TW201920776A - Surface-treated copper foil, and copper-clad laminate sheet and printed wiring board using same - Google Patents

Surface-treated copper foil, and copper-clad laminate sheet and printed wiring board using same Download PDF

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TW201920776A
TW201920776A TW107125309A TW107125309A TW201920776A TW 201920776 A TW201920776 A TW 201920776A TW 107125309 A TW107125309 A TW 107125309A TW 107125309 A TW107125309 A TW 107125309A TW 201920776 A TW201920776 A TW 201920776A
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particles
copper foil
roughened
treated copper
ratio
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TW107125309A
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Chinese (zh)
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TWI751359B (en
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齋藤貴広
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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
    • 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
    • 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
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0237—High frequency adaptations
    • 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
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating

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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)
  • Manufacturing & Machinery (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

The present invention provides a surface-treated copper foil and the like, capable of achieving both excellent high-frequency characteristics and high adhesiveness. The surface-treated copper foil has a copper foil substrate and a surface-treated film including at least a roughened layer formed by the formation of roughening particles at least on one surface of the copper foil substrate. The surface-treated copper foil is characterized in that when the number of roughening particles having a long-side dimension t1 of 0.1 [mu]m or larger is counted in an analysis region where a surface of the surface-treated film is observed with a scanning electron microscope (SEM), the number ratio of roughening particles having a long-side dimension t1 of 3.0 [mu]m or less is 99.0% or higher, the number ratio of roughening particles having a long-side dimension t1 of 1.0-3.0 μm within the aforementioned number ratio is 2.0-20.0%, and the number ratio of roughening particles having a ratio (t1/t2), that is, a ratio of long-side dimension t1 to short-side dimension t2, of 2 or larger among the roughening particles having the long-side dimension t1 of 1.0-3.0 μm is 20% or higher.

Description

表面處理銅箔、以及使用其之覆銅積層板及印刷配線板Surface-treated copper foil, copper-clad laminated board and printed wiring board using the same

本發明係關於一種表面處理銅箔，尤其係關於一種適用於在高頻帶下使用之印刷配線板的表面處理銅箔。進而，本發明係關於一種使用上述表面處理銅箔之覆銅積層板及印刷配線板。The present invention relates to a surface-treated copper foil, and more particularly, to a surface-treated copper foil suitable for a printed wiring board used in a high frequency band. Furthermore, this invention relates to the copper clad laminated board and printed wiring board using the said surface-treated copper foil.

近年來，開發有如超過20 GHz的高頻對應機器。但是，當在導體電路中傳輸頻率為GHz波段的高頻訊號時，電流流通之表皮深度約形成為2 µm或其以下，造成電流僅僅在導體的極為表層上流動。因此，當導體之表面凹凸大時，導體之傳輸路徑（亦即表皮部分之傳輸路徑）變長，傳輸損耗增加。從而，對上述高頻對應機器中所採用的覆銅積層板之銅箔，期望能減小其表面粗度，以抑制傳輸損耗的增加。In recent years, high-frequency devices such as those exceeding 20 GHz have been developed. However, when transmitting high-frequency signals in the GHz band in a conductor circuit, the depth of the skin through which the current flows is about 2 µm or less, causing the current to flow only on the extreme surface of the conductor. Therefore, when the surface of the conductor is uneven, the transmission path of the conductor (that is, the transmission path of the skin portion) becomes longer, and the transmission loss increases. Therefore, it is desirable to reduce the surface roughness of the copper foil of the copper-clad laminated board used in the above-mentioned high-frequency corresponding equipment to suppress an increase in transmission loss.

另外，通常，對於印刷配線板中所使用之銅箔，除傳輸特性以外，亦要求與樹脂基材之高接著性。一般而言，作為提高樹脂基材與銅箔表面之間的接著力之方法，可列舉以下之方法：藉由電氣電鍍、蝕刻等，於其表面形成粗化處理層（形成有粗化粒子之層），獲得與樹脂基材之物理接著效果（投錨效應），藉此提高接著力。不過，若為了有效提升銅箔表面與樹脂基材之間的接著性，而增大形成於銅箔表面上的粗化粒子的粒子尺寸時，如上所述，將導致傳輸損耗的增加。In addition, copper foils used in printed wiring boards generally require high adhesion to resin substrates in addition to transmission characteristics. In general, as a method of improving the adhesion between the resin substrate and the surface of the copper foil, the following methods can be mentioned: a roughening treatment layer is formed on the surface by electroplating, etching, etc. Layer) to obtain a physical bonding effect (anchoring effect) with the resin substrate, thereby improving the bonding force. However, if the particle size of the roughened particles formed on the surface of the copper foil is increased in order to effectively improve the adhesion between the surface of the copper foil and the resin substrate, as described above, the transmission loss will increase.

如此，在銅箔積層板中，抑制傳輸損耗以及提升（提升耐久性）銅箔與樹脂基材間之密接性（接著性），存在著一種相互權衡取捨(trade‐off)的關係。因此，先前以來，對於覆銅積層板中所使用之銅箔，一直在研究兼顧抑制傳輸損耗以及與樹脂基材之密接性，例如，專利文獻1中，提出有將粗化形狀控制為預定形狀之方法。另外，專利文獻2中，提出有為了兼顧銅箔與樹脂基材之密接性及精細圖案性，而形成規定了粒徑範圍之一次突起物群及二次突起物群之方法。專利文獻3中，提出有為了兼顧銅箔與樹脂基材之密接性及蝕刻後之樹脂之透明性，而針對每粒徑範圍規定粒子密度之方法。專利文獻4中，提出有為了兼顧銅箔與樹脂基材之密接性及抑制粗化粒子脫落，而針對每粒徑範圍規定粒子密度之方法。As described above, in a copper foil laminate, there is a trade-off relationship between suppression of transmission loss and improvement (improved durability) of the adhesion (adhesion) between the copper foil and the resin substrate. Therefore, the copper foil used in the copper-clad laminated board has been researched to suppress transmission loss and the adhesion to the resin substrate. For example, Patent Document 1 proposes to control the roughened shape to a predetermined shape. Method. In addition, Patent Document 2 proposes a method of forming a primary protrusion group and a secondary protrusion group having a predetermined particle size range in order to take into consideration the adhesion between the copper foil and the resin substrate and the fine patternability. Patent Document 3 proposes a method of specifying the particle density for each particle size range in order to take into consideration the adhesion between the copper foil and the resin substrate and the transparency of the resin after etching. Patent Document 4 proposes a method of specifying the particle density for each particle size range in order to take into consideration the adhesion between the copper foil and the resin substrate and to suppress the coarse particles from falling off.

且說，近年來，高頻對應印刷配線板在更加要求高可靠度之領域中迅速發展。例如，作為車載用印刷配線基板等移動通訊機器用印刷配線基板，要求即使在高溫環境等嚴苛環境下仍可使用的高可靠度。為了因應此種高可靠度的要求，必須要高度提升銅箔與樹脂基材間的密接性，例如，要求即使在150℃的溫度下仍可承受1000小時之嚴苛實驗的密接性。因此，如上所述之先前之方法中，無法滿足近年來所要求之嚴苛高溫環境下的密接性（耐熱密接性）。In addition, in recent years, high-frequency compatible printed wiring boards have been rapidly developed in a field that requires higher reliability. For example, as printed wiring boards for mobile communication devices such as printed wiring boards for automobiles, high reliability is required even in severe environments such as high-temperature environments. In order to meet such high reliability requirements, it is necessary to highly improve the adhesion between the copper foil and the resin substrate. For example, it is required to be able to withstand the rigorous test of 1000 hours even at a temperature of 150 ° C. Therefore, in the previous method as described above, the adhesion (heat-resistant adhesion) under the severe high-temperature environment required in recent years cannot be satisfied.

另一方面，於印刷配線板中所使用的銅箔，為了提高與樹脂基材之接著力，除了形成前述粗化處理層之外，還可使用藉由矽烷偶合劑而將銅箔表面進行處理，藉此獲得對樹脂基材之化學接著性之方法。但是，為了提升矽烷偶合劑與樹脂基材之間的化學性接著性，樹脂基材必須要具有一定程度之極性大的置換基。然而，為了抑制介電損耗，使用減少樹脂基材中極性大的置換基之量的低介電性基材時，即便利用矽烷偶合劑對銅箔表面進行處理亦難以獲得化學接著性，難以確保銅箔與樹脂基材間之充分的接著性。
先前技術文獻
專利文獻On the other hand, in order to improve the adhesion with the resin substrate, the copper foil used in the printed wiring board can be treated with a silane coupling agent in addition to the roughening layer described above. In this way, a method for obtaining chemical adhesiveness to a resin substrate is obtained. However, in order to improve the chemical adhesion between the silane coupling agent and the resin substrate, the resin substrate must have a certain degree of highly polar substituents. However, in order to suppress dielectric loss, when using a low-dielectric substrate that reduces the amount of polar substituents in the resin substrate, it is difficult to obtain chemical adhesion even if the surface of the copper foil is treated with a silane coupling agent, which is difficult to ensure. Sufficient adhesion between copper foil and resin substrate.
Prior art literature patent literature

專利文獻1：日本專利第5972486號公報
專利文獻2：日本專利特開平10-341066號公報
專利文獻3：日本專利特開2015-24515號公報
專利文獻4：日本專利特開2016-145390號公報Patent Literature 1: Japanese Patent No. 5972486 Patent Literature 2: Japanese Patent Laid-Open No. 10-341066 Patent Literature 3: Japanese Patent Laid-Open No. 2015-24515 Patent Literature 4: Japanese Patent Laid-Open No. 2016-145390

發明欲解決之課題Problems to be solved by the invention

本發明係鑒於上述實際情況而完成者，其目的在於提供一種尤其是用於印刷配線板之導體電路時可兼顧優異的高頻特性（低介電損耗）與高密接性（常態密接性及耐熱密接性）的表面處理銅箔、以及使用其之覆銅積層板及印刷配線板。
解決問題之技術手段The present invention has been made in view of the above-mentioned circumstances, and an object thereof is to provide an excellent high-frequency characteristic (low dielectric loss) and high adhesion (normal-state adhesion and heat resistance) especially when used for conductor circuits of printed wiring boards. (Adhesiveness) surface-treated copper foil, and copper-clad laminated board and printed wiring board using the same.
Technical means to solve problems

本發明者反覆進行努力研究，結果發現，於銅箔基體之至少一面，具有至少包含形成有粗化粒子之粗化處理層的表面處理皮膜之表面處理銅箔中，在藉由掃描式電子顯微鏡(SEM, Scanning Electron Microscope)觀察前述表面處理皮膜之表面所得的分析區域中，計算長邊方向尺寸t1為0.1 µm以上之粗化粒子之個數時，長邊方向尺寸t1為3.0 µm以下之粗化粒子之個數比率為99.0%以上，且前述個數比率中長邊方向尺寸t1為1.0至3.0 µm之粗化粒子所佔之個數比率為2.0至20.0%，長邊方向尺寸t1相對於短邊方向尺寸t2之比(t1/t2)為2以上之粗化粒子於前述長邊方向尺寸t1為1.0至3.0 µm之粗化粒子中所佔之個數比率為20%以上，藉此可獲得尤其是用於印刷配線板之導體電路時可兼顧優異的高頻特性（低介電損耗）與高密接性（常態密接性及耐熱密接性）的表面處理銅箔，基於該見解而完成了本發明。The present inventors have conducted diligent research and found that, on at least one side of the copper foil substrate, a surface-treated copper foil having a surface-treated film including at least a roughened layer formed with roughened particles was subjected to a scanning electron microscope. (SEM, Scanning Electron Microscope) In the analysis area obtained by observing the surface of the aforementioned surface-treated film, when the number of roughened particles whose length dimension t1 is 0.1 μm or more is calculated, the length dimension t1 is coarser than 3.0 μm. The ratio of the number of coarsened particles is 99.0% or more, and the ratio of the number of coarsened particles with a length dimension t1 of 1.0 to 3.0 µm in the foregoing number ratio is 2.0 to 20.0%. The ratio of the number of roughened particles with a ratio of t2 in the short-side direction (t1 / t2) of 2 or more to the number of the roughened particles in the long-side direction with t1 of 1.0 to 3.0 µm is 20% or more. Based on this knowledge, we obtained a surface-treated copper foil that achieves both high-frequency characteristics (low dielectric loss) and high adhesion (normal adhesion and heat-resistant adhesion), especially for conductor circuits used in printed wiring boards. Invention.

