200300726 玖、發明說明 【發明所屬之技術領域】 本發明係關於廣泛地使用於軟式線路基板等之聚醯亞胺 金屬層合板及其製造方法，更詳細言之，係關於金屬層與 聚醯亞胺層的密著性優異，適合使用作爲高密度電路基板 材料的光透過性優異之聚醯亞胺金屬層合板及其製造方 法。 【先前技術】 近年來，隨著電子器材的小型攜帶化，作爲電路基板可 將零件、元件作高密度安裝的聚醯亞胺金屬層合板的利用 曰益增加。而且，爲因應更加高密度化的趨勢，適於線路 寬爲 1 G〜5 0 // m的微細圖案之加工的聚醯亞胺金屬層合 板受到殷切的企盼，由線路的可靠性之觀點考量，作爲金 屬與聚醯亞胺間的密著性之指標的抗剝離強度必須要高。 然而，使用於聚醯亞胺金屬層合板之金屬箔，爲使其發 揮和聚醯亞胺間的抗剝離強度，係施行稱爲粗化處理或表 面處理之鎳、鋅、鉻等之金屬成分的鍍敷處理或浸漬處理， 且於最外層塗佈各種砂院親合劑並使其乾燥。金屬箔表面 的粗化處理雖爲用以得到高的抗剝離強度之適合的方法， 但會產生所謂「殘根」之金屬蝕刻殘留物，於線路間容易 發生短路的問題，最近，爲了解決此問題，而有將粗化處 理減小的嘗試在進行著。然而，於使用粗化處理小的金屬 箔（亦即作爲表面粗度的指標之R a爲0 . 3 0 // m未滿者）之 情況，雖可改善殘根之問題，惟，抗剝離強度爲由0 . 1程 6 312/發明說明書(補件)/92-02/91135063 200300726 度至1.0kN/m程度有甚大的參差，故顯著地收率會變差， 實際製造上有困難。 於幾乎未施行粗化處理之表面粗度低的金屬箔，在聚醯 亞胺層與金屬層之間的所謂之錨合（a n c h 〇 r )效果之物理 性密著力無法發揮，爲使抗剝離強度發揮，在聚醯亞胺與 金屬箔的表面處理間之化學性相互作用是必要的。因此， 必須就金屬箔的表面處理的種類與濃度的組合作最適化， 惟，迄今尙無此最適化的成功例。 另一方面’於絕緣層使用聚醯亞胺系樹脂之軟式金屬層 合物，由於具有耐熱性、耐藥品性、尺寸安定性、電氣特 性等之優異特性，故可廣泛地使用於各種軟式線路基板 (FPC)、1C 及 LSI 的捲帶自動接合（TAB，tapautometic b ο n d i n g )、薄膜晶片焊接技術（c O F，c h i p 〇 n f i 1 m )等。 又，近年來，電路設計日益微細化，於電路的位置對準 或於電路上安裝I C之時等’經由影像處理來精確地偵測 出電路的位置是必要的。 例如，於TAB及C OF的製造線之稱爲內部引線接合（ILB) 之用以將i c及L s I晶片與電路接合的步驟中，必須能夠 對於電路側的位置對準標記或線路本身與晶片側的稱爲標 記與凸起電極（blimp )的接合點經由影像處理來辨識，俾可 在接合前對晶片與電路的位置偏差作微調整，由於在通常 的TAB中之稱爲裝置孔（deviCe hole)的孔穴係開設於 絕緣層’故晶片側的標記與凸起電極的辨識容易，位置偏 移的問題少。 312/發明說明書(補件)/92-〇2/91135063 7 200300726 然而’在如此之沒有裝置孔的稱爲區域標記之TAB或 C 0 F中’由於必須透過絕緣層來辨識晶片側的標記與凸起 電極，絕緣層的光透過性若低，影像會不淸晰，致位置對 準精度差致良率降低。 爲了克服這樣的問題，迄今係使用著對主要爲聚醯亞胺 系樹脂薄膜（例如東麗杜邦（股）公司製之聚醯亞胺薄膜） 經由將金屬濺鍍於其上形成金屬膜，其後經由電鍍法使銅 等之金屬析出其上的軟式金屬層合物。於此方法中，使用 於絕緣層之薄膜表面本身爲平滑的，而且於濺鍍蒸鍍後也 幾乎不會改變仍爲平坦，故光透過性高，而可進行時 的影像辨識，惟’製造成本高，並且，金屬與絕緣層間的 密著力弱’尤其在組裝I C晶片之時有加熱步驟，濺鍍品 於如此之加熱後的密著力會顯著地降低，而有著電路加工 時及其後的步驟中線路剝落的嚴重的問題，爲了將其改善 之各種努力雖在進行著，惟，迄今尙未能解決。 又，亦有稱爲鑄膜法之軟式金屬層合物（係將溶解在溶 劑中的聚醯亞胺系樹脂直接塗佈到金屬箔上施以乾燥所得 者），此方法中，爲了確保密著力，向來係必須使用金屬 箔的表面粗度較大者，與金屬箔相接的絕緣層表面會有凹 凸，由於會將光散射反射，故光透過性差，致無法使用於 須要透過絕緣層進行影像辨識之用途。 【發明所欲解決之課題】 本發明之目的在於解決上述的問題，而提供一種金屬箔 與聚醯亞胺層的抗剝離強度優異，且參差少，可形成微細 8 312/發明說明書(補件)/92-02/91135063 200300726 線路圖案之具有高可靠性，且可適合使用作爲高密度 基板材料之聚醯亞胺金屬層合板及其製造方法。又， 可透過絕緣層進行影像辨識的絕緣層之光透過性優異 式金屬層合物，並且具有高的密著力之軟式金屬層合 其製造方法。 【發明內容】 本發明之聚醯亞胺金屬層合板，係在聚醯亞胺層的 1面形成有金屬層的層合板；其特徵在於，金屬層與 亞胺層之接面之鋅的附著量爲0.07 mg/dm2以下。 又，本發明之聚醯亞胺金屬層合板之較佳樣態，爲 屬層與聚醯亞胺層之接面的表面粗度，爲算術平均 (Ra)未滿0.3〇//m，金屬層與聚醯亞胺層之接面之矽 著量爲 0.001〜O.Olmg/dm2，絡的附著量爲 〇·( 0.05mg/dm2，鎳的附著量爲 0.07〜〇.5mg/dm20 又’本發明之聚醯亞胺金屬層合板之較佳樣態，爲 屬層以蝕刻除去後之聚醯亞胺層的光透過率爲1 Q %以_ 本發明中，較佳者爲，上述金屬層，係由經由依照 鎳及/或鎳-鋅合金、（2)鋅及/或鋅-鉻合金、（3)絡及 鋅-鉻合金的順序進行表面處理形成處理層，並在該 層上施有矽烷耦合劑處理的金屬箔所得者。 上述處理層，以含有選自釩、鉬、鈷、錫、鐵、磷、 鎢、鋁及錳中之至少1種的成分爲佳。 於本發明中，上述聚醯亞胺層，亦可爲由鄰接之層 相異的成分之2層以上的聚醯亞胺層所成之多層者。 312/發明說明書(補件)/92_〇2/9〗〗3 5 〇63 電路 提供 的軟 物及 至少 聚醯 其金 粗度 的附 〕1〜 將金 L· ° (1 ) :/或 處獲 銦、 互爲 200300726 與上述金屬層鄰接之聚醯亞胺，較佳者爲_·選自由1 , 3 -雙（3 -胺基苯氧基）苯、4 , 4 -雙（3 -胺基苯氧基）聯苯及 3 , 3 '-二胺基二苯甲酮所構成的群中之至少1種的二胺， 與選自 3,3^4, 4'-二苯基醚四羧酸二酐、3, 3/-4,4/-二苯甲酮四羧酸二酐及苯均四甲酸二酐所構成的群中之至 少1種的四羧酸二酐，所合成之熱可塑性聚醯亞胺或含有 該熱可塑性聚醯亞胺之組成物。 本發明之聚醯亞胺金屬層合板之製造方法，其特徵在 於，係將單層或多層之聚醯亞胺薄膜與金屬箔進行加熱壓 合。 又，本發明之聚醯亞胺金屬層合板之製造方法，以將聚 醯亞胺的前驅體淸漆（v a r n i s h )塗佈於金屬箔後，使其乾 燥，以製造上述之聚醯亞胺金屬層合板爲佳。 再者，本發明之聚醯亞胺金屬層合板之製造方法，較佳 者爲，以將下述層合物（i)或層合物（ii)，與下述層合物 (i)或（ii)，以使金屬層作爲最外層的方式進行層合來製 造聚醯亞胺金屬層合板。 層合物（i ): 將單層或多層的聚醯亞胺薄膜與金屬箔，進行加熱壓合 所得到之只在一面有金屬層的層合物； 層合物（i i ): 將聚醯亞胺前驅體淸漆塗佈於金屬箔上之後，使其乾燥 所得到之只在一面有金屬層的層合物。 10 3 π/發明說明書(補件)/92-02/91135063 200300726 【發明之效果】 本發明之聚醯亞胺金屬層合板，其金屬層與聚醯亞胺層 之間的抗剝離強度高，且抗剝離強度安定。本發明之聚醯 亞胺金屬層合物，可形成微細的線路圖案，適合於作爲高 可靠性且高密度的電路基板材料。 又，依據本發明，可廉價地提供透過絕緣層可進行影像 辨識、絕緣層的光透過性優異之軟式金屬層合物’且具有 高的密著力之軟式金屬層合物。 【實施方式】 以下，就本發明之聚醯亞胺金屬層合板及其製造方法具 體地加以說明。 本發明之聚醯亞胺金屬層合板，係於聚醯亞肢層的至少 1面形成有金屬層。 [金屬層] 用以形成本發明之聚醯亞胺金屬層合板的金屬層’係由 選自銅及銅合金、不銹鋼及其合金、鎳及鎳合金（含4 2合 金）、銘及銘合金等之中的金屬所形成，而以銅或銅合金 爲佳。 金屬層之與聚醯亞胺層相接的面之表面粗度，宜爲算術 平均粗度（Ra)未滿〇·3//γτι，而以0.28//m以下爲佳’以 〇.25//m以下更佳，尤以以下爲特佳。與聚醯亞 胺層相接側的金屬層之表面粗度，若在上述範圔內，則金 屬殘根有減少的傾向。有關算術平均粗度的測定方法’將 於後敘述。 11 312/發明說明*：(補件)/92-02/91135063 200300726 又 ％屬層與聚醯亞胺層之接面，作爲用以表示表面粗 &的=斗的指標之1 ◦點平均粗度（R z )宜爲2 . 5 μ m以 下，而 1 · 5 μ m以下爲佳，以丄· 〇 # m以下更佳。1 〇點 平均粗降 X (尺Z )可與後述之算術平均粗度（R a )之同樣的方 法測定。 金屬層與聚醯亞胺層之接面，鋅的附著量宜爲〇〜 0 . 0 5 m 〇 / η 2 / dm ’較佳者爲，矽的附著量爲〇 . 〇 ζ〜q . 〇工 9 絡的附著量爲0·01〜0 .OStHg/dm2，鋅的附著量 爲 0〜 η '' Q_Q7m9/dm2，鎳的附著量爲 〇.〇7〜〇.5 mg/dm2 的範^ ;更佳者爲，矽的附著量爲Q. 〇〇2〜〇.006 9 鉻的附者量爲〇.〇2〜0.03mg/dm2，鋅的附著量200300726 (1) Description of the invention [Technical field to which the invention belongs] The present invention relates to a polyimide metal laminate widely used in flexible circuit boards and the like, and a method for manufacturing the same. More specifically, the present invention relates to metal layers and polyimide The amine layer is excellent in adhesion, and it is suitable to use a polyimide metal laminate having excellent light transmittance as a high-density circuit board material and a method for producing the same. [Prior Art] In recent years, with the miniaturization of electronic equipment, the use of polyimide metal laminates that can be used as circuit boards to mount components and components at high density has increased. In addition, in response to the trend toward higher densities, polyimide metal laminates suitable for processing fine patterns with a line width of 1 G to 5 0 // m have been eagerly anticipated, and considered from the viewpoint of circuit reliability. The peel resistance must be high as an index of the adhesion between the metal and polyfluorene. However, metal foils used in polyimide metal laminates have metal components such as nickel, zinc, chromium, etc., which are roughened or surface-treated in order to exert their peel strength with polyimide. Plating treatment or immersion treatment, and coating various sand garden affinity agents on the outermost layer and drying them. Although the roughening treatment of the surface of the metal foil is a suitable method for obtaining high peeling resistance, so-called "residual root" metal etching residues are generated and short circuits are prone to occur between circuits. Recently, in order to solve this Problems, and there are attempts to reduce the roughening process. However, in the case of using a small roughened metal foil (that is, R a as an index of surface roughness is 0.30 / m), the problem of residual roots can be improved, but peeling resistance The strength varies from 0.1 to 6 312 / Invention Specification (Supplement) / 92-02 / 91135063 200300726 degrees to 1.0 kN / m degree, so there is a great difference in yield, so the yield will be significantly deteriorated, and it is difficult to manufacture it. In a metal foil with a low surface roughness that is hardly subjected to roughening treatment, the physical adhesion of the so-called anchor effect between the polyimide layer and the metal layer cannot be exerted. In order to exert strength, a chemical interaction between polyimide and the surface treatment of metal foil is necessary. Therefore, it is necessary to optimize the combination of the type and concentration of the surface treatment of the metal foil. However, there has been no successful example of this optimization so far. On the other hand, a soft metal laminate using a polyimide-based resin as an insulating layer can be widely used in various flexible circuits due to its excellent properties such as heat resistance, chemical resistance, dimensional stability, and electrical characteristics. Substrate (FPC), 1C and LSI tape auto-bonding (TAB, tapautometic b nding), thin film wafer welding technology (c OF, chip ONFI 1 m), etc. In recent years, circuit design has been increasingly miniaturized, and it is necessary to accurately detect the position of the circuit through image processing when the position of the circuit is aligned or when IC is mounted on the circuit. For example, in the step of manufacturing the TAB and C OF lines called internal wire bonding (ILB) to bond the IC and L s I chips to the circuit, it is necessary to be able to align the mark on the circuit side or the line itself with the circuit. The bonding point on the wafer side called a marker and a bump electrode (blimp) is identified through image processing. You can fine-tune the position deviation of the wafer and the circuit before bonding. Because it is called a device hole in a common TAB ( The holes of the deviCe hole) are provided on the insulating layer, so the identification of the mark on the wafer side and the bump electrode are easy, and the problem of position shift is small. 