TWI387017B - Copper clad laminate for cof and carrier tape for cof - Google Patents
Copper clad laminate for cof and carrier tape for cof Download PDFInfo
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本發明係有關一種COF(膜上晶片型,chip on film)用被銅積層板(copper clad laminate,亦稱鍍銅層壓板，本文中稱為被銅積層板)以及將此被銅積層板加工而得之COF用載置帶(carrier tape)。The present invention relates to a COF (chip on film) copper clad laminate (also referred to as a copper clad laminate, referred to herein as a copper laminate) and processing the copper laminate. The COF is used as a carrier tape.
COF係將半導體IC搭載於薄膜狀電路板上之複合零件。COF大多使用在連接較大之剛性電路板或顯示板。然後，薄膜狀之電路板係由層積聚醯亞胺等之有機聚合物薄膜與銅箔之被銅積層板(copper clad laminate)所成。The COF is a composite component in which a semiconductor IC is mounted on a film-formed circuit board. COF is mostly used in connecting rigid boards or display boards. Then, the film-shaped circuit board is formed by laminating an organic polymer film of ruthenium or the like and a copper clad laminate of copper foil.
薄膜狀電路板所採用之方法係將感光性樹脂層層積在被銅積層板之銅箔面上，進行對應於所期待之電路圖案的曝光，經使必要部分之感光性樹脂產生光硬化、顯影，將未曝光部分之感光性樹脂去除之後，經蝕刻而去除無硬化阻劑覆蓋之基板的被覆銅層，或經鍍敷而在無硬化阻劑覆蓋之部分析出鍍敷金屬。最後，經剝離而去除硬化阻劑而得到具有所期待之導體圖案的電路板。感光性樹脂之層積方法方面係有：將液態阻劑塗佈、乾燥之方法，以及將感光性樹脂薄膜層積(laminate)之方法。In the method of the film-formed circuit board, a photosensitive resin layer is laminated on the copper foil surface of the copper laminate, and exposure is performed in accordance with the desired circuit pattern, and the photosensitive resin of the necessary portion is photohardened. After development, the photosensitive resin in the unexposed portion is removed, and then the coated copper layer of the substrate not covered with the hard resist is removed by etching, or the plating metal is analyzed by plating without the hard resist. Finally, the hardening resist is removed by peeling to obtain a circuit board having the desired conductor pattern. The method of laminating a photosensitive resin includes a method of applying a liquid resist, drying, and a method of laminating a photosensitive resin film.
COF用之被銅積層板方面，歷來係主要使用將銅濺鍍(sputtering)在聚醯亞胺樹脂薄膜而得之聚醯亞胺被銅積層板。以濺鍍方式之時，由於金屬層之針孔(pinhole)而使收率變差，故而期待能有一種無針孔之聚醯亞胺被銅積層板。無針孔之被銅積層板方面則有將壓軋(rolling)銅箔或電解銅箔與聚醯亞胺積層者。該積層板雖經鑄塑(casting)或層積方式在銅箔上層積聚醯亞胺而得，但為了提昇接著力等，亦有在金屬箔上形成熱塑性聚醯亞胺層者。In the case of a copper-clad laminate for COF, a poly-plylimide copper-clad laminate obtained by sputtering copper on a polyimide film has been mainly used. In the case of the sputtering method, the yield is deteriorated by the pinhole of the metal layer. Therefore, it is expected that a pinhole-free polyimine-imide copper-clad laminate can be obtained. In the case of a copper-clad laminate without a pinhole, there is a laminate of a rolled copper foil or an electrolytic copper foil and a polyimide. Although the laminated board is obtained by casting or stacking a bismuth imide on a copper foil, it is also possible to form a thermoplastic polyimide layer on the metal foil in order to improve the adhesion or the like.
另一方面，晶片之安裝雖有由ACF(Anisotropic Conductive Film：各向異性導電膜)、NCP(Non－Conductive Paste：非導電膠)、超音波接合等在低溫中安裝之方式，至Au－Au接合、Au－Sn接合等在300℃以上之高溫中安裝之方式，但由在COF及TAB線之安裝方式，或晶片與電路之連接可靠性的觀點而言，一般多採用Au－Au接合、Au－Sn接合。On the other hand, the mounting of the wafer is carried out at a low temperature by ACF (Anisotropic Conductive Film), NCP (Non-Conductive Paste), ultrasonic bonding, etc., to Au-Au. Bonding, Au-Sn bonding, etc. are mounted at a high temperature of 300 ° C or higher. However, Au-Au bonding is generally used from the viewpoint of mounting the COF and TAB wires, or the connection reliability between the wafer and the circuit. Au-Sn bonding.
(專利文獻1)日本專利特開2004－207670號公報(專利文獻2)日本專利特開2004－153194號公報(專利文獻3)日本專利特開2004－128337號公報(專利文獻4)日本專利特開2004－31685號公報(專利文獻5)日本專利特開2004－315256號公報(專利文獻6)日本專利特開2004－71984號公報(專利文獻7)日本專利特開2004－23046號公報(Patent Document 1) Japanese Patent Laid-Open No. 2004-153194 (Patent Document 3) Japanese Patent Laid-Open Publication No. 2004-128337 (Patent Document 4) Japanese Laid-Open Patent Publication No. 2004-315256 (Patent Document 6) Japanese Patent Laid-Open Publication No. 2004-71984 (Patent Document 7) Japanese Patent Laid-Open Publication No. 2004-23046
在專利文獻1記載一種COF用柔性印刷電路板(flexible print circuit board)，例如：在與安裝絕緣層之半導體晶片側的相反側之面上，設置矽烷化合物、矽溶膠(silica sol)等脫模劑層。Patent Document 1 discloses a flexible printed circuit board for COF. For example, a mold such as a decane compound or a silica sol is provided on the surface opposite to the semiconductor wafer side on which the insulating layer is mounted. Agent layer.
在專利文獻2記載一種COF用電路板之製造方法，且該方法係具備：進行圖案化(patterning)之光蝕顯影(photo－lithography)步驟後，在絕緣層形成脫模劑層(release agent layer)之步驟。然後，除了記載該絕緣層係由將聚醯亞胺前驅物樹脂溶液塗佈或熱壓在導體層之熱塑性樹脂層以及絕緣薄膜所形成者，並記載有關絕緣層係由經熱壓之熱硬化性樹脂層以及絕緣薄膜所形成者。Patent Document 2 describes a method of manufacturing a circuit board for COF, which comprises: forming a release agent layer on an insulating layer after performing a photo-lithography step of patterning; ) The steps. Then, it is described that the insulating layer is formed of a thermoplastic resin layer and an insulating film which are coated or heat-pressed on the conductive layer of the polyimide film, and the insulating layer is thermally hardened by hot pressing. A resin layer and an insulating film are formed.