即，本發明之主旨構成如下。
[1]一種表面處理銅箔，其係具有銅箔基體，且於該銅箔基體之至少一面，具有至少包含形成有粗化粒子之粗化處理層的表面處理皮膜之表面處理銅箔，其特徵在於：
在藉由掃描式電子顯微鏡(SEM)觀察前述表面處理皮膜之表面所得的分析區域中，計算長邊方向尺寸t1為0.1 µm以上之粗化粒子之個數時，
長邊方向尺寸t1為3.0 µm以下之粗化粒子之個數比率為99.0%以上，且前述個數比率中長邊方向尺寸t1為1.0至3.0 µm之粗化粒子所佔之個數比率為2.0至20.0%，
長邊方向尺寸t1相對於短邊方向尺寸t2之比(t1/t2)為2以上之粗化粒子於前述長邊方向尺寸t1為1.0至3.0 µm之粗化粒子中所佔之個數比率為20%以上。
[2]如上述[1]所記載之表面處理銅箔，其中前述長邊方向尺寸t1為1.0至3.0 µm之粗化粒子之個數在前述分析區域每300 µm2 中為20至100個。
[3]如上述[1]或[2]所記載之表面處理銅箔，其中長邊方向尺寸t1未達1.0 µm之粗化粒子之個數在前述分析區域每300 µm2 中為300至1200個。
[4]如上述[1]至[3]中任一項所記載之表面處理銅箔，其中長邊方向尺寸t1超過3.0 µm之粗化粒子之個數在前述分析區域每300 µm2 中為0至3個。
[5]如上述[1]至[4]中任一項所記載之表面處理銅箔，其中長邊方向尺寸t1為1.0至3.0 µm且長邊方向尺寸t1相對於短邊方向尺寸t2之比(t1/t2)為2以上之粗化粒子之個數在前述分析區域每300 µm2 中為8個以上。
[6]如上述[1]至[5]中任一項所記載之表面處理銅箔，其中前述長邊方向尺寸t1為1.0至3.0 µm之粗化粒子之個數在前述分析區域每300 µm2 中為40至80個。
[7]如上述[1]至[6]中任一項所記載之表面處理銅箔，其中前述表面處理皮膜之表面的十點平均粗糙度Rzjis值為0.5至2.0 µm。
[8]如上述[1]至[7]中任一項所記載之表面處理銅箔，其係用於高頻帶用印刷配線板。
[9]如上述[1]至[8]中任一項所記載之表面處理銅箔，其係用於車載用印刷配線板。
[10]一種覆銅積層板，其係使用如上述[1]至[9]中任一項所記載之表面處理銅箔而形成。
[11]一種印刷配線板，其係使用如上述[10]所記載之覆銅積層板而形成。
發明效果That is, the gist of the present invention is structured as follows.
[1] A surface-treated copper foil having a copper foil substrate, and a surface-treated copper foil including at least one side of the copper foil substrate, a surface-treated film including at least a roughened layer formed with a roughened particle, Features are:
In the analysis area obtained by observing the surface of the surface-treated film with a scanning electron microscope (SEM), when the number of roughened particles having a dimension t1 of 0.1 µm or more in the longitudinal direction is calculated,
The ratio of the number of roughened particles with a length t1 of 3.0 µm or less in the longitudinal direction is 99.0% or more, and the ratio of the number of coarsened particles with a length t1 of 1.0 to 3.0 µm in the aforementioned number ratio is 2.0 To 20.0%,
The ratio of the number of coarse particles having a ratio (t1 / t2) of the long-side dimension t1 to the short-side dimension t2 of 2 or more in the coarse particles having the long-side dimension t1 of 1.0 to 3.0 µm is 20% or more.
[2] The surface-treated copper foil according to the above [1], wherein the number of roughened particles in the longitudinal direction dimension t1 is 1.0 to 3.0 µm is 20 to 100 per 300 µm 2 in the analysis area.
[3] The surface-treated copper foil according to the above [1] or [2], wherein the number of roughened particles whose length dimension t1 is less than 1.0 µm in the foregoing analysis area is 300 to 1200 per 300 µm 2 Each.
[4] The surface-treated copper foil according to any one of the above [1] to [3], wherein the number of roughened particles whose length dimension t1 exceeds 3.0 µm in the analysis area is 300 µm 2 0 to 3.
[5] The surface-treated copper foil according to any one of the above [1] to [4], wherein the length t1 in the longitudinal direction is 1.0 to 3.0 µm and the ratio of the length t1 to the length t2 in the short direction The number of roughened particles whose (t1 / t2) is 2 or more is 8 or more per 300 µm 2 in the analysis area.
[6] The surface-treated copper foil according to any one of the above [1] to [5], wherein the number of roughened particles in the longitudinal direction dimension t1 is 1.0 to 3.0 µm per 300 µm in the aforementioned analysis area 2 is 40-80.
[7] The surface-treated copper foil according to any one of the above [1] to [6], wherein the ten-point average roughness Rzjis value of the surface of the surface-treated film is 0.5 to 2.0 µm.
[8] The surface-treated copper foil according to any one of the above [1] to [7], which is used for a high-frequency band printed wiring board.
[9] The surface-treated copper foil according to any one of the above [1] to [8], which is used for a printed wiring board for a vehicle.
[10] A copper-clad laminated board formed by using the surface-treated copper foil according to any one of the above [1] to [9].
[11] A printed wiring board formed using the copper-clad laminated board according to [10] above.
Invention effect

根據本發明，於具有銅箔基體，且於該銅箔基體之至少一面，具有至少包含形成有粗化粒子之粗化處理層的表面處理皮膜之表面處理銅箔中，在藉由掃描式電子顯微鏡(SEM)觀察前述表面處理皮膜之表面所得的分析區域中，計算長邊方向尺寸t1為0.1 µm以上之粗化粒子之個數時，長邊方向尺寸t1為3.0 µm以下之粗化粒子之個數比率為99.0%以上，且前述個數比率中長邊方向尺寸t1為1.0至3.0 µm之粗化粒子所佔之個數比率為2.0至20.0%，長邊方向尺寸t1相對於短邊方向尺寸t2之比(t1/t2)為2以上之粗化粒子於前述長邊方向尺寸t1為1.0至3.0 µm之粗化粒子中所佔之個數比率為20%以上，藉此可獲得尤其是用於印刷配線板之導體電路時可兼顧優異的高頻特性（低介電損耗）與高密接性（常態密接性及耐熱密接性）的表面處理銅箔、以及使用其之覆銅積層板及印刷配線板。According to the present invention, in a surface-treated copper foil having a copper foil substrate and at least one side of the copper foil substrate, the surface-treated copper foil including a surface-treated film having a roughened layer on which roughened particles are formed, in a scanning electron In the analysis area obtained by observing the surface of the surface-treated film with a microscope (SEM), when calculating the number of roughened particles having a dimension t1 of 0.1 µm or more in the longitudinal direction, the number of roughened particles having a dimension t1 of 3.0 µm or less in the longitudinal direction is calculated. The number ratio is 99.0% or more, and the number ratio of the coarse particles having a length dimension t1 of 1.0 to 3.0 µm in the foregoing number ratio is 2.0 to 20.0%, and the length dimension t1 is relative to the short direction. The ratio of the number of roughened particles having a ratio of t2 (t1 / t2) of 2 or more to the aforementioned roughened particles having a size t1 of 1.0 to 3.0 µm in the longitudinal direction is 20% or more. When used for conductor circuits of printed wiring boards, a surface-treated copper foil, which has both excellent high-frequency characteristics (low dielectric loss) and high adhesion (normal adhesion and heat-resistant adhesion), and a copper-clad laminated board using the same, and Printed wiring board.

以下，對本發明之表面處理銅箔之較佳實施形態進行詳細說明。
依據本發明之表面處理銅箔之特徵在於：具有銅箔基體，且於該銅箔基體之至少一面，具有至少包含形成有粗化粒子之粗化處理層的表面處理皮膜，在藉由掃描式電子顯微鏡(SEM)觀察前述表面處理皮膜之表面所得的分析區域中，計算長邊方向尺寸t1為0.1 µm以上之粗化粒子之個數時，長邊方向尺寸t1為3.0 µm以下之粗化粒子之個數比率為99.0%以上，且前述個數比率中長邊方向尺寸t1為1.0至3.0 µm之粗化粒子所佔之個數比率為2.0至20.0%，長邊方向尺寸t1相對於短邊方向尺寸t2之比(t1/t2)為2以上之粗化粒子於前述長邊方向尺寸t1為1.0至3.0 µm之粗化粒子中所佔之個數比率為20%以上。Hereinafter, preferred embodiments of the surface-treated copper foil of the present invention will be described in detail.
The surface-treated copper foil according to the present invention is characterized in that it has a copper foil substrate, and on at least one side of the copper foil substrate, a surface-treated film including at least a roughened layer on which roughened particles are formed. In the analysis area obtained by observing the surface of the aforementioned surface-treated film with an electron microscope (SEM), when the number of roughened particles having a dimension t1 of 0.1 µm or more in the longitudinal direction is calculated, the roughened particles having a dimension t1 of 3.0 µm or less in the longitudinal direction are calculated. The number ratio is 99.0% or more, and the number ratio of the coarsened particles with the long-side dimension t1 of 1.0 to 3.0 µm in the foregoing number ratio is 2.0 to 20.0%. The long-side dimension t1 is relative to the short side. The ratio of the number of roughened particles having a ratio (t1 / t2) of two or more in the direction dimension t2 to the roughened particles having a dimension t1 of 1.0 to 3.0 µm in the longitudinal direction is 20% or more.

本發明之表面處理銅箔具有銅箔基體，且於該銅箔基體之至少一個面，具有至少包含形成有粗化粒子之粗化處理層的表面處理皮膜。此種表面處理皮膜之表面係表面處理銅箔之最表面（表面及背面）中的至少一個面，且為形成於銅箔基體之至少一個面的反映出粗化粒子之形成狀態及粒子形狀等的具有微細凹凸表面形狀之粗化面。此種表面處理皮膜之表面（以下亦稱為「粗化面」）例如可為形成於銅箔基體上之粗化處理層之表面，或者亦可為直接形成於該粗化處理層上之矽烷偶合劑層之表面或於該粗化處理層上隔著含有鎳(Ni)之基底層、含有鋅(Zn)之耐熱處理層及防銹處理層等的中間層而間接地形成的矽烷偶合劑層之表面。再者，本發明之表面處理銅箔例如在用於印刷配線板之導體電路時，上述粗化面成為用以貼附積層樹脂基材之表面（貼附面）。The surface-treated copper foil of the present invention has a copper foil substrate, and at least one surface of the copper foil substrate has a surface-treated film including at least a roughened layer formed with roughened particles. The surface of such a surface-treated film is at least one of the outermost surfaces (front and back) of the surface-treated copper foil, and reflects the formation state and particle shape of the roughened particles formed on at least one surface of the copper foil substrate. Rough surface with fine uneven surface shape. The surface of such a surface-treated film (hereinafter also referred to as a "roughened surface") may be, for example, the surface of a roughened layer formed on a copper foil substrate, or may be a silane formed directly on the roughened layer. Silane coupling agent formed indirectly on the surface of the coupling agent layer or on the roughened layer through an intermediate layer such as a base layer containing nickel (Ni), a heat-resistant treatment layer containing zinc (Zn), and an anti-rust treatment layer. The surface of the layer. Moreover, when the surface-treated copper foil of this invention is used for the conductor circuit of a printed wiring board, for example, the said roughened surface becomes the surface (attachment surface) for attaching a laminated resin base material.

進而，本發明中，對粗化面自正上方（自相對於該表面垂直之方向）藉由掃描式電子顯微鏡(SEM)進行觀察，藉此分析粗化面中之粗化粒子之形成狀態。再者，本發明中，所謂粗化粒子，係指例如藉由後述之粗化處理所形成的粒狀的電沉積物。進而，關於粗化粒子之大小，在藉由SEM所觀察的分析區域中，俯視（例如，如圖1(b)所示，以X-Y平面觀察）粗化粒子，繪製相對於該粗化粒子外接之最小面積之長方形P時的長方形P之長邊t1及短邊t2分別定義為粗化粒子之長邊方向尺寸t1及短邊方向尺寸t2。再者，俯視下相對於粗化粒子外接之最小面積之長方形P為正方形時，長邊方向尺寸t1及短邊方向尺寸t2為相同長度。Furthermore, in the present invention, the roughened surface is observed from directly above (from a direction perpendicular to the surface) by a scanning electron microscope (SEM) to analyze the formation state of roughened particles in the roughened surface. In addition, in the present invention, the roughened particles refer to, for example, granular electrodeposits formed by a roughening process described later. Furthermore, regarding the size of the roughened particles, in the analysis area observed by the SEM, the roughened particles are viewed in a plan view (for example, as viewed in the XY plane as shown in FIG. 1 (b)), and the outer part of the roughened particles is plotted. The long side t1 and the short side t2 of the rectangle P when the rectangle P has the smallest area are defined as the long side dimension t1 and the short side dimension t2 of the roughened particles, respectively. In addition, when the rectangle P with the smallest area circumscribed with respect to the roughened particles is square in plan view, the long-side dimension t1 and the short-side dimension t2 have the same length.