312 / Invention Note (Supplement) / 92-〇2 / 91135063 7 200300726 However, 'in the TAB or C 0 F called the area mark, which has no device hole,' because the mark on the wafer side must be identified through the insulating layer, and If the light transmittance of the bump electrode and the insulating layer is low, the image will be unclear, resulting in poor positioning accuracy and lower yield. In order to overcome such a problem, a polyimide-based resin film (for example, a polyimide film manufactured by Toray DuPont Co., Ltd.) has been used so far to form a metal film by sputtering a metal. Then, a soft metal laminate is deposited on the metal such as copper by electroplating. In this method, the surface of the thin film used for the insulation layer is smooth itself, and it hardly changes after sputtering and is still flat, so the light transmittance is high, and the image recognition at the time can be performed. The cost is high, and the adhesion between the metal and the insulating layer is weak. In particular, there is a heating step during the assembly of the IC wafer. The adhesion of the sputtered product after such heating will be significantly reduced. Although the serious problem of the line peeling in the step is being worked, various efforts are being made to improve it, but so far, it has not been solved. In addition, there is a soft metal laminate called a cast film method (a polyimide resin dissolved in a solvent is directly applied to a metal foil and dried). In this method, in order to ensure a dense Attention, it has always been necessary to use a thicker surface of metal foil. The surface of the insulating layer in contact with the metal foil will have unevenness. Since it will scatter and reflect light, the light permeability is poor, and it cannot be used for applications that need to pass through the insulating layer. The purpose of image recognition. [Problems to be Solved by the Invention] The object of the present invention is to solve the above-mentioned problems, and to provide a metal foil and a polyimide layer with excellent peel resistance and small variations, which can form fine 8 312 / Invention Specification (Supplementary Document) ) / 92-02 / 91135063 200300726 The circuit pattern has high reliability, and can be suitably used as a high-density substrate material of polyimide metal laminate and its manufacturing method. In addition, an insulating layer capable of image recognition through an insulating layer is a flexible metal laminate having excellent light transmittance and high adhesion and a method for manufacturing the same. [Summary of the Invention] The polyimide metal laminate of the present invention is a laminate in which a metal layer is formed on one side of the polyimide layer; it is characterized in that the zinc on the interface between the metal layer and the imine layer is attached The amount is below 0.07 mg / dm2. In addition, the preferred aspect of the polyimide metal laminate of the present invention is the surface roughness of the interface between the metal layer and the polyimide layer, and the arithmetic average (Ra) is less than 0.30 // m. The silicon content of the interface between the layer and the polyimide layer is 0.001 to 0.01 mg / dm2, and the adhesion amount of the network is 0.05 (0.05 mg / dm2, and the adhesion amount of nickel is 0.07 to 0.5 mg / dm20. The preferred aspect of the polyimide metal laminate of the present invention is that the light transmittance of the polyimide layer after the metal layer is etched and removed is 1 Q%. In the present invention, it is preferred that the above metal The layer is formed by performing a surface treatment in the order of nickel and / or nickel-zinc alloy, (2) zinc and / or zinc-chromium alloy, (3) complex and zinc-chromium alloy, and on the layer A metal foil obtained by treatment with a silane coupling agent. The treatment layer preferably contains at least one component selected from the group consisting of vanadium, molybdenum, cobalt, tin, iron, phosphorus, tungsten, aluminum, and manganese. In the present invention In the above, the polyimide layer may be a multilayer made of two or more polyimide layers having different components adjacent to each other. 312 / Description of the Invention (Supplement) / 92_〇2 / 9 〖3 5 〇63 The soft material provided by the circuit and at least the thickness of the gold is attached.] 1 ~ Gold L · ° (1): / or poly indium, each of which is 300300726 and adjacent to the above metal layer An amine, preferably _ · is selected from the group consisting of 1, 3-bis (3-aminophenoxy) benzene, 4,4-bis (3-aminophenoxy) biphenyl, and 3,3'-diamine At least one type of diamine in the group consisting of benzophenone, and selected from 3,3 ^ 4, 4'-diphenyl ether tetracarboxylic dianhydride, 3, 3 / -4, 4 /- Tetracarboxylic dianhydride of at least one of the group consisting of benzophenone tetracarboxylic dianhydride and pyromellitic dianhydride, or a thermoplastic polyimide containing the same or a thermoplastic polyimide The composition of the polyimide metal laminate of the present invention is characterized in that a single-layer or multi-layer polyimide film and a metal foil are heated and pressed together. In addition, the polyimide of the present invention In the method for producing an amine metal laminate, a precursor of polyimide varnish (varnish) is applied to a metal foil and then dried to produce the above-mentioned polyimide metal laminate. The hair The method for manufacturing a polyimide metal laminate of the Ming Dynasty is preferably to use the following laminate (i) or (ii) and the following laminate (i) or (ii) to A metal layer is laminated with the metal layer as the outermost layer to produce a polyimide metal laminate. Laminate (i): A single or multiple layers of a polyimide film and a metal foil are obtained by heating and laminating. Laminate with a metal layer on only one side; Laminate (ii): After coating polyimide precursor lacquer on a metal foil, drying it to obtain a laminate with a metal layer on only one side Thing. 