentioned copper-clad laminate by UV exposure, and then etching was performed to form a strip line with a length of 200 mm. A microstrip line is used to obtain a substrate for measuring transmission characteristics (size: length 210 mm, width 30 mm). A network analyzer (Keysight Technology N5247A) was used on the substrate for measurement of transmission characteristics, and the pass characteristic S21 was measured at a frequency of 40 GHz with a characteristic impedance of 50 Ω. For transmission characteristics, the case where the pass characteristic S21 is -28 dB or more is evaluated as "◎", the case where the pass characteristic S21 is -30 dB or more and less than -28 dB is evaluated as "○", and the case where the pass characteristic S21 is greater than and less than -33 dB The case of -30 dB is evaluated as "Δ", and the case of less than -33 dB is evaluated as "×". In the present invention, "◎", "○" and "Δ" are regarded as passing levels.

[表1]

Figure 106143933-A0304-0012
[Table 1]
Figure 106143933-A0304-0012

[表2]

Figure 106143933-A0304-0013
[Table 2]
Figure 106143933-A0304-0013

[表3]

Figure 106143933-A0304-0014
[table 3]
Figure 106143933-A0304-0014

由表3所示之性能評價結果得知，實施例1~42均係Sdr之值為本發明之適當範圍內，因此，回焊耐熱性及傳輸特性兩者處於合格水準。 相對於此，比較例1~7均係Sdr之值為本發明之適當範圍外，因此，回焊耐熱性及傳輸特性之至少一者並非合格水準而較差。 [產業上之可利用性]From the performance evaluation results shown in Table 3, it is known that the values of Sdr in Examples 1 to 42 are all within the appropriate range of the present invention. Therefore, both the reflow heat resistance and the transmission characteristics are at acceptable levels. In contrast, the values of Sdr in Comparative Examples 1 to 7 are all outside the appropriate range of the present invention. Therefore, at least one of the reflow heat resistance and the transmission characteristics is not at the acceptable level and is inferior. [Industrial availability]

根據本發明，可提供一種表面處理銅箔及覆銅積層板，可穩定地製造具有藉由表面積或表面粗糙度等先前使用之指標（參數）難以控制的表面粗化形狀之表面處理銅箔，上述表面處理銅箔用作，例如，在超過幾GHz之高頻帶使用的高頻印刷配線板用之銅箔時，可製造高頻電氣訊號之傳輸損耗少，且具有優異之回焊耐熱性的印刷配線板。另外，藉由使用三維光干涉式顯微鏡，可適當控制表面處理銅箔之表面的凹凸之尖銳程度（表面梯度）、展開面積等。進而，本發明之表面處理銅箔能以較高水準實現傳輸特性、樹脂密接性及回焊耐熱性，且可實現要求在超過幾十GHz之高頻帶使用的路由器或伺服器用等之高多層印刷配線板，於工業上極為有用。According to the present invention, it is possible to provide a surface-treated copper foil and a copper-clad laminate, which can stably manufacture surface-treated copper foils with roughened shapes that are difficult to control by previously used indicators (parameters) such as surface area or surface roughness. The above-mentioned surface-treated copper foil is used as, for example, copper foil for high-frequency printed wiring boards used in high frequency bands exceeding several GHz. It can be used to produce high-frequency electrical signals with low transmission loss and excellent reflow heat resistance. Printed wiring board. In addition, by using a three-dimensional light interference microscope, the sharpness (surface gradient) and the development area of the surface of the surface-treated copper foil can be appropriately controlled. Furthermore, the surface-treated copper foil of the present invention can achieve high-level transmission characteristics, resin adhesion, and reflow heat resistance, and can achieve high-level multilayers for routers or servers that require high frequency bands exceeding tens of GHz. Printed wiring boards are extremely useful in industry.

無。none.

圖1係針對經表皮深度d標準化的粗化粒子之高度h及寬度w，分為多個區域而示出於各種表面處理銅箔之表面測定的表觀導電率之圖。 圖2(a)及(b)係於電磁場分析上於紙面水平方向上施加高頻電場，並將此時所流動之高頻傳導電流密度於銅箔剖面上示出的概念圖，且圖2(a)表示於銅箔表面具有寬度w相對較大之粗化粒子的情形，圖2(b)表示於銅箔表面具有寬度w相對較小之粗化粒子的情形。 圖3(a)~(c)表示各種銅箔（原箔）之表面狀態，且圖3(a)係原箔A之M面之表面SEM（Scanning Electron Microscope，掃描式電子顯微鏡）照片（倍率：1000倍），圖3(b)係原箔B之M面之表面SEM照片（倍率：1000倍），而且圖3(c)係原箔B之S面之表面SEM照片（倍率：1000倍）。 圖4(a)及圖4(b)係從幾何學上觀看而表面積相同但具有不同表面粗糙度之兩個表面狀態之概念圖，且圖4(a)表示山之高度及寬度相對較大之表面狀態，圖4(b)表示山之高度及寬度相對較小之表面狀態。Fig. 1 is a graph showing the apparent conductivity measured on the surface of various surface-treated copper foils with respect to the height h and the width w of the roughened particles normalized by the skin depth d, divided into a plurality of regions. Figure 2 (a) and (b) are conceptual diagrams showing the high-frequency electric field applied in the horizontal direction of the paper in the electromagnetic field analysis, and the high-frequency conduction current density flowing at this time is shown on the cross-section of the copper foil, and Figure 2 (a) shows the case where there are roughened particles with a relatively large width w on the surface of the copper foil, and FIG. 2(b) shows the case where there are roughened particles with a relatively small width w on the surface of the copper foil. Figure 3(a)~(c) show the surface conditions of various copper foils (original foils), and Figure 3(a) is the surface SEM (Scanning Electron Microscope, Scanning Electron Microscope) photo of the M side of the original foil A (magnification) : 1000 times), Figure 3(b) is the surface SEM photo of the M side of the original foil B (magnification: 1000 times), and Figure 3(c) is the surface SEM photo of the S side of the original foil B (magnification: 1000 times) ). Figure 4(a) and Figure 4(b) are conceptual diagrams of two surface states with the same surface area but different surface roughness viewed from the geometry, and Figure 4(a) shows that the height and width of the mountain are relatively large Figure 4(b) shows the surface condition of the mountain with relatively small height and width.

