TWI745585B - Surface treatment copper foil - Google Patents

Surface treatment copper foil Download PDF

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TWI745585B
TWI745585B TW107113994A TW107113994A TWI745585B TW I745585 B TWI745585 B TW I745585B TW 107113994 A TW107113994 A TW 107113994A TW 107113994 A TW107113994 A TW 107113994A TW I745585 B TWI745585 B TW I745585B
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copper foil
treated copper
silane coupling
coupling agent
olefin
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TW107113994A
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TW201900927A (en
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鶴田隆宏
宇野岳夫
奧野裕子
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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
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • 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
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • 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

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

Abstract

本發明之目的在於：消除銅箔與樹脂之壓製接合所致之接著不良，該銅箔於銅箔之粗糙化處理面藉由烯烴系矽烷偶合劑實施有矽烷偶合處理。本發明係一種表面處理銅箔，其粗糙化處理層側之面的表面粗糙度Rz利用接觸式粗糙度測定器測定時為1.10 µm以下，且前述粗糙化處理側之面的最小自相關長度Sal為0.20 µm以上且0.85 µm以下，且前述粗糙化處理側之面的界面展開面積比(Sdr)為20至300%之範圍。The object of the present invention is to eliminate the poor bonding caused by the pressing and joining of the copper foil and the resin. The copper foil is subjected to a silane coupling treatment on the roughened surface of the copper foil with an olefin-based silane coupling agent. The present invention is a surface-treated copper foil whose surface roughness Rz on the side of the roughened layer is 1.10 µm or less when measured by a contact roughness meter, and the minimum autocorrelation length of the surface on the roughened side Sal It is 0.20 µm or more and 0.85 µm or less, and the interface development area ratio (Sdr) of the surface on the roughened side is in the range of 20 to 300%.

Description

表面處理銅箔Surface treatment copper foil

本發明係關於一種表面處理銅箔，其與包含高頻對應基板之絕緣樹脂、尤其是聚苯醚(以下稱為PPE)系樹脂之樹脂基板之密接性優異。The present invention relates to a surface-treated copper foil that has excellent adhesion to insulating resins containing high-frequency-compatible substrates, especially polyphenylene ether (hereinafter referred to as PPE) resin substrates.

近年來，伴隨著電腦或是資訊通訊機器的高性能、高功能化，以及網路化的發展，為了將大容量之資訊以高速的方式進行傳輸處理，訊號有逐漸高頻化之傾向。此種資訊通訊機器使用覆銅積層板。此種覆銅積層板係將高頻對應絕緣基板(樹脂基板)與銅箔進行加熱並加壓而製作。In recent years, with the development of high-performance, high-functionality, and networking of computers or information communication equipment, in order to transmit and process large-capacity information in a high-speed manner, signals have gradually become more frequent. This type of information communication equipment uses copper clad laminates. Such a copper-clad laminated board is produced by heating and pressing a high-frequency-compatible insulating substrate (resin substrate) and copper foil.

通常，構成伺服器、路由器用電路基板等高頻對應之覆銅積層板之絕緣基板中，使用介電特性優異之樹脂。作為相對介電常數或介電損耗正切低之樹脂，使用聚苯醚(PPE)系樹脂，就與PPE系樹脂之化學親和性良好而言，作為銅箔之矽烷偶合處理劑，主要採用利用烯烴系矽烷偶合劑之處理。其原因在於，藉由矽烷偶合處理於銅箔表面形成矽氧烷交聯結構，可期待該矽氧烷交聯結構發揮作為與PPE系樹脂之接著劑的功能。Generally, resins with excellent dielectric properties are used for insulating substrates that constitute copper-clad laminates for high-frequency applications such as circuit substrates for servers and routers. As a resin with low relative permittivity or dielectric loss tangent, polyphenylene ether (PPE)-based resin is used. In terms of its good chemical affinity with PPE-based resin, as a silane coupling treatment agent for copper foil, olefins are mainly used It is the treatment of silane coupling agent. The reason is that the silicone cross-linked structure is formed on the surface of the copper foil by the silane coupling treatment, and the silicone cross-linked structure can be expected to function as an adhesive with the PPE-based resin.

例如，專利文獻1中，提出有於銅箔表面形成耐熱處理層，於該耐熱處理層上實施烯烴系矽烷偶合處理，藉此謀求接著強度及防銹性提高。 [先前技術文獻] (專利文獻)For example, in Patent Document 1, it is proposed to form a heat-resistant treatment layer on the surface of a copper foil, and to perform an olefin-based silane coupling treatment on the heat-resistant treatment layer, thereby improving adhesion strength and rust resistance. [Prior Art Document] (Patent Document)

專利文獻1：日本特開2003-201585號公報 　　專利文獻2：日本專利第4927463號 　　專利文獻3：日本專利第5242710號Patent Document 1: Japanese Patent Laid-Open No. 2003-201585 　　 Patent Document 2: Japanese Patent No. 4927463 　　 Patent Document 3: Japanese Patent No. 5242710

然而，專利文獻1中，雖然確保了實用上無問題之密接強度，但是並未提及關於高頻對應不可或缺之傳輸特性。專利文獻1中，於實施例中使用粗糙化後之表面粗糙度Rz為1.20 µm以上之銅箔，但若粗糙化後之表面粗糙度過大，則集膚效應(skin effect)變大，因此成為傳輸特性降低之主要原因。另外，即便是實用上無問題之密接強度，於實際製造步驟中，將PPE系樹脂與藉由烯烴系矽烷偶合劑進行處理後之銅箔積層而進行高溫壓製成形時，亦會於銅箔與樹脂之界面屢屢產生稱作所謂鼓起之局部接著不良區域，而導致樹脂基板之良率降低，但並未提及關於該方面。另外，專利文獻2中，於實施例中使用表面粗糙度為1.10 µm以下之銅箔，雖然獲得了可撓性基板用途中實用上無問題之傳輸特性，但是並未提及關於使用PPE系樹脂時的特性改善、和如鼓起之局部接著不良之問題。However, in Patent Document 1, although practically problem-free adhesion strength is ensured, there is no mention of transmission characteristics that are indispensable for high-frequency correspondence. In Patent Document 1, in the examples, a copper foil having a roughened surface roughness Rz of 1.20 µm or more is used. However, if the roughened surface roughness is too large, the skin effect becomes larger, and therefore it becomes The main reason for the decrease in transmission characteristics. In addition, even if the adhesive strength is practically no problem, in the actual manufacturing process, when the PPE resin and the copper foil treated with an olefin-based silane coupling agent are laminated and subjected to high-temperature compression molding, the copper foil and the The resin interface often produces a so-called bulging local adhesion poor area, which leads to a decrease in the yield of the resin substrate, but this aspect is not mentioned. In addition, in Patent Document 2, copper foil with a surface roughness of 1.10 µm or less is used in the examples, and although the transmission characteristics are practically problem-free for flexible substrate applications, there is no mention of the use of PPE-based resins. The characteristics of time are improved, and the problem of poor local adhesion such as bulging.

本發明之目的在於：消除銅箔與樹脂之壓製接合中的接著不良、尤其是於銅箔之粗糙化處理面藉由烯烴系矽烷偶合劑實施有矽烷偶合處理之銅箔與樹脂之壓製接合中的接著不良。 The purpose of the present invention is to eliminate poor adhesion in the press-bonding of copper foil and resin, especially in the press-bonding of copper foil and resin that has been subjected to silane coupling treatment with an olefin-based silane coupling agent on the roughened surface of the copper foil The connection is poor.

本發明之一實施形態之表面處理銅箔中，粗糙化處理側之面的表面粗糙度Rzjis利用接觸式粗糙度測定器測定時為1.10μm以下，且前述粗糙化處理側之面的最小自相關長度(Sal)為0.20μm以上且0.85μm以下之範圍，前述粗糙化處理側之面的界面展開面積比(Sdr)為20%以上且300%以下之範圍。 In the surface-treated copper foil of one embodiment of the present invention, the surface roughness Rzjis of the surface on the roughened side is 1.10 μm or less when measured with a contact roughness meter, and the minimum autocorrelation of the surface on the roughened side The length (Sal) is in the range of 0.20 μm or more and 0.85 μm or less, and the interface expansion area ratio (Sdr) of the surface on the roughened side is in the range of 20% or more and 300% or less.

本發明人等對將PPE樹脂與銅箔積層而進行高溫壓製成形時於銅箔與樹脂之界面所產生之鼓起之原因進行調查研究，結果得知，烯烴系矽烷偶合劑有如下之傾向，亦即，使粗糙化處理表面產生應力，產生使粗糙化處理面側朝內之捲曲。藉由烯烴系矽烷偶合劑之處理而於表面產生應力之機制並不確定，但可認為或許是附著於銅箔表面之官能基彼此之斥力弱，或者相互吸引，因此產生應力而產生捲曲。可認為此時所產生之應力於壓製時變得更大而產生接著不良。 The inventors of the present invention investigated the cause of bulging at the interface between the copper foil and the resin when the PPE resin and the copper foil were laminated and subjected to high-temperature press forming. As a result, they found that the olefin-based silane coupling agent has the following tendency: That is, stress is generated on the roughened surface, which causes curling of the roughened surface side inward. The mechanism of stress on the surface caused by the treatment of the olefin-based silane coupling agent is uncertain, but it may be considered that the functional groups attached to the surface of the copper foil have weak repulsive forces or are attracted to each other, thus generating stress and causing curling. It can be considered that the stress generated at this time becomes greater during pressing, resulting in poor adhesion.