10 3 π / Invention specification (Supplement) / 92-02 / 91135063 200300726 [Effect of the invention] The polyimide metal laminate of the present invention has a high peel resistance between the metal layer and the polyimide layer, And the peel strength is stable. The polyfluorene imide metal laminate of the present invention can form a fine circuit pattern, and is suitable as a high-reliability and high-density circuit board material. In addition, according to the present invention, a soft metal laminate having a high adhesion can be provided at a low cost because the soft metal laminate is capable of image recognition through an insulating layer and has excellent light transmittance of the insulating layer. [Embodiment] Hereinafter, the polyimide metal laminate of the present invention and a method for manufacturing the same will be specifically described. The polyfluorene imide metal laminate of the present invention has a metal layer formed on at least one side of the polyfluorene sublime layer. [Metal layer] The metal layer used to form the polyimide metal laminate of the present invention is selected from the group consisting of copper and copper alloys, stainless steel and its alloys, nickel and nickel alloys (including 42 alloys), inscriptions and inscription alloys. It is preferably formed of a metal such as copper, or copper or a copper alloy. The surface roughness of the surface of the metal layer in contact with the polyimide layer should preferably be an arithmetic average roughness (Ra) of less than 0.3 // γτι, and preferably 0.28 // m or less. // m is better below, especially below. If the surface roughness of the metal layer in contact with the polyimide layer is within the above range, the metal root tends to decrease. The method for measuring the arithmetic mean roughness' will be described later. 11 312 / Explanation of the invention *: (Supplement) / 92-02 / 91135063 200300726 The interface between the% layer and the polyimide layer is used as one of the indicators of the surface roughness & = point average The thickness (R z) is preferably 2.5 μm or less, and preferably 1.5 μm or less, and more preferably 丄 · 〇 # m or less. The 10-point average coarse drop X (feet Z) can be measured in the same manner as the arithmetic mean coarseness (Ra) described later. At the interface between the metal layer and the polyimide layer, the zinc adhesion amount is preferably 0 to 0.5 m 〇 / η 2 / dm 'preferably, the silicon adhesion amount is 0.0 to ζ to q. 〇 The amount of adhesion of G9 is 0 · 01 ~ 0. OStHg / dm2, the amount of zinc is 0 ~ η '' Q_Q7m9 / dm2, and the amount of nickel is 0.07 ~ 0.5 mg / dm2. Better yet, the amount of silicon attached is Q. 〇〇2〜〇.006 9 The amount of attached chromium is 0.02 ~ 0.03mg / dm2, the amount of zinc attached
肖 〇〜 Q J m9/dm2，鎳的附著量爲 〇.：L 〜0.35 mg/dm2 白勺範圍 ο -ΤΗ 、 鉻、鋅及鎳的附著量若爲上述的範圍，則有 發揮出鹚聚醯亞胺層之高的抗剝離強度的傾向。有關矽、 絡、辞及鎳的附著量之測定方法，將於後敘述。 此金_層中的矽，以來自矽烷耦合劑爲佳。 而且’以由經由依下述順序·· (1 )鎳及/或鎳-鋅合金、 (2 )鋅及/或鋅-鉻合金、 (3 )鉻及/或鋅—鉻合金 進行表面處理形成處理層，並在該處理層上施有矽烷耦合 劑處理的金屬箔所得到者爲佳。 若依照這樣的順序施行表面處理，則金屬層之抗剝離強 度優異，且耐熱性、鈾刻性也優異。 12 312/發明說明書(補件)/92-02/91135063 200300726 又’上述處理層’以含有選自釩、鉬、鈷、錫、鐵、磷、 銦、鎢、鋁及锰中之至少1種的成分爲佳。此等成分之含 有量，宜在〇〜O.Smg/dm2的範圍。若含有選自此等金屬 中的金屬，則金屬層之蝕刻性與耐熱性可提高，且，加熱 後的抗剝離強度有安定化的傾向。常溫及加熱後的抗剝離 強度以Q.SkN/iri以上爲佳，而以Q.skN/m以上更佳，尤 以0.5kN/m以上爲特佳。 [聚醯亞胺層] 用以形成本發明之聚醯亞胺金屬層合板之聚醯亞胺層， 爲單層或多層’於多層的情況’以由鄰接之層互爲相異的 成分之2層以上的聚醯亞胺層所成者爲佳。又，所謂「聚 醯亞胺的成分互爲相異」者，係指單體單位的種類及/或 含有量相異。又’用以形成單層之聚醯亞胺層或多層之聚 醯亞胺層的層之至少1層亦可由2種以上相異的聚酸亞胺 所構成之組成物（混合物）所形成。 於聚醯亞胺層爲單層的情況，以由熱可塑性聚酿亞胺或 熱可塑性或含有熱可塑性聚醯亞胺組成物爲佳。於多層的 情況，以由非熱可塑性聚醯亞胺層，與熱可塑性聚醯亞胺 層或含有熱可塑性聚醯亞胺組成物層所構成爲佳，爲使其 與金屬層的密著性優異，與金屬層相接的面以熱可塑性聚 醯亞胺或含有熱可塑性聚醯亞胺組成物爲佳。 作爲用於聚醯亞胺層之熱可塑性聚醯亞胺，較佳者爲： 選自由 1,3 -雙（3 -胺基苯氧基）苯、4, 4 -雙（3 -胺基苯氧 基）聯苯及 3 , 3 '-二胺基二苯甲酮所構成的群中之至少工 13 312/發明說明書(補件)/92-02/91135063 200300726 種的二胺，與選自3 , 3，- 4 , 4 '-二苯基醚四羧酸 3, 3, ~4, 4'-二苯甲酮四羧酸二酐及苯均四甲酸二 成的群中之至少1種的四羧酸二酐，所合成之熱可 醯亞胺或含有該熱可塑性聚醯亞胺。又，於爲含有 醯亞胺層之熱可塑性聚醯亞胺之聚醯亞胺組成物的 以含有熱可塑性聚醯亞胺i 〇重量％以上爲佳。 作爲用於聚醯亞胺層之非熱可塑性聚釀亞胺薄膜 可用非熱可塑性聚醯亞胺的前驅體淸漆塗佈並施以 得到之外，亦可使用市售的非熱可塑性聚醯亞胺薄 列舉例如：優匹雷克斯S、優匹雷克斯S G A、優匹 SN (宇部興產（股）製，商品名），卡卜通H、卡卜通 卜通E N (東麗·杜邦（股）製，商品名），阿匹卡爾 匹卡爾NPI、阿匹卡爾HP(鐘淵化學工業（股）製造 名）等。 於使用市售的非熱可塑性聚醯亞胺薄膜的情況， 常宜爲3〜75//ΤΠ，而以7.5〜40//m的範圍爲佳。 以非熱可塑性聚醯亞胺的前驅體淸漆塗佈並加以乾 況，厚度宜爲 0.1〜4〇//m，而以 0.5〜25// m爲 以Q . 5〜1 6 // m爲最佳。又，熱可塑性聚醯亞胺層 宜爲0.1〜20/zm，而以〇·1〜爲佳，尤以 JU m爲最佳。 再者，聚醯亞胺層的總厚度若過厚，由於剛性會 致無法使用於必須折曲的用途’若過薄’由於在絕 取用方面會變得無法使用而受到限制’故以使總厚 312/發明說明書(補件)/92-02/91135〇63 二酐、 酐所構 塑性聚 用於聚 場合’， ，除了 乾燥而 膜。可 雷克斯 [V、卡 AH、阿 ，商品 厚度通 又，於 燥的情 佳，尤 的厚度 0 · 1 〜5 較強， 緣性及 度成爲 14 200300726 3〜75// m (而以10〜45//m更佳）的方式將熱可塑性聚醯 亞胺層與非熱可塑性聚醯亞胺層的厚度調整於上述範圍內 爲佳。聚酿亞胺層的厚度若在上述範圍內，則聚醯亞胺金 屬層合物之絕緣性、柔軟性、作業性優異，且有成本低的 傾向。 又’作爲未與金屬箔直接相接之聚醯亞胺系樹脂層，不 3有上述熱可塑性聚醯亞胺樹脂亦可，可由既有的聚醒亞 胺層及/或聚醯亞胺層樹脂選擇，惟，由於作爲絕緣層以 具有1 〇 %以上的光透過性者爲佳，故以具有光透過容易的 非晶性構造的樹脂爲佳，且，在使用各種混合材料於絕緣 層樹fl曰中的彳胃況，以不使光透過率降低到1 〇 %以下的程度 來決定混合比例爲佳。 將金屬箔蝕刻除去後的聚醯亞胺的光透過率，於透過聚 醯亞胺薄膜之配線圖案之辨識及在配線上安裝I c等的晶 片之時’透過聚醯亞胺薄膜之對準標記的辨識等，係影像 處理上所必要的。尤其是，所用的金屬箔的表面粗度大的 情況’即使於將金屬箔蝕刻除去後，金屬箔表面的凹凸由 於經轉印到聚醯亞胺層，故會使光散射反射致無法作影像 辨識。因此之故’亦須依存於聚醯亞胺的膜厚，以其膜厚 爲3 5 // m舉例的情況，則光的波長爲6 Q 〇 nm時的光透過 率且爲10%以上’而以4〇%以上爲佳，尤以以上更佳。 [聚醯亞胺金屬層合物之製造方法] 本發明之聚醯亞胺金屬層合物，可用例如下述的方法製 造。 312/發明說明書(補件)/92-02/91135063 15 200300726 (1 )將單層或多層的聚醯亞胺薄膜與金屬箔加熱壓合的 方法。 (2 )以聚醯亞胺的前驅體淸漆塗佈於金屬箔上之後，加 以乾燥的方法。 (3 )將下述層合物（i )或層合物（i i )，與下述層合物（i ) 或（i i )，以使金屬層作爲最外層的方式進行層合的方法。 層合物（i ):將單層或多層的聚醯亞胺薄膜與金屬箔， 進行加熱壓合所得到之只在一面有金屬層的層合物； 層合物（i i ):將聚醯亞胺前驅體淸漆塗佈於金屬箔上之 後，使其乾燥所得到之只在一面有金屬層的層合物。 更具體而言，有下述的方法： (1 )於熱可塑性聚醯亞胺的單層薄膜的單面或雙面上將 金屬箔加熱壓合的方法。熱可塑性聚醯亞胺薄膜，可由例 如以熱可塑性聚醯亞胺的淸漆塗佈並加以乾燥而得到。 (2 )於非熱可塑性聚醯亞胺薄膜上，以至少1種的熱可 塑性聚醯亞胺的前驅體淸漆，在該非熱可塑性聚醯亞胺薄 膜的單面或雙面上塗佈至少1層使其乾燥，以製造在非熱 可塑性聚醯亞胺薄膜的至少1面上有熱可塑性聚醯亞胺層 的層合物，然後，在該層合物的單面或雙面上將金屬箔加 熱壓合的方法。此情況，金屬箔以使其與多層的聚醯亞胺 薄膜的熱可塑性聚醯亞胺層相密接的方式進行層合爲佳。 作爲非熱可塑性聚醯亞胺薄膜，可列舉如上述者。 (3 )於非熱可塑性聚醯亞胺薄膜的一面上，以同一成分 或相異成分之非熱可塑性聚醯亞胺的前驅體淸漆塗佈至少 16 312/發明說明書(補件)/92-02/91135063 200300726 1層使其乾燥，並且在該非熱可塑性聚醯亞胺薄膜的另一 面上以熱可塑性聚醯亞胺的前驅體淸漆塗佈至少1層使其 乾燥，以製造層合物，然後，於該層合物的熱可塑性聚醯 亞胺的面以金屬箔進行加熱壓合的方法。 (4 )以至少1種的聚醯亞胺的前驅體淸漆在金屬箔上塗 佈至少1層並加以乾燥的方法。 (5 )以至少1種的聚醯亞胺的前驅體淸漆在金屬箔上塗 佈至少1層並加以乾燥以製造層合物，然後，以上述（1 ) 〜（4 )之任一方法所製造的聚醯亞胺金屬層合物進行加熱 壓合而進行層合的方法。又，此方法中，係以使金屬層成 爲最外層的方式層合作成層合物。 用於聚醯亞胺金屬層合物的製造之金屬箔，宜由選自銅 及銅合金、不銹鋼及其合金、鎳及鎳合金（含42合金）、 鋁及鋁合金等之中的金屬所形成，而以銅或銅合金爲佳。 金屬箔，其與聚醯亞胺之接面的表面粗度，宜爲算術平 均粗度（R a )未滿0 · 3 Q // m，而以◦ · 2 8 // m以下爲佳，以 0.2 5//m以下更佳，尤以0·20//τη以下爲最佳。 又，金屬層與聚醯亞胺之接面，作爲用以表示表面粗度 的另外的指標之1 ◦點平均粗度（R ζ )宜爲2 . 5 // m以下， 而以1 · 5 // m以下爲佳，以1 · 0 // m以下更佳。 金屬層與聚醯亞胺之接面，鋅的附著量宜爲 0〜 〇.07mg/dm2，較佳者爲，矽的附著量爲 0.001〜 〇.〇lmg/dm2，鉻的附著量爲 0·01〜0.〇5mg/dm2，鋅的 附著量爲 ◦〜◦•◦▽mg/dm2以下，鎳的附著量爲 〇.〇7〜 17 312/發明說明書(補件)/92-02/91135063 200300726 0 . 5 m g / d m 2的範圍；更佳者爲，砂的附著量爲 0.002〜 〇.〇〇6mg/dm2，鉻的附著量爲0.02〜〇.03mg/dm2，鋅的 附著量爲 ◦〜〇 · 〇5mg/dm2以下，鎳的附著量爲 0 · 1〜 0.35mg/dm2 0 此金屬層中的矽，以來自矽烷耦合劑爲佳。 而且，以由經由依下述順序： (1 )鎳及/或鎳-鋅合金、 (2 )鋅及/或鋅·鉻合金、 (3 )鉻及/或鋅-鉻合金 進行表面處理形成處理層，並在該處理層上施有矽烷耦合 劑處理的金屬箔所得到者爲佳。 若依照這樣的順序施行表面處理，則金屬層之抗剝離強 度優異，且耐熱性、鈾刻性也優異。 又，上述處理層，以含有釩、鉬、鈷、錫、鐵、磷、銦、 鎢、銘及猛爲佳。此等成分之含有量，以在0〜Q.5mg/dm2 的範圍爲佳。 這樣的矽、鉻、鋅及鎳的附著量在特定的範圍內之金屬 箔，可藉由例如將金屬箔以下述的方法進行表面處理而得 到。 經由矽烷耦合劑處理，通常使用浸漬法。作爲矽烷耦合 劑處理以外的處理方法，可舉出：浸漬法、電鍍法、化學 鍍法、蒸鍍法、濺鍍法、金屬噴鍍法等，若就生產性考量， 以浸漬法、電鍍法爲佳。 此金屬箔的厚度，只要是能以膠帶狀使用的厚度即可， 18 312/發明說明書(補件)/92-02/91135063 200300726 並無特別限定，通常宜爲0.1〜150//ΤΠ，而以2〜150μτη 爲佳，以3〜5 ◦ m爲更佳，尤以3〜3 5 μ m爲特佳，更 以3〜1 2 // m的範圍爲最佳。 於製造聚醯亞胺金屬層合物之時，非熱可塑性聚醯亞胺 的表面亦可施以電漿處理、電暈放電處理等。 作爲此處之加熱壓合方法，有：在以油等作爲熱媒之加 熱或感應加熱（in duction heating)所加熱之金屬輕與 金屬輥表面經橡膠等襯覆的輥之間進行壓合的方法，及經 由熱沖壓的方法等，前者適合於連續的成捲品之製造，後 者則適於切片狀的片狀製品，可依用途而適當地使用。 