TW201739958A - Surface-treated copper foil for printed circuit board, copper-clad laminate for printed circuit board, and printed circuit board - Google Patents

Surface-treated copper foil for printed circuit board, copper-clad laminate for printed circuit board, and printed circuit board Download PDF

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TW201739958A
TW201739958A TW105140618A TW105140618A TW201739958A TW 201739958 A TW201739958 A TW 201739958A TW 105140618 A TW105140618 A TW 105140618A TW 105140618 A TW105140618 A TW 105140618A TW 201739958 A TW201739958 A TW 201739958A
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copper foil
wiring board
printed wiring
coupling agent
roughened
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TW105140618A
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Chinese (zh)
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TWI627307B (en
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Takahiro Saito
Takeshi Ezura
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Furukawa Electric Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils

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

Abstract

A surface-treated copper foil that is for a printed circuit board and that has a silane coupling agent layer on a surface on which roughened particles have been formed. The average height of the roughened particles on the silane-coupling-agent-layer surface is 0.05 [mu]m or more but less than 0.5 [mu]m, and the BET surface area ratio of the silane-coupling-agent-layer surface is 1.2 or higher.

Description

印刷配線板用表面處理銅箔、印刷配線板用覆銅積層板及印刷配線板 Surface-treated copper foil for printed wiring board, copper-clad laminate for printed wiring board, and printed wiring board

本發明係有關於一種印刷配線板用表面處理銅箔。此外，本發明係有關於一種使用該印刷配線板用表面處理銅箔的印刷配線板用覆銅積層板及使用該印刷配線板用表面處理銅箔的印刷配線板。 The present invention relates to a surface treated copper foil for a printed wiring board. Further, the present invention relates to a copper-clad laminate for a printed wiring board using the surface-treated copper foil for a printed wiring board, and a printed wiring board using the surface-treated copper foil for the printed wiring board.

近年來，伴隨著電腦或是資訊通訊機器的高性能、高機能化，或網際網路化的發展，有必要將大容量之資訊以更加高速的方式進行傳輸處理。因此，所傳輸的訊號有趨於更加高頻化的傾向，而要求印刷配線板可抑制高頻訊號的傳輸損耗。在製作印刷配線板中，通常為積層銅箔與絕緣性基材(樹脂基材)製作將其等進行加熱、加壓而接著的覆銅積層板，使用該覆銅積層板而形成導體電路。當將高頻訊號傳輸(高頻傳輸)至上述導體電路之際的傳輸損耗方面，為與導體損耗、介電損耗、輻射損耗這三個要素有關。 In recent years, with the development of high performance, high performance, or Internet of computers or information communication equipment, it is necessary to transmit large-capacity information in a more high-speed manner. Therefore, the transmitted signal tends to be more high-frequency, and the printed wiring board is required to suppress the transmission loss of the high-frequency signal. In the production of a printed wiring board, a laminated copper foil and an insulating base material (resin base material) are usually produced by heating and pressurizing the copper-clad laminate, and a copper-clad laminate is used to form a conductor circuit. The transmission loss of the high-frequency signal (high-frequency transmission) to the above-mentioned conductor circuit is related to the three factors of conductor loss, dielectric loss, and radiation loss.

導體損耗，係起因於導體電路之表面電阻而產生者。在使用覆銅積層板而形成的導體電路中傳輸高頻訊號後，產生集膚效應(skin-effect)現象。亦即，當在導體電路中流通交流電後，磁束便產生變化，而在導體電路之中心部產生反電動勢，其結果，造成電流難以在導體中心部流動，反而產生導體表面部分(表皮部分)的電流密度升高的現象。此種集膚效應現象使導體之有效斷面積減少，而產生所謂的表面電阻。電流所 流動的表皮部分之厚度(集膚深度)，為與頻率的平方根成反比例。 The conductor loss is caused by the surface resistance of the conductor circuit. After a high frequency signal is transmitted in a conductor circuit formed using a copper clad laminate, a skin-effect phenomenon occurs. That is, when alternating current is passed through the conductor circuit, the magnetic flux changes, and a counter electromotive force is generated at the center of the conductor circuit. As a result, it is difficult for the current to flow in the center portion of the conductor, and the surface portion (the skin portion) of the conductor is generated. The phenomenon of increased current density. This skin effect phenomenon reduces the effective sectional area of the conductor and produces a so-called surface resistance. Current The thickness of the skinned skin portion (depth of the skin) is inversely proportional to the square root of the frequency.

近年來，開發有如超過20GHz的高頻對應機器。當頻率在導體電路中傳輸GHz波段的高頻訊號時，集膚深度約形成為2μm或其以下，造成電流僅僅在導體的極為表層上流動。因此，在該高頻對應機器中使用的覆銅積層板中，若銅箔的表面粗度變大時，由該銅箔所形成之導體的傳輸路徑(也就是表皮部分的傳輸路徑)也會變長，增加傳輸損耗。因為如此，對高頻對應機器種所採用的覆銅積層板之銅箔，期望能減小其表面粗度。 In recent years, high-frequency counterpart machines such as more than 20 GHz have been developed. When the frequency transmits a high frequency signal of the GHz band in the conductor circuit, the skin depth is formed to be about 2 μm or less, causing the current to flow only on the extremely surface layer of the conductor. Therefore, in the copper-clad laminate used in the high-frequency-compatible machine, when the surface roughness of the copper foil is increased, the transmission path of the conductor formed by the copper foil (that is, the transmission path of the skin portion) is also Increase in length and increase transmission loss. Because of this, it is desirable to reduce the surface roughness of the copper foil of the copper clad laminate used for the high frequency corresponding machine type.

另一方面，一般在印刷配線板中所使用的銅箔，為利用電鍍或蝕刻等手法，在其表面形成粗化處理層(形成粗化粒子之層)，藉由物理性的效果(定準效應Anchoring Effect)而提升與樹脂基材之間的接著力。不過，若為了有效提升與樹脂基材之間的接著力，而增大形成於銅箔表面上的粗化粒子時，如上所述，將導致傳輸損耗的増加。 On the other hand, the copper foil generally used in a printed wiring board is formed by a method such as plating or etching to form a roughened layer (a layer forming roughened particles) on the surface thereof, and a physical effect (predetermined Effectring) enhances the adhesion between the resin substrate and the resin substrate. However, when the roughened particles formed on the surface of the copper foil are increased in order to effectively increase the adhesion force with the resin substrate, as described above, the transmission loss is increased.

介電損耗，係起因於樹脂基材之介電率或正切損耗(dissipation factor)。當將脈衝訊號流動於導體電路時，導體電路周遭的電場便會產生變化。當上述電場進行變化的周期(頻率)接近樹脂基材之分極的緩和時間(產生分極之荷電體的移動時間)時(亦即，進行高頻化後)，在電場變化中便會發生遲延。在該種狀態之下，樹脂內部產生分子摩擦而有熱產生，造成傳輸損耗。為了抑制該介電損耗，作為覆銅積層板之樹脂基材，為必須採用極性較大、且置換基之量較少的樹脂，或是須採用極性大之不具有置換基的樹脂，而使得難以產生伴隨於電場變化的樹脂基材之分極。 The dielectric loss is caused by the dielectric constant or the scission factor of the resin substrate. When the pulse signal flows to the conductor circuit, the electric field around the conductor circuit changes. When the period (frequency) at which the above-described electric field changes is close to the relaxation time of the polarization of the resin substrate (the time when the polarization of the charge is generated) (that is, after the frequency is high-frequency), a delay occurs in the electric field change. In this state, molecular friction occurs inside the resin and heat is generated, resulting in transmission loss. In order to suppress the dielectric loss, as the resin substrate of the copper clad laminate, it is necessary to use a resin having a large polarity and a small amount of a substituent, or a resin having a large polarity and having no substituent. It is difficult to generate a polarization of a resin substrate accompanying a change in an electric field.

另一方面，印刷配線板中所使用的銅箔，除了形成上述粗化處理層之外，還藉由矽烷耦合劑而將銅箔表面進行處理，藉此以化學性的提升與樹脂基材之間的接著力。為了提升矽烷耦合劑與樹脂基材之間的化學性接著性，樹脂基材必須要具有一定程度之大極性置換基。然而，為了抑制介電損耗，使用減少樹脂基材中極性大的置換基之量的低介電性基材時，將造成化學性接著力降低，難以確保銅箔與樹脂基材間之充分的接著性。 On the other hand, in the copper foil used in the printed wiring board, in addition to the above-described roughening treatment layer, the surface of the copper foil is treated by a decane coupling agent, thereby chemically enhancing the resin substrate. The force between the two. In order to improve the chemical adhesion between the decane coupling agent and the resin substrate, the resin substrate must have a certain degree of polar substitution. However, in order to suppress dielectric loss, when a low dielectric substrate having a large amount of a substituent having a large polarity in a resin substrate is used, chemical adhesion is lowered, and it is difficult to ensure sufficient copper foil and resin substrate. Follow-up.

如此，在覆銅積層板中，抑制傳輸損耗以及提升(提升耐久性)銅箔與樹脂基材間之密接性(接著性)，存在著一種相互權衡取捨(trade-off)的關係。 As described above, in the copper clad laminate, the transmission loss and the adhesion (adhesion) between the copper foil and the resin substrate are suppressed, and there is a trade-off relationship.

近年來，高頻對應印刷配線板在更加要求可靠度之領域中迅速發展。例如，作為在車載用途等移動通訊的印刷配線基板的使用上，要求即使在高溫環境等嚴苛環境下，為仍可使用的高可靠度。為了因應此種要求，於覆銅積層板方面，則必須要高度提升銅箔與樹脂基材間的密接性，例如，要求即使在150℃的溫度下仍可承受1000小時之嚴苛實驗的密接性。 In recent years, high-frequency corresponding printed wiring boards have rapidly developed in the field of more demanding reliability. For example, as a printed wiring board for mobile communication such as in-vehicle use, high reliability is required even in a severe environment such as a high-temperature environment. In order to meet such requirements, in the case of copper clad laminates, it is necessary to highly improve the adhesion between the copper foil and the resin substrate, for example, it is required to withstand the rigid experiment of 1000 hours even at a temperature of 150 ° C. Sex.

為了滿足該等需求，展開有各式技術的開發。例如，在專利文獻1中記載有一種表面處理銅箔，為使粗化粒子附著至銅箔，形成表面粗度Rz為1.5~4.0μm、亮度值為30以下的粗化面，該粗化粒子以指定密度呈現略均等狀的分布，而該表面處理銅箔則具有由該粗化粒子所形成之突起物，該突起物為具有指定的高度及寬度，且於專利文獻1中還記載，藉由使用該種表面處理銅箔，可提升以液晶聚合物為始之與高頻電路基板用樹脂基材之間的密接性。 In order to meet these needs, development of various technologies has been carried out. For example, Patent Document 1 discloses a surface-treated copper foil in which roughened particles are adhered to a copper foil to form a roughened surface having a surface roughness Rz of 1.5 to 4.0 μm and a luminance value of 30 or less. A slightly uniform distribution is present at a predetermined density, and the surface-treated copper foil has a projection formed of the roughened particles, and the projection has a specified height and width, and is also described in Patent Document 1, By using such a surface-treated copper foil, the adhesion between the liquid crystal polymer and the resin substrate for a high-frequency circuit substrate can be improved.

在智慧型手機或平板電腦這一類型的小型電子機器中，由容易配線或輕量性的觀點來看，係採用可撓性印刷配線板(以下，簡稱為FPC)。近年來，伴隨著該等小型電子機器的高機能化，亦有訊號傳輸速度高速化的傾向，FPC之阻抗匹配(輸出阻抗與輸入阻抗的匹配)便成為重要的課題。為實現對訊號傳輸速度之高速化的阻抗匹配，實施有將作為FPC基礎的樹脂基材(具代表性為聚醯亞胺)厚層化的措施。 In a small electronic device such as a smart phone or a tablet, a flexible printed wiring board (hereinafter abbreviated as FPC) is used from the viewpoint of easy wiring or light weight. In recent years, with the high performance of these small electronic devices, there has been a tendency for the signal transmission speed to increase, and impedance matching of FPC (matching of output impedance and input impedance) has become an important issue. In order to achieve high-speed impedance matching of the signal transmission speed, a measure of thickening a resin substrate (typically polyimine) which is the basis of FPC has been implemented.

