TW201512467A - Copper foil for high frequency circuit, copper-clad plate for high frequency circuit, printed wiring plate, copper foil with carrier, electronic equipment and manufacturing method for printed wiring plate - Google Patents

Copper foil for high frequency circuit, copper-clad plate for high frequency circuit, printed wiring plate, copper foil with carrier, electronic equipment and manufacturing method for printed wiring plate Download PDF

Info

Publication number
TW201512467A
TW201512467A TW103113620A TW103113620A TW201512467A TW 201512467 A TW201512467 A TW 201512467A TW 103113620 A TW103113620 A TW 103113620A TW 103113620 A TW103113620 A TW 103113620A TW 201512467 A TW201512467 A TW 201512467A
Authority
TW
Taiwan
Prior art keywords
layer
copper foil
copper
carrier
plating
Prior art date
Application number
TW103113620A
Other languages
Chinese (zh)
Other versions
TWI509115B (en
Inventor
Hideta Arai
Atsushi Miki
Ryo Fukuchi
Tomota Nagaura
Original Assignee
Jx Nippon Mining & Metals Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jx Nippon Mining & Metals Corp filed Critical Jx Nippon Mining & Metals Corp
Publication of TW201512467A publication Critical patent/TW201512467A/en
Application granted granted Critical
Publication of TWI509115B publication Critical patent/TWI509115B/en

Links

Classifications

    • 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
    • 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
    • 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

Landscapes

  • 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)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

The invention provides copper foil for a high frequency circuit. The copper foil is applied to a substrate of the high frequency circuit and can inhibit transmission loss and prevent falling powder on the surface of the copper foil. According to the copper foil for the high frequency circuit, a primary particle layer of copper is formed on the surface of the copper foil, then a secondary particle layer of copper foil including three-element alloy of copper, cobalt and nickel. The ratio of a three-dimensional surface area to a two-dimensional surface area is larger than 2.0 and less than 2.2, wherein the ratio is obtained based on a laser microscope in a certain area on a roughening surface.

Description

高頻電路用銅箔、高頻電路用覆銅積層板、高頻電路用印刷配線板、高頻電路用附載體銅箔、電子機器、及印刷配線板之製造方法 Copper foil for high-frequency circuit, copper-clad laminate for high-frequency circuit, printed wiring board for high-frequency circuit, copper foil with high-frequency circuit, electronic device, and manufacturing method of printed wiring board

本發明係關於一種高頻電路用銅箔、高頻電路用覆銅積層板、高頻電路用印刷配線板、高頻電路用附載體銅箔、電子機器、及印刷配線板之製造方法。 The present invention relates to a copper foil for a high-frequency circuit, a copper-clad laminate for a high-frequency circuit, a printed wiring board for a high-frequency circuit, a copper foil with a carrier for a high-frequency circuit, an electronic device, and a method for producing a printed wiring board.

印刷配線板於此半個世紀取得了較大發展，目前已用於幾乎所有電子機器中。近年來，隨著電子機器之小型化、高性能化需求之增大，搭載零件之高密度安裝化或訊號之高頻化逐步推進，對於印刷配線板要求優異之高頻對應。 Printed wiring boards have made great progress in this half century and are now used in almost all electronic machines. In recent years, with the increase in the demand for miniaturization and high performance of electronic equipment, the high-density mounting of components and the high-frequency of signals have been gradually advanced, and high-frequency correspondence is required for printed wiring boards.

為了確保輸出訊號之品質，對高頻用基板要求傳輸損耗之減少。傳輸損耗主要包括由樹脂(基板側)引起之介電體損耗、及由導體(銅箔側)引起之導體損耗。樹脂之介電常數及介電損耗正切越小，介電體損耗越少。於高頻訊號中，導體損耗之主要原因在於：因頻率越高電流越僅於導體之表面流動之集膚效應而使電流流動之截面積減少、電阻提高。 In order to ensure the quality of the output signal, the transmission loss of the high frequency substrate is required. The transmission loss mainly includes dielectric loss caused by the resin (substrate side) and conductor loss caused by the conductor (copper foil side). The smaller the dielectric constant and dielectric loss tangent of the resin, the less the dielectric loss. In the high-frequency signal, the main reason for the conductor loss is that the higher the frequency, the more the current flows on the surface of the conductor, and the cross-sectional area of the current flow is reduced and the resistance is improved.

作為以減少高頻用銅箔之傳輸損耗為目的之技術，例如於專利文獻1中揭示一種高頻電路用金屬箔，其於金屬箔表面之單面或雙面被覆銀或銀合金，於該銀或銀合金被覆層上，較上述銀或銀合金被覆層之厚度更薄地施加銀或銀合金以外之被覆層。並且，記載有藉此可提供即便於 如衛星通訊中使用之超高頻區域中亦減少由集膚效應引起之損耗的金屬箔。 As a technique for reducing the transmission loss of the high-frequency copper foil, for example, Patent Document 1 discloses a metal foil for a high-frequency circuit in which silver or a silver alloy is coated on one surface or both surfaces of a metal foil. On the silver or silver alloy coating layer, a coating layer other than silver or a silver alloy is applied thinner than the thickness of the above silver or silver alloy coating layer. Moreover, it is recorded that it can be provided even if For example, in the ultra-high frequency region used in satellite communication, the metal foil caused by the skin effect is also reduced.

又，專利文獻2中揭示一種高頻電路用粗化處理壓延銅箔，其特徵在於：壓延銅箔之再結晶退火後之壓延面上之利用X射線繞射求出之(200)面之積分強度(I(200))相對於微粉末銅之利用X射線繞射求出之(200)面之積分強度(I0(200))即I(200)/I0(200)>40，對該壓延面進行利用電解鍍敷之粗化處理後之粗化處理面之算術平均粗糙度(以下設為Ra)為0.02μm~0.2μm，十點平均粗糙度(以下設為Rz)為0.1μm~1.5μm，並且其為印刷電路基板用原材料。並且，記載有藉此可提供可於超過1GHz之高頻下使用之印刷電路板。 Further, Patent Document 2 discloses a roughened copper foil for roughening a high-frequency circuit, which is characterized in that (200) plane integral obtained by X-ray diffraction on a rolling surface after recrystallization annealing of a rolled copper foil The intensity (I(200)) is the integrated strength (I0(200)) of the (200) plane obtained by X-ray diffraction with respect to the fine powder copper, that is, I(200)/I0(200)>40, the calendering The arithmetic mean roughness (hereinafter referred to as Ra) of the roughened surface after the roughening treatment by electrolytic plating is 0.02 μm to 0.2 μm, and the ten point average roughness (hereinafter referred to as Rz) is 0.1 μm to 1.5. Μm, and it is a raw material for a printed circuit board. Further, it is described that a printed circuit board which can be used at a high frequency exceeding 1 GHz can be provided.

進而，專利文獻3中揭示一種電解銅箔，其特徵在於：銅箔之表面之一部分為由結瘤狀突起構成之表面粗糙度為2μm~4μm之凹凸面。並且，記載有藉此可提供高頻傳輸特性優異之電解銅箔。 Further, Patent Document 3 discloses an electrolytic copper foil characterized in that one of the surfaces of the copper foil is an uneven surface having a surface roughness of 2 μm to 4 μm composed of nodular protrusions. Further, an electrolytic copper foil excellent in high-frequency transmission characteristics can be provided.

[專利文獻1]日本專利第4161304號公報 [Patent Document 1] Japanese Patent No. 4161304

[專利文獻2]日本專利第4704025號公報 [Patent Document 2] Japanese Patent No. 4704025

[專利文獻3]日本特開2004-244656號公報 [Patent Document 3] Japanese Laid-Open Patent Publication No. 2004-244656

已知由導體(銅箔側)引起之導體損耗之原因在於如上所述般因集膚效應而使電阻變大，但該電阻不僅存在銅箔本身之電阻之影響，亦存在藉由於銅箔表面為了確保與樹脂基板之接著性而進行之粗化處理所形成的表面處理層之電阻之影響，具體而言，銅箔表面之粗糙度為導體損耗之主要因素，粗糙度越小傳輸損耗越減少。 It is known that the conductor loss caused by the conductor (copper foil side) is caused by the skin effect as described above, but the resistance is not only affected by the electrical resistance of the copper foil itself but also by the surface of the copper foil. In order to ensure the influence of the electric resistance of the surface treatment layer formed by the roughening treatment with the adhesion of the resin substrate, specifically, the roughness of the surface of the copper foil is a main factor of the conductor loss, and the smaller the roughness, the smaller the transmission loss. .

本發明者等人對銅箔表面之粗糙度與傳輸損耗之關係進一步進行了深入研究，結果發現：銅箔表面之粗糙度越小未必傳輸損耗越減少，尤其是若銅箔表面之粗糙度減小至某一程度，則於傳輸損耗之減少與銅箔表面之粗糙度之關係上可見明顯之波動，難以僅藉由控制銅箔表面之粗糙度而良好地減少傳輸損耗。 The inventors of the present invention further studied the relationship between the roughness of the surface of the copper foil and the transmission loss, and found that the smaller the roughness of the surface of the copper foil, the less the transmission loss is, especially if the roughness of the surface of the copper foil is reduced. To a certain extent, significant fluctuations in the relationship between the reduction in transmission loss and the roughness of the surface of the copper foil are observed, and it is difficult to reduce the transmission loss well by merely controlling the roughness of the surface of the copper foil.

又，作為銅箔表面之粗化處理，已知形成鈷-鎳合金鍍層，關於習知之形成有鈷-鎳合金鍍層之銅箔，由於形成於其表面之由銅-鈷-鎳合金鍍敷構成之粗化粒子之形狀為樹枝狀，故而會產生自該樹枝之上部或根部剝離脫落、通常稱為落粉現象之問題。 Further, as a roughening treatment of the surface of the copper foil, it is known to form a cobalt-nickel alloy plating layer, and a copper foil having a cobalt-nickel alloy plating layer formed thereon is formed of a copper-cobalt-nickel alloy plating layer formed on the surface thereof. The shape of the roughened particles is dendritic, and thus there is a problem that peeling off from the upper portion or the root portion of the branch, which is generally called a falling powder phenomenon.

該落粉現象為麻煩之問題，雖銅-鈷-鎳合金鍍敷之粗化處理層具有耐熱性優異之特徵，但粒子容易因外力而脫落，從而出現如下問題：產生由處理中之「摩擦」引起之剝離、由剝離粉引起之輥之髒污、由剝離粉引起之蝕刻殘渣。 The powder falling phenomenon is a problem of trouble. Although the roughened layer of the copper-cobalt-nickel alloy plating has the characteristics of excellent heat resistance, the particles are easily peeled off due to external force, and the following problem occurs: generation of "friction" by the treatment The peeling caused by the peeling, the dirt caused by the peeling powder, and the etching residue caused by the peeling powder.

因此，本發明之目的在於提供一種即便用於高頻電路基板亦可良好地抑制傳輸損耗，並且良好地抑制形成於銅箔表面之粗化粒子自該表面剝離脫落之現象即所謂「落粉」之產生的高頻電路用銅箔。 Therefore, an object of the present invention is to provide a phenomenon in which a high-frequency circuit substrate can be satisfactorily suppressed from transmission loss, and a phenomenon in which roughened particles formed on a surface of a copper foil are peeled off from the surface is suppressed. The resulting high-frequency circuit is made of copper foil.

本發明者發現對於抑制用於高頻電路基板時之傳輸損耗、及抑制銅箔表面之落粉極為有效的是：於附載體銅箔之極薄銅層表面形成特定之粗化粒子層，且控制該粗化粒子層之三維表面積相對於二維表面積之比。 The present inventors have found that it is extremely effective for suppressing transmission loss when used for a high-frequency circuit substrate and suppressing powder falling on the surface of a copper foil by forming a specific roughened particle layer on the surface of an extremely thin copper layer of a copper foil with a carrier, and The ratio of the three-dimensional surface area of the roughened particle layer to the two-dimensional surface area is controlled.

本發明係基於上述見解而完成者，於一態樣中係一種高頻電路用銅箔，其係於銅箔表面形成銅之一次粒子層之後，於該一次粒子層上 形成由銅、鈷及鎳構成之三元系合金之二次粒子層而成的銅箔，粗化處理面之一定區域利用雷射顯微鏡獲得之三維表面積相對於二維表面積的比為2.0以上且未達2.2。 The present invention is based on the above findings, and in one aspect is a copper foil for a high-frequency circuit which is formed on a surface of a copper foil to form a primary particle layer of copper on the primary particle layer. a copper foil formed by forming a secondary particle layer of a ternary alloy composed of copper, cobalt, and nickel, and a ratio of a three-dimensional surface area obtained by a laser microscope to a two-dimensional surface area in a certain region of the roughened surface is 2.0 or more Not up to 2.2.

本發明之高頻電路用銅箔於一實施形態中，該銅之一次粒子層的平均粒徑為0.25~0.45μm，由銅、鈷及鎳構成之三元系合金所形成之二次粒子層的平均粒徑為0.35μm以下。 In one embodiment, the copper foil for high-frequency circuit of the present invention has a secondary particle layer formed of a ternary alloy composed of copper, cobalt, and nickel having an average particle diameter of 0.25-0.45 μm. The average particle diameter is 0.35 μm or less.

本發明之高頻電路用銅箔於另一實施形態中，該一次粒子層及二次粒子層為電鍍層。 In another embodiment of the copper foil for high-frequency circuit of the present invention, the primary particle layer and the secondary particle layer are electroplated layers.

本發明之高頻電路用銅箔於進而另一實施形態中，該二次粒子為於該一次粒子上成長之1個或複數個樹枝狀粒子或於該一次粒子上成長之正常鍍層。 In still another embodiment of the copper foil for high-frequency circuit of the present invention, the secondary particles are one or a plurality of dendritic particles grown on the primary particles or a normal plating layer grown on the primary particles.

本發明之高頻電路用銅箔於進而另一實施形態中，該一次粒子層及二次粒子層之接著強度為0.80kg/cm以上。 In still another embodiment of the copper foil for high-frequency circuit of the present invention, the adhesion strength between the primary particle layer and the secondary particle layer is 0.80 kg/cm or more.

本發明之高頻電路用銅箔於進而另一實施形態中，該一次粒子層及二次粒子層之接著強度為0.90kg/cm以上。 In still another embodiment of the copper foil for high-frequency circuit of the present invention, the secondary strength of the primary particle layer and the secondary particle layer is 0.90 kg/cm or more.

本發明之高頻電路用銅箔於進而另一實施形態中，於該二次粒子層上形成有：(A)由Ni與選自由Fe、Cr、Mo、Zn、Ta、Cu、Al、P、W、Mn、Sn、As及Ti組成之群中一種以上之元素構成的合金層，及(B)鉻酸鹽層之任一者或兩者。 In still another embodiment, the copper foil for high-frequency circuit of the present invention is formed on the secondary particle layer: (A) is made of Ni and is selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, and P. Any one or both of an alloy layer composed of one or more elements of the group consisting of W, Mn, Sn, As, and Ti, and (B) a chromate layer.

本發明之高頻電路用銅箔於進而另一實施形態中，於該二次 粒子層上依序形成有：(A)由Ni與選自由Fe、Cr、Mo、Zn、Ta、Cu、Al、P、W、Mn、Sn、As及Ti組成之群中一種以上之元素構成之合金層，及(B)鉻酸鹽層之任一者或兩者，及矽烷偶合層。 In another embodiment of the copper foil for high-frequency circuit of the present invention, the second The particle layer is sequentially formed by: (A) consisting of Ni and one or more elements selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As, and Ti. Either or both of the alloy layer, and (B) the chromate layer, and the decane coupling layer.

本發明之高頻電路用銅箔於進而另一實施形態中，於該二次粒子層上形成有Ni-Zn合金層及鉻酸鹽層之任一者或兩者。 In still another embodiment of the copper foil for high-frequency circuit of the present invention, either or both of a Ni-Zn alloy layer and a chromate layer are formed on the secondary particle layer.

本發明之高頻電路用銅箔於進而另一實施形態中，於該二次粒子層上依序形成有：Ni-Zn合金層及鉻酸鹽層之任一者或兩者，及矽烷偶合層。 In still another embodiment of the copper foil for high-frequency circuit of the present invention, either or both of a Ni-Zn alloy layer and a chromate layer and a decane coupling are sequentially formed on the secondary particle layer. Floor.

本發明之高頻電路用銅箔於進而另一實施形態中，於該二次粒子層之表面具備樹脂層。 In still another embodiment of the copper foil for high-frequency circuit of the present invention, a resin layer is provided on the surface of the secondary particle layer.

本發明之高頻電路用銅箔於進而另一實施形態中，於該由Ni與選自由Fe、Cr、Mo、Zn、Ta、Cu、Al、P、W、Mn、Sn、As及Ti組成之群中一種以上之元素構成的合金層、或該鉻酸鹽層、或該矽烷偶合層、或該Ni-Zn合金層之表面具備樹脂層。 In still another embodiment, the copper foil for high-frequency circuit of the present invention comprises Ni and a material selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As, and Ti. The alloy layer composed of one or more elements in the group, or the chromate layer, or the decane coupling layer, or the surface of the Ni-Zn alloy layer is provided with a resin layer.

本發明於另一態樣中係一種附載體銅箔，係於載體之一面或雙面依序具有中間層、極薄銅層者，該極薄銅層為本發明之高頻電路用銅箔。 In another aspect, the invention is a copper foil with carrier, which is provided on the one or both sides of the carrier, and has an intermediate layer and an ultra-thin copper layer. The ultra-thin copper layer is the copper foil for high-frequency circuit of the invention. .

本發明之附載體銅箔於一實施形態中，於該載體之一面依序具有該中間層、該極薄銅層，於該載體之另一面具有粗化處理層。 In one embodiment, the copper foil with a carrier of the present invention has the intermediate layer and the ultra-thin copper layer on one side of the carrier, and has a roughened layer on the other side of the carrier.

本發明於進而另一態樣中係一種高頻電路用覆銅積層板，其使用有本發明之銅箔。 In still another aspect of the invention, a copper-clad laminate for a high-frequency circuit using the copper foil of the invention is used.

本發明於進而另一態樣中係一種高頻電路用印刷配線板，其使用有本發明之銅箔。 In still another aspect of the invention, a printed wiring board for a high-frequency circuit using the copper foil of the invention is used.

本發明之高頻電路用覆銅積層板於一實施形態中，積層有該銅箔與聚醯亞胺、液晶聚合物或氟樹脂。 In one embodiment of the copper-clad laminate for high-frequency circuits of the present invention, the copper foil is laminated with a polyimide, a liquid crystal polymer or a fluororesin.

本發明於進而另一態樣中係本發明之高頻電路用印刷配線板，其使用有聚醯亞胺、液晶聚合物或氟樹脂之任一者。 In still another aspect of the invention, there is provided a printed wiring board for a high-frequency circuit of the invention, which comprises any one of a polyimide, a liquid crystal polymer or a fluororesin.

本發明於進而另一態樣中係一種電子機器，其使用有本發明之印刷配線板。 In still another aspect of the invention, an electronic apparatus using the printed wiring board of the invention is used.

本發明於進而另一態樣中係一種印刷配線板之製造方法，其含有如下步驟：準備本發明之附載體銅箔與絕緣基板；將該附載體銅箔與絕緣基板積層；及於將該附載體銅箔與絕緣基板積層後，經過將該附載體銅箔之載體剝離之步驟而形成覆銅積層板，然後，藉由半加成法、減成法、部分加成法或改良半加成法之任一種方法形成電路。 In still another aspect, the present invention provides a method of manufacturing a printed wiring board, comprising the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; laminating the copper foil with the carrier and the insulating substrate; After laminating the carrier copper foil and the insulating substrate, the copper-clad laminate is formed by the step of peeling off the carrier with the carrier copper foil, and then, by semi-additive method, subtractive method, partial addition method or modified half-addition Any method of forming a circuit forms a circuit.

本發明於進而另一態樣中係一種印刷配線板之製造方法，其含有如下步驟：於本發明之附載體銅箔的該極薄銅層側表面形成電路；以埋沒該電路之方式於該附載體銅箔之該極薄銅層側表面形成樹脂 層；於該樹脂層上形成電路；於該樹脂層上形成電路後，剝離該載體；及藉由在剝離該載體後去除該極薄銅層，而使形成於該極薄銅層側表面之埋沒於該樹脂層的電路露出。 In still another aspect, the present invention provides a method of manufacturing a printed wiring board, comprising the steps of: forming a circuit on a side surface of the ultra-thin copper layer of the copper foil with carrier of the present invention; The side surface of the extremely thin copper layer with the carrier copper foil forms a resin Forming a circuit on the resin layer; after forming a circuit on the resin layer, peeling off the carrier; and removing the ultra-thin copper layer after peeling off the carrier to form a side surface of the ultra-thin copper layer The circuit buried in the resin layer is exposed.

藉由本發明，可提供一種即便用於高頻電路基板亦可良好地抑制傳輸損耗，並且良好地抑制形成於銅箔表面之粗化粒子自該表面剝離脫落之現象即所謂「落粉」之產生的高頻電路用銅箔。 According to the present invention, it is possible to satisfactorily suppress the transmission loss even when used for a high-frequency circuit board, and to suppress the occurrence of the phenomenon that the roughened particles formed on the surface of the copper foil are peeled off from the surface, that is, the so-called "falling powder" The high frequency circuit uses copper foil.

圖1係表示於習知之銅箔上進行由銅-鈷-鎳合金鍍敷構成之粗化處理的情形時落粉之情況的概念說明圖。 Fig. 1 is a conceptual explanatory view showing a state in which powder is dropped in a case where a roughening treatment by copper-cobalt-nickel alloy plating is performed on a conventional copper foil.

圖2係本發明之於銅箔上預先形成一次粒子層、於該一次粒子層上形成由銅-鈷-鎳合金鍍敷構成之二次粒子層之無落粉之銅箔處理層的概念說明圖。 2 is a conceptual illustration of a copper foil-treated layer of a copper foil which is formed by pre-forming a primary particle layer on a copper foil and forming a secondary particle layer composed of a copper-cobalt-nickel alloy plating on the primary particle layer. Figure.

圖3係於習知之銅箔上進行由銅-鈷-鎳合金鍍敷構成之粗化處理之情形時表面的顯微鏡照片。 Fig. 3 is a photomicrograph of the surface of a conventional copper foil subjected to roughening treatment by copper-cobalt-nickel alloy plating.

圖4係本發明之於銅箔上預先形成一次粒子層、於該一次粒子層上形成由銅-鈷-鎳合金鍍敷構成之二次粒子層之無落粉之銅箔處理面之層的顯微鏡照片。 4 is a layer of a copper foil-treated surface of a copper foil which is formed by pre-forming a primary particle layer on a copper foil and forming a secondary particle layer composed of a copper-cobalt-nickel alloy plating on the primary particle layer; Microscope photo.

圖5之A~C係使用本發明之附載體銅箔的印刷配線板之製造方法之具體例的至鍍敷電路、去除抗蝕劑為止之步驟中之配線板剖面的示意圖。 A to C of Fig. 5 is a schematic view showing a cross section of the wiring board in the step of removing the resist from the plating circuit and the specific example of the method of manufacturing the printed wiring board with the carrier copper foil of the present invention.

圖6之D~F係使用本發明之附載體銅箔之印刷配線板之製造方法之具體例的自積層樹脂及第2層附載體銅箔至雷射開孔為止之步驟中之配線板剖面的示意圖。 FIG. 6 is a cross-sectional view of the wiring board in the step from the self-laminated resin and the second-layer carrier-attached copper foil to the laser opening using the specific example of the method for producing a printed wiring board with a carrier copper foil according to the present invention. Schematic diagram.

圖7之G~I係使用本發明之附載體銅箔之印刷配線板之製造方法之具體例的自形成通孔填充物至剝離第1層之載體為止之步驟中之配線板剖面的示意圖。 Fig. 7 is a schematic view showing a cross section of the wiring board in the step from the formation of the through-hole filler to the step of peeling off the carrier of the first layer, using a specific example of the method for producing a printed wiring board with a carrier copper foil according to the present invention.

圖8之J~K係使用本發明之附載體銅箔之印刷配線板之製造方法之具體例的自快速蝕刻至形成凸塊、銅柱為止之步驟中之配線板剖面的示意圖。 Fig. 8 is a schematic view showing a cross section of the wiring board in the step of forming a bump or a copper pillar in a specific example of the method for producing a printed wiring board with a carrier copper foil according to the present invention.

可於本發明中使用之銅箔基材之形態並無特別限制，典型而言，本發明中使用之銅箔可為電解銅箔或壓延銅箔中任一者。通常，電解銅箔係利用硫酸銅鍍浴將銅電解析出至鈦或不鏽鋼之轉筒上而製造，壓延銅箔係重複進行利用壓延輥之塑性加工與熱處理而製造。於要求彎曲性之用途中，多數情況下應用壓延銅箔。 The form of the copper foil substrate which can be used in the present invention is not particularly limited. Typically, the copper foil used in the present invention may be either an electrolytic copper foil or a rolled copper foil. Usually, an electrolytic copper foil is produced by electrolyzing copper into a drum of titanium or stainless steel by a copper sulfate plating bath, and the rolled copper foil is repeatedly produced by plastic working and heat treatment by a calender roll. In applications where flexibility is required, rolled copper foil is used in most cases.