又’加熱壓合條件，環境氣體可適當地使用空氣、氮氣、 氬氣等’加熱溫度須在對應於熱可塑性聚醯亞胺爲主之玻 璃轉移溫度的溫度下進行，通常可在 1 0 0〜4 0 0 °C之間進 行，較佳者爲1 5 0〜3 0 0 t。又，加熱時間宜爲0 · 0 1秒〜 15小時，加熱壓力爲 0.1〜30MPa即可，通常爲 0.5〜 1 0 Μ P a 0 又，爲使密著力更加提高的目的，亦可使用高壓釜等進 行後處理。後處理可在下述的條件下進行。後處理的溫度 通常爲1 5 0〜4 0 0 °C，而以2 0 0〜3 5 0 t爲佳，處理時間爲 1分〜5〇小時，壓力爲常壓〜3MPa的範圍，高壓釜裝釐 內以作成爲真空或以氮氣或氬氣等惰性氣體取代可防止金 屬箔的氧化，故爲較佳。 又，對金屬箔或聚醯亞胺薄膜以聚醯亞胺的前驅體淸漆 塗佈時，可使用溶劑。作爲這樣的溶劑，只要是可溶解所 19 312/發明說明書(補件)/92-02/91135063 200300726 使用之聚醯亞胺的前驅體淸漆的溶劑即可，並無特別限 疋可使用例如· N-甲基—四氫吡略酮、Ν,Ν -二甲基乙 醯胺等。 作爲聚醯亞胺的前驅體淸漆之塗佈裝置，可利用輥塗佈 機、壓模（die)塗佈機、凹板塗佈機、浸漬塗佈機、噴霧 式塗佈機、逗點塗佈機、簾幕式塗佈機、棒式塗佈機等一 般的塗佈裝置，可依聚醯亞胺的前驅體淸漆的黏度與塗佈 厚度作適當的選擇。 作爲聚醯亞胺的前驅體淸漆的乾燥裝置，可適當地利用 以電力加熱或燃油加熱的熱風或以紅外線等作爲熱源之輥 載ί寸（roll support)式、氣浮方式的乾燥爐，爲了防止 樹脂的變質或因於金屬箔之氧化的變色之目的，必要時亦 可將乾燥環境氣體以空氣以外的氮氣、氬氣、氫氣等之氣 體取代。 聚醯亞胺的前驅體淸漆之乾燥溫度，可爲6 0〜6 0 0 °C的 溫度範圍，較佳者爲使溫度作階段性的昇高，由於在絕緣 層的膜形成上不會產生發泡及橘皮等的問題，而可得到膜 厚均一且尺寸安定性亦優異的樹脂，故爲較佳；乾燥時間 可於0 · 0 5〜5 0 0分之間適當地選擇。 實施例 以下，就本發明經由實施例更詳細地加以說明。又，實 施例中所示之金屬箔的表面處理附著量、金屬箔的表面之 最大粗度、金屬箔與熱可塑性聚醯亞胺層之抗剝離強度’ 係經由下述的方法測定。 20 312/發明說明書(補件)/9102/91135063 200300726 (1 )表面處理附著量 用分析用螢光X射線測定裝置，對切成直徑4 0 mm的圓 盤狀的樣品進行測定。換算成單位面積的附者M而求出。 單位爲mg/dm2。 (2 )算術平均粗度：R a ( // m ) 用表面粗度計（小阪硏究所製，型式：莎福科達 SE-3QD)，依據 JIS_B-0601，切斷（cut-〇ff)値作爲 〇 . 2 5 m m，測定長度作爲2 · 5 m m，在與絕緣層相接之金屬箔 表面，沿著金屬箔製造時的行進方向、沿著金屬箔製造時 的行進方向以成爲直角及平行的任意的點各3點加以測 定，以得到之較大的値之3點的平均作爲算術平均粗度。 (3 )常溫及耐熱試驗後的抗剝離強度（kN / m ) 對平行於金屬箔的行進方向之長5 〇mm、寬1mm的試料， 在常溫2 3 °C 5 0 % R Η的環境下進行試驗；又耐熱性試驗係在 1 5 〇 °C的烘箱中進行 1 6 8小時加熱處理後，依據 J工S C - 6 4 7 1，以使金屬箔成爲9 0度的角度的方式自絕緣層以 剝離速度5 0 m m / m i η進行剝離，測定其應力。 又，測定片，係依金屬箔的寬方向採取1 0點等間隔， 抗剝離強度係定爲1 Q點的平均値。 (4 )光透過率（％ ) s式料係使用令金屬箱在氧化鐵鹽酸溶液中蝕刻除去者， 用光透過率測定裝置（日本分光公司製uv_Vis〜NiR)求出 於6〇0]1111下之光透過率。 又，實施例中所用之溶劑、酸二酐、二胺的簡稱係如下 312/發明說明書(補件)/92-02/91135063 91 200300726 述： D MAC ·· N , N -二 :亏 3基 L S 證胺 NM P ：N ~ 甲 基 - 2 _ 四 氫 吡 咯 酮 P Ρ D :對 苯 二 胺 〇 DA :4 , 4 i 二 胺: 基 二 苯 基 醚 m -BP :4 , 4 > - 雙 (3 _胺: 基 苯 氧 基 )聯苯 A Ρ B • 1 , 3 - -雙 :( 3 - 胺 基 苯 氧 基 ) 苯 B PDA :3 , 3 9 / 4 , 4 7 - 二 苯 基 四 羧 酸二酐 Ρ M D A :苯 均 四 甲 酸 二 酐 Β T D A :3 , 3 ‘ 9 / 4 , 4 , - 二 苯 甲 酮 四 羧酸二酐 (合 成例： L ) 將作爲溶劑之DMAc 1636g加入備有攪拌機及氮氣導入 管的容器中，對其加入A P B 1 4 6 . 2 g，於室溫下進行攪拌 直到其溶解。然後，加入B P D 1 4 2 · 5 g，於6 0 °C進行攪拌， 得到聚醯胺酸（ρ Ο 1 y a m i c a c i d )溶液。得到之聚醯胺酸溶 液之聚醯胺酸的含有率爲15重量％，25 °C下之E型黏度爲 5 5 0 c p s 〇 (合成例2 ) 將作爲溶劑之DMAc 1718.6g加入備有攪拌機及氮氣導 入管的容器中，對其加入APB 146.2g，於室溫下進行攪 拌直到其溶解。然後，加入B T D A 1 5 7 · 1 g，於6 ◦ t：下進 行攪拌，得到聚醯胺酸溶液。得到之聚醯胺酸溶液之聚醯 胺酸的含有率爲15重量％，25t：下之E型黏度爲50QCPs。 (合成例3 ) 22 312/發明說明書(補件)/92-02/91135063 200300726 將作爲溶劑之DMAC 644g與NMP 16lg加入備有攪泮 機及氮氣導入管的容器中，對其加入PPD4〇.59(75莫耳 %)、及ODA 17.5g(17.5莫耳％)，於一邊攪拌下加熱至 5 0〜6 0 °C使其溶解。然後，以冰冷卻至約成爲3 0 °C後’ 加入B P D A 7 8 · 0 g，加熱至6 0 °C，進行攪泮約2小時。再 加入m-BP 13.8g(7.5莫耳％)，於保持於溫度60°C下進 行攪拌。最後，力□入p M D A 5 1 · 3 9 ’於6 0 °C下進行攪拌2 小時，得到聚醯胺酸溶液。得到之聚醯胺酸溶液之聚醯胺 酸的含有率爲20重量％，25°C下之E型黏度爲lsoQGcps。 (合成例4 ) 將作爲溶齊!J之DMAC 846. 9g與NM P 362.9g力口入備有 攪拌機及氮氣導入管的容器中，對其加入PPD n2g(3〇 莫耳％)、及 〇DA 49.1g(49莫耳％) ’於一邊攪拌下加熱 至5 0〜6 Q °C使其溶解。然後，以冰冷卻至成爲約3 〇 °C後， 加入B P D A 2 5 . 1 g，加熱至6 Q °C，進行攪拌約2小時。再 加入m-BP38.7g(21莫耳％)，於保持於溫度60°C下進行 攪拌。最後，加入p M D A 8 4 · 4 g ’於6 0 °C下進行攪拌2小 時，得到聚醯胺酸溶液。得到之聚醯胺酸溶液之聚醯胺酸 的含有率爲15重量％，25°C下之£!型黏度爲40C)cPs。 (實施例1 ) 在市售之聚醯亞胺樹脂薄膜（東麗·杜邦（股）製’商品 名：卡卜通100EN)的一面上，以合成例1所調製的聚醯 胺酸溶液（以下，稱爲「淸漆」），經由輥塗佈機以使乾燥 後的膜厚成爲4 // m的方式塗佈，以1 5 〇 °C 2分鐘乾燥後’ 23 312/發明說明書(補件)/92-02/91135063 200300726 於另一面上，以合成例4所調製的淸漆’經由輕塗佈機以 使乾燥後的膜厚成爲5 // m的方式塗佈’以7 0艺5分鐘、 1 1 0 °C 5分鐘乾燥後，再進行1 4 0 °C 2分鐘、1 8 0 °C 5分鐘、 2 6 5 °C 2分鐘，於氣浮方式的乾燥爐進行乾燥，得到依熱 可塑性聚醯亞胺樹脂層、聚醯亞胺樹脂薄膜層、非熱可塑 性聚醯亞胺樹脂層的順序進行層合而成之聚醯亞胺的絕緣 薄膜。 然後’用上述絕緣薄膜與市售的銅箔（古河 c i r c u 土 t fi〇l (股）製，商品名：F0-WS，厚度 9//m，Ra: 0.17// m，表面處理如表1所記述），經由以矽橡膠被覆之輥式層 合機，於2 4 〇 °C下，壓力1 . 4 Μ P a的條件下，將銅箱與絕 緣薄膜以與熱可塑性聚醯亞胺層相接的方式張覆，其後， 以批次式的高壓釜在溫度2 8 0 °C氮氣環境下進行回火4小 時，得到聚醯亞胺金屬層合物。 對所得之聚醯亞胺金屬層合物進行評價之結果’得到常 態下及耐熱試驗後的抗剝離強度分別爲 〇 · 9 7、 0 . 4 5 kN / m >光透過率爲55%。 (實施例2 ) 除了如表1所示般之金屬箔的表面處理相異之外’其餘 係與實施例1同樣的作法，得到聚醯亞胺金屬層合物° 對所得之聚醯亞胺金屬層合物進行評價之結果’得到胃 態下及耐熱試驗後的抗剝離強度分別爲 0 · 8 8 ' 0.40kN/m，光透過率爲55%。 (實施例3 ) 24 312/發明說明書(補件)/92-02/91135〇63 200300726 除了如表1所示般之金屬箔的表面處理相異之外，其餘 係與實施例1同樣的作法，得到聚醯亞胺金屬層合物。 對所得之聚醯亞胺金屬層合物進行評價之結果，得到常 態下及耐熱試驗後的抗剝離強度分別爲 〇 · 8 6、 0.45kN/m，光透過率爲55%° (實施例4 ) 除了如表 1所示般之金屬箔的厚度與表面處理相異之 外，其餘係與實施例1同樣的作法，得到聚醯亞胺金屬層 合物。 ， 對所得之聚醯亞胺金屬層合物進行評價之結果，得到常 態下及耐熱試驗後的抗剝離強度分別爲1 . 1、◦ · 4 5 k N / m， 光透過率爲55%。 (實施例5 ) 除了將合成例1中所調製的淸漆改用合成例2所調製的 淸漆，且使用實施例4所用的金屬箔之外，其餘係與實施 例1同樣的作法，得到聚醯亞胺金屬層合物。 對所得之聚醯亞胺金屬層合物進行評價之結果，得到常 態下及耐熱試驗後的抗剝離強度分別爲 0.78、 0.40kN/m，光透過率爲55%。 (實施例6 ) 於市售的銅箔（古河 c i r c u i t f i ο 1 (股）製，商品名： F1-WS，厚度12//m，Ra: 0.28// m »表面處理參照表1) 之金屬箔上，以合成例3中調製的淸漆，用輥式塗佈機以 使乾燥後的厚度成爲〇 · 7 // m的方式塗佈，於8 Q °C乾燥1 25 312/發明說明書(補件)/92-02/91135063 200300726 分鐘後，接著以實施例3中調製的淸漆，經由壓模塗佈機 以使乾燥後的厚度成爲1 m的方式塗佈，於1 1 5 °C乾燥 3分鐘後，接著以合成例1的淸漆經由輥式塗佈機以使乾 燥後的厚度成爲2 // m的方式塗佈，於8 0 °C下1分鐘，於 1 4 0 °C 、 1 5 0 °C 、 160°C 、：L7〇°C ' 1 8 0 °C 、 190°C 下各 2 分 鐘在氣浮方式的乾燥爐進行乾燥，再於 2 8 0 °C、3 8 0 °C下 各3分鐘在氮氣環境下的爐中進行乾燥，得到單面有金屬 箔的聚醯亞胺金屬層合物。 用所得之聚醯亞胺金屬層合物，以使最外層成爲金屬箔 層的方式將該單面金屬箔的聚醯亞胺金屬層合物彼此以與 實施例1同樣的條件下進行張覆，得到雙面金屬箔的聚醯 亞胺金屬層合物。所得之雙面金屬箔的聚醯亞胺金屬層合 物之常態下及耐熱試驗後的抗剝離強度分別爲 Q . 8 8、 0.75kN/m，光透過率爲13%° (比較例1 ) 除了如表1所示般之金屬箔的表面處理相異之外，其餘 係與實施例1同樣的作法，得到聚醯亞胺金屬層合物。 對所得之聚醯亞胺金屬層合物進行評價之結果，得到常 態下及耐熱試驗後的抗剝離強度分別爲 Q . 1 8、 0.10kN/m，光透過率爲55%° (比較例2 ) 除了如表1所示般之金屬箔的表面處理相異之外，其餘 係與實施例1同樣的作法，得到聚醯亞胺金屬層合物。 對所得之聚醯亞胺金屬層合物進行評價之結果，得到常 26 312/發明說明書(補件)/92-02/91135063 200300726 態下及耐熱試驗後的抗剝離強度分別爲 0.54、 0.20kN/m，光透過率爲55%。 (實施例7 ) 除了如表1所示般之金屬箔的表面處理相異之外，其餘 係與實施例1同樣的作法，得到聚醯亞胺金屬層合物。 對所得之聚醯亞胺金屬層合物進行評價之結果，得到常 態下及耐熱試驗後的抗剝離強度分別爲 0.85、 0.7 6kN/m，光透過率爲2%。Xiao 〇 ~ QJ m9 / dm2, the amount of nickel attached is 〇: L ~ 0.35 mg / dm2 range ο -ΤΗ, the amount of chromium, zinc, and nickel adhered to the above range, it will show the polymer The imide layer tends to have high peel strength. The method for measuring the adhesion amount of silicon, iron, silicon, and nickel will be described later. The silicon in the gold layer is preferably derived from a silane coupling agent. Furthermore, it is formed by surface treatment in the following order: (1) nickel and / or nickel-zinc alloy, (2) zinc and / or zinc-chromium alloy, (3) chromium and / or zinc-chromium alloy It is preferable to obtain a treatment layer and a metal foil treated with a silane coupling agent on the treatment layer. When the surface treatment is performed in this order, the metal layer has excellent peel resistance, and also has excellent heat resistance and uranium etchability. 