TWI468559B - Surface treatment of copper foil and copper clad laminate - Google Patents

Surface treatment of copper foil and copper clad laminate Download PDF

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Publication number
TWI468559B
TWI468559B TW98124822A TW98124822A TWI468559B TW I468559 B TWI468559 B TW I468559B TW 98124822 A TW98124822 A TW 98124822A TW 98124822 A TW98124822 A TW 98124822A TW I468559 B TWI468559 B TW I468559B
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copper foil
adhesion amount
adhesion
less
peel strength
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TW98124822A
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English (en)
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TW201022485A (en
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Satoshi Fujisawa
Yuji Suzuki
Takeo Uno
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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
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
    • 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
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • 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
    • B32B15/04—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
    • B32B15/088—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 comprising polyamides
    • 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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B32B2255/205—Metallic coating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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
    • 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
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/0723—Electroplating, e.g. finish plating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12431—Foil or filament smaller than 6 mils
    • Y10T428/12438—Composite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12472—Microscopic interfacial wave or roughness
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12556—Organic component
    • Y10T428/12569—Synthetic resin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12882—Cu-base component alternative to Ag-, Au-, or Ni-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12903—Cu-base component
    • Y10T428/1291—Next to Co-, Cu-, or Ni-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12944—Ni-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12993—Surface feature [e.g., rough, mirror]

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  • Metallurgy (AREA)
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  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Mechanical Engineering (AREA)
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Description