作為銅箔基材之材料，除了通常用作印刷配線板之導體圖案之精銅或無氧銅等高純度銅以外，亦可使用例如摻Sn銅、摻Ag銅、添加有Cr、Zr或Mg等之銅合金、添加有Ni及Si等之卡遜系銅合金之類的銅合金。再者，於本說明書中，單獨使用用語「銅箔」時，亦包含銅合金箔。 As the material of the copper foil substrate, in addition to high-purity copper such as refined copper or oxygen-free copper which is usually used as a conductor pattern of a printed wiring board, for example, Sn-doped copper, Ag-doped copper, Cr, Zr or Mg added may be used. A copper alloy such as a copper alloy or a Cason copper alloy to which Ni and Si are added. In addition, in the present specification, when the term "copper foil" is used alone, a copper alloy foil is also included.

再者，銅箔基材之板厚無需特別限定，例如為1~1000μm、1~500μm、1~300μm、3~100μm、5~70μm、6~35μm、或9~18μm。 Further, the thickness of the copper foil substrate is not particularly limited, and is, for example, 1 to 1000 μm, 1 to 500 μm, 1 to 300 μm, 3 to 100 μm, 5 to 70 μm, 6 to 35 μm, or 9 to 18 μm.

又，本發明之另一態樣係一種附載體銅箔，係依序具有載體、中間層、極薄銅層者，上述極薄銅層為本發明之高頻電路用銅箔。即，於本發明之 另一態樣中，可使用依序具有載體、中間層、極薄銅層之附載體銅箔作為銅箔基材。於本發明中使用附載體銅箔之情形時，於極薄銅層表面設置以下粗化處理層等表面處理層。再者，附載體銅箔之另一實施之形態係如下所述。 Further, another aspect of the present invention is a copper foil with a carrier which has a carrier, an intermediate layer, and an extremely thin copper layer in this order, and the ultra-thin copper layer is a copper foil for a high-frequency circuit of the present invention. That is, in the present invention In another aspect, a copper foil with a carrier having a carrier, an intermediate layer, and an extremely thin copper layer in this order can be used as the copper foil substrate. In the case where the carrier copper foil is used in the present invention, a surface treatment layer such as a roughening treatment layer is provided on the surface of the ultra-thin copper layer. Further, another embodiment of the carrier-attached copper foil is as follows.

通常，為了提高銅箔與樹脂基材接著之面即粗化面於積層後之銅箔之剝離強度，於脫脂後之銅箔之表面實施進行「結瘤」狀之電鍍之粗化處理。電解銅箔於製造時具有凹凸，藉由粗化處理增強電解銅箔之凸部而進一步擴大凹凸。有進行通常之銅鍍敷等作為粗化前之前處理之情況，亦有為防止電鍍物之脫落而進行通常之銅鍍敷等作為粗化後之完工處理之情況。 Usually, in order to improve the peeling strength of the rough surface of the copper foil and the resin substrate, that is, the copper foil after lamination, the surface of the copper foil after degreasing is subjected to roughening treatment in the form of "nodulation". The electrolytic copper foil has irregularities at the time of production, and the convex portion of the electrolytic copper foil is reinforced by the roughening treatment to further enlarge the unevenness. There are cases where normal copper plating or the like is performed as a pre-roughening treatment, and normal copper plating or the like is performed as a roughening completion treatment to prevent the plating material from falling off.

於本發明中，所謂「粗化處理」包括此種前處理及完工處理，視需要亦包括與銅箔粗化相關之公知之處理。 In the present invention, the "roughening treatment" includes such pre-treatment and completion treatment, and includes a known treatment relating to roughening of copper foil as needed.

將該粗化處理設為藉由銅-鈷-鎳合金鍍敷進行(以下說明中，為明確與前步驟之差異，將銅-鈷-鎳合金鍍敷之粗化處理稱為「二次粒子層」)，但若如上所述般僅單純地於銅箔之上形成銅-鈷-鎳合金鍍層，則會產生如上所述之落粉等問題。 This roughening treatment is performed by copper-cobalt-nickel alloy plating (in the following description, the roughening treatment of copper-cobalt-nickel alloy plating is referred to as "secondary particle" in order to clarify the difference from the previous step. Layer"), however, if the copper-cobalt-nickel alloy plating layer is formed only on the copper foil as described above, problems such as falling powder as described above occur.

將銅箔之上形成有銅-鈷-鎳合金鍍層之銅箔之表面的顯微鏡照片示於圖3。如該圖3所示，可見延伸成樹枝狀之微細粒子。通常，該圖3所示之延伸成樹枝狀之微細粒子以高電流密度製作。 A micrograph of the surface of a copper foil on which a copper-cobalt-nickel alloy plating layer was formed on a copper foil is shown in Fig. 3. As shown in Fig. 3, fine particles extending in a dendritic shape can be seen. Generally, the fine particles extending in a dendritic shape as shown in Fig. 3 are produced at a high current density.

於在此種高電流密度進行處理之情形時，可抑制於初期電鍍中產生粒子核，且於粒子前端形成新的粒子核，因此細長之粒子逐漸成長為樹枝狀。 When the treatment is carried out at such a high current density, the particle nucleus is prevented from being generated in the initial plating, and a new particle nucleus is formed at the tip end of the particle, so that the elongated particle gradually grows into a dendritic shape.

因此，若為防止此種情況而降低電流密度並進行電鍍，則尖減少，粒 子增加，帶弧度之形狀之粒子成長。於此種狀況下，落粉亦得以略微改善，但無法獲得充分之剝離強度，無法充分地達成本發明之目的。 Therefore, if the current density is lowered and electroplating is performed to prevent this, the tip is reduced, and the pellet is reduced. Sub-increased, particles with a curved shape grow. Under such circumstances, the falling powder was also slightly improved, but sufficient peel strength could not be obtained, and the object of the present invention could not be sufficiently achieved.

將如圖3所示之形成銅-鈷-鎳合金鍍層之情形時的落粉之情況示於圖1之概念說明圖。該落粉之原因在於：如上所述般於銅箔上微細粒子生成為樹枝狀，該樹枝狀之粒子容易因外力使樹枝之一部分折斷，又自根部脫落。該微細樹枝狀之粒子係由處理中之「摩擦」引起之剝離、由剝離粉引起之輥之髒污、由剝離粉引起之產生蝕刻殘渣的原因。 The case where the powder is dropped in the case of forming a copper-cobalt-nickel alloy plating layer as shown in Fig. 3 is shown in the conceptual diagram of Fig. 1. The reason why the powder is dropped is that the fine particles are formed into a dendritic shape on the copper foil as described above, and the dendritic particles are likely to be partially broken by the external force and fall off from the root portion. The fine dendritic particles are caused by peeling due to "friction" during the treatment, contamination of the roll by the peeling powder, and generation of etching residue by the peeling powder.

於本發明中，於銅箔之表面預先形成銅之一次粒子層後，於該一次粒子層上形成由銅、鈷及鎳構成之三元系合金所形成之二次粒子層。將於銅箔上形成有該一次粒子及二次粒子之表面之顯微鏡照片示於圖4(詳細內容係如下所述)。 In the present invention, after the primary particle layer of copper is formed on the surface of the copper foil, a secondary particle layer formed of a ternary alloy composed of copper, cobalt and nickel is formed on the primary particle layer. A micrograph of the surface on which the primary particles and secondary particles are formed on the copper foil is shown in Fig. 4 (details are as follows).

藉此，使由處理中之「摩擦」引起之剝離、由剝離粉引起之輥之髒污、由剝離粉引起之蝕刻殘渣消失，即可抑制稱為落粉之現象與處理不均，可獲得能夠提高剝離強度且提高耐熱性之銅箔。 Thereby, the peeling caused by the "friction" during the treatment, the dirt caused by the peeling powder, and the etching residue caused by the peeling powder are eliminated, so that the phenomenon called falling powder and the processing unevenness can be suppressed, and it is possible to obtain A copper foil capable of improving peel strength and improving heat resistance.

根據下述所示之實施例可闡明，防止落粉最佳之條件係將上述一次粒子層之平均粒徑設為0.25~0.45μm、將由銅、鈷及鎳構成之三元系合金所形成之二次粒子層之平均粒徑設為0.35μm以下。上述一次粒子層之平均粒徑之下限較佳為0.27μm以上，更佳為0.29μm以上，更佳為0.30μm以上，進而較佳為0.33μm以上。上述一次粒子層之平均粒徑之上限較佳為0.44μm以下，更佳為0.43μm以下，更佳為0.40μm以下，進而較佳為0.39μm以下。又，上述二次粒子層之平均粒徑之上限較佳為0.34μm以下，更佳為0.33μm以下，更佳為0.32μm以下，更佳為0.31μm以下， 進而較佳為0.30μm以下，進而較佳為0.28μm以下，進而更佳為0.27μm以下。又，二次粒子層之平均粒徑之下限無需特別限定，例如為0.001μm以上、0.01μm以上、0.05μm以上、0.09μm以上、0.10μm以上、0.12μm以上、或0.15μm以上。 According to the examples shown below, it is clarified that the optimum condition for preventing the falling powder is that the average particle diameter of the primary particle layer is 0.25 to 0.45 μm, and the ternary alloy composed of copper, cobalt and nickel is formed. The average particle diameter of the secondary particle layer is set to 0.35 μm or less. The lower limit of the average particle diameter of the primary particle layer is preferably 0.27 μm or more, more preferably 0.29 μm or more, still more preferably 0.30 μm or more, and still more preferably 0.33 μm or more. The upper limit of the average particle diameter of the primary particle layer is preferably 0.44 μm or less, more preferably 0.43 μm or less, still more preferably 0.40 μm or less, still more preferably 0.39 μm or less. Further, the upper limit of the average particle diameter of the secondary particle layer is preferably 0.34 μm or less, more preferably 0.33 μm or less, still more preferably 0.32 μm or less, still more preferably 0.31 μm or less. Further, it is preferably 0.30 μm or less, further preferably 0.28 μm or less, and still more preferably 0.27 μm or less. Further, the lower limit of the average particle diameter of the secondary particle layer is not particularly limited, and is, for example, 0.001 μm or more, 0.01 μm or more, 0.05 μm or more, 0.09 μm or more, 0.10 μm or more, 0.12 μm or more, or 0.15 μm or more.

上述一次粒子層及二次粒子層藉由電鍍層而形成。該二次粒子之特徵在於：於上述一次粒子上成長之1個或複數個樹枝狀之粒子。或者於上述一次粒子上成長之正常鍍敷。即，於本說明書中使用用語「二次粒子層」之情形時，亦包含被覆鍍敷等正常鍍層。又，二次粒子層可為具有一層以上由粗化粒子形成之層者，可為具有一層以上正常鍍層者，亦可為分別具有一層以上由粗化粒子形成之層與正常鍍層者。 The primary particle layer and the secondary particle layer are formed by a plating layer. The secondary particles are characterized by one or a plurality of dendritic particles grown on the primary particles. Or normal plating grown on the above primary particles. In other words, when the term "secondary particle layer" is used in the present specification, a normal plating layer such as coating plating is also included. Further, the secondary particle layer may have one or more layers formed of roughened particles, and may have one or more layers of normal plating, or may have one or more layers of roughened particles and a normal plating layer, respectively.

如此形成之一次粒子層及二次粒子層之接著強度可達到0.80kg/cm以上，進而接著強度達到0.90kg/cm以上。 The bonding strength between the primary particle layer and the secondary particle layer thus formed can be 0.80 kg/cm or more, and further the subsequent strength is 0.90 kg/cm or more.

於形成有一次粒子層及二次粒子層之銅箔中，進而重要的是將粗化處理面之一定區域之利用雷射顯微鏡獲得之三維表面積相對於二維表面積之比設為2.0以上且未達2.2。再者，所謂「利用雷射顯微鏡獲得之三維表面積相對於二維表面積之比」中之「粗化處理面」係表示最終製品上之表面，為形成一次粒子層及二次粒子層側之最表面。又，於在二次粒子層上形成例如耐熱層、防銹層、矽烷偶合處理層等表面處理層時，係意指該表面處理層之最表面。再者，於形成下述「樹脂層」時，係意指該樹脂層除外之銅箔之形成一次粒子層及二次粒子層側之最表面。 In the copper foil in which the primary particle layer and the secondary particle layer are formed, it is further important that the ratio of the three-dimensional surface area obtained by the laser microscope to the two-dimensional surface area in a certain region of the roughened surface is set to 2.0 or more. Up to 2.2. In addition, the "roughening surface" in the "ratio of the three-dimensional surface area obtained by the laser microscope to the two-dimensional surface area" means the surface on the final product, and is the largest on the side of the primary particle layer and the secondary particle layer. surface. Further, when a surface treatment layer such as a heat-resistant layer, a rustproof layer, or a decane coupling treatment layer is formed on the secondary particle layer, it means the outermost surface of the surface treatment layer. In addition, when forming the following "resin layer", it means that the copper foil except the resin layer forms the outermost surface of the primary particle layer and the secondary particle layer side.

關於此種表面積比之限制與調整，銅箔之粗化處理面由作為各粗化粒子之集合體之粒子層形成，並藉由在遠大於粒子成長控制之範圍內控制粒 子層，而具有提高無波動即穩定之剝離強度、與可防止穩定之落粉現象的效果。又，即便控制各粗化粒子尺寸，於微細之粗化粒子堆積於高度方向之情形時亦會產生落粉。因此，成為三維之粗化粒子構成之表面積比之限制與調整變得重要。 Regarding the limitation and adjustment of the surface area ratio, the roughened surface of the copper foil is formed of a particle layer as an aggregate of the roughened particles, and the particles are controlled by a range far greater than the particle growth control. The sub-layer has the effect of improving the non-fluctuation, that is, the stable peel strength, and preventing the stable falling powder phenomenon. Further, even if the size of each of the roughened particles is controlled, fine powder is generated when finely roughened particles are deposited in the height direction. Therefore, it is important to limit and adjust the surface area ratio of the three-dimensional roughened particles.

若上述表面積比未達2.0，則剝離強度變得不充分。使用雷射顯微鏡對標準壓延銅箔於粗化處理前之無粗化之狀態下之三維表面粗糙度進行測定，結果為20043μm2，三維表面積相對於二維表面積之比為2.02，因此為確保剝離強度，可謂理想為至少2.0以上。又，若超過2.20，則容易產生落粉現象，因此可謂理想為設為上述範圍。再者，上述表面積比(三維表面積相對於二維表面積之比)之上限較佳為2.19以下，更佳為2.17以下，進而較佳為2.15以下。又，上述表面積比(三維表面積相對於二維表面積之比)之下限較佳為2.02以上，更佳為2.04以上，進而較佳為2.05以上，進而更佳為2.06以上。 When the surface area ratio is less than 2.0, the peel strength becomes insufficient. The three-dimensional surface roughness of the standard rolled copper foil before the roughening treatment was measured using a laser microscope, and as a result, it was 20043 μm 2 , and the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.02, so that the peeling was ensured. The strength is desirably at least 2.0 or more. Moreover, when it exceeds 2.20, it is easy to produce a powder falling phenomenon, and it is desirable to set it as the said range. Further, the upper limit of the surface area ratio (ratio of the three-dimensional surface area to the two-dimensional surface area) is preferably 2.19 or less, more preferably 2.17 or less, still more preferably 2.15 or less. Further, the lower limit of the surface area ratio (ratio of the three-dimensional surface area to the two-dimensional surface area) is preferably 2.02 or more, more preferably 2.04 or more, still more preferably 2.05 or more, still more preferably 2.06 or more.

利用雷射顯微鏡之測定法係使用基恩斯股份有限公司製造之雷射顯微鏡VK8500對粗化處理面之相當於100×100μm之面積、實際數據為9924.4μm2之範圍的三維表面積進行測定，並利用設為三維表面積÷二維表面積=表面積比之方法進行設定。 The measurement method using a laser microscope uses a laser microscope VK8500 manufactured by Keyence Co., Ltd. to measure the three-dimensional surface area of the roughened surface corresponding to an area of 100 × 100 μm and an actual data of 9924.4 μm 2 . The method is set for a three-dimensional surface area ÷ two-dimensional surface area = surface area ratio.

可於二次粒子層上形成： Can be formed on the secondary particle layer:

(A)由Ni與選自由Fe、Cr、Mo、Zn、Ta、Cu、Al、P、W、Mn、Sn、As及Ti組成之群中一種以上之元素構成之合金層，及(B)鉻酸鹽層之任一者或兩者。 (A) an alloy layer composed of Ni and one or more elements selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, As, and Ti, and (B) Either or both of the chromate layers.

又，可於二次粒子層上依序形成(A)由Ni與選自由Fe、Cr、Mo、Zn、 Ta、Cu、Al、P、W、Mn、Sn、As及Ti組成之群中一種以上之元素構成之合金層，及(B)鉻酸鹽層之任一者或兩者，及矽烷偶合層。 Further, (A) from Ni and selected from Fe, Cr, Mo, Zn, may be sequentially formed on the secondary particle layer. An alloy layer composed of one or more elements of a group consisting of Ta, Cu, Al, P, W, Mn, Sn, As, and Ti, and (B) either or both of chromate layers, and a decane coupling layer .

進而，可於二次粒子層上形成Ni-Zn合金層及鉻酸鹽層之任一者或兩者。 Further, either or both of the Ni-Zn alloy layer and the chromate layer may be formed on the secondary particle layer.

進而，可於二次粒子層上依序形成Ni-Zn合金層及鉻酸鹽層之任一者或兩者，及矽烷偶合層。 Further, either or both of the Ni-Zn alloy layer and the chromate layer and the decane coupling layer may be sequentially formed on the secondary particle layer.

藉由此種構成，可於維持剝離強度之狀態下提高高頻傳輸特性。 According to this configuration, the high-frequency transmission characteristics can be improved while maintaining the peel strength.

[傳輸損耗] [transmission loss]

於傳輸損耗較小之情形時，可抑制以高頻進行訊號傳輸時訊號之衰減，因此以高頻進行訊號之傳輸之電路可進行穩定之訊號之傳輸。因此，傳輸損耗之值較小者適合用於以高頻進行訊號之傳輸之電路用途，故而較佳。將表面處理銅箔與市售之液晶聚合物樹脂(Kuraray股份有限公司製造之Vecstar CTZ-50μm)貼合後，利用蝕刻以特性阻抗成為50Ω之方式形成微帶線路，使用HP公司製造之網路分析儀HP8720C測定穿透係數，求出於頻率20GHz及頻率40GHz之傳輸損耗，於此情形時，頻率20GHz之傳輸損耗較佳為未達5.0dB/10cm，更佳為未達4.1dB/10cm，進而較佳為未達3.7dB/10cm。 In the case where the transmission loss is small, the attenuation of the signal when the signal is transmitted at a high frequency can be suppressed, so that the circuit for transmitting the signal at a high frequency can perform stable signal transmission. Therefore, the smaller value of the transmission loss is suitable for circuit use for transmitting signals at high frequencies, and thus is preferable. After the surface-treated copper foil was bonded to a commercially available liquid crystal polymer resin (Vecstar CTZ-50 μm manufactured by Kuraray Co., Ltd.), a microstrip line was formed by etching to have a characteristic impedance of 50 Ω, and a network manufactured by HP was used. The analyzer HP8720C measures the transmission coefficient and determines the transmission loss at a frequency of 20 GHz and a frequency of 40 GHz. In this case, the transmission loss at a frequency of 20 GHz is preferably less than 5.0 dB/10 cm, more preferably less than 4.1 dB/10 cm. Further preferably, it is less than 3.7 dB/10 cm.

可將本發明之表面處理銅箔自粗化處理面側與樹脂基板貼合而製造積層體。樹脂基板只要具有可應用於印刷配線板等之特性，則不受特別限制，例如，剛性PWB用中可使用紙基材酚系樹脂、紙基材環氧樹脂、合成纖維布基材環氧樹脂、玻璃布/紙複合基材環氧樹脂、玻璃布/玻璃不織布複合基材環氧樹脂及玻璃布基材環氧樹脂等，FPC用中可使用 聚酯膜或聚醯亞胺膜、液晶聚合物(LCP)膜、氟樹脂等。再者，於使用液晶聚合物(LCP)膜或氟樹脂膜之情形時，與使用聚醯亞胺膜之情形時相比，有該膜與表面處理銅箔之剝離強度變小之傾向。因此，於使用液晶聚合物(LCP)膜或氟樹脂膜之情形時，藉由於形成銅電路後以覆蓋層被覆銅電路，該膜與銅電路不易剝離，可防止因剝離強度之降低引起之該膜與銅電路之剝離。 The surface-treated copper foil of the present invention can be bonded to the resin substrate from the roughened surface side to produce a laminate. The resin substrate is not particularly limited as long as it has characteristics applicable to a printed wiring board or the like. For example, a paper substrate phenol resin, a paper substrate epoxy resin, or a synthetic fiber cloth substrate epoxy resin can be used for the rigid PWB. , glass cloth / paper composite substrate epoxy resin, glass cloth / glass non-woven composite substrate epoxy resin and glass cloth substrate epoxy resin, etc., can be used in FPC A polyester film or a polyimide film, a liquid crystal polymer (LCP) film, a fluororesin or the like. Further, when a liquid crystal polymer (LCP) film or a fluororesin film is used, the peeling strength of the film and the surface-treated copper foil tends to be smaller than in the case of using a polyimide film. Therefore, when a liquid crystal polymer (LCP) film or a fluororesin film is used, since the copper circuit is coated with a cap layer after the copper circuit is formed, the film and the copper circuit are not easily peeled off, and the peeling strength can be prevented from being lowered. Peeling of the film from the copper circuit.

再者，液晶聚合物(LCP)膜或氟樹脂膜之介電損耗正切小，因此使用液晶聚合物(LCP)膜或氟樹脂膜與本發明之表面處理銅箔之覆銅積層板、印刷配線板、印刷電路板適於高頻電路(以高頻進行訊號之傳輸之電路)用途。又，本發明之表面處理銅箔之表面粗糙度Rz小，光澤度高，因此表面平滑，亦適於高頻電路用途。 Further, since the liquid crystal polymer (LCP) film or the fluororesin film has a small dielectric loss tangent, a liquid crystal polymer (LCP) film or a fluororesin film and a copper-clad laminate of the surface-treated copper foil of the present invention and a printed wiring are used. The board and the printed circuit board are suitable for high-frequency circuits (circuits for transmitting signals at high frequencies). Further, the surface-treated copper foil of the present invention has a small surface roughness Rz and a high gloss, so that the surface is smooth and suitable for high-frequency circuit applications.

關於貼合之方法，於剛性PWB用之情形時，準備將樹脂含浸於玻璃布等基材而使樹脂硬化至半硬化狀態的預浸體。可藉由將銅箔自與被覆層相反之側之面與預浸體重疊並進行加熱加壓而進行。於FPC之情形時，可藉由如下方式製造積層板：於聚醯亞胺膜等基材經由接著劑或不使用接著劑而於高溫高壓下積層接著銅箔，或者對聚醯亞胺前驅物進行塗佈、乾燥、硬化等。 In the case of the rigid PWB, the method of bonding is prepared by impregnating a resin with a substrate such as a glass cloth to cure the resin to a semi-hardened state. The copper foil can be formed by superposing the surface of the copper foil from the side opposite to the coating layer with the prepreg and heating and pressing. In the case of FPC, a laminate can be produced by laminating a copper foil with a substrate such as a polyimide film via an adhesive or without an adhesive under high temperature and high pressure, or a polyimide precursor. Coating, drying, hardening, and the like.

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

進而，藉由於印刷配線板搭載電子零件類，而完成印刷電路 板。於本發明中，「印刷配線板」亦包括如此搭載有電子零件類之印刷配線板及印刷電路板及印刷基板。 Furthermore, the printed circuit is completed by mounting electronic components on the printed wiring board. board. In the present invention, the "printed wiring board" also includes a printed wiring board, a printed circuit board, and a printed circuit board on which electronic components are mounted.

又，可使用該印刷配線板製作電子機器，可使用搭載有該電子零件類之印刷電路板製作電子機器，亦可使用搭載有該電子零件類之印刷基板製作電子機器。 Moreover, an electronic device can be produced using the printed wiring board, and an electronic device can be produced using a printed circuit board on which the electronic component is mounted, or an electronic device can be manufactured using the printed circuit board on which the electronic component is mounted.

(銅之一次粒子之鍍敷條件) (plating conditions of primary particles of copper)

若舉出銅之一次粒子之鍍敷條件之一例，則係如下所述。 An example of the plating conditions of the primary particles of copper is as follows.