在專利文獻3記載一種COF之製造方法，該方法係具備：在絕緣膠帶之表面進行絕緣性樹脂之塗佈的樹脂塗佈步驟；將半導體元件由絕緣性樹脂之上加壓而壓接在電路圖案上之半導體元件壓接步驟；以及使絕緣性樹脂硬化並將半導體元件壓接於電路圖案上成為電性連接狀態下固著之樹脂硬化步驟。Patent Document 3 describes a method for producing a COF, which comprises a resin coating step of applying an insulating resin on the surface of an insulating tape, and pressing the semiconductor element over the insulating resin to be crimped to the circuit. a semiconductor element crimping step on the pattern; and a resin hardening step of curing the insulating resin and crimping the semiconductor element to the circuit pattern to be fixed in an electrically connected state.
在專利文獻4記載一種COF薄膜載置帶之製造方法，該方法係具備：將補強薄膜黏貼在與絕緣層之導電層的相反側之熱壓步驟；在寬度方向之兩側領域形成孔列(perforation)之步驟；再度進行補強薄膜與絕緣層之熱壓之步驟；在導電層上形成光阻圖案並經由蝕刻而形成電路圖案，同時在孔列之複數個孔周圍形成虛擬電路(dummy circuit)之步驟。Patent Document 4 describes a method for producing a COF film mounting tape, which comprises: a step of thermally pressing a reinforcing film on a side opposite to a conductive layer of an insulating layer; and forming a row of holes in both sides of the width direction ( a step of perforation; re-pressing the step of reinforcing the film and the insulating layer; forming a photoresist pattern on the conductive layer and forming a circuit pattern by etching while forming a dummy circuit around the plurality of holes of the hole array The steps.
在專利文獻5記載一種於HDD用、COF用等中所使用之柔性(可撓性)被金屬箔積層板，包括金屬箔、熱塑性聚醯亞胺層與耐熱性基膜，並各自使用熱塑性聚醯亞胺層具有150至300℃以下之玻璃轉移溫度(glass transition temperature)與1%以下之吸水率的熱塑性聚醯亞胺，耐熱性基膜兼具有350℃以上之玻璃轉換溫度與2%以下之吸水率的熱塑性聚醯亞胺薄膜。Patent Document 5 describes a flexible (flexible) metal foil laminate used for HDD, COF, etc., including a metal foil, a thermoplastic polyimide layer, and a heat resistant base film, each of which uses a thermoplastic polymer. The quinone imine layer has a glass transition temperature of 150 to 300 ° C or less and a thermoplastic polyimine of 1% or less, and the heat resistant base film has a glass transition temperature of 350 ° C or more and 2%. The following thermoplasticity polyimide film of water absorption.
在專利文獻6記載一種聚醯亞胺被銅積層板，在非熱塑性聚醯亞胺層之至少一面形成熱塑性聚醯亞胺層，係於熱塑性聚醯亞胺層之表面層積銅箔的聚醯亞胺被銅積層板，與熱塑性聚醯亞胺接合之銅箔厚度在5μm以下，並記載聚醯亞胺被銅積層板使用於COF用等。Patent Document 6 describes a polyimide-copper-clad laminate in which a thermoplastic polyimide layer is formed on at least one side of a non-thermoplastic polyimide layer, and is laminated on a surface-layered copper foil of a thermoplastic polyimide layer. The yttrium imide is a copper laminate, and the thickness of the copper foil bonded to the thermoplastic polyimide is 5 μm or less, and the polyimine is used for COF or the like by a copper laminate.
在專利文獻7記載一種具有銅箔特徵之COF用被銅積層板。Patent Document 7 describes a copper-clad laminate for COF having a copper foil feature.
通常，在以濺鍍方式而得聚醯亞胺積層板之情況下，由於無須有熱塑性樹脂層，所以在300℃以上之晶片安裝時，雖然沒有發生金屬線路沉沒於聚醯亞胺層中之現象，卻有如上所述之問題。將聚醯亞胺層經塗佈或延壓等而層積於銅箔時，為了提高銅箔與聚醯亞胺層間之接著力，則通常必須使用熱塑性之聚醯亞胺，而有沉沒現象等之問題。尤其，在安裝使用COF製造步驟中之Au－Sn共晶的晶片時，由於暴露在高溫、高壓下，便有引起熱變形、導體沉沒於聚醯亞胺層之問題。在此，亦提案當將聚醯亞胺樹脂或該前驅物溶液，以塗佈法(亦稱鑄塑法,casting method)製造積層板之際，將銅箔粗糙化並發揮定錨(anchoring)效應，不使用熱塑性之聚醯亞胺而提昇接著強度。然而，該方法中，COF用材料需形成微細圖案之電路，但卻有阻礙此形成之問題。In general, in the case of a polyimide laminate which is obtained by sputtering, since there is no need for a thermoplastic resin layer, when a wafer of 300 ° C or more is mounted, although no metal line is sunk in the polyimide layer. Phenomenon, but there are problems as mentioned above. When the polyimide layer is laminated or copper-clad, or the like, in order to increase the adhesion between the copper foil and the polyimide layer, it is usually necessary to use a thermoplastic polyimide and sink. Waiting for the problem. In particular, when the wafer using the Au-Sn eutectic in the COF manufacturing step is mounted, there is a problem that thermal deformation occurs and the conductor sinks into the polyimide layer due to exposure to high temperature and high pressure. Here, it is also proposed to roughen the copper foil and play an anchor when the polyimide resin or the precursor solution is formed by a coating method (also called a casting method). The effect is to increase the strength of the bond without the use of thermoplastic polyimides. However, in this method, the material for COF needs to form a circuit of a fine pattern, but there is a problem that hinders the formation.
本發明之目的係提供一種COF用被銅積層板，可形成微細圖案之電路，並防止Au－Sn共晶時沉沒於導體之聚醯亞胺層中。SUMMARY OF THE INVENTION An object of the present invention is to provide a copper-clad laminate for COF which can form a fine pattern circuit and prevent the Au-Sn eutectic from sinking in the polyimide layer of the conductor.
本發明之COF用被銅積層板係於銅箔上設置聚醯亞胺層之被銅積層板，其特徵係：聚醯亞胺層係以溶液狀態塗佈在銅箔上，並經乾燥、硬化而得者；而在350℃下呈現非熱塑性之特性，而且，銅箔之聚醯亞胺積層面的表面粗糙度(Rz)在0.5至1.5μm之範圍，銅－聚醯亞胺間之常溫中的180度(折曲角度)剝離強度為0.6kN/m以上。並且，本發明係將上述COF用被銅積層板加工而得之COF用載置帶。A copper-clad laminate in which a copper-clad laminate of the present invention is provided with a copper-clad laminate on a copper foil, wherein the polyimine layer is coated on a copper foil in a solution state, and dried. Hardened; and exhibits non-thermoplastic properties at 350 ° C, and the surface roughness (Rz) of the polyimide layer of the copper foil is in the range of 0.5 to 1.5 μm, between copper and polyimide. The 180 degree (bending angle) peel strength at normal temperature is 0.6 kN/m or more. Further, the present invention relates to a COF mounting tape obtained by processing the COF with a copper laminate.