此處，圖1(b)係自正上方藉由掃描式電子顯微鏡(SEM)觀察本發明之表面處理銅箔之粗化面所得的SEM圖像之一例。另外，為了比較，利用與圖1(b)所示之本發明之表面處理銅箔相同之方法觀察的2種先前之表面處理銅箔之粗化面的SEM圖像分別示於圖1(a)及圖1(c)。Here, FIG. 1 (b) is an example of an SEM image obtained by observing the roughened surface of the surface-treated copper foil of the present invention with a scanning electron microscope (SEM) from directly above. In addition, for comparison, the SEM images of the roughened surfaces of the two previous surface-treated copper foils observed by the same method as the surface-treated copper foil of the present invention shown in FIG. 1 (b) are shown in FIG. 1 (a). ) And Figure 1 (c).

圖1(a)所示之先前之表面處理銅箔中，粗化面中之粗化粒子在俯視下為圓形，且具有微細且均勻的粒徑。專利文獻1至4中所記載之表面處理銅箔相當於該例，此種表面處理銅箔由於粗化面之凹凸小，因此高頻特性非常優異，但無法充分地獲得密接性、尤其是加熱處理後之密接性（耐熱密接性）。In the conventional surface-treated copper foil shown in FIG. 1 (a), the roughened particles in the roughened surface are circular in plan view and have a fine and uniform particle size. The surface-treated copper foils described in Patent Documents 1 to 4 correspond to this example. Such surface-treated copper foils are excellent in high-frequency characteristics because they have small unevenness on the roughened surface, but cannot sufficiently obtain adhesion, especially heating. Adhesiveness after treatment (heat-resistant adhesiveness).

另一方面，圖1(c)所示之先前之表面處理銅箔中，粗化面中之粗化粒子在俯視下為圓形，且具有粗大且均勻的粒徑。此種表面處理銅箔由於粗化面之凹凸大，因此密接性（常態密接性及耐熱密接性）優異，但無法充分地獲得高頻特性。On the other hand, in the conventional surface-treated copper foil shown in FIG. 1 (c), the roughened particles in the roughened surface are circular in plan view and have a coarse and uniform particle diameter. Since such a surface-treated copper foil has large unevenness on the roughened surface, it has excellent adhesion (normal adhesion and heat-resistant adhesion), but cannot sufficiently obtain high-frequency characteristics.

本發明者針對上述先前之表面處理銅箔中的問題，著眼於高頻特性與密接性之權衡取捨之關係而進行了努力研究，結果發現，藉由將粗化面中的粗化粒子的大小及形狀刻意控制為不均勻，可兼顧作為上述相反特性之高頻特性與密接性（常態密接性及耐熱密接性）。The present inventors made diligent research on the above-mentioned problems in the surface-treated copper foil, focusing on the trade-off relationship between high-frequency characteristics and adhesion, and found that the size of the roughened particles in the roughened surface was reduced. And the shape is intentionally controlled to be non-uniform, and the high-frequency characteristics and adhesion (normal state adhesion and heat resistance adhesion) which are the opposite characteristics can be taken into consideration.

亦即，例如，如圖1(b)所示，本發明之表面處理銅箔係以將粗化面中的粗化粒子的大小及形狀設為不均勻，尤其是使微細之粗化粒子（後述之A粒子）與具有預定大小之粗化粒子（後述之B粒子）以一定比率混合存在，並且具有預定大小之粗化粒子中一定比率成為細長形狀之粗化粒子（後述之b1粒子）之方式進行控制。此種本發明之表面處理銅箔由於粗化面中的粗化粒子的大小及形狀被控制為預定關係，因此可兼顧良好的高頻特性與適度的密接性（常態密接性及耐熱密接性）。That is, for example, as shown in FIG. 1 (b), the surface-treated copper foil of the present invention is designed to make the size and shape of the roughened particles in the roughened surface non-uniform, and particularly to make fine roughened particles ( A particle described later) and roughened particles having a predetermined size (B particles described later) are mixed in a certain ratio, and a certain ratio of the roughened particles having a predetermined size becomes elongated shaped coarse particles (b1 particles described later). Way to control. Since the size and shape of the roughened particles in the roughened surface of the surface-treated copper foil of the present invention are controlled to a predetermined relationship, it is possible to balance good high-frequency characteristics and moderate adhesion (normal-state adhesion and heat-resistant adhesion). .

本發明之表面處理銅箔藉由以使粗化面中微細之粗化粒子與具有預定大小之粗化粒子以一定比率混合存在，並且具有預定大小之粗化粒子中一定比率成為細長形狀之粗化粒子之方式控制，可兼顧高頻特性與密接性。獲得此種作用效果之機制未必明確，但可認為藉由相對於微細之粗化粒子，添加一定比率之具有預定大小之粗化粒子，與僅微細粒子時（圖1(a)時）相比可提高密接性。進而，藉由將具有預定大小之粗化粒子之一部分設為細長形狀，抑制由增大粒子尺寸所帶來之介電損耗上升，可維持接近僅微細粒子時的優異的高頻特性。The surface-treated copper foil of the present invention mixes fine roughened particles in a roughened surface with roughened particles having a predetermined size to exist at a certain ratio, and a certain ratio of roughened particles having a predetermined size becomes a coarse shape with an elongated shape. The method of controlling the particles can take into account both high-frequency characteristics and adhesion. The mechanism for obtaining such an effect may not be clear, but it can be considered that by adding a certain ratio of coarse particles with a predetermined size to fine coarse particles, compared with when only fine particles are used (when Fig. 1 (a)). Improves adhesion. Furthermore, by making a part of the roughened particles having a predetermined size into an elongated shape, it is possible to suppress an increase in dielectric loss caused by an increase in particle size, and it is possible to maintain excellent high-frequency characteristics when approaching only fine particles.

圖2係自Z軸方向俯視具有預定大小之細長形狀之粗化粒子時的概略圖（X-Y平面圖）。另外，圖3係自Z軸方向俯視具有與圖2所示之細長形狀之粗化粒子之長邊方向尺寸t1相同長度之直徑(t1、t2)的球形狀之粗化粒子時的概略圖（X-Y平面圖）。另外，圖2、3之各(b)及(c)係以示意方式用實線表示自各自的虛線箭頭方向流通電流時，粗化粒子之表面上之傳輸路徑的示例。FIG. 2 is a schematic view (X-Y plan view) when roughened particles having a slender shape having a predetermined size are viewed from the Z-axis direction. In addition, FIG. 3 is a schematic view of a spherical roughened particle having a diameter (t1, t2) having the same length as the long side dimension t1 of the elongated roughened particle shown in FIG. 2 when viewed from the Z axis direction ( XY plan). In addition, each of (b) and (c) of FIGS. 2 and 3 is an example of a roughened transmission path on the surface of a particle when a current flows in the direction of the arrow of the dotted line in a schematic manner.

如由圖2(b)及圖3(b)之比較可知，假如電流沿著Y軸流過X-Y平面時，細長形狀之粗化粒子與具有相同長邊方向尺寸t1之球狀粒子相比，於粗化粒子之表面上之傳輸路徑變短。另外，如由圖2(c)及圖3(c)之比較可知，假如電流沿著X軸流過X-Y平面時，細長形狀之粗化粒子與具有相同長邊方向尺寸t1之球狀粒子相比，電流流過粗化粒子之表面之機率變低。As can be seen from the comparison of Fig. 2 (b) and Fig. 3 (b), if the current flows along the Y-axis through the XY plane, compared with spherical particles with the same length dimension t1 when the slender roughened particles are compared, The transmission path on the surface of the roughened particles becomes shorter. In addition, as can be seen from the comparison between Fig. 2 (c) and Fig. 3 (c), if the current flows along the X axis through the XY plane, the coarse particles with a slender shape and the spherical particles with the same length dimension t1 In contrast, the probability of current flowing through the surface of the coarsened particles becomes lower.

如上所述，可認為細長形狀之粗化粒子無論其長邊方向相對於電流沿哪一方向配向，與具有相同長邊方向尺寸t1之球形狀之粗化粒子相比，於粗化粒子之表面上之傳輸路徑均變短，或者原本電流流過粗化粒子之表面之頻率少，因此傳輸損耗變小。As described above, it can be considered that, regardless of which direction the longitudinal direction of the elongated roughened particles is aligned with respect to the current, the roughened particles are on the surface of the roughened particles in comparison with spherical roughened particles having the same longitudinal direction size t1. The transmission paths are shorter, or the frequency of current flowing through the surface of the roughened particles is less, so the transmission loss is smaller.

另外，可知就密接性之觀點而言，若含有一定量之長邊方向尺寸t1為預定大小以上之粗化粒子，則即便其形狀為細長形狀，亦可獲得充分之密接性。In addition, from the viewpoint of adhesiveness, it can be seen that if a certain amount of roughened particles with a dimension t1 in the longitudinal direction of at least a predetermined size is included, sufficient adhesiveness can be obtained even if the shape is an elongated shape.

基於該等見解，本發明者藉由使表面處理銅箔之粗化面中微細之粗化粒子與具有預定大小之粗化粒子以一定比率混合存在，並且將具有預定大小之粗化粒子之一部分設為細長形狀之粗化粒子，成功抑制高頻特性惡化，實現密接性提高，從而完成了本發明。Based on these findings, the present inventors mixed fine roughened particles and roughened particles having a predetermined size in a certain ratio in the roughened surface of the surface-treated copper foil, and part of the roughened particles having a predetermined size. The roughened particles having an elongated shape successfully suppress the deterioration of high-frequency characteristics and improve the adhesion, thereby completing the present invention.

本發明中，藉由掃描式電子顯微鏡(SEM)對表面處理銅箔之粗化面進行觀察，藉此確認粗化面中之粗化粒子之形成狀態。再者，本發明中，在對表面處理皮膜之表面進行SEM觀察所得的分析區域中，將長邊方向尺寸t1為0.1 µm以上之粗化粒子作為計算對象，計算該粗化粒子之個數。如此規定之原因在於，長邊方向尺寸t1未達0.1 µm之微細粒子在本發明所要求之可兼顧高頻特性與密接性之範圍內幾乎不會造成影響。
以下，關於本發明之表面處理銅箔之粗化面，對粗化粒子之大小及形狀、以及分析區域中的每種粒子形狀之粗化粒子之個數比率等詳細地進行說明。In the present invention, the roughened surface of the surface-treated copper foil is observed with a scanning electron microscope (SEM), thereby confirming the formation state of the roughened particles in the roughened surface. Furthermore, in the present invention, in the analysis region obtained by SEM observation of the surface of the surface-treated film, roughened particles having a dimension t1 of 0.1 μm or more in the longitudinal direction are used as a calculation object, and the number of the roughened particles is calculated. The reason for this is that fine particles having a dimension t1 of less than 0.1 µm in the longitudinal direction hardly affect the range required for the present invention to satisfy both the high-frequency characteristics and the adhesion.
Hereinafter, regarding the roughened surface of the surface-treated copper foil of the present invention, the size and shape of the roughened particles, and the ratio of the number of roughened particles of each particle shape in the analysis region will be described in detail.

粗化面主要由微細之粗化粒子及具有預定大小之粗化粒子構成。此處，微細之粗化粒子係長邊方向尺寸t1未達1.0 µm之粗化粒子（以下，稱為A粒子），具有預定大小之粗化粒子係長邊方向尺寸t1為1.0至3.0 µm之粗化粒子（以下，稱為B粒子）。亦即，粗化面主要由上述A粒子及B粒子構成，於上述分析區域中，計算長邊方向尺寸t1為0.1 µm以上之粗化粒子之個數時，長邊方向尺寸t1為3.0 µm以下之粗化粒子（A粒子及B粒子之合計）之個數比率為99.0%以上，較佳為99.5%以上。藉由設為上述範圍，可良好地控制高頻特性。The roughened surface is mainly composed of fine roughened particles and roughened particles having a predetermined size. Here, the coarsened particles are coarse particles (hereinafter, referred to as A particles) having a size t1 of less than 1.0 µm in the longitudinal direction, and coarse particles having a predetermined size in the longitudinal direction have a size t1 of 1.0 to 3.0 µm. Particles (hereinafter referred to as B particles). That is, the roughened surface is mainly composed of the above-mentioned A particles and B particles. When the number of roughened particles whose length dimension t1 is 0.1 μm or more is calculated in the analysis area, the length dimension t1 is 3.0 μm or less. The ratio of the number of roughened particles (total of A particles and B particles) is 99.0% or more, preferably 99.5% or more. By setting it as the said range, a high frequency characteristic can be controlled well.