表面處理銅箔及覆銅層積板
本發明關於表面處理銅箔，尤其關於與聚醯亞胺薄膜進行高溫接著而使用的覆銅層積板(以下稱為CCL)(CCL：Capper Clad Laminate)用之合適表面處理銅箔，而且關於使用該銅箔可形成正確線路之CCL。
CCL用銅箔係必須在將該銅箔接合於樹脂基板之際，提高其接著強度，滿足作為印刷電路板所要的電氣特性、蝕刻特性、耐熱性、耐藥品性。因此對製箔後的銅箔(以下亦稱為未處理銅箔)之與樹脂基板接合的接合表面施予粗化處理，再對施有該粗化處理的表面上施予鍍鋅(Zn)或鍍鎳(Ni)等，以及更對施有該鍍Zn或鍍Ni等的表面上施予鉻酸鹽處理等，而施予各種工夫。
在用於驅動個人電腦、攜帶式電話或PDA的顯示部之液晶顯示器的IC安裝基板中，往高密度化進展，其製造過程中要求正確的線路構成及高溫的處理。
為了對應於此要求，作為製造的印刷電路板CCL，為了應付正確的線路構成及高溫的處理之要求，有提供接著有形成正確導電線路的電解銅箔與可高溫使用的樹脂基板之聚醯亞胺薄膜的CCL，但是此CCL係以數百度的高溫將銅箔與聚醯亞胺薄膜熱接著。
對於此高溫的接著處理，提高銅箔在高溫與聚醯亞胺薄膜的接著強度係成為課題。作為解決此課題的手段。例如專利文獻1中揭示以含Zn的合金來粗化處理銅箔表面的技術。
又，作為將銅箔與聚醯亞胺薄膜進行高溫接著的手段，有提案對與聚醯亞胺薄膜接著的未處理銅箔之表面，以含有鉬及鐵、鈷、鎳、鎢之內的至少1種之電解液進行表面處理，再於此鍍層之上設有鍍Ni層或鍍Zn層或鍍Ni層+鍍Zn層的表面處理銅箔(參照專利文獻2)。
前述專利文獻1及2中所記載之含Zn層的粗化處理層，在提高高溫下的銅箔與聚醯亞胺薄膜(樹脂基板)之間的接著強度之點係有效果。然而，於將銅箔接著於聚醯亞胺薄膜(樹脂基板)後，若以酸溶液的蝕刻處理來形成電路線路而構成線路基板，則由於鋅易溶於酸中，故就連接著銅箔與聚醯亞胺薄膜(樹脂基板)之間的Zn層係溶出，線路形成後的銅箔與聚醯亞胺薄膜(樹脂基板)之接著強度係極度降低，在線路基板的使用中有發生電路線路(銅箔)自聚醯亞胺薄膜(樹脂基板)剝離的事故之慮。為了防止如此的事故，必須縮短蝕刻時間，使Zn層的溶解流出停留在最小限度，在蝕刻處理需要高度的技術及管理制度，而降低線路基板的生產性，同時導致成本高的不利。
如此地，前述專利文獻1、2所揭示的粗化處理，係如前述地無法完全滿足對聚醯亞胺薄膜的接著強度、耐藥品性、蝕刻性，因此現狀為尚未提供滿足此等特性的表面處理銅箔。
又，尚未提供完全滿足接著強度、耐藥品性、蝕刻性的CCL。
再者，專利文獻3中揭示作為銅箔的表面處理，於鍍浴中使用焦磷酸浴，施予Ni-Zn合金鍍敷，由該表面處理銅箔與聚醯亞胺薄膜所成的CCL，藉由使用焦磷酸浴而得到膜厚均勻性優異的Ni-Zn合金層，在對於線路形成後的端子部進行鍍錫時，於線路與聚醯亞胺樹脂基板的界面，不易發生錫的潛入現象。
然而，已知於使用焦磷酸浴的鍍敷中，P對所鍍敷的皮膜中之共析，由於所共析的P，而具有所鍍敷的皮膜之溶解性變高的性質。如此的性質，在蝕刻銅箔以形成線路，對此形成的線路之端子部進行鍍錫時，無法充分防止鍍錫液的潛入現象(耐藥品性的變差)，由於鍍錫液而使表面處理層劣化，有對電路線線路的密接性產生影響之不良情況。
近年來，線路係往細間距化進展，電路線路寬度係變細，線路與樹脂基材的接合面積係減少。於如此細間距的線路中，若發生鍍錫液的潛入現象，則線路的密接性降低，發生可靠性的問題，故希望可抑制此鍍錫液的潛入現象之銅箔。
[先前技術文獻]
[專利文獻1]特開2000-269637號公報
[專利文獻2]特開平11-256389號公報
[專利文獻3]特開2005-344174號公報
鑒於如此的狀況，本發明之目的為提供完全滿足對聚醯亞胺薄膜的接著強度、耐藥品性、蝕刻性的表面處理銅箔，及使用該表面處理銅箔的CCL。
本案發明者對Ni-Zn合金鍍層的溶解性進行專心致力的檢討，得到即使在細間距的線路，線路的密接性也不易降低，而可靠性優異的銅箔。
本發明的表面處理銅箔係由在未處理銅箔的至少一面上附著Ni-Zn合金而成的表面處理銅箔，Zn含有率(wt%)=Zn附著量/(Ni附著量+Zn附著量)×100為6%以上15%以下，而且Zn附著量為0.08mg/dm2 以上。
於前述表面處理銅箔中，在未處理銅箔的至少一面上所附著的Ni-Zn合金之Ni附著量較佳為0.45~3mg/dm2 。
本發明的覆銅層積板，係貼合有由在未處理銅箔的至少一面上附著Ni-Zn合金而成的表面處理銅箔，即Zn含有率(wt%)=Zn附著量/(Ni附著量+Zn附著量)×100為6%以上15%以下，而且Zn附著量為0.08mg/dm2 以上的表面處理銅箔與聚醯亞胺薄膜之覆銅層積板，貼合面的初期剝離強度為0.6kN/m以上，大氣中150℃、168小時加熱後的剝離強度為初期剝離強度的90%以上之強度。
本發明可提供完全滿足對聚醯亞胺薄膜的接著強度、耐藥品性、蝕刻性之表面處理銅箔。
又，使用本發明的表面處理銅箔，可提供完全滿足接著強度、耐藥品性、蝕刻性之層積線路基板(CCL)。
本發明中的未處理銅箔係可為電解銅箔、軋製銅箔的任一者(特別地，當沒有需要區別此等時，可僅以銅箔或未處理銅箔來表示)。未處理銅箔的厚度較佳為5~35μm。此係因為若銅箔的厚度比5μm薄，則在製造時例如會引入皺紋，薄的銅箔之製造係花費成本，不符合現實。
又，此係因為當銅箔比35μm厚時，不符合用於驅動個人電腦、攜帶式電話或PDA的顯示部之液晶顯示器的IC安裝基板等的薄型．小型化之規格。
本發明中的未處理銅箔表面之表面粗糙度較佳係Rz為0.1μm~1.0μm，Ra為0.15μm以下。
又，為了提高剝離強度、耐藥品性，進行粗化處理係有效。然而，若考慮彎曲性等，則較佳為粗化到Rz為1.5μm以下。
本發明係對上述未處理銅箔表面，或對在未處理銅箔表面施有粗化的粗化處理銅箔之表面，施予以Ni-Zn的2元合金層當作主體的表面處理。
對銅箔表面施予以Ni-Zn的2元合金層當作主體的表面處理之理由係如下。作為Ni-Zn表面處理層，使含有Ni者係為了在表面處理層中防止來自銅箔的銅之擴散，故其Ni的附著量較佳為0.45mg/dm2 ~3mg/dm2 。Ni的附著量為3mg/dm2 以上時，若以不殘留殘渣的方式進行蝕刻加工，由於處理時間變長，線路有發生梯形化的問題，故不宜。另一方面，Ni的附著量為0.45mg/dm2 以下時，由於來自銅箔的銅擴散變容易發生，大氣加熱後的剝離強度變成無法維持初期剝離強度的90%以上，故不宜。Ni的附著量若考慮蝕刻、剝離強度等，則較佳為0.5mg/dm2 ~2mg/dm2 ，更佳為0.5mg/dm2 ~1.5mg/dm2 。