12 312 / Invention (Supplement) / 92-02 / 91135063 200300726 The above-mentioned treatment layer contains at least one selected from the group consisting of vanadium, molybdenum, cobalt, tin, iron, phosphorus, indium, tungsten, aluminum, and manganese The ingredients are better. The content of these ingredients should preferably be in the range of 0 to 0.1 mg / dm2. When a metal selected from these metals is contained, the etchability and heat resistance of the metal layer can be improved, and the peel strength after heating tends to stabilize. The peel strength at room temperature and after heating is preferably Q.SkN / iri or more, more preferably Q.skN / m or more, and particularly preferably 0.5kN / m or more. [Polyimide layer] The polyimide layer used to form the polyimide metal laminate of the present invention is a single layer or multiple layers 'in the case of multiple layers' with adjacent layers as mutually different components. A polyimide layer having two or more layers is preferred. The term "polyimide components are different from each other" means that the types and / or contents of the monomer units are different. Also, at least one of the layers for forming a single polyimide layer or a multiple polyimide layer may be formed of a composition (mixture) composed of two or more different types of polyimide. When the polyimide layer is a single layer, a thermoplastic polyimide or a thermoplastic polyimide composition is preferred. In the case of multiple layers, a non-thermoplastic polyimide layer, a thermoplastic polyimide layer, or a thermoplastic polyimide-containing composition layer is preferable to make it adhere to the metal layer. Excellent. The surface in contact with the metal layer is preferably a thermoplastic polyimide or a composition containing a thermoplastic polyimide. As the thermoplastic polyimide for the polyimide layer, it is preferably: selected from the group consisting of 1,3-bis (3-aminophenoxy) benzene, 4,4-bis (3-aminobenzene (Oxy) biphenyl and 3,3'-diaminobenzophenone in a group consisting of at least 13 312 / Invention Specification (Supplement) / 92-02 / 91135063 200300726, and a diamine selected from 3, 3, -4, 4'-diphenyl ether tetracarboxylic acid 3, 3, ~ 4, 4'-benzophenone tetracarboxylic dianhydride and pyromellitic acid two at least one group Tetracarboxylic dianhydride, the synthesized thermal fluorene imide or a thermoplastic polyfluorene imide. In addition, the polyimide composition which is a thermoplastic polyimide containing a fluorene imine layer is preferably a thermoplastic polyimide i containing 0% by weight or more. As the non-thermoplastic polyimide film used for the polyimide layer, a non-thermoplastic polyimide precursor lacquer can be used for coating and application, and a commercially available non-thermoplastic polyimide can also be used. Examples of imine thin: Upirex S, Upirex SGA, Upi SN (Ube Kosan Co., Ltd., trade name), Capstone H, Capstone EN (Toray · DuPont (stock) system, trade name), Apical Pical NPI, Apical HP (Zhongyuan Chemical Industry (stock) manufacturing name), etc. In the case of using a commercially available non-thermoplastic polyimide film, it is often preferred to be 3 to 75 // TΠ, and a range of 7.5 to 40 // m is preferred. Coated with dry precursor of non-thermoplastic polyimide and dried, the thickness should be 0.1 ~ 4〇 // m, and 0.5 ~ 25 // m as Q. 5 ~ 1 6 // m For the best. The thermoplastic polyimide layer is preferably 0.1 to 20 / zm, more preferably 0.1 to 1 and most preferably JU m. Furthermore, if the total thickness of the polyimide layer is too thick, it will not be used for applications that must be bent because of its rigidity. If it is too thin, it will be restricted because it will become unusable in terms of absolute use. Total thickness 312 / Explanation of the invention (Supplement) / 92-02 / 91135〇63 The dianhydride and anhydride are plastically polymerized for use in polymer applications, except for drying and film. Can Rex [V, card AH, Ah, the thickness of the product is passable, and the dryness is good, especially the thickness of 0 · 1 ~ 5 is stronger, the fate and degree become 14 200300726 3 ~ 75 // m (and It is better to adjust the thickness of the thermoplastic polyimide layer and the non-thermoplastic polyimide layer within the above range. When the thickness of the polyimide layer is within the above range, the polyimide metal laminate is excellent in insulation, flexibility, and workability, and tends to be low in cost. Also, as the polyimide-based resin layer not directly in contact with the metal foil, the thermoplastic polyimide resin described above may not be used, and the existing polyimide layer and / or polyimide layer may be used. Resin is selected, but as the insulating layer, it is preferable to have a light transmittance of 10% or more. Therefore, it is preferable to use a resin having an amorphous structure with easy light transmission. In addition, various mixed materials are used in the insulating layer tree. It is better to determine the mixing ratio so that the light-transmitting condition in fl is not reduced to less than 10%. After the metal foil is etched and removed, the light transmittance of the polyimide is passed through the polyimide film to recognize the wiring pattern of the polyimide film and to mount a wafer such as IC on the wiring. Identification of markers is necessary for image processing. In particular, when the surface roughness of the metal foil used is large, even after the metal foil is etched and removed, the unevenness on the surface of the metal foil is transferred to the polyimide layer, which makes light scattering and reflection impossible to make an image. Identify. For this reason, 'it must also depend on the film thickness of polyimide, with the film thickness of 3 5 // m as an example, the light transmittance at a wavelength of 6 Q 〇nm is 10% or more' Above 40% is better, especially above. [Method for producing polyimide metal laminate] The polyimide metal laminate of the present invention can be produced by the following method, for example. 312 / Description of the Invention (Supplement) / 92-02 / 91135063 15 200300726 (1) A method of heating and pressing a single-layer or multi-layer polyimide film and a metal foil. (2) A method in which a polyimide precursor varnish is applied to a metal foil and then dried. (3) A method of laminating the following laminate (i) or laminate (i i) with the following laminate (i) or (i i) so that the metal layer is the outermost layer. Laminate (i): A laminate obtained by heating and pressing a single-layer or multi-layer polyfluorene imide film and a metal foil with a metal layer on only one side; laminate (ii): polymer After the imine precursor lacquer is coated on a metal foil, it is dried to obtain a laminate having a metal layer only on one side. More specifically, there are the following methods: (1) A method of heat-pressing a metal foil on one or both sides of a single-layer film of thermoplastic polyfluorene. The thermoplastic polyfluorene imide film can be obtained by, for example, coating with a thermoplastic polyfluorene imide varnish and drying it. (2) Applying at least one kind of thermoplastic polyimide precursor paint on a non-thermoplastic polyimide film, coating at least one side or both sides of the non-plastic polyimide film One layer was dried to produce a laminate having a thermoplastic polyimide layer on at least one side of a non-thermoplastic polyimide film, and then, one side or both sides of the laminate were laminated. Method for heat-pressing metal foil. In this case, the metal foil is preferably laminated so as to be in close contact with the thermoplastic polyimide layer of the multilayer polyimide film. Examples of the non-thermoplastic polyfluorene imide film include those described above. (3) Coat at least 16 312 / Explanation of the invention (Supplement) / 92 on one side of the non-thermoplastic polyimide film with a precursor of non-thermoplastic polyimide of the same or different composition -02/91135063 200300726 One layer is allowed to dry, and at least one layer is coated with a thermoplastic polyimide precursor paint on the other side of the