另外，粗化面之特徵在於A粒子與B粒子以一定比率混合存在。亦即，B粒子於上述長邊方向尺寸t1為3.0 µm以下之粗化粒子（A粒子及B粒子之合計）中所佔之個數比率為2.0至20.0%，較佳為3.5至15.0%。若上述B粒子之個數比率未達2.0%，則無法充分地獲得密接性提高之效果，若超過20.0%，則傳輸損耗增大之影響變大。另外，更具體而言，B粒子之個數在上述分析區域每300 µm2 中，較佳為20至100個，更佳為40至80個。The roughened surface is characterized in that A particles and B particles are mixed in a certain ratio. That is, the ratio of the number of B particles in the roughened particles (total of A particles and B particles) having a dimension t1 of 3.0 µm or less in the longitudinal direction is 2.0 to 20.0%, preferably 3.5 to 15.0%. If the number ratio of the B particles is less than 2.0%, the effect of improving the adhesion cannot be sufficiently obtained, and if it exceeds 20.0%, the influence of the increase in transmission loss becomes large. In addition, more specifically, the number of B particles per 300 µm 2 in the analysis region is preferably 20 to 100, and more preferably 40 to 80.

進而，粗化面係將B粒子之一部分設為細長形狀之粗化粒子。此種細長形狀之粗化粒子係長邊方向尺寸t1相對於短邊方向尺寸t2之比(t1/t2)為2以上之粗化粒子（以下，稱為b1粒子）。亦即，b1粒子於B粒子中所佔之個數比率為20%以上，較佳為30%以上。若b1粒子於B粒子中所佔之個數比率為20%以上，則可確保密接性，並且可將對傳輸損耗之不良影響抑制為最小限度。另一方面，若未達20%，則球狀粒子（如圖3之粒子）於B粒子中所佔之個數比率增大，因此傳輸損耗惡化。再者，b1粒子於B粒子中所佔之個數比率之上限例如為80%以下。另外，更具體而言，b1粒子之個數在上述分析區域每300 µm2 中，較佳為8個以上。再者，b1粒子之長邊方向尺寸t1相對於短邊方向尺寸t2之比(t1/t2)之上限例如為4以下。Furthermore, the roughened surface is a roughened particle having a part of B particles as an elongated shape. Such a slender roughened particle is a roughened particle having a ratio (t1 / t2) of a dimension t1 in the long direction to a dimension t2 in the short direction (hereinafter, referred to as b1 particle). That is, the ratio of the number of b1 particles in the B particles is 20% or more, and preferably 30% or more. If the ratio of the number of b1 particles in the B particles is 20% or more, adhesion can be ensured, and adverse effects on transmission loss can be minimized. On the other hand, if it is less than 20%, the ratio of the number of spherical particles (such as the particles in FIG. 3) to the B particles increases, and therefore the transmission loss deteriorates. The upper limit of the number ratio of the b1 particles to the B particles is, for example, 80% or less. In addition, more specifically, the number of b1 particles is preferably 8 or more per 300 µm 2 of the analysis region. The upper limit of the ratio (t1 / t2) of the dimension t1 in the long direction to the dimension t2 in the short direction of the b1 particle is, for example, 4 or less.

另外，如上所述，粗化面主要由作為微細之粗化粒子之A粒子、及作為具有預定大小之粗化粒子之B粒子構成。A粒子之個數比率係藉由B粒子之個數比率相對地決定，A粒子多時，可估計傳輸損耗降低，但無法確保充分之密接性。因此，如上所述，就獲得充分之密接性之觀點而言，必須使粗化面中A粒子與B粒子以一定比率混合存在。再者，更具體而言，A粒子之個數在上述分析區域每300 µm2 中，較佳為300至1200個。In addition, as described above, the roughened surface is mainly composed of A particles as fine roughened particles and B particles as roughened particles having a predetermined size. The ratio of the number of A particles is relatively determined by the ratio of the number of B particles. When there are many A particles, it is estimated that the transmission loss is reduced, but sufficient adhesion cannot be ensured. Therefore, as described above, from the viewpoint of obtaining sufficient adhesiveness, it is necessary to mix A particles and B particles in a certain ratio in the roughened surface. Furthermore, more specifically, the number of A particles is preferably 300 to 1200 per 300 µm 2 of the analysis region.

進而，粗化面係以粗大之粗化粒子成為一定比率以下之方式進行控制。此種粗大之粗化粒子係長邊方向尺寸t1超過3.0 µm之粗化粒子（以下，稱為C粒子）。亦即，粗化面係以C粒子成為一定比率以下之方式控制，C粒子於計算對象之粗化粒子中所佔之個數比率為1%以下，較佳為0.5%以下。C粒子有助於提高密接性，但若超過1.0%，則會招致傳輸損耗增大。再者，更具體而言，C粒子之個數在上述分析區域每300 µm2 中，較佳為0至3個。Furthermore, the roughened surface is controlled so that the coarsened roughened particles become a certain ratio or less. Such coarse coarse particles are coarse particles (hereinafter, referred to as C particles) whose size t1 in the longitudinal direction exceeds 3.0 µm. That is, the roughened surface is controlled so that the C particles become equal to or lower than a certain ratio, and the ratio of the number of the C particles to the coarse particles to be calculated is 1% or less, and preferably 0.5% or less. C particles help to improve the adhesion, but if it exceeds 1.0%, transmission loss will increase. Furthermore, more specifically, the number of C particles is preferably 0 to 3 per 300 µm 2 of the analysis region.

本發明之表面處理銅箔藉由具備具有如上所述之特徵之粗化面，可兼顧作為相互權衡取捨之關係的抑制傳輸損耗以及提高與樹脂基材之密接性（常態密接性及耐熱密接性）。The surface-treated copper foil of the present invention is provided with a roughened surface having the characteristics described above, and can balance the suppression of transmission loss as a trade-off relationship and the improvement of the adhesion with the resin substrate (normal adhesion and heat-resistant adhesion). ).

另外，本發明之表面處理銅箔之粗化面較佳為十點平均粗糙度Rzjis之值為0.5至2.0 µm。藉由設為上述範圍，可更確實地抑制傳輸損耗。In addition, the roughened surface of the surface-treated copper foil of the present invention preferably has a value of ten-point average roughness Rzjis of 0.5 to 2.0 µm. By setting it as the said range, transmission loss can be suppressed more reliably.

另外，本發明之表面處理銅箔係藉由將其使用在印刷配線板之導體電路，而可獲得可高度抑制傳輸GHz波段之高頻訊號時的傳輸損耗，並且，即使在高溫下，仍可良好地維持表面處理銅箔與樹脂基材（樹脂層）間之密接性，在嚴苛條件仍具有優異的耐久性的印刷配線板。In addition, the surface-treated copper foil of the present invention uses a conductor circuit of a printed wiring board to obtain transmission loss that can highly suppress transmission of high-frequency signals in the GHz band, and can be used even at high temperatures. A printed wiring board that maintains the good adhesion between the surface-treated copper foil and the resin substrate (resin layer) and has excellent durability under severe conditions.

接著，對本發明之表面處理銅箔之較佳製造方法說明其一例。本發明中，較佳為進行於銅箔基體之表面形成粗化粒子之粗化處理。Next, an example of a preferable manufacturing method of the surface-treated copper foil of this invention is demonstrated. In the present invention, the roughening treatment for forming roughened particles on the surface of the copper foil substrate is preferably performed.

銅箔基體可使用習知者，例如可使用電解銅箔或壓延銅箔。As a copper foil base, a conventional person can be used, For example, an electrolytic copper foil or a rolled copper foil can be used.

粗化處理例如較佳為將下述所示之粗化電鍍處理(1)與固定電鍍處理(2)組合而進行。The roughening treatment is preferably performed by combining, for example, a roughening plating treatment (1) and a fixed plating treatment (2) described below.

粗化電鍍處理(1)
粗化電鍍處理(1)係於銅箔基體之至少一個面上形成粗化粒子之處理。具體而言，利用硫酸銅浴進行高電流密度之電鍍處理。此種硫酸銅浴（粗化電鍍液基本浴）中，可以防止粗化粒子之脫落、亦即「落粉」為目的，添加鉬(Mo)、砷(As)、銻(Sb)、鉍(Bi)、硒(Se)、碲(Te)、鎢(W)等自先前以來為已知之添加劑，較佳為添加鉬(Mo)。本發明者進行了努力研究，結果發現，下述之因素會對表面處理銅箔之表面性狀造成影響，且發現，藉由適當地設定該等之條件，可以高水準滿足作為本發明之效果之高頻特性及密接性（常態密接性及耐熱密接性）之要求特性。Rough plating (1)
The roughening plating process (1) is a process of forming roughened particles on at least one surface of a copper foil substrate. Specifically, a high-current-density plating process is performed using a copper sulfate bath. In this kind of copper sulfate bath (basic bath of roughening plating solution), molybdenum (Mo), arsenic (As), antimony (Sb), and bismuth (Mo), arsenic (As), antimony (Sb), and bismuth ( Bi), selenium (Se), tellurium (Te), tungsten (W), and the like have been known additives from the past, and molybdenum (Mo) is preferably added. The present inventors conducted diligent research and found that the following factors affect the surface properties of the surface-treated copper foil, and found that by appropriately setting such conditions, high levels of satisfaction can be satisfied as the effects of the present invention. High frequency characteristics and adhesion (normal adhesion and heat resistance adhesion) required characteristics.

首先，列舉粗化電鍍處理(1)之粗化電鍍浴中所添加之添加劑、例如鉬(Mo)為例進行說明。若鉬(Mo)濃度未達100 mg/L，則難以微細地形成粗化粒子，B粒子及C粒子之個數比率增加，因此存在高頻特性惡化之傾向。另外，若鉬(Mo)濃度超過400 mg/L，則粗化粒子容易過度地微細化，B粒子之個數比率減少，因此存在耐熱密接性惡化之傾向。因此，鉬(Mo)濃度較佳為設為100至400 mg/L。First, as an example, an additive, such as molybdenum (Mo), added to the roughening plating bath of the roughening plating process (1) will be described as an example. If the concentration of molybdenum (Mo) is less than 100 mg / L, it is difficult to form coarse particles finely, and the ratio of the number of B particles and C particles is increased. Therefore, high-frequency characteristics tend to deteriorate. In addition, when the concentration of molybdenum (Mo) exceeds 400 mg / L, the coarsened particles tend to be excessively refined, and the number ratio of the B particles is reduced. Therefore, the heat-resistant adhesiveness tends to deteriorate. Therefore, the concentration of molybdenum (Mo) is preferably set to 100 to 400 mg / L.

其次，說明粗化電鍍處理(1)之電解條件。
若電極間隙間的流速(極間流速)未達0.05 m/s，則難以微細地形成粗化粒子，B粒子及C粒子之個數比率增加，因此存在高頻特性惡化之傾向。另外，若電極間隙間的流速超過0.14 m/s，則粗化粒子容易過度地微細化，B粒子之個數比率減少，因此存在耐熱密接性惡化之傾向。因此，電極間隙間的流速較佳為設為0.05至0.14 m/s。Next, the electrolytic conditions for the rough plating treatment (1) will be described.
If the flow rate (inter-electrode flow rate) between the electrode gaps is less than 0.05 m / s, it is difficult to form coarse particles finely, and the ratio of the number of B particles and C particles is increased. Therefore, the high-frequency characteristics tend to deteriorate. In addition, if the flow velocity between the electrode gaps exceeds 0.14 m / s, the coarsened particles tend to be excessively refined, and the number ratio of the B particles is reduced, so that the heat-resistant adhesiveness tends to deteriorate. Therefore, the flow velocity between the electrode gaps is preferably set to 0.05 to 0.14 m / s.

若電流密度(A/dm2 )與處理時間（秒）之積(=S)未達100{(A/dm2 )・秒}，則難以獲得本發明所要求之充分之常態密接性。另外，若上述積S超過300{(A/dm2 )・秒}，則粗化粒子過度地生長，難以獲得本發明所要求之良好之高頻特性。因此，上述積S較佳為設為100至300{(A/dm2 )・秒}。If the product (= S) of the current density (A / dm 2 ) and the processing time (seconds) is less than 100 {(A / dm 2 ) · sec}, it is difficult to obtain sufficient normal-state adhesiveness required by the present invention. In addition, if the above-mentioned product S exceeds 300 {(A / dm 2 ) · s}, coarse particles grow excessively, and it is difficult to obtain the good high-frequency characteristics required by the present invention. Therefore, the product S is preferably set to 100 to 300 {(A / dm 2 ) · second}.