於施予銅箔表面的表面處理層中使含有Zn者，係為了提高與樹脂基板(尤其聚醯亞胺薄膜)的接著強度，同時防止接著時的熱所致的接著強度之變差。
Zn的附著量0.08mg/dm2 以上，而且相對於(Ni附著量+Zn附著量)而言，Zn的附著比例(Zn的含有率)為6%以上且低於15%(wt%，以下同樣)，較佳為7%以上且低於12%，更佳為8%以上且低於10%。
Zn的附著量為0.08mg/dm2 以上，Zn的附著比例為6%以上且低於15%，係因為附著比例為6%以上時顯示改善耐熱性，但若附著比例為15%以上時則耐藥品性變差。
進行上述表面處理後，對其表面施予Cr金屬、Cr水合物或氧化物、或有機被膜。Cr的附著量較佳為0.01mg/dm2 以上0.3mg/dm2 以下。Cr附著量若多，則由於蝕刻變困難而不宜。又，Cr附著量若少，則在防銹方面會發生問題，故0.01mg/dm2 以下係不宜。又，作為有機被膜，施予市售的矽烷偶合劑而形成皮膜。
[實施形態1](實施例1~9、比較例1~5)
以厚度12μm、表面粗糙度Rz=1.0的古河Circuit Foil(股)製的WZ銅箔當作未處理銅箔。
對此未處理銅箔，藉由以下程序來進行表面處理，而得到表1所示之金屬含有率及金屬附著量的表面處理銅箔。
1. Ni-Zn合金鍍敷
於下述的鍍浴及鍍敷條件下，對前述未處理銅箔表面施予Ni-Zn合金鍍敷。
(鍍浴及鍍敷條件)
硫酸鎳；鎳濃度為0.1g/L~200g/L，較佳為20g/L~60g/L
硫酸鋅；鋅濃度為0.01g/L~100g/L，較佳為0.05g/L~5.0g/L
硫酸銨；0.1g/L~100g/L，較佳為0.5g/L~40g/L
液溫20~60℃
pH2~7
電流密度0.3~10A/dm2
2.表面處理
在Ni-Zn合金鍍敷處理後，對該合金表面施予Cr處理層、矽烷偶合處理層以成為試驗片。
作為Cr處理，使用無水鉻酸，在該無水鉻酸為0.1g/L~100g/L的浴中，於液溫20~50℃、電流密度0.1~20A/dm2 下進行處理。
作為矽烷偶合處理，使用γ-胺基丙基三甲氧基矽烷，成為0.1g/L~10g/L的浴，藉由在液溫20~50℃下浸漬或噴霧等的方法而進行處理。
對於所作成的表面處理銅箔，進行下述的測定。表1中顯示測定結果。
初期剝離強度(單位kN/m)
×：低於0.6 △：0.6以上且低於0.7 ○：0.7以上且低於0.8 ◎：0.8以上
耐熱性試驗後剝離強度(單位kN/m)
×：低於0.54 △：0.54以上且低於0.63 ○：0.63以上且低於0.72 ◎：0.72以上
耐藥品試驗後剝離強度(單位kN/m)
×：低於0.6 ○：0.6以上且低於0.7 △：0.7以上且低於0.8 ×：0.8以上
蝕刻性(單位μm)
◎：低於4.0 △：4.0以上且低於5.0 ○：5.0以上且低於6.0 ◎：6.0以上
金屬附著量
藉由螢光X射線((股)Rigaku製ZSXPrimus,分析直徑：35Φ)來分析。
(2)初期剝離強度
在330℃、20kg/cm2 下，將經表面處理的試驗片(銅箔)與聚醯亞胺樹脂(宇部興業(股)製Upilex 25VT)接著15分鐘。測定接著後剝離強度。初期剝離強度係將0.6kN/m以上當作合格，其判定基準係顯示於表1中。
(3)耐熱性(熱處理後的剝離強度)
將與聚醯亞胺接著後的試驗片在150℃加熱處理168小時後，測定剝離強度。熱處理後的剝離強度之判定基準係將初期剝離強度的90%以上當作合格，其判定基準(算出方法)係顯示於表1中
(4)耐藥品性(酸處理後的剝離強度)
將與聚醯亞胺接著後的試驗片，在水：鹽酸=1：1的鹽酸溶液中，於常溫浸漬1小時。測定其後的剝離強度。
(5)蝕刻性
藉由氯化銅溶液，將與聚醯亞胺接著後的試驗片作成1mm寬的線路，藉由SEM來測定底部寬及頂部寬，求得其差。判定基準係顯示於表1中。
表1所示的判斷基準在各評價中，◎：更佳，○：較佳，△：基準值內，×：基準值外。
如表1所示地，實施例1~2的Ni附著量為0.90~1.30mg/dm2 (在更佳的範圍之0.5~1.5mg/dm2 內)，Zn含有率為9%(在更佳的範圍之8~10%內)，各評價項目係在更佳的範圍內(綜合評價◎)。
實施例3的Zn附著比例為9%，Ni附著量為1.7mg/dm2 ，Ni的附著量係在比更佳範圍的1.5mg/dm2 多之較佳範圍內。因此，蝕刻性在較佳的範圍，全體在較佳的範圍內(綜合評價○)。
實施例4的Zn附著比例為9%，Ni附著量為2.1mg/dm2 ，Ni的含量係比較佳範圍的2mg/dm2 多。因此，蝕刻性為△，全體在基準值內(綜合評價△)。
實施例5的Zn附著比例為6%(範圍內)，耐熱性為△，全體在基準值內(綜合評價△)。
實施例6的Zn附著比例為7%，耐熱性在較佳的範圍內，全體在較佳的範圍內(綜合評價○)
實施例7的Zn附著比例為較佳範圍的11%，耐藥品性在較佳的範圍內，全體在較佳的範圍內(綜合評價○)。
實施例8的Zn附著比例為13%，耐藥品性為△，全體在基準值內(綜合評價△)。
實施例9的Zn附著量為0.08mg/dm2 ，附著比例為14%，Ni為0.48mg/dm2 ，故耐熱性、耐藥品性皆為△，全體在基準值內(綜合評價△)。
比較例1的Zn附著量為9%，Ni附著量為3.1mg/dm2 ，由於Ni的附著量多(範圍外)，蝕刻性差，微細線路的作成係困難(綜合評價×)。
比較例2的Zn附著量為0.08mg/dm2 以上，但由於附著比例比6%低，耐熱性為基準值外(綜合評價×)。
比較例3的Zn附著比例為9%，附著量為0.07mg/dm2 ，由於比0.08mg/dm2 低，耐熱性為基準值外(綜合評價×)。
比較例4的Zn附著量為0.13mg/dm2 ，雖然為0.08mg/dm2 以上，但附著比例為16%，由於高而耐藥品性為基準值外(綜合評價×)。
比較例5的Zn附著量為0.08mg/dm2 ，由於附著比例為17%的高，蝕刻性為基準值外，而且Ni為0.40mg/dm2 ，耐熱性亦為基準值外(綜合評價×)。
如上述地，本發明的表面處理銅箔係滿足與聚醯亞胺的接著強度、耐酸性、蝕刻性，為工業上優異之表面處理銅箔。
又，依照本發明的銅箔之表面處理方法，可提供工業上滿足與聚醯亞胺的接著強度、耐酸性、蝕刻性之銅箔的表面處理方法。
再者，依照本發明的層積線路基板，可提供與樹脂基板尤其聚醯亞胺與銅箔的接著強度強，在線路形成時具有耐酸性，滿足蝕刻性的層積線路基板，為具有優異的效果者。