此外，在有關FPC的專利文獻2中記載有一種適用於晶粒軟模封裝(COF)形式的FPC，上述FPC所具有的電解銅箔係構成為在接著至絕緣層的接著面上，具備由鎳-鋅合金形成的防鏽處理層，該接著面的表面粗度(Rz)為0.05~1.5μm，於入射角60°中的鏡面光澤度達250以上。根據專利文獻2所揭內容，該種FPC顯示出優越的透光率，且銅箔與樹脂基材間之密接性亦呈現良好狀。 Further, Patent Document 2 related to FPC discloses an FPC which is applied to a die-mode (COF) form, and the electrolytic copper foil of the FPC is configured to be provided on the subsequent surface of the insulating layer. The rust-preventing layer formed of the nickel-zinc alloy has a surface roughness (Rz) of 0.05 to 1.5 μm and a specular gloss of 250 or more at an incident angle of 60°. According to the disclosure of Patent Document 2, the FPC exhibits excellent light transmittance, and the adhesion between the copper foil and the resin substrate is also good.

此外，在專利文獻3中則記載有一種表面處理銅箔，為藉由粗化處理形成粗化粒子，係將粗化處理面的平均粗度Rz設為0.5~1.3μm、光澤度設為4.8~68、粗化粒子的表面積A與由上述銅箔表面側俯視觀察粗化粒子所得的面積B間之比A/B設為2.00~2.45。在專利文獻3中還記載，積層上述表面處理銅箔與樹脂基板而形成的覆銅積層板，在蝕刻除去銅箔後的樹脂透明性良好，且銅箔與樹脂間之密接性亦呈現良好狀。 Further, Patent Document 3 describes a surface-treated copper foil in which roughened particles are formed by roughening treatment, and the average roughness Rz of the roughened surface is set to 0.5 to 1.3 μm, and the gloss is set to 4.8. The ratio A/B between the surface area A of the roughened particles and the area B obtained by observing the roughened particles from the surface side of the copper foil was set to 2.00 to 2.45. Further, Patent Document 3 discloses that a copper clad laminate formed by laminating the surface-treated copper foil and a resin substrate has good transparency after etching and removing the copper foil, and the adhesion between the copper foil and the resin is also good. .

【先前技術】[Prior Art] 專利文獻Patent literature

專利文獻1：日本專利第4833556號公報 Patent Document 1: Japanese Patent No. 4833556

專利文獻2：日本專利第4090467號公報 Patent Document 2: Japanese Patent No. 4090467

專利文獻3：日本專利第5497808號公報 Patent Document 3: Japanese Patent No. 5497808

上述專利文獻1所記載的表面處理銅箔，在與高頻對應樹脂基材之間具有優越的密接性。不過，使用該種表面處理銅箔的覆銅積層板在GHz波段之高頻波段中，傳輸損耗高、無法充分滿足高頻對應印刷配線板所需之高要求。 The surface-treated copper foil described in Patent Document 1 has excellent adhesion to a high-frequency-corresponding resin substrate. However, the copper-clad laminate using such a surface-treated copper foil has high transmission loss in the high-frequency band of the GHz band, and cannot sufficiently satisfy the high requirements required for the high-frequency corresponding printed wiring board.

此外，在上述專利文獻2中記載之FPC所採用的電解銅箔，並未實施粗化處理，除了COF以外，並無法實現在印刷配線板中所要求之與樹脂基材之間的高密接性。 In addition, the electrolytic copper foil used in the FPC described in the above-mentioned Patent Document 2 is not subjected to the roughening treatment, and the high adhesion to the resin substrate required for the printed wiring board cannot be achieved except for the COF. .

此外，上述專利文獻3中記載之表面處理銅箔，在高溫下與樹脂基材間之密接性並不充分。因此，使用該種表面處理銅箔的印刷配線板，例如在溫度150℃、1000小時之嚴苛條件下，並無法滿足高可靠度的要求。 Further, the surface-treated copper foil described in Patent Document 3 is insufficient in adhesion to a resin substrate at a high temperature. Therefore, the printed wiring board using such a surface-treated copper foil cannot meet the requirements of high reliability under severe conditions of a temperature of 150 ° C for 1,000 hours.

本發明之課題在於提供一種如後所述之印刷配線板用表面處理銅箔，藉由該印刷配線板用表面處理銅箔，即便傳輸GHz波段之高頻訊號時，仍高度抑制傳輸損耗，且即使在高溫下，仍提高銅箔與樹脂基材之間的密接性，在嚴苛條件下仍具有優越的耐久性，更可獲得難以短路之印刷配線板。此外，本發明之課題在於提供使用該印刷配線板用表面處理銅箔的印刷配線板用覆銅積層板、以及使用該印刷配線板用表面處理銅箔的印刷配線板(電路基板)。 An object of the present invention is to provide a surface-treated copper foil for a printed wiring board as described later, and the surface-treated copper foil for the printed wiring board can highly suppress transmission loss even when a high-frequency signal of a GHz band is transmitted. Even at a high temperature, the adhesion between the copper foil and the resin substrate is improved, the durability is excellent under severe conditions, and a printed wiring board which is difficult to short-circuit can be obtained. In addition, an object of the present invention is to provide a copper-clad laminate for a printed wiring board using the surface-treated copper foil for a printed wiring board, and a printed wiring board (circuit board) using the surface-treated copper foil for the printed wiring board.

本發明之上述課題係可藉由下述手段獲得解決。 The above problems of the present invention can be solved by the following means.

〔1〕一種印刷配線板用表面處理銅箔，在形成有粗化粒子的表面上具有矽烷耦合劑層，其中，在上述矽烷耦合劑層表面中，粗化粒子的平均高度為0.05μm以上且未達0.5μm，上述矽烷耦合劑層表面之BET表面積比為1.2以上。 [1] A surface-treated copper foil for a printed wiring board having a decane coupling agent layer on a surface on which the roughened particles are formed, wherein an average height of the roughened particles in the surface of the decane coupling agent layer is 0.05 μm or more Below 0.5 μm, the BET surface area ratio of the surface of the above decane coupling agent layer is 1.2 or more.

〔2〕如〔1〕之印刷配線板用表面處理銅箔，其中，在上述矽烷耦合劑層表面中，粗化粒子的平均高度為0.05μm以上且未達0.3μm。 [2] The surface-treated copper foil for a printed wiring board according to [1], wherein the average height of the roughened particles in the surface of the decane coupling agent layer is 0.05 μm or more and less than 0.3 μm.

〔3〕如〔1〕或〔2〕之印刷配線板用表面處理銅箔，其中，在上述矽烷耦合劑層表面中，細微表面係數Cms為0.6以上且未達2.0。 [3] The surface-treated copper foil for a printed wiring board according to [1] or [2], wherein the fine surface coefficient Cms is 0.6 or more and less than 2.0 on the surface of the decane coupling agent layer.

〔4〕如〔1〕~〔3〕中任一項之印刷配線板用表面處理銅箔，其中，形成有上述粗化粒子的表面具有含鎳之金屬處理層，在上述金屬處理層中所含有的鎳元素量為0.1mg/dm2以上且未達0.3mg/dm2。 [4] The surface-treated copper foil for a printed wiring board according to any one of [1] to [3] wherein the surface of the roughened particles has a metal-treated layer containing nickel, and the metal-treated layer is The amount of the nickel element contained is 0.1 mg/dm 2 or more and less than 0.3 mg/dm 2 .

〔5〕如〔1〕~〔4〕中任一項之印刷配線板用表面處理銅箔，其中，在上述矽烷耦合劑層中所含有的矽元素量為0.5μg/dm2以上且未達15μg/dm2。 [5] The surface-treated copper foil for a printed wiring board according to any one of [1], wherein the amount of the lanthanum element contained in the decane coupling agent layer is 0.5 μg/dm 2 or more and is not reached. 15 μg/dm 2 .

〔6〕如〔1〕~〔5〕中任一項之印刷配線板用表面處理銅箔，其中，上述矽烷耦合劑，具有選自由環氧基、胺基、乙烯基、(甲基)丙烯醯基、苯乙烯基、脲基、異氰脲酸酯基、巰基、硫化物基、及異氰酸酯基中之至少一種官能基。 [6] The surface-treated copper foil for a printed wiring board according to any one of [1], wherein the decane coupling agent has an epoxy group, an amine group, a vinyl group, or a (meth) propylene group. At least one functional group of a mercapto group, a styryl group, a urea group, an isocyanurate group, a mercapto group, a sulfide group, and an isocyanate group.

〔7〕一種印刷配線板用覆銅積層板，其中在〔1〕~〔6〕中任一項之印刷配線板用表面處理銅箔的上述矽烷耦合劑層表面上，積層有樹脂層。 [7] A copper-clad laminate for a printed wiring board, wherein a resin layer is laminated on a surface of the ruthenium coupling agent layer of the surface-treated copper foil for a printed wiring board according to any one of [1] to [6].

〔8〕一種印刷配線板，其使用〔7〕之印刷配線板用覆銅積層板。 [8] A printed wiring board using the copper clad laminate for a printed wiring board of [7].

本發明之印刷配線板用表面處理銅箔係藉由將其使用在印刷配線板之導體電路，從而可獲得在嚴苛條件仍具有優越的耐久性、更具有優越絕緣可靠度的印刷配線板，其可高度抑制傳輸GHz波段之高頻訊號時的傳輸損耗，並且即使在高溫下，仍可提升銅箔與樹脂基材(樹脂層)間之密接性。 The surface-treated copper foil for a printed wiring board of the present invention can be used in a conductor circuit of a printed wiring board, thereby obtaining a printed wiring board which has excellent durability under severe conditions and has superior insulation reliability. It can highly suppress transmission loss when transmitting high-frequency signals in the GHz band, and can improve the adhesion between the copper foil and the resin substrate (resin layer) even at high temperatures.

本發明之印刷配線板用覆銅積層板係藉由將其作為印刷配線板的基板使用，所獲得的印刷配線板將具有傳輸GHz波段之高頻訊號時的傳輸損耗得以受到高度抑制，並且即使在高溫下仍可提升銅箔與樹脂基材間之密接性，而在嚴苛條件下的耐久性亦顯優越，更具有極佳的絕緣可靠度。 The copper-clad laminate for a printed wiring board of the present invention is used as a substrate of a printed wiring board, and the obtained printed wiring board is highly suppressed in transmission loss when transmitting a high-frequency signal of a GHz band, and even if At high temperatures, the adhesion between the copper foil and the resin substrate can be improved, and the durability under severe conditions is also superior, and the insulation reliability is excellent.

本發明之印刷基板係在傳輸GHz波段之高頻訊號時的傳輸損耗得以受到高度抑制，並且即使在高溫下仍可提升銅箔與樹脂基材間之密接性，而在嚴苛條件下的耐久性亦顯優越，更難以產生短路。 The printed circuit board of the present invention is highly resistant to transmission loss when transmitting high frequency signals in the GHz band, and can improve the adhesion between the copper foil and the resin substrate even at high temperatures, and is durable under severe conditions. Sex is also superior, and it is more difficult to create a short circuit.

適當參照附圖並根據下述記載，可明確瞭解本發明之上述及其他特徵以及優點。 The above and other features and advantages of the present invention will be apparent from the description of the appended claims.

圖1所示為測定粗化粒子高度之方法之一例的說明圖。 Fig. 1 is an explanatory view showing an example of a method of measuring the height of roughened particles.

圖2所示為測定粗化粒子高度之方法之一例的說明圖。 Fig. 2 is an explanatory view showing an example of a method of measuring the height of the roughened particles.

關於本發明之印刷配線板用表面處理銅箔較佳實施形態，說明如下。 A preferred embodiment of the surface-treated copper foil for a printed wiring board of the present invention will be described below.

〔印刷配線板用表面處理銅箔〕 [Surface treated copper foil for printed wiring board]

本發明之印刷配線板用表面處理銅箔(以下，簡稱為「本發明之表面處理銅箔」)係藉由矽烷耦合劑處理(亦即，在形成有粗化粒子之表面上具有矽烷耦合劑層)形成有粗化粒子的表面(因應需要，又附著有防腐金屬之面)，在該矽烷耦合劑層表面(表面處理銅箔最表面)，粗化粒子之平均高度為0.05μm以上且未達0.5μm，該矽烷耦合劑層表面之BET表面積比為1.2以上。本發明之表面處理銅箔係當使其兩面以矽烷耦合劑進行處理，而該處理後之表面具有平均高度為0.05μm以上且未達0.5μm之粗化粒子的情況下，只要至少一面的BET表面積比達1.2以上即可，亦可為兩面之BET表面積比達1.2以上。 The surface-treated copper foil for a printed wiring board of the present invention (hereinafter, simply referred to as "the surface-treated copper foil of the present invention") is treated with a decane coupling agent (that is, a decane coupling agent is formed on the surface on which the roughened particles are formed). The surface on which the roughened particles are formed (the surface of the anticorrosive metal is attached as needed), and the average height of the roughened particles is 0.05 μm or more on the surface of the decane coupling agent layer (the surface of the surface-treated copper foil) Up to 0.5 μm, the BET surface area ratio of the surface of the decane coupling agent layer was 1.2 or more. The surface-treated copper foil of the present invention is treated with a decane coupling agent on both sides thereof, and the treated surface has a roughened particle having an average height of 0.05 μm or more and less than 0.5 μm, as long as at least one side of the BET The surface area ratio may be 1.2 or more, and the BET surface area ratio of both sides may be 1.2 or more.