發現對於解決該問題而言有效的是具有如下之表面性質狀態之銅箔，該表面性質狀態可保持與矽烷之反應性以確保樹脂密接性，並且使粗糙化處理面側之應力分散。亦即，得知藉由將銅箔之粗糙化處理側之面的表面粗糙度Rzjis設為利用接觸式粗糙度測定器測定時為1.10μm以下，將粗糙化處理側之面的最小自相關長度(Sal)設為0.20μm以上且0.85μm以下之範圍，將粗糙化處理側之面的界面展開面積比(Sdr)設為20%以上且未達300%之範圍，可使粗糙化處理面側之應力分散，消除銅箔之捲曲、壓製接著時之積層板之接著不良。 It has been found that effective for solving this problem is a copper foil having a surface property state that can maintain reactivity with silane to ensure resin adhesion and disperse the stress on the roughened surface side. That is, it is known that by setting the surface roughness Rzjis of the surface on the roughened side of the copper foil to be 1.10 μm or less when measured with a contact roughness meter, the minimum autocorrelation length of the surface on the roughened side (Sal) is set in the range of 0.20 μm or more and 0.85 μm or less, and the interface spread area ratio (Sdr) of the surface on the roughened side is set to 20% or more and less than 300%, so that the roughened side can be made The stress disperses, eliminates the curling of copper foil, and the poor adhesion of laminated boards during pressing and bonding.

表面粗糙度Rzjis係使用接觸式表面粗糙度測定器進行測定。於本發明之一實施形態中，使用小阪研究所股份有限公司製造之SURFCORDER SE1700 α，測定由JIS B 0601-2001所規定之十點平均表面粗糙度Rzjis。 The surface roughness Rzjis is measured using a contact surface roughness meter. In one embodiment of the present invention, SURFCORDER SE1700 α manufactured by Kosaka Research Institute Co., Ltd. was used to measure the ten-point average surface roughness Rzjis specified by JIS B 0601-2001.

最小自相關長度(Sal)係ISO25178中所規定之值，定義為表面形狀之自相關衰減至相關值s之面內的最短距離(只要無特別說明，則係指自s=1衰減至s=0.2的最短距離)，藉由三維白色干涉型顯微鏡進行測定。Sal可用作銅箔中，藉由粗糙化前之箔所具有之表面之起伏、和利用粗糙化形成之凹凸等所產生的表面形狀之陡峭度之指標。亦即，可謂Sa1之值越小，高低差以越短之距離變化，因此表面形狀越陡峭。於本發明之一實施形態中，使用Bruker股份有限公司製造之白色光干涉式表面形狀裝置Wyko，以倍率50倍，進行利用F-算子處理之斜率去除(經圓柱傾斜修正)、資料補全(既有方法(legacy method)，反覆5次)、利用高斯濾波器之高頻截止(250 KHz)，測定最小自相關長度(Sal)。The minimum autocorrelation length (Sal) is the value specified in ISO25178, which is defined as the shortest distance within the plane where the autocorrelation of the surface shape decays to the correlation value s (unless otherwise specified, it means the attenuation from s=1 to s= 0.2 shortest distance), measured with a three-dimensional white interference microscope. Sal can be used as an indicator of the steepness of the surface shape produced by the undulation of the surface of the foil before roughening and the unevenness formed by the roughening in the copper foil. That is, it can be said that the smaller the value of Sa1, the shorter the distance between the height difference and the steeper the surface shape. In one embodiment of the present invention, a white light interference surface shape device Wyko manufactured by Bruker Co., Ltd. is used to perform slope removal (corrected by cylinder tilt) and data completion using F-operator processing at a magnification of 50 times (Legacy method, repeated 5 times), using the high-frequency cutoff (250 KHz) of the Gaussian filter to determine the minimum autocorrelation length (Sal).

所謂界面展開面積比(Sdr)，係ISO25178中所規定之值，係指以具有測定區域之尺寸之理想面作為基準，根據表面性質狀態所增加之表面積之比率，由下式定義。The so-called interface development area ratio (Sdr) is the value specified in ISO25178, which refers to the ratio of the surface area increased by the surface properties based on the ideal surface with the size of the measurement area as a reference, and is defined by the following formula.

Figure 02_image001
Figure 02_image001

此處，式中之x、y係平面座標，z係高度方向之座標。z(x,y)表示某點之座標，將該座標進行微分，藉此成為該座標點處之斜率。另外，A係測定區域之平面面積。界面展開面積比(Sdr)可藉由三維白色干涉型顯微鏡、掃描型電子顯微鏡(Scanning Electron Microscope，SEM)、電子束三維粗糙度解析裝置等，測定、評估銅箔表面之凹凸差而求出。於本發明之一實施形態中，使用Bruker股份有限公司製造之白色光干涉式表面形狀裝置Wyko，以倍率50倍，進行利用F-算子處理之斜率去除(經圓柱傾斜修正)、資料補全(既有方法，反覆5次)、利用高斯濾波器之高頻截止(250KHz)，測定界面展開面積比Sdr。通常，Sdr與表面粗糙度Sa之變化無關，而是有若表面性質狀態之空間複雜性增加則增大之傾向。 Here, x and y in the formula are plane coordinates, and z are the coordinates in the height direction. z(x,y) represents the coordinate of a certain point, and the coordinate is differentiated to become the slope at the coordinate point. In addition, A is the plane area of the measurement area. The interface spread area ratio (Sdr) can be determined by measuring and evaluating the unevenness of the copper foil surface with a three-dimensional white interference microscope, a scanning electron microscope (Scanning Electron Microscope, SEM), an electron beam three-dimensional roughness analyzer, etc. In one embodiment of the present invention, a white light interference surface shape device Wyko manufactured by Bruker Co., Ltd. is used to perform slope removal (corrected by cylinder tilt) and data completion using F-operator processing at a magnification of 50 times (Existing method, repeat 5 times), use Gaussian filter's high frequency cut-off (250KHz), measure the interface spread area ratio Sdr. Generally, Sdr has nothing to do with the change of the surface roughness Sa, but tends to increase if the spatial complexity of the surface properties increases.

若銅箔之粗糙化處理側之面的表面粗糙度Rzjis利用接觸式粗糙度測定器測定時為1.10μm以下，則將PPE樹脂與銅箔積層而進行高溫壓製接著時，於銅箔與樹脂之界面不易產生鼓起。另外，若超過1.10μm，則有進行高溫壓製接著時，於銅箔與樹脂之界面產生鼓起，產生接著不良之傾向。 If the surface roughness Rzjis of the surface on the roughened side of the copper foil is 1.10μm or less when measured with a contact roughness tester, when the PPE resin and the copper foil are laminated and subjected to high-temperature press bonding, the surface roughness between the copper foil and the resin The interface is not easy to bulge. In addition, if it exceeds 1.10 μm, there is a tendency that swelling occurs at the interface between the copper foil and the resin when high-temperature press bonding is performed, and poor bonding tends to occur.

若銅箔之粗糙化處理側之面的最小自相關長度Sal為0.20μm以上且0.85μm以下之範圍，則可兼顧將PPE樹脂與銅箔積層而用作高頻對應之覆銅積層板時傳輸特性良好、以及防止捲曲及高溫壓製時接觸不良。若Sal未達0.20μm，則有表面形狀之陡峭度變得過大，用作高頻對應之覆銅積層板時，集膚效應變大，傳輸特性惡化之傾向。另一方面，若Sal超過0.85μm，則表面形狀之陡峭度得到緩和，因此用作高頻對應之覆銅積層板時，集膚效應受到抑制而傳輸特性無問題，但有起因於烯烴系矽烷偶合劑之應力不易分散，容易引起捲曲、高溫壓製時之接觸不良之傾向。 If the minimum autocorrelation length Sal of the roughened surface of the copper foil is within the range of 0.20μm or more and 0.85μm or less, it can be used as a copper-clad laminate for high-frequency transmission by laminating PPE resin and copper foil. Good properties, and prevent crimping and poor contact during high-temperature pressing. If Sal is less than 0.20μm, the steepness of the surface shape will become too large. When used as a copper-clad laminate for high frequency, the skin effect will increase and the transmission characteristics will tend to deteriorate. On the other hand, if Sal exceeds 0.85μm, the steepness of the surface shape is alleviated. Therefore, when it is used as a copper-clad laminate for high-frequency applications, the skin effect is suppressed and the transmission characteristics are not problematic, but it is caused by olefin-based silane The stress of the coupling agent is not easy to disperse, which tends to cause crimping and poor contact during high-temperature pressing.