其中，聚醯亞胺層為單一層者使COF用被銅積層板容易製造。而且，銅箔為無粗糙化之電解銅箔，而銅箔之聚醯亞胺積層側之面含有：選自鉬、鈷、鎳以及鋅之組群的一種或一種以上之金屬所處理之金屬處理層，與鉻酸鹽處理層以及矽烷偶合劑處理層者有利於提高聚醯亞胺層與銅箔之接著強度。再且，上述金屬處理層為以鋅與鎳作為必要成份之合金層，此可帶來更高之接著強度。再者，銅箔之厚度在5至20μm之範圍，且聚醯亞胺層之厚度如在5至50μm之範圍時，便提昇COF用載置帶之使用性。Among them, the polyimine layer is a single layer, and the COF is easily produced by the copper laminate. Further, the copper foil is a non-roughened electrolytic copper foil, and the surface of the copper foil on the polythene laminate side contains: a metal selected from one or more metals selected from the group consisting of molybdenum, cobalt, nickel, and zinc. The treatment layer, with the chromate treatment layer and the decane coupling agent treatment layer, is advantageous for increasing the adhesion strength of the polyimide layer and the copper foil. Further, the metal treatment layer is an alloy layer containing zinc and nickel as essential components, which brings about a higher bonding strength. Further, the thickness of the copper foil is in the range of 5 to 20 μm, and when the thickness of the polyimide layer is in the range of 5 to 50 μm, the usability of the COF mounting tape is improved.
以下，更詳細說明本發明。Hereinafter, the present invention will be described in more detail.
COF用被銅積層板係由銅箔與聚醯亞胺層所組成，銅箔可在單面，亦可在雙面。The copper-clad laminate for COF is composed of a copper foil and a polyimide layer, and the copper foil may be on one side or on both sides.
聚醯亞胺層雖可由單層或雙層所組成，如為單層則易於製造。當由複數層所組成時，理想之構造係在接著面側具有為提高與銅箔間之接著強度的薄聚醯亞胺層，以及在表面側具有於高溫下呈現高彈性之厚聚醯亞胺層。此時之厚度比以1：2至1：100之範圍為佳。並且，聚醯亞胺層較好是在350℃(以400℃為佳)呈現非熱塑性之特性。另外，當聚醯亞胺層由複數層所組成時，則任何一層聚醯亞胺層均呈現上述特性。其中，非熱塑性之特性係指儲存模數(storage modulus)呈現0.5GPa以上者。如儲存模數過高則接著性有降低的傾向，因此，在上述條件下，以呈現3.0GPa以下者為佳。以下，將本發明中所使用之呈現非熱塑性之特性的聚醯亞胺(層)也稱之為非熱塑性聚醯亞胺(層)或單稱為聚醯亞胺(層)。The polyimine layer may be composed of a single layer or a double layer, and is easy to manufacture if it is a single layer. When composed of a plurality of layers, the ideal structure has a thin polyimine layer on the side of the back surface for improving the adhesion strength with the copper foil, and a thick polyimide layer having high elasticity at a high temperature on the surface side. Amine layer. The thickness ratio at this time is preferably in the range of 1:2 to 1:100. Further, the polyimide layer preferably exhibits non-thermoplastic properties at 350 ° C (preferably at 400 ° C). Further, when the polyimide layer is composed of a plurality of layers, any of the layers of the polyimide layer exhibits the above characteristics. Among them, the non-thermoplastic property means that the storage modulus exhibits 0.5 GPa or more. If the storage modulus is too high, the adhesiveness tends to decrease. Therefore, it is preferable to exhibit 3.0 GPa or less under the above conditions. Hereinafter, the polyimine (layer) which exhibits non-thermoplastic properties used in the present invention is also referred to as a non-thermoplastic polyimide (layer) or simply as a polyimide (layer).
本發明之COF用被銅積層板係在銅箔上塗佈聚醯亞胺或聚醯亞胺之前驅物溶液，並經由乾燥、硬化並形成聚醯亞胺層而製造。雙面具有銅箔之積層板係在該聚醯亞胺層之表面將銅箔(可具有聚醯亞胺層)經由熱壓而製造。The COF of the present invention is produced by coating a prepreg solution of a polyimide or a polyimide on a copper foil with a copper laminate, and drying and hardening to form a polyimide layer. A laminated board having a copper foil on both sides is produced by hot pressing a copper foil (which may have a polyimide layer) on the surface of the polyimide layer.
形成非熱塑性聚醯亞胺層之非熱塑性聚醯亞胺雖無特別限制，但由特定之二胺與特定之四羧酸二酐所合成之聚醯亞胺可利於使用。該二胺之例可列舉如：鄰苯二胺、對苯二胺、間苯二胺、4,4'－二胺基苯醚、3,4'－二胺基二苯醚、3,3'－二胺基二苯醚、4,4'－二胺基聯苯、4,4'－二胺基－2,2'－二甲基聯苯、2,2－雙[4－(4－胺基苯氧基)苯基]丙烷、可具有烷基或烷氧基等取代基之4,4'－二胺基－N－苯甲醯基苯胺等。該等可單獨使用或使用兩種以上。亦可與其他之二胺併用，然上述二胺成分之使用量係以70%莫耳以上者為佳。The non-thermoplastic polyimine which forms the non-thermoplastic polyimide layer is not particularly limited, but a polyimine synthesized from a specific diamine and a specific tetracarboxylic dianhydride can be advantageously used. Examples of the diamine include o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminophenyl ether, 3,4'-diaminodiphenyl ether, and 3,3. '-Diaminodiphenyl ether, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl, 2,2-bis[4-(4 -Aminophenoxy)phenyl]propane, 4,4'-diamino-N-benzimidinoanilide which may have a substituent such as an alkyl group or an alkoxy group. These may be used alone or in combination of two or more. It may be used in combination with other diamines, and it is preferred that the diamine component is used in an amount of 70% by mole or more.
該特定之四羧酸二酐之例可列舉如：均苯四甲酸二酐、3,3',4,4'－聯苯四羧酸二酐、2,2',3,3'－聯苯四羧酸等。該等可單獨使用或使用兩種以上。而且，亦可與其他之四羧酸二酐併用，然上述特定之四羧酸二酐之使用量係以70%莫耳以上者為佳。Examples of the specific tetracarboxylic dianhydride include, for example, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-linked. Pyromellitic acid and the like. These may be used alone or in combination of two or more. Further, it may be used in combination with other tetracarboxylic dianhydrides, and it is preferred that the specific tetracarboxylic dianhydride is used in an amount of 70% by mole or more.