在本發明之表面處理銅箔中，是矽烷耦合劑層表面，且於該表面所測定之粗化粒子的平均高度為0.05μm以上且未達0.5μm，並且將該表面之BET表面積比達1.2以上的表面，單純稱之為「粗化處理面」。粗化處理面雖較佳可使其整體由矽烷耦合劑所覆蓋，不過，只要可達到本發明之效果，亦可使矽烷耦合劑僅覆蓋粗化處理面的一部分(亦即，只要可達到本發明之效果，即使粗化處理面之矽烷耦合劑層的一部分發生有膜缺損的情況亦是可允許的，該形態亦包含於本發明中之「具有矽烷耦合劑層」的形態中)。 In the surface-treated copper foil of the present invention, the surface of the decane coupling agent layer, and the average height of the roughened particles measured on the surface is 0.05 μm or more and less than 0.5 μm, and the BET surface area ratio of the surface is 1.2. The above surface is simply referred to as "roughening surface". Although the roughening treatment surface is preferably covered by the decane coupling agent as a whole, the decane coupling agent may cover only a part of the roughened surface as long as the effect of the present invention can be achieved (that is, as long as the present invention can be achieved) According to the effect of the invention, it is permissible to cause a film defect in a part of the decane coupling agent layer on the roughened surface, and this aspect is also included in the "having a decane coupling agent layer" in the present invention.

本發明之表面處理銅箔，僅至少單面為粗化處理面即可，亦可雙面皆為粗化處理面。本發明之表面處理銅箔，一般為僅有單面為粗化 處理面之形態。 In the surface-treated copper foil of the present invention, at least one side may be a roughened surface, or both sides may be a roughened surface. The surface treated copper foil of the present invention generally has only one side for roughening The form of the processing surface.

在本發明之表面處理銅箔中，粗化處理面即使粗化粒子的平均高度未達0.5μm而呈現較低狀，BET表面積比仍為1.2以上而呈較大值。因此，在經由該粗化處理面積層表面處理銅箔與樹脂層，製作覆銅積層板之際，伴隨著粗化粒子的定準效應與較大的表面積，將可高度提升銅箔與樹脂層間之密接性，獲得具優越耐熱性的覆銅積層板。此外，由於該粗化處理面，其粗化粒子的平均高度未達0.5μm而呈現較低狀，故而可降低存在的粗化粒子對傳輸路徑長度的影響。因此，在使用該覆銅積層板之導體電路中，當傳輸GHz波段之高頻訊號之際，亦可有效的抑制傳輸損耗。 In the surface-treated copper foil of the present invention, the roughened surface has a lower value even if the average height of the roughened particles is less than 0.5 μm, and the BET surface area ratio is 1.2 or more. Therefore, when the copper foil and the resin layer are treated on the surface of the roughened area layer to form a copper clad laminate, the leveling effect of the roughened particles and the large surface area increase the copper foil and the resin layer. The adhesion is obtained to obtain a copper-clad laminate having superior heat resistance. Further, since the roughened surface has an average height of the roughened particles of less than 0.5 μm and is low, the influence of the existing roughened particles on the length of the transport path can be reduced. Therefore, in the conductor circuit using the copper clad laminate, when the high frequency signal of the GHz band is transmitted, the transmission loss can be effectively suppressed.

在此之前，即使在銅箔表面上形成平均高度未達0.5μm之微小粗化粒子，仍無法得知將BET表面積比提升至1.2以上的方法。本發明者們在此種狀況下，藉由採用後述之特定的粗化鍍敷處理條件，成功製作出具有平均高度為0.05μm以上且未達0.5μm的粗化粒子，且BET表面積比達1.2以上的銅箔表面，進而完成本發明。 Prior to this, even if minute roughened particles having an average height of less than 0.5 μm were formed on the surface of the copper foil, the method of raising the BET surface area ratio to 1.2 or more was not known. In this case, the inventors succeeded in producing roughened particles having an average height of 0.05 μm or more and less than 0.5 μm by using specific rough plating treatment conditions to be described later, and the BET surface area ratio was 1.2. The above copper foil surface further completes the present invention.

從維持與樹脂基材間之高密接性的同時並更加有效的減低傳輸損耗的觀點而言，在上述粗化處理面中之上述粗化粒子的平均高度，較佳為0.05μm以上且未達0.5μm，更佳為0.05μm以上且未達0.3μm。在粗化處理面中之粗化粒子的平均高度，係利用後述之實施例中所記載的方法來測定。 The average height of the roughened particles in the roughened surface is preferably 0.05 μm or more and less than the viewpoint of maintaining high adhesion to the resin substrate and reducing transmission loss more effectively. 0.5 μm, more preferably 0.05 μm or more and less than 0.3 μm. The average height of the roughened particles in the roughened surface was measured by the method described in the examples below.

在本發明中，粗化粒子較佳係形成為在粗化處理面整體呈一様(均質)狀。粗化粒子的平均高度則藉由後述實施例所記載的方法進行測定。 In the present invention, the roughened particles are preferably formed to have a uniform (homogeneous) shape on the roughened surface. The average height of the roughened particles was measured by the method described in the examples below.

上述BET表面積比，為藉由BET法而依據表面積的測定方法計算而得。亦即，上述BET表面積比係為，使吸附占有面積為已知的氣體分子吸附至試料表面，根據該吸附量而求出試料的表面積(BET測定表面積)，從該BET測定表面積減去假設於試料表面無凹凸狀態之表面積(試料切出面積)之值，該值對該試料切出面積之比則為BET表面積比，藉由後述實施例中所記載的方法來進行測定。 The BET surface area ratio is calculated by a method of measuring the surface area by the BET method. In other words, the BET surface area ratio is such that a gas molecule having a known adsorption occupied area is adsorbed onto the surface of the sample, and the surface area (BET measurement surface area) of the sample is determined based on the adsorption amount, and the assumption is subtracted from the BET measurement surface area. The surface area of the sample having no surface roughness (sample cut-out area), and the ratio of the value to the cut-out area of the sample was a BET surface area ratio, and the measurement was carried out by the method described in the examples below.

在本發明之表面處理銅箔中，粗化處理面的BET表面積比值如係越大，則意味著表面積越大。從而，粗化處理面之上述BET表面積比越大，則更加提升與樹脂間之相互作用性，伴隨著粗化粒子的定準效應，提升積層樹脂層時之銅箔與樹脂層間之密接性。在本發明之表面處理銅箔中，粗化處理面之BET表面積比係以1.2以上且10以下為佳，以1.2以上且4以下為更佳。 In the surface-treated copper foil of the present invention, the larger the BET surface area ratio of the roughened surface, the larger the surface area. Therefore, the larger the BET surface area ratio of the roughened surface, the more the interaction with the resin is enhanced, and the adhesion between the copper foil and the resin layer when the resin layer is laminated is improved with the quenching effect of the roughened particles. In the surface-treated copper foil of the present invention, the BET surface area ratio of the roughened surface is preferably 1.2 or more and 10 or less, more preferably 1.2 or more and 4 or less.

在銅箔的表面積測定中，一般採用之利用雷射顯微鏡所實施的表面積測定方面，在原理上，因粗化粒子的形狀而造成雷射光無法到達的形成為「陰」部分的測定是不可能的，此外，亦難以藉由高感度的方式檢測出極細微的凹凸部分之表面積。例如，即使是高度與直徑相同的粗化粒子，但比較根部內縮的粗化粒子與無內縮的粗化粒子，雖然與樹脂密接面積較多為前者，但在藉由雷射顯微鏡所進行的表面積測定中，則呈現幾乎相同的測定值。 In the measurement of the surface area of the copper foil, in general, the measurement of the surface area by a laser microscope is generally impossible, and in principle, the measurement of the "yin" portion due to the shape of the roughened particles and the unreachable laser light is impossible. In addition, it is also difficult to detect the surface area of the extremely fine uneven portion by a high-sensitivity method. For example, even if the roughened particles have the same height and diameter, the coarsened particles which are retracted in the root portion and the roughened particles which are not retracted have a larger adhesion area with the resin, but are performed by a laser microscope. In the measurement of the surface area, almost the same measured value is exhibited.

相較之下，在利用BET法所進行的表面積之測定中，由於利用氣體分子的吸附來測定表面積，因此對細微凹凸有較高的感度，且亦可測定對雷射光而言形成為「陰」的部分。從而，相較於使用雷射顯微鏡 進行測定的情況，一般而言可以較高的精度測定已形成有粗化粒子之試料的表面積。 In contrast, in the measurement of the surface area by the BET method, since the surface area is measured by the adsorption of gas molecules, the fine unevenness is highly sensitive, and the measurement can be made to be "yin" for the laser light. "part. Thus, compared to using a laser microscope In the case of performing measurement, generally, the surface area of the sample in which the roughened particles have been formed can be measured with high precision.

本發明者們係藉由實施後述之特定的粗化鍍敷處理，成功的增大在雷射顯微鏡中無法測定之「陰」的部分或細微凹凸部分之表面積的比例。藉此，抑制粗化粒子之平均高度，有效的抑制傳輸高頻訊號時的傳輸損耗，同時發現到可大幅度提高與樹脂基材間之密接性，進而達成本發明。 The present inventors succeeded in increasing the ratio of the surface area of the "female" which cannot be measured in the laser microscope or the surface area of the fine uneven portion by performing the specific rough plating treatment described later. Thereby, the average height of the roughened particles is suppressed, the transmission loss at the time of transmitting the high-frequency signal is effectively suppressed, and the adhesion to the resin substrate can be greatly improved, and the present invention can be attained.

細微表面積係數(Cms)係指，藉由BET法所測定之表面積比相對於以雷射顯微鏡所測定之表面積比的比較值，該值係將在雷射顯微鏡中無法測定之「陰」的部分或細微凹凸部分之表面積的比例進行數值化後的結果。Cms的計算方法之細部內容，如同後述實施例中所記載之內容。在本發明之表面處理銅箔中，粗化處理面之Cms較佳為0.6以上且未達2.0。藉由將粗化處理面的Cms形成為0.6以上且未達2.0，而可更加提高該表面與樹脂基材間之密接性，以獲得在高溫下具有優越可靠度的覆銅積層板。 The fine surface area factor (Cms) is a comparison of the surface area ratio measured by the BET method with respect to the surface area ratio measured by a laser microscope, which is a portion of the "female" that cannot be measured in a laser microscope. Or the result of numerically calculating the ratio of the surface area of the fine uneven portion. The details of the calculation method of Cms are as described in the examples described later. In the surface-treated copper foil of the present invention, the Cms of the roughened surface is preferably 0.6 or more and less than 2.0. By forming the Cms of the roughened surface to 0.6 or more and less than 2.0, the adhesion between the surface and the resin substrate can be further improved, and a copper clad laminate having excellent reliability at a high temperature can be obtained.

在本發明之表面處理銅箔中，粗化處理面的Cms過大時，在高溫下之密接性有略顯降低的傾向。其理由雖尚未有所定論，不過可推斷為，當在雷射顯微鏡中無法測定之細微凹凸部分的表面積比例過大時，未填充樹脂之凹凸部便容易作為空隙而殘留，而以該空隙部分作為起點，在加熱時將加速樹脂界面之銅的氧化，造成密接性降低的原因之一。 In the surface-treated copper foil of the present invention, when the Cms of the roughened surface is too large, the adhesion at a high temperature tends to be slightly lowered. Although the reason for this has not been determined, it can be inferred that when the ratio of the surface area of the fine uneven portion which cannot be measured in the laser microscope is too large, the uneven portion of the unfilled resin is likely to remain as a void, and the void portion is used as the void portion. The starting point, which accelerates the oxidation of copper at the resin interface during heating, causes one of the reasons for the decrease in adhesion.

此外，在本發明之表面處理銅箔中，粗化處理面的Cms雖可未達0.6，不過，當Cms過小時，在高溫下會有降低密接性的傾向。其詳細的機制雖未有定論，不過，所謂Cms過小，係意味著在雷射顯微鏡中無 法測定的「陰」部分、或是細微的凹凸部分的比例較少的意思，可推斷其為機械性密接效果(一般而言，又稱之為定準效應)降低，使得在高溫下容易加速樹脂界面之銅的氧化的原因之一。因此，粗化處理面之Cms較佳為0.6以上且未達2.0，更佳為0.8以上且未達1.8。 Further, in the surface-treated copper foil of the present invention, the Cms of the roughened surface may not be 0.6, but when Cms is too small, the adhesion tends to be lowered at a high temperature. Although the detailed mechanism is not conclusive, the so-called Cms is too small, meaning that there is no laser microscope. The meaning of the "female" part measured by the method or the small proportion of the uneven portion can be inferred to be a mechanically dense effect (generally, also called a quasi-effect), which makes it easy to accelerate at high temperatures. One of the causes of oxidation of copper at the resin interface. Therefore, the Cms of the roughened surface is preferably 0.6 or more and less than 2.0, more preferably 0.8 or more and less than 1.8.