若銅箔之粗糙化處理側之面的界面展開面積比Sdr為20%以上且300%以下之範圍，則可兼顧將PPE樹脂與銅箔積層而用作高頻對應之覆銅積層板時傳輸特性良好、以及防止捲曲及高溫壓製時接觸不良。若Sdr未達20%，則有粗糙化處理側之面中的局部應力不易分散，進行上述高溫壓製接著時，於銅箔與樹脂之界面容易產生鼓起之傾向。若Sdr超過300%，則有用作高頻對應之覆銅積層板時的集膚效應變大而傳輸特性惡化之傾向。If the interface expansion area ratio Sdr of the roughened side of the copper foil is 20% or more and 300% or less, the PPE resin and copper foil can be laminated and used as a copper-clad laminate for high-frequency transmission. Good properties, and prevent crimping and poor contact during high-temperature pressing. If the Sdr is less than 20%, the local stress on the surface of the roughening treatment side is not easy to disperse. When the high-temperature press bonding is performed as described above, bulging tends to occur at the interface between the copper foil and the resin. If Sdr exceeds 300%, the skin effect when used as a copper-clad laminate for high-frequency applications will increase and the transmission characteristics will tend to deteriorate.

根據本發明，可提供一種表面處理銅箔，其可消除將經表面處理之銅箔與樹脂基板進行壓製接合時的接合不良，與樹脂基板之密接性優異。According to the present invention, it is possible to provide a surface-treated copper foil which can eliminate bonding defects when the surface-treated copper foil and a resin substrate are press-bonded, and has excellent adhesion to the resin substrate.

本發明之另一實施形態之表面處理銅箔進而較佳為，於上述實施形態之表面處理銅箔中，前述粗糙化處理側之面的界面展開面積比Sdr為200%以上且260%以下之範圍。若銅箔之粗糙化處理側之面的界面展開面積比(Sdr)超過200%，則有粗糙化處理側之面的應力進一步分散，更不易產生銅箔之捲曲之傾向，若未達260%，則有用作高頻對應之覆銅積層板時的傳輸特性更優異之傾向。 　　本發明之另一實施形態之表面處理銅箔可為，於上述實施形態之表面處理銅箔中，前述表面處理包含烯烴系矽烷偶合處理。尤其是，進而較佳為矽烷偶合劑為γ-丙烯醯氧基丙基三甲氧基矽烷。另外，本發明之另一實施形態之表面處理銅箔與包含PPE樹脂之樹脂基板之密接性優異。The surface-treated copper foil of another embodiment of the present invention is more preferably that, in the surface-treated copper foil of the above-mentioned embodiment, the interface development area ratio Sdr of the surface on the roughened side is 200% or more and 260% or less Scope. If the interface expansion area ratio (Sdr) of the roughened side of the copper foil exceeds 200%, the stress on the roughened side will be further dispersed, and it will be less likely to cause curling of the copper foil. If it is less than 260% , There is a tendency for better transmission characteristics when used as a copper-clad laminate for high-frequency applications. "The surface-treated copper foil of another embodiment of the present invention may be that in the surface-treated copper foil of the above-mentioned embodiment, the surface treatment includes an olefin-based silane coupling treatment. In particular, it is more preferable that the silane coupling agent is γ-acryloxypropyltrimethoxysilane. In addition, the surface-treated copper foil of another embodiment of the present invention has excellent adhesion to the resin substrate containing PPE resin.

已知通常藉由烯烴系矽烷偶合劑進行處理後之銅箔與PPE系樹脂基板之化學親和性良好。可認為於銅箔表面形成矽氧烷交聯結構，該矽氧烷交聯結構發揮作為與PPE系樹脂之接著劑的功能。然而，如上所述，若將PPE系樹脂與經矽烷偶合處理之銅箔積層而進行高溫壓製成形，則有於銅箔與樹脂之界面產生稱作所謂鼓起之接著不良區域，產生接著不良之傾向。本發明之實施形態之銅箔即便是藉由烯烴系矽烷偶合劑、尤其是丙烯醯基系矽烷進行矽烷偶合處理後之銅箔，與包含PPE樹脂之樹脂基板之密接性亦優異。It is generally known that copper foil treated with an olefin-based silane coupling agent has a good chemical affinity with the PPE-based resin substrate. It is considered that a silicone cross-linked structure is formed on the surface of the copper foil, and the silicone cross-linked structure functions as an adhesive with the PPE-based resin. However, as described above, if the PPE resin and the copper foil treated with silane coupling are laminated and subjected to high-temperature press molding, a so-called bulging adhesion defect area occurs at the interface between the copper foil and the resin, resulting in poor adhesion. tendency. The copper foil of the embodiment of the present invention has excellent adhesion to a resin substrate containing a PPE resin even if the copper foil is subjected to a silane coupling treatment with an olefin-based silane coupling agent, especially an acryl-based silane.

(製造銅箔) 　　本發明中所使用之銅箔可為電解銅箔、壓延銅箔中之任一者。通常，印刷配線板中廣泛使用電解銅箔。該情形時，可於作為製箔步驟之滾筒面側之電解析出起始面(S面)、或作為非滾筒面側之電解析出結束面(M面)中之任一面，形成後述之耐熱處理層及烯烴系矽烷偶合劑層。通常，將M面用作接著面，但本發明之表面處理銅箔無論將哪一面用作接著面，只要藉由包含粗糙化處理之表面處理而使粗糙化處理側之面的界面展開面積比(Sdr)為20%以上且300%以下之範圍，則與樹脂之密接性均優異，且用作高頻對應之覆銅積層板時的傳輸特性優異。(Production of copper foil) 　　 The copper foil used in the present invention may be any of electrolytic copper foil and rolled copper foil. Generally, electrolytic copper foil is widely used in printed wiring boards. In this case, it can be formed on either the electrolysis starting surface (S surface) on the side of the drum surface as the foil making step or the electrolysis ending surface (M surface) on the side of the non-drum surface to form the following surface Heat-resistant treatment layer and olefin-based silane coupling agent layer. Normally, the M side is used as the bonding surface, but no matter which side is used as the bonding surface of the surface-treated copper foil of the present invention, as long as the surface treatment including the roughening treatment is used to make the interface expansion area ratio of the surface on the roughened side When (Sdr) is in the range of 20% or more and 300% or less, the adhesion to the resin is excellent, and the transmission characteristics when used as a copper-clad laminated board corresponding to high frequency is excellent.

(形成粗糙化層) 　　於銅箔之單面上，藉由微細銅粒子之電沈積，形成具有微細凹凸表面之粗糙化層。粗糙化處理層係藉由電鍍而形成，較佳為於鍍覆浴中添加螯合劑，螯合劑之濃度以0.2至0.4 mg/L為適當。作為螯合劑，可列舉：DL-蘋果酸、EDTA(ethylene diamine tetraacetic acid，乙二胺四乙酸)鈉溶液、葡萄糖酸鈉、二伸乙基三胺五乙酸(diethylene triamine pentaacetic acid，DTPA)五鈉等螯合劑等。粗糙化處理可分為2次，首先以相對較低之銅濃度進行鍍覆，其次以相對更高之銅濃度進行粗糙化鍍覆。(Formation of roughened layer) 　　On a single surface of the copper foil, a roughened layer with fine uneven surface is formed by electrodeposition of fine copper particles. The roughening treatment layer is formed by electroplating. Preferably, a chelating agent is added to the plating bath, and the concentration of the chelating agent is suitably 0.2 to 0.4 mg/L. Examples of chelating agents include: DL-malic acid, EDTA (ethylene diamine tetraacetic acid) sodium solution, sodium gluconate, diethylene triamine pentaacetic acid (diethylene triamine pentaacetic acid, DTPA) pentasodium And other chelating agents. The roughening treatment can be divided into 2 times, firstly plating with a relatively low copper concentration, and then roughening plating with a relatively higher copper concentration.

電解浴中，除硫酸銅、硫酸鈀(Pd)以外，還添加鐵(Fe)、鎢(W)等金屬，藉此可使起因於矽烷偶合劑之應力分散，從而可形成理想的表面形狀。通常，於銅濃度為15至25 g/L、硫酸濃度為130至180 g/L、液溫為20至30℃、電流密度為30至40 A/dm2 、處理時間為5秒至30秒之條件下進行電沈積。In the electrolytic bath, in addition to copper sulfate and palladium sulfate (Pd), metals such as iron (Fe) and tungsten (W) are added to disperse the stress caused by the silane coupling agent to form an ideal surface shape. Generally, the copper concentration is 15 to 25 g/L, the sulfuric acid concentration is 130 to 180 g/L, the liquid temperature is 20 to 30°C, the current density is 30 to 40 A/dm 2 , and the treatment time is 5 seconds to 30 seconds. Electrodeposition is carried out under the same conditions.

(形成鎳層、鋅層、鉻酸鹽處理層) 　　於本發明中，較佳為於粗糙化處理面上，進而依序形成鎳層、鋅層。該鋅層發揮如下之作為耐熱處理層之作用，亦即，將薄銅箔與樹脂基板進行熱壓接時，防止因薄銅箔與基板樹脂之反應所致之該基板樹脂之劣化、薄銅箔之表面氧化，提高與基板之接合強度。另外，鎳層發揮如下之作為鋅層之基底層之作用，用以防止對樹脂基板之熱壓接時該鋅層之鋅向銅箔(電解鍍銅層)側熱擴散，藉此使得鋅層之上述功能有效地發揮。(Formation of a nickel layer, a zinc layer, and a chromate treatment layer) "In the present invention, it is preferable to form a nickel layer and a zinc layer on the roughened surface in this order. The zinc layer functions as a heat-resistant treatment layer as follows, that is, when the thin copper foil and the resin substrate are thermally compressed, it prevents the substrate resin from deteriorating due to the reaction between the thin copper foil and the substrate resin, and the thin copper The surface of the foil is oxidized to improve the bonding strength with the substrate. In addition, the nickel layer functions as the base layer of the zinc layer as follows to prevent the zinc of the zinc layer from thermally diffusing to the copper foil (electrolytic copper plating layer) side during thermocompression bonding to the resin substrate, thereby making the zinc layer The above functions are effectively exerted.