Claims (7)

一種表面處理銅箔，其係於銅箔之至少單面，以前述銅箔為基準而依序積層有粗化處理層、防銹處理層及矽烷偶合層之表面處理銅箔，其特徵在於：作為自前述矽烷偶合層之表面測定的三維表面性狀之複合參數的界面之展開面積率Sdr之值為8~140%之範圍，均方根表面梯度Sdq之值為25~70°之範圍，且自前述矽烷偶合層之表面測定的三維表面性狀之空間參數的表面性狀之縱橫比Str之值為0.25~0.79。 A surface-treated copper foil, which is on at least one side of the copper foil, and has a roughening treatment layer, an anti-rust treatment layer, and a silane coupling layer sequentially laminated on the basis of the aforementioned copper foil, and is characterized in that: The value of the spread area ratio Sdr of the interface, which is the composite parameter of the three-dimensional surface properties measured from the surface of the aforementioned silane coupling layer, is in the range of 8~140%, and the value of the root mean square surface gradient Sdq is in the range of 25~70°, and The value of the aspect ratio Str of the spatial parameters of the three-dimensional surface properties measured from the surface of the aforementioned silane coupling layer is 0.25~0.79. 如申請專利範圍第1項所述之表面處理銅箔，其中自前述矽烷偶合層之表面測定的十點平均粗糙度Rzjis為0.9~1.5μm之範圍。 The surface-treated copper foil described in the first item of the scope of patent application, wherein the ten-point average roughness Rzjis measured from the surface of the aforementioned silane coupling layer is in the range of 0.9~1.5μm. 如申請專利範圍第1或2項所述之表面處理銅箔，其中前述粗化處理層及前述防銹處理層中的銅以外之金屬及該金屬之氧化物之合計含量換算成金屬元素而為0.15~0.50mg/dm2。 The surface-treated copper foil described in item 1 or 2 of the scope of the patent application, wherein the total content of the metal other than copper and the oxide of the metal in the roughening treatment layer and the anti-corrosion treatment layer is converted into a metal element 0.15~0.50mg/dm 2 . 如申請專利範圍第1項所述之表面處理銅箔，其中前述粗化處理層及前述防銹處理層中之Ni及Zn之含量分別為0.05~0.30mg/dm2。 The surface-treated copper foil described in the first item of the scope of patent application, wherein the contents of Ni and Zn in the roughening treatment layer and the anti-rust treatment layer are 0.05 to 0.30 mg/dm 2 respectively . 如申請專利範圍第2項所述之表面處理銅箔，其中前述粗化處理層及前述防銹處理層中之Ni及Zn之含量分別為0.05~0.30mg/dm2。 In the surface-treated copper foil described in item 2 of the scope of patent application, the contents of Ni and Zn in the roughening treatment layer and the anti-rust treatment layer are respectively 0.05 to 0.30 mg/dm 2 . 如申請專利範圍第3項所述之表面處理銅箔，其中前述粗化處理層及前述防銹處理層中之Ni及Zn之含量分別為0.05~0.30mg/dm2。 The surface-treated copper foil described in item 3 of the scope of patent application, wherein the contents of Ni and Zn in the roughening treatment layer and the anti-rust treatment layer are respectively 0.05 to 0.30 mg/dm 2 . 種覆銅積層板，其特徵在於：具有如申請專利範圍第1至6項中任一項所述之表面處理銅箔、及積層於該表面處理銅箔之前述矽烷偶合層上的樹脂，前述樹脂在頻率10GHz下之介電常數為3.5以下且介電損耗正切為0.006以下。 A copper-clad laminate, characterized in that it has the surface-treated copper foil as described in any one of items 1 to 6 in the scope of the patent application, and a resin laminated on the silane coupling layer of the surface-treated copper foil, the aforementioned The resin has a dielectric constant of 3.5 or less at a frequency of 10 GHz and a dielectric loss tangent of 0.006 or less.
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