再者，該鍍敷條件僅表示較佳例，銅之一次粒子之形成於銅箔上之平均粒徑擔負落粉防止之作用。因此，若平均粒徑處於本發明之範圍，則下述所示內容以外之鍍敷條件不會造成任何阻礙。本發明包含該等。 Further, the plating conditions are only a preferred example, and the average particle diameter of the primary particles of copper formed on the copper foil acts to prevent falling powder. Therefore, if the average particle diameter is within the range of the present invention, the plating conditions other than those shown below will not cause any hindrance. The present invention encompasses such.

液組成：銅10~20g/L、硫酸50~100g/L Liquid composition: copper 10~20g/L, sulfuric acid 50~100g/L

液溫：25~50℃ Liquid temperature: 25~50°C

電流密度：1~58A/dm2 Current density: 1~58A/dm 2

庫侖量：4~81As/dm2 Coulomb amount: 4~81As/dm 2

(二次粒子之鍍敷條件) (plating conditions of secondary particles)

再者，與上述同樣，該鍍敷條件僅表示較佳例，二次粒子形成於一次粒子上，並且平均粒徑擔負落粉防止之作用。因此，若平均粒徑處於本發明之範圍，則下述所示內容以外之鍍敷條件不會造成任何阻礙。本發明包含該等。 Further, similarly to the above, the plating conditions are only a preferred example, and secondary particles are formed on the primary particles, and the average particle diameter acts as a powder falling prevention. Therefore, if the average particle diameter is within the range of the present invention, the plating conditions other than those shown below will not cause any hindrance. The present invention encompasses such.

液組成：銅10~20g/L、鎳5~15g/L、鈷5~15g/L Liquid composition: copper 10~20g/L, nickel 5~15g/L, cobalt 5~15g/L

pH值：2~3 pH: 2~3

液溫：30~50℃ Liquid temperature: 30~50°C

電流密度：24~50A/dm2 Current density: 24~50A/dm 2

庫侖量：34~48As/dm2 Coulomb amount: 34~48As/dm 2

(形成耐熱層1之鍍敷條件)(Co-Ni鍍敷：鈷鎳合金鍍敷) (Formation conditions for forming the heat-resistant layer 1) (Co-Ni plating: cobalt-nickel alloy plating)

本發明可於上述二次粒子層上進而形成耐熱層。將該鍍敷條件表示如下。 In the present invention, a heat-resistant layer can be further formed on the secondary particle layer. This plating condition is shown as follows.

液組成：鎳5~20g/L、鈷1~8g/L Liquid composition: nickel 5~20g/L, cobalt 1~8g/L

pH值：2~3 pH: 2~3

液溫：40~60℃ Liquid temperature: 40~60°C

電流密度：5~20A/dm2 Current density: 5~20A/dm 2

庫侖量：10~20As/dm2 Coulomb amount: 10~20As/dm 2

(形成耐熱層2之鍍敷條件)(Ni-Zn鍍敷：鎳鋅合金鍍敷) (Formation conditions for forming the heat-resistant layer 2) (Ni-Zn plating: nickel-zinc alloy plating)

本發明可於上述二次粒子層上進而形成下述耐熱層。將該鍍敷條件表示如下。 In the present invention, the following heat-resistant layer can be further formed on the secondary particle layer. This plating condition is shown as follows.

液組成：鎳2~30g/L、鋅2~30g/L Liquid composition: nickel 2~30g/L, zinc 2~30g/L

pH值：3~4 pH: 3~4

液溫：30~50℃ Liquid temperature: 30~50°C

電流密度：1~2A/dm2 Current density: 1~2A/dm 2

庫侖量：1~2As/dm2 Coulomb amount: 1~2As/dm 2

(形成耐熱層3之鍍敷條件)(Ni-Cu鍍敷：鎳銅合金鍍敷) (plating conditions for forming the heat-resistant layer 3) (Ni-Cu plating: nickel-copper alloy plating)

本發明可於上述二次粒子層上進而形成下述耐熱層。將該鍍敷條件表示如下。 In the present invention, the following heat-resistant layer can be further formed on the secondary particle layer. This plating condition is shown as follows.

液組成：鎳2~30g/L、銅2~30g/L Liquid composition: nickel 2~30g/L, copper 2~30g/L

pH值：3~4 pH: 3~4

液溫：30~50℃ Liquid temperature: 30~50°C

電流密度：1~2A/dm2 Current density: 1~2A/dm 2

庫侖量：1~2As/dm2 Coulomb amount: 1~2As/dm 2

(形成耐熱層4之鍍敷條件)(Ni-Mo鍍敷：鎳鉬合金鍍敷) (plating conditions for forming the heat-resistant layer 4) (Ni-Mo plating: nickel-molybdenum alloy plating)

本發明可於上述二次粒子層上進而形成下述耐熱層。將該鍍敷條件表示如下。 In the present invention, the following heat-resistant layer can be further formed on the secondary particle layer. This plating condition is shown as follows.

液組成：硫酸Ni六水合物：45~55g/dm3、鉬酸鈉二水合物：50~70g/dm3、檸檬酸鈉：80~100g/dm3 Liquid composition: Ni hexahydrate: 45~55g/dm 3 , sodium molybdate dihydrate: 50~70g/dm 3 , sodium citrate: 80~100g/dm 3

液溫：20~40℃ Liquid temperature: 20~40°C

電流密度：1~4A/dm2 Current density: 1~4A/dm 2

庫侖量：1~2As/dm2 Coulomb amount: 1~2As/dm 2

(形成耐熱層5之鍍敷條件)(Ni-Sn鍍敷：鎳錫合金鍍敷) (plating conditions for forming the heat-resistant layer 5) (Ni-Sn plating: nickel-tin alloy plating)

本發明可於上述二次粒子層上進而形成下述耐熱層。將該鍍敷條件表示如下。 In the present invention, the following heat-resistant layer can be further formed on the secondary particle layer. This plating condition is shown as follows.

液組成：鎳2~30g/L、錫2~30g/L Liquid composition: nickel 2~30g/L, tin 2~30g/L

pH值：1.5~4.5 pH: 1.5~4.5

液溫：30~50℃ Liquid temperature: 30~50°C

電流密度：1~2A/dm2 Current density: 1~2A/dm 2

庫侖量：1~2As/dm2 Coulomb amount: 1~2As/dm 2

(形成耐熱層6之鍍敷條件)(Ni-P鍍敷：鎳磷合金鍍敷) (plating conditions for forming the heat-resistant layer 6) (Ni-P plating: nickel-phosphorus alloy plating)

本發明可於上述二次粒子層上進而形成下述耐熱層。將該鍍敷條件表 示如下。 In the present invention, the following heat-resistant layer can be further formed on the secondary particle layer. Plating condition table Shown as below.

液組成：鎳30~70g/L、磷0.2~1.2g/L Liquid composition: nickel 30~70g/L, phosphorus 0.2~1.2g/L

pH值：1.5~2.5 pH: 1.5~2.5

液溫：30~40℃ Liquid temperature: 30~40°C

電流密度：1~2A/dm2 Current density: 1~2A/dm 2

庫侖量：1~2As/dm2 Coulomb amount: 1~2As/dm 2

(形成耐熱層7之鍍敷條件)(Ni-W鍍敷：鎳鎢合金鍍敷) (plating conditions for forming the heat-resistant layer 7) (Ni-W plating: nickel-tungsten alloy plating)

本發明可於上述二次粒子層上進而形成下述耐熱層。將該鍍敷條件表示如下。 In the present invention, the following heat-resistant layer can be further formed on the secondary particle layer. This plating condition is shown as follows.

液組成：鎳2~30g/L、W0.01~5g/L Liquid composition: nickel 2~30g/L, W0.01~5g/L

pH值：3~4 pH: 3~4

液溫：30~50℃ Liquid temperature: 30~50°C

電流密度：1~2A/dm2 Current density: 1~2A/dm 2

庫侖量：1~2As/dm2 Coulomb amount: 1~2As/dm 2

(形成耐熱層8之鍍敷條件)(Ni-Cr鍍敷：鎳鉻合金鍍敷) (plating conditions for forming the heat-resistant layer 8) (Ni-Cr plating: nickel-chromium alloy plating)

本發明可於上述二次粒子層上進而形成下述耐熱層。將該鍍敷條件表示如下。 In the present invention, the following heat-resistant layer can be further formed on the secondary particle layer. This plating condition is shown as follows.

使用Ni：65~85mass%、Cr：15~35mass%之組成之濺鍍靶形成鎳鉻合金鍍層。 A nickel-chromium alloy plating layer is formed using a sputtering target having a composition of Ni: 65 to 85 mass% and Cr: 15 to 35 mass%.

靶：Ni：65~85mass%、Cr：15~35mass% Target: Ni: 65~85mass%, Cr: 15~35mass%

裝置：ULVAC股份有限公司製造之濺鍍裝置 Device: Sputtering device manufactured by ULVAC Co., Ltd.

輸出：DC50W Output: DC50W

氬氣壓力：0.2Pa Argon pressure: 0.2Pa

(形成防銹層之鍍敷條件) (Formation conditions for forming a rustproof layer)

本發明可進而形成下述防銹層。將該鍍敷條件表示如下。下述表示浸漬鉻酸鹽處理之條件，亦可為電解鉻酸鹽處理。 The present invention can further form the following rust preventive layer. This plating condition is shown as follows. The conditions for impregnating the chromate treatment are as follows, and may also be an electrolytic chromate treatment.

液組成：重鉻酸鉀1~10g/L、鋅0~5g/L Liquid composition: potassium dichromate 1~10g/L, zinc 0~5g/L

pH值：3~4 pH: 3~4

液溫：50~60℃ Liquid temperature: 50~60°C

電流密度：0~2A/dm2(0A/dm2為浸漬鉻酸鹽處理之情形) Current density: 0~2A/dm 2 (0A/dm 2 is the case of impregnated chromate treatment)

庫侖量：0~2As/dm2(0As/dm2為浸漬鉻酸鹽處理之情形) Coulomb amount: 0~2As/dm 2 (0As/dm 2 is the case of impregnated chromate treatment)

(耐候性層(矽烷偶合層)之種類) (Type of weather resistant layer (decane coupling layer))

作為一例，可列舉二胺基矽烷水溶液之塗佈。 As an example, the application of the diamino decane aqueous solution is mentioned.

再者，有藉由濺鍍等乾式鍍敷設置耐熱層等金屬層、鍍層之情況，及藉由濕式鍍敷設置耐熱層等金屬層、鍍層之情況，並且有以正常鍍敷(平滑鍍敷即於未達界限電流密度之電流密度下進行鍍敷)而具有耐熱層等金屬層、鍍層之情況，該金屬層、鍍層不會對銅箔之表面之形狀造成影響。 In addition, a metal layer such as a heat-resistant layer or a plating layer is provided by dry plating such as sputtering, and a metal layer such as a heat-resistant layer or a plating layer is provided by wet plating, and normal plating (smooth plating) is used. The coating is performed at a current density that does not reach the limit current density, and has a metal layer such as a heat-resistant layer or a plating layer. The metal layer and the plating layer do not affect the shape of the surface of the copper foil.

界限電流密度係根據金屬濃度、pH值、給液速度、極間距離、鍍敷液溫度而變化，於本發明中，將正常鍍敷(經鍍敷之金屬析出為層狀之狀態)與粗化鍍敷(燒鍍，經鍍敷之金屬析出為結晶狀(球狀或針狀或樹掛狀等)之狀態，存在凹凸)之交界之電流密度定義為界限電流密度，將利用霍爾槽試驗成為正常鍍敷之界限(即將成為燒鍍前)之電流密度(目視判斷)設為界限電流密度。 The limit current density varies depending on the metal concentration, the pH value, the feed rate, the interelectrode distance, and the temperature of the plating solution. In the present invention, the normal plating (the state in which the plated metal is deposited as a layer) is coarse and thick. The current density at the junction of the plating (the state in which the plated metal is crystallized (spherical or needle-like or tree-like), and the unevenness is defined as the limit current density, and the Hall groove test will be used. The current density (visual judgment) which is the limit of normal plating (that is, immediately before baking) is set as the limit current density.

具體而言，將金屬濃度、pH值、鍍敷液溫度設定為鍍敷之製造條件， 進行霍爾槽試驗。然後，調查於該鍍敷液組成、鍍敷液溫度之金屬層形成狀態(經鍍敷之金屬析出為層狀或形成為結晶狀)。然後，基於山本鍍金試驗器股份有限公司製造之電流密度一覽表，根據試片之正常鍍敷與粗化鍍敷之交界所存在之部位之試片位置，求出該交界之位置之電流密度。並且，將該交界之位置之電流密度規定為界限電流密度。藉此，可知於該鍍敷液組成、鍍敷液溫度之界限電流密度。通常，若極間距離較短，則有界限電流密度變高之傾向。 Specifically, the metal concentration, the pH value, and the plating solution temperature are set as the manufacturing conditions of the plating. Perform a Hall slot test. Then, the formation state of the plating solution and the temperature of the plating solution were investigated (the metal to be plated was precipitated into a layer or formed into a crystal). Then, based on the current density list manufactured by Yamamoto Gold Platter Tester Co., Ltd., the current density at the position of the boundary was obtained from the position of the test piece at the boundary where the normal plating and the rough plating of the test piece exist. Further, the current density at the position of the boundary is defined as the limit current density. Thereby, the current density of the plating solution composition and the plating solution temperature can be known. In general, if the distance between the electrodes is short, the limit current density tends to be high.

霍爾槽試驗之方法例如記載於「鍍敷實務讀本」丸山清著，日刊工業報社1983年6月30日之157頁至160頁中。 The method of the Hall-slot test is described, for example, in the "Plating Practice Book" Maruyama Seiji, the Nikkan Kogyo Shimbun, June 30, 1983, pp. 157-160.

再者，為了以未達界限電流密度進行鍍敷處理，因此較佳為將鍍敷處理時之電流密度設為20A/dm2以下，更佳為設為10A/dm2以下，進而較佳為設為8A/dm2以下。 Further, in order to perform the plating treatment at a current density lower than the limit current, it is preferable to set the current density during the plating treatment to 20 A/dm 2 or less, more preferably 10 A/dm 2 or less, and still more preferably Set to 8A/dm 2 or less.

又，鉻酸鹽層、矽烷偶合層之厚度極薄，因此不會對銅箔之表面之形狀造成影響。 Further, since the thickness of the chromate layer and the decane coupling layer is extremely thin, it does not affect the shape of the surface of the copper foil.

作為上述二次粒子之銅-鈷-鎳合金鍍敷可藉由電解鍍敷而形成附著量為10~30mg/dm2銅-100~3000μg/dm2鈷-50~500μg/dm2鎳之三元系合金層。 As the secondary particle of copper - cobalt - nickel alloy can be deposited by electroless plating and the plating deposition amount of 10 ~ 30mg / dm 2 of copper -100 ~ 3000μg / dm 2 of cobalt -50 ~ 500μg / dm 2 of nickel ter Elemental alloy layer.

若Co附著量未達100μg/dm2，則耐熱性變差，又，蝕刻性亦變差。若Co附著量超過3000μg/dm2，則於必須考慮磁性之影響方面欠佳，產生蝕刻斑，又，可認為耐酸性及耐化學品性惡化。 When the Co adhesion amount is less than 100 μg/dm 2 , the heat resistance is deteriorated, and the etching property is also deteriorated. When the Co adhesion amount exceeds 3000 μg/dm 2 , it is necessary to consider the influence of magnetic properties to be inferior, and an etching spot is generated, and the acid resistance and chemical resistance are considered to be deteriorated.

若Ni附著量未達50μg/dm2，則耐熱性變差。另一方面，若Ni附著量超過500μg/dm2，則蝕刻性降低。即，雖並非存在蝕刻殘渣 又無法蝕刻之等級，但難以進行微細圖案化。較佳之Co附著量為500~2000μg/dm2，並且，較佳之鎳附著量為50~300μg/dm2。 When the Ni adhesion amount is less than 50 μg/dm 2 , the heat resistance is deteriorated. On the other hand, when the Ni adhesion amount exceeds 500 μg/dm 2 , the etching property is lowered. That is, although there is no etching residue and it is impossible to etch, it is difficult to perform fine patterning. Preferably, the Co adhesion amount is 500 to 2000 μg/dm 2 , and preferably, the nickel adhesion amount is 50 to 300 μg/dm 2 .

根據以上，銅-鈷-鎳合金鍍敷之附著量可謂理想為10~30mg/dm2銅-100~3000μg/dm2鈷-50~500μg/dm2鎳。該三元系合金層之各附著量僅為理想之條件，並非否定超過該量之範圍。 According to the above, copper - cobalt - nickel alloy plating can be described over the plating deposition amount is 10 ~ 30mg / dm 2 of copper -100 ~ 3000μg / dm 2 of cobalt -50 ~ 500μg / dm 2 of nickel. The adhesion amount of the ternary alloy layer is only an ideal condition, and does not negate the range exceeding the amount.

此處，所謂蝕刻斑，係意指於以氯化銅進行蝕刻之情形時Co未溶解而殘存之情況，並且，所謂蝕刻殘渣，係意指於以氯化銨進行鹼蝕刻之情形時Ni未溶解而殘存之情況。 Here, the term "etching spot" means a case where Co is not dissolved and remains in the case of etching with copper chloride, and the term "etching residue" means that Ni is not used in the case of alkali etching with ammonium chloride. Dissolved and remains.

通常，於形成電路之情形時，使用下述實施例中說明之鹼蝕刻液及氯化銅系蝕刻液而進行。該蝕刻液及蝕刻條件具有通用性，但並不限定於該條件，應理解可任意地選擇。 Usually, in the case of forming a circuit, it is carried out using the alkali etching liquid and the copper chloride-based etching liquid described in the following examples. The etching liquid and the etching conditions are versatile, but are not limited to the conditions, and it should be understood that they can be arbitrarily selected.

本發明係如上所述，可於形成二次粒子後(粗化處理後)，於粗化面上形成鈷-鎳合金鍍層。 In the present invention, as described above, a cobalt-nickel alloy plating layer may be formed on the roughened surface after the secondary particles are formed (after the roughening treatment).

該鈷-鎳合金鍍層理想為鈷之附著量為200~3000μg/dm2，且鈷之比率為60~66質量%。該處理於廣義上可視為一種防銹處理。 The cobalt-nickel alloy plating layer preferably has a cobalt adhesion amount of 200 to 3000 μg/dm 2 and a cobalt ratio of 60 to 66 mass%. This treatment can be regarded as a rust-proof treatment in a broad sense.

該鈷-鎳合金鍍層必須於實質性地不使銅箔與基板之接著強度降低之程度下進行。若鈷附著量未達200μg/dm2，則耐熱剝離強度降低，耐氧化性及耐化學品性變差，又，處理表面泛紅，故而欠佳。 The cobalt-nickel alloy plating layer must be carried out to such an extent that the strength of the copper foil and the substrate is not substantially lowered. When the cobalt adhesion amount is less than 200 μg/dm 2 , the heat-resistant peel strength is lowered, the oxidation resistance and chemical resistance are deteriorated, and the treated surface is reddish, which is not preferable.

又，若鈷附著量超過3000μg/dm2，則有必須考慮磁性之影響之情況，故而欠佳，並產生蝕刻斑，又，認為耐酸性及耐化學品性惡化。較佳之鈷附著量為400~2500μg/dm2。 In addition, when the cobalt adhesion amount exceeds 3000 μg/dm 2 , it is necessary to take into consideration the influence of the magnetic properties, so that the etching spot is not preferable, and the acid resistance and the chemical resistance are deteriorated. A preferred amount of cobalt adhesion is 400 to 2500 μg/dm 2 .

又，若鈷附著量多，則有成為產生軟蝕刻之滲入之原因之情 況。因此，可謂理想為將鈷之比率設為60~66質量%。 Moreover, if there is a large amount of cobalt adhesion, there is a cause of infiltration of soft etching. condition. Therefore, it is desirable to set the ratio of cobalt to 60 to 66% by mass.

如下所述，產生軟蝕刻之滲入之直接且較大之原因係由鋅-鎳合金鍍層構成之耐熱防銹層，但亦存在鈷亦成為產生軟蝕刻時滲入之原因之情況，因此更理想之條件係如上述般進行調整。 As described below, the direct and large cause of the infiltration of the soft etching is a heat-resistant rust-preventing layer composed of a zinc-nickel alloy plating layer, but cobalt is also a cause of infiltration during soft etching, and thus it is more preferable. The conditions were adjusted as described above.

另一方面，於鎳附著量少之情形時，耐熱剝離強度降低，耐氧化性及耐化學品性降低。又，於鎳附著量過多之情形時，鹼蝕刻性變差，因此理想為以與上述鈷含量之平衡而決定。 On the other hand, when the amount of nickel adhesion is small, the heat-resistant peel strength is lowered, and oxidation resistance and chemical resistance are lowered. Moreover, when the amount of nickel adhesion is too large, the alkali etching property is deteriorated, and therefore it is preferable to determine the balance with the cobalt content.

本發明可於鈷-鎳合金鍍敷上進而形成鋅-鎳合金鍍層。將鋅-鎳合金鍍層之總量設為150~500μg/dm2，且將鎳之比率設為16~40質量%。其具有耐熱防銹層之作用。該條件亦僅為較佳之條件，可使用其他公知之鋅-鎳合金鍍敷。於本發明中，該鋅-鎳合金鍍敷可理解為較佳之附加條件。 The present invention can further form a zinc-nickel alloy plating layer on a cobalt-nickel alloy plating. The total amount of the zinc-nickel alloy plating layer is set to 150 to 500 μg/dm 2 , and the ratio of nickel is set to 16 to 40% by mass. It has the function of a heat-resistant rust-proof layer. This condition is also only a preferred condition, and other known zinc-nickel alloy plating can be used. In the present invention, the zinc-nickel alloy plating can be understood as a preferred additional condition.

電路之製造步驟中進行之處理成為更高溫，又，於製成製品後，使用機器時會產生熱。例如，於以熱壓接將銅箔接合於樹脂即所謂二層材中，於接合時會受到300℃以上之熱。於此種狀況之中，必須防止銅箔與樹脂基材之間之接合力之降低，該鋅-鎳合金鍍敷較為有效。 The processing performed in the manufacturing steps of the circuit becomes higher temperature, and after the product is formed, heat is generated when the machine is used. For example, in a so-called two-layer material in which a copper foil is bonded to a resin by thermocompression bonding, heat of 300 ° C or more is received at the time of bonding. In such a situation, it is necessary to prevent a decrease in the bonding strength between the copper foil and the resin substrate, and the zinc-nickel alloy plating is effective.

又，於習知之技術中，以熱壓接將銅箔接合於樹脂而成之二層材中的具備鋅-鎳合金鍍層之微小電路係於軟蝕刻時，在電路之邊緣部產生由滲入引起之變色。鎳具有抑制於軟蝕刻時使用之蝕刻劑(H2SO4：10wt%、H2O2：2wt%之蝕刻水溶液)之滲入的效果。 Further, in the conventional technique, a microcircuit having a zinc-nickel alloy plating layer in a two-layer material obtained by bonding a copper foil to a resin by thermocompression bonding is caused by infiltration at the edge portion of the circuit during soft etching. Discoloration. Nickel has an effect of suppressing penetration of an etchant (H 2 SO 4 : 10 wt%, H 2 O 2 : 2 wt% of an etching solution) used in soft etching.

如上所述，於將上述鋅-鎳合金鍍層之總量設為150~500μg/dm2，並且將該合金層中之鎳比率之下限值設為16質量%、將上限值設為40質量 %，且將鎳之含量設為50μg/dm2以上時，具有如下效果：具備耐熱防銹層之作用，並且抑制於軟蝕刻時使用之蝕刻劑之滲入，可防止因腐蝕使電路之接合強度之弱化。 As described above, the total amount of the zinc-nickel alloy plating layer is 150 to 500 μg/dm 2 , and the lower limit of the nickel ratio in the alloy layer is 16% by mass, and the upper limit is 40. When the content of nickel is 50 μg/dm 2 or more, the effect is as follows: the heat-resistant rust-preventing layer is provided, and the penetration of the etchant used in the soft etching is suppressed, and the bonding of the circuit due to corrosion can be prevented. Weakening of strength.

再者，若鋅-鎳合金鍍層之總量未達150μg/dm2，則耐熱防銹力降低，難以擔負作為耐熱防銹層之作用，若相同之總量超過500μg/dm2，則有耐鹽酸性變差之傾向。 Further, if the total amount of the zinc-nickel alloy plating layer is less than 150 μg/dm 2 , the heat-resistant rust-preventing force is lowered, and it is difficult to function as a heat-resistant rust-proof layer, and if the same total amount exceeds 500 μg/dm 2 , it is resistant. The tendency of hydrochloric acid to deteriorate.