再者，該等鎳層、鋅層可應用眾所周知之電解鍍覆法、無電解鍍覆法而形成。另外，該鎳層可由純鎳形成，亦可由含磷鎳合金形成。 　　另外，若對鋅層之表面進而進行鉻酸鹽處理，則於該表面形成抗氧化層，因此較佳。作為所應用之鉻酸鹽處理，依據眾所周知之方法即可，例如可列舉日本特開昭60-86894號公報中所揭示之方法。藉由使換算為鉻量為0.01至0.3 mg/dm2 左右之鉻氧化物及其水合物等附著，可對銅箔賦予優異之防銹能力。Furthermore, the nickel layer and zinc layer can be formed by applying well-known electrolytic plating methods and electroless plating methods. In addition, the nickel layer may be formed of pure nickel, or may be formed of a phosphorus-containing nickel alloy. In addition, if the surface of the zinc layer is further subjected to chromate treatment, an anti-oxidation layer is formed on the surface, which is preferable. As the chromate treatment to be applied, a well-known method may be used. For example, the method disclosed in Japanese Patent Application Laid-Open No. 60-86894 can be cited. By attaching chromium oxides and their hydrates, which are converted to chromium in the amount of about 0.01 to 0.3 mg/dm 2 , it is possible to impart excellent rust resistance to copper foil.

(矽烷處理) 　　對於以上述之方式實施有表面處理之銅箔，接下來塗佈與PPE系樹脂之親和性優異之烯烴系矽烷偶合劑而形成該烯烴系矽烷偶合劑之薄膜。該矽烷偶合劑之附著量較佳為0.25至0.40 mg/dm2 ，亦可為0.20至0.50 mg/dm2 。塗佈溶液係以有效成分之濃度成為0.001至10質量%、較佳為0.01至6質量%之方式，使用水、弱酸性水溶液等作為溶劑而製備。若未達0.001質量%，則有接著之改善效果變少之傾向，另外，若超過10質量%，則有效果飽和，並且溶解性變差之傾向。(Silane treatment) The copper foil that has been surface-treated in the above-mentioned manner is then coated with an olefin-based silane coupling agent having excellent affinity with the PPE-based resin to form a thin film of the olefin-based silane coupling agent. The adhesion amount of the silane coupling agent is preferably 0.25 to 0.40 mg/dm 2 , and can also be 0.20 to 0.50 mg/dm 2 . The coating solution is prepared using water, a weakly acidic aqueous solution, etc. as a solvent so that the concentration of the active ingredient becomes 0.001 to 10% by mass, preferably 0.01 to 6% by mass. If it is less than 0.001% by mass, the subsequent improvement effect tends to decrease, and if it exceeds 10% by mass, the effect is saturated and the solubility tends to deteriorate.

作為烯烴系矽烷偶合劑，例如可列舉：乙烯基系矽烷、丙烯醯基系矽烷、甲基丙烯醯基系矽烷。乙烯基系矽烷為乙烯基三氯矽烷、乙烯基三烷氧基矽烷、乙烯基二烷氧基烷基矽烷等，例如為乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(β-甲氧基乙氧基)矽烷、乙烯基二甲氧基甲基矽烷、乙烯基二乙氧基甲基矽烷等。丙烯醯基系矽烷可列舉γ-丙烯醯氧基丙基三甲氧基矽烷。甲基丙烯醯基系矽烷可列舉：γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、γ-甲基丙烯醯氧基丙基三乙氧基矽烷等。尤其是，可使用丙烯醯基系矽烷等。Examples of the olefin-based silane coupling agent include vinyl-based silane, acryl-based silane, and methacryl-based silane. Vinyl silanes are vinyl trichlorosilane, vinyl trialkoxy silane, vinyl dialkoxy alkyl silane, etc., such as vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri (β-Methoxyethoxy) silane, vinyl dimethoxy methyl silane, vinyl diethoxy methyl silane, etc. Examples of the acryl-based silanes include γ-acryloxypropyltrimethoxysilane. Examples of methacrylic silanes include: γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and γ-methacryloxy Propyl propyl methyl diethoxy silane, γ-methacryloxy propyl triethoxy silane, etc. In particular, acryl-based silane and the like can be used.

於銅箔塗佈上述之烯烴系矽烷偶合劑後，對處理銅箔進行風乾或加熱乾燥。水蒸發即可，充分發揮本發明之效果，但若於50至180℃下進行乾燥，則矽烷偶合劑與銅箔之反應得到促進，因而較佳。另外，可視需要適宜添加調配其他矽烷偶合劑、pH調整劑、緩衝劑等添加劑。 　　對於本發明之銅箔，作為矽烷處理之預處理，亦可形成矽氧烷覆膜。藉由形成矽氧烷覆膜，可進一步提高銅箔之耐酸性，且可提高與絕緣樹脂之接著強度。關於形成矽氧烷覆膜之方法，將矽酸鹽溶液或四烷氧基矽烷等矽化合物，利用水、甲醇、乙醇、丙酮、乙酸乙酯、甲苯等溶劑，以成為0.001至20重量%之方式進行稀釋，並藉由利用噴霧器之吹送、利用塗佈機之塗佈、浸漬、澆注等任一種方法，塗佈於銅箔即可。After coating the above-mentioned olefin-based silane coupling agent on the copper foil, air-dry or heat-dry the treated copper foil. The water evaporates, and the effect of the present invention is fully exhibited. However, if the drying is performed at 50 to 180°C, the reaction between the silane coupling agent and the copper foil is promoted, which is preferable. In addition, other additives such as silane coupling agent, pH adjusting agent, buffering agent, etc. can be appropriately added and formulated as needed. "For the copper foil of the present invention, as a pretreatment of silane treatment, a siloxane film can also be formed. By forming the silicone film, the acid resistance of the copper foil can be further improved, and the bonding strength with the insulating resin can be improved. Regarding the method of forming a silicone film, a silicate solution or a silicon compound such as tetraalkoxysilane is used in a solvent such as water, methanol, ethanol, acetone, ethyl acetate, toluene, etc., to make 0.001 to 20% by weight The method is diluted, and the copper foil can be applied to the copper foil by any method such as blowing with a sprayer, coating with a coating machine, dipping, and pouring.

(製造覆銅積層板) 　　於混合有包含聚苯醚樹脂之樹脂、例如聚苯醚樹脂及聚苯乙烯樹脂等的電絕緣性基板之表面，重疊載置薄銅箔之銅箔面(粗糙化處理層面)，進行加熱、加壓而製造覆銅積層板。 [實施例](Manufacture of copper clad laminate) 　　 On the surface of an electrically insulating substrate mixed with resin containing polyphenylene ether resin, such as polyphenylene ether resin and polystyrene resin, overlap the copper foil surface on which thin copper foil is placed (roughened Processing layer), heat and pressurize to produce copper clad laminate. [Example]

以下，基於實施例進一步具體說明本發明。再者，該等實施例表示較佳實施形態之一例，實施時可於不超出本發明之要旨之範圍內採用各種方式。Hereinafter, the present invention will be described in further detail based on examples. Furthermore, these embodiments represent one of the preferred embodiments, and various methods can be adopted in the implementation without departing from the scope of the present invention.

(製造電解銅箔) 　　為了製造實施例1至12及比較例1至13之銅箔，製備以下所示之組成之電解液，在下述之條件下，陽極使用貴金屬氧化物被覆鈦電極，陰極使用鈦製旋轉滾筒，以電流密度＝50至100 A/dm2 ，製造厚度18 µm之電解銅箔。 銅：70至130 g/L 硫酸：80至140 g/L 添加劑：3-巰基-1-丙烷磺酸鈉＝1至10 ppm 羥乙基纖維素＝1至100 ppm 低分子量膠(分子量3,000)＝1至50 ppm 氯化物離子濃度＝10至50 ppm 溫度：50至60℃(Production of Electrolytic Copper Foil) In order to produce the copper foils of Examples 1 to 12 and Comparative Examples 1 to 13, an electrolyte solution with the composition shown below was prepared. Under the following conditions, the anode was used to coat the titanium electrode with a noble metal oxide, and the cathode was used Titanium rotating drum, with current density = 50 to 100 A/dm 2 , to manufacture electrolytic copper foil with a thickness of 18 µm. Copper: 70 to 130 g/L Sulfuric acid: 80 to 140 g/L Additives: Sodium 3-mercapto-1-propane sulfonate = 1 to 10 ppm Hydroxyethyl cellulose = 1 to 100 ppm Low molecular weight gum (molecular weight 3,000) = 1 to 50 ppm chloride ion concentration = 10 to 50 ppm temperature: 50 to 60°C

(粗糙化處理) 　　接下來，針對實施例1至12之銅箔，藉由以下之條件進行首先之粗糙化處理1及其次之粗糙化處理2。(Roughening treatment) 　　 Next, with respect to the copper foils of Examples 1 to 12, the first roughening treatment 1 and the second roughening treatment 2 were performed under the following conditions.