再者，形成非熱塑性聚醯亞胺層之非熱塑性聚醯亞胺則可使用市售之非熱塑性聚醯亞胺膜之中間物的聚醯亞胺溶液或該前驅物溶液。可列舉如：宇部興產(股)公司之UPILEX(登記商標)S、SGA、SN；東麗．杜邦(股)公司之KAPTON(登記商標)H、V、EN；鐘淵化學工業(股)公司之APICAL(登記商標)AH、NPI、HP等之中間物。聚醯亞胺層之厚度雖無特別限制，以2至100μm為佳，又以5至50μm為更佳。Further, the non-thermoplastic polyimide of the non-thermoplastic polyimide layer may be a solution of a commercially available non-thermoplastic polyimide film or a precursor solution of the intermediate of the non-thermoplastic polyimide film. For example, UPILEX (registered trademark) S, SGA, SN of Ube Industries Co., Ltd.; Toray. KAPTON (registered trademark) H, V, EN of DuPont Co., Ltd.; intermediate of APICAL (registered trademark) AH, NPI, HP, etc. of Zhongyuan Chemical Industry Co., Ltd. The thickness of the polyimide layer is not particularly limited, and is preferably 2 to 100 μm, more preferably 5 to 50 μm.
本發明中所使用之銅箔係由銅或含90%以上之銅合金所成，其厚度雖無特別限制，以3至30μm為佳，又以5至20μm為更佳。銅箔可為電解銅箔或壓軋銅箔，但以電解銅箔為適用。然後，該銅箔適合為未經粗糙化處理者。The copper foil used in the present invention is made of copper or a copper alloy containing 90% or more, and the thickness thereof is not particularly limited, and is preferably 3 to 30 μm, more preferably 5 to 20 μm. The copper foil may be an electrolytic copper foil or a rolled copper foil, but an electrolytic copper foil is suitable. Then, the copper foil is suitable for those who have not been roughened.
為改善與聚醯亞胺層之接著性，銅箔表面(所謂與聚醯亞胺層相接之面)宜實施表面處理。該表面處理宜在銅箔表面經由依序設置金屬處理層、鉻酸鹽處理層以及矽烷偶合劑處理層而進行。In order to improve the adhesion to the polyimide layer, the surface of the copper foil (so-called surface in contact with the polyimide layer) is preferably subjected to surface treatment. The surface treatment is preferably carried out by sequentially providing a metal treatment layer, a chromate treatment layer, and a decane coupling agent treatment layer on the surface of the copper foil.
設置金屬處理層之方法係使至少一種選自Mo、Co、Ni以及Zn之金屬(較佳者係以Zn、Ni之兩者為必要金屬)附著於銅箔表面。該金屬之附著量約為1至50μg/cm2 左右，而以5至50μg/cm2 左右為佳。Zn、Ni之兩者為必要金屬時，Zn為1至5μg/cm2 ，Ni為1至15μg/cm2 ，較佳者係使Ni/(Ni＋Zn)之比成為0.70以上。使金屬附著之方法則可使用電或化學之鍍敷法(plating method)、真空或化學之蒸鍍法等習知之方法。The method of providing the metal treatment layer is such that at least one metal selected from the group consisting of Mo, Co, Ni, and Zn (preferably, both of Zn and Ni are necessary metals) is attached to the surface of the copper foil. The adhesion amount of the metal is about 1 to 50 μg/cm 2 , and preferably about 5 to 50 μg/cm 2 . When both of Zn and Ni are essential metals, Zn is 1 to 5 μg/cm 2 and Ni is 1 to 15 μg/cm 2 , and preferably Ni/(Ni + Zn) ratio is 0.70 or more. The method of attaching the metal may be a conventional method such as an electroplating method, a vacuum method, or a chemical vapor deposition method.
設置鉻酸鹽處理層之方法則可使用：將設有金屬處理層之銅箔浸漬於重鉻酸鈉溶液並使之通電的陰極處理等習知之方法。設置矽烷偶合劑處理層之方法則可使用：將含有3－環氧丙氧基丙基三甲氧基矽烷(3－glycidoxypropyltrimethoxysilane)等矽烷偶合劑之溶液以噴霧法等塗佈在設有鉻酸鹽處理層之銅箔，並將此乾燥等之習知方法。As a method of providing a chromate treatment layer, a conventional method such as a cathode treatment in which a copper foil provided with a metal treatment layer is immersed in a sodium dichromate solution and is electrified can be used. A method of providing a decane coupling agent treatment layer may be carried out by applying a solution containing a decane coupling agent such as 3-glycidoxypropyltrimethoxysilane to a solution by spraying or the like. A conventional method of treating the copper foil of the layer and drying it.
本發明中所使用之銅箔表面(經表面處理之情況時，係指經表面處理後之表面)，其粗糙度(Rz)在0.5至1.5μm之範圍。當表面粗糙度(Rz)小於該範圍時，便有無法得到良好之接著強度等之問題，如大於該範圍時，便容易產生難以形成微細電路等之問題。The surface of the copper foil used in the present invention (in the case of surface treatment refers to the surface after surface treatment), and its roughness (Rz) is in the range of 0.5 to 1.5 μm. When the surface roughness (Rz) is less than the above range, there is a problem that a good bonding strength or the like cannot be obtained. If it is larger than this range, it is likely to cause a problem that it is difficult to form a fine circuit or the like.
本發明之COF用被銅積層板係使用將非熱塑性聚醯亞胺或前驅物之溶液(以下亦稱為清漆：varnish)塗佈在銅箔表面，並使乾燥、硬化之方法而製造。塗佈清漆之方法可採用：狹縫式塗佈(die coater)、雙輥筒塗佈(comma coater)、滾輪塗佈(roller coater)、凹版塗佈(gravure coater)、幕聯式塗佈(curtain coater)、噴霧塗佈(spray coater)等習知之方法。此時，可依需要而塗佈多層。使塗佈之清漆乾燥、硬化之方法可使用一般的加熱乾燥爐。乾燥爐之環境則可利用空氣、惰性氣體(氮氣、氬氣)等。乾燥、硬化之溫度適用於60至400℃左右之溫度範圍，硬化係將聚醯亞胺前驅物進行至成為聚醯亞胺為止。另外，在必須薄化銅箔厚度之時，以相同厚度將部分之銅箔依蝕刻處理等而去除，便做成既定厚度之銅箔厚度。The copper-clad laminate for COF of the present invention is produced by applying a solution of a non-thermoplastic polyimide or a precursor (hereinafter also referred to as varnish) to a surface of a copper foil, and drying and hardening it. The method of applying the varnish may be: die coater, comma coater, roller coater, gravure coater, curtain-linked coating ( A conventional method such as curtain coater or spray coater. At this time, a plurality of layers can be applied as needed. A general heating and drying furnace can be used for the method of drying and hardening the applied varnish. Air, inert gas (nitrogen, argon), etc. can be used in the environment of the drying furnace. The temperature of drying and hardening is suitable for a temperature range of about 60 to 400 ° C, and the hardening is carried out until the polyimide precursor is made into a polyimide. Further, when it is necessary to thin the thickness of the copper foil, a part of the copper foil is removed by etching treatment or the like with the same thickness to obtain a copper foil thickness of a predetermined thickness.