又，若合金層中之鎳比率之下限值未達16質量%，則軟蝕刻時之滲入量超過9μm，故而欠佳。鎳比率之上限值40質量%係可形成鋅-鎳合金鍍層之技術上之界限值。 Further, when the lower limit of the nickel ratio in the alloy layer is less than 16% by mass, the amount of penetration during soft etching exceeds 9 μm, which is not preferable. The upper limit of the nickel ratio of 40% by mass is a technical limit value at which a zinc-nickel alloy plating layer can be formed.

如上所述，本發明可於作為二次粒子層之銅-鈷-鎳合金鍍層上，視需要依序形成鈷-鎳合金鍍層、進而鋅-鎳合金鍍層。亦可調節該等層中之合計量之鈷附著量及鎳附著量。理想為將鈷之合計附著量設為300~4000μg/dm2，將鎳之合計附著量設為100~1500μg/dm2。 As described above, in the present invention, a cobalt-nickel alloy plating layer and a zinc-nickel alloy plating layer can be sequentially formed on the copper-cobalt-nickel alloy plating layer as the secondary particle layer. It is also possible to adjust the amount of cobalt adhesion and the amount of nickel attached in the total amount of the layers. It is preferable to set the total adhesion amount of cobalt to 300 to 4000 μg/dm 2 and the total adhesion amount of nickel to 100 to 1500 μg/dm 2 .

若鈷之合計附著量未達300μg/dm2，則耐熱性及耐化學品性降低，若鈷之合計附著量超過4000μg/dm2，則有產生蝕刻斑之情況，又，有傳輸損耗變大之情況。又，若鎳之合計附著量未達100μg/dm2，則有耐熱性及耐化學品性降低之情況。若鎳之合計附著量超過1500μg/dm2，則有產生蝕刻殘渣之情況，又，有傳輸損耗變大之情況。 When the total amount of adhesion of cobalt is less than 300 μg/dm 2 , heat resistance and chemical resistance are lowered. When the total amount of cobalt adheres exceeds 4000 μg/dm 2 , an etching spot is generated, and transmission loss is increased. The situation. In addition, when the total amount of adhesion of nickel is less than 100 μg/dm 2 , heat resistance and chemical resistance may be lowered. When the total amount of adhesion of nickel exceeds 1,500 μg/dm 2 , there is a case where an etching residue is generated, and a transmission loss is increased.

鈷之合計附著量較佳為300~3500μg/dm2，更佳為300~3000μg/dm2，進而較佳為300~2500μg/dm2，進而更佳為300~2000μg/dm2，鎳之合計附著量較佳為100~1000μg/dm2，更佳為100~900μg/dm2。若滿足上述條件，則無需特別受限於該段落中記載之條件。 The total deposited mass of cobalt is preferably 300 ~ 3500μg / dm 2, more preferably 300 ~ 3000μg / dm 2, and further preferably 300 ~ 2500μg / dm 2, and further more preferably 300 ~ 2000μg / dm 2, the total nickel The amount of adhesion is preferably from 100 to 1000 μg/dm 2 , more preferably from 100 to 900 μg/dm 2 . If the above conditions are satisfied, it is not necessary to be particularly limited to the conditions described in the paragraph.

其後，視需要實施防銹處理。本發明中較佳之防銹處理係鉻氧化物單獨之皮膜處理或鉻氧化物與鋅/鋅氧化物之混合物皮膜處理。所謂鉻氧化物與鋅/鋅氧化物之混合物皮膜處理，係指使用含有鋅鹽或氧化鋅與鉻酸鹽之鍍浴，藉由電鍍被覆由鋅或氧化鋅與鉻氧化物構成之鋅-鉻基混合物之防銹層的處理。 Thereafter, anti-rust treatment is performed as needed. The preferred rust-preventing treatment in the present invention is a treatment of a chromium oxide alone film or a mixture of chromium oxide and zinc/zinc oxide. The so-called treatment of a mixture of chromium oxide and zinc/zinc oxide refers to zinc-chromium consisting of zinc or zinc oxide and chromium oxide by electroplating using a plating bath containing zinc salt or zinc oxide and chromate. Treatment of the rustproof layer of the base mixture.

作為鍍浴，代表性地使用K2Cr2O7、Na2Cr2O7等重鉻酸鹽或CrO3等之至少一種、水溶性鋅鹽例如ZnO、ZnSO4-7H2O等至少一種、與氫氧化鹼(alkali hydroxide)之混合水溶液。代表之鍍浴組成與電解條件例係如下所述。 As the plating bath, at least one of a dichromate such as K 2 Cr 2 O 7 or Na 2 Cr 2 O 7 or a CrO 3 or the like, and at least one of a water-soluble zinc salt such as ZnO, ZnSO 4 -7H 2 O or the like is used. And a mixed aqueous solution with alkali hydroxide. Representative plating bath compositions and electrolytic conditions are as follows.

如此獲得之銅箔具有優異之耐熱性剝離強度、耐氧化性及耐鹽酸性。又，可利用CuCl2蝕刻液對150μm間距電路寬度以下之電路進行蝕刻，而且亦可設為鹼蝕刻。又，可抑制於軟蝕刻時向電路邊緣部滲入。 The copper foil thus obtained has excellent heat-resistant peel strength, oxidation resistance, and hydrochloric acid resistance. Further, a circuit having a circuit width of 150 μm or less can be etched by a CuCl 2 etching solution, or an alkali etching can be used. Further, it is possible to suppress penetration into the edge portion of the circuit during soft etching.

軟蝕刻液可使用H2SO4：10wt%、H2O2：2wt%之水溶液。處理時間與溫度可任意調節。 As the soft etching liquid, an aqueous solution of H 2 SO 4 : 10 wt%, H 2 O 2 : 2 wt% can be used. Processing time and temperature can be adjusted arbitrarily.

作為鹼蝕刻液，例如已知有NH4OH：6莫耳/升、NH4Cl：5莫耳/升、CuCl2：2莫耳/升(溫度50℃)等液。 As the alkali etching solution, for example, a liquid such as NH 4 OH: 6 mol/liter, NH 4 Cl: 5 mol/liter, CuCl 2 : 2 mol/liter (temperature: 50 ° C) is known.

上述全部步驟中獲得之銅箔具有黑色~灰色。黑色~灰色於對位精度及熱吸收率高之方面較有意義。例如，包含剛性基板及軟性基板之電路基板係以自動步驟搭載IC或電阻、電容器等零件，此時，一面利用感測器讀取電路一面進行晶片安裝。此時，有通過Kapton等膜進行銅箔處理面之對位之情況。又，通孔形成時之定位亦同樣。 The copper foil obtained in all the above steps has a black to gray color. Black to gray is more meaningful in terms of alignment accuracy and high heat absorption rate. For example, a circuit board including a rigid substrate and a flexible substrate is mounted with an IC, a resistor, a capacitor, or the like in an automatic step. In this case, the wafer is mounted while being read by the sensor. At this time, there is a case where the copper foil-treated surface is aligned by a film such as Kapton. Moreover, the positioning at the time of forming the through holes is also the same.

處理面越接近黑色，光之吸收越良好，因此定位之精度提高。進而，於製作基板時，多數情況下一面對銅箔與膜施加熱一面進行固化而接著。 此時，於藉由使用遠紅外線、紅外線等長波段進行加熱之情形時，處理面之色調較黑者之加熱效率良好。 The closer the processing surface is to black, the better the absorption of light, so the accuracy of positioning is improved. Further, in the case of producing a substrate, in many cases, the copper foil and the film are cured while applying heat. In this case, when heating is performed by using a long wavelength band such as far infrared rays or infrared rays, the heating efficiency of the blackened surface of the treated surface is good.

最後，視需要以改善銅箔與樹脂基板之接著力為主要目的，實施於防銹層上之至少粗化面塗佈矽烷偶合劑之矽烷處理。作為該矽烷處理中使用之矽烷偶合劑，可列舉：烯烴系矽烷、環氧系矽烷、丙烯酸系矽烷、胺基系矽烷、巰基系矽烷，可適當選擇該等而使用。再者，於使用液晶聚合物作為樹脂之情形時，較佳為使用胺基系矽烷(具有胺基之矽烷)作為矽烷偶合劑。又，更佳為使用二胺基矽烷作為矽烷偶合劑。 Finally, the decane treatment of the decane coupling agent is applied to at least the roughened surface of the rustproof layer for the main purpose of improving the adhesion between the copper foil and the resin substrate as needed. The decane coupling agent to be used for the decane treatment may, for example, be an olefin decane, an epoxy decane, an acrylic decane, an amine decane or a decyl decane, and may be appropriately selected and used. Further, in the case where a liquid crystal polymer is used as the resin, it is preferred to use an amino decane (a decane having an amine group) as a decane coupling agent. Further, it is more preferred to use diaminodecane as a decane coupling agent.

塗佈方法可為利用矽烷偶合劑溶液之噴霧之吹附、利用塗佈機之塗佈、浸漬、流延等之任一種。例如，日本特公昭60-15654號中記載有藉由於銅箔之粗面側實施鉻酸鹽處理後進行矽烷偶合劑處理，而改善銅箔與樹脂基板之接著力。詳細內容請參照此。其後，如有需要，亦有為了改善銅箔之延展性而實施退火處理之情況。 The coating method may be any one of blowing by a spray of a decane coupling agent solution, coating by a coater, dipping, casting, or the like. For example, Japanese Patent Publication No. Sho 60-15654 discloses an improvement in the adhesion between a copper foil and a resin substrate by performing a chromate treatment on the rough side of the copper foil and then performing a decane coupling agent treatment. Please refer to this for details. Thereafter, if necessary, annealing treatment is also performed to improve the ductility of the copper foil.

[附載體銅箔] [with carrier copper foil]

本發明之另一實施之形態之附載體銅箔係於載體之一面或雙面依序具有中間層、極薄銅層。並且，上述極薄銅層為上述本發明之一實施之形態之高頻電路用銅箔。 The copper foil with a carrier according to another embodiment of the present invention has an intermediate layer and an extremely thin copper layer on one side or both sides of the carrier. Further, the ultra-thin copper layer is a copper foil for high-frequency circuit of the embodiment of the present invention.

<載體> <carrier>

可於本發明中使用之載體典型為金屬箔或樹脂膜，例如可以銅箔、銅合金箔、鎳箔、鎳合金箔、鐵箔、鐵合金箔、不鏽鋼箔、鋁箔、鋁合金箔、絕緣樹脂膜(例如聚醯亞胺膜、液晶聚合物(LCP)膜、聚對苯二甲酸乙二酯(PET)膜、聚醯胺膜、聚酯膜、氟樹脂膜等)之形態提供。 The carrier which can be used in the present invention is typically a metal foil or a resin film, for example, a copper foil, a copper alloy foil, a nickel foil, a nickel alloy foil, an iron foil, a ferroalloy foil, a stainless steel foil, an aluminum foil, an aluminum alloy foil, an insulating resin film. (Available, for example, in the form of a polyimide film, a liquid crystal polymer (LCP) film, a polyethylene terephthalate (PET) film, a polyamide film, a polyester film, a fluororesin film, or the like).

作為可於本發明中使用之載體，較佳為使用銅箔。由於銅箔之導電率較高，故而容易形成其後之中間層、極薄銅層。典型而言，載體係以壓延銅箔或電解銅箔之形態提供。通常，電解銅箔係於鈦或不鏽鋼之轉筒上將銅自硫酸銅鍍浴電解析出而製造，壓延銅箔係重複進行利用壓延輥之塑性加工及熱處理而製造。作為銅箔之材料，除了精銅或無氧銅等高純度銅以外，亦可使用例如摻Sn銅、摻Ag銅、添加有Cr、Zr或Mg等之銅合金、添加有Ni及Si等之卡遜系銅合金之類的銅合金。 As the carrier which can be used in the present invention, copper foil is preferably used. Since the copper foil has a high electrical conductivity, it is easy to form an intermediate layer and an extremely thin copper layer. Typically, the support is provided in the form of a rolled copper foil or an electrolytic copper foil. Usually, an electrolytic copper foil is produced by electrically analyzing copper from a copper sulfate plating bath on a drum of titanium or stainless steel, and the rolled copper foil is repeatedly produced by plastic working and heat treatment using a calender roll. As the material of the copper foil, in addition to high-purity copper such as refined copper or oxygen-free copper, for example, Sn-doped copper, Ag-doped copper, a copper alloy to which Cr, Zr, or Mg is added, or Ni and Si may be added. A copper alloy such as a copper alloy.

可於本發明中使用之載體之厚度亦無特別限制，只要發揮作為載體之作用並且適當調節為適合之厚度即可，例如可設為5μm以上。但是，若過厚，則生產成本提高，因此通常較佳為設為35μm以下。因此，載體之厚度典型為12~70μm，更典型為18~35μm。 The thickness of the carrier which can be used in the present invention is not particularly limited as long as it functions as a carrier and is appropriately adjusted to a suitable thickness, and can be, for example, 5 μm or more. However, if the thickness is too large, the production cost is increased. Therefore, it is usually preferably 35 μm or less. Therefore, the thickness of the carrier is typically 12 to 70 μm, more typically 18 to 35 μm.

再者，亦可於與設置載體之極薄銅層側之表面相反之側的表面設置粗化處理層。可使用公知之方法設置該粗化處理層，亦可藉由上述粗化處理設置。於與設置載體之極薄銅層側之表面相反之側的表面設置粗化處理層之情況具有如下優點：將載體自具有該粗化處理層之表面側積層於樹脂基板等支撐體時，載體與樹脂基板不易剝離。 Further, a roughened layer may be provided on the surface opposite to the surface on the side of the ultra-thin copper layer on which the carrier is provided. The roughening treatment layer can be provided by a known method, or can be set by the above-described roughening treatment. The case where the roughened layer is provided on the surface opposite to the surface on the side where the ultra-thin copper layer side of the carrier is provided has the advantage that when the carrier is laminated on the surface of the resin substrate or the like from the surface side having the roughened layer, the carrier It is not easily peeled off from the resin substrate.

<中間層> <intermediate layer>

於載體上設置中間層。亦可於載體與中間層之間設置其他層。本發明中使用之中間層只要為如下構成則並無特別限定：於附載體銅箔向絕緣基板積層之步驟前極薄銅層不易自載體剝離，另一方面，於向絕緣基板之積層之步驟後極薄銅層可自載體剝離。例如，本發明之附載體銅箔之中間層亦可含有選自由Cr、Ni、Co、Fe、Mo、Ti、W、P、Cu、Al、Zn、該等之合 金、該等之水合物、該等之氧化物、有機物組成之群中一種或二種以上。又，中間層亦可為複數層。 An intermediate layer is provided on the carrier. Other layers may also be provided between the carrier and the intermediate layer. The intermediate layer used in the present invention is not particularly limited as long as it is a structure in which the ultra-thin copper layer is not easily peeled off from the carrier before the step of laminating the carrier copper foil to the insulating substrate, and the step of laminating the insulating substrate is performed. The rear ultra-thin copper layer can be peeled off from the carrier. For example, the intermediate layer of the copper foil with a carrier of the present invention may further contain a combination selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn. One or more of gold, the hydrates, the oxides, and the organic compounds. Also, the intermediate layer may be a plurality of layers.

又，例如，中間層可藉由如下方式構成：自載體側形成由選自由Cr、Ni、Co、Fe、Mo、Ti、W、P、Cu、Al、Zn組成之元素群中一種元素構成的單一金屬層，或者由選自由Cr、Ni、Co、Fe、Mo、Ti、W、P、Cu、Al、Zn組成之元素群中一種或二種以上之元素構成的合金層，於其上形成由選自由Cr、Ni、Co、Fe、Mo、Ti、W、P、Cu、Al、Zn組成之元素群中一種或二種以上之元素之水合物或氧化物或有機物構成的層，或者由選自由Cr、Ni、Co、Fe、Mo、Ti、W、P、Cu、Al、Zn組成之元素群中一種之元素構成的單一金屬層，或者由選自由Cr、Ni、Co、Fe、Mo、Ti、W、P、Cu、Al、Zn組成之元素群中一種或二種以上之元素構成的合金層。 Further, for example, the intermediate layer may be configured by forming an element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn from the carrier side. a single metal layer or an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, formed thereon a layer composed of a hydrate or an oxide or an organic substance selected from one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, or Selecting a single metal layer composed of one element of a group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or selected from Cr, Ni, Co, Fe, Mo An alloy layer composed of one or more elements of the element group consisting of Ti, W, P, Cu, Al, and Zn.

於僅於單面設置中間層之情形時，較佳為於與載體相反之面設置Ni鍍層等防銹層。再者，於利用鉻酸鹽處理或鋅鉻酸鹽處理或鍍敷處理設置中間層之情形時，可認為有鉻或鋅等附著之金屬之一部分成為水合物或氧化物之情形。 In the case where the intermediate layer is provided only on one side, it is preferable to provide a rustproof layer such as a Ni plating layer on the surface opposite to the carrier. Further, in the case where the intermediate layer is provided by chromate treatment or zinc chromate treatment or plating treatment, it is considered that a part of the metal to which the chromium or zinc adheres is a hydrate or an oxide.

又，例如，中間層可於載體上依序積層鎳、鎳-磷合金或鎳-鈷合金、以及鉻而構成。鎳與銅之接著力高於鉻與銅之接著力，因此於剝離極薄銅層時，於極薄銅層與鉻之界面剝離。又，對中間層之鎳期待防止銅成分自載體擴散至極薄銅層之障壁效果。中間層中之鎳之附著量較佳為100μg/dm2以上40000μg/dm2以下，更佳為100μg/dm2以上4000μg/dm2以下，進而較佳為100μg/dm2以上2500μg/dm2以下，進而更佳為100μg/dm2以上且未達1000μg/dm2，中間層中之鉻之附著量較佳為5μg/dm2以上 100μg/dm2以下。 Further, for example, the intermediate layer may be formed by sequentially laminating nickel, a nickel-phosphorus alloy, a nickel-cobalt alloy, and chromium on a carrier. The adhesion between nickel and copper is higher than the adhesion between chromium and copper. Therefore, when the ultra-thin copper layer is peeled off, the interface between the ultra-thin copper layer and chromium is peeled off. Further, the nickel of the intermediate layer is expected to have a barrier effect of preventing the copper component from diffusing from the carrier to the extremely thin copper layer. Adhesion amount of the intermediate layer of nickel, preferably 100μg / dm 2 or more 40000μg / dm 2 or less, more preferably 100μg / dm 2 or more 4000μg / dm 2 or less, and further preferably 100μg / dm 2 or more 2500μg / dm 2 or less More preferably, it is 100 μg/dm 2 or more and less than 1000 μg/dm 2 , and the amount of chromium deposited in the intermediate layer is preferably 5 μg/dm 2 or more and 100 μg/dm 2 or less.

<極薄銅層> <very thin copper layer>

於中間層上設置極薄銅層。亦可於中間層與極薄銅層之間設置其他層。極薄銅層可藉由利用硫酸銅、焦磷酸銅、胺基磺酸銅、氰化銅等之電解浴之電鍍而形成，就以通常之電解銅箔之形式使用，以高電流密度可形成銅箔之方面而言，較佳為硫酸銅浴。極薄銅層之厚度並無特別限制，通常薄於載體例如為12μm以下。典型為0.5~12μm，更典型為1~5μm，進而典型為1.5~5μm，進而典型為2~5μm。再者，亦可於載體之雙面設置極薄銅層。 An extremely thin copper layer is provided on the intermediate layer. Other layers may be provided between the intermediate layer and the ultra-thin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath of copper sulfate, copper pyrophosphate, copper sulfonate, copper cyanide or the like, and is used in the form of a usual electrolytic copper foil to form at a high current density. In terms of copper foil, a copper sulfate bath is preferred. The thickness of the ultra-thin copper layer is not particularly limited, and is usually thinner than the carrier, for example, 12 μm or less. It is typically 0.5 to 12 μm, more typically 1 to 5 μm, and is typically 1.5 to 5 μm, and is typically 2 to 5 μm. Furthermore, an extremely thin copper layer can be provided on both sides of the carrier.

如此製造具備載體、積層於載體上之中間層、積層於中間層上之極薄銅層的附載體銅箔。關於附載體銅箔本身之使用方法為業者所周知，例如可將極薄銅層之表面貼合於紙基材酚系樹脂、紙基材環氧樹脂、合成纖維布基材環氧樹脂、玻璃布/紙複合基材環氧樹脂、玻璃布/玻璃不織布複合基材環氧樹脂及玻璃布基材環氧樹脂、聚酯膜、聚醯亞胺膜等絕緣基板上並進行熱壓接後，剝離載體製成覆銅積層板，將接著於絕緣基板之極薄銅層蝕刻成目標導體圖案，最終可製造印刷配線板。 A carrier-attached copper foil having a carrier, an intermediate layer laminated on the carrier, and an extremely thin copper layer laminated on the intermediate layer was produced in this manner. The method of using the copper foil itself is well known. For example, the surface of the ultra-thin copper layer can be bonded to a paper substrate phenol resin, a paper substrate epoxy resin, a synthetic fiber cloth substrate epoxy resin, or a glass. After the cloth/paper composite substrate epoxy resin, the glass cloth/glass non-woven composite substrate epoxy resin, the glass cloth substrate epoxy resin, the polyester film, the polyimide film, and the like, and is thermocompression bonded, The peeling carrier is used to form a copper clad laminate, and the ultra-thin copper layer next to the insulating substrate is etched into a target conductor pattern, and finally a printed wiring board can be manufactured.

又，具備載體、積層於載體上之中間層、與積層於中間層上之極薄銅層的附載體銅箔可於上述極薄銅層上具備粗化處理層，於上述粗化處理層上具備一種以上之選自由耐熱層、防銹層、鉻酸鹽(處理)層及矽烷偶合(處理)層所組成之群之層。 Further, the carrier-attached copper foil including a carrier, an intermediate layer laminated on the carrier, and an ultra-thin copper layer laminated on the intermediate layer may have a roughened layer on the ultra-thin copper layer on the roughened layer There is provided one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate (treatment) layer, and a decane coupling (treatment) layer.

[樹脂層] [resin layer]

亦可於本發明之高頻電路用銅箔(亦包含高頻電路用銅箔為附載體銅 箔之極薄銅層之情形)之二次粒子層之表面形成樹脂層。又，樹脂層可形成於分別形成在高頻電路用銅箔之二次粒子層上的由Ni與選自由Fe、Cr、Mo、Zn、Ta、Cu、Al、P、W、Mn、Sn、As及Ti組成之群中一種以上之元素構成之合金層之表面，可形成於鉻酸鹽層之表面，可形成於矽烷偶合層之表面，亦可形成於Ni-Zn合金層之表面。又，樹脂層更佳為形成於高頻電路用銅箔之最表面。又，上述附載體銅箔亦可於上述粗化處理層上、或者上述耐熱層、防銹層、或鉻酸鹽(處理)層、或矽烷偶合(處理)層上具備樹脂層。上述樹脂層亦可為絕緣樹脂層。 It can also be used for the copper foil for high-frequency circuits of the present invention (including copper foil for high-frequency circuit as carrier copper) The surface of the secondary particle layer in the case of the extremely thin copper layer of the foil forms a resin layer. Further, the resin layer may be formed of Ni and selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, Sn, respectively, formed on the secondary particle layer of the high-frequency circuit copper foil. The surface of the alloy layer composed of one or more elements of the group consisting of As and Ti may be formed on the surface of the chromate layer, may be formed on the surface of the decane coupling layer, or may be formed on the surface of the Ni-Zn alloy layer. Further, the resin layer is more preferably formed on the outermost surface of the copper foil for high-frequency circuits. Further, the copper foil with a carrier may be provided with a resin layer on the roughened layer or the heat-resistant layer, the rustproof layer, the chromate (treatment) layer, or the decane coupling (treatment) layer. The above resin layer may also be an insulating resin layer.

上述樹脂層可為接著劑，亦可為接著用半硬化狀態(B階段狀態)之絕緣樹脂層。半硬化狀態(B階段狀態)包括如下狀態：即便用手指觸摸其表面亦無黏著感，可將該絕緣樹脂層重疊而保管，若進而進行加熱處理，則會引起硬化反應。 The resin layer may be an adhesive or an insulating resin layer which is followed by a semi-hardened state (B-stage state). The semi-hardened state (B-stage state) includes a state in which the insulating resin layer is superimposed and stored even if the surface is touched with a finger, and the heat-treated reaction is caused by the heat treatment.

又，上述樹脂層可含有熱硬化性樹脂，亦可為熱塑性樹脂。又，上述樹脂層亦可含有熱塑性樹脂。其種類並無特別限定，作為較佳者，例如可列舉包括環氧樹脂、聚醯亞胺樹脂、多官能性氰酸酯化合物、順丁烯二醯亞胺化合物、聚乙烯醇縮乙醛樹脂、胺酯樹脂等之樹脂。 Further, the resin layer may contain a thermosetting resin or a thermoplastic resin. Further, the resin layer may contain a thermoplastic resin. The type thereof is not particularly limited, and examples thereof include an epoxy resin, a polyimide resin, a polyfunctional cyanate compound, a maleimide compound, and a polyvinyl acetal resin. A resin such as an amine ester resin.