另外，利用雷射顯微鏡所測定之表面積與利用BET法所測定的表面積之間，由於表面積的測定原理不同，因此有可能會依據粗化處理面的形狀，產生Cms未達1的情況。 Further, since the surface area measured by the laser microscope and the surface area measured by the BET method differ in the principle of measuring the surface area, there is a possibility that the Cms does not reach 1 depending on the shape of the roughened surface.

在本發明之表面處理銅箔中，矽烷耦合劑處理前之形成有粗化粒子的表面，係具有由鉻(Cr)、鐵(Fe)、鈷(Co)、鎳(Ni)、銅(Cu)、鋅(Zn)、鉬(Mo)、及錫(Sn)選擇至少一種金屬的金屬處理層，或是較佳為具有由鉻、鐵、鈷、鎳、銅、鋅、鉬、及錫選擇至少兩種以上之金屬所形成之合金的金屬處理層。該金屬處理層係一種具有由鎳、鋅、及鉻選擇至少一種金屬的金屬處理層，或是較佳為一種具有由鎳、鋅、及鉻選擇兩種以上之金屬所形成之合金的金屬處理層。 In the surface-treated copper foil of the present invention, the surface on which the roughened particles are formed before the treatment with the decane coupling agent has chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), and copper (Cu). a zinc metal layer selected from the group consisting of chromium, iron, cobalt, nickel, nickel a metal treated layer of an alloy formed of at least two or more metals. The metal treatment layer is a metal treatment layer having at least one metal selected from nickel, zinc, and chromium, or preferably a metal treatment having an alloy formed by selecting two or more metals selected from nickel, zinc, and chromium. Floor.

本發明之表面處理銅箔所採用的覆銅積層板或印刷配線板的製作程序中，例如在樹脂與銅箔之間的接著程序、或是焊接程序等，經常進行加熱。藉由該加熱，使銅擴散至樹脂側，雖使銅與樹脂之間的密接性降低，不過，藉由設置上述金屬處理層而可防止銅的擴散，進而更加穩定的維持與樹脂基材之間的高度密接性。此外，構成金屬處理層的金屬，亦可作用為防止銅鏽之防鏽金屬 In the preparation procedure of the copper-clad laminate or the printed wiring board used for the surface-treated copper foil of the present invention, for example, a follow-up procedure between the resin and the copper foil, or a welding procedure is often performed. By this heating, copper is diffused to the resin side, and the adhesion between the copper and the resin is lowered. However, by providing the metal treatment layer, diffusion of copper can be prevented, and the resin substrate can be more stably maintained. High degree of closeness. In addition, the metal constituting the metal treatment layer can also act as a rust preventive metal for preventing rust.

從更加提升銅箔之蝕刻性的觀點來看，矽烷耦合劑處理前之在已形成粗化粒子的表面上，控制作為防鏽金屬之鎳量亦相當重要。亦即， 鎳附著量較多的情況下，雖然有難以產生銅鏽、且提升在高溫下之與樹脂間的密接性的傾向，但在蝕刻後卻容易殘留鎳，難以獲得充分的絕緣可靠度。在本發明之表面處理銅箔具有金屬處理層的情況下，從兼具高溫下之密接性與蝕刻性的觀點來看，金屬處理層中所含有的鎳元素量較佳為0.1mg/dm2以上且未達0.3mg/dm2。 From the viewpoint of further improving the etching property of the copper foil, it is also important to control the amount of nickel as a rust preventive metal on the surface on which the roughened particles have been formed before the decane coupling agent treatment. In other words, when there is a large amount of nickel adhesion, there is a tendency that copper rust is hard to occur and adhesion to a resin at a high temperature is promoted. However, nickel is likely to remain after etching, and it is difficult to obtain sufficient insulation reliability. In the case where the surface-treated copper foil of the present invention has a metal-treated layer, the amount of the nickel element contained in the metal-treated layer is preferably 0.1 mg/dm 2 from the viewpoint of having both high-temperature adhesion and etching property. Above and less than 0.3mg/dm 2 .

〔製造印刷配線板用表面處理銅箔〕 [Manufacture of surface treated copper foil for printed wiring board]

<銅箔> <copper foil>

作為在製造本發明之表面處理銅箔中所採用的銅箔，可因應用途或其他目的，選擇如壓延銅箔、電解銅箔等。 As the copper foil used in the production of the surface-treated copper foil of the present invention, for example, a rolled copper foil, an electrolytic copper foil or the like can be selected depending on the purpose of use or other purposes.

本發明之表面處理銅箔中所採用之銅箔的箔厚，並未有特別限制，可因應目的而做適當之挑選。而上述箔厚，一般為4~120μm，以5~50μm為佳，6~18μm為較佳。 The foil thickness of the copper foil used in the surface-treated copper foil of the present invention is not particularly limited, and may be appropriately selected depending on the purpose. The thickness of the foil is generally 4 to 120 μm, preferably 5 to 50 μm, and preferably 6 to 18 μm.

<粗化鍍敷處理> <Coarse plating treatment>

在製造本發明之表面處理銅箔中，上述粗化處理面的形成，可為在銅箔表面上以特定條件實施粗化鍍敷處理。亦即，本發明之依據為，本發明者們在將鉬濃度設定在特定範圍內，並且藉由在後述特定條件下實施電鍍處理，據此發現出可形成上述粗化處理面。 In the production of the surface-treated copper foil of the present invention, the roughening treatment surface may be formed by subjecting the surface of the copper foil to a roughening plating treatment under specific conditions. In other words, the present inventors have found that the molybdenum concentration is set within a specific range, and the plating treatment is performed under specific conditions described later, whereby it is found that the roughened surface can be formed.

(粗化鍍敷處理條件) (roughening plating treatment conditions)

為了可形成上述粗化處理面，在粗化鍍敷處理(電鍍處理)中，必須將鉬濃度控制在50mg/L以上且600mg/L以下。若鉬濃度未達50mg/L，則容易發生如粉體掉落等問題。此外，若超過600mg/L時，雖然能滿足其他特性，但卻難以將矽烷耦合劑處理後的表面(也就是粗化 處理面)之BET表面積比提升至1.2以上。 In order to form the roughened surface, it is necessary to control the molybdenum concentration to be 50 mg/L or more and 600 mg/L or less in the rough plating treatment (plating treatment). If the molybdenum concentration is less than 50 mg/L, problems such as powder falling are likely to occur. In addition, when it exceeds 600 mg/L, although it can satisfy other characteristics, it is difficult to roughen the surface after silane coupling agent treatment (that is, roughening) The BET surface area ratio of the treated surface is increased to 1.2 or more.

為了可形成上述粗化處理面，在粗化鍍敷處理中，必須將電極間隙間的流速設定在0.15m/秒以上且0.4m/秒以下。倘若電極間隙間的流速未達0.15m/秒時，在銅箔上發生之氫氣的脫離作業無法進行，難以獲得鉬的效果而導致發生粉體剝落等問題。此外，當電極間隙間的流速超過0.4m/秒後，對細微凹部之銅離子的供應便會過剩，使得凹部被電鍍所掩埋，難以將矽烷耦合劑處理後的表面之BET表面積比提高至1.2以上。 In order to form the roughened surface, the flow rate between the electrode gaps must be set to 0.15 m/sec or more and 0.4 m/sec or less in the roughening plating treatment. If the flow rate between the electrode gaps is less than 0.15 m/sec, the hydrogen gas detachment operation occurring on the copper foil cannot be performed, and it is difficult to obtain the effect of molybdenum, which causes problems such as powder peeling. Further, when the flow velocity between the electrode gaps exceeds 0.4 m/sec, the supply of copper ions to the fine recesses is excessive, so that the recesses are buried by plating, and it is difficult to increase the BET surface area ratio of the surface treated with the decane couplant to 1.2. the above.

為了可形成上述粗化處理面，在粗化鍍敷處理中，必須將電流密度乘以處理時間值設定在20(A/dm2)‧秒以上且250(A/dm2)‧秒以下。當該值未達20(A/dm2)‧秒時，在矽烷耦合劑處理後，由於粗化處理面之粗化粒子的高度難以形成為0.05μm以上，因此不容易確保與積層之樹脂間有充分的密接性。此外，若超過250(A/dm2)‧秒時，在矽烷耦合劑處理後，由於粗化處理面之粗化粒子的高度難以形成為未達0.5μm，因此容易造成傳輸損耗的惡化。上述之電流密度乘以處理時間值，較佳為20(A/dm2)‧秒以上、未達160(A/dm2)‧秒。 In order to form the roughened surface, in the rough plating process, it is necessary to set the current density multiplied by the processing time value to 20 (A/dm 2 ) ‧ seconds or more and 250 (A/dm 2 ) ‧ seconds or less. When the value is less than 20 (A/dm 2 ) ‧ seconds, the height of the roughened particles of the roughened surface is difficult to be formed to 0.05 μm or more after the decane coupling agent treatment, so that it is not easy to ensure the resin with the laminate There is sufficient adhesion. In addition, when it exceeds 250 (A/dm 2 ) ‧ seconds, it is difficult to form the roughened particles of the roughened surface to be less than 0.5 μm after the decane coupling agent treatment, and thus the transmission loss is likely to be deteriorated. The above current density is multiplied by the processing time value, preferably 20 (A/dm 2 ) ‧ seconds or more and less than 160 (A/dm 2 ) ‧ seconds

為了可形成上述粗化處理面，在粗化鍍敷處理中，必須將電流密度乘以處理時間值，且以鉬濃度所除之值設定在0.2{(A/dm2)‧秒}/(mg/L)以上。當該值未達0.2{(A/dm2)‧秒}/(mg/L)時，雖然可滿足其他特性，卻形成為難以將矽烷耦合劑處理後的表面之BET表面積比提高至1.2以上。此外，即使該值超過3.0{(A/dm2)‧秒}/(mg/L)，雖可能形成上述粗化處理面，但卻在滿足其他特性的同時，出現難以將粗化處理面之Cms形成為未達2.0的傾向。將上述電流密度乘以處理 時間值，除以Mo濃度之值，較佳為0.2{(A/dm2)‧秒}/(mg/L)以上、3.0{(A/dm2)‧秒}/(mg/L)以下，更佳為0.2{(A/dm2)‧秒}/(mg/L)以上、未達1.0{(A/dm2)‧秒}/(mg/L)。 In order to form the roughened surface, in the rough plating process, the current density must be multiplied by the processing time value, and the value divided by the molybdenum concentration is set at 0.2 {(A/dm 2 ) ‧ seconds}/( Mg/L) or more. When the value is less than 0.2 {(A/dm 2 ) ‧ sec}/(mg/L), although other characteristics can be satisfied, it is difficult to increase the BET surface area ratio of the surface treated with the decane coupling agent to 1.2 or more. . Further, even if the value exceeds 3.0 {(A/dm 2 ) ‧ sec}/(mg/L), the roughened surface may be formed, but it is difficult to roughen the surface while satisfying other characteristics. Cms is formed to a tendency of less than 2.0. The current density is multiplied by the processing time value and divided by the value of Mo concentration, preferably 0.2{(A/dm 2 )‧ seconds}/(mg/L) or more, 3.0{(A/dm 2 )‧ seconds} / (mg / L) or less, more preferably 0.2 {(A / dm 2 ) ‧ seconds} / (mg / L) or more, less than 1.0 { (A / dm 2 ) ‧ seconds} / (mg / L).

為可形成上述粗化處理面，而將較佳的粗化鍍敷處理條件揭示如下。 In order to form the roughened surface, the preferred rough plating treatment conditions are disclosed below.