另外，若電流密度與處理時間之積S相對於鉬(Mo)濃度之比（＝S/Mo濃度）設為未達0.5[{(A/dm2 )・秒}/(mg/L)]，則粗化粒子容易過度地微細化，B粒子之個數比率減少，因此存在耐熱密接性惡化之傾向。另外，若S/Mo濃度超過2.5[{(A/dm2 )・秒}/(mg/L)]，則難以微細地形成粗化粒子，B粒子及C粒子之個數比率增加，因此存在高頻特性惡化之傾向。因此，S/Mo濃度較佳為設為0.5至2.5[{(A/dm2 )・秒}/(mg/L)]。In addition, if the ratio of the product S of the current density and the processing time to the concentration of molybdenum (Mo) (= S / Mo concentration) is set to less than 0.5 [{(A / dm 2 ) · s} / (mg / L)] , The coarsened particles tend to be excessively fined, and the ratio of the number of B particles is reduced. Therefore, the heat-resistant adhesiveness tends to deteriorate. In addition, if the S / Mo concentration exceeds 2.5 [{(A / dm 2 ) · sec} / (mg / L)], it becomes difficult to form coarse particles finely, and the number ratio of B particles and C particles increases, so The tendency for high frequency characteristics to deteriorate. Therefore, the S / Mo concentration is preferably set to 0.5 to 2.5 [{(A / dm 2 ) · sec} / (mg / L)].

固定電鍍處理(2)
固定電鍍處理(2)係對上述粗化電鍍處理(1)中經表面處理之銅箔基體進行平滑之覆蓋電鍍之處理。該處理係為了防止粗化粒子之脫落，亦即為了使粗化粒子固定化而進行。具體而言，利用硫酸銅浴進行電鍍處理。本發明者進行了努力研究，結果發現，除添加通常固定電鍍中不刻意地添加之氯，下述之因素亦會對表面處理銅箔之表面性狀造成影響，且發現，藉由適當地設定該等之條件，可以高水準滿足作為本發明之效果之高頻特性及密接性（常態密接性及耐熱密接性）之要求特性。Fixed plating treatment (2)
The fixed electroplating process (2) is a process for smooth covering and electroplating the surface-treated copper foil substrate in the roughening electroplating process (1). This treatment is performed in order to prevent the roughened particles from falling out, that is, to fix the roughened particles. Specifically, a copper sulfate bath is used for the plating treatment. The present inventors conducted diligent research and found that, in addition to the chlorine which is not added intentionally in the ordinary fixed plating, the following factors also affect the surface properties of the surface-treated copper foil, and found that by appropriately setting the The conditions such as these can satisfy the required characteristics of high-frequency characteristics and adhesiveness (normal-state adhesiveness and heat-resistant adhesiveness) as the effects of the present invention at a high level.

首先，對固定電鍍處理(2)之固定電鍍浴中所添加之氯濃度進行說明。若氯(Cl)濃度未達50 mg/L，則粗化粒子容易生長為球形，b1粒子之個數比率減少，因此存在高頻特性惡化之傾向。另外，若氯(Cl)濃度超過200 mg/L，則招致預想外之電沉積異常之可能性變高。因此，氯(Cl)濃度較佳為設為50至200 mg/L。First, the concentration of chlorine added to the fixed plating bath in the fixed plating process (2) will be described. If the concentration of chlorine (Cl) is less than 50 mg / L, the roughened particles tend to grow into a sphere, and the number ratio of the b1 particles decreases. Therefore, the high-frequency characteristics tend to deteriorate. In addition, if the concentration of chlorine (Cl) exceeds 200 mg / L, the possibility of causing an unexpected electrodeposition abnormality becomes high. Therefore, the chlorine (Cl) concentration is preferably set to 50 to 200 mg / L.

其次，對固定電鍍處理(2)之電解條件等進行說明。
若電極間隙間的流速未達0.15 m/s，則難以實施正常之固定電鍍，容易產生落粉。另外，若電極間隙間的流速超過0.40 m/s，則粗化粒子容易生長為球形，b1粒子之個數比率減少，因此存在高頻特性惡化之傾向。因此，電極間隙間的流速較佳為設為0.15至0.40 m/s。Next, the electrolytic conditions and the like of the fixed plating process (2) will be described.
If the flow velocity between the electrode gaps is less than 0.15 m / s, it is difficult to perform normal fixed plating, and it is easy to cause powder falling. In addition, if the flow velocity between the electrode gaps exceeds 0.40 m / s, the coarsened particles tend to grow into a sphere, and the number ratio of the b1 particles decreases. Therefore, the high-frequency characteristics tend to deteriorate. Therefore, the flow velocity between the electrode gaps is preferably set to 0.15 to 0.40 m / s.

尤其是，若電流密度與處理時間之積（＝K）未達30{(A/dm2 )・秒}，則難以實施充分之固定電鍍。另外，若上述積K超過100{(A/dm2 )・秒}，則粗化粒子過度地生長，因此難以獲得本發明所要求之良好之高頻特性。因此，上述積K較佳為設為30至100{(A/dm2 )・秒}。In particular, if the product (= K) of the current density and the processing time is less than 30 {(A / dm 2 ) · sec}, it is difficult to implement sufficient fixed plating. In addition, if the above-mentioned product K exceeds 100 {(A / dm 2 ) · s}, the coarsened particles are excessively grown, and therefore it is difficult to obtain the good high-frequency characteristics required by the present invention. Therefore, the above-mentioned product K is preferably set to 30 to 100 {(A / dm 2 ) · second}.

另外，若電流密度與處理時間之積K相對於氯(Cl)濃度之比（＝K/Cl濃度）未達0.2[{(A/dm2 )・秒}/(mg/L)]，則招致預想外之電沉積異常之可能性變高。另外，若K/Cl濃度超過2.0[{(A/dm2 )・秒}/(mg/L)]，則粗化粒子容易生長為球形，b1粒子之個數比率減少，因此存在高頻特性惡化之傾向。因此，電流密度與處理時間之積K相對於氯(Cl)濃度之比（＝K/Cl濃度）較佳為設為0.2至2.0。In addition, if the ratio of the product of current density and processing time K to the concentration of chlorine (Cl) (= K / Cl concentration) is less than 0.2 [{(A / dm 2 ) · sec} / (mg / L)], then The possibility of inducing unexpected electrodeposition becomes higher. In addition, if the K / Cl concentration exceeds 2.0 [{(A / dm 2 ) · sec} / (mg / L)], the roughened particles tend to grow into a sphere, and the ratio of the number of b1 particles decreases, so there is a high-frequency characteristic. Tendency to worsen. Therefore, the ratio of the product K of the current density and the processing time to the concentration of chlorine (Cl) (= K / Cl concentration) is preferably set to 0.2 to 2.0.

進而，若固定電鍍處理(2)之電流密度與處理時間之積K相對於粗化電鍍處理(1)之電流密度與處理時間之積S的比率((K/S)×100(%))未達25%，則難以實施充分之固定電鍍，容易產生落粉。若上述比率[(K/S)×100]超過50%，則粗化粒子容易過度地生長，難以獲得本發明所要求之良好之高頻特性。因此，上述比率[(K/S)×100]較佳為設為25至50%。Furthermore, if the product K of the current density and the processing time of the fixed plating process (2) is relative to the product S of the current density and the processing time of the rough plating process (1) ((K / S) × 100 (%)) If it is less than 25%, it is difficult to implement sufficient fixed plating, and powder fall easily occurs. If the ratio [(K / S) × 100] exceeds 50%, coarsened particles tend to grow excessively, and it is difficult to obtain good high-frequency characteristics required by the present invention. Therefore, the ratio [(K / S) × 100] is preferably set to 25 to 50%.

以下示出粗化電鍍處理用電鍍液的組成及電解條件的示例。另外，下述條件為較佳示例，在不影響本發明的效果的範圍內，可根據需要適當變更及調節添加劑的種類及用量、電解條件。Examples of the composition and electrolytic conditions of the plating solution for roughening plating are shown below. In addition, the following conditions are preferred examples, and the types and amounts of additives, and electrolytic conditions may be appropriately changed and adjusted as needed within a range that does not affect the effects of the present invention.

＜粗化電鍍處理(1)之條件＞
硫酸銅五水合物・・・以銅（原子）換算計為15至30 g/L
硫酸・・・100至250 g/L
鉬酸銨・・・以鉬（原子）換算計為100至400 mg/L
電極間隙間的流速・・・0.05至0.14 m/s
電流密度・・・45至70 A/dm2
處理時間・・・2至5秒
浴溫・・・15至30℃<Conditions of roughening plating treatment (1)>
Copper sulfate pentahydrate: 15 to 30 g / L in terms of copper (atomic)
Sulfuric acid ... 100 to 250 g / L
Ammonium molybdate: 100 to 400 mg / L in terms of molybdenum (atomic)
Velocity between electrode gaps ... 0.05 to 0.14 m / s
Current density: 45 to 70 A / dm 2
Processing time ... 2 to 5 seconds bath temperature ... 15 to 30 ° C

＜固定電鍍處理(2)之條件＞
硫酸銅五水合物・・・以銅（原子）換算計為50至70 g/L
硫酸・・・80至160 g/L
氯化鈉・・・以氯（原子）換算計為50至200 mg/L
電極間隙間的流速・・・0.15至0.40 m/s
電流密度・・・5至15 A/dm2
處理時間・・・4至15秒
浴溫・・・50至70℃＜ Conditions of fixed plating treatment (2) ＞
Copper sulfate pentahydrate ... 50 to 70 g / L in terms of copper (atomic)
Sulfuric acid ... 80 to 160 g / L
Sodium chloride: 50 to 200 mg / L in terms of chlorine (atomic)
Velocity between electrode gaps ... 0.15 to 0.40 m / s
Current density: 5 to 15 A / dm 2
Processing time ... 4 to 15 seconds bath temperature ... 50 to 70 ° C

進而，本發明之表面處理銅箔亦可於銅箔基體之至少一個面，具有藉由粗化粒子之電沉積而形成的具有預定之微細凹凸表面形狀的粗化處理層，進而於該粗化處理層上，直接或隔著含有Ni之基底層、含有Zn之耐熱處理層及防銹處理層等的中間層而間接地進一步形成有矽烷偶合劑層。再者，上述中間層及矽烷偶合劑層由於其厚度非常薄，因此不會對表面處理銅箔之粗化面中之粗化粒子之粒子形狀造成影響。表面處理銅箔之粗化面中之粗化粒子之粒子形狀，實質上係由與該粗化面相對應之粗化處理層之表面中之粗化粒子之粒子形狀決定。Furthermore, the surface-treated copper foil of the present invention may have a roughened layer having a predetermined fine uneven surface shape formed by electrodeposition of roughened particles on at least one side of the copper foil substrate, and further roughen the roughened surface. A silane coupling agent layer is further formed on the treatment layer directly or indirectly through an intermediate layer such as a base layer containing Ni, a heat-resistant treatment layer containing Zn, and an anti-rust treatment layer. In addition, since the intermediate layer and the silane coupling agent layer are very thin, they do not affect the particle shape of the roughened particles on the roughened surface of the surface-treated copper foil. The particle shape of the roughened particles in the roughened surface of the surface-treated copper foil is essentially determined by the particle shape of the roughened particles in the surface of the roughened layer corresponding to the roughened surface.

另外，作為矽烷偶合劑層之形成方法，例如可列舉：於表面處理銅箔之前述粗化處理層之凹凸表面上，直接或隔著中間層而間接地塗佈矽烷偶合劑溶液之後，進行風乾（自然乾燥）或加熱乾燥而形成之方法。所塗佈之矽烷偶合劑溶液只要溶液中的水蒸發，則可形成矽烷偶合劑層，藉此充分地發揮本發明之效果。若於50至180℃進行加熱乾燥，則於促進矽烷偶合劑與銅箔之反應之方面而言較佳。In addition, as a method for forming the silane coupling agent layer, for example, the silane coupling agent solution is directly or indirectly coated on the uneven surface of the roughened layer of the surface-treated copper foil, or indirectly, via an intermediate layer, and then air-dried. (Natural drying) or heating and drying. As long as the water in the applied silane coupling agent solution evaporates, a silane coupling agent layer can be formed, thereby fully exerting the effects of the present invention. Heating and drying at 50 to 180 ° C is preferred in terms of promoting the reaction between the silane coupling agent and the copper foil.

矽烷偶合劑層較佳為含有環氧系矽烷、胺基系矽烷、乙烯基系矽烷、甲基丙烯酸系矽烷、丙烯酸系矽烷、苯乙烯基系矽烷、脲系矽烷、巰基系矽烷、硫醚系矽烷及異氰酸酯系矽烷中之任一種以上之矽烷偶合劑。The silane coupling agent layer preferably contains epoxy-based silane, amine-based silane, vinyl-based silane, methacrylic-based silane, acrylic-based silane, styryl-based silane, urea-based silane, mercapto-based silane, and thioether-based Silane and isocyanate are any one or more of silane coupling agents.