(粗糙化處理1) 硫酸銅(按Cu濃度計算)：15至25 g-Cu/L 硫酸濃度：130至180 g/L 鈀化合物(按鈀濃度計算)：0.01至0.05 g-Pd/L 鐵化合物(按鐵濃度計算)：0.1至0.3 g-Fe/L 鎢化合物(按鎢濃度計算)：0.5至1.5 g-W/L 液溫：20至30℃ 電流密度：30至40 A/dm2 (Roughening treatment 1) Copper sulfate (calculated based on Cu concentration): 15 to 25 g-Cu/L Sulfuric acid concentration: 130 to 180 g/L Palladium compound (calculated based on palladium concentration): 0.01 to 0.05 g-Pd/L iron Compound (calculated based on iron concentration): 0.1 to 0.3 g-Fe/L Tungsten compound (calculated based on tungsten concentration): 0.5 to 1.5 gW/L Liquid temperature: 20 to 30°C Current density: 30 to 40 A/dm 2

(粗糙化處理2) 硫酸銅(按Cu濃度計算)：40至70 g-Cu/L 硫酸濃度：80至120 g/L 液溫：20至30℃ 電流密度：1.5至4 A/dm2 另一方面，針對比較例1至4之銅箔，基於專利文獻2之實施例，進行粗糙化鍍覆，針對比較例5至8，基於專利文獻3之實施例，進行粗糙化鍍覆。另外，針對比較例9至13，組合進行以下所示之粗糙化處理3及前述之粗糙化處理2，針對比較例14至17，組合進行以下所示之粗糙化處理4及粗糙化處理2，針對比較例18至21，組合進行以下所示之粗糙化處理5及粗糙化處理2。(Roughening treatment 2) Copper sulfate (calculated based on Cu concentration): 40 to 70 g-Cu/L Sulfuric acid concentration: 80 to 120 g/L Liquid temperature: 20 to 30°C Current density: 1.5 to 4 A/dm 2 On the one hand, for the copper foils of Comparative Examples 1 to 4, roughening plating was performed based on the examples of Patent Document 2, and for Comparative Examples 5 to 8, roughening plating was performed based on the Examples of Patent Document 3. In addition, for Comparative Examples 9 to 13, the following roughening treatment 3 and the aforementioned roughening treatment 2 were combined, and for Comparative Examples 14 to 17, the following roughening treatment 4 and roughening treatment 2 were combined, For Comparative Examples 18 to 21, the roughening treatment 5 and the roughening treatment 2 shown below were performed in combination.

(粗糙化處理3) 硫酸銅(按Cu濃度計算)：15至25 g-Cu/L 硫酸濃度：130至180 g/L 鉬化合物(按鉬濃度計算)：0.1至0.5 g-Mo/L 鐵化合物(按鐵濃度計算)：0.1至0.3 g-Fe/L 液溫：20至60℃ 電流密度：20至50 A/dm2 (Roughening treatment 3) Copper sulfate (calculated based on Cu concentration): 15 to 25 g-Cu/L Sulfuric acid concentration: 130 to 180 g/L Molybdenum compound (calculated based on molybdenum concentration): 0.1 to 0.5 g-Mo/L Iron Compound (calculated according to iron concentration): 0.1 to 0.3 g-Fe/L Liquid temperature: 20 to 60℃ Current density: 20 to 50 A/dm 2

(粗糙化處理4) 硫酸銅(按Cu濃度計算)：15至25 g-Cu/L 硫酸濃度：130至180 g/L 鐵化合物(按鐵濃度計算)：0.1至0.3 g-Fe/L 液溫：20至60℃ 電流密度：20至50 A/dm2 (Roughening treatment 4) Copper sulfate (calculated based on Cu concentration): 15 to 25 g-Cu/L Sulfuric acid concentration: 130 to 180 g/L Iron compound (calculated based on iron concentration): 0.1 to 0.3 g-Fe/L solution Temperature: 20 to 60℃ Current density: 20 to 50 A/dm 2

(粗糙化處理5) 硫酸銅(按Cu濃度計算)：15至25 g-Cu/L 硫酸濃度：130至180 g/L 鎢化合物(按鎢濃度計算)：0.5至1.5 g-W/L 液溫：20至60℃ 電流密度：20至50 A/dm2 (Roughening treatment 5) Copper sulfate (calculated based on Cu concentration): 15 to 25 g-Cu/L Sulfuric acid concentration: 130 to 180 g/L Tungsten compound (calculated based on tungsten concentration): 0.5 to 1.5 gW/L Liquid temperature: 20 to 60℃ current density: 20 to 50 A/dm 2

(金屬鍍覆處理) 　　接下來，針對實施例1至12及比較例1至21之銅箔，按照鍍鎳、鍍鋅、鍍鉻酸之順序，進行以下之條件之金屬鍍覆處理。(Metal plating treatment) 　　 Next, the copper foils of Examples 1 to 12 and Comparative Examples 1 to 21 were subjected to metal plating treatment under the following conditions in the order of nickel plating, zinc plating, and chromic acid plating.

(鍍鎳) 　　在下述之鍍覆浴及鍍覆條件下，實施一次處理層。 硫酸鎳六水合物：200至300 g/L 氯化鎳六水合物：30至60 g/L 硼酸：20至40 g/L 液溫：40至60℃ 電流密度：0.1至10 A/dm2 通電時間：1秒至2分鐘(Nickel plating) Under the following plating bath and plating conditions, a primary treatment layer is implemented. Nickel sulfate hexahydrate: 200 to 300 g/L Nickel chloride hexahydrate: 30 to 60 g/L Boric acid: 20 to 40 g/L Liquid temperature: 40 to 60℃ Current density: 0.1 to 10 A/dm 2 Power-on time: 1 second to 2 minutes

(鍍鋅) 　　在下述之鍍覆浴及鍍覆條件下，實施二次處理層。 硫酸鋅七水合物：1至30 g/L 氫氧化鈉：10至150 g/L 液溫：10至30℃ 電流密度：0.1至10 A/dm2 通電時間：1秒至2分鐘(Zinc plating) Under the following plating bath and plating conditions, the secondary treatment layer is applied. Zinc sulfate heptahydrate: 1 to 30 g/L Sodium hydroxide: 10 to 150 g/L Liquid temperature: 10 to 30°C Current density: 0.1 to 10 A/dm 2 Power-on time: 1 second to 2 minutes

(鍍鉻酸) 　　在上述各金屬鍍覆層處理後，在下述條件下，實施鉻酸鹽處理。 無水鉻酸：0.1至10 g/L 液溫：20至40℃ 電流密度：0.1至2 A/dm2 通電時間：1秒至2分鐘(Chromic acid plating) After the above-mentioned metal plating layer treatment, chromate treatment was performed under the following conditions. Anhydrous chromic acid: 0.1 to 10 g/L Liquid temperature: 20 to 40°C Current density: 0.1 to 2 A/dm 2 Power-on time: 1 second to 2 minutes

接下來，針對實施例1至12及比較例1至21之銅箔，使用屬於表1所示之烯烴系矽烷種之矽烷偶合劑之1 vol.%水溶液，在室溫下塗佈於上述表面處理銅箔。更詳細而言，在使銅箔傾斜之狀態下，歷時1分鐘使矽烷偶合劑水溶液均勻地流下，其後，進行利用滾筒之脫液並進行乾燥。Next, for the copper foils of Examples 1 to 12 and Comparative Examples 1 to 21, a 1 vol.% aqueous solution of a silane coupling agent belonging to the olefin-based silane species shown in Table 1 was applied to the above surface at room temperature Handle copper foil. More specifically, in the state where the copper foil was inclined, the silane coupling agent aqueous solution was allowed to uniformly flow down over 1 minute, and thereafter, the liquid was drained by a drum and dried.

Figure 107113994-A0305-02-0018-1
Figure 107113994-A0305-02-0018-1

針對進行上述表面處理後之實施例1至12及比較例1至21之銅箔，藉由以下所示之方法，測定界面展開面積比Sdr、最小自相關長度Sal、及表面粗糙度Rzjis，接下來，評估捲曲程度。 For the copper foils of Examples 1 to 12 and Comparative Examples 1 to 21 after the above surface treatment, the interface spread area ratio Sdr, the minimum autocorrelation length Sal, and the surface roughness Rzjis were measured by the methods shown below. Next, evaluate the degree of curling.