上述樹脂層可含有公知之樹脂、樹脂硬化劑、化合物、硬化促進劑、介電體(可使用含有無機化合物及/或有機化合物之介電體、含有金屬氧化物之介電體等任一種介電體)、反應觸媒、交聯劑、聚合物、預浸體、骨架材料等。又，上述樹脂層例如可使用如下文獻中記載之物質(樹脂、樹脂硬化劑、化合物、硬化促進劑、介電體、反應觸媒、交聯劑、聚合物、預浸體、骨架材料等)及/或樹脂層之形成方法、形成裝置而形成： 國際公開編號WO2008/004399、國際公開編號WO2008/053878、國際公開編號WO2009/084533、日本特開平11-5828號、日本特開平11-140281號、日本專利第3184485號、國際公開編號WO97/02728、日本專利第3676375號、日本特開2000-43188號、日本專利第3612594號、日本特開2002-179772號、日本特開2002-359444號、日本特開2003-304068號、日本專利第3992225號、日本特開2003-249739號、日本專利第4136509號、日本特開2004-82687號、日本專利第4025177號、日本特開2004-349654號、日本專利第4286060號、日本特開2005-262506號、日本專利第4570070號、日本特開2005-53218號、日本專利第3949676號、日本專利第4178415號、國際公開編號WO2004/005588、日本特開2006-257153號、日本特開2007-326923號、日本特開2008-111169號、日本專利第5024930號、國際公開編號WO2006/028207、日本專利第4828427號、日本特開2009-67029號、國際公開編號WO2006/134868、日本專利第5046927號、日本特開2009-173017號、國際公開編號WO2007/105635、日本專利第5180815號、國際公開編號WO2008/114858、國際公開編號WO2009/008471、日本特開2011-14727號、國際公開編號WO2009/001850、國際公開編號WO2009/145179、國際公開編號WO2011/068157、日本特開2013-19056號。 The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, and a dielectric (a dielectric containing an inorganic compound and/or an organic compound, or a dielectric containing a metal oxide may be used. Electrochemical), reaction catalyst, crosslinking agent, polymer, prepreg, framework material, and the like. Further, as the resin layer, for example, those described in the following documents (resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, etc.) can be used. And/or a method of forming a resin layer and forming a device to form: International Publication No. WO2008/004399, International Publication No. WO2008/053878, International Publication No. WO2009/084533, Japanese Patent Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-304068, and Japanese Patent No. 3992225 Japanese Patent Laid-Open No. 2003-249739, Japanese Patent No. 4136509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004/005588, Japanese Patent Laid-Open No. 2006-257153, Japanese Patent Publication No. 2007-326923, Japan JP-A-2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, Japanese Patent Laid-Open No. 2009-67029, International Publication No. WO2006/134868 Japanese Patent No. 5046927, Japanese Patent Laid-Open No. 2009-173017, International Publication No. WO2007/105635, Japanese Patent No. 5180815, International Publication No. WO2008/114858, International Publication No. WO2009/008471, Japanese Patent Publication No. 2011-14727, International The publication number WO2009/001850, the international publication number WO2009/145179, the international publication number WO2011/068157, and the Japanese Patent Publication No. 2013-19056.

將該等樹脂溶解於例如甲基乙基酮(MEK)、甲苯等之溶劑中而製成樹脂液，藉由例如輥塗佈法等將其塗佈於上述銅箔上或極薄銅層上、或上述耐熱層、防銹層、或上述鉻酸鹽皮膜層、或上述矽烷偶合劑層上，繼而視需要進行加熱乾燥去除溶劑而成為B階段狀態。乾燥只要使用例如熱風乾燥爐即可，乾燥溫度只要為100~250℃、較佳為130~200℃即 可。 The resin is dissolved in a solvent such as methyl ethyl ketone (MEK) or toluene to prepare a resin liquid, which is applied onto the copper foil or the ultra-thin copper layer by, for example, a roll coating method. Or the heat-resistant layer, the rust-preventive layer, or the chromate film layer or the decane coupling agent layer, and then heat-dried as needed to remove the solvent to be in a B-stage state. For drying, for example, a hot air drying oven may be used, and the drying temperature is preferably 100 to 250 ° C, preferably 130 to 200 ° C. can.

具備上述樹脂層之高頻電路用銅箔(附有樹脂之高頻電路用銅箔)係將其樹脂層與基材重疊後將整體熱壓接而使該樹脂層熱硬化，繼而以使銅箔形成特定之配線圖案之態樣使用。 A copper foil for a high-frequency circuit (a copper foil for a high-frequency circuit with a resin) having the above-mentioned resin layer is formed by laminating a resin layer and a base material, and then thermally bonding the entire resin layer to thermally cure the resin layer, and then copper is used. The foil is used in the form of a specific wiring pattern.

又，具備上述樹脂層之附載體銅箔(附有樹脂之附載體銅箔)係將其樹脂層與基材重疊後將整體熱壓接而使該樹脂層熱硬化，繼而將載體剝離而露出極薄銅層(當然，露出的是該極薄銅層之中間層側之表面)，因此以形成特定之配線圖案之態樣使用。 Further, the carrier-attached copper foil (resin-attached copper foil with resin) having the resin layer is formed by laminating a resin layer and a base material, and then thermally bonding the entire resin layer to thermally cure the resin layer, and then peeling off the carrier to expose The ultra-thin copper layer (of course, the surface on the intermediate layer side of the ultra-thin copper layer is exposed) is thus used in the form of forming a specific wiring pattern.

若使用該附有樹脂之高頻電路用銅箔或附有樹脂之附載體銅箔，則可減少製造多層印刷配線基板時之預浸體材料之使用片數。而且，將樹脂層之厚度設為可確保層間絕緣之厚度，或者即便完全不使用預浸體材料亦可製造覆銅積層板。又，此時，亦可於基材之表面底塗絕緣樹脂而進一步改善表面之平滑性。 When the copper foil for a high-frequency circuit with a resin or a copper foil with a resin attached thereto is used, the number of sheets of the prepreg material used in the production of the multilayer printed wiring board can be reduced. Further, the thickness of the resin layer is set to ensure the thickness of the interlayer insulation, or the copper clad laminate can be produced even if the prepreg material is not used at all. Further, at this time, the surface of the substrate may be primed with an insulating resin to further improve the smoothness of the surface.

再者，於不使用預浸體材料之情形時，可節約預浸體材料之材料成本，又，積層步驟亦變得簡略，因此於經濟上較為有利，而且，具有如下優點：僅製造預浸體材料之厚度程度的多層印刷配線基板之厚度變薄，可製造1層厚度為100μm以下之極薄之多層印刷配線基板。 Moreover, when the prepreg material is not used, the material cost of the prepreg material can be saved, and the lamination step is also simplified, which is economically advantageous, and has the following advantages: only prepreg is manufactured. The thickness of the multilayer printed wiring board of the thickness of the bulk material is reduced, and it is possible to manufacture a very thin multilayer printed wiring board having a thickness of 100 μm or less.

該樹脂層之厚度較佳為0.1~80μm。 The thickness of the resin layer is preferably from 0.1 to 80 μm.

若樹脂層之厚度薄於0.1μm，則有如下情況：接著力降低，不經由預浸體材料而將該附有樹脂之附載體銅箔積層於具備內層材之基材上時，難以確保內層材與電路之間之層間絕緣。 When the thickness of the resin layer is less than 0.1 μm, there is a case where the adhesion is lowered, and it is difficult to ensure that the resin-attached copper foil with a resin is laminated on the substrate having the inner layer material without passing through the prepreg material. The interlayer insulation between the inner layer and the circuit.

另一方面，若樹脂層之厚度厚於80μm，則難以利用1次塗 佈步驟形成目標厚度之樹脂層，而需要多餘之材料費和步驟數，因此於經濟上變得不利。進而，所形成之樹脂層之可撓性較差，因此存在如下情況：於操作時容易產生龜裂等，又，於熱壓接於內層材時會引起過度之樹脂流動而難以圓滑地進行積層。 On the other hand, if the thickness of the resin layer is thicker than 80 μm, it is difficult to apply once. The cloth step forms a resin layer of a target thickness, and requires an extra material cost and a number of steps, and thus becomes economically disadvantageous. Further, since the resin layer formed is inferior in flexibility, cracks and the like are likely to occur during handling, and excessive resin flow is caused when thermocompression bonding to the inner layer material, and it is difficult to smoothly laminate. .

再者，作為附有樹脂之附載體銅箔之另一個製品形態，亦可以樹脂層被覆於上述極薄銅層上、或上述耐熱層、防銹層、或上述鉻酸鹽層、或上述矽烷偶合層上，於成為半硬化狀態後，繼而將載體剝離，以不存在載體之附有樹脂之銅箔(極薄銅層)之形式進行製造。 Further, as another product form of the copper foil with a resin attached thereto, a resin layer may be coated on the ultra-thin copper layer, or the heat-resistant layer, the rust-proof layer, or the chromate layer or the decane described above. On the coupling layer, after being in a semi-hardened state, the carrier is subsequently peeled off, and it is produced in the form of a resin-attached copper foil (very thin copper layer) in which no carrier is present.

此處，以下，表示若干使用本發明之附載體銅箔之印刷配線板之製造步驟之例。 Here, the following is an example of a manufacturing procedure of a plurality of printed wiring boards using the copper foil with a carrier of the present invention.

本發明之印刷配線板之製造方法之一實施形態含有如下步驟：準備本發明之附載體銅箔與絕緣基板；將上述附載體銅箔與絕緣基板積層；及以使極薄銅層側與絕緣基板對向之方式將上述附載體銅箔與絕緣基板積層後，經過將上述附載體銅箔之載體剝離之步驟而形成覆銅積層板，其後，藉由半加成法、改良半加成法、部分加成法及減成法之任一種方法形成電路。絕緣基板亦可設為內層電路入口。 An embodiment of the method for producing a printed wiring board according to the present invention comprises the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; laminating the copper foil with the carrier and the insulating substrate; and insulating the side of the ultra-thin copper layer After the substrate is faced, the copper foil with the carrier and the insulating substrate are laminated, and then the copper-clad laminate is formed by peeling off the carrier of the copper foil with the carrier, and then the semi-additive is modified by a semi-additive method. A method of forming a circuit by any one of a method, a partial addition method, and a subtractive method. The insulating substrate can also be set as an inner layer circuit inlet.

於本發明中，所謂半加成法，係指含有如下情況之方法：於絕緣基板或銅箔晶種層上進行薄之無電解鍍敷，形成鍍敷阻劑之圖案後，進行電鍍、鍍敷阻劑之去除及蝕刻，藉此形成導體圖案。 In the present invention, the term "semi-additive method" refers to a method of performing electroless plating on an insulating substrate or a copper foil seed layer, forming a pattern of a plating resist, and then performing electroplating and plating. The resist is removed and etched, thereby forming a conductor pattern.

於本發明中，所謂改良半加成法，係指含有如下情況之方法：於絕緣層上積層金屬箔，利用鍍敷阻劑保護非電路形成部，藉由電解鍍敷增厚電路形成部之銅厚後，去除抗蝕劑，利用(快速)蝕刻去除上述 電路形成部以外之金屬箔，藉此於絕緣層上形成電路。 In the present invention, the modified semi-additive method refers to a method of laminating a metal foil on an insulating layer, protecting a non-circuit forming portion by a plating resist, and thickening the circuit forming portion by electrolytic plating. After the copper is thick, the resist is removed and the (fast) etching is used to remove the above A metal foil other than the circuit forming portion forms an electric circuit on the insulating layer.

於本發明中，所謂部分加成法，係指利用含有如下情況之方法而製造印刷配線板的方法：於設置導體層而成之基板、視需要穿過通孔或輔助孔用之孔而成之基板上賦予觸媒核，進行蝕刻形成導體電路，視需要設置阻焊劑或鍍敷阻劑後，於上述導體電路上藉由無電解鍍敷處理對通孔或輔助孔等進行增厚。 In the present invention, the partial addition method refers to a method of manufacturing a printed wiring board by a method in which a substrate having a conductor layer is formed, and a hole for a through hole or an auxiliary hole is formed as needed. A catalyst core is applied to the substrate, and a conductor circuit is formed by etching. If a solder resist or a plating resist is provided as needed, the via hole or the auxiliary hole or the like is thickened on the conductor circuit by electroless plating.

於本發明中，所謂減成法，係指含有如下情況之方法：藉由蝕刻等選擇性地去除覆銅積層板上之銅箔之不需要部分而形成導體圖案。 In the present invention, the subtractive method refers to a method of forming a conductor pattern by selectively removing unnecessary portions of the copper foil on the copper clad laminate by etching or the like.

再者，於本發明中，可使用公知之方法作為半加成法、改良半加成法、部分加成法及減成法。又，於本發明中，上述半加成法、改良半加成法、部分加成法及減成法中，亦可於絕緣基板等設置通孔或/及盲孔。 Further, in the present invention, a known method can be used as a semi-additive method, a modified semi-additive method, a partial addition method, and a subtractive method. Further, in the present invention, in the semi-additive method, the modified semi-additive method, the partial addition method, and the subtractive method, through holes or/and blind holes may be provided in the insulating substrate or the like.

此處，使用圖式對本發明之使用附載體銅箔之印刷配線板之製造方法之具體例詳細地進行說明。 Here, a specific example of a method of manufacturing a printed wiring board using a carrier-attached copper foil of the present invention will be described in detail with reference to the drawings.

首先，如圖5-A所示，準備具有表面形成有粗化處理層之極薄銅層的附載體銅箔(第1層)。 First, as shown in Fig. 5-A, a carrier-attached copper foil (first layer) having an extremely thin copper layer having a roughened layer formed thereon is prepared.

其次，如圖5-B所示，於極薄銅層之粗化處理層上塗佈抗蝕劑，進行曝光、顯影，將抗蝕劑蝕刻為特定之形狀。 Next, as shown in FIG. 5-B, a resist is applied onto the roughened layer of the ultra-thin copper layer, exposed and developed, and the resist is etched into a specific shape.

其次，如圖5-C所示，於形成電路用鍍敷後，去除抗蝕劑，藉此形成特定之形狀之電路鍍敷。 Next, as shown in FIG. 5-C, after the plating for forming the circuit, the resist is removed, thereby forming a circuit plating of a specific shape.

其次，如圖6-D所示，以被覆電路鍍敷之方式(以埋沒電路鍍敷之方式)於極薄銅層上設置埋入樹脂而積層樹脂層，繼而，自極薄銅層側接著 另一附載體銅箔(第2層)。 Next, as shown in FIG. 6-D, a resin layer is laminated on the ultra-thin copper layer by plating the coated circuit (by plating the buried circuit), and then the resin layer is laminated on the side of the ultra-thin copper layer. Another carrier copper foil (layer 2).

其次，如圖6-E所示，自第2層之附載體銅箔剝離載體。 Next, as shown in Fig. 6-E, the carrier is peeled off from the carrier copper foil of the second layer.

其次，如圖6-F所示，於樹脂層之特定位置進行雷射開孔，露出電路鍍敷而形成盲孔。 Next, as shown in Fig. 6-F, a laser opening is performed at a specific position of the resin layer to expose the circuit plating to form a blind hole.

其次，如圖7-G所示，於盲孔中埋入銅，形成通孔填充物。 Next, as shown in Fig. 7-G, copper is buried in the blind via to form a via fill.

其次，如圖7-H所示，於通孔填充物上，以上述圖5-B及圖5-C之方式形成電路鍍敷。 Next, as shown in Fig. 7-H, circuit plating is formed on the via fill in the manner of Fig. 5-B and Fig. 5-C described above.

其次，如圖7-I所示，自第1層之附載體銅箔剝離載體。 Next, as shown in Fig. 7-I, the carrier is peeled off from the carrier copper foil of the first layer.

其次，如圖8-J所示，藉由快速蝕刻去除兩表面之極薄銅層，使樹脂層內之電路鍍敷之表面露出。 Next, as shown in Fig. 8-J, the extremely thin copper layer on both surfaces is removed by rapid etching to expose the surface of the circuit plating in the resin layer.

其次，如圖8-K所示，於樹脂層內之電路鍍敷上形成凸塊，於該焊料上形成銅柱。如此製作使用本發明之附載體銅箔之印刷配線板。 Next, as shown in Fig. 8-K, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. Thus, a printed wiring board using the copper foil with a carrier of the present invention was produced.

上述另一附載體銅箔(第2層)可使用本發明之附載體銅箔，可使用習知之附載體銅箔，進而亦可使用通常之銅箔。又，可於圖7-H所示之第2層之電路上進而形成1層或複數層電路，可藉由半加成法、減成法、部分加成法或改良半加成法之任一種方法形成該等電路。 The above-mentioned other carrier copper foil (second layer) can be used with the copper foil with a carrier of the present invention, and a conventional copper foil with a carrier can be used, and a usual copper foil can also be used. Further, a layer 1 or a plurality of layers may be further formed on the circuit of the second layer shown in FIG. 7-H, and may be subjected to a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. One method forms the circuits.

藉由如上所述之印刷配線板之製造方法，形成使電路鍍敷埋入樹脂層之構成，因此於例如圖8-J所示之利用快速蝕刻去除極薄銅層時，藉由樹脂層保護電路鍍敷，並保持其形狀，藉此容易形成微細電路。又，由於藉由樹脂層保護電路鍍敷，故而耐電子遷移性提高，可良好地抑制電路之配線之導通。因此，容易形成微細電路。又，於圖8-J及圖8-K所表示般藉由快速蝕刻去除極薄銅層時，電路鍍敷之露出面成為自樹脂層 凹陷之形狀，因此容易於該電路鍍敷上形成凸塊，進而於其上形成銅柱，從而提高製造效率。 According to the manufacturing method of the printed wiring board as described above, the structure in which the circuit plating is embedded in the resin layer is formed. Therefore, when the ultra-thin copper layer is removed by rapid etching as shown in, for example, FIG. 8-J, the resin layer is protected. The circuit is plated and maintained in shape, whereby it is easy to form a fine circuit. Moreover, since the resin layer protection circuit is plated, the electron mobility resistance is improved, and the wiring of the circuit can be satisfactorily suppressed. Therefore, it is easy to form a fine circuit. Moreover, when the ultra-thin copper layer is removed by rapid etching as shown in FIG. 8-J and FIG. 8-K, the exposed surface of the circuit plating becomes a self-resin layer. The shape of the recess makes it easy to form bumps on the circuit plating, thereby forming a copper pillar thereon, thereby improving manufacturing efficiency.

再者，埋入樹脂(Resin)可使用公知之樹脂、預浸體。例如可使用BT(雙順丁烯二醯亞胺三)樹脂或含浸BT樹脂之玻璃布即預浸體、Ajinomoto Fine-Techno股份有限公司製造之ABF膜或ABF。又，上述埋入樹脂(Resin)可使用本說明書中記載之樹脂層及/或樹脂及/或預浸體。 Further, a well-known resin or prepreg can be used as the resin (Resin). For example, BT (bis-s-butylene diimide III) can be used. A resin or a glass cloth impregnated with a BT resin, that is, a prepreg, an ABF film manufactured by Ajinomoto Fine-Techno Co., Ltd. or ABF. Further, as the above-mentioned embedded resin (Resin), the resin layer and/or the resin and/or the prepreg described in the present specification can be used.

又，關於上述用於第一層之附載體銅箔，於該附載體銅箔之表面可具有基板或樹脂層。藉由具有該基板或樹脂層而用於第一層之附載體銅箔受到支撐，變得不易產生皺褶，因此有提高生產性之優點。再者，只要上述基板或樹脂層具有支撐上述用於第一層之附載體銅箔之效果，則可使用全部基板或樹脂層。例如，可使用本案說明書中記載之載體、預浸體、樹脂層或公知之載體、預浸體、樹脂層、金屬板、金屬箔、無機化合物之板、無機化合物之箔、有機化合物之板、有機化合物之箔作為上述基板或樹脂層。 Further, the above-mentioned copper foil with a carrier for the first layer may have a substrate or a resin layer on the surface of the copper foil with the carrier. The copper foil with a carrier used for the first layer having the substrate or the resin layer is supported, and wrinkles are less likely to occur, so that productivity is improved. Further, as long as the substrate or the resin layer has an effect of supporting the above-described carrier-attached copper foil for the first layer, all of the substrate or the resin layer can be used. For example, a carrier, a prepreg, a resin layer or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, a plate of an inorganic compound, a foil of an inorganic compound, a plate of an organic compound, or a plate of an organic compound, which are described in the present specification, may be used. A foil of an organic compound is used as the above substrate or resin layer.

[實施例] [Examples]

以下，基於實施例及比較例進行說明。再者，本實施例僅為一例，並不僅受限於該例。即，包含本發明所含之其他態樣或變形。再者，以下實施例1~8、13~17及比較例1~5之原箔使用標準壓延銅箔TPC(以JIS H3100 C1100為標準之精銅，JX Nippon Mining & Metals製造)18μm。 Hereinafter, description will be made based on examples and comparative examples. Furthermore, this embodiment is only an example and is not limited to this example. That is, other aspects or modifications included in the present invention are included. Further, the original foils of the following Examples 1 to 8, 13 to 17, and Comparative Examples 1 to 5 were made of a standard rolled copper foil TPC (fine copper of JIS H3100 C1100, manufactured by JX Nippon Mining & Metals) of 18 μm.

又，實施例9~12之原箔使用藉由以下方法製造之附載體銅箔。 Further, the original foils of Examples 9 to 12 used the carrier-attached copper foil produced by the following method.

實施例9~11係準備厚度18μm之電解銅箔(JX Nippon Mining & Metals 製造之JTC箔)作為載體，實施例12係準備上述厚度18μm之標準壓延銅箔TPC作為載體。並且，於下述條件下於載體之表面形成中間層，於中間層之表面形成極薄銅層。再者，於載體為電解銅箔之情形時，於光澤面(S面)形成中間層。 Examples 9 to 11 are prepared for electrolytic copper foil having a thickness of 18 μm (JX Nippon Mining & Metals) The manufactured JTC foil was used as a carrier, and in Example 12, a standard rolled copper foil TPC having a thickness of 18 μm was prepared as a carrier. Further, an intermediate layer was formed on the surface of the carrier under the following conditions, and an extremely thin copper layer was formed on the surface of the intermediate layer. Further, in the case where the carrier is an electrolytic copper foil, an intermediate layer is formed on the shiny side (S surface).

‧實施例9 ‧Example 9

<中間層> <intermediate layer>

(1)Ni層(Ni鍍敷) (1) Ni layer (Ni plating)

於以下條件下，利用輥對輥型之連接鍍敷線對載體進行電鍍，藉此形成1000μg/dm2之附著量之Ni層。具體之鍍敷條件記載如下。 The carrier was plated by a roll-to-roll type connection plating line under the following conditions, thereby forming a Ni layer having an adhesion amount of 1000 μg/dm 2 . The specific plating conditions are described below.

硫酸鎳：270~280g/L Nickel sulfate: 270~280g/L

氯化鎳：35~45g/L Nickel chloride: 35~45g/L

乙酸鎳：10~20g/L Nickel acetate: 10~20g/L

硼酸：30~40g/L Boric acid: 30~40g/L

光澤劑：糖精、丁炔二醇等 Gloss agent: saccharin, butynediol, etc.

十二烷基硫酸鈉：55~75ppm Sodium lauryl sulfate: 55~75ppm

pH值：4~6 pH: 4~6

浴溫：55~65℃ Bath temperature: 55~65°C

電流密度：10A/dm2 Current density: 10A/dm 2

(2)Cr層(電解鉻酸鹽處理) (2) Cr layer (electrolytic chromate treatment)

其次，將(1)中所形成之Ni層表面水洗及酸洗後，繼而，於輥對輥型之連接鍍敷線上，藉由於以下條件下對11μg/dm2之附著量之Cr層進行電解鉻酸鹽處理而使之附著於Ni層上。 Next, the surface of the Ni layer formed in (1) is washed with water and pickled, and then, on the roll-to-roll type connection plating line, the Cr layer of 11 μg/dm 2 is electrolyzed by the following conditions. The chromate is treated to adhere to the Ni layer.

重鉻酸鉀1~10g/L、鋅0g/L Potassium dichromate 1~10g/L, zinc 0g/L

pH值：7~10 pH: 7~10

液溫：40~60℃ Liquid temperature: 40~60°C

電流密度：2A/dm2 Current density: 2A/dm 2

<極薄銅層> <very thin copper layer>

其次，將(2)中所形成之Cr層表面水洗及酸洗後，繼而，於輥對輥型之連接鍍敷線上，藉由於以下條件下電鍍厚度1.5μm之極薄銅層而使之形成於Cr層上，從而製作附載體銅箔。 Next, the surface of the Cr layer formed in (2) is washed with water and pickled, and then formed on a roll-to-roll type connection plating line by plating an extremely thin copper layer having a thickness of 1.5 μm under the following conditions. On the Cr layer, a copper foil with a carrier was produced.