non-thermoplastic polyimide film and dried to produce a laminate. Then, a method of heating and pressing metal foil on the surface of the thermoplastic polyimide of the laminate is performed. (4) A method in which at least one layer of a polyfluorine imide precursor paint is applied to a metal foil and dried. (5) Apply at least one layer of a precursor of polyfluorene imine to a metal foil and dry at least one layer to produce a laminate, and then use any one of the methods (1) to (4) above. A method for laminating the produced polyfluoreneimide metal laminate by heating and pressing. Further, in this method, a metal layer is laminated to form an outermost layer. The metal foil used in the manufacture of polyimide metal laminates should preferably be made of a metal selected from copper and copper alloys, stainless steel and its alloys, nickel and nickel alloys (including 42 alloys), aluminum and aluminum alloys, and the like. Formation, preferably copper or copper alloy. The surface roughness of the metal foil's interface with polyimide should preferably be less than 0 · 3 Q // m, and preferably less than 2 8 // m, It is more preferably 0.2 5 // m or less, and particularly preferably 0.20 // τη or less. In addition, the interface between the metal layer and the polyimide is 1 of another index used to indicate the surface roughness. The average point roughness (R ζ) should be 2.5 5 m or less, and 1 · 5 // below m is better, 1 · 0 // below m is better. At the interface between the metal layer and the polyimide, the zinc adhesion amount should preferably be 0 to 0.07 mg / dm2, and more preferably, the silicon adhesion amount is 0.001 to 0.01 mg / dm2, and the chromium adhesion amount is 0. · 01 ~ 0. 05mg / dm2, the amount of zinc attached is ◦ ~ ◦ • ◦ ▽ mg / dm2 or less, and the amount of nickel attached is 0.07 ~ 17 312 / Invention Specification (Supplement) / 92-02 / 91135063 200300726 0.5 mg / dm 2 range; more preferably, the amount of sand adhered is 0.002 to 0.06 mg / dm2, the amount of chromium adhered is 0.02 to 0.03 mg / dm2, and the amount of adhered zinc is ◦ ~ 〇 · 〇5 mg / dm2 or less, and the amount of nickel attached is 0 · 1 to 0.35 mg / dm2 0 The silicon in the metal layer is preferably derived from a silane coupling agent. In addition, the following processes are followed: (1) nickel and / or nickel-zinc alloy, (2) zinc and / or zinc-chromium alloy, and (3) chromium and / or zinc-chromium alloy by surface treatment. And a metal foil treated with a silane coupling agent on the treated layer is preferred. When the surface treatment is performed in this order, the metal layer has excellent peel resistance, and also has excellent heat resistance and uranium etchability. It is preferable that the treatment layer contains vanadium, molybdenum, cobalt, tin, iron, phosphorus, indium, tungsten, Ming and Meng. The content of these ingredients is preferably in the range of 0 to Q.5 mg / dm2. Such a metal foil in which the adhesion amount of silicon, chromium, zinc, and nickel is within a specific range can be obtained, for example, by subjecting the metal foil to surface treatment in the following manner. After treatment with a silane coupling agent, a dipping method is usually used. Examples of treatment methods other than the silane coupling agent treatment include dipping method, electroplating method, electroless plating method, vapor deposition method, sputtering method, metal spraying method, and the like. For productivity considerations, dipping method and electroplating method are used. Better. The thickness of the metal foil may be any thickness that can be used in the form of an adhesive tape. 18 312 / Invention Specification (Supplement) / 92-02 / 91135063 200300726 is not particularly limited, and it is usually preferably 0.1 to 150 // TΠ, and 2 to 150 μτη is preferable, 3 to 5 ◦ m is more preferable, 3 to 3 5 μ m is particularly preferable, and a range of 3 to 1 2 // m is more preferable. When the polyfluorene imide metal laminate is manufactured, the surface of the non-thermoplastic polyimide may also be subjected to a plasma treatment, a corona discharge treatment, or the like. As the heating and pressing method here, there is a method of pressing between a metal light heated by oil or the like as a heat medium or inductive heating, and a roller whose surface is lined with rubber or the like. The former is suitable for the production of continuous rolls, and the latter is a method of hot stamping. The latter is suitable for slicing sheet-like products and can be appropriately used depending on the application. Also, 'heating and pressing conditions, ambient gas can be appropriately used air, nitrogen, argon, etc.' The heating temperature must be performed at a temperature corresponding to the glass transition temperature of the thermoplastic polyimide-based glass, which can usually be at 100 ° C. It is carried out between ~ 400 ° C, and preferably between 150 and 300 t. In addition, the heating time should preferably be from 0.1 to 15 hours, and the heating pressure should be from 0.1 to 30 MPa, usually from 0.5 to 10 MPa. In addition, for the purpose of further improving the adhesion, an autoclave can also be used. Wait for post-processing. Post-treatment can be performed under the following conditions. Post-treatment temperature is usually 150 ~ 4 0 ° C, and preferably 200 ~ 3 50 t, the treatment time is 1 minute ~ 50 hours, the pressure is in the range of normal pressure ~ 3MPa, autoclave It is preferable that the inside of the container be vacuumed or replaced with an inert gas such as nitrogen or argon to prevent oxidation of the metal foil. When the metal foil or polyimide film is coated with a polyimide precursor lacquer, a solvent can be used. As such a solvent, any solvent can be used as long as it dissolves the precursor of the polyimide used in 19 312 / Invention Specification (Supplement) / 92-02 / 91135063 200300726, and is not particularly limited. For example, it can be used. · N-methyl-tetrahydropyrrolidone, N, N-dimethylacetamide and the like. As a coating device for the precursor of polyimide, a roll coater, a die coater, a gravure coater, a dip coater, a spray coater, and a comma can be used. Coaters, curtain coaters, bar coaters and other general coating devices can be appropriately selected according to the viscosity and coating thickness of the polyimide precursor paint. As a drying device for the precursor of polyimide, it is possible to appropriately use a hot air heated by electric power or fuel oil, or a roller-supported, air-floating drying furnace using infrared rays as a heat source. In order to prevent the deterioration of the resin or the discoloration due to the oxidation of the metal foil, if necessary, the dry ambient gas may be replaced with a gas other than air such as nitrogen, argon, or hydrogen. The drying temperature of polyimide precursor lacquer can be in the temperature range of 60 ~ 600 ° C. It is preferable to increase the temperature stepwise because it will not affect the film formation of the insulating layer. Problems such as foaming and orange peel occur, and a resin with uniform film thickness and excellent dimensional stability is obtained, so it is preferable; the drying time can be appropriately selected between 0. 