(測定界面展開面積比Sdr、及最小自相關長度Sal) (Determine the interface spread area ratio Sdr and the minimum autocorrelation length Sal)

使用Bruker股份有限公司製造之白色光干涉式表面形狀測定裝置Wyko，以倍率50倍，進行利用F-算子處理之斜率去除(經圓柱傾斜修正)、資料補全(既有方法，反覆5次)、利用高斯濾波器之高頻截止(250KHz)，測定表面處理銅箔之粗糙化面側的界面展開面積比Sdr及最小自相關長度Sal。測定部位係設為5個部位，將該等之平均值設為測定結果。結果如表2所示。 Using the white light interference type surface profile measuring device Wyko manufactured by Bruker Co., Ltd., with a magnification of 50 times, the slope removal (corrected by the cylinder tilt) and data completion (existing method, repeated 5 times) using F-operator processing ). Using the high frequency cut-off of the Gaussian filter (250KHz), measure the interface expansion area ratio Sdr and the minimum autocorrelation length Sal on the roughened surface side of the surface-treated copper foil. The measurement site was set to 5 sites, and the average value of these was set as the measurement result. The results are shown in Table 2.

(測定表面粗糙度Rzjis) (Measure the surface roughness Rzjis)

作為接觸式表面粗糙度測定機，使用小阪研究所股份有限公司製造之SURFCORDER SE1700，測定10點平均粗糙度Rzjis。結果如表2所示。 As a contact type surface roughness measuring machine, a SURFCORDER SE1700 manufactured by Kosaka Laboratory Co., Ltd. was used to measure the 10-point average roughness Rzjis. The results are shown in Table 2.

Figure 107113994-A0305-02-0020-2
Figure 107113994-A0305-02-0020-2

(評估捲曲程度) (Assess the degree of curling)

如圖1所示，將進行矽烷偶合處理後之銅箔10切成長10cm×寬5cm之長方形，以銅箔10之粗糙化面(M面)側為表面，靜置於水平台上，以左端超出寬度2cm之方式，放置Kokuyo製TZ-1343(商品名稱)之不銹鋼直尺(C型JIS1級30 cm)作為壓重物。其後，對於銅箔10之縱向中央部分(圖中之A之位置)以及其上下2 cm之部分(圖中之B及C之位置)合計3處，測定自銅箔10之靜置面算起之端部立起之高度[mm]，藉由計算3處之平均值，測定捲曲值。As shown in Figure 1, the copper foil 10 after the silane coupling treatment is cut into a rectangle with a length of 10 cm × a width of 5 cm, and the roughened surface (M surface) of the copper foil 10 is used as the surface. To exceed the width by 2cm, place a stainless steel ruler (Type C JIS1 class 30 cm) made by Kokuyo TZ-1343 (trade name) as a weight. After that, for the vertical center part of the copper foil 10 (the position of A in the figure) and the part 2 cm above and below it (the positions of B and C in the figure) in total, the measurement is calculated from the standing surface of the copper foil 10 The height of the raised end [mm] is calculated by calculating the average value of 3 places to determine the curl value.

依據以下基準評估所獲得之捲曲之程度。亦即，捲曲值未達0.5 mm之試片設為優而記為「◎」，捲曲值為0.5 mm以上且未達1.5 mm之試片設為良而記為「○」，捲曲值為1.5 mm以上之試片設為不合格而記為「×」，分別如表2所示。 　　接下來，為了評估對樹脂基板之熱壓接時的鼓起及傳輸特性，針對進行上述表面處理後之實施例1至12及比較例1至21之銅箔，利用以下之方法，進行對樹脂基板之壓接，評估鼓起程度及傳輸特性。Evaluate the degree of curl obtained based on the following criteria. That is, the test piece with a curl value of less than 0.5 mm is regarded as excellent and recorded as "◎", and the test piece with a curl value of 0.5 mm or more and less than 1.5 mm is regarded as good and recorded as "○", and the curl value is 1.5 Test pieces above mm are regarded as unqualified and marked as "×", as shown in Table 2 respectively. Next, in order to evaluate the swelling and transmission characteristics during thermocompression bonding to the resin substrate, the copper foils of Examples 1 to 12 and Comparative Examples 1 to 21 after the above surface treatment were applied to the resin by the following method Crimping of substrates, evaluation of bulging degree and transmission characteristics.

(對樹脂基板之壓接) 　　將聚苯醚樹脂及聚苯乙烯樹脂以特定比率混合，成形為厚度0.2 mm之板狀，而製作樹脂基材。將上述表面處理銅箔之矽烷偶合劑之塗佈面與樹脂基材重疊，藉由使用熱壓製加工機(東洋精機製作所公司製造，MINI TEST PRESS(商品名))之熱加壓成形法(壓製溫度＝200℃、壓製壓力＝3.0 MPa)，製作由表面處理銅箔及樹脂基材構成之覆銅積層板，作為試片。(Compression bonding to the resin substrate) 　　 Polyphenylene ether resin and polystyrene resin are mixed in a specific ratio and formed into a plate with a thickness of 0.2 mm to produce a resin substrate. The coating surface of the silane coupling agent of the above-mentioned surface-treated copper foil is overlapped with the resin base material, and the hot press molding method (pressing) is performed using a hot press machine (manufactured by Toyo Seiki Seisakusho Co., Ltd., MINI TEST PRESS (trade name)). Temperature=200°C, pressing pressure=3.0 MPa), a copper-clad laminated board composed of surface-treated copper foil and resin base material was produced as a test piece.

(測定密接強度) 　　密接強度係使用Tensilon試驗機(A&D股份有限公司製造)，將絕緣基板與銅箔壓製後，將試片蝕刻加工成10 mm寬度之電路圖案，測定將電路圖案沿90度方向以50 mm/分鐘之速度拉伸時的剝離強度。測定樣品係設為5個，將該等之平均值設為測定結果。 　　關於密接強度之程度，依據以下基準進行評估。亦即，將剝離強度為0.7kN/m以上之樣品設為優而記為「◎」，將剝離強度為0.5 kN/m以上且未達0.7 kN/m之樣品設為良而記為「○」，將剝離強度為0.4 kN/m以上且未達0.5 kN/m之樣品設為不合格而記為「×」，分別如表2所示。(Measurement of Adhesion Strength) 　　 Adhesion Strength is measured by using a Tensilon testing machine (manufactured by A&D Co., Ltd.) to press the insulating substrate and copper foil, and then etch the test piece into a circuit pattern with a width of 10 mm, and measure the circuit pattern along a 90 degree direction Peel strength when stretched at a speed of 50 mm/min. There are five measurement samples, and the average value of these samples is used as the measurement result.　　 The degree of adhesion strength is evaluated based on the following criteria. That is, a sample with a peel strength of 0.7 kN/m or more was regarded as excellent and marked as "◎", and a sample with a peel strength of 0.5 kN/m or more and less than 0.7 kN/m was regarded as good and marked as "○" ", the sample with a peel strength of 0.4 kN/m or more and less than 0.5 kN/m was regarded as unqualified and marked as "×", as shown in Table 2.

(評估鼓起程度) 　　將100 mm×100 mm(1 dm2 )之上述樹脂基材與銅箔在上述條件下藉由熱加壓成形而積層後，使用氯化銅溶液，對銅箔進行蝕刻，於銅箔經溶解去除之面，重疊另一聚苯醚系樹脂基材，進行熱加壓成形，製作試片。實施使該試片以頂部溫度260℃通過回流爐之回流加熱，觀察於冷卻後之試片是否產生鼓起。 　　依據以下基準評估捲曲之程度。亦即，將所產生之鼓起之個數為0個/dm2 之試片設為優而記為「◎」，將所產生之鼓起之個數為1至2個/dm2 之試片設為良而記為「○」，將所產生之鼓起之個數為3個/dm2 以上之試片設為不合格而記為「×」，分別如表2所示。(Evaluation of the degree of swelling) After laminating the 100 mm×100 mm (1 dm 2 ) resin base material and copper foil under the above conditions by heat and pressure forming, the copper foil is etched using a copper chloride solution , Overlay another polyphenylene ether resin base material on the surface where the copper foil has been dissolved and removed, and perform thermo-compression molding to make a test piece. Perform reflow heating of the test piece through a reflow oven at a top temperature of 260°C, and observe whether the test piece bulges after cooling. Evaluate the degree of curling based on the following criteria. That is, set the test piece with the number of bulges generated at 0 pcs/dm 2 as excellent and record it as "◎", and set the number of bulges generated at 1 to 2 pcs/dm 2 If the piece is good, it is recorded as "○", and the test piece with the number of bulging generated at 3 pieces/dm 2 or more is regarded as unqualified and recorded as "×", as shown in Table 2 respectively.