-粗化鍍敷處理條件- - roughening plating treatment conditions -

Cu：10~30g/L Cu: 10~30g/L

H2SO4：100~200g/L H 2 SO 4 : 100~200g/L

浴溫：20~30℃ Bath temperature: 20~30°C

鉬濃度：50~600mg/L Molybdenum concentration: 50~600mg/L

電極間隙間的流速：0.15~0.4m/秒 Flow rate between electrode gaps: 0.15~0.4m/sec

電流密度：15~70A/dm2 Current density: 15~70A/dm 2

電流密度×處理時間：0.1~10秒 Current density × processing time: 0.1~10 seconds

電流密度×處理時間：20~250(A/dm2)‧秒 Current density × processing time: 20~250 (A/dm 2 ) ‧ seconds

電流密度×處理時間÷鉬濃度：0.2~3.0{(A/dm2)‧秒}/(mg/L) Current density × treatment time ÷ molybdenum concentration: 0.2~3.0{(A/dm 2 ) ‧ seconds}/(mg/L)

此外，將鉬添加至電鍍液係指，將鉬作為離子而溶解的形態、只要不包含使硫酸銅電鍍液的pH發生變化，且併入至鍍銅皮膜中的金屬不純物，則未有特別的限制。例如，可將鉬酸鹽(例如，鉬酸鈉或鉬酸鉀)的水溶液添加至硫酸銅電鍍液中。 Further, the addition of molybdenum to the plating solution means that the form in which molybdenum is dissolved as an ion does not have a special shape as long as it does not contain a metal impurity which changes the pH of the copper sulfate plating solution and is incorporated into the copper plating film. limit. For example, an aqueous solution of a molybdate (eg, sodium molybdate or potassium molybdate) can be added to the copper sulfate plating bath.

<金屬處理層> <Metal treatment layer>

當本發明之表面處理銅箔具有金屬處理層的情況下，金屬處理層的形成方法並未有特別限制，可利用一般方式來形成。例如，以形成具有鎳、鋅及鉻之金屬處理層的情況為例，在下述條件中，例如以鍍鎳、鍍鋅、鍍鉻的順序，而可形成金屬處理層。 In the case where the surface-treated copper foil of the present invention has a metal-treated layer, the method of forming the metal-treated layer is not particularly limited and can be formed by a general method. For example, in the case of forming a metal-treated layer having nickel, zinc, and chromium, a metal-treated layer can be formed in the following conditions, for example, in the order of nickel plating, zinc plating, or chrome plating.

(鍍鎳) (nickel plating)

Ni：10~100g/L Ni: 10~100g/L

H3BO3：1~50g/L H 3 BO 3 : 1~50g/L

PO2：0~10g/L PO 2 : 0~10g/L

浴溫：10~70℃ Bath temperature: 10~70°C

電流密度：1~50A/dm2 Current density: 1~50A/dm 2

處理時間：1秒~2分鐘 Processing time: 1 second ~ 2 minutes

pH：2.0~4.0 pH: 2.0~4.0

〔鍍鋅〕 [Zinc plating]

Zn：1~30g/L Zn: 1~30g/L

NaOH：10~300g/L NaOH: 10~300g/L

浴溫：5~60℃ Bath temperature: 5~60°C

電流密度：0.1~10A/dm2 Current density: 0.1~10A/dm 2

處理時間：1秒~2分鐘 Processing time: 1 second ~ 2 minutes

〔鍍鉻〕 〔chrome〕

Cr：0.5~40g/L Cr: 0.5~40g/L

浴溫：20~70℃ Bath temperature: 20~70°C

電流密度：0.1~10A/dm2 Current density: 0.1~10A/dm 2

處理時間：1秒~2分鐘 Processing time: 1 second ~ 2 minutes

pH：3.0以下 pH: 3.0 or less

本發明之表面處理銅箔，較佳為存在於粗化處理面上的矽元素量(亦即，於矽烷耦合劑層中所含有的矽元素量)為0.5μg/dm2以上且未達15μg/dm2。藉由將上述矽元素量設定為0.5μg/dm2以上且未達15μg/dm2，在抑制矽烷耦合劑之使用量的同時，還可有效的提高與樹脂間之密接性。矽烷耦合劑層中所含有的矽元素量，更佳為2μg/dm2以上且未達8μg/dm2。 In the surface-treated copper foil of the present invention, it is preferable that the amount of the lanthanum element present on the roughened surface (that is, the amount of lanthanum element contained in the decane coupling agent layer) is 0.5 μg/dm 2 or more and less than 15 μg. /dm 2 . By setting the amount of the lanthanum element to 0.5 μg/dm 2 or more and less than 15 μg/dm 2 , the amount of the decane coupling agent used can be suppressed, and the adhesion to the resin can be effectively improved. The amount of the lanthanum element contained in the decane coupling agent layer is more preferably 2 μg/dm 2 or more and less than 8 μg/dm 2 .

上述矽烷耦合劑係因應於構成與本發明之表面處理銅箔所積層之樹脂層的樹脂之分子構造(官能基的種類等)，而進行適當的選擇。其中，上述矽烷耦合劑較佳為由環氧基、胺基、乙烯基、(甲基)丙烯醯基、 苯乙烯基、脲基、異氰脲酸酯基、巰基、硫化物基、及異氰酸酯基選擇至少一種的官能基。「(甲基)丙烯醯基」為表示「丙烯醯基及/或甲基丙烯醯基」之意。 The decane coupling agent is appropriately selected in accordance with the molecular structure (type of functional group, etc.) of the resin constituting the resin layer laminated with the surface-treated copper foil of the present invention. Wherein, the above decane coupling agent is preferably an epoxy group, an amine group, a vinyl group, a (meth) acrylonitrile group, A functional group of at least one selected from the group consisting of a styryl group, a urea group, an isocyanurate group, a fluorenyl group, a sulfide group, and an isocyanate group. The "(meth)acryloyl group" means "acryloyl fluorenyl group and/or methacryl fluorenyl group".

藉由已形成粗化粒子之銅箔表面的矽烷耦合劑的處理，可藉由一般方式處理。例如，調製矽烷耦合劑的溶液(塗覆液)，將該塗覆液塗覆於已形成有粗化粒子的銅箔表面，並加以乾燥，藉此可使矽烷耦合劑吸附甚至是結合於已形成有粗化粒子的銅箔表面上。作為上述塗覆液，例如，採用的溶液可為使用純水而含有0.05wt%~1wt%之濃度的矽烷耦合劑。 The treatment of the decane coupling agent on the surface of the copper foil on which the roughened particles have been formed can be handled in a general manner. For example, a solution (coating liquid) of a decane coupling agent is prepared, and the coating liquid is applied to the surface of a copper foil on which roughened particles have been formed, and dried, whereby the decane coupling agent can be adsorbed or even bonded to The surface of the copper foil on which the roughened particles are formed. As the above coating liquid, for example, a solution to be used may be a decane coupling agent having a concentration of 0.05% by weight to 1% by weight using pure water.

上述塗覆液的塗覆方法並未有特別限制，例如可在傾斜銅箔的狀態下，將塗覆液均勻地流動於已形成有粗化粒子的表面上，使用輥輪而去除多餘液體後加以加熱乾燥，在輥輪間，在使已形成粗化粒子之表面朝下而撐開的銅箔上，噴霧塗覆液，再以輥輪去除多餘液體後進行加熱乾燥等作業，而實施塗覆。塗覆溫度並未有特別限制，通常係以10~40℃來實施。 The coating method of the above coating liquid is not particularly limited. For example, the coating liquid can be uniformly flowed on the surface on which the roughened particles have been formed in the state of the inclined copper foil, and the excess liquid can be removed by using a roller. It is heated and dried, and the coating liquid is sprayed on the copper foil which has the surface on which the roughened particles are formed to face downward, and the excess liquid is removed by a roller, and then heat-drying is performed, and the coating is performed. cover. The coating temperature is not particularly limited and is usually carried out at 10 to 40 °C.

〔印刷配線板用覆銅積層板〕 [Copper-clad laminate for printed wiring board]

本發明之印刷配線板用覆銅積層板(以下，簡稱為「本發明之覆銅積層板」)，係在本發明之表面處理銅箔之粗化處理面上，具有已積層樹脂層(樹脂基材)的構造。關於該樹脂層並未有特別限制，所採用之樹脂層，可以是在用以製作印刷配線板的覆銅積層板中，一般所採用的樹脂層。舉例來說，可採用在硬板(rigid board)(硬印刷配線板)中所使用的玻璃-環氧系(glass epoxy-based)之無鹵素低介電樹脂基材，或是採用可撓性基板中所經常使用的聚醯亞胺系之低介電樹脂基材。 The copper-clad laminate for a printed wiring board of the present invention (hereinafter, simply referred to as "the copper-clad laminate of the present invention") has a laminated resin layer (resin) on the roughened surface of the surface-treated copper foil of the present invention. The structure of the substrate). The resin layer is not particularly limited, and the resin layer to be used may be a resin layer generally used in a copper-clad laminate for producing a printed wiring board. For example, a glass epoxy-based halogen-free low dielectric resin substrate used in a rigid board (hard printed wiring board) may be used, or flexibility may be employed. A polyimide-based low dielectric resin substrate which is often used in substrates.

表面處理銅箔與樹脂基材之間的積層方法並未有特別限制，例如，藉由使用熱壓加工機的熱壓成形法等，使銅箔與樹脂基材接著。在上述熱壓成形法中的加壓溫度，係以設定成150~400℃左右為佳。此外，加壓面壓力以設定成1~50MPa左右為佳。 The method of laminating between the surface-treated copper foil and the resin substrate is not particularly limited. For example, the copper foil is bonded to the resin substrate by a hot press forming method using a hot press machine or the like. The pressurization temperature in the above hot press forming method is preferably set to about 150 to 400 °C. Further, the pressure of the pressurizing surface is preferably set to about 1 to 50 MPa.

覆銅積層板的厚度以10~1000μm為佳。 The thickness of the copper clad laminate is preferably 10 to 1000 μm.

〔印刷配線板〕 [Printed wiring board]

本發明之印刷配線板係使用本發明之覆銅積層板而製作。亦即，將本發明之覆銅積層板實施蝕刻等處理，形成導體電路圖形，更可因應需要，而藉由一般方式形成或是搭載其他構件而形成者。 The printed wiring board of the present invention is produced by using the copper clad laminate of the present invention. In other words, the copper clad laminate of the present invention is subjected to etching or the like to form a conductor circuit pattern, and may be formed by a general method or by mounting another member as needed.

實施例 Example

以下，根據實施例，更加詳細說明本發明。此外，以下為本發明之一例，在本發明的實施中，只要在不背離本發明之要旨的範圍內，均可採用各種形態。 Hereinafter, the present invention will be described in more detail based on examples. In addition, the following is an example of the invention, and various aspects can be employed in the practice of the invention without departing from the spirit and scope of the invention.

〔製造銅箔〕 [Manufacture of copper foil]

作為用以實施粗化處理之基材的銅箔，使用電解銅箔或壓延銅箔。 As the copper foil for performing the roughening treatment, an electrolytic copper foil or a rolled copper foil is used.

在實施例2~4、6~16、比較例1~4、6、7及參考例1之中，使用的係由以下述條件所製造之厚度為12μm的電解銅箔。 In Examples 2 to 4, 6 to 16, Comparative Examples 1 to 4, 6, and 7 and Reference Example 1, an electrolytic copper foil having a thickness of 12 μm which was produced under the following conditions was used.

<電解銅箔的製造條件> <Manufacturing conditions of electrolytic copper foil>

CuSO4：280g/L CuSO 4 : 280g / L

H2SO4：70g/L H 2 SO 4 : 70g/L

氯濃度：25mg/L Chlorine concentration: 25mg/L

浴溫：55℃ Bath temperature: 55 ° C

電流密度：45A/dm2 Current density: 45A/dm 2

添加劑 additive

‧3-巰基1-丙烷磺酸鈉：2mg/L ‧3-Sodium 1-propanesulfonate: 2mg/L

‧羥乙基纖維素：10mg/L ‧ Hydroxyethyl cellulose: 10mg/L

‧低分子量膠(分子量3000)：50mg/L ‧Low molecular weight glue (molecular weight 3000): 50mg/L

在實施例1、5、及比較例5中，對於市售的12μm之精煉銅壓延箔(株式會社UACJ製)，為使用以下述條件實施脫脂處理之物。 In the first and fifth examples and the comparative example 5, the commercially available 12 μm refined copper rolled foil (manufactured by UACJ Co., Ltd.) was subjected to degreasing treatment under the following conditions.

<脫脂處理條件> <Degreasing treatment conditions>

脫脂溶液：清洗劑160S(Meltec株式會社製)的水溶液 Degreasing solution: an aqueous solution of a cleaning agent 160S (manufactured by Meltec Co., Ltd.)