05 and 50 minutes. Examples Hereinafter, the present invention will be described in more detail through examples. The surface treatment adhesion amount of the metal foil, the maximum thickness of the surface of the metal foil, and the peel resistance of the metal foil and the thermoplastic polyimide layer shown in the examples were measured by the following methods. 20 312 / Invention Manual (Supplement) / 9102/91135063 200300726 (1) Surface treatment adhesion amount A fluorescent X-ray measuring device for analysis was used to measure a sample cut into a disc shape with a diameter of 40 mm. It is calculated | required by converting it into appendage M per unit area. The unit is mg / dm2. (2) Arithmetic average thickness: R a (// m) Using a surface roughness meter (manufactured by Kosaka Laboratories, type: SAFCODA SE-3QD), according to JIS_B-0601, cut (cut-〇ff ) 値 is 0.25 mm, and the measured length is 2.5 mm. On the surface of the metal foil in contact with the insulating layer, it goes along the direction of travel of the metal foil during production and along the direction of travel of the metal foil at right angles. And parallel arbitrary points are measured at 3 points, and the average of the larger 3 points is used as the arithmetic mean thickness. (3) Peel strength after normal temperature and heat resistance test (kN / m) For a specimen 50mm in length and 1mm in width parallel to the direction of travel of the metal foil, at an ambient temperature of 2 3 ° C and 50% R Η The test was performed; the heat resistance test was performed in a 150 ° C oven for 168 hours, and then the metal foil was self-insulated in accordance with J.SC-6 4 7 1 so that the metal foil had an angle of 90 degrees. The layer was peeled at a peeling speed of 50 mm / mη, and its stress was measured. In addition, the measurement sheet was spaced at equal intervals of 10 points in the width direction of the metal foil, and the peel resistance was set to an average value of 1 Q point. (4) Light transmittance (%) The s-type material is obtained by etching a metal box in an iron oxide hydrochloric acid solution, and using a light transmittance measuring device (uv_Vis ~ NiR manufactured by JASCO Corporation), it is calculated to be 60%] 1111 Light transmittance below. In addition, the abbreviations of the solvents, acid dianhydrides, and diamines used in the examples are as follows: 312 / Invention Specification (Supplement) / 92-02 / 91135063 91 200300726 Description: D MAC ·· N, N-二: 3 groups LS Syndrome NM P: N ~ methyl- 2_tetrahydropyrrolidone P P D: p-phenylenediamine oDA: 4, 4 i diamine: diphenyl ether m-BP: 4, 4 >- Bis (3-amine: phenylphenoxy) biphenyl A P B • 1, 3--bis :( 3 -aminophenoxy) benzene B PDA: 3, 3 9/4, 4 7 -diphenyl Tetracarboxylic dianhydride P MDA: pyromellitic dianhydride B TDA: 3, 3 '9/4, 4,,-benzophenone tetracarboxylic dianhydride (Synthesis Example: L) 1636 g of DMAc as a solvent was added In a container equipped with a stirrer and a nitrogen introduction tube, APB 1 6.2 g was added thereto, and the mixture was stirred at room temperature until it was dissolved. Then, B P D 1 4 2 · 5 g was added, and the mixture was stirred at 60 ° C to obtain a polyamic acid (ρ Ο 1 y a m i c a c i d) solution. The polyamic acid content of the obtained polyamic acid solution was 15% by weight, and the E-type viscosity at 25 ° C was 5 50 cps. (Synthesis Example 2) 1718.6 g of DMAc as a solvent was added to a blender. Into a container with a nitrogen introduction tube, 146.2 g of APB was added thereto, and the mixture was stirred at room temperature until it was dissolved. Then, B T D A 1 5 7 · 1 g was added and stirred at 6 ◦ t: to obtain a polyamic acid solution. The polyamic acid content of the obtained polyamic acid solution was 15% by weight, and the E-type viscosity at 25 t: 50 QCPs. (Synthesis Example 3) 22 312 / Invention Specification (Supplement) / 92-02 / 91135063 200300726 As a solvent, DMAC 644g and NMP 16lg were added to a container equipped with a stirrer and a nitrogen introduction tube, and PPD4 was added thereto. 59 (75 mol%) and 17.5 g (17.5 mol%) of ODA, and heated to 50 to 60 ° C while stirring to dissolve. Then, after cooling to about 30 ° C with ice, B P D A 7 8 · 0 g was added, and the mixture was heated to 60 ° C and stirred for about 2 hours. Further, 13.8 g (7.5 mole%) of m-BP was added, and the mixture was stirred while maintaining the temperature at 60 ° C. Finally, p M D A 5 1 · 3 9 ′ was forced in and stirred at 60 ° C for 2 hours to obtain a polyamic acid solution. The polyamic acid content of the obtained polyamic acid solution was 20% by weight, and the E-type viscosity at 25 ° C was lsoQGcps. (Synthesis Example 4) DMAC 846. 9g and NM P 362.9g as dissolved solvents were put into a container equipped with a stirrer and a nitrogen introduction tube, and PPD n2g (30 mole%) was added thereto, and DA 49.1 g (49 mole%) 'Dissolve by heating to 50 ~ 6 Q ° C while stirring. Then, after cooling with ice to about 30 ° C, B P D A 25.1 g was added, and the mixture was heated to 6 Q ° C and stirred for about 2 hours. 38.7 g (21 mole%) of m-BP was further added, and the mixture was stirred while maintaining the temperature at 60 ° C. Finally, p M D A 8 4 · 4 g 'was added and stirred at 60 ° C for 2 hours to obtain a polyamic acid solution. The polyamic acid content of the obtained polyamic acid solution was 15% by weight, and its viscosity at 25 ° C was 40C) cPs. (Example 1) On one side of a commercially available polyimide resin film ("trade name: Capton 100EN manufactured by Toray DuPont Co., Ltd."), a polyamic acid solution prepared in Synthesis Example 1 ( Hereinafter, it is referred to as "smoke paint"), and coated with a roll coater so that the film thickness after drying becomes 4 // m, and dried at 15 ° C for 2 minutes. '23 312 / Invention Specification (Supplement Pieces) / 92-02 / 91135063 200300726 On the other side, the varnish prepared by Synthesis Example 4 was applied through a light coater so that the film thickness after drying became 5 // m. After drying for 5 minutes and 110 ° C for 5 minutes, it is further dried at 140 ° C for 2 minutes, 180 ° C for 5 minutes, and 2 6 5 ° C for 2 minutes, and dried in an air-floating drying oven to obtain A polyimide insulating film formed by laminating a thermoplastic polyimide resin layer, a polyimide resin film layer, and a non-thermoplastic polyimide resin layer in this order. Then 'use the above-mentioned insulating film and a commercially available copper foil (made by Furukawa Circu Soil Co., Ltd., trade name: F0-WS, thickness 9 // m, Ra: 0.17 // m, surface treatment as shown in Table 1 (Described)), through a roller laminator covered with silicone rubber, at a temperature of 240 ° C and a pressure of 1.4 MPa, the copper box and the insulating film were bonded to the thermoplastic polyimide layer. The sheets were stretched in a continuous manner, and then tempered in a batch-type autoclave under a nitrogen atmosphere at a temperature of 280 ° C for 4 hours to obtain