如此所得之本發明的COF用被銅積層板的銅－聚醯亞胺間之常溫中的180度(折曲角度)剝離強度需有0.6kN/m以上之必要。較佳之剝離強度在0.8至2.0kN/m之範圍。如此之剝離強度可經由從如上述之聚醯亞胺選擇適當的聚醯亞胺，或從銅箔或銅箔之表面處理條件選擇適當之銅箔或處理條件而獲得。其中，180度(折曲角度)剝離強度在具體上係依實施例所記載之條件而測定。The 180 degree (bending angle) peeling strength at room temperature between the copper-polyimine of the copper-clad laminate of the COF of the present invention thus obtained is required to be 0.6 kN/m or more. A preferred peel strength is in the range of 0.8 to 2.0 kN/m. Such peel strength can be obtained by selecting an appropriate polyimine from the above-mentioned polyimide, or selecting a suitable copper foil or processing conditions from the surface treatment conditions of the copper foil or the copper foil. Among them, the 180-degree (bending angle) peel strength was specifically measured according to the conditions described in the examples.
由COF用被銅積層板而製造COF用載置帶之方法可依照習知之方法而適當選擇使用。例如：將COF用被銅積層板切成既定寬度之薄膜，在薄膜兩側設孔列之後，於銅箔面側設置感光性樹脂層，通過可得既定電路之遮罩並曝光，接著，進行蝕刻處理並去除未曝光部份或曝光部分之任一者。其次，以殘餘樹脂層作為光阻(resist)，將露出之銅箔經蝕刻處理而形成電路圖案，之後經由去除阻劑而製成COF用載置帶等之方法。The method for producing a COF mounting tape from a copper-clad laminate for COF can be appropriately selected and used according to a conventional method. For example, a COF laminate sheet is cut into a film having a predetermined width, and after a hole array is provided on both sides of the film, a photosensitive resin layer is provided on the copper foil surface side, and a mask of a predetermined circuit is obtained and exposed, and then, The etching process and removing either of the unexposed portions or the exposed portions. Next, a method in which the exposed resin layer is used as a resist and the exposed copper foil is etched to form a circuit pattern, and then the resist is removed to form a COF mounting tape or the like.
依照本發明，即可提供一種無針孔，經Au－Au接合或Au－Sn接合，即使在晶片安裝時，電路偏移亦少之COF用被銅積層板。而因應需要亦可提供一種可底部充填(underfill)之COF用被銅積層板。According to the present invention, it is possible to provide a pinhole-free, copper-clad laminate for COF which is less in circuit offset even when the wafer is mounted by Au-Au bonding or Au-Sn bonding. A copper-clad laminate for COF that can be underfilled can also be provided as needed.
第1圖係呈示將IC晶片安裝在COF用載置帶之例的概念圖，IC晶片1之經鍍金的凸塊(bump)2係呈示與COF用載置帶之聚醯亞胺層3上形成的電路4(可做成將COF用被銅積層板之銅箔經電路加工所得之鍍錫等)之接合狀態。此時，為了以350至400℃左右之高溫熱壓，壓著部之聚醯亞胺層3的厚度則由原先厚度T1沉沒至成為T2。該厚度之差T1－T2可望盡可能的小。Fig. 1 is a conceptual diagram showing an example in which an IC wafer is mounted on a COF mounting tape, and a gold-plated bump 2 of the IC wafer 1 is shown on the polyimine layer 3 of the COF mounting tape. The formed circuit 4 (which can be formed by tin-plating a copper foil of a copper-clad laminate with a COF) can be joined. At this time, in order to heat-press at a high temperature of about 350 to 400 ° C, the thickness of the polyimide layer 3 of the pressed portion is sunk from the original thickness T1 to become T2. The difference in thickness T1-T2 is expected to be as small as possible.
以下，係依實施例而更詳細說明本發明。Hereinafter, the present invention will be described in more detail by way of examples.
實施例中所使用之簡略語係如下所述。The abbreviations used in the examples are as follows.
PMDA：均苯四甲酸二酐BPDA：3,3',4,4'－聯苯四羧酸m－TB：4,4'－二胺基－2,2'－二甲基聯苯BAPP：2,2－雙[4－(4－胺基苯氧基)苯基]丙烷DAPE：4,4'－二胺基二苯醚MABA：4,4'－二胺基－2'－二甲氧基－N－苯甲醯基苯胺DMAc：二甲基乙醯胺PMDA: pyromellitic dianhydride BPDA: 3,3',4,4'-biphenyltetracarboxylic acid m-TB: 4,4'-diamino-2,2'-dimethylbiphenyl BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane DAPE: 4,4'-diaminodiphenyl ether MABA: 4,4'-diamino-2'-dimethyl oxy-N-benzylidene aniline DMAc: dimethyl acetamide
合成例1：將21.78g(102.63 X 10－ 3 mol)之m－TB以及13.70g(68.42×10－ 3 mol)之DAPE加入於425g之DMAc，並置於1L分離瓶中一邊攪拌使之溶解。接著，將29.55g(135.49 X 10－ 3 mol)之PMDA與9.96g(33.87 X 10－ 3 mol)之BPDA以逐次少量投入該溶液中並進行聚合反應，得到高黏度之聚醯亞胺前驅物溶液A。Synthesis Example 1: 21.78g (102.63 X 10 - 3 mol ) of m-TB and 13.70g (68.42 × 10 - 3 mol ) of DAPE was added to the DMAc 425g, separated and placed in 1L flask and dissolved while stirring. Next, 29.55 g (135.49 X 10 - 3 mol) of PMDA and 9.96 g (33.87 X 10 - 3 mol) of BPDA were successively introduced into the solution in small amounts and subjected to polymerization to obtain a high-viscosity polyimine precursor. Solution A.