(傳輸特性) 　　將表面處理銅箔藉由熱加壓成形而積層於樹脂基材後，製作傳輸特性測定用之樣品，測定高頻帶域中的傳輸損耗。評估傳輸特性時，使用適於1至25 GHz帶域之測定的眾所周知之帶線共振器法(在微帶結構：介電體厚度50 µm、導體長度1.0 mm、導體厚度18 µm、導體電路寬度120 µm、特性阻抗50 Ω且無覆蓋層膜之狀態下，測定S21參數之方法)，計測頻率10 GHz下之傳輸損耗(dB/100 mm)。傳輸損耗越大，負絕對值越大。測定樣品係設為5個，將該等之平均值設為測定結果。 　　基於所獲得之傳輸損耗，依據以下基準評估傳輸特性。亦即，將傳輸損耗之絕對值未達16 dB之樣品設為優而記為「◎」，將傳輸損耗之絕對值為16 dB以上且未達20 dB之樣品設為良而記為「○」，將傳輸損耗之絕對值為20 dB以上之樣品設為不合格而記為「×」，分別如表2所示。(Transmission characteristics) "After the surface-treated copper foil is laminated on a resin substrate by heat and pressure forming, a sample for transmission characteristics measurement is prepared, and the transmission loss in the high frequency band is measured. When evaluating transmission characteristics, use the well-known stripline resonator method suitable for measurement in the 1 to 25 GHz band (in the microstrip structure: dielectric thickness 50 µm, conductor length 1.0 mm, conductor thickness 18 µm, conductor circuit width 120 µm, characteristic impedance 50 Ω, and no overlayer film, the method of measuring S21 parameters), measure the transmission loss (dB/100 mm) at a frequency of 10 GHz. The greater the transmission loss, the greater the negative absolute value. There are five measurement samples, and the average value of these samples is used as the measurement result.　　 Based on the obtained transmission loss, evaluate the transmission characteristics according to the following criteria. That is, the samples with the absolute value of the transmission loss less than 16 dB are regarded as excellent and marked as "◎", and the samples with the absolute value of the transmission loss above 16 dB and less than 20 dB are regarded as good and marked as "○" ”, the samples with the absolute value of the transmission loss of 20 dB or more are regarded as unqualified and marked as “×”, as shown in Table 2.

(銅箔特性的綜合評估) 　　考慮前述之密接強度、捲曲、鼓起、及傳輸特性之程度，依據以下基準進行銅箔的綜合評估。亦即，若完全無「×」而全部項目為「◎」，則設為「S」，若「◎」為2至3個，則設為「A」，若「◎」為1個，則設為「B」。另一方面，存在「×」時，若「×」之個數為1個，則設為「C」，若為2個，則設為「D」，若為3個，則設為「E」，若全部項目為「×」，則設為「F」，分別如表2所示。(Comprehensive evaluation of copper foil characteristics) 　　Considering the aforementioned degree of adhesion strength, curling, bulging, and transmission characteristics, a comprehensive evaluation of copper foil is carried out based on the following criteria. That is, if there is no "×" at all and all items are "◎", then set to "S", if "◎" is 2 to 3, then set to "A", if "◎" is 1, then Set to "B". On the other hand, when there is "×", if the number of "×" is 1, it is set to "C", if it is 2, it is set to "D", and if it is 3, it is set to "E" ", if all the items are "×", set to "F", as shown in Table 2.

如由表2可知，實施例1至4中，捲曲程度、鼓起程度均非常良好，傳輸特性亦良好。接下來，實施例5至8與實施例1相比，Sdr值略小，因此捲曲程度、鼓起程度稍差，但為品質上無問題之程度，傳輸特性亦良好。進而，實施例9至12與實施例1相比，Sdr值略大，因此捲曲程度、鼓起程度良好，關於傳輸特性，電流之集膚效應變大，因此傳輸特性稍差，但為品質上無問題之程度。 As can be seen from Table 2, in Examples 1 to 4, the degree of curling and the degree of bulging are very good, and the transmission characteristics are also good. Next, compared with Example 1, in Examples 5 to 8, the Sdr value is slightly smaller, so the degree of curling and bulging are slightly inferior, but the quality is not problematic, and the transmission characteristics are also good. Furthermore, in Examples 9 to 12, compared with Example 1, the Sdr value is slightly larger, so the degree of curling and swelling are good. Regarding the transmission characteristics, the skin effect of the current becomes larger, so the transmission characteristics are slightly inferior, but the quality is higher. No problem level.

相對於此，比較例1至4中，Sdr值為20%以下，因此捲曲程度、鼓起程度均於品質上不合格。比較例5至8中，Sdr值超過300%，因此捲曲程度、鼓起程度無問題，但集膚效應變得過大，作為品質而言不合格。比較例9至13中，粗糙化面之粗糙度Rzjis超過1.10μm而過大，因此無論Sdr之值如何，捲曲程度、鼓起程度均不合格。因為集膚效應亦變得過大，所以傳輸損耗亦不合格。比較例14至17中，Sal值未達0.20μm而過小，因此集膚效應變大，傳輸特性不合格。進而，比較例18至21中，Sal值超過0.85μm而過大，因此捲曲程度、鼓起程度不合格。 In contrast, in Comparative Examples 1 to 4, since the Sdr value is 20% or less, the degree of curling and the degree of bulging are both unacceptable in terms of quality. In Comparative Examples 5 to 8, the Sdr value exceeded 300%, so there was no problem with the degree of curl and the degree of bulging, but the skin effect became too large, and the quality was unacceptable. In Comparative Examples 9 to 13, the roughness Rzjis of the roughened surface exceeded 1.10 μm and was too large, so regardless of the value of Sdr, the degree of curl and the degree of bulging were unacceptable. Because the skin effect has become too large, the transmission loss is also unqualified. In Comparative Examples 14 to 17, the Sal value did not reach 0.20 μm and was too small, so the skin effect became large, and the transmission characteristics were unacceptable. Furthermore, in Comparative Examples 18 to 21, the Sal value exceeded 0.85 μm and was too large, so the degree of curling and the degree of bulging were unacceptable.

[產業上之可利用性] [Industrial availability]

根據本發明，可提供一種表面處理銅箔及覆銅積層板，該表面處理銅箔可消除將經表面處理之銅箔與樹脂基板進行壓製接合時的接合不良，與樹脂基板之密接性優異，該覆銅積層板的傳輸特性優異，因而產業上之可利用性高。According to the present invention, it is possible to provide a surface-treated copper foil and a copper-clad laminated board, which can eliminate the bonding failure when the surface-treated copper foil and the resin substrate are press-bonded, and have excellent adhesion to the resin substrate. The copper clad laminate has excellent transmission characteristics, and therefore has high industrial applicability.

10‧‧‧銅箔20‧‧‧尺10‧‧‧Copper foil 20‧‧‧ feet

圖1係表示實施例之銅箔之用以計算捲曲值的測定部位之圖。Fig. 1 is a diagram showing the measurement location for calculating the curl value of the copper foil of the example.

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Claims (9)