銅濃度：90~110g/L Copper concentration: 90~110g/L

硫酸濃度：90~110g/L Sulfuric acid concentration: 90~110g/L

氯化物離子濃度：50~90ppm Chloride ion concentration: 50~90ppm

調平劑1(雙(3-磺丙基)二硫醚)：10~30ppm Leveling agent 1 (bis(3-sulfopropyl) disulfide): 10~30ppm

調平劑2(胺化合物)：10~30ppm Leveling agent 2 (amine compound): 10~30ppm

再者，使用下述胺化合物作為調平劑2。 Further, the following amine compound was used as the leveling agent 2.

(上述化學式中，R1及R2選自由羥基烷基、醚基、芳基、芳香族取代烷基、不飽和烴基、烷基所組成之群) (In the above chemical formula, R 1 and R 2 are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group)

電解液溫度：50~80℃ Electrolyte temperature: 50~80°C

電流密度：100A/dm2 Current density: 100A/dm 2

電解液線速度：1.5~5m/sec Electrolyte line speed: 1.5~5m/sec

‧實施例10 ‧Example 10

<中間層> <intermediate layer>

(1)Ni-Mo層(鎳鉬合金鍍敷) (1) Ni-Mo layer (nickel-molybdenum alloy plating)

於以下條件下，利用輥對輥型之連接鍍敷線對載體進行電鍍，藉此形成3000μg/dm2之附著量之Ni-Mo層。具體之鍍敷條件記載如下。 The carrier was plated by a roll-to-roll type connection plating line under the following conditions, thereby forming a Ni-Mo layer having an adhesion amount of 3000 μg/dm 2 . The specific plating conditions are described below.

(液組成)硫酸Ni六水合物：50g/dm3、鉬酸鈉二水合物：60g/dm3、檸檬酸鈉：90g/dm3 (liquid composition) sulfuric acid Ni hexahydrate: 50 g/dm 3 , sodium molybdate dihydrate: 60 g/dm 3 , sodium citrate: 90 g/dm 3

(液溫)30℃ (liquid temperature) 30 ° C

(電流密度)1~4A/dm2 (current density) 1~4A/dm 2

(通電時間)3~25秒 (Power-on time) 3~25 seconds

<極薄銅層> <very thin copper layer>

於(1)中所形成之Ni-Mo層上形成極薄銅層。將極薄銅層之厚度設為2μm，除此以外，於與實施例9相同之條件下形成極薄銅層。 An extremely thin copper layer is formed on the Ni-Mo layer formed in (1). An extremely thin copper layer was formed under the same conditions as in Example 9 except that the thickness of the ultra-thin copper layer was set to 2 μm.

‧實施例11 ‧Example 11

<中間層> <intermediate layer>

(1)Ni層(Ni鍍敷) (1) Ni layer (Ni plating)

於與實施例9相同之條件下形成Ni層。 A Ni layer was formed under the same conditions as in Example 9.

(2)有機物層(有機物層形成處理) (2) Organic layer (organic layer formation treatment)

其次，將(1)中所形成之Ni層表面水洗及酸洗後，繼而，於下述條 件下對Ni層表面淋浴並噴霧含有濃度1~30g/L之羧基苯并***(CBTA)之液溫40℃、pH值5之水溶液20~120秒，藉此形成有機物層。 Next, the surface of the Ni layer formed in (1) is washed with water and pickled, and then, in the following The surface of the Ni layer was showered and sprayed with an aqueous solution containing a carboxybenzotriazole (CBTA) having a concentration of 1 to 30 g/L at a liquid temperature of 40 ° C and a pH of 5 for 20 to 120 seconds, thereby forming an organic layer.

<極薄銅層> <very thin copper layer>

於(2)中所形成之有機物層上形成極薄銅層。將極薄銅層之厚度設為3μm，除此以外，於與實施例9相同之條件下形成極薄銅層。 An extremely thin copper layer is formed on the organic layer formed in (2). An extremely thin copper layer was formed under the same conditions as in Example 9 except that the thickness of the ultra-thin copper layer was set to 3 μm.

‧實施例12 ‧Example 12

<中間層> <intermediate layer>

(1)Co-Mo層(鈷鉬合金鍍敷) (1) Co-Mo layer (cobalt-molybdenum alloy plating)

於以下條件下，利用輥對輥型之連接鍍敷線對載體進行電鍍，藉此形成4000μg/dm2之附著量之Co-Mo層。具體之鍍敷條件記載如下。 The carrier was plated by a roll-to-roll type connection plating line under the following conditions, thereby forming a Co-Mo layer having an adhesion amount of 4000 μg/dm 2 . The specific plating conditions are described below.

(液組成)硫酸Co：50g/dm3、鉬酸鈉二水合物：60g/dm3、檸檬酸鈉：90g/dm3 (liquid composition) sulfuric acid Co: 50 g/dm 3 , sodium molybdate dihydrate: 60 g/dm 3 , sodium citrate: 90 g/dm 3

(液溫)30℃ (liquid temperature) 30 ° C

(電流密度)1~4A/dm2 (current density) 1~4A/dm 2

(通電時間)3~25秒 (Power-on time) 3~25 seconds

<極薄銅層> <very thin copper layer>

於(1)中所形成之Co-Mo層上形成極薄銅層。將極薄銅層之厚度設為5μm，除此以外，於與實施例9相同之條件下形成極薄銅層。 An extremely thin copper layer is formed on the Co-Mo layer formed in (1). An extremely thin copper layer was formed under the same conditions as in Example 9 except that the thickness of the ultra-thin copper layer was set to 5 μm.

(實施例1~17) (Examples 1 to 17)

於下述所示之條件範圍，於壓延銅箔(實施例1~8、13~17)或附載體銅箔之極薄銅層表面(實施例9~12)形成一次粒子層(Cu)、二次粒子層(銅-鈷-鎳合金鍍敷)。 Forming a primary particle layer (Cu) on the surface of the ultra-thin copper layer (Examples 9 to 12) of the rolled copper foil (Examples 1 to 8, 13 to 17) or the copper foil with a carrier, in the range of conditions shown below, Secondary particle layer (copper-cobalt-nickel alloy plating).

所使用之浴組成及鍍敷條件係如下所述。 The bath composition and plating conditions used are as follows.

[浴組成及鍍敷條件] [Bath composition and plating conditions]

(A)一次粒子層之形成(Cu鍍敷) (A) Formation of primary particle layer (Cu plating)

液組成：銅15g/L、硫酸75g/L Liquid composition: copper 15g / L, sulfuric acid 75g / L

液溫：25~30℃ Liquid temperature: 25~30°C

電流密度：1~70A/dm2 Current density: 1~70A/dm 2

庫侖量：2~90As/dm2 Coulomb amount: 2~90As/dm 2

(B)二次粒子層之形成(Cu-Co-Ni合金鍍敷) (B) Formation of secondary particle layer (Cu-Co-Ni alloy plating)

液組成：銅15g/L、鎳8g/L、鈷8g/L Liquid composition: copper 15g / L, nickel 8g / L, cobalt 8g / L

pH值：2 pH: 2

液溫：40℃ Liquid temperature: 40 ° C

電流密度：10~50A/dm2 Current density: 10~50A/dm 2

庫侖量：10~80As/dm2 Coulomb amount: 10~80As/dm 2

調整上述一次粒子層之形成(Cu鍍敷)及二次粒子層之形成(Cu-Co-Ni合金鍍敷)之條件，粗化處理面之一定區域之利用雷射顯微鏡獲得之三維表面積相對於二維表面積之比成為2.0以上且未達2.2。表面積之測定係使用上述利用雷射顯微鏡之測定法。 The conditions of the formation of the primary particle layer (Cu plating) and the formation of the secondary particle layer (Cu-Co-Ni alloy plating) are adjusted, and the three-dimensional surface area obtained by the laser microscope in a certain region of the roughened surface is compared with The ratio of the two-dimensional surface area is 2.0 or more and less than 2.2. The measurement of the surface area uses the above-described measurement using a laser microscope.

(比較例1~5) (Comparative examples 1 to 5)

於比較例中，所使用之浴組成及鍍敷條件係如下所述。 In the comparative examples, the bath composition and plating conditions used were as follows.

[浴組成及鍍敷條件] [Bath composition and plating conditions]

(A)一次粒子層之形成(銅鍍敷) (A) Formation of primary particle layer (copper plating)

液組成：銅15g/L、硫酸75g/L Liquid composition: copper 15g / L, sulfuric acid 75g / L

液溫：25~35℃ Liquid temperature: 25~35°C

電流密度：1~70A/dm2 Current density: 1~70A/dm 2

庫侖量：2~90As/dm2 Coulomb amount: 2~90As/dm 2

(B)二次粒子層之形成(Cu-Co-Ni合金鍍敷條件) (B) Formation of secondary particle layer (Cu-Co-Ni alloy plating conditions)

液組成：銅15g/L、鎳8g/L、鈷8g/L Liquid composition: copper 15g / L, nickel 8g / L, cobalt 8g / L

pH值：2 pH: 2

液溫：40℃ Liquid temperature: 40 ° C

電流密度：20~50A/dm2 Current density: 20~50A/dm 2

庫侖量：30~80As/dm2 Coulomb amount: 30~80As/dm 2

<一次粒子層及二次粒子層以外之表面處理層> <surface treatment layer other than primary particle layer and secondary particle layer>

於形成一次粒子層及二次粒子層後，一部分之實施例及比較例係進行利用以下條件之表面處理層。 After forming the primary particle layer and the secondary particle layer, a part of the examples and comparative examples were subjected to a surface treatment layer under the following conditions.

(實施例3、4、10、11、比較例1~5) (Examples 3, 4, 10, 11, and Comparative Examples 1 to 5)

‧Co-Ni鍍敷：鈷鎳合金鍍敷 ‧Co-Ni plating: cobalt-nickel alloy plating

液組成：鎳5~20g/L、鈷1~8g/L Liquid composition: nickel 5~20g/L, cobalt 1~8g/L

pH值：2~3 pH: 2~3

液溫：40~60℃ Liquid temperature: 40~60°C

電流密度：5~20A/dm2 Current density: 5~20A/dm 2

庫侖量：10~20As/dm2 Coulomb amount: 10~20As/dm 2

(實施例5、12) (Examples 5 and 12)

‧Ni-Zn鍍敷：鎳鋅合金鍍敷 ‧Ni-Zn plating: nickel-zinc alloy plating

液組成：鎳2~30g/L、鋅2~30g/L Liquid composition: nickel 2~30g/L, zinc 2~30g/L

pH值：3~4 pH: 3~4

液溫：30~50℃ Liquid temperature: 30~50°C

電流密度：1~2A/dm2 Current density: 1~2A/dm 2

庫侖量：1~2As/dm2 Coulomb amount: 1~2As/dm 2

再者，實施例5及12係於Ni-Zn鍍敷後，進行電解鉻酸鹽處理以及使用二胺基矽烷之矽烷偶合處理。 Further, Examples 5 and 12 were subjected to electrolytic chromate treatment and decane coupling treatment using diamino decane after Ni-Zn plating.

(實施例7) (Example 7)

‧Ni-Cu鍍敷：鎳銅合金鍍敷 ‧Ni-Cu plating: nickel-copper alloy plating

液組成：鎳2~30g/L、銅2~30g/L Liquid composition: nickel 2~30g/L, copper 2~30g/L

pH值：3~4 pH: 3~4

液溫：30~50℃ Liquid temperature: 30~50°C

電流密度：1~2A/dm2 Current density: 1~2A/dm 2

庫侖量：1~2As/dm2 Coulomb amount: 1~2As/dm 2

(實施例13) (Example 13)

‧Ni-Mo鍍敷：鎳鉬合金鍍敷 ‧Ni-Mo plating: nickel-molybdenum alloy plating

液組成：硫酸Ni六水合物：45~55g/dm3、鉬酸鈉二水合物：50~70g/dm3、檸檬酸鈉：80~100g/dm3 Liquid composition: Ni hexahydrate: 45~55g/dm 3 , sodium molybdate dihydrate: 50~70g/dm 3 , sodium citrate: 80~100g/dm 3

液溫：20~40℃ Liquid temperature: 20~40°C

電流密度：1~4A/dm2 Current density: 1~4A/dm 2

庫侖量：1~2As/dm2 Coulomb amount: 1~2As/dm 2

再者，實施例13係於Ni-Mo鍍敷後進行電解鉻酸鹽處理。 Further, Example 13 was subjected to electrolytic chromate treatment after Ni-Mo plating.

(實施例14) (Example 14)

‧Ni-Sn鍍敷：鎳錫合金鍍敷 ‧Ni-Sn plating: nickel-tin alloy plating

液組成：鎳2~30g/L、錫2~30g/L Liquid composition: nickel 2~30g/L, tin 2~30g/L

pH值：1.5~4.5 pH: 1.5~4.5

液溫：30~50℃ Liquid temperature: 30~50°C

電流密度：1~2A/dm2 Current density: 1~2A/dm 2

庫侖量：1~2As/dm2 Coulomb amount: 1~2As/dm 2

再者，實施例14係於Ni-Sn鍍敷後，進行使用二胺基矽烷之矽烷偶合處理。 Further, in Example 14, after Ni-Sn plating, a decane coupling treatment using diamine decane was carried out.

(實施例15) (Example 15)

‧Ni-P鍍敷：鎳磷合金鍍敷 ‧Ni-P plating: nickel-phosphorus alloy plating

液組成：鎳30~70g/L、磷0.2~1.2g/L Liquid composition: nickel 30~70g/L, phosphorus 0.2~1.2g/L

pH值：1.5~2.5 pH: 1.5~2.5

液溫：30~40℃ Liquid temperature: 30~40°C

電流密度：1~2A/dm2 Current density: 1~2A/dm 2

庫侖量：1~2As/dm2 Coulomb amount: 1~2As/dm 2

(實施例16) (Embodiment 16)

‧Ni-W鍍敷：鎳鎢合金鍍敷 ‧Ni-W plating: nickel-tungsten alloy plating

液組成：鎳2~30g/L、W 0.01~5g/L Liquid composition: nickel 2~30g/L, W 0.01~5g/L

pH值：3~4 pH: 3~4

液溫：30~50℃ Liquid temperature: 30~50°C

電流密度：1~2A/dm2 Current density: 1~2A/dm 2

庫侖量：1~2As/dm2 Coulomb amount: 1~2As/dm 2

再者，實施例16係於Ni-W鍍敷後，進行電解鉻酸鹽處理以及使用二胺基矽烷之矽烷偶合處理。 Further, in Example 16, after Ni-W plating, electrolytic chromate treatment and decane coupling treatment using diamino decane were carried out.

(實施例17) (Example 17)

‧Ni-Cr鍍敷：鎳鉻合金鍍敷 ‧Ni-Cr plating: nickel-chromium alloy plating

使用Ni：80mass%、Cr：20mass%之組成之濺鍍靶而形成鎳鉻合金鍍層。 A nickel-chromium alloy plating layer was formed using a sputtering target having a composition of Ni: 80 mass% and Cr: 20 mass%.

靶：Ni：80mass%、Cr：20mass% Target: Ni: 80 mass%, Cr: 20 mass%

裝置：ULVAC股份有限公司製造之濺鍍裝置 Device: Sputtering device manufactured by ULVAC Co., Ltd.

輸出：DC50W Output: DC50W

氬氣壓力：0.2Pa Argon pressure: 0.2Pa

對於形成藉由上述實施例形成之銅箔上之一次粒子層(Cu鍍敷)及二次粒子層(Cu-Co-Ni合金鍍敷)之情形時的一次粒子之平均粒徑、二次粒子之平均粒徑、落粉、剝離強度、耐熱性、粗化處理面之一定區域之利用雷射顯微鏡獲得之三維表面積相對於二維表面積之比進行測量，測得之結果示於表1。此處，所測量之「粗化處理面」係設為形成一次粒子層及二次粒子層之側之最表面。再者，於二次粒子層上形成有Co-Ni鍍敷、Ni-Zn鍍敷、鉻酸鹽層、矽烷偶合層等之，一次粒子層及二次粒子層以外之表面處理層者係將該等層中之最表層之表面作為粗化處理面而進行測量(即，對形成銅箔之全部表面處理層後之存在一次粒子層及二次粒子層側之表面進行測量)。 The average particle diameter of the primary particles and the secondary particles in the case of forming the primary particle layer (Cu plating) and the secondary particle layer (Cu-Co-Ni alloy plating) on the copper foil formed by the above embodiment The average particle diameter, the falling powder, the peel strength, the heat resistance, and the ratio of the three-dimensional surface area obtained by a laser microscope to a two-dimensional surface area in a certain region of the roughened surface were measured, and the results are shown in Table 1. Here, the measured "roughening surface" is the outermost surface on which the primary particle layer and the secondary particle layer are formed. Further, a Co-Ni plating, a Ni-Zn plating, a chromate layer, a decane coupling layer, or the like is formed on the secondary particle layer, and a surface treatment layer other than the primary particle layer and the secondary particle layer is formed. The surface of the outermost layer among the layers was measured as a roughened surface (that is, the surface on which the primary particle layer and the secondary particle layer were present after the entire surface-treated layer of the copper foil was formed).

粗化處理面之一次粒子及二次粒子之平均粒徑係使用日立高新技術股份有限公司製造之S4700(掃描型電子顯微鏡)以30000倍之倍率進行粒子觀察及照片拍攝，基於所獲得之照片分別對各一次粒子及二次粒子測量粒 徑。然後，將該所獲得之各一次粒子及二次粒子之粒徑之算術平均值設為一次粒子之平均粒徑及二次粒子之平均粒徑之值。再者，於在掃描型電子顯微鏡照片之粒子之上畫直線之情形時，將橫切粒子之直線長度為最長部分之粒子長度設為該粒子之粒徑。再者，測量視野之大小係設為每1視野面積13.44μm2(=4.2μm×3.2μm)，對1視野進行測量。再者，於利用掃描型電子顯微鏡照片進行觀察時，將可見重疊且存在於銅箔側(下方)之粒子、及未重疊之粒子判定為一次粒子，將可見重疊且存在於其他粒子之上之粒子判定為二次粒子。落粉特性係藉由於銅箔之粗化處理面上貼附透明之隱形膠帶，剝離該膠帶時附著於膠帶黏著面之脫落粗化粒子而膠帶變色，根據該情況對落粉特性進行評價。即，於膠帶無變色或極少之情形時係設為落粉良好(OK)，於膠帶變色為灰色之情形時係設為落粉不良(NG)。常態剝離強度係以熱壓貼合銅箔粗化處理面與表1中記載之樹脂基板而製作覆銅積層板，使用通常之氯化銅電路蝕刻液製作10mm電路，將10mm電路銅箔自基板剝離，一面於90°方向拉伸一面測量常態剝離強度。 The average particle diameter of the primary particles and the secondary particles on the roughened surface was observed by a S4700 (scanning electron microscope) manufactured by Hitachi High-Technologies Co., Ltd. at a magnification of 30,000 times, and photographs were taken based on the photographs obtained. The particle diameter was measured for each of the primary particles and the secondary particles. Then, the arithmetic mean of the particle diameters of the obtained primary particles and secondary particles is defined as the average particle diameter of the primary particles and the average particle diameter of the secondary particles. Further, in the case where a straight line is drawn on the particles of the scanning electron microscope photograph, the length of the longest portion of the straight line transverse to the particle is defined as the particle diameter of the particle. Further, the size of the measurement field of view was set to 13.44 μm 2 (=4.2 μm × 3.2 μm) per one field of view, and one field of view was measured. In addition, when observed by a scanning electron microscope photograph, particles which are superimposed on the side of the copper foil (below) and particles which are not overlapped are judged as primary particles, and are superposed and existed on other particles. The particles are determined to be secondary particles. In the powder falling property, a transparent invisible tape was attached to the roughened surface of the copper foil, and when the tape was peeled off, the peeled coarse particles adhered to the adhesive surface of the tape and the tape was discolored, and the powder falling characteristics were evaluated based on the above. That is, in the case where the tape is not discolored or extremely small, it is set to be good in powdering (OK), and in the case where the tape is discolored to gray, it is set as a powder falling defect (NG). The normal peel strength is a copper-clad laminate produced by hot-pressing a copper foil roughening treatment surface and the resin substrate described in Table 1, and a 10 mm circuit is formed using a normal copper chloride circuit etching solution, and a 10 mm circuit copper foil is applied from the substrate. After peeling, the normal peel strength was measured while stretching in the direction of 90°.

(傳輸損耗之測量) (Measurement of transmission loss)

對18μm厚之各樣品貼合表1記載之樹脂基板(LCP：液晶聚合物樹脂(Kuraray股份有限公司製造之Vecstar CTZ-50μm)、聚醯亞胺：Kaneka製造之厚度50μm、氟樹脂厚度50μm：Dupont製造)後，利用蝕刻以特性阻抗成為50Ω之方式形成微帶線路，使用HP公司製造之網路分析儀HP8720C測量穿透係數，求出於頻率20GHz及頻率40GHz下之傳輸損耗。再者，實施例9~12係於將附載體銅箔之極薄銅層側之表面與表1記載之樹脂基板貼合後，剝離載體，其後進行銅鍍敷，將極薄銅層與銅鍍敷之合計 厚度設為18μm後，進行與上述相同之傳輸損耗之測量。作為於頻率20GHz下之傳輸損耗之評價，將未達3.7dB/10cm設為◎，將3.7dB/10cm以上且未達4.1dB/10cm設為○，將4.1dB/10cm以上且未達5.0dB/10cm設為△，將5.0dB/10cm以上設為×。 The resin substrate described in Table 1 (LCP: liquid crystal polymer resin (Vecstar CTZ-50 μm manufactured by Kuraray Co., Ltd.), polyimine: Kaneka thickness 50 μm, and fluororesin thickness 50 μm were bonded to each sample having a thickness of 18 μm: After the manufacturing of Dupont, the microstrip line was formed by etching with a characteristic impedance of 50 Ω, and the transmission coefficient was measured using a network analyzer HP8720C manufactured by HP, and the transmission loss at a frequency of 20 GHz and a frequency of 40 GHz was obtained. Further, in Examples 9 to 12, the surface of the ultra-thin copper layer side of the copper foil with a carrier was bonded to the resin substrate described in Table 1, and then the carrier was peeled off, followed by copper plating to form an extremely thin copper layer. Total copper plating After the thickness was set to 18 μm, the measurement of the same transmission loss as described above was performed. As an evaluation of the transmission loss at a frequency of 20 GHz, it is set to ◎ of 3.7 dB/10 cm, 3.7 dB/10 cm or more and less than 4.1 dB/10 cm, and it is 4.1 dB/10 cm or more and less than 5.0 dB. /10 cm is set to Δ, and 5.0 dB/10 cm or more is set to ×.

又，作為比較例，將相同之結果示於表1。 Further, as a comparative example, the same results are shown in Table 1.

再者，表1之一次粒子電流條件欄記載有2個電流條件、庫侖量之例係意指於左側記載之條件下進行鍍敷後，於右側記載之條件下進一步進行鍍敷。例如，於實施例1之一次粒子電流條件欄中記載為「(65A/dm2、80As/dm2)+(20A/dm2、30As/dm2)」時，其係表示將形成一次粒子之電流密度設為65A/dm2、將庫侖量設為80As/dm2而進行鍍敷後，進而將形成一次粒子之電流密度設為20A/dm2、將庫侖量設為30As/dm2而進行鍍敷。 In addition, in the primary particle current condition column of Table 1, two current conditions and the coulomb amount are described as follows, and plating is performed under the conditions described on the left side, and further plating is performed under the conditions described on the right side. For example, when the column of primary particle current conditions in the first embodiment is described as "(65A/dm 2 , 80As/dm 2 ) + (20A/dm 2 , 30As/dm 2 )", it means that primary particles will be formed. after the current density was 65A / dm 2, the coulomb amount to 80As / dm 2 and plating, thus forming primary particles of the current density is set to 20A / dm 2, the coulomb amount to 30As / dm 2 and for Plating.

根據表1可揭明本發明之實施例之結果係如下所述。 According to Table 1, the results of the examples of the present invention are as follows.

實施例1係如下情況：將形成一次粒子之電流密度設為65A/dm2與20A/dm2，將庫侖量設為80As/dm2與30As/dm2，並將形成二次粒子之電流密度設為28A/dm2，將庫侖量設為20As/dm2。 Example 1 based the following: the formation of the primary particles of the current density is set to 65A / dm 2 to 20A / dm 2, the coulomb amount to 80As / dm 2 and 30As / dm 2, the current density and the formation of secondary particles Set to 28 A/dm 2 and set the coulomb amount to 20 As/dm 2 .