脫脂溶液濃度：60g/L水溶液 Degreasing solution concentration: 60g / L aqueous solution

浴溫：60℃ Bath temperature: 60 ° C

電流密度：3A/dm2 Current density: 3A/dm 2

通電時間：10秒 Power-on time: 10 seconds

〔形成粗化處理面〕 [Formation of roughened surface]

藉由電鍍處理，而於上述銅箔的單面實施粗化鍍敷處理。上述粗化鍍敷處理面，係使用下述粗化鍍敷液基本浴組成，將鉬濃度設定為如下述表1所記載之內容，且將電極間隙間的流速、電流密度、處理時間設定成如下述表1所記載，形成上述粗化鍍敷處理面。鉬濃度為藉由將鉬酸鈉已溶解至純水中的水溶液添加至基本浴中而進行調整。 The roughening plating treatment is performed on one surface of the copper foil by a plating treatment. The roughening plating treatment surface is a basic bath composition using the following roughening plating solution, and the molybdenum concentration is set as described in Table 1 below, and the flow velocity, current density, and treatment time between the electrode gaps are set to The roughened plating treatment surface was formed as described in Table 1 below. The molybdenum concentration is adjusted by adding an aqueous solution in which sodium molybdate has been dissolved to pure water to the base bath.

<粗化鍍敷液基本浴組成> <Coarse plating solution basic bath composition>

Cu：25g/L Cu: 25g/L

H2SO4：180g/L H 2 SO 4 : 180g/L

浴溫：25℃ Bath temperature: 25 ° C

<金形成屬處理層> <Gold forming genus treatment layer>

接著，針對實施例1~6、8~16及比較例1~3、5~7，在如上所 述而形成的粗化鍍敷處理面上，再以表2所記載的電鍍條件，以Ni、Zn、Cr的順序實施金屬電鍍，形成金屬處理層。 Next, with respect to Examples 1 to 6, 8 to 16, and Comparative Examples 1 to 3 and 5 to 7, as described above The roughened plating surface formed as described above was subjected to metal plating in the order of Ni, Zn, and Cr in the plating conditions described in Table 2 to form a metal treated layer.

<鍍鎳> <nickel plating>

Ni：40g/L Ni: 40g/L

H3BO3：5g/L H 3 BO 3 : 5g/L

浴溫：20℃ Bath temperature: 20 ° C

pH：3.6 pH: 3.6

<鍍鋅> <galvanized>

Zn：2.5g/L Zn: 2.5g/L

NaOH：40g/L NaOH: 40g / L

浴溫：20℃ Bath temperature: 20 ° C

〔鍍鉻〕 〔chrome〕

Cr：5g/L Cr: 5g/L

浴溫：30℃ Bath temperature: 30 ° C

pH：2.2 pH: 2.2

<塗覆矽烷耦合劑(形成粗化處理面)> <Coated decane coupling agent (formation of roughened surface)>

針對實施例1~16及比較例1~7，在粗化鍍敷處理面(若已形成金屬處理層的情況下則為金屬處理層表面)之整體上，塗覆於表2所記載之市售矽烷耦合劑的溶液(30℃)，以刮刀(squeegee)去除多餘溶液後，在120℃大氣下乾燥30秒的期間，形成粗化處理面。各矽烷耦合劑之溶液的調製方法如下所述。 With respect to Examples 1 to 16 and Comparative Examples 1 to 7, the entire surface of the roughened plating treatment surface (the surface of the metal treatment layer in the case where the metal treatment layer was formed) was applied to the market described in Table 2. A solution of the decane coupling agent (30 ° C) was sold, and the excess solution was removed by a squeegee, and then dried at 120 ° C for 30 seconds to form a roughened surface. The preparation method of the solution of each decane coupling agent is as follows.

3-環氧丙氧基丙基甲基二甲氧基矽烷(3-Glycidoxypropylmethyldimethoxysilane)(信越化學株式會社製KBM-402)：以純水調製0.3wt%溶液。 3-Glycidoxypropylmethyldimethoxysilane (KBM-402, manufactured by Shin-Etsu Chemical Co., Ltd.): A 0.3 wt% solution was prepared in pure water.

3-胺丙基三甲氧基矽烷(3-Aminopropyltrimethoxysilane)(信越化學株式會社製KBM-903)：以純水調製0.25wt%溶液。 3-Aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.): A 0.25 wt% solution was prepared with pure water.

乙烯基三甲氧基矽烷(Vinyltrimethoxysilane)(信越化學株式會社製KBM-1003)：在純水添加硫酸，以調整為pH3的溶液調製0.2wt%溶液。 Vinyltrimethoxysilane (KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.): sulfuric acid was added to pure water, and a 0.2 wt% solution was prepared by adjusting the solution to pH 3.

3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷(3-Methacryloxypropylmethyldimethoxysilane)(信越化學株式會社製KBM-502)：在純水添加硫酸，以調整為pH3的溶液調製0.25wt%溶液。 3-Methacryloxypropylmethyldimethoxysilane (KBM-502, manufactured by Shin-Etsu Chemical Co., Ltd.): sulfuric acid was added to pure water to prepare a 0.25 wt% solution with a solution adjusted to pH 3. .

3-異氰酸酯丙基三乙氧基矽烷(3-Isocyanatopropyl triethoxysilane)(信越化學株式會社製KBE-9007)：在純水中添加硫酸，以調整為pH3的溶液調製0.2wt%溶液。 3-Isocyanatopropyl triethoxysilane (KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.): sulfuric acid was added to pure water to prepare a 0.2 wt% solution with a solution adjusted to pH 3.

3-脲基丙基三乙氧基矽烷(3-Ureidopropyltriethoxysilane)(信越化學株式會社製KBE-585)：將乙醇與純水以1：1混合，將該混合溶液調製0.3wt%溶液。 3-Ureidopropyltriethoxysilane (KBE-585, manufactured by Shin-Etsu Chemical Co., Ltd.): Ethanol was mixed with pure water at 1:1, and the mixed solution was adjusted to a 0.3 wt% solution.

〔測定粗化粒子的平均高度〕 [Measure the average height of roughened particles]

藉由SEM影像觀察與經過離子研磨處理所得之銅箔厚度方向呈平行之斷面，求出在粗化處理面中之粗化粒子的平均高度。詳細內容說明如下。 The average height of the roughened particles in the roughened surface was determined by observing the cross section in the thickness direction of the copper foil obtained by the ion milling treatment by SEM image. The details are explained below.

圖1所示的SEM影像，係平行於在實施例5製造之表面處理銅箔的粗化處理面(矽烷耦合劑處理後的表面)之厚度方向的斷面。同様的，在各個表面處理銅箔的斷面中，在視野範圍內可確認到粗化粒子之頭頂部與底部，並且，將倍率調節至可觀察到約十個左右的粗化粒子，在無限制之下針對不同的五個視野進行SEM影像觀察。分別對一個表面處理銅箔中之五個視野範圍內，測定高度最高之粗化粒子的高度，將所得之五個測定值(最大值)之平均，設為在該表面處理銅箔之粗化處理面中的粗化粒子之平均高度。 The SEM image shown in Fig. 1 is a section parallel to the thickness direction of the roughened surface (the surface after the decane coupling agent treatment) of the surface-treated copper foil produced in Example 5. In the cross section of each surface treated copper foil, the top and bottom of the roughened particles can be confirmed in the field of view, and the magnification is adjusted to observe about ten rough particles, in the absence of SEM imaging was performed for different five fields of view under the restriction. The heights of the coarsest particles having the highest height were measured in the five fields of view of one surface-treated copper foil, and the average of the obtained five measured values (maximum values) was set as the roughening of the surface-treated copper foil. The average height of the roughened particles in the treated surface.

使用圖面詳細說明粗化粒子之高度的測定方法。如圖1所示，針對作為測定對象的粗化粒子，連結左右最底部之直線(連結a點與b點的直線)的最短距離為最長，將該粗化粒子之頭頂部(c點)與連結a點及b點之直線間的最短距離，設為粗化粒子的高度H。 The method of measuring the height of the roughened particles will be described in detail using the drawings. As shown in Fig. 1, the shortest distance between the left and right straight lines (the straight line connecting the a point and the b point) is the longest for the roughened particles to be measured, and the top of the roughened particles (point c) is The shortest distance between the straight lines connecting the points a and b is the height H of the roughened particles.

圖2所示的SEM影像係平行於在實施例6製造之表面處理銅箔的粗化處理面(矽烷耦合劑處理後的表面)之厚度方向的斷面。當粗化粒子形成如所示之分枝狀況時，為將包含分枝構造的整體視為一個粗化粒子。亦即，連結形成為樹枝狀之粗化粒子的左右最底部之直線(連結d點與e點的直線)的最短距離為最長，將該粗化粒子之頭頂部(f點)與連結d點及e點之直線間的最短距離，設為粗化粒子的高度H。 The SEM image shown in Fig. 2 is parallel to the cross section in the thickness direction of the roughened surface (surface after the decane coupling agent treatment) of the surface-treated copper foil produced in Example 6. When the roughened particles form a branching condition as shown, the whole comprising the branched structure is considered to be one roughened particle. In other words, the shortest distance between the left and rightmost straight lines (the straight line connecting the d point and the e point) which are formed into dendritic roughened particles is the longest, and the top of the roughened particle (point f) and the connected d point The shortest distance between the straight lines of the point e and the height H of the roughened particles.

將結果揭示於下述表3。 The results are disclosed in Table 3 below.

〔測定BET表面積比A〕 [Measure BET surface area ratio A]

BET表面積比A的計算，為將以BET法所測定之粗化處理面的表面積(BET測定表面積)，除以形成俯視面積之試料切出面積而求得。 The calculation of the BET surface area ratio A is obtained by dividing the surface area (BET measurement surface area) of the roughened surface measured by the BET method by the sample cut-out area in which the plan view area is formed.

BET測定表面積係使用Micromeritics公司製氣體吸附細孔分布測定裝置ASAP2020型，利用氪氣吸附BET多點法進行測定。在測定前，前處理係在150℃的溫度下進行6小時的減壓乾燥。 The BET measurement surface area was measured using a gas adsorption pore size distribution measuring apparatus ASAP2020 manufactured by Micromeritics Co., Ltd., and measured by a helium gas adsorption BET multipoint method. Prior to the measurement, the pretreatment was dried under reduced pressure for 6 hours at a temperature of 150 °C.

在測定中使用的試料(銅箔)係在切出形成約3g的3dm2，再切割成5mm方形後，導入測定裝置內。 The sample (copper foil) used for the measurement was cut into a 3 dm 2 of about 3 g, cut into a 5 mm square, and then introduced into a measuring apparatus.

在藉由BET法進行表面積測定中，由於是測定導入至裝置內的試料全面之表面積，因此，無法只測定已實施單面粗化處理之上述表面處理銅箔中僅實施該粗化處理面的表面積。在此，BET表面積比A，實 際上係如下所述計算而得。 In the surface area measurement by the BET method, since the total surface area of the sample introduced into the apparatus is measured, it is not possible to measure only the roughened surface of the surface-treated copper foil subjected to the one-side roughening treatment. Surface area. Here, the BET surface area ratio A, The system is calculated as follows.

<計算BET表面積比A> <Calculate BET surface area ratio A>

將未實施粗化處理之面(與上述粗化處理面相反側之面)的表面積比設為1，也就是視為與試料切出面積相同，利用下述式而計算出BET表面積比A。 The surface area ratio of the surface on which the roughening treatment was not performed (the surface opposite to the roughened surface) was set to 1, that is, the same as the sample cut-out area, and the BET surface area ratio A was calculated by the following formula.

(BET表面積比A)=〔(BET測定表面積)-(試料切出面積)〕/(試料切出面積) (BET surface area ratio A) = [(BET measurement surface area) - (sample cut-out area)] / (sample cut-out area)

此外，在BET法的表面積測定方面，對於粗化處理面以及未實施粗化處理之面以外的面(側面)的表面積亦進行測定，不過，在本發明所推定的箔厚(例如，即使最大也在120μm左右)中，在全俯視面積中側面所佔的比例極少，實際上可以忽略。 Further, in terms of surface area measurement by the BET method, the surface area of the roughened surface and the surface (side surface) other than the roughened surface is also measured, but the thickness of the foil estimated in the present invention (for example, even the largest Also in the case of about 120 μm, the proportion of the side surface in the entire plan view area is extremely small, and can be practically ignored.

如參考例1所示，在表面未實施粗化處理的對象物中，由於BET法的測定原理，而有BET測定表面積小於切出面積的情況(亦即，BET表面積比A有形成未達1的情況)。另一方面，因粗化處理而形成表面具有細微凹凸的情況下，由於適用BET法，因此可高感度的檢測出細微的凹凸等，其結果，形成BET表面積比A超過1。 As shown in Reference Example 1, in the object whose surface was not subjected to the roughening treatment, the BET measurement surface area was smaller than the cut-out area due to the measurement principle of the BET method (that is, the BET surface area ratio A was not formed up to 1). Case). On the other hand, when the surface is formed with fine unevenness by the roughening treatment, since the BET method is applied, fine unevenness or the like can be detected with high sensitivity, and as a result, the BET surface area ratio A is more than 1.