a polyimide metal laminate. As a result of the evaluation of the obtained polyfluorene imide metal laminate, the peel resistances in the normal state and after the heat resistance test were 0.97, 0.45 kN / m > and the light transmittance was 55%. (Example 2) Except that the surface treatments of the metal foils shown in Table 1 are different, the rest is the same method as in Example 1 to obtain a polyimide metal laminate. As a result of evaluation of the metal laminate, the peel resistances obtained in the stomach state and after the heat resistance test were 0 · 8 8 '0.40 kN / m, and the light transmittance was 55%. (Example 3) 24 312 / Invention Specification (Supplement) / 92-02 / 91135〇63 200300726 Except that the surface treatment of the metal foil as shown in Table 1 is different, the rest is the same as that of Example 1. To obtain a polyfluorene imide metal laminate. As a result of evaluation of the obtained polyfluorene imide metal laminate, the peel resistances under normal conditions and after heat resistance tests were 0.86, 0.45 kN / m, and light transmittance were 55% ° (Example 4 ) Except that the thickness of the metal foil and the surface treatment are different as shown in Table 1, the same procedure as in Example 1 was performed to obtain a polyfluorene imide metal laminate. As a result of evaluation of the obtained polyfluorene imide metal laminate, the peel strengths in the normal state and after the heat resistance test were 1.1 and 4 5 kN / m, respectively, and the light transmittance was 55%. (Example 5) Except that the varnish prepared in Synthesis Example 1 was replaced by the varnish prepared in Synthesis Example 2, and the metal foil used in Example 4 was used, the rest was the same as that of Example 1, and obtained Polyfluorene imide metal laminate. As a result of evaluation of the obtained polyfluorene imide metal laminate, the peel resistances in the normal state and after the heat resistance test were 0.78 and 0.40 kN / m, respectively, and the light transmittance was 55%. (Example 6) Commercially available copper foil (made by Furukawa circuitfi 1 (stock), trade name: F1-WS, thickness 12 // m, Ra: 0.28 // m »surface treatment refer to Table 1) As above, the varnish prepared in Synthesis Example 3 was applied with a roll coater so that the thickness after drying became 0.7 · m, and dried at 8 Q ° C for 1 25 312 / Invention Specification (Supplement Pieces) / 92-02 / 91135063 200300726 minutes, then the varnish prepared in Example 3 was applied through a die coater so that the thickness after drying became 1 m, and dried at 1 15 ° C After 3 minutes, the lacquer of Synthesis Example 1 was then applied through a roll coater so that the thickness after drying became 2 // m. It was then dried at 80 ° C for 1 minute and at 140 ° C. 1 50 ° C, 160 ° C ,: L7 ° C, 180 ° C, 190 ° C, 2 minutes each in a drying furnace of the air-floating method, and then dried at 2800 ° C, 3800 Each was dried in a furnace under a nitrogen atmosphere for 3 minutes at ° C to obtain a polyfluoreneimide metal laminate with a metal foil on one side. Using the obtained polyimide metal laminate, the polyimide metal laminate of the single-sided metal foil was stretched under the same conditions as in Example 1 so that the outermost layer became a metal foil layer. To obtain a polyimide metal laminate of a double-sided metal foil. The peel resistance of the obtained polyimide metal laminate of the double-sided metal foil in the normal state and after the heat resistance test were Q.8.8, 0.75kN / m, and the light transmittance was 13% ° (Comparative Example 1) A polyimide metal laminate was obtained in the same manner as in Example 1 except that the surface treatment of the metal foil was different as shown in Table 1. As a result of evaluation of the obtained polyfluorene imide metal laminate, the peel resistances in the normal state and after the heat resistance test were Q. 18, 0.10 kN / m, and the light transmittance were 55% ° (Comparative Example 2) ) A polyimide metal laminate was obtained in the same manner as in Example 1 except that the surface treatment of the metal foil was different as shown in Table 1. As a result of evaluation of the obtained polyimide metal laminate, the peel resistances in the state of 26 312 / Invention Specification (Supplement) / 92-02 / 91135063 200300726 and after the heat resistance test were 0.54 and 0.20 kN, respectively. / m, light transmittance is 55%. (Example 7) A polyimide metal laminate was obtained in the same manner as in Example 1 except that the surface treatments of the metal foils shown in Table 1 were different. As a result of evaluation of the obtained polyfluorene imide metal laminate, the peel resistances in the normal state and after the heat resistance test were 0.85 and 0.7 6 kN / m, respectively, and the light transmittance was 2%.
27 312/發明說明書(補件)/92-02/91135063 200300726 表1 實施例 比較例 1 2 3 4 5 6 7 1 2 構成 圖1 圖1 圖1 圖1 圖1 圖2 圖1 圖1 圖1 絕緣層總厚度（//m) 35 35 35 35 35 25 35 35 35 金屬層厚度（//m) 9 9 9 9 9 12 9 9 9 表面粗度Ra ( win) 0.17 0.17 0.17 0.17 0.17 0.28 0.30 0.17 0.17 Ni S (mg/dm2) 0.32 0.11 0.25 0.11 0.11 0.11 0.32 0.32 0.25 Zn m. (mg/dm2) 0.02 0.04 0.03 0.03 0 . 03 0.07 0.02 0.19 0.08 Cr 量（mg/dm2) 0.028 0.025 0.028 0.025 0.025 0.026 0.028 0.028 0.028 Si m (mg/dm2) 0.005 0.005 0.004 0.002 0.002 0.005 0.005 0.005 0.004 常態抗剝離強度（kN/m) 0.97 0.88 0.86 1.1 0.78 0.88 0.85 0,18 0.54 耐熱試驗後抗剝離強度 (kN/m) 0.45 0.40 0.45 0.45 0.40 0.75 0.76 0.10 0.20 光透過率（％) 55 55 55 55 55 13 2 55 55 28 312/發明說明書(補件)/92-02/91135063 200300726 【圖式簡單說明】 圖1爲本發明之一個態樣之軟式金屬層合物的槪略截面 圖。 Η 2爲本發明之其他的態樣之軟式金屬層合物的槪略俯 視圖。 (元件符號說明） 1 聚醯亞胺層 la 非熱可塑性聚醯亞胺層 la'非熱可塑性聚醯亞胺層 lb 熱可塑性聚醯亞胺層 2 金屬層 29 312/發明說明書(補件)/92-02/9113 506327 312 / Instruction of the Invention (Supplement) / 92-02 / 91135063 200300726 Table 1 Example Comparative Example 1 2 3 4 5 6 7 1 2 Configuration Figure 1 Figure 1 Figure 1 Figure 1 Figure 2 Figure 1 Figure 1 Figure 1 Figure 1 Total insulation layer thickness (// m) 35 35 35 35 35 25 35 35 35 35 Metal layer thickness (// m) 9 9 9 9 9 12 9 9 9 Surface roughness Ra (win) 0.17 0.17 0.17 0.17 0.17 0.28 0.30 0.17 0.17 Ni S (mg / dm2) 0.32 0.11 0.25 0.11 0.11 0.11 0.32 0.32 0.25 Zn m. (Mg / dm2) 0.02 0.04 0.03 0.03 0. 03 0.07 0.02 0.19 0.08 Cr Amount (mg / dm2) 0.028 0.025 0.028 0.025 0.025 0.026 0.028 0.028 0.028 Si m (mg / dm2) 0.005 0.005 0.004 0.002 0.002 0.005 0.005 0.005 0.004 Normal peel strength (kN / m) 0.97 0.88 0.86 1.1 0.78 0.88 0.85 0,18 0.54 Peel strength (kN / m) 0.45 after heat resistance test 0.45 0.40 0.45 0.45 0.40 0.75 0.76 0.10 0.20 Light transmittance (%) 55 55 55 55 55 13 2 55 55 28 312 / Explanation of the invention (Supplement) / 92-02 / 91135063 200300726 [Simplified illustration of the drawing] Figure 1 is the invention A schematic cross-sectional view of one aspect of the soft metal laminate. Fig. 2 is a schematic plan view of a soft metal laminate in another aspect of the present invention. (Explanation of Symbols) 1 Polyimide layer la Non-thermoplastic polyimide layer la 'Non-thermoplastic polyimide layer lb Thermoplastic polyimide layer 2 Metal layer 29 312 / Invention specification (Supplement) / 92-02 / 9113 5063