再者，形成一次粒子之電流密度與庫侖量成為2階段，於通常形成一次粒子之情形時，必需2階段之電鍍。即，係第1階段之核粒子形成之鍍敷條件與第2階段之核粒子之成長之電鍍。 Further, the current density and the coulomb amount of the primary particles are formed into two stages, and in the case where the primary particles are usually formed, two-stage plating is necessary. That is, the plating conditions for the formation of the core particles in the first stage and the growth of the core particles in the second stage are performed.

最初之鍍敷條件係用於第1階段之核形成粒子形成之電鍍條件，下一鍍敷條件係用於第2階段之核粒子之成長之電鍍條件。以下實施例及比較例亦同樣，因此省略說明。 The initial plating conditions are the plating conditions for the formation of the core-forming particles in the first stage, and the next plating conditions are the plating conditions for the growth of the core particles in the second stage. The following examples and comparative examples are also the same, and thus the description thereof is omitted.

其結果，一次粒子之平均粒徑為0.45μm，二次粒子之平均粒徑為0.30μm，粒子形成後之利用雷射顯微鏡獲得之三維表面積為21589μm2。另一方面，相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.18，滿足本發明之條件。 As a result, the average particle diameter of the primary particles was 0.45 μm, the average particle diameter of the secondary particles was 0.30 μm, and the three-dimensional surface area obtained by the laser microscope after the formation of the particles was 21589 μm 2 . On the other hand, the two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.18, which satisfies the conditions of the present invention.

其結果，具備如下特徵：落粉少，常態剝離強度為較高之1.16kg/cm，耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將該差設為劣化率)為較小之30%以下。 As a result, the powder has a small amount of falling powder, and the normal peel strength is 1.16 kg/cm, and the heat resistance deterioration rate (after the normal peeling measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set. The rate of deterioration is less than 30%.

再者，耐熱劣化率係利用以下之式求出。 In addition, the heat deterioration rate is obtained by the following formula.

耐熱劣化率(%)=(常態剝離強度(kg/cm)-於180℃加熱48小時後之剝離強度(kg/cm))/常態剝離強度(kg/cm)×100 Heat deterioration rate (%) = (normal peel strength (kg/cm) - peel strength (kg/cm) after heating at 180 ° C for 48 hours) / normal peel strength (kg / cm) × 100

實施例2係如下情況：將形成一次粒子之電流密度設為65A /dm2與2A/dm2，將庫侖量設為80As/dm2與4As/dm2，並將形成二次粒子之電流密度設為25A/dm2，將庫侖量設為15As/dm2。 Example 2 based the following: the current density of the primary particles forming the set to 65A / dm 2 and 2A / dm 2, the coulomb amount to 80As / dm 2 and 4As / dm 2, the current density and the formation of secondary particles Set to 25 A/dm 2 and set the coulomb amount to 15 As/dm 2 .

其結果，一次粒子之平均粒徑為0.40μm，二次粒子之平均粒徑為0.15μm，利用雷射顯微鏡獲得之粒子形成後之表面積為20978μm2。另一方面，相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.11，滿足本發明之條件。 As a result, the average particle diameter of the primary particles was 0.40 μm, the average particle diameter of the secondary particles was 0.15 μm, and the surface area after formation of the particles obtained by the laser microscope was 20978 μm 2 . On the other hand, the two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.11, which satisfies the conditions of the present invention.

其結果，具備如下特徵：無落粉，常態剝離強度為較高之1.08kg/cm，耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將其差設為劣化率)為較小之30%以下。 As a result, it has the following characteristics: no powder falling, normal peel strength is 1.08 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set. The rate of deterioration is less than 30%.

實施例3係如下情況：將形成一次粒子之電流密度設為60A/dm2與10A/dm2，將庫侖量設為80As/dm2與20As/dm2，並將形成二次粒子之電流密度設為25A/dm2，將庫侖量設為30As/dm2。 Example 3 is a case where the current density of the primary particles is set to 60 A/dm 2 and 10 A/dm 2 , the coulomb amount is set to 80 As/dm 2 and 20 As/dm 2 , and the current density of the secondary particles is formed. Set to 25 A/dm 2 and set the coulomb amount to 30 As/dm 2 .

其結果，一次粒子之平均粒徑為0.30μm，二次粒子之平均粒徑為0.25μm，利用雷射顯微鏡獲得之粒子形成後之三維表面積為21010μm2。另一方面，相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.12，滿足本發明之條件。 As a result, the average particle diameter of the primary particles was 0.30 μm, the average particle diameter of the secondary particles was 0.25 μm, and the three-dimensional surface area after the formation of the particles obtained by the laser microscope was 21010 μm 2 . On the other hand, the two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.12, which satisfies the conditions of the present invention.

具備如下特徵：無落粉；常態剝離強度為較高之0.92kg/cm，又，耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將其差設為劣化率)為較小之30%以下。 It has the following characteristics: no powder; normal peel strength is 0.92 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set to The deterioration rate is 30% or less.

實施例4係如下情況：將形成一次粒子之電流密度設為55A/dm2與1A/dm2，將庫侖量設為75As/dm2與5As/dm2，並將形成二次粒子之電流密度設為25A/dm2，將庫侖量設為30As/dm2。 Example 4 based the following: the formation of the primary particles of the current density is set to 55A / dm 2 and 1A / dm 2, the coulomb amount to 75As / dm 2 and 5As / dm 2, the current density and the formation of secondary particles Set to 25 A/dm 2 and set the coulomb amount to 30 As/dm 2 .

其結果，一次粒子之平均粒徑為0.35μm，二次粒子之平均粒徑為0.25μm，利用雷射顯微鏡獲得之粒子形成後之表面積為20847μm2。相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.10，滿足本發明之條件。 As a result, the average particle diameter of the primary particles was 0.35 μm, the average particle diameter of the secondary particles was 0.25 μm, and the surface area after formation of the particles obtained by the laser microscope was 20847 μm 2 . The two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.10, which satisfies the conditions of the present invention.

具備如下特徵：無落粉，常態剝離強度為較高之0.94kg/cm，耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將其差設為劣化率)為較小之30%以下。 It has the following characteristics: no powder drop, normal peel strength is 0.94 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set as the deterioration rate. ) is less than 30%.

實施例5係如下情況：將形成一次粒子之電流密度設為50A/dm2與5A/dm2，將庫侖量設為70As/dm2與10As/dm2，並將形成二次粒子之電流密度設為25A/dm2，將庫侖量設為30As/dm2。 Example 5 based the following: the current density of the primary particles forming the set to 50A / dm 2 and 5A / dm 2, the coulomb amount to 70As / dm 2 and 10As / dm 2, the current density and the formation of secondary particles Set to 25 A/dm 2 and set the coulomb amount to 30 As/dm 2 .

其結果，一次粒子之平均粒徑為0.30μm，二次粒子之平均粒徑為0.25μm，利用雷射顯微鏡獲得之粒子形成後之表面積為20738μm2。相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.09，滿足本發明之條件。 As a result, the average particle diameter of the primary particles was 0.30 μm, the average particle diameter of the secondary particles was 0.25 μm, and the surface area after the formation of the particles obtained by the laser microscope was 20738 μm 2 . The two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.09, which satisfies the conditions of the present invention.

具備如下特徵：無落粉，常態剝離強度為較高之0.94kg/cm，耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將其差設為劣化率)為較小之30%以下。 It has the following characteristics: no powder drop, normal peel strength is 0.94 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set as the deterioration rate. ) is less than 30%.

實施例6係如下情況：將形成一次粒子之電流密度設為50A/dm2與2A/dm2，將庫侖量設為70As/dm2與3As/dm2，並將形成二次粒子之電流密度設為15A/dm2，將庫侖量設為30As/dm2。 Example 6 based the following: the formation of the primary particles of the current density is set to 50A / dm 2 and 2A / dm 2, the coulomb amount to 70As / dm 2 and 3As / dm 2, the current density and the formation of secondary particles Set to 15 A/dm 2 and set the coulomb amount to 30 As/dm 2 .

其結果，一次粒子之平均粒徑為0.25μm，二次粒子幾乎成為被覆(正常)鍍敷狀態(粒徑未達0.1μm)，利用雷射顯微鏡獲得之粒子形成後之表 面積為20112μm2。相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.03，滿足本發明之條件。 As a result, the average particle diameter of the primary particles was 0.25 μm, the secondary particles were almost coated (normal) plating state (the particle diameter was less than 0.1 μm), and the surface area after the formation of the particles obtained by the laser microscope was 20112 μm 2 . The two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.03, which satisfies the conditions of the present invention.

具備如下特徵：無落粉，常態剝離強度為較高之0.81kg/cm，耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將其差設為劣化率)為較小之30%以下。 It has the following characteristics: no falling powder, normal peel strength is 0.81 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set as the deterioration rate. ) is less than 30%.

實施例7係如下情況：將形成一次粒子之電流密度設為60A/dm2與15A/dm2，將庫侖量設為80As/dm2與20As/dm2，並將形成二次粒子(二次粒子層)之電流密度設為20A/dm2，將庫侖量設為60As/dm2而進行被覆鍍敷(正常鍍敷)後，進而將電流密度設為20A/dm2，將庫侖量設為20As/dm2而形成粒子。 Example 7 is a case where the current density of the primary particles is set to 60 A/dm 2 and 15 A/dm 2 , the coulomb amount is set to 80 As/dm 2 and 20 As/dm 2 , and secondary particles are formed (secondary The current density of the particle layer is 20 A/dm 2 , and the coulomb amount is 60 As/dm 2 , and after coating plating (normal plating), the current density is 20 A/dm 2 , and the coulomb amount is set to 20As/dm 2 forms particles.

其結果，一次粒子之平均粒徑為0.35μm，二次粒子成為被覆(正常)鍍敷狀態(粒徑未達0.1μm)及平均粒徑0.15μm之2階段構成，利用雷射顯微鏡獲得之粒子形成後之表面積為20975μm2。相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.11，滿足本發明之條件。 As a result, the average particle diameter of the primary particles was 0.35 μm, and the secondary particles were composed of two stages of a coated (normal) plating state (having a particle diameter of less than 0.1 μm) and an average particle diameter of 0.15 μm, and the particles obtained by a laser microscope were used. The surface area after formation was 20975 μm 2 . The two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.11, which satisfies the conditions of the present invention.

具備如下特徵：無落粉，常態剝離強度為0.83kg/cm，耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將其差設為劣化率)為較小之30%以下。 It has the following characteristics: no falling powder, normal peel strength is 0.83 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours, and the difference is the deterioration rate) is compared. Less than 30%.

實施例8係如下情況：將形成一次粒子之電流密度設為40A/dm2與1A/dm2，將庫侖量設為40As/dm2與2As/dm2，並將形成二次粒子之電流密度設為20A/dm2，將庫侖量設為20As/dm2。 Example 8 is a case where the current density of the primary particles is set to 40 A/dm 2 and 1 A/dm 2 , the Coulomb amount is set to 40 As/dm 2 and 2 As/dm 2 , and the current density of the secondary particles is formed. Set to 20 A/dm 2 and set the coulomb amount to 20 As/dm 2 .

其結果，一次粒子之平均粒徑為0.15μm，二次粒子之平均粒徑為0.15μm，粒子形成後之表面積20345μm2。相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.05，滿足本發明之條件。 As a result, the average particle diameter of the primary particles was 0.15 μm, the average particle diameter of the secondary particles was 0.15 μm, and the surface area after particle formation was 20345 μm 2 . The two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.05, which satisfies the conditions of the present invention.

落粉未產生。又，常態剝離強度為0.71kg/cm，耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將其差設為劣化率)為35%。 Falling powder did not occur. Further, the normal peel strength was 0.71 kg/cm, and the heat resistance deterioration rate (the peel strength after heating at 180 ° C for 48 hours after the normal peel measurement was measured, and the difference was the deterioration rate) was 35%.

實施例9係如下情況：將形成一次粒子之電流密度設為65A/dm2與2A/dm2，將庫侖量設為80As/dm2與4As/dm2，並將形成二次粒子之電流密度設為25A/dm2，將庫侖量設為15As/dm2。 Example 9 based the following: the formation of the primary particles of the current density is set to 65A / dm 2 and 2A / dm 2, the coulomb amount to 80As / dm 2 and 4As / dm 2, the current density and the formation of secondary particles Set to 25 A/dm 2 and set the coulomb amount to 15 As/dm 2 .

其結果，一次粒子之平均粒徑為0.41μm，二次粒子之平均粒徑為0.16μm，利用雷射顯微鏡獲得之粒子形成後之表面積為21177μm2。另一方面，相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.13，滿足本發明之條件。 As a result, the average particle diameter of the primary particles was 0.41 μm, the average particle diameter of the secondary particles was 0.16 μm, and the surface area after formation of the particles obtained by the laser microscope was 21177 μm 2 . On the other hand, the two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.13, which satisfies the conditions of the present invention.

其結果，具備如下特徵：無落粉，常態剝離強度為較高之1.09kg/cm，耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將其差設為劣化率)為較小之30%以下。 As a result, it has the following characteristics: no falling powder, normal peel strength is 1.09 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set. The rate of deterioration is less than 30%.

實施例10係如下情況：將形成一次粒子之電流密度設為60A/dm2與10A/dm2，將庫侖量設為80As/dm2與20As/dm2，並將形成二次粒子之電流密度設為25A/dm2，將庫侖量設為30As/dm2。 Example 10 is a case where the current density of the primary particles is set to 60 A/dm 2 and 10 A/dm 2 , the Coulomb amount is set to 80 As/dm 2 and 20 As/dm 2 , and the current density of the secondary particles is formed. Set to 25 A/dm 2 and set the coulomb amount to 30 As/dm 2 .

其結果，一次粒子之平均粒徑為0.31μm，二次粒子之平均粒徑為0.25μm，利用雷射顯微鏡獲得之粒子形成後之三維表面積為21208μm2。 另一方面，相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.14，滿足本發明之條件。 As a result, the average particle diameter of the primary particles was 0.31 μm, the average particle diameter of the secondary particles was 0.25 μm, and the three-dimensional surface area after the formation of the particles obtained by the laser microscope was 21208 μm 2 . On the other hand, the two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.14, which satisfies the conditions of the present invention.

具備如下特徵：無落粉；常態剝離強度為較高之0.93kg/cm，又，耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將其差設為劣化率)為較小之30%以下。 It has the following characteristics: no powder; normal peel strength is 0.93kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 °C for 48 hours is measured, and the difference is set to The deterioration rate is 30% or less.

實施例11係如下情況：將形成一次粒子之電流密度設為55A/dm2與1A/dm2，將庫侖量設為75As/dm2與5As/dm2，並將形成二次粒子之電流密度設為25A/dm2，將庫侖量設為30As/dm2。 Example 11 lines the following: the current density of the primary particles forming the set to 55A / dm 2 and 1A / dm 2, the coulomb amount to 75As / dm 2 and 5As / dm 2, the current density and the formation of secondary particles Set to 25 A/dm 2 and set the coulomb amount to 30 As/dm 2 .

其結果，一次粒子之平均粒徑為0.35μm，二次粒子之平均粒徑為0.26μm，利用雷射顯微鏡獲得之粒子形成後之表面積為21010μm2。相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.12，滿足本發明之條件。 As a result, the average particle diameter of the primary particles was 0.35 μm, the average particle diameter of the secondary particles was 0.26 μm, and the surface area after formation of the particles obtained by the laser microscope was 21010 μm 2 . The two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.12, which satisfies the conditions of the present invention.

具備如下特徵：無落粉，常態剝離強度為較高之0.95kg/cm，耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將其差設為劣化率)為較小之30%以下。 It has the following characteristics: no falling powder, normal peel strength is 0.95 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set as the deterioration rate. ) is less than 30%.

實施例12係如下情況：將形成一次粒子之電流密度設為50A/dm2與5A/dm2，將庫侖量設為70As/dm2與10As/dm2，並將形成二次粒子之電流密度設為25A/dm2，將庫侖量設為30As/dm2。 Example 12 lines the following: the current density of the primary particles forming the set to 50A / dm 2 and 5A / dm 2, the coulomb amount to 70As / dm 2 and 10As / dm 2, the current density and the formation of secondary particles Set to 25 A/dm 2 and set the coulomb amount to 30 As/dm 2 .

其結果，一次粒子之平均粒徑為0.30μm，二次粒子之平均粒徑為0.25μm，利用雷射顯微鏡獲得之粒子形成後之表面積為20978μm2。相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.11，滿足本發明之條件。 As a result, the average particle diameter of the primary particles was 0.30 μm, the average particle diameter of the secondary particles was 0.25 μm, and the surface area after formation of the particles obtained by the laser microscope was 20978 μm 2 . The two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.11, which satisfies the conditions of the present invention.

具備如下特徵：無落粉，常態剝離強度為較高之0.94kg/cm，耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將其差設為劣化率)為較小之30%以下。 It has the following characteristics: no powder drop, normal peel strength is 0.94 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set as the deterioration rate. ) is less than 30%.

實施例13係如下情況：將形成一次粒子之電流密度設為60A/dm2與10A/dm2，將庫侖量設為80As/dm2與20As/dm2，並將形成二次粒子之電流密度設為25A/dm2，將庫侖量設為30As/dm2。 Example 13 is a case where the current density of the primary particles is set to 60 A/dm 2 and 10 A/dm 2 , the coulomb amount is set to 80 As/dm 2 and 20 As/dm 2 , and the current density of the secondary particles is formed. Set to 25 A/dm 2 and set the coulomb amount to 30 As/dm 2 .

其結果，一次粒子之平均粒徑為0.30μm，二次粒子之平均粒徑為0.25μm，利用雷射顯微鏡獲得之粒子形成後之三維表面積為21008μm2。另一方面，相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.12，滿足本發明之條件。 As a result, the average particle diameter of the primary particles was 0.30 μm, the average particle diameter of the secondary particles was 0.25 μm, and the three-dimensional surface area after the formation of the particles obtained by the laser microscope was 21,008 μm 2 . On the other hand, the two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.12, which satisfies the conditions of the present invention.

具備如下特徵：無落粉；常態剝離強度為較高之0.93kg/cm，又，耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將其差設為劣化率)為較小之30%以下。 It has the following characteristics: no powder; normal peel strength is 0.93kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 °C for 48 hours is measured, and the difference is set to The deterioration rate is 30% or less.

實施例14係如下情況：將形成一次粒子之電流密度設為60A/dm2與10A/dm2，將庫侖量設為80As/dm2與20As/dm2，並將形成二次粒子之電流密度設為25A/dm2，將庫侖量設為30As/dm2。 Example 14 is a case where the current density of the primary particles is set to 60 A/dm 2 and 10 A/dm 2 , the Coulomb amount is set to 80 As/dm 2 and 20 As/dm 2 , and the current density of the secondary particles is formed. Set to 25 A/dm 2 and set the coulomb amount to 30 As/dm 2 .

其結果，一次粒子之平均粒徑為0.30μm，二次粒子之平均粒徑為0.25μm，利用雷射顯微鏡獲得之粒子形成後之三維表面積為21009μm2。另一方面，相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.12，滿足本發明之條件。 As a result, the average particle diameter of the primary particles was 0.30 μm, the average particle diameter of the secondary particles was 0.25 μm, and the three-dimensional surface area after the formation of the particles obtained by the laser microscope was 21009 μm 2 . On the other hand, the two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.12, which satisfies the conditions of the present invention.

具備如下特徵：無落粉；常態剝離強度為較高之0.92kg/cm，又，耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度， 將其差設為劣化率)為較小之30%以下。 It has the following characteristics: no powder; normal peel strength is 0.92kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 °C for 48 hours, The difference is set to a deterioration rate of 30% or less.

實施例15係如下情況：將形成一次粒子之電流密度設為55A/dm2與1A/dm2，將庫侖量設為75As/dm2與5As/dm2，並將形成二次粒子之電流密度設為25A/dm2，將庫侖量設為30As/dm2。 Example 15 lines the following: the formation of the primary particles of the current density is set to 55A / dm 2 and 1A / dm 2, the coulomb amount to 75As / dm 2 and 5As / dm 2, the current density and the formation of secondary particles Set to 25 A/dm 2 and set the coulomb amount to 30 As/dm 2 .

其結果，一次粒子之平均粒徑為0.35μm，二次粒子之平均粒徑為0.25μm，利用雷射顯微鏡獲得之粒子形成後之表面積為20848μm2。相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.10，滿足本發明之條件。 As a result, the average particle diameter of the primary particles was 0.35 μm, the average particle diameter of the secondary particles was 0.25 μm, and the surface area after formation of the particles obtained by the laser microscope was 20848 μm 2 . The two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.10, which satisfies the conditions of the present invention.

具備如下特徵：無落粉，常態剝離強度為較高之0.94kg/cm，耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將其差設為劣化率)為較小之30%以下。 It has the following characteristics: no powder drop, normal peel strength is 0.94 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set as the deterioration rate. ) is less than 30%.

實施例16係如下情況：將形成一次粒子之電流密度設為50A/dm2與5A/dm2，將庫侖量設為70As/dm2與10As/dm2，並將形成二次粒子之電流密度設為25A/dm2，將庫侖量設為30As/dm2。 Example 16 lines the following: the formation of the primary particles of the current density is set to 50A / dm 2 and 5A / dm 2, the coulomb amount to 70As / dm 2 and 10As / dm 2, the current density and the formation of secondary particles Set to 25 A/dm 2 and set the coulomb amount to 30 As/dm 2 .

其結果，一次粒子之平均粒徑為0.30μm，二次粒子之平均粒徑為0.25μm，利用雷射顯微鏡獲得之粒子形成後之表面積為20737μm2。相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.09，滿足本發明之條件。 As a result, the average particle diameter of the primary particles was 0.30 μm, the average particle diameter of the secondary particles was 0.25 μm, and the surface area after formation of the particles obtained by the laser microscope was 20737 μm 2 . The two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.09, which satisfies the conditions of the present invention.

具備如下特徵：無落粉，常態剝離強度為較高之0.94kg/cm，耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將其差設為劣化率)為較小之30%以下。 It has the following characteristics: no powder drop, normal peel strength is 0.94 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set as the deterioration rate. ) is less than 30%.

實施例17係如下情況：將形成一次粒子之電流密度設為50A /dm2與2A/dm2，將庫侖量設為70As/dm2與3As/dm2，並將形成二次粒子之電流密度設為15A/dm2，將庫侖量設為30As/dm2。 Example 17 lines the following: the current density of the primary particles forming the set to 50A / dm 2 and 2A / dm 2, the coulomb amount to 70As / dm 2 and 3As / dm 2, the current density and the formation of secondary particles Set to 15 A/dm 2 and set the coulomb amount to 30 As/dm 2 .

其結果，一次粒子之平均粒徑為0.25μm，二次粒子幾乎成為被覆(正常)鍍敷狀態(粒徑未達0.1μm)，利用雷射顯微鏡獲得之粒子形成後之表面積為20108μm2。相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.03，滿足本發明之條件。 As a result, the average particle diameter of the primary particles was 0.25 μm, the secondary particles were almost coated (normal) plating state (the particle diameter was less than 0.1 μm), and the surface area after the formation of the particles obtained by the laser microscope was 20108 μm 2 . The two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.03, which satisfies the conditions of the present invention.

具備如下特徵：無落粉，常態剝離強度為較高之0.81kg/cm，耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將其差設為劣化率)為較小之30%以下。 It has the following characteristics: no falling powder, normal peel strength is 0.81 kg/cm, and heat resistance deterioration rate (after normal peel measurement, the peel strength after heating at 180 ° C for 48 hours is measured, and the difference is set as the deterioration rate. ) is less than 30%.

相對於此，比較例係以下結果。 On the other hand, the comparative example is the following result.

比較例1係如下情況：將形成一次粒子之電流密度設為63A/dm2與10A/dm2，將庫侖量設為80As/dm2與30As/dm2，並無形成二次粒子。其結果，一次粒子之平均粒徑為0.50μm，利用雷射顯微鏡獲得之粒子形成後之表面積為20804μm2。相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.10，滿足本發明之條件。 In Comparative Example 1, the current density of the primary particles was set to 63 A/dm 2 and 10 A/dm 2 , and the Coulomb amount was set to 80 As/dm 2 and 30 As/dm 2 , and secondary particles were not formed. As a result, the average particle diameter of the primary particles was 0.50 μm, and the surface area after the formation of the particles obtained by the laser microscope was 20,804 μm 2 . The two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.10, which satisfies the conditions of the present invention.

無落粉，常態剝離強度為較高之1.38kg/cm，且為實施例等級。然而，若耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將其差設為劣化率)為60%，則明顯較差。作為整體高頻電路用銅箔之評價不良。 In the absence of powder, the normal peel strength was 1.38 kg/cm higher and was of the example grade. However, if the heat resistance deterioration rate (measured after the normal peeling measurement, the peel strength after heating at 180 ° C for 48 hours, and the difference is the deterioration rate) is 60%, it is remarkably inferior. The evaluation of the copper foil for the entire high-frequency circuit was poor.