〔測定雷射表面積比B〕 [Measurement of laser surface area ratio B]

雷射表面積比B，為根據使用雷射顯微鏡VK8500(Keyence公司製)之表面積測定值而計算。更詳細來說，以倍率1000倍觀察試料(銅箔)的粗化處理面，測定平面視面積6550μm2部分的三維表面積，藉由將該三維表面積除以6550μm2而求得雷射表面積比B。測定間距設為0.01μm。將結果揭示於表3。 The laser surface area ratio B was calculated based on the surface area measurement value using a laser microscope VK8500 (manufactured by Keyence Corporation). More specifically, the roughened surface of the sample (copper foil) was observed at a magnification of 1000 times, and the three-dimensional surface area of the portion of the plane viewing area of 6550 μm 2 was measured, and the laser surface area ratio B was determined by dividing the three-dimensional surface area by 6550 μm 2 . . The measurement pitch was set to 0.01 μm. The results are disclosed in Table 3.

〔計算細微表面係數Cms〕 [Calculate the fine surface coefficient Cms]

細微表面係數Cms係使用上述BET表面積比A與上述雷射表面積比B，根據下述公式計算而得。將結果揭示於下述表3。 The fine surface coefficient Cms is calculated by the following formula using the above BET surface area ratio A and the above-described laser surface area ratio B. The results are disclosed in Table 3 below.

細微表面係數Cms=BET表面積比A/雷射表面積比B Fine surface coefficient Cms = BET surface area ratio A / laser surface area ratio B

〔鎳的測定〕 [Measurement of Nickel]

鎳元素量(mg/dm2)的測定係在以塗料標記試料之未實施粗化鍍敷處理的面後，切出10cm方形，以加溫至80℃之混合酸(硝酸2：鹽酸1：純水5(體積比))僅溶解表面部後，將所獲得之溶液中的鎳質量，使用日立High-Tech Science公司製的原子吸光光度計(型式：Z-2300)，藉由原子吸光分析法進行定量分析而求出。將結果於下述表3以鎳元素量所揭示。此外，以上述方式測定的鎳元素量，亦即金屬處理層中所含有的鎳元素量。 The amount of nickel element (mg/dm 2 ) was measured after the surface of the paint-labeled sample which was not subjected to the roughening plating treatment, and a mixed acid of 10 cm square was prepared to be heated to 80 ° C (nitric acid 2: hydrochloric acid 1: Pure water 5 (volume ratio)) After only dissolving the surface portion, the mass of nickel in the obtained solution was analyzed by atomic absorption using an atomic absorption spectrophotometer (type: Z-2300) manufactured by Hitachi High-Tech Science Co., Ltd. The method is obtained by quantitative analysis. The results are shown in Table 3 below as the amount of nickel element. Further, the amount of the nickel element measured in the above manner, that is, the amount of the nickel element contained in the metal treated layer.

〔矽的測定〕 [Measurement of 矽]

粗化處理面之矽元素量(μg/dm2)(亦即，在矽烷耦合劑層中所含有的矽元素量)，係設定成與鎳元素量相同，藉由原子吸光分析法實施定量分析而求得矽元素量。將結果以矽元素量揭示於下述表3。 The amount of lanthanum element (μg/dm 2 ) in the roughened surface (that is, the amount of lanthanum element contained in the decane coupling agent layer) is set to be the same as the amount of nickel element, and quantitative analysis is performed by atomic absorption spectrometry. And find the amount of 矽 element. The results are disclosed in Table 3 below as the amount of ruthenium element.

〔高頻特性的評估〕 [Evaluation of high frequency characteristics]

測定在高頻波段中的傳輸損耗，作為高頻特性的評估。將上述各實施例及比較例所製造之具有粗化處理面的表面處理銅箔之該粗化處理面(以矽烷耦合劑所處理之面)，張貼至株式會社KANEKA製的貼合用聚醯亞胺之PIXEO(FRS-522厚度12.5μm)，以溫度350℃、面壓5MPa的條件加壓20分鐘，將其作為覆銅積層板，接著形成寬度為100μm、長度40mm之微帶線(microstripline)的傳輸路徑。在該傳輸路徑中，使用網路分析儀，傳輸100GHz為止的高頻訊號，測定傳輸損耗。特性阻抗為50Ω。 The transmission loss in the high frequency band was measured as an evaluation of the high frequency characteristics. The roughened surface (the surface treated with the decane coupling agent) of the surface-treated copper foil having the roughened surface produced in each of the above-mentioned Examples and Comparative Examples was attached to a bonding polysiloxane manufactured by KANEKA Co., Ltd. The imine PIXEO (FRS-522 thickness 12.5 μm) was pressed at a temperature of 350 ° C and a surface pressure of 5 MPa for 20 minutes, and this was used as a copper clad laminate, followed by formation of a microstrip line having a width of 100 μm and a length of 40 mm. ) The transmission path. In this transmission path, a high-frequency signal up to 100 GHz is transmitted using a network analyzer to measure transmission loss. The characteristic impedance is 50Ω.

傳輸損耗的測定值係如果絕對值越小，則傳輸損耗越少，意味著具有良好的高頻特性。在表4中，係記載於20GHz與70GHz中之傳輸損耗的評估結果。其評估基準係如下所述。 The measured value of the transmission loss is such that the smaller the absolute value is, the smaller the transmission loss is, which means that it has good high frequency characteristics. In Table 4, the evaluation results of the transmission loss in 20 GHz and 70 GHz are described. The evaluation criteria are as follows.

<20GHz的傳輸損耗評估基準> <20GHz transmission loss evaluation benchmark>

◎：傳輸損耗為-6.2dB以上 ◎: Transmission loss is -6.2dB or more

○：傳輸損耗未達-6.2dB至-6.5dB以上 ○: Transmission loss does not reach -6.2dB to -6.5dB or more

×：傳輸損耗未達-6.5dB ×: Transmission loss is less than -6.5dB

<70GHz之傳輸損耗評估基準> <70GHz transmission loss evaluation benchmark>

◎：傳輸損耗為-20.6dB以上 ◎: Transmission loss is -20.6dB or more

○：傳輸損耗未達-20.6dB至-24.0dB以上 ○: Transmission loss is less than -20.6dB to -24.0dB

×：未達-24.0dB ×: not up to -24.0dB

再著，根據上述傳輸損耗的評估結果，綜合評估依據下述評估基準的高頻特性。將結果揭示於下述表4。 Further, based on the above evaluation results of the transmission loss, the high frequency characteristics based on the following evaluation criteria are comprehensively evaluated. The results are disclosed in Table 4 below.

<高頻特性綜合評估基準> <High-frequency characteristics comprehensive evaluation criteria>

◎(優良)：20GHz之傳輸損耗與70GHz之傳輸損耗的評估結果，均為◎。 ◎ (Excellent): The evaluation results of the transmission loss of 20 GHz and the transmission loss of 70 GHz are both ◎.

○(良)：20GHz之傳輸損耗的評估結果為◎，70GHz之傳輸損耗的評估結果為○。 ○ (good): The evaluation result of the transmission loss at 20 GHz was ◎, and the evaluation result of the transmission loss at 70 GHz was ○.

△(合格)：70GHz之傳輸損耗的評估結果雖為×，但20GHz之傳輸損耗為◎或○。 △ (pass): Although the evaluation result of the transmission loss at 70 GHz is ×, the transmission loss at 20 GHz is ◎ or ○.

×(不合格)：20GHz之傳輸損耗與70GHz之傳輸損耗的評估結果，均為×。 × (failed): The evaluation results of the transmission loss of 20 GHz and the transmission loss of 70 GHz are both ×.

〔耐熱密接性的評估〕 [Evaluation of heat-resistance adhesion]

以上述〔高頻特性的評估〕製作之覆銅積層板相同的方式製作覆銅積層板，將所獲得的覆銅積層板之銅箔部以寬度10mm的膠帶進行標記。在對該覆銅積層板實施氯化銅蝕刻後去除膠帶，製作出10mm寬的電路配線板。將該電路配線板在150℃的加熱爐中加熱1000小時後，於常溫下使用東洋精機製作所社製的Tensilon(拉伸/壓縮)測試機，就電路配線板之寬度10mm的電路配線部分(銅箔部分)，在90度方向上以50mm/分的速度，測定自聚醯亞胺樹脂基材剝離時的剝離強度。將所得之測定 值作為指標，根據下述評估基準而評估耐熱密接性。將結果揭示於下述表4。 A copper clad laminate was produced in the same manner as the copper clad laminate produced in the above [Evaluation of high frequency characteristics], and the copper foil portion of the obtained copper clad laminate was marked with a tape having a width of 10 mm. After the copper clad laminate was subjected to copper chloride etching, the tape was removed to produce a circuit board having a width of 10 mm. After heating the circuit board in a heating furnace at 150 ° C for 1,000 hours, a Tensilon (stretching/compression) tester manufactured by Toyo Seiki Seisakusho Co., Ltd. was used at room temperature, and a circuit wiring portion having a width of 10 mm of the circuit wiring board (copper) The foil portion) was measured for peel strength at the time of peeling from the polyimide film substrate at a speed of 50 mm/min in a 90-degree direction. The resulting measurement The value was used as an index to evaluate the heat-resistant adhesion according to the following evaluation criteria. The results are disclosed in Table 4 below.

<耐熱密接性的評估基準> <Evaluation criteria for heat-resistant adhesion>

◎：剝離強度為0.7kN/m以上 ◎: Peel strength is 0.7kN/m or more

○：剝離強度為0.6kN/m以上且未達0.7kN/m ○: Peel strength is 0.6 kN/m or more and less than 0.7 kN/m

△：剝離強度為0.5kN/m以上且未達0.6kN/m △: Peel strength is 0.5 kN/m or more and less than 0.6 kN/m

×：剝離強度未達0.5kN/m ×: Peel strength is less than 0.5kN/m

〔蝕刻性的評估〕 [Evaluation of etching property]

若對銅箔表面之金屬附著量過多時，在進行為了形成電路的蝕刻之際，將形成為金屬殘渣容易殘留於樹脂基材表面。當金屬殘渣殘留在樹脂基材表面後，將會導致絕緣阻抗降低之不良情況。尤其因為鎳的蝕刻速度小於銅，因此當附著量過大時，將會降低絕緣性，容易造成短路。 When the amount of metal adhesion to the surface of the copper foil is too large, the metal residue is likely to remain on the surface of the resin substrate when etching for forming a circuit. When the metal residue remains on the surface of the resin substrate, the insulation resistance is lowered. In particular, since the etching speed of nickel is smaller than that of copper, when the amount of adhesion is too large, the insulation property is lowered and a short circuit is easily caused.

在此，使用與以上述〔高頻特性的評估〕所製作之覆銅積層板相同的方式而製作之覆銅積層板，根據IPC實驗規格TM-650的2.5.17，測定絕緣阻抗值。更加詳細來說，為將上述覆銅積層板切出10cm×10cm的尺寸，以蝕刻形成銅箔圖形。根據實驗規格，以三次實施表面阻抗的測定，求得三次測定值的平均值。將所獲得之表面阻抗值的平均值作為指標，依據下述評估基準進行蝕刻性的評估。將結果揭示於下述表3。 Here, the copper clad laminate produced in the same manner as the copper clad laminate produced in the above [Evaluation of High Frequency Characteristics] was used, and the insulation resistance value was measured in accordance with 2.5.17 of IPC Test Specification TM-650. More specifically, in order to cut the copper clad laminate by a size of 10 cm × 10 cm, a copper foil pattern was formed by etching. The average value of the three measured values was obtained by measuring the surface impedance three times in accordance with the experimental specifications. The average value of the obtained surface resistance values was used as an index, and the etching property was evaluated based on the following evaluation criteria. The results are disclosed in Table 3 below.

<蝕刻性的評估基準> <Evaluation criteria for etching property>

◎：表面阻抗值的平均值為1014Ω以上。 ◎: The average value of the surface resistance value is 1014 Ω or more.

○：表面阻抗值的平均值為1013Ω以上且未達1014Ω。 ○: The average value of the surface resistance values was 1013 Ω or more and less than 1014 Ω.

×：表面阻抗值的平均值為未達1013Ω。 ×: The average value of the surface resistance values is less than 1013 Ω.

〔綜合評估〕 〔Comprehensive Evaluation〕

綜整上述之高頻特性、耐熱密接性及蝕刻性之全數資料，根據下述評估基準進行綜合評估。 The above-mentioned full-scale data of high-frequency characteristics, heat-resistant adhesion, and etchability are comprehensively evaluated based on the following evaluation criteria.

<綜合評估的評估基準> <Evaluation criteria for comprehensive evaluation>

AA(優良)：高頻特性之綜合評估、耐熱密接性及蝕刻性的評估結果，均為◎。 AA (excellent): The evaluation results of the high-frequency characteristics, the heat-resistant adhesion, and the etching property were all ◎.