作為其他實施形態，更佳為於粗化處理層與矽烷偶合劑層之間，具有選自含有Ni之基底層、含有Zn之耐熱處理層及含有Cr之防銹處理層中的至少一層之中間層。As another embodiment, it is more preferable that the intermediate layer includes at least one layer selected from a base layer containing Ni, a heat-resistant treatment layer containing Zn, and a rust-resistant treatment layer containing Cr between the roughening treatment layer and the silane coupling agent layer. Floor.

例如，於有銅箔基體或粗化處理層中之銅(Cu)擴散至樹脂基材側，密接性因產生銅害而降低之虞時，較佳為含有鎳(Ni)之基底層形成於粗化處理層與矽烷偶合劑層之間。含有Ni之基底層較佳為由選自鎳(Ni)、鎳(Ni)-磷(P)、鎳(Ni)-鋅(Zn)中之至少1種形成。For example, when copper (Cu) in a copper foil substrate or a roughened layer is diffused to the resin substrate side, and the adhesion may be reduced due to copper damage, it is preferable that the base layer containing nickel (Ni) is formed on Between the roughening treatment layer and the silane coupling agent layer. The Ni-containing base layer is preferably formed of at least one selected from the group consisting of nickel (Ni), nickel (Ni) -phosphorus (P), and nickel (Ni) -zinc (Zn).

含有鋅(Zn)之耐熱處理層較佳為於需要進一步提高耐熱性時形成。耐熱處理層例如較佳為由鋅或含有鋅之合金、即選自鋅(Zn)-錫(Sn)、鋅(Zn)-鎳(Ni)、鋅(Zn)-鈷(Co)、鋅(Zn)-銅(Cu)、鋅(Zn)-鉻(Cr)及鋅(Zn)-釩(V)等中的至少一種含有鋅之合金所形成。The heat-resistant treatment layer containing zinc (Zn) is preferably formed when it is necessary to further improve heat resistance. The heat-resistant treatment layer is preferably made of, for example, zinc or an alloy containing zinc, that is, selected from zinc (Zn) -tin (Sn), zinc (Zn) -nickel (Ni), zinc (Zn) -cobalt (Co), and zinc ( Zn) -copper (Cu), zinc (Zn) -chromium (Cr), zinc (Zn) -vanadium (V), and the like are formed of an alloy containing zinc.

含有Cr之防銹處理層較佳為於需要進一步提高耐蝕性時形成。作為防銹處理層，例如可列舉藉由鉻電鍍所形成之鉻層、藉由鉻酸鹽處理所形成之鉻酸鹽層。The rust-containing treatment layer containing Cr is preferably formed when it is necessary to further improve the corrosion resistance. Examples of the anti-rust treatment layer include a chromium layer formed by chromium plating and a chromate layer formed by chromate treatment.

上述基底層、耐熱處理層及防銹處理層於形成該等所有三層時，較佳為於粗化處理層上依該順序而形成，另外，亦可根據用途或目標特性而僅形成任一層或兩層。The above-mentioned base layer, heat-resistant treatment layer, and rust-proof treatment layer are preferably formed on the roughened treatment layer in this order when forming all three layers. In addition, only one layer may be formed according to the purpose or target characteristics. Or two layers.

[表面處理銅箔之製作]
以下，整合本發明之表面處理銅箔之製造方法。
本發明中，依照以下之形成步驟(S1)至(S5)製作表面處理銅箔。
(S1)粗化處理層之形成步驟
藉由粗化粒子之電沉積，而在銅箔基體上形成具有微細凹凸表面之粗化處理層。
(S2)基底層之形成步驟
視需要，於粗化處理層上形成含有Ni之基底層。
(S3)耐熱處理層之形成步驟
視需要，於粗化處理層上或基底層上形成含有Zn之耐熱處理層。
(S4)防銹處理層之形成步驟
於粗化處理層上、或視需要形成於粗化處理層上之基底層及/或耐熱處理層上，視需要形成含有Cr之防銹處理層。
(S5)矽烷偶合劑層之形成步驟
於粗化處理層上直接形成矽烷偶合劑層，或隔著形成有基底層、耐熱處理層及防銹處理層中之至少一層的中間層而間接地形成矽烷偶合劑層。[Production of surface treated copper foil]
Hereinafter, the manufacturing method of the surface-treated copper foil of this invention is integrated.
In the present invention, a surface-treated copper foil is produced according to the following formation steps (S1) to (S5).
(S1) The step of forming a roughening treatment layer is to form a roughening treatment layer having a fine uneven surface on a copper foil substrate by electrodeposition of roughening particles.
(S2) Forming step of base layer If necessary, a base layer containing Ni is formed on the roughening treatment layer.
(S3) Step of forming a heat-resistant treatment layer If necessary, a heat-resistant treatment layer containing Zn is formed on the roughening treatment layer or the base layer.
(S4) The step of forming a rust-preventive treatment layer is formed on the roughened process layer, or a base layer and / or a heat-resistant treated layer formed on the roughened process layer as needed, and a rust-preventive treatment layer containing Cr is formed as necessary.
(S5) The step of forming the silane coupling agent layer is to directly form the silane coupling agent layer on the roughening treatment layer, or to form the silane coupling agent layer indirectly via an intermediate layer having at least one of a base layer, a heat-resistant treatment layer, and a rust-proof treatment layer formed thereon. Silane coupling agent layer.

另外，本發明之表面處理銅箔可較佳地用於製造覆銅積層板。此種覆銅積層板可較佳地用於製造高密接性及高頻傳輸特性優異之印刷配線板，發揮優異之效果。尤其是，本發明之表面處理銅箔適用作為高頻帶用印刷配線板及車載用印刷配線基板的情況。In addition, the surface-treated copper foil of the present invention can be preferably used for manufacturing a copper-clad laminated board. Such a copper-clad laminated board can be preferably used for producing a printed wiring board having high adhesion and excellent high-frequency transmission characteristics, and exhibits excellent effects. In particular, the surface-treated copper foil of the present invention is suitably used as a printed wiring board for a high frequency band and a printed wiring board for a vehicle.

另外，覆銅積層板可使用本發明之表面處理銅箔，藉由習知之方法而形成。例如，覆銅積層板可藉由以下方式製造：將表面處理銅箔與樹脂基材（絕緣基板），以表面處理銅箔之粗化面（貼附面）與樹脂基材相向的方式積層貼附。作為絕緣基板，例如可列舉出可撓性樹脂基板或剛性樹脂基板等。In addition, the copper-clad laminated board can be formed by a conventional method using the surface-treated copper foil of the present invention. For example, a copper-clad laminated board can be manufactured by laminating a surface-treated copper foil and a resin substrate (insulating substrate) so that the roughened surface (attachment surface) of the surface-treated copper foil faces the resin substrate. Attached. Examples of the insulating substrate include a flexible resin substrate and a rigid resin substrate.

另外，於製造覆銅積層板時，只要藉由利用加熱壓製使具有矽烷偶合劑層之表面處理銅箔與絕緣基板貼合而製造即可。再者，藉由在絕緣基板上塗佈矽烷偶合劑，並利用加熱壓製，使塗佈有矽烷偶合劑之絕緣基板與於最表面具有防銹處理層之表面處理銅箔貼合而製作的覆銅積層板，亦具有與本發明同等之效果。Moreover, when manufacturing a copper clad laminated board, what is necessary is just to manufacture by bonding the surface-treated copper foil which has a silane coupling agent layer to an insulating substrate by heat pressing. In addition, a coating produced by applying a silane coupling agent on an insulating substrate and bonding the insulating substrate coated with the silane coupling agent to a surface-treated copper foil having a rust-proof treatment layer on the outermost surface by heating and pressing. The copper laminated board has the same effect as the present invention.

另外，印刷配線板可使用上述覆銅積層板，藉由習知之方法而形成。In addition, the printed wiring board can be formed by a conventional method using the above-mentioned copper-clad laminated board.

以上對本發明的實施方式進行了說明，但上述實施方式只不過是本發明的一例。本發明包含本發明之概念及申請專利範圍所含之所有態樣，可於本發明之範圍內進行各種改變。
實施例As mentioned above, although embodiment of this invention was described, the said embodiment is only an example of this invention. The present invention includes the concept of the present invention and all aspects included in the scope of the patent application, and various changes can be made within the scope of the present invention.
Examples

以下基於實施例進一步詳細說明本發明，以下為本發明的一例。Hereinafter, the present invention will be described in more detail based on examples, and the following is an example of the present invention.

(實施例1）
於實施例1中，進行以下之步驟[1]至[4]，獲得表面處理銅箔。以下加以詳細說明。(Example 1)
In Example 1, the following steps [1] to [4] were performed to obtain a surface-treated copper foil. This is explained in detail below.

[1]銅箔基體之準備
作為成為用以實施粗化處理之基材的銅箔基體，準備電解銅箔（厚度18 µm）。電解銅箔係藉由下述條件而製造。[1] Preparation of copper foil base As a copper foil base to be used as a base material for roughening, an electrolytic copper foil (thickness: 18 µm) was prepared. The electrolytic copper foil is manufactured under the following conditions.

＜電解銅箔之製造條件＞
Cu：80 g/L
H2 SO4 ：70 g/L
氯濃度：25 mg/L
浴溫：55°Ｃ
電流密度：45 A/dm2
添加劑
• 3-巰基1-丙烷磺酸鈉：2 mg/L
• 羥乙基纖維素：10mg/L
• 低分子量膠（分子量3000）：50mg/L＜ Manufacturing conditions of electrolytic copper foil ＞
Cu: 80 g / L
H 2 SO 4 : 70 g / L
Chlorine concentration: 25 mg / L
Bath temperature: 55 ° C
Current density: 45 A / dm 2
Additives • Sodium 3-mercapto1-propanesulfonate: 2 mg / L
• Hydroxyethyl cellulose: 10mg / L
• Low molecular weight glue (molecular weight 3000): 50mg / L

[2]粗化處理面的形成
接下來，對上述[1]中準備之銅箔基體之單面實施粗化電鍍處理。該粗化電鍍處理係藉由二階段之電氣電鍍處理而進行。粗化電鍍處理(1)係使用下述粗化電鍍液基本浴組成，將鉬(Mo)濃度設定為如下述表1所記載，且將電極間隙間的流速、電流密度、處理時間設定為如下述表1所記載。鉬(Mo)濃度係藉由將鉬酸鈉已溶解至純水中的水溶液添加至粗化電鍍液基本浴中而進行調整。另外，接下來進行之固定電鍍處理(2)係使用下述固定電鍍液組成，將氯(Cl)濃度、電極間隙間的流速、電流密度、處理時間設定為如下述表1所記載而進行。[2] Formation of roughened surface Next, a roughened plating process is performed on one side of the copper foil substrate prepared in [1] above. This roughening plating process is performed by a two-stage electric plating process. The roughening plating process (1) uses the following basic plating bath composition, sets the concentration of molybdenum (Mo) as described in Table 1 below, and sets the flow rate, current density, and processing time between the electrode gaps as follows As described in Table 1. The molybdenum (Mo) concentration is adjusted by adding an aqueous solution in which sodium molybdate has been dissolved in pure water to a roughening plating bath basic bath. In addition, the fixed plating process (2) performed next was performed using the following fixed plating solution composition, and setting the chlorine (Cl) concentration, the flow rate between the electrode gaps, the current density, and the processing time as described in Table 1 below.

＜粗化電鍍液基本浴組成＞
Cu：25 g/L
H2 SO4 ：180 g/L
浴溫：25℃＜ Basic composition of roughened plating solution ＞
Cu: 25 g / L
H 2 SO 4 : 180 g / L
Bath temperature: 25 ℃

＜固定電鍍液組成＞
Cu：60 g/L
H2 SO4 ：120 g/L
浴溫：60℃＜ Fixed plating solution composition ＞
Cu: 60 g / L
H 2 SO 4 : 120 g / L
Bath temperature: 60 ℃

[表1]
[Table 1]

[3]金屬處理層的形成
接著，於上述[2]中形成之粗化處理層之表面上，於下述條件下以Ni、Zn、Cr之順序實施金屬電鍍而形成金屬處理層（中間層）。[3] Formation of metal treatment layer Next, on the surface of the roughened treatment layer formed in [2] above, metal plating was performed in the order of Ni, Zn, and Cr under the following conditions to form a metal treatment layer (intermediate layer ).