合成例2：將6651.3g(25.85mol)之MABA以及3450.9g(17.23mol)之DAPE加入於110.5Kg之DMAc，並置於130L之不鏽鋼容器中一邊攪拌使之溶解。接著，將9266.2g(42.48mol)之PMDA以逐次少量投入該溶液中並進行聚合反應，得到高黏度之聚醯亞胺前驅物溶液B。Synthesis Example 2: 6651.3 g (25.85 mol) of MABA and 3450.9 g (17.23 mol) of DAPE were added to 110.5 kg of DMAc, and placed in a 130 L stainless steel container while stirring to dissolve. Next, 9266.2 g (42.48 mol) of PMDA was gradually introduced into the solution in a small amount and polymerization was carried out to obtain a high-viscosity polyimine precursor solution B.
合成例3：將1294.43g(3.153mol)之BAPP溶解於17386g之DMAc後，將708.49g(3.248mol)之PMDA投入該溶液中並進行聚合反應，得到高黏度之聚醯亞胺前驅物溶液C。Synthesis Example 3: After dissolving 1294.43 g (3.153 mol) of BAPP in 17386 g of DMAc, 708.49 g (3.248 mol) of PMDA was put into the solution and polymerization was carried out to obtain a high-viscosity polyimine precursor solution C. .
將各合成例中所得之聚醯亞胺前驅物溶液在耐熱玻璃板進行刮棒塗佈以使轉化成醯亞胺後之薄膜厚度成為40μm，並在130℃下進行5分鐘之乾燥。之後，將其各投入真空恆溫槽中，分別在200℃、300℃、350℃下進行30分鐘之熱處理，並從玻璃板剝離而得到厚度40μm之聚醯亞胺薄膜。將所得之聚醯亞胺薄膜以微差掃描熱量儀(DSC：Differential scanning calorimetry)分析以及熱機械分析(TMA：Thermal Mechanical Analysis)測定Tg，並以動態熱機分析法(DMA：Dynamic Mechanical Analysis)進行黏彈性測定。The polyimine precursor solution obtained in each of the synthesis examples was subjected to bar coating on a heat-resistant glass plate to have a film thickness of 40 μm after conversion into quinone, and dried at 130 ° C for 5 minutes. Thereafter, each was placed in a vacuum oven, and heat-treated at 200 ° C, 300 ° C, and 350 ° C for 30 minutes, and peeled off from the glass plate to obtain a polyimide film having a thickness of 40 μm. The obtained polyimine film was measured by differential scanning calorimetry (DSC) and thermomechanical analysis (TMA: Thermal Mechanical Analysis), and subjected to dynamic mechanical analysis (DMA: Dynamic Mechanical Analysis). Viscoelasticity measurement.
由合成例1之聚醯亞胺前驅物溶液A所得的聚醯亞胺A並無觀察到Tg，係350℃中儲存模數為1GPa之非熱塑性聚醯亞胺。The polyethylenimine A obtained from the polyamidene precursor solution A of Synthesis Example 1 had no Tg observed, and was a non-thermoplastic polyimide having a storage modulus of 1 GPa at 350 °C.
由合成例2之聚醯亞胺前驅物溶液B所得的聚醯亞胺B並無觀察到Tg，係350℃中儲存模數為1GPa之非熱塑性聚醯亞胺。The polyimine B obtained from the polybendimimine precursor solution B of Synthesis Example 2 had no Tg observed, and was a non-thermoplastic polyimide having a storage modulus of 1 GPa at 350 °C.
由合成例3之聚醯亞胺前驅物溶液C所得的聚醯亞胺C觀察到在300℃至350℃之間之Tg，係350℃中儲存模數為0.1GPa之熱塑性聚醯亞胺。Polyethyleneimine C obtained from the polyimine precursor solution C of Synthesis Example 3 was observed to have a Tg of between 300 ° C and 350 ° C, and a thermoplastic polyimide having a storage modulus of 0.1 GPa at 350 ° C.
處理例1：準備平均厚度為18μm之無粗糙化電解銅箔，將該表面在30℃之稀硫酸中去除油成分與表面之氧化皮膜。再者，使用由硫酸鎳、焦磷酸鋅、焦磷酸鉀所成之電鍍液，使銅箔面之鎳－鋅合金層電解。Treatment Example 1: A roughened electrolytic copper foil having an average thickness of 18 μm was prepared, and the surface was subjected to removal of an oil component and an oxide film on the surface in a dilute sulfuric acid at 30 °C. Further, a nickel-zinc alloy layer on the copper foil surface was electrolyzed using a plating solution made of nickel sulfate, zinc pyrophosphate, and potassium pyrophosphate.
處理例2：準備平均厚度為18μm之無粗糙化電解銅箔，將該表面在30℃之稀硫酸中去除油成分與表面之氧化皮膜。再者，使用由硫酸鎳、焦磷酸鋅、焦磷酸鉀、硫酸鈷所成之電鍍液，使銅箔面之鈷－鎳－鋅合金層電解。Treatment Example 2: A roughened electrolytic copper foil having an average thickness of 18 μm was prepared, and the surface was subjected to removal of an oil component and an oxide film on the surface in dilute sulfuric acid at 30 °C. Further, a cobalt-nickel-zinc alloy layer on the copper foil surface was electrolyzed using a plating solution made of nickel sulfate, zinc pyrophosphate, potassium pyrophosphate, and cobalt sulfate.
處理例3：準備平均厚度為18μm之無粗糙化電解銅箔，將該表面在30℃之稀硫酸中去除油成分與表面之氧化皮膜。再者，使用由硫酸鎳、焦磷酸鋅、焦磷酸鉀所成之電鍍液，使銅箔面之鎳－鋅合金層電解。Treatment Example 3: A roughened electrolytic copper foil having an average thickness of 18 μm was prepared, and the surface was subjected to removal of an oil component and an oxide film on the surface in a dilute sulfuric acid at 30 °C. Further, a nickel-zinc alloy layer on the copper foil surface was electrolyzed using a plating solution made of nickel sulfate, zinc pyrophosphate, and potassium pyrophosphate.
處理例4：再將形成處理例1至3所得金屬處理層之銅箔進行水洗，使用無水鉻酸鈉二水合物2g/L、pH值4、浴溫30℃之電解溶液，以電流密度1A/dm2 通電5秒鐘，形成電解鉻酸鹽處理層。Treatment Example 4: The copper foils forming the metal treated layers obtained in Treatment Examples 1 to 3 were further washed with water, and an electrolytic solution of anhydrous sodium chromate dihydrate 2 g/L, pH 4, and a bath temperature of 30 ° C was used to have a current density of 1 A. /dm 2 was energized for 5 seconds to form an electrolytic chromate treatment layer.