A(良)：高頻特性之綜合評估、耐熱密接性及蝕刻性中之○評估有一個，其餘的兩個評估為◎。 A (good): There is one evaluation of the high-frequency characteristics, the heat-resistant adhesion and the etching property, and the other two evaluations are ◎.

B(合格)：不屬於上述AA及A之任一狀況，但無評估為×的狀況。 B (Qualified): A condition that does not belong to any of the above AA and A, but has no evaluation as ×.

C(不合格)：高頻特性之綜合評估、耐熱密接性及蝕刻性中，至少一個的評估結果為×。 C (failed): At least one of the evaluation results of the high-frequency characteristics, the heat-resistant adhesion, and the etching property is ×.

在此，探討上述各表中所示之結果。 Here, the results shown in the above tables are discussed.

比較例1係存在於表面處理銅箔之粗化處理面上的粗化粒子之平均高度小於本發明所規定之例。當使用比較例1之表面處理銅箔製作覆銅積層板的情況下，發生有銅箔與樹脂基材間之耐熱密接性惡化的結果。 In Comparative Example 1, the average height of the roughened particles present on the roughened surface of the surface-treated copper foil was smaller than that stipulated in the present invention. When a copper-clad laminate was produced using the surface-treated copper foil of Comparative Example 1, the heat-resistant adhesiveness between the copper foil and the resin substrate deteriorated.

比較例2、3、6及7分別係表面處理銅箔之粗化處理面的 BET表面積比小於本發明所規定之例。當使用比較例2、3、6及7之表面處理銅箔製作覆銅積層板的情況下，發生有銅箔與樹脂基材間之耐熱密接性惡化的結果。 Comparative Examples 2, 3, 6, and 7 are the roughened surfaces of the surface treated copper foil, respectively. The BET surface area ratio is smaller than the example stipulated by the present invention. When the copper-clad laminate was produced using the surface-treated copper foils of Comparative Examples 2, 3, 6, and 7, the heat-resistant adhesiveness between the copper foil and the resin substrate was deteriorated.

比較例4及5分別係存在於表面處理銅箔之粗化處理面上的粗化粒子之平均高度大於本發明所規定之例。當使用比較例4及5之表面處理銅箔製作覆銅積層板、形成導體電路的情況下，發生有高頻特性大幅惡化的結果。 In Comparative Examples 4 and 5, the average height of the roughened particles present on the roughened surface of the surface-treated copper foil was larger than that stipulated in the present invention. When a copper clad laminate was produced using the surface-treated copper foils of Comparative Examples 4 and 5 to form a conductor circuit, the high-frequency characteristics were greatly deteriorated.

此外，參考例1係在銅箔上未實施粗化處理的例子。在使用參考例1之銅箔來製作覆銅積層板的情況下，形成有銅箔與樹脂基材間之耐熱密接性大幅惡化的結果。 Further, Reference Example 1 is an example in which the roughening treatment is not performed on the copper foil. When the copper clad laminate was produced using the copper foil of Reference Example 1, the heat-resistant adhesiveness between the copper foil and the resin substrate was greatly deteriorated.

相較之下，已形成在表面處理銅箔之粗化處理面上的粗化粒子之平均高度為在本發明所規定的範圍內，且該粗化處理面之BET表面積比亦滿足本發明規定之實施例1~16的表面處理銅箔，將用該表面處理銅箔製作覆銅積層板之際，銅箔與樹脂基材間呈現出優越的耐熱密接性。此外，由使用實施例1~16之表面處理銅箔之覆銅積層板所形成的導體電路，即使傳輸高頻訊號，仍可有效的抑制傳輸損耗，更具有極佳的絕緣可靠度。 In contrast, the average height of the roughened particles formed on the roughened surface of the surface treated copper foil is within the range specified by the present invention, and the BET surface area ratio of the roughened surface also satisfies the requirements of the present invention. In the surface-treated copper foils of Examples 1 to 16, when the copper-clad laminate was produced using the surface-treated copper foil, the copper foil and the resin substrate exhibited excellent heat-resistant adhesion. Further, the conductor circuit formed by the copper clad laminate using the surface-treated copper foils of Examples 1 to 16 can effectively suppress the transmission loss even if a high-frequency signal is transmitted, and has excellent insulation reliability.

本申請案為主張2015年12月9日於日本國提出專利申請之專利申請號特願2015-240006的優先權，在此為參照該優先權，將其內容作為本說明書之記載內容的一部分。 Priority is claimed on Japanese Patent Application No. 2015-240006, the entire disclosure of which is hereby incorporated by reference.

Claims (8)

一種印刷配線板用表面處理銅箔，在形成有粗化粒子的表面上具有矽烷耦合劑層，其特徵在於：在上述矽烷耦合劑層表面中，粗化粒子的平均高度為0.05μm以上且未達0.5μm，上述矽烷耦合劑層表面之BET表面積比為1.2以上。 A surface-treated copper foil for a printed wiring board having a decane coupling agent layer on a surface on which roughened particles are formed, wherein an average height of the roughened particles is 0.05 μm or more on the surface of the decane coupling agent layer Up to 0.5 μm, the BET surface area ratio of the surface of the above decane coupling agent layer was 1.2 or more. 如申請專利範圍第1項之印刷配線板用表面處理銅箔，其中，在上述矽烷耦合劑層表面中，粗化粒子的平均高度為0.05μm以上且未達0.3μm。 The surface-treated copper foil for a printed wiring board according to the first aspect of the invention, wherein the average height of the roughened particles in the surface of the decane coupling agent layer is 0.05 μm or more and less than 0.3 μm. 如申請專利範圍第1或2項之印刷配線板用表面處理銅箔，其中，在上述矽烷耦合劑層表面中，細微表面係數Cms為0.6以上且未達2.0。 The surface-treated copper foil for a printed wiring board according to the first or second aspect of the invention, wherein the fine surface coefficient Cms is 0.6 or more and less than 2.0 on the surface of the decane coupling agent layer. 如申請專利範圍第1或2項之印刷配線板用表面處理銅箔，其中，形成有上述粗化粒子的表面具有含鎳之金屬處理層，在上述金屬處理層中所含有的鎳元素量為0.1mg/dm2以上且未達0.3mg/dm2。 The surface-treated copper foil for a printed wiring board according to claim 1 or 2, wherein the surface on which the roughened particles are formed has a metal layer containing nickel, and the amount of nickel contained in the metal treated layer is 0.1 mg/dm 2 or more and less than 0.3 mg/dm 2 . 如申請專利範圍第1或2項之印刷配線板用表面處理銅箔，其中，在上述矽烷耦合劑層中所含有的矽元素量為0.5μg/dm2以上且未達15μg/dm2。 The surface-treated copper foil for a printed wiring board according to the first or second aspect of the invention, wherein the amount of the lanthanum element contained in the decane coupling agent layer is 0.5 μg/dm 2 or more and less than 15 μg/dm 2 . 如申請專利範圍第1或2項之印刷配線板用表面處理銅箔，其中，上述矽烷耦合劑具有選自由環氧基、胺基、乙烯基、(甲基)丙烯醯基、苯乙烯基、脲基、異氰脲酸酯基、巰基、硫化物基、及異氰酸酯基中之至少一種官能基。 The surface-treated copper foil for a printed wiring board according to claim 1 or 2, wherein the decane coupling agent has an epoxy group, an amine group, a vinyl group, a (meth) acrylonitrile group, a styryl group, or the like. At least one of a ureido group, an isocyanurate group, a thiol group, a sulfide group, and an isocyanate group. 一種印刷配線板用覆銅積層板，其特徵在於：在申請專利範圍第1至6項中任一項之印刷配線板用表面處理銅箔的上述矽烷耦合劑層表面 上，積層有樹脂層。 A copper-clad laminate for a printed wiring board, characterized by the surface of the above-mentioned decane coupling agent layer for a surface-treated copper foil for a printed wiring board according to any one of claims 1 to 6. On the upper layer, there is a resin layer. 一種印刷配線板，其使用申請專利範圍第7項之印刷配線板用覆銅積層板。 A printed wiring board using the copper clad laminate for a printed wiring board according to claim 7 of the patent application.
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Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6623320B2 (en) * 2017-12-05 2019-12-18 古河電気工業株式会社 Surface-treated copper foil, and copper-clad laminate and printed wiring board using the same
WO2020162068A1 (en) 2019-02-04 2020-08-13 パナソニックＩｐマネジメント株式会社 Surface-treated copper foil, and copper-clad laminate plate, resin-attached copper foil and circuit board each using same
WO2020162056A1 (en) 2019-02-04 2020-08-13 パナソニックＩｐマネジメント株式会社 Copper-clad laminate plate, resin-attached copper foil, and circuit board using same
CN110838408A (en) * 2019-10-10 2020-02-25 深圳市峰泳科技有限公司 Planar capacitor with high stripping force and high dielectric constant and preparation method thereof
JPWO2021079817A1 (en) * 2019-10-25 2021-04-29
WO2021132191A1 (en) * 2019-12-26 2021-07-01 ナミックス株式会社 Composite copper member treated with silane coupling agent
CN112708909A (en) * 2020-12-18 2021-04-27 江西省江铜耶兹铜箔有限公司 Composite electroplating solution and preparation method of low-profile electrolytic copper foil for high-frequency PCB
JP7273883B2 (en) * 2021-04-09 2023-05-15 福田金属箔粉工業株式会社 Surface-treated copper foil and copper-clad laminate and printed wiring board using the surface-treated copper foil
WO2022244828A1 (en) * 2021-05-20 2022-11-24 三井金属鉱業株式会社 Roughened copper foil, copper foil with carrier, copper-clad laminate, and printed wiring board
CN117321253A (en) * 2021-05-20 2023-12-29 三井金属矿业株式会社 Roughened copper foil, copper foil with carrier, copper-clad laminate, and printed wiring board
JPWO2022244827A1 (en) * 2021-05-20 2022-11-24

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4833556B1 (en) 1968-10-12 1973-10-15
JPS57184295A (en) * 1981-05-08 1982-11-12 Furukawa Circuit Foil Copper foil for printed circuit and method of producing same
CN1301046C (en) 2002-05-13 2007-02-14 三井金属鉱业株式会社 Flexible printed wiring board for chip-on-film
JP4470917B2 (en) * 2006-06-29 2010-06-02 ソニー株式会社 Electrode current collector, battery electrode and secondary battery
JP5512273B2 (en) * 2007-09-28 2014-06-04 Ｊｘ日鉱日石金属株式会社 Copper foil and copper clad laminate for printed circuit
JP2010212470A (en) * 2009-03-11 2010-09-24 Hitachi Cable Ltd Copper foil for printed wiring board and method of manufacturing the same, and printed wiring board
JP5242710B2 (en) * 2010-01-22 2013-07-24 古河電気工業株式会社 Roughening copper foil, copper clad laminate and printed wiring board
JP2011162860A (en) * 2010-02-12 2011-08-25 Furukawa Electric Co Ltd:The Surface-roughened copper foil, method of producing the same and copper-clad laminate plate
KR20130027484A (en) * 2010-03-01 2013-03-15 후루카와 덴키 고교 가부시키가이샤 Surface treatment method for copper foil, surface-treated copper foil, and copper foil for negative electrode collector of lithium ion secondary battery
JP5634103B2 (en) * 2010-04-06 2014-12-03 福田金属箔粉工業株式会社 A treated copper foil for a copper clad laminate, a copper clad laminate obtained by bonding the treated copper foil to an insulating resin substrate, and a printed wiring board using the copper clad laminate.
KR101740092B1 (en) * 2010-09-27 2017-05-25 제이엑스금속주식회사 Copper foil for printed wiring board, method for producing said copper foil, resin substrate for printed wiring board, and printed wiring board
JP5497808B2 (en) 2012-01-18 2014-05-21 Ｊｘ日鉱日石金属株式会社 Surface-treated copper foil and copper-clad laminate using the same
WO2015016271A1 (en) * 2013-08-01 2015-02-05 古河電気工業株式会社 Copper foil for printed wiring board
JP6343204B2 (en) * 2013-08-20 2018-06-13 Ｊｘ金属株式会社 Surface-treated copper foil and copper foil with carrier using the same, laminated board, printed wiring board, electronic device, and method for producing printed wiring board
JP2015061757A (en) * 2013-08-21 2015-04-02 Jx日鉱日石金属株式会社 Copper foil with carrier and laminated board, printed wiring board and electronic device using same, as well as method for producing printed wiring board
KR101887791B1 (en) * 2013-12-10 2018-08-10 제이엑스금속주식회사 Treated surface copper foil, copper-clad laminate, printed wiring board, electronic device, and printed wiring board manufacturing method

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