＜Ni電鍍＞
Ni：40 g/L
H3 BO3 ：5 g/L
浴溫：20℃
pH：3.6
電流密度：0.2 A/dm2
處理時間：10秒＜ Ni plating ＞
Ni: 40 g / L
H 3 BO 3 : 5 g / L
Bath temperature: 20 ℃
pH: 3.6
Current density: 0.2 A / dm 2
Processing time: 10 seconds

＜Zn電鍍＞
Zn：2.5 g/L
NaOH：40 g/L
浴溫：20℃
電流密度：0.3 A/dm2
處理時間：5秒＜ Zn plating ＞
Zn: 2.5 g / L
NaOH: 40 g / L
Bath temperature: 20 ℃
Current density: 0.3 A / dm 2
Processing time: 5 seconds

＜Cr電鍍＞
Cr：5 g/L
浴溫：30℃
pH：2.2
電流密度：5 A/dm2
處理時間：5秒＜ Cr plating ＞
Cr: 5 g / L
Bath temperature: 30 ℃
pH: 2.2
Current density: 5 A / dm 2
Processing time: 5 seconds

[4]矽烷偶合劑層的形成]
最後，於上述[3]中形成之金屬處理層（尤其是最表面之Cr電鍍層）上，塗佈濃度0.2質量%之3-縮水甘油氧基丙基三甲氧基矽烷水溶液，於100℃下乾燥，形成矽烷偶合劑層。[4] Formation of silane coupling agent layer]
Finally, a 3-glycidoxypropyltrimethoxysilane aqueous solution with a concentration of 0.2% by mass was applied on the metal-treated layer (especially the Cr electroplated layer on the outermost surface) formed in the above [3], at 100 ° C. Dry to form a silane coupling agent layer.

（實施例2至5及比較例1至4）
實施例2至5及比較例1至4係於粗化處理層之形成步驟[2]中，如上述表1所記載般設定粗化電鍍處理(1)及固定電鍍處理(2)之各條件，除此以外，利用與實施例1相同之方法獲得表面處理銅箔。(Examples 2 to 5 and Comparative Examples 1 to 4)
In Examples 2 to 5 and Comparative Examples 1 to 4, in the step [2] of forming the roughened layer, the conditions for the rough plating process (1) and the fixed plating process (2) were set as described in Table 1 above. Other than that, a surface-treated copper foil was obtained by the same method as in Example 1.

[評估]
對於上述實施例及比較例之表面處理銅箔，進行下述所示之特性評估。各特性之評估條件如下所述。結果如表2所示。[Evaluation]
About the surface-treated copper foil of the said Example and the comparative example, the characteristic evaluation shown below was performed. The evaluation conditions of each characteristic are as follows. The results are shown in Table 2.

[粗化粒子的測量]
表面處理銅箔之粗化面中之粗化粒子之測量係藉由對粗化面自正上方（與具有粗化處理層之銅箔基體之表面正交之方向）進行掃描式電子顯微鏡(SEM)觀察而求出。詳細內容說明如下。再者，掃描式電子顯微鏡係使用場發射型掃描式電子顯微鏡（SU8020，日立高新技術股份有限公司製造）。
基於自正上方觀察粗化面所得的SEM圖像，測定粗化粒子之長邊方向尺寸t1及短邊方向尺寸t2。再者，測定中所使用之SEM圖像係設為可確認0.1 µm之粗化粒子之倍率之圖像。具體而言，例如，如圖4所示，係於倍率1萬倍下為960×720像素之數位圖像。圖4係自正上方觀察實施例1中所製造之表面處理銅箔之粗化面所得的SEM圖像。進而，該測定係針對各表面處理銅箔，於隨機選擇之不同之3個視野進行，將分析區域（觀察視野）之合計設為300 µm2 。
根據長邊方向尺寸t1，以如下之方式區分分析區域300 µm2 之範圍內所獲得之資料，計算分別區分之粗化粒子之個數。
･ A粒子：長邊方向尺寸t1為0.1 µm以上且未達1.0 µm之粗化粒子
･ B粒子：長邊方向尺寸t1為1.0 µm至3.0 µm之粗化粒子
･ b1粒子：上述B粒子中，長邊方向尺寸t1相對於短邊方向尺寸t2之比(t1/t2)為2以上之粗化粒子
･ C粒子：長邊方向尺寸t1超過3.0 µm之粗化粒子
進而，基於上述測定中所求出之各區分之粗化粒子之個數，分別算出成為計算對象之粗化粒子（A粒子、B粒子、及C粒子。以下，稱為計算對象粒子）之個數、長邊方向尺寸t1為3.0 µm以下之粗化粒子（A粒子＋B粒子）之個數、及長邊方向尺寸t1為3.0 µm以下之粗化粒子（A粒子＋B粒子）於計算對象粒子中所佔之個數比率(%)、B粒子於長邊方向尺寸t1為3.0 µm以下之粗化粒子（A粒子＋B粒子）中所佔之個數比率(%)、以及b1粒子於B粒子中所佔之個數比率(%)。[Measurement of coarsened particles]
The measurement of the roughened particles in the roughened surface of the surface-treated copper foil is performed by scanning electron microscope (SEM) of the roughened surface from directly above (in a direction orthogonal to the surface of the copper foil substrate having the roughened layer). ) Observe it. Details are explained below. The scanning electron microscope uses a field emission scanning electron microscope (SU8020, manufactured by Hitachi High-tech Co., Ltd.).
Based on the SEM image obtained by observing the roughened surface from directly above, the long-side dimension t1 and the short-side dimension t2 of the roughened particles were measured. The SEM image used in the measurement is an image that can confirm the magnification of the coarsened particles of 0.1 µm. Specifically, for example, as shown in FIG. 4, it is a digital image of 960 × 720 pixels at a magnification of 10,000 times. FIG. 4 is an SEM image of the roughened surface of the surface-treated copper foil manufactured in Example 1 as viewed from directly above. Furthermore, this measurement was performed for each surface-treated copper foil in three different visual fields selected at random, and the total analysis area (observation visual field) was set to 300 µm 2 .
According to the dimension t1 in the longitudinal direction, the data obtained in the range of 300 µm 2 of the analysis area is distinguished in the following manner, and the number of roughened particles that are separately distinguished is calculated.
粒子 Particle A: Roughened particles with a length t1 of 0.1 µm or more and less than 1.0 µm 粒子 Particle B: Roughened particles with a length t1 of 1.0 µm to 3.0 µm ･ b1: Among the above B particles, Coarse particles with a ratio (t1 / t2) of the length dimension t1 to the length dimension t2 of the short direction ･ C particles: Coarse particles whose length dimension t1 exceeds 3.0 µm. The number of roughened particles of each division is calculated, and the number of roughened particles (A particles, B particles, and C particles to be calculated) is calculated, and the length dimension t1 is calculated as Number of coarse particles (A particles + B particles) below 3.0 µm and lengthwise dimension t1 of 3.0 μm or less (A particles + B particles) in the calculation target particles (% ), The ratio of the number of B particles in the coarse particles (A particles + B particles) with a length t1 of 3.0 μm or less, and the ratio of the number of b particles in the B particles (%) ).

[表面粗糙度的測定]
於表面處理銅箔之粗化面中，使用接觸式表面粗糙度測定機（Surfcorder SE1700，小阪研究所股份有限公司製造），測定JIS B 0601：2001中所定義之十點平均粗糙度Rzjis(µm)。[Measurement of surface roughness]
On the roughened surface of the surface-treated copper foil, a ten-point average roughness Rzjis (µm as defined in JIS B 0601: 2001) was measured using a contact surface roughness measuring machine (Surfcorder SE1700, manufactured by Kosaka Research Co., Ltd.). ).

[高頻特性的評估]
測定在高頻波段中的傳輸損耗，作為高頻特性的評估。詳細內容說明如下。
將表面處理銅箔之粗化面，藉由於面壓3 MPa、200℃之條件下進行2小時壓製，而貼合於作為Panasonic股份有限公司製造之聚苯醚系低介電常數樹脂基材之MEGTRON6（厚度50至100 µm）的兩面，製作兩面覆銅積層板。對所獲得之積層板進行電路加工，形成傳輸路徑寬度100 µm、長度40 mm之微帶傳輸線。在該傳輸路徑中，使用網路分析儀，傳輸高頻訊號，測定傳輸損耗。特性阻抗為50Ω。
傳輸損耗的測定値係為，絕對値越小，則傳輸損耗越少，意味著具有良好的高頻特性。將所得之測定值作為指標，根據下述評估基準而評估高頻特性。
◎：40 GHz下之傳輸損耗為-26 dB以上
○：40 GHz下之傳輸損耗為未達-26 dB至-28 dB以上
×：40 GHz下之傳輸損耗未達-28 dB[Evaluation of high-frequency characteristics]
The transmission loss in the high-frequency band was measured as an evaluation of the high-frequency characteristics. Details are explained below.
The roughened surface of the surface-treated copper foil was pressed under the conditions of a surface pressure of 3 MPa and 200 ° C for 2 hours, and then bonded to a polyphenylene ether-based low-dielectric-constant resin substrate manufactured by Panasonic Corporation. MEGTRON6 (thickness 50 to 100 µm) on both sides, making double-sided copper clad laminates. The obtained laminated board was subjected to circuit processing to form a microstrip transmission line with a transmission path width of 100 µm and a length of 40 mm. In this transmission path, a network analyzer is used to transmit high-frequency signals and measure transmission loss. The characteristic impedance is 50Ω.
The measurement of transmission loss is that the smaller the absolute value, the smaller the transmission loss, which means that it has good high-frequency characteristics. Using the obtained measurement value as an index, the high-frequency characteristics were evaluated according to the following evaluation criteria.
◎: Transmission loss at 40 GHz is above -26 dB ○: Transmission loss at 40 GHz is below -26 dB to -28 dB ×: Transmission loss at 40 GHz is below -28 dB

[常態密接性的評估]
作為常態密接性的評估，進行剝離試驗。詳細內容說明如下。
以與上述[高頻特性的評估]中所記載之方法相同的方法製作覆銅積層板，將所獲得的覆銅積層板之銅箔部分（表面處理銅箔）以10 mm寬的膠帶進行遮蔽。在對該銅箔積層板實施氯化銅蝕刻後去除膠帶，製作出10 mm寬的電路配線板。使用東洋精機製作所公司製造的Tensilon試驗機，將該電路配線板之10 mm寬的電路配線部分（銅箔部分），在90度方向上以50 mm/分的速度，自樹脂基材剝離，測定此時的剝離強度。將所得之測定值作為指標，根據下述評估基準而評估密接性。
＜常態密接性的評估基準＞
◎：剝離強度為0.5 kN/m以上
×：剝離強度未達0.5kN/m[Assessment of Normal Adhesion]
As an evaluation of the normal adhesion, a peel test was performed. Details are explained below.
A copper-clad laminate was produced by the same method as described in [Evaluation of high-frequency characteristics], and the copper foil portion (surface-treated copper foil) of the obtained copper-clad laminate was masked with a 10 mm wide tape. . After copper chloride etching was performed on the copper foil laminate, the tape was removed to produce a 10 mm wide circuit wiring board. Using a Tensilon tester manufactured by Toyo Seiki Seisakusho Co., Ltd., a 10 mm wide circuit wiring portion (copper foil portion) of the circuit wiring board was peeled from the resin substrate at a speed of 50 mm / min in a direction of 90 degrees, and measured. Peel strength at this time. Using the obtained measured value as an index, the adhesion was evaluated based on the following evaluation criteria.
＜ Evaluation Criteria for Normal Adhesion ＞
◎: Peel strength is 0.5 kN / m or more ×: Peel strength is less than 0.5 kN / m

[耐熱密接性的評估]
作為常態密接性的評估，進行加熱處理後之剝離試驗。詳細內容說明如下。
以與上述[高頻特性的評估]中所記載之方法相同的方法製作覆銅積層板，將所獲得的覆銅積層板之銅箔部分以10 mm寬的膠帶進行遮蔽。在對該銅箔積層板實施氯化銅蝕刻後去除膠帶，製作出10 mm寬的電路配線板。將該電路配線板在300℃的加熱爐中加熱1小時後，於常溫下使用東洋精機製作所公司製造的Tensilon試驗機，將電路配線板之10 mm寬的電路配線部分（銅箔部分），在90度方向上以50 mm/分的速度，自樹脂基材剝離，測定此時的剝離強度。將所得之測定値作為指標，根據下述評估基準而評估耐熱密接性。
＜耐熱密接性的評估基準＞
◎：剝離強度為0.5 kN/m以上
○：剝離強度為0.4 kN/m以上且未達0.5 kN/m
×：剝離強度未達0.4 kN/m[Evaluation of heat-resistant adhesiveness]
As an evaluation of the normal state adhesion, a peel test after heat treatment was performed. Details are explained below.
A copper-clad laminate was produced by the same method as described in the above [Evaluation of High Frequency Characteristics], and the copper foil portion of the obtained copper-clad laminate was masked with a 10 mm wide tape. After copper chloride etching was performed on the copper foil laminate, the tape was removed to produce a 10 mm wide circuit wiring board. After heating the circuit wiring board in a heating furnace at 300 ° C for 1 hour, a Tensilon tester manufactured by Toyo Seiki Seisakusho Co., Ltd. was used at room temperature to place a 10 mm wide circuit wiring section (copper foil) of the circuit wiring board in The resin substrate was peeled from the resin substrate at a speed of 50 mm / min in the 90-degree direction, and the peel strength at this time was measured. Using the obtained measurement 値 as an index, the heat-resistant adhesiveness was evaluated according to the following evaluation criteria.
<Evaluation criteria for heat-resistant adhesiveness>
◎: Peel strength is 0.5 kN / m or more ○: Peel strength is 0.4 kN / m or more and less than 0.5 kN / m
×: Peel strength is less than 0.4 kN / m

[綜合評估]
將上述高頻特性、常態密接性及耐熱密接性全部綜合，基於下述評估基準進行綜合評估。再者，本實施例中，綜合評估中將A及B設為合格基準。
＜綜合評估的評估基準＞
A（優異）：所有評估為◎。
B（合格）：所有評估中無×評估。
C（不合格）：至少一個評估為×。[Comprehensive Evaluation]
All of the above-mentioned high-frequency characteristics, normal-state adhesiveness, and heat-resistant adhesiveness are integrated, and comprehensive evaluation is performed based on the following evaluation criteria. Furthermore, in this embodiment, A and B are set as the eligibility criteria in the comprehensive evaluation.
＜ Evaluation criteria for comprehensive evaluation ＞
A (Excellent): All evaluations were ◎.
B (Pass): No × evaluation in all evaluations.
C (Failed): At least one was evaluated as ×.