處理例5：將處理例4所得3種類之經鉻酸鹽處理之銅箔進行水洗，在0.1wt%γ－環氧丙氧基丙基三甲氧基矽烷水溶液之矽烷偶合劑中浸漬10秒鐘後立即在80℃下乾燥，並形成矽烷偶合劑處理層。由於所得之表面處理銅箔係由形成處理例1至3所得之金屬處理層的3種類之銅箔所得者，因而依序稱為表面處理銅箔1、2、3。Treatment Example 5: Three types of chromate-treated copper foils obtained in Treatment Example 4 were washed with water, and immersed in a 0.1 wt% γ-glycidoxypropyltrimethoxydecane aqueous solution in a decane coupling agent for 10 seconds. Immediately thereafter, it was dried at 80 ° C and a decane coupling agent treatment layer was formed. Since the obtained surface-treated copper foil was obtained from the three types of copper foils which formed the metal-treated layer obtained in Process Examples 1 to 3, it was referred to as surface-treated copper foils 1, 2, and 3 in order.
對於表面處理銅箔1至3方面，該表面粗糙度Rz係根據JIS B 0601－1994「作為表面粗糙之定義」之5.0＋點平均粗糙為定義，以觸針式表面粗糙度計KLA(丹克爾公司製造)之P－15測定該測定長度為0.8mm、測定速度為20μm/秒，荷重為2g。其結果，表面處理銅箔1及2之Rz均為0.8μm，表面處理銅箔3之Rz為2.5μm。For the surface-treated copper foil 1 to 3, the surface roughness Rz is defined by the 5.0+ point average roughness of JIS B 0601-1994 "Defined as surface roughness", with a stylus surface roughness meter KLA (Dankel) The P-15 of the company was measured to have a length of 0.8 mm, a measurement speed of 20 μm/sec, and a load of 2 g. As a result, the Rz of the surface-treated copper foils 1 and 2 was 0.8 μm, and the Rz of the surface-treated copper foil 3 was 2.5 μm.
實施例1：將聚醯亞胺前驅物溶液A在表面處理銅箔1進行刮棒塗佈(bar coating)以使轉化成醯亞胺後之薄膜厚度成為40μm，並在130℃下進行5分鐘之乾燥。之後，將其投入真空恆溫槽中，各在200℃、300℃、350℃下進行30分鐘之熱處理，而得到厚度40μm之被銅積層板。將該被銅積層板之銅箔表面以光學顯微鏡觀察，查看5μm以上之針孔以及由針孔所引起之表面凹陷。其結果，針孔以及凹處之個數(稱為針孔等之數)為0個/cm2 。Example 1: Polyethylenimine precursor solution A was subjected to bar coating on surface-treated copper foil 1 so that the film thickness after conversion to ruthenium was 40 μm, and carried out at 130 ° C for 5 minutes. Dry. Thereafter, the mixture was placed in a vacuum bath, and heat-treated at 200 ° C, 300 ° C, and 350 ° C for 30 minutes to obtain a copper-clad laminate having a thickness of 40 μm. The surface of the copper foil of the copper laminate was observed under an optical microscope, and pinholes of 5 μm or more and surface depressions caused by the pinholes were observed. As a result, the number of pinholes and recesses (referred to as the number of pinholes or the like) was 0/cm 2 .
將該被銅積層板於硫酸濃度5.0g/l、過氧化氫50g/l、銅濃度20g/l之蝕刻液中，全面均勻地淋浴1分鐘，得到導體厚度8.0μm、聚醯亞胺層厚度40μm之COF用被銅積層板。The copper-clad laminate was uniformly and uniformly showered for 1 minute in an etching solution having a sulfuric acid concentration of 5.0 g/l, hydrogen peroxide of 50 g/l, and a copper concentration of 20 g/l to obtain a conductor thickness of 8.0 μm and a thickness of the polyimide layer. The 40 μm COF is a copper laminate.
將該COF用被銅積層板之銅箔加工為寬度1mm的電路，在測定由聚醯亞胺之180°剝離強度時，為1.0kN/m。再者，該電路即使在熱風烤箱中以150℃、168小時處理後，亦不過為0.5kN/m。經確認為可實用者。The copper foil of the copper laminate was processed into a circuit having a width of 1 mm, and when the 180° peel strength of the polyimide was measured, it was 1.0 kN/m. Furthermore, the circuit was only 0.5 kN/m after being treated at 150 ° C for 168 hours in a hot air oven. It has been confirmed to be practical.
實施例2至3以及比較例1至4：除了示於表1中之表面處理銅箔種類以及聚醯亞胺前驅物溶液之種類以外，與實施例1之相同處理，得到COF用被銅積層板。對於所得之COF用被銅積層板方面，將與實施例1相同評價之結果示於表1。另外，在表1中，銅箔之種類表示表面處理銅箔種類、聚醯亞胺之種類表示聚醯亞胺前驅物溶液之種類。剝離強度之前表示加熱處理前之剝離強度，剝離強度之後係表示經150℃、168小時之加熱處理後的剝離強度。微細加工性表示50μm間距加工之精密度。變形量表示以下述方法測驗之量。Examples 2 to 3 and Comparative Examples 1 to 4: The same treatment as in Example 1 was carried out except for the type of the surface-treated copper foil and the type of the polyimide intermediate solution shown in Table 1, to obtain a copper-clad layer for COF. board. The results of the same evaluation as in Example 1 regarding the obtained copper-clad laminate for COF are shown in Table 1. Further, in Table 1, the type of the copper foil indicates the type of the surface-treated copper foil, and the type of the polyimide, which indicates the type of the polyimide precursor solution. The peel strength before the peel strength indicates the peel strength before the heat treatment, and the peel strength indicates the peel strength after the heat treatment at 150 ° C for 168 hours. The fine workability indicates the precision of the 50 μm pitch processing. The amount of deformation represents the amount measured by the following method.
比較例5：市售之依濺鍍法的無接著劑被銅積層板方面，將與上述相同評價之結果示於表1。另外將該無接著劑被銅積層板之聚醯亞胺層在由33.5g之水、33.5g之氫氧化鉀、11g之乙二胺、22g之乙二醇所成之70℃水溶液中浸漬3小時，而得到導體層，在測定成為與聚醯亞胺之界面的導體層表面之粗糙度Rz時，為0.8μm。Comparative Example 5: The results of the same evaluation as described above are shown in Table 1 in the case of a copper-clad laminate which is commercially available by the sputtering method. Further, the non-adhesive layer was immersed in a 70 ° C aqueous solution of 33.5 g of water, 33.5 g of potassium hydroxide, 11 g of ethylenediamine, and 22 g of ethylene glycol in an aqueous solution of a copper laminate. In the hour, the conductor layer was obtained, and when the roughness Rz of the surface of the conductor layer which is the interface with the polyimide was measured, it was 0.8 μm.