比較例2表示不存在一次粒徑而僅具有二次粒子層之習知 例。即，係將形成二次粒子之電流密度設為50A/dm2，將庫侖量設為30As/dm2之情況。 Comparative Example 2 shows a conventional example in which only the secondary particle layer was present without the primary particle diameter. That is, the current density of the secondary particles was set to 50 A/dm 2 and the coulomb amount was set to 30 As/dm 2 .

其結果，二次粒子之平均粒徑為0.30μm，利用雷射顯微鏡獲得之粒子形成後之三維表面積為21834μm2。相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.20，未滿足本發明之條件。 As a result, the average particle diameter of the secondary particles was 0.30 μm, and the three-dimensional surface area after the formation of the particles obtained by the laser microscope was 21,834 μm 2 . The two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.20, which did not satisfy the conditions of the present invention.

產生大量粗化粒子之落粉。常態剝離強度為1.25kg/cm，為實施例等級，耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將其差設為劣化率)為較小之30%以下，為實施例等級。如上所述，存在產生大量落粉之問題，因此作為整體高頻電路用銅箔之綜合評價不良。 A large amount of coarse particles are produced. The normal peel strength was 1.25 kg/cm, which was the example grade, and the heat resistance deterioration rate (after the normal peel measurement was measured, the peel strength after heating at 180 ° C for 48 hours, and the difference was made the deterioration rate) was 30. Below %, is the embodiment level. As described above, there is a problem that a large amount of falling powder is generated, and thus the overall evaluation of the copper foil for the high-frequency circuit is poor.

比較例3係如下情況：將形成一次粒子之電流密度設為63A/dm2與1A/dm2，將庫侖量設為80As/dm2與2As/dm2，並將形成二次粒子之電流密度設為28A/dm2，將庫侖量設為73As/dm2。 Comparative Example 3 is a case where the current density of the primary particles is set to 63 A/dm 2 and 1 A/dm 2 , the coulomb amount is set to 80 As/dm 2 and 2 As/dm 2 , and the current density of the secondary particles is formed. Set to 28 A/dm 2 and set the coulomb amount to 73 As/dm 2 .

其結果，一次粒子之平均粒徑為0.35μm，二次粒子之平均粒徑為0.60μm，利用雷射顯微鏡獲得之粒子形成後之三維表面積為21797μm2。相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.20，未滿足本發明之條件。產生大量落粉。常態剝離強度為較高之1.42kg/cm、耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將其差設為劣化率)為較小之30%以下，為實施例等級，但產生大量落粉。作為整體高頻電路用銅箔之評價不良。 As a result, the average particle diameter of the primary particles was 0.35 μm, the average particle diameter of the secondary particles was 0.60 μm, and the three-dimensional surface area after the formation of the particles obtained by the laser microscope was 21797 μm 2 . The two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.20, which did not satisfy the conditions of the present invention. Produce a lot of falling powder. The normal peel strength is 1.42 kg/cm, and the heat resistance deterioration rate (after the normal peel measurement is measured, the peel strength after heating at 180 ° C for 48 hours, and the difference is the deterioration rate) is 30% or less. , for the example grade, but produced a lot of falling powder. The evaluation of the copper foil for the entire high-frequency circuit was poor.

比較例4係如下情況：將形成一次粒子之電流密度設為63A/dm2與1A/dm2，將庫侖量設為80As/dm2與2As/dm2，並將形成二次粒子之電流密度設為31A/dm2，將庫侖量設為40As/dm2。 Comparative Example 4 is a case where the current density of the primary particles is set to 63 A/dm 2 and 1 A/dm 2 , the coulomb amount is set to 80 As/dm 2 and 2 As/dm 2 , and the current density of the secondary particles is formed. Set to 31 A/dm 2 and set the coulomb amount to 40 As/dm 2 .

其結果，一次粒子之平均粒徑為0.35μm，二次粒子之平均粒徑為0.40μm，粒子形成後之表面積22448μm2。相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.26，未滿足本發明之條件。 As a result, the average particle diameter of the primary particles was 0.35 μm, the average particle diameter of the secondary particles was 0.40 μm, and the surface area after the formation of the particles was 22448 μm 2 . The two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.26, which did not satisfy the conditions of the present invention.

常態剝離強度為較高之1.37kg/cm、耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將其差設為劣化率)為較小之30%以下，為實施例等級，但產生大量落粉。作為整體高頻電路用銅箔之評價不良。 The normal peel strength is 1.37 kg/cm, and the heat resistance deterioration rate (after the normal peel measurement is measured, the peel strength after heating at 180 ° C for 48 hours, and the difference is the deterioration rate) is 30% or less. , for the example grade, but produced a lot of falling powder. The evaluation of the copper foil for the entire high-frequency circuit was poor.

比較例5係如下情況：將形成一次粒子之電流密度設為63A/dm2與10A/dm2，將庫侖量設為80As/dm2與30As/dm2，並將形成二次粒子之電流密度設為31A/dm2，將庫侖量設為40As/dm2。其結果，一次粒子之平均粒徑為0.50μm，二次粒子之平均粒徑為0.40μm，粒子形成後之表面積22086μm2。相同區域之二維表面積為9924.4μm2(其相當於100×100μm面積)，因此三維表面積相對於二維表面積之比為2.23，未滿足本發明之條件。 Comparative Example 5 is a case where the current density of the primary particles is set to 63 A/dm 2 and 10 A/dm 2 , the Coulomb amount is set to 80 As/dm 2 and 30 As/dm 2 , and the current density of the secondary particles is formed. Set to 31 A/dm 2 and set the coulomb amount to 40 As/dm 2 . As a result, the average particle diameter of the primary particles was 0.50 μm, the average particle diameter of the secondary particles was 0.40 μm, and the surface area after the formation of the particles was 22086 μm 2 . The two-dimensional surface area of the same region was 9924.4 μm 2 (which corresponds to an area of 100 × 100 μm), so the ratio of the three-dimensional surface area to the two-dimensional surface area was 2.23, which did not satisfy the conditions of the present invention.

常態剝離強度為1.35kg/cm、耐熱性劣化率(於常態剝離測量後，測量於180℃加熱48小時後之剝離強度，將其差設為劣化率)為較小之30%以下，為實施例等級，但產生落粉。作為整體高頻電路用銅箔之評價不良。 The normal peel strength is 1.35 kg/cm, and the heat resistance deterioration rate (the peel strength after heating at 180 ° C for 48 hours after the normal peel measurement is measured, and the difference is the deterioration rate) is 30% or less. Example level, but produces falling powder. The evaluation of the copper foil for the entire high-frequency circuit was poor.

根據上述實施例及比較例之對比可揭明，於在銅箔(原箔) 之表面形成銅之一次粒子層後，於該一次粒子層上形成由銅、鈷及鎳構成之三元系合金所形成之二次粒子層之情形時，將粗化處理面之一定區域之利用雷射顯微鏡獲得之三維表面積相對於二維表面積之比設為2.0以上且未達2.2，藉此可具有能夠穩定地抑制稱為落粉之現象之優異效果，進而，提高剝離強度且提高高頻特性。 According to the comparison of the above examples and comparative examples, it can be revealed in copper foil (original foil) When a secondary particle layer of copper is formed on the surface, and a secondary particle layer formed of a ternary alloy composed of copper, cobalt, and nickel is formed on the primary particle layer, the use of a certain region of the roughened surface is utilized. The ratio of the three-dimensional surface area to the two-dimensional surface area obtained by the laser microscope is set to 2.0 or more and less than 2.2, whereby the excellent effect of suppressing the phenomenon called falling powder can be stably suppressed, and the peel strength and the high frequency can be improved. characteristic.

又，將一次粒子層之平均粒徑設為0.25~0.45μm、將由銅、鈷及鎳構成之三元系合金所形成之二次粒子層之平均粒徑設為0.35μm以下可達成上述效果，並且進而有效。 In addition, the average particle diameter of the primary particle layer is 0.25 to 0.45 μm, and the average particle diameter of the secondary particle layer formed of the ternary alloy composed of copper, cobalt, and nickel is 0.35 μm or less. And then effective.

再者，於耐熱處理層含有Co之情形時，有傳輸損耗變大之傾向。 Further, when the heat-resistant treatment layer contains Co, the transmission loss tends to increase.

Claims (23)

一種高頻電路用銅箔，係於銅箔表面形成銅之一次粒子層之後，於該一次粒子層上形成由銅、鈷及鎳構成之三元系合金之二次粒子層而成的銅箔，粗化處理面之一定區域利用雷射顯微鏡獲得之三維表面積相對於二維表面積的比為2.0以上且未達2.2。 A copper foil for a high-frequency circuit is a copper foil formed by forming a primary particle layer of copper on a surface of a copper foil, and forming a secondary particle layer of a ternary alloy composed of copper, cobalt, and nickel on the primary particle layer. The ratio of the three-dimensional surface area obtained by the laser microscope to the two-dimensional surface area in a certain region of the roughened surface is 2.0 or more and less than 2.2. 如申請專利範圍第1項之高頻電路用銅箔，其中，該銅之一次粒子層的平均粒徑為0.25~0.45μm，由銅、鈷及鎳構成之三元系合金所形成之二次粒子層的平均粒徑為0.35μm以下。 The copper foil for high-frequency circuit according to the first aspect of the invention, wherein the primary particle layer of the copper has an average particle diameter of 0.25 to 0.45 μm, and the ternary alloy composed of copper, cobalt and nickel is formed twice. The average particle diameter of the particle layer is 0.35 μm or less. 如申請專利範圍第1項之高頻電路用銅箔，其中，該一次粒子層及二次粒子層為電鍍層。 The copper foil for high-frequency circuits according to the first aspect of the invention, wherein the primary particle layer and the secondary particle layer are electroplated layers. 如申請專利範圍第1項之高頻電路用銅箔，其中，該二次粒子為於該一次粒子上成長之1個或複數個樹枝狀粒子或於該一次粒子上成長之正常鍍層。 The copper foil for high-frequency circuits according to the first aspect of the invention, wherein the secondary particles are one or a plurality of dendritic particles grown on the primary particles or a normal plating layer grown on the primary particles. 如申請專利範圍第1項之高頻電路用銅箔，其中，該一次粒子層及二次粒子層之接著強度為0.80kg/cm以上。 The copper foil for high-frequency circuits according to the first aspect of the invention, wherein the primary particle layer and the secondary particle layer have a bonding strength of 0.80 kg/cm or more. 如申請專利範圍第1項之高頻電路用銅箔，其中，該一次粒子層及二次粒子層之接著強度為0.90kg/cm以上。 The copper foil for high-frequency circuits according to the first aspect of the invention, wherein the primary particle layer and the secondary particle layer have a bonding strength of 0.90 kg/cm or more. 如申請專利範圍第1項之高頻電路用銅箔，其中，於該二次粒子層上形成有：(A)由Ni與選自由Fe、Cr、Mo、Zn、Ta、Cu、Al、P、W、Mn、Sn、As及Ti組成之群中一種以上之元素構成的合金層，及(B)鉻酸鹽層 之任一者或兩者。 The copper foil for high-frequency circuit according to the first aspect of the invention, wherein the secondary particle layer is formed with: (A) Ni and selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P An alloy layer composed of one or more elements of the group consisting of W, Mn, Sn, As, and Ti, and (B) a chromate layer Either or both. 如申請專利範圍第1項之高頻電路用銅箔，其中，於該二次粒子層上依序形成有：(A)由Ni與選自由Fe、Cr、Mo、Zn、Ta、Cu、Al、P、W、Mn、Sn、As及Ti組成之群中一種以上之元素構成之合金層，及(B)鉻酸鹽層之任一者或兩者，及矽烷偶合層。 The copper foil for high-frequency circuit according to claim 1, wherein the secondary particle layer is sequentially formed with: (A) Ni and selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, and Al. And an alloy layer composed of one or more elements of the group consisting of P, W, Mn, Sn, As, and Ti, and (B) either or both of the chromate layers, and a decane coupling layer. 如申請專利範圍第1項之高頻電路用銅箔，其中，於該二次粒子層上形成有Ni-Zn合金層及鉻酸鹽層之任一者或兩者。 The copper foil for high-frequency circuits according to claim 1, wherein either or both of a Ni-Zn alloy layer and a chromate layer are formed on the secondary particle layer. 如申請專利範圍第1項之高頻電路用銅箔，其中，於該二次粒子層上依序形成有：Ni-Zn合金層及鉻酸鹽層之任一者或兩者，及矽烷偶合層。 The copper foil for high-frequency circuits according to claim 1, wherein one or both of a Ni-Zn alloy layer and a chromate layer and a decane coupling are sequentially formed on the secondary particle layer. Floor. 如申請專利範圍第1項之高頻電路用銅箔，其中，於該二次粒子層之表面具備樹脂層。 A copper foil for a high-frequency circuit according to the first aspect of the invention, wherein a resin layer is provided on a surface of the secondary particle layer. 如申請專利範圍第7至10項中任一項之高頻電路用銅箔，其中，於該由Ni與選自由Fe、Cr、Mo、Zn、Ta、Cu、Al、P、W、Mn、Sn、As及Ti組成之群中一種以上之元素構成的合金層、或該鉻酸鹽層、或該矽烷偶合層、或該Ni-Zn合金層之表面具備樹脂層。 The copper foil for high-frequency circuit according to any one of claims 7 to 10, wherein the Ni is selected from the group consisting of Fe, Cr, Mo, Zn, Ta, Cu, Al, P, W, Mn, An alloy layer composed of one or more elements of the group consisting of Sn, As, and Ti, or the chromate layer, or the decane coupling layer, or the surface of the Ni-Zn alloy layer is provided with a resin layer. 一種附載體銅箔，係於載體之一面或雙面依序具有中間層、極薄銅層者，該極薄銅層為申請專利範圍第1至12項中任一項之高頻電路用銅 箔。 A copper foil with a carrier is a copper layer for a high-frequency circuit according to any one of claims 1 to 12, which has an intermediate layer or an ultra-thin copper layer on one or both sides of the carrier. Foil. 如申請專利範圍第13項之附載體銅箔，其中，於該載體之一面依序具有該中間層、該極薄銅層，於該載體之另一面具有粗化處理層。 The carrier-attached copper foil according to claim 13, wherein the intermediate layer and the ultra-thin copper layer are sequentially provided on one side of the carrier, and the roughened layer is provided on the other side of the carrier. 如申請專利範圍第13項之附載體銅箔，其中，於該載體之一面依序具有該中間層、該極薄銅層，於該載體之另一面具有粗化處理層。 The carrier-attached copper foil according to claim 13, wherein the intermediate layer and the ultra-thin copper layer are sequentially provided on one side of the carrier, and the roughened layer is provided on the other side of the carrier. 一種高頻電路用覆銅積層板，其使用有申請專利範圍第1至15項中任一項之銅箔。 A copper-clad laminate for a high-frequency circuit, which uses the copper foil of any one of claims 1 to 15. 一種高頻電路用印刷配線板，其使用有申請專利範圍第1至15項中任一項之銅箔。 A printed wiring board for a high-frequency circuit using the copper foil according to any one of claims 1 to 15. 如申請專利範圍第16項之高頻電路用覆銅積層板，其積層有該銅箔與聚醯亞胺、液晶聚合物或氟樹脂。 The copper-clad laminate for high-frequency circuits of claim 16 is laminated with the copper foil and polyimide, liquid crystal polymer or fluororesin. 如申請專利範圍第17項之高頻電路用印刷配線板，其使用有聚醯亞胺、液晶聚合物或氟樹脂之任一者。 A printed wiring board for a high-frequency circuit according to the seventeenth aspect of the invention is the use of any of a polyimide, a liquid crystal polymer or a fluororesin. 一種電子機器，其使用有申請專利範圍第17項之印刷配線板。 An electronic machine using the printed wiring board of claim 17 of the patent application. 一種電子機器，其使用有申請專利範圍第19項之印刷配線板。 An electronic machine using the printed wiring board of claim 19 of the patent application. 一種印刷配線板之製造方法，其含有如下步驟：準備申請專利範圍第14或15項之附載體銅箔與絕緣基板；將該附載體銅箔與絕緣基板積層；及於將該附載體銅箔與絕緣基板積層後，經過將該附載體銅箔之載體剝離之步驟而形成覆銅積層板，然後，藉由半加成法、減成法、部分加成法或改良半加成法之任一種方法形成電路。 A manufacturing method of a printed wiring board, comprising the steps of: preparing a copper foil and an insulating substrate with a carrier of claim 14 or 15; laminating the copper foil with the insulating substrate; and forming a copper foil with the carrier After laminating with the insulating substrate, the copper-clad laminate is formed by the step of peeling off the carrier with the carrier copper foil, and then, by semi-additive method, subtractive method, partial addition method or modified semi-additive method One method forms a circuit. 一種印刷配線板之製造方法，其含有如下步驟：於申請專利範圍第14或15項之附載體銅箔的該極薄銅層側表面形成電路；以埋沒該電路之方式於該附載體銅箔之該極薄銅層側表面形成樹脂層；於該樹脂層上形成電路；於該樹脂層上形成電路後，剝離該載體；及藉由在剝離該載體後去除該極薄銅層，而使形成於該極薄銅層側表面之埋沒於該樹脂層的電路露出。 A manufacturing method of a printed wiring board, comprising the steps of: forming a circuit on a side surface of the ultra-thin copper layer of a copper foil with a carrier of claim 14 or 15; and depositing the copper foil with the circuit in a manner of burying the circuit Forming a resin layer on the side surface of the ultra-thin copper layer; forming a circuit on the resin layer; peeling off the carrier after forming a circuit on the resin layer; and removing the ultra-thin copper layer after peeling off the carrier A circuit buried in the resin layer on the side surface of the ultra-thin copper layer is exposed.
TW103113620A 2013-04-26 2014-04-15 High-frequency circuit copper foil, high-frequency circuit with copper laminated board, high-frequency circuit with a carrier copper foil, electronic equipment, and printed wiring board manufacturing methods TWI509115B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013094613 2013-04-26
JP2014079002A JP6425401B2 (en) 2013-04-26 2014-04-07 Copper foil for high frequency circuit, copper clad laminate for high frequency circuit, printed wiring board for high frequency circuit, copper foil with carrier for high frequency circuit, electronic device, and method of manufacturing printed wiring board

Publications (2)

Publication Number Publication Date
TW201512467A true TW201512467A (en) 2015-04-01
TWI509115B TWI509115B (en) 2015-11-21

Family

ID=52124081

Family Applications (1)

Application Number Title Priority Date Filing Date
TW103113620A TWI509115B (en) 2013-04-26 2014-04-15 High-frequency circuit copper foil, high-frequency circuit with copper laminated board, high-frequency circuit with a carrier copper foil, electronic equipment, and printed wiring board manufacturing methods

Country Status (3)

Country Link
JP (1) JP6425401B2 (en)
KR (1) KR101607381B1 (en)
TW (1) TWI509115B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI707070B (en) * 2017-02-07 2020-10-11 日商Ｊｘ金屬股份有限公司 Surface-treated copper foil, copper foil with a carrier, laminates, methods for manufacturing printed wiring boards, and methods for manufacturing electronic devices

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US10383222B2 (en) 2016-01-04 2019-08-13 Jx Nippon Mining & Metals Corporation Surface-treated copper foil
JP6854114B2 (en) * 2016-01-04 2021-04-07 Ｊｘ金属株式会社 Surface-treated copper foil
JP6601675B2 (en) * 2016-01-14 2019-11-06 パナソニックＩｐマネジメント株式会社 Metal-clad laminate and resin-coated metal foil
JP7055049B2 (en) * 2017-03-31 2022-04-15 Ｊｘ金属株式会社 Surface-treated copper foil and laminated boards using it, copper foil with carriers, printed wiring boards, electronic devices, and methods for manufacturing printed wiring boards.
JP6430092B1 (en) * 2017-05-19 2018-11-28 三井金属鉱業株式会社 Roughened copper foil, copper foil with carrier, copper clad laminate and printed wiring board
KR102413300B1 (en) * 2020-12-10 2022-06-27 와이엠티 주식회사 Metal foil, carrier with metal foil comprising the same and printed circuit board comprising the same
KR20230169770A (en) * 2022-06-09 2023-12-18 와이엠티 주식회사 Metal foil, carrier with metal layer comprising the same and printed circuit board comprising the same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4329953B2 (en) 1999-05-19 2009-09-09 古河電気工業株式会社 Copper foil for high-density ultra-fine wiring boards
JP5181618B2 (en) * 2007-10-24 2013-04-10 宇部興産株式会社 Metal foil laminated polyimide resin substrate
KR101298999B1 (en) * 2009-09-01 2013-08-23 일진머티리얼즈 주식회사 Embedded Copper foil for fine pattern
WO2011138876A1 (en) * 2010-05-07 2011-11-10 Jx日鉱日石金属株式会社 Copper foil for printed circuit
US8980414B2 (en) * 2011-08-31 2015-03-17 Jx Nippon Mining & Metals Corporation Carrier-attached copper foil

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI707070B (en) * 2017-02-07 2020-10-11 日商Ｊｘ金屬股份有限公司 Surface-treated copper foil, copper foil with a carrier, laminates, methods for manufacturing printed wiring boards, and methods for manufacturing electronic devices
US11401612B2 (en) 2017-02-07 2022-08-02 Jx Nippon Mining & Metals Corporation Surface-treated copper foil, copper foil having carrier, laminated material, method for producing printed wiring board, and method for producing electronic apparatus

Also Published As

Publication number Publication date
KR20140128269A (en) 2014-11-05
TWI509115B (en) 2015-11-21
JP6425401B2 (en) 2018-11-21
KR101607381B1 (en) 2016-03-29
JP2014225650A (en) 2014-12-04

Similar Documents

Publication Publication Date Title
TWI509115B (en) High-frequency circuit copper foil, high-frequency circuit with copper laminated board, high-frequency circuit with a carrier copper foil, electronic equipment, and printed wiring board manufacturing methods
CN104125711B (en) High-frequency circuit copper foil, copper-clad plate, printed wiring board, the copper foil with carrier, the manufacture method of electronic equipment and printed wiring board
US9788423B2 (en) Copper foil with carrier
TWI619409B (en) Method for manufacturing surface-treated copper foil, laminated board, printed wiring board, electronic device, copper foil with carrier and printed wiring board
TWI699459B (en) Surface-treated copper foil and laminated board using the same, copper foil with carrier, printed wiring board, electronic equipment, and manufacturing method of printed wiring board
KR101614624B1 (en) Copper foil with carrier
TWI632054B (en) Copper foil for high-frequency circuits, copper-clad laminated board for high-frequency circuits, printed wiring boards for high-frequency circuits, copper foil with carrier for high-frequency circuits, electronic equipment, and methods for manufacturing printed wiring boards
TWI526299B (en) Manufacturing method of supporting copper foil, printed wiring board, copper clad sheet, electronic machine and printed wiring board
CN104120471B (en) High-frequency circuit copper foil, copper-clad plate, printing distributing board, the copper foil with carrier, electronic equipment and printing distributing board manufacturing method
TW201446495A (en) Copper foil with attached carrier, copper-clad laminate using same, printed circuit board, electronic device, and method for manufacturing printed circuit board
TW201822597A (en) Surface Treated Copper Foil, Copper Foil With Carrier, Laminate, Method for Manufacturing Printed Wiring Board, and Method for Manufacturing Electronic Device
TW201438890A (en) Surface treated copper foil, laminate board, copper foil with carrier, printed wiring board, printed circuit board, electronic device, and method for production of printed wiring board
JP6511225B2 (en) Copper foil for high frequency circuit, copper clad laminate for high frequency circuit, printed wiring board for high frequency circuit, copper foil with carrier for high frequency circuit, electronic device, and method of manufacturing printed wiring board
TWI520662B (en) Copper foil for printed circuit
JP6140481B2 (en) Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board
JP5449596B1 (en) Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board
JP5386652B1 (en) Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board
JP5298252B1 (en) Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board
JP2014172179A (en) Carrier-provided copper foil, method of producing carrier-provided copper foil, printed wiring board, printed circuit board, copper-clad laminate and method of producing printed wiring board
JP6329731B2 (en) Copper foil with carrier, method for producing copper-clad laminate, and method for producing printed wiring board
JP6329727B2 (en) Copper foil with carrier, method for producing copper foil with carrier, printed wiring board, printed circuit board, copper-clad laminate, and method for producing printed wiring board
JP6176948B2 (en) Copper foil with carrier, method for producing copper foil with carrier, method for producing printed circuit board, method for producing copper-clad laminate, and method for producing printed wiring board
JP6336142B2 (en) Copper foil with carrier, method for producing copper foil with carrier, method for producing printed circuit board, method for producing copper-clad laminate, and method for producing printed wiring board
TW201900934A (en) Electrolytic copper foil, production method therefor, copper-clad laminate, printed wiring board, production method therefor, electronic device, and production method therefor