[表2]
（注）表中之粗體字下劃線表示本發明之適當範圍外者、及評估結果之指標未達到本實施例之合格基準者。[Table 2]
(Note) The underlined boldface in the table indicates those outside the appropriate range of the present invention and those whose evaluation results do not meet the eligibility criteria of this embodiment.

如表2所示，確認到實施例1至5之表面處理銅箔由於以如下方式進行控制，亦即，在藉由掃描式電子顯微鏡(SEM)觀察粗化面所得的分析區域中，計算長邊方向尺寸t1為0.1 µm以上之粗化粒子之個數時，長邊方向尺寸t1為3.0 µm以下之粗化粒子（A粒子及B粒子之合計）之個數比率為99.0%以上，且該個數比率中長邊方向尺寸t1為1.0至3.0 µm之粗化粒子（B粒子）所佔之個數比率為2.0至20.0%，進而，長邊方向尺寸t1相對於短邊方向尺寸t2之比(t1/t2)為2以上之粗化粒子（b1粒子）於B粒子中所佔之個數比率成為20%以上，因此高頻特性優異，且發揮高密接性（常態密接性及耐熱密接性）。As shown in Table 2, it was confirmed that the surface-treated copper foils of Examples 1 to 5 were controlled in such a manner that the length was calculated in the analysis area obtained by observing the roughened surface with a scanning electron microscope (SEM). When the number of roughened particles with a lateral dimension t1 of 0.1 µm or more, the ratio of the number of roughened particles (the total of A particles and B particles) with a longitudinal dimension t1 of 3.0 µm or less is 99.0% or more, and the In the number ratio, the ratio of the number of coarse particles (B particles) in the long-side dimension t1 of 1.0 to 3.0 µm is 2.0 to 20.0%. Furthermore, the ratio of the long-side dimension t1 to the short-side dimension t2 The ratio of the number of roughened particles (b1 particles) in which the (t1 / t2) is 2 or more to the B particles is 20% or more. Therefore, it has excellent high-frequency characteristics and exhibits high adhesion (normal adhesion and heat resistance adhesion) ).

相對於此，確認到比較例1之表面處理銅箔之粗化面中，長邊方向尺寸t1為1.0至3.0 µm之粗化粒子（B粒子）於長邊方向尺寸t1為3.0 µm以下之粗化粒子（A粒子及B粒子之合計）中所佔之個數比率未達2.0%，因此耐熱密接性差。On the other hand, it was confirmed that, in the roughened surface of the surface-treated copper foil of Comparative Example 1, roughened particles (B particles) having a dimension t1 of 1.0 to 3.0 µm in the longitudinal direction were coarser than 3.0 µm in dimension t1 in the longitudinal direction. The number ratio of the chemical particles (total of A particles and B particles) is less than 2.0%, so the heat-resistant adhesiveness is poor.

另外，確認到比較例2由於長邊方向尺寸t1相對於短邊方向尺寸t2之比(t1/t2)為2以上之粗化粒子（b1粒子）於長邊方向尺寸t1為1.0至3.0 µm之粗化粒子（B粒子）中所佔之個數比率未達20%，因此高頻特性差。確認到比較例3由於長邊方向尺寸t1為1.0至3.0 µm之粗化粒子（B粒子）於長邊方向尺寸t1為3.0 µm以下之粗化粒子（A粒子及B粒子之合計）中所佔之個數比率超過20.0%，因此高頻特性差。進而，確認到比較例4由於長邊方向尺寸t1為3.0 µm以下之粗化粒子於計算對象之粗化粒子中所佔之個數比率未達99.0%（亦即，長邊方向尺寸t1超過3.0 µm之粗化粒子為1.0%以上），因此高頻特性差。In addition, roughened particles (b1 particles) having a ratio (t1 / t2) of the long side dimension t1 to the short side dimension t2 of 2 or more in Comparative Example 2 were confirmed to be 1.0 to 3.0 µm in the long side dimension t1. The ratio of the number of particles in the roughened particles (B particles) is less than 20%, so the high-frequency characteristics are poor. In Comparative Example 3, coarse particles (B particles) having a dimension t1 of 1.0 to 3.0 µm in the longitudinal direction were confirmed to occupy coarse particles (total A particles and B particles) having a dimension t1 of 3.0 µm or less in the longitudinal direction. Since the number ratio exceeds 20.0%, the high-frequency characteristics are poor. Furthermore, it was confirmed that the ratio of the number of roughened particles of the comparative example 4 to the coarsened particles of the calculation target is less than 99.0% because the roughened particles with the longitudinal dimension t1 of 3.0 μm or less (that is, the longitudinal dimension t1 exceeds 3.0). The coarse particles of µm are 1.0% or more), so the high frequency characteristics are poor.

P‧‧‧長方形P‧‧‧ Rectangle

t1‧‧‧長邊方向尺寸 t1‧‧‧Longitudinal dimension

t2‧‧‧短邊方向尺寸 t2‧‧‧Side dimension

圖1係藉由掃描式電子顯微鏡(SEM)觀察表面處理銅箔之表面處理皮膜之表面所得的SEM圖像，尤其是，圖1(a)係先前之表面處理銅箔之一例，圖1(b)係本發明之表面處理銅箔之一例，圖1(c)係先前之表面處理銅箔之另一例。Fig. 1 is an SEM image obtained by observing the surface of a surface-treated film of a surface-treated copper foil with a scanning electron microscope (SEM). In particular, Fig. 1 (a) is an example of a previous surface-treated copper foil, and Fig. 1 ( b) is an example of the surface-treated copper foil of the present invention, and FIG. 1 (c) is another example of the previous surface-treated copper foil.

圖2係表示細長形狀之粗化粒子之一例的概略圖。 FIG. 2 is a schematic view showing an example of a roughened particle having an elongated shape.

圖3係表示球形狀之粗化粒子之一例的概略圖。 FIG. 3 is a schematic diagram showing an example of rough particles having a spherical shape.

圖4係藉由掃描式電子顯微鏡觀察實施例1中所製造之表面處理銅箔之表面處理皮膜之表面所得的SEM圖像。 FIG. 4 is an SEM image obtained by observing the surface of the surface-treated film of the surface-treated copper foil produced in Example 1 with a scanning electron microscope.

Claims (11)

一種表面處理銅箔，其係具有銅箔基體，且於該銅箔基體之至少一面，具有至少包含形成有粗化粒子之粗化處理層的表面處理皮膜之表面處理銅箔，其特徵在於： 在藉由掃描式電子顯微鏡(SEM)觀察前述表面處理皮膜之表面所得的分析區域中，計算長邊方向尺寸t1為0.1 µm以上之粗化粒子之個數時， 長邊方向尺寸t1為3.0 µm以下之粗化粒子之個數比率為99.0%以上，且前述個數比率中長邊方向尺寸t1為1.0至3.0 µm之粗化粒子所佔之個數比率為2.0至20.0%， 長邊方向尺寸t1相對於短邊方向尺寸t2之比(t1/t2)為2以上之粗化粒子於前述長邊方向尺寸t1為1.0至3.0 µm之粗化粒子中所佔之個數比率為20%以上。A surface-treated copper foil comprising a copper foil substrate, and at least one side of the copper foil substrate, a surface-treated copper foil including at least a surface-treated film having a roughened layer formed with roughened particles, characterized in that: In the analysis area obtained by observing the surface of the surface-treated film with a scanning electron microscope (SEM), when the number of roughened particles having a dimension t1 of 0.1 µm or more in the longitudinal direction is calculated, The ratio of the number of roughened particles with a length t1 of 3.0 µm or less in the longitudinal direction is 99.0% or more, and the ratio of the number of coarsened particles with a length t1 of 1.0 to 3.0 µm in the aforementioned number ratio is 2.0 To 20.0%, The ratio of the number of coarse particles having a ratio (t1 / t2) of the long-side dimension t1 to the short-side dimension t2 of 2 or more in the coarse particles having the long-side dimension t1 of 1.0 to 3.0 µm is 20% or more. 如申請專利範圍第1項所述之表面處理銅箔，其中前述長邊方向尺寸t1為1.0至3.0 µm之粗化粒子之個數在前述分析區域每300 µm2 中為20至100個。The surface-treated copper foil according to item 1 of the scope of the patent application, wherein the number of roughened particles in the longitudinal direction dimension t1 is 1.0 to 3.0 µm is 20 to 100 per 300 µm 2 in the aforementioned analysis area. 如申請專利範圍第1或2項所述之表面處理銅箔，其中長邊方向尺寸t1未達1.0 µm之粗化粒子之個數在前述分析區域每300 µm2 中為300至1200個。The surface-treated copper foil according to item 1 or 2 of the scope of patent application, wherein the number of roughened particles whose length dimension t1 is less than 1.0 µm is 300 to 1200 per 300 µm 2 in the aforementioned analysis area. 如申請專利範圍第1至3項中任一項所述之表面處理銅箔，其中長邊方向尺寸t1超過3.0 µm之粗化粒子之個數在前述分析區域每300 µm2 中為0至3個。The surface-treated copper foil according to any one of claims 1 to 3, wherein the number of roughened particles whose length dimension t1 exceeds 3.0 µm in the aforementioned analysis area is 0 to 3 per 300 µm 2 Each. 如申請專利範圍第1至4項中任一項所述之表面處理銅箔，其中長邊方向尺寸t1為1.0至3.0 µm且長邊方向尺寸t1相對於短邊方向尺寸t2之比(t1/t2)為2以上之粗化粒子之個數在前述分析區域每300 µm2 中為8個以上。The surface-treated copper foil according to any one of claims 1 to 4 in which the length dimension t1 is 1.0 to 3.0 µm and the ratio of the length dimension t1 to the short dimension t2 (t1 / t2) The number of roughened particles of 2 or more is 8 or more per 300 µm 2 in the analysis area. 如申請專利範圍第1至5項中任一項所述之表面處理銅箔，其中前述長邊方向尺寸t1為1.0至3.0 µm之粗化粒子之個數在前述分析區域每300 µm2 中為40至80個。The surface-treated copper foil according to any one of claims 1 to 5, wherein the number of roughened particles in the longitudinal direction dimension t1 is 1.0 to 3.0 µm in each of the foregoing analysis areas is 300 µm 2 40 to 80. 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，其中前述表面處理皮膜之表面的十點平均粗糙度Rzjis值為0.5至2.0 µm。The surface-treated copper foil according to any one of claims 1 to 6, wherein the ten-point average roughness Rzjis value of the surface of the aforementioned surface-treated film is 0.5 to 2.0 µm. 如申請專利範圍第1至7項中任一項所述之表面處理銅箔，其係用於高頻帶用印刷配線板。The surface-treated copper foil according to any one of claims 1 to 7 of the scope of patent application, which is used for a printed wiring board for high frequency bands. 如申請專利範圍第1至8項中任一項所述之表面處理銅箔，其係用於車載用印刷配線板。The surface-treated copper foil according to any one of claims 1 to 8 of the scope of patent application, which is used for printed wiring boards for vehicles. 一種覆銅積層板，其係使用如申請專利範圍第1至9項中任一項所述之表面處理銅箔而形成。A copper-clad laminated board is formed by using the surface-treated copper foil according to any one of claims 1 to 9 of the scope of patent application. 一種印刷配線板，其係使用如申請專利範圍第10項所述之覆銅積層板而形成。A printed wiring board is formed by using a copper-clad laminated board as described in item 10 of the scope of patent application.
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