實施例4：在實施例1至3中所得3種類之被銅積層板方面，切成寬度35mm之後以沖孔(punching)形成孔列。其次，使用光蝕顯影法將負型光阻劑塗佈乾燥，在銅箔上形成光阻層，介由50μm間距之COF用光罩曝光，並進行顯影，將光阻層圖案化。接著，將光阻層之圖案作為遮罩，銅箔層在氯化亞鐵水溶液中溶解去除並形成銅箔之圖案。再者，光阻層係以鹼性水溶液去除。觀察所得之導體層圖案時，得到無短路、斷線、剝離等良好之薄膜載置帶。將所得電路在硫酸水溶液中進行酸洗後，於Shipley公司製造之Tinposit LT－34中實施鍍錫，而得到完成鍍錫之薄膜載置帶。Example 4: In the case of the three types of copper-clad laminates obtained in Examples 1 to 3, a hole array was formed by punching after cutting into a width of 35 mm. Next, the negative photoresist was dried by a photo-etching method, a photoresist layer was formed on the copper foil, exposed to a COF mask of 50 μm pitch, and developed to pattern the photoresist layer. Next, the pattern of the photoresist layer is used as a mask, and the copper foil layer is dissolved and removed in an aqueous solution of ferrous chloride to form a pattern of copper foil. Furthermore, the photoresist layer is removed with an aqueous alkaline solution. When the obtained conductor layer pattern was observed, a film mounting tape excellent in short circuit, disconnection, peeling, and the like was obtained. After the obtained circuit was pickled in an aqueous sulfuric acid solution, tin plating was carried out in a Tinposit LT-34 manufactured by Shipley, and a tin-plated film mounting tape was obtained.
之後，將具有金凸塊之IC安裝在薄膜載置帶之內引腳部(inner leads)。安裝係使用芝浦(SHIBAURA MECHATRONICS CORPORATION)(股)公司製造之覆晶焊接機(flip chip bonder)「TFC－2100」，bonding head tool溫度為400℃、stage溫度為100℃、接合壓力係使平均1凸塊之荷重成為20gf而進行。Thereafter, an IC having gold bumps is mounted on the inner leads of the film mounting tape. The mounting system uses a flip chip bonder "TFC-2100" manufactured by SHIBAURA MECHATRONICS CORPORATION. The bonding head tool temperature is 400 ° C, the stage temperature is 100 ° C, and the bonding pressure is averaged 1. The load of the bump is 20 gf.
其次，觀察安裝IC之COF薄膜載置帶的剖面，如第1圖所示之T1(薄膜厚度)－T2(安裝部薄膜厚度)＝T3(因安裝之樹脂變形量)而測定。在本實施例中，任一變形量T3均為1μm，內引腳與凸塊之連接狀態良好。Next, the cross section of the COF film mounting tape on which the IC was mounted was observed, and T1 (thickness thickness) - T2 (mounting portion film thickness) = T3 (the amount of deformation of the resin to be mounted) as shown in Fig. 1 was measured. In the present embodiment, any of the deformation amounts T3 is 1 μm, and the connection state of the inner leads and the bumps is good.
1．．．IC晶片1. . . IC chip
2．．．凸塊2. . . Bump
3．．．聚醯亞胺層3. . . Polyimine layer
4．．．電路4. . . Circuit
第1圖係呈示將IC晶片安裝在COF用載置帶之例的概念圖。Fig. 1 is a conceptual diagram showing an example in which an IC wafer is mounted on a COF mounting tape.
1．．．IC晶片1. . . IC chip
2．．．凸塊2. . . Bump
3．．．聚醯亞胺層3. . . Polyimine layer
4．．．電路4. . . Circuit
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| JP2004320938A JP4564336B2 (en) | 2004-11-04 | 2004-11-04 | Copper-clad laminate for COF and carrier tape for COF |
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| TWI387017B true TWI387017B (en) | 2013-02-21 |
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| JP4958045B2 (en) * | 2006-10-27 | 2012-06-20 | 三井金属鉱業株式会社 | Surface-treated copper foil for producing flexible copper-clad laminate and flexible copper-clad laminate obtained using the surface-treated copper foil |
| KR20090080978A (en) * | 2006-11-29 | 2009-07-27 | 닛코 킨조쿠 가부시키가이샤 | Bilayer copper clad laminate |
| JP4907580B2 (en) * | 2008-03-25 | 2012-03-28 | 新日鐵化学株式会社 | Flexible copper clad laminate |
| CN101570679B (en) * | 2008-05-03 | 2012-10-10 | 新高电子材料（中山）有限公司 | Filling-free polyimide bonding agent applicable to once coating |
| US8512873B2 (en) * | 2008-07-22 | 2013-08-20 | Furukawa Electric Co., Ltd. | Surface treated copper foil and copper clad laminate |
| JP5524475B2 (en) * | 2008-11-28 | 2014-06-18 | 株式会社有沢製作所 | Two-layer double-sided flexible metal laminate and its manufacturing method |
| JP6287840B2 (en) | 2013-04-16 | 2018-03-07 | 東洋紡株式会社 | Metal foil laminate |
| JP7212480B2 (en) * | 2017-09-29 | 2023-01-25 | 日鉄ケミカル＆マテリアル株式会社 | Polyimide films, metal-clad laminates and circuit boards |
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| TW544827B (en) * | 2001-07-11 | 2003-08-01 | Mitsui Mining & Smelting Co | Laminated film for COF and film carrier tape for COF |
| TW200408321A (en) * | 2002-05-13 | 2004-05-16 | Mitsui Mining & Smelting Co | Fiexible printed wiring board for chip on flexible |
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| JP2000299359A (en) * | 1999-04-16 | 2000-10-24 | Kanegafuchi Chem Ind Co Ltd | Tape for tab |
| JP2003041334A (en) * | 2001-08-01 | 2003-02-13 | Nippon Mining & Metals Co Ltd | Copper alloy foil for laminate |
| JP2004025778A (en) * | 2002-06-28 | 2004-01-29 | Arakawa Chem Ind Co Ltd | Metallic-foil laminated body and double-faced metallic-foil laminated body |
| JP3664708B2 (en) * | 2001-12-10 | 2005-06-29 | 三井化学株式会社 | Polyimide metal laminate and manufacturing method thereof |
| JP2004083885A (en) * | 2002-07-01 | 2004-03-18 | Du Pont Toray Co Ltd | Polyamic acid mixture, polyimide, polyimide film and use of the same |
| JP2004244656A (en) * | 2003-02-12 | 2004-09-02 | Furukawa Techno Research Kk | Copper foil which can deal with high-frequency application and method for manufacturing the same |
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| TW544827B (en) * | 2001-07-11 | 2003-08-01 | Mitsui Mining & Smelting Co | Laminated film for COF and film carrier tape for COF |
| TW200408321A (en) * | 2002-05-13 | 2004-05-16 | Mitsui Mining & Smelting Co | Fiexible printed wiring board for chip on flexible |
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