Claims (2)

  1. 一種表面處理銅箔，由在未處理銅箔的至少一面上附著Ni-Zn合金而成，其中Zn含有率(wt%)=Zn附著量/(Ni附著量+Zn附著量)×100為6%以上9%以下，而且Zn附著量為0.08mg/dm2 以上，且Ni附著量為1.20~3mg/dm2 。
  2. 一種覆銅層積板，貼合有由在未處理銅箔的至少一面上附著Ni-Zn合金而成，其中Zn含有率(wt%)=Zn附著量/(Ni附著量+Zn附著量)×100為6%以上9%以下，而且Zn附著量為0.08mg/dm2 以上，且Ni附著量為1.20~3mg/dm2 的表面處理銅箔與聚醯亞胺薄膜之覆銅層積板，貼合面的初期剝離強度為0.6kN/m以上，大氣中150℃、168小時加熱後的剝離強度為初期剝離強度的90%以上之強度。
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TW200618145A (en) * 2004-11-04 2006-06-01 Nippon Steel Chemical Co Copper clad laminate for COF and carrier tape for COF

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JP5638952B2 (ja) 2014-12-10
US8512873B2 (en) 2013-08-20
KR20110052647A (ko) 2011-05-18
EP2312022A1 (en) 2011-04-20
KR101318871B1 (ko) 2013-10-17
TW201022485A (en) 2010-06-16
WO2010010893A1 (ja) 2010-01-28
US20110189499A1 (en) 2011-08-04
EP2312022A4 (en) 2012-11-14
CN102165104B (zh) 2013-07-24
CN102165104A (zh) 2011-08-24
JPWO2010010893A1 (ja) 2012-01-05

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