一種表面處理銅箔，其粗糙化處理側之面的由JIS B 0601-2001所規定之十點平均表面粗糙度Rzjis利用接觸式粗糙度測定器測定時為1.10μm以下，且前述粗糙化處理側之面的最小自相關長度(Sal)為0.20μm以上且0.85μm以下之範圍，且前述粗糙化處理側之面的界面展開面積比(Sdr)為20%以上且300%以下之範圍。 A surface-treated copper foil whose ten-point average surface roughness Rzjis specified by JIS B 0601-2001 on the roughened side is 1.10 μm or less when measured with a contact roughness meter, and the roughened side The minimum autocorrelation length (Sal) of the surface is within the range of 0.20 μm or more and 0.85 μm or less, and the interface spread area ratio (Sdr) of the surface on the roughened side is within the range of 20% or more and 300% or less. 如請求項1所述之表面處理銅箔，其中，前述界面展開面積比(Sdr)為200%以上且260%以下之範圍。 The surface-treated copper foil according to claim 1, wherein the interface spread area ratio (Sdr) is in the range of 200% or more and 260% or less. 如請求項1所述之表面處理銅箔，其中，於前述表面處理銅箔形成有由烯烴系矽烷偶合劑構成之矽烷偶合劑層。 The surface-treated copper foil according to claim 1, wherein a silane coupling agent layer composed of an olefin-based silane coupling agent is formed on the surface-treated copper foil. 如請求項2所述之表面處理銅箔，其中，於前述表面處理銅箔形成有由烯烴系矽烷偶合劑構成之矽烷偶合劑層。 The surface-treated copper foil according to claim 2, wherein a silane coupling agent layer composed of an olefin-based silane coupling agent is formed on the surface-treated copper foil. 如請求項3所述之表面處理銅箔，其中，前述烯烴系矽烷偶合劑為γ-丙烯醯氧基丙基三甲氧基矽烷。 The surface-treated copper foil according to claim 3, wherein the olefin-based silane coupling agent is γ-acryloxypropyltrimethoxysilane. 如請求項4所述之表面處理銅箔，其中，前述烯烴系矽烷偶合劑為γ-丙烯醯氧基丙基三甲氧基矽烷。 The surface-treated copper foil according to claim 4, wherein the olefin-based silane coupling agent is γ-acryloxypropyltrimethoxysilane. 如請求項1至6中任一項所述之表面處理銅 箔，其與包含聚苯醚系樹脂之樹脂基板之剝離強度為0.5kN/m以上，前述剝離強度係藉由將前述樹脂基板與前述表面處理銅箔壓製後，將試片蝕刻加工成10mm寬度之電路圖案，使用Tensilon試驗機(A&D股份有限公司製造)，將電路圖案沿90度方向以50mm/分鐘之速度拉伸來測定。 Surface-treated copper as described in any one of claims 1 to 6 Foil, the peel strength between it and the resin substrate containing polyphenylene ether resin is 0.5kN/m or more. The peel strength is obtained by pressing the resin substrate and the surface-treated copper foil, and then etching the test piece to a width of 10mm The circuit pattern was measured by using a Tensilon testing machine (manufactured by A&D Co., Ltd.) to stretch the circuit pattern in a 90-degree direction at a speed of 50 mm/min. 如請求項1至6中任一項所述之表面處理銅箔，其係於表面具有烯烴系矽烷偶合劑層的表面處理銅箔，並且，藉由下述方式而獲得之捲曲值未達0.5mm，亦即，將前述表面處理銅箔切成長10cm×寬5cm之長方形，以前述表面處理銅箔粗糙化面(M面)側為表面而靜置於水平台上，以左端超出寬度2cm之方式，放置不銹鋼直尺，對於前述表面處理銅箔縱向之中央部分以及其上下2cm之部分之合計3處，測定自前述表面處理銅箔之靜置面算起之端部立起之高度[mm]，計算前述3處之前述立起之高度之平均值。 The surface-treated copper foil according to any one of claims 1 to 6, which is a surface-treated copper foil having an olefin-based silane coupling agent layer on the surface, and the curl value obtained by the following method is less than 0.5 mm, that is, cut the aforementioned surface-treated copper foil into a rectangle with a length of 10 cm × 5 cm in width, and place it on a horizontal platform with the roughened surface (M surface) side of the aforementioned surface-treated copper foil as the surface, with the left end exceeding the width by 2 cm Method, place a stainless steel ruler, and measure the height of the end of the surface treatment copper foil from the standing surface of the surface treatment copper foil at 3 points in total at the central part of the surface treatment copper foil longitudinal direction and the part 2cm above and below it [mm ], Calculate the average of the heights of the aforementioned 3 locations. 如請求項1至6中任一項所述之表面處理銅箔，其係於表面具有烯烴系矽烷偶合劑層的表面處理銅箔，並且，將具有聚苯醚樹脂之厚度0.2mm之混合樹脂基材、與前述表面處理銅箔之前述烯烴系矽烷偶合劑層側積層而成之覆銅積層板中，所測定之鼓起之個數為0個， 前述測定係將該覆銅積層板切成100mm×100mm，於對前述表面處理銅箔藉由氯化銅溶液進行蝕刻而溶解去除之面，重疊另一聚苯醚系樹脂基材，進行熱加壓成形，製作試片，實施使該試片以頂部溫度260℃通過回流爐之回流加熱，測定於冷卻後之前述試片所產生之前述鼓起之個數。 The surface-treated copper foil according to any one of claims 1 to 6, which is a surface-treated copper foil having an olefin-based silane coupling agent layer on the surface, and a mixed resin having a thickness of 0.2 mm of polyphenylene ether resin In the copper clad laminate formed by laminating the substrate and the olefin-based silane coupling agent layer side of the surface-treated copper foil, the number of bulges measured is 0. The aforementioned measurement was performed by cutting the copper-clad laminate into 100mm×100mm, and superimposing another polyphenylene ether-based resin substrate on the surface where the surface-treated copper foil was dissolved and removed by etching with a copper chloride solution, and then heated Press molding to prepare a test piece, and heat the test piece through a reflow oven at a top temperature of 260° C., and measure the number of bulges generated by the test piece after cooling.
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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019198610A1 (en) * 2018-04-10 2019-10-17 Dic株式会社 Composite structure and manufacturing method therefor
CN113795615A (en) * 2019-06-07 2021-12-14 古河电气工业株式会社 Surface-treated copper foil, copper-clad laminate, and printed wiring board
JP7270579B2 (en) * 2019-06-19 2023-05-10 金居開發股▲分▼有限公司 Micro-roughened electrodeposited copper foil and copper-clad laminate
JPWO2021132191A1 (en) * 2019-12-26 2021-07-01
WO2021157362A1 (en) * 2020-02-04 2021-08-12 三井金属鉱業株式会社 Roughened copper foil, carrier-attached copper foil, copper clad laminate plate, and printed wiring board
JP7177956B2 (en) * 2020-02-04 2022-11-24 三井金属鉱業株式会社 Roughened copper foil, copper foil with carrier, copper clad laminate and printed wiring board
CN112455020B (en) * 2020-11-23 2023-04-07 江苏晟大元通新材料科技有限公司 High-frequency high-speed PCB copper-clad laminate and preparation method thereof
JP7051988B1 (en) 2020-11-27 2022-04-11 古河電気工業株式会社 Roughened copper foil, copper-clad laminate, and printed wiring board
TWI756155B (en) 2021-07-19 2022-02-21 長春石油化學股份有限公司 Surface-treated copper foil and copper clad laminate
KR20240033095A (en) * 2021-12-22 2024-03-12 미쓰이금속광업주식회사 Method for measuring surface parameters of copper foil, method for selecting copper foil, and method for producing surface-treated copper foil

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101126168A (en) * 2006-06-07 2008-02-20 古河电路铜箔株式会社 Surface treatment electrolysis copper foil, method for manufacturing the same , and circuit board
CN103260897A (en) * 2010-12-14 2013-08-21 3M创新有限公司 Images and method of making the same
JP2015013474A (en) * 2013-06-07 2015-01-22 古河電気工業株式会社 Copper clad laminate for high-frequency substrate and surface-treated copper foil
CN104812945A (en) * 2012-11-26 2015-07-29 Jx日矿日石金属株式会社 Surface-treated electrolytic copper foil, laminate, and printed circuit board

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5242710B2 (en) 1973-06-20 1977-10-26
JPS5810479B2 (en) * 1980-06-12 1983-02-25 新田 信市 Surface treatment method
JPH08309918A (en) * 1995-05-22 1996-11-26 Nippon Denkai Kk Copper clad laminated sheet, printed circuit board using the same and production of them
JP4379854B2 (en) 2001-10-30 2009-12-09 日鉱金属株式会社 Surface treated copper foil
JP2005190945A (en) * 2003-12-26 2005-07-14 Tdk Corp Member for electronic component, and electronic component using the same
JP4927463B2 (en) 2006-07-10 2012-05-09 パナソニック株式会社 Semiconductor integrated circuit
JP2008309918A (en) * 2007-06-13 2008-12-25 Panasonic Corp Plasma display device, and driving method of plasma display panel
JP4927963B2 (en) * 2010-01-22 2012-05-09 古河電気工業株式会社 Surface-treated copper foil, method for producing the same, and copper-clad laminate
JP2011216598A (en) * 2010-03-31 2011-10-27 Kuraray Co Ltd High-frequency circuit board
JP5871426B2 (en) * 2012-01-31 2016-03-01 古河電気工業株式会社 Surface treated copper foil for high frequency transmission, laminated plate for high frequency transmission and printed wiring board for high frequency transmission
WO2013115069A1 (en) * 2012-01-31 2013-08-08 三菱瓦斯化学株式会社 Resin composition for printed wiring board material, and prepreg, resin sheet, metal foil-clad laminate, and printed wiring board using same
CN103060882B (en) * 2013-01-21 2015-11-04 福建清景铜箔有限公司 The method and system of electrolytic copper foil are produced in a kind of copper-bath countercurrent flow
JP5885790B2 (en) * 2013-08-20 2016-03-15 Ｊｘ金属株式会社 Surface treated copper foil and laminated board using the same, copper foil with carrier, printed wiring board, electronic device, method for manufacturing electronic device, and method for manufacturing printed wiring board
JP5710737B1 (en) * 2013-11-29 2015-04-30 Jx日鉱日石金属株式会社 Surface-treated copper foil, laminated board, printed wiring board, printed circuit board, and electronic equipment
WO2016117498A1 (en) * 2015-01-19 2016-07-28 古河電気工業株式会社 Surface-treated electrolytic copper foil for lithium-ion secondary cell, electrode for lithium-ion secondary cell in which same is used, and lithium-ion secondary cell
CN107429417B (en) * 2015-03-31 2019-11-22 三井金属矿业株式会社 Roughening treatment copper foil, band carrier copper foil, copper-clad laminated board and printed circuit board
CN107532322B (en) * 2015-04-28 2019-07-16 三井金属矿业株式会社 Roughening treatment copper foil and printed circuit board
KR102413674B1 (en) * 2015-09-25 2022-06-27 후루카와 덴키 고교 가부시키가이샤 Electrolytic copper foil and various products using electrolytic copper foil
JP6294862B2 (en) * 2015-12-09 2018-03-14 古河電気工業株式会社 Surface-treated copper foil for printed wiring board, copper-clad laminate for printed wiring board, and printed wiring board
JP7114500B2 (en) * 2019-01-30 2022-08-08 Ｊｘ金属株式会社 Surface treated copper foil, copper clad laminate and printed wiring board

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101126168A (en) * 2006-06-07 2008-02-20 古河电路铜箔株式会社 Surface treatment electrolysis copper foil, method for manufacturing the same , and circuit board
CN103260897A (en) * 2010-12-14 2013-08-21 3M创新有限公司 Images and method of making the same
CN104812945A (en) * 2012-11-26 2015-07-29 Jx日矿日石金属株式会社 Surface-treated electrolytic copper foil, laminate, and printed circuit board
JP2015013474A (en) * 2013-06-07 2015-01-22 古河電気工業株式会社 Copper clad laminate for high-frequency substrate and surface-treated copper foil

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