200905014 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種使用作為可撓性印刷基板、TAB、 COF等電子零件之構裝材料之無接著劑可撓性積層材，特 別是關於一種耐熱老化特性優異之被覆有金屬之聚醯亞胺 樹脂基板之製造方法。 【先前技術】 主要將由銅所構成之金屬導體層積層於聚醯亞胺膜之 FCCL(Flexible Copper Clad Laminate)，係被廣泛使用作為 電子產業中之電路基板之材料。其中，在聚醯亞胺膜與金 屬層之間沒有接著劑層之無接著劑可撓性積層體（特別是二 層可撓性積層體），隨著電路配線寬度之細間距化，特別受 到矚目。 無接著劑可撓性積層體，特別因應細間距之無接著劑 可撓f生積層體之製造方法，4有一般所稱之金屬噴敷法， ί 亦f7 S聚醯亞胺膜上，藉由濺鍍、cvd、蒸鍍等之乾式 鑛敷法’事先形成金屬|，接著以濕式鍍敷法，將為導體 層之金屬層加以成膜。 金屬喷敷法’為了提高金屬層與聚醯亞胺膜之密合 ft成金屬層則，係'藉由電聚處理，冑聚醯亞胺膜表 面進行改質，以险土主t ^ 、 ’、表面之汚染物質、及提高表面粗糙度 (參照專利文獻彳β 路)。此方法雖然極為有效，但是於電 路形成時之熱處理、使 人*姑视々 史用衣^下之長期可靠度等’會有密 °力稍微降低的問題。 5 200905014 又，二出-種方法，係不使用接著劑，而是對聚醯亞 胺樹脂膜實施無電鍍鎳，並且將銅鍍敷於其上。 此方法，鍍鎳係為了達成用以防止銅擴散於聚醯亞胺 樹脂之作為障壁的功用，且利用無電鑛錄與聚酿亞胺樹脂 膜具有優異之接著性的特性。然而，此方法在具有熱負擔 的情形時，會有接著強度降低、發生剝離的問題。 。 此原因係在於聚醯亞胺樹脂具有吸濕性之故。例如在 電路3又计時，於焊接等之加熱的情形，若聚醯亞胺樹脂所 吸收之水分因熱而膨脹變形’則會在聚醯亞胺樹脂膜與鑛 鎖之間產生微小的空隙，導致接著力降低。如上述，若為 濕式法之無電鍍鎳係無法避免之處理步驟，則此接著強度 之降低將會是無法避免的問題。 因此，提出一種方法，係將無電鍍鎳步驟分為2步驟， 於第1步驟鍍上厚度較薄之錄，且使複數之微細孔形成於 所析出之錄粒子間，然後進行乾燥，使聚醯亞胺樹脂所吸 收之水分通過錄粒子間之複數之微細孔使其蒸發，接著於 第2步驟’鍍上厚度較厚之錄至既定之厚度（參照專利文獻 3)。以2步驟來進行無電鍍鎳雖然有效，但是具有未必可 使充分之接著性持久的問題。 其原因，係認為因第2步驟中，於再次進行厚度較厚 之…電鍍錄的階段，會產生前述帛i步㈣形成之複數微 細孔成為無電鍍鎳液通往聚酿亞胺樹脂之通道孔此 現象。 又’雖‘然提出Ni-P系無電锻Ni液來作為—般所使 200905014 用之無電鍍Ni液’然而所成膜之Ni_ p系無電鍍妬被膜， 雖然耐姓性佳，但是餘刻性差，且亦具有難以形成微細圖 • 案之問題。 專利文獻1:日本特許第317351 1號公報 專利文獻2:曰本特表2003-519901號公報 專利文獻3:日本特開2〇〇5·154895號公報 【發明内容】 r I發明t冑肖’係在於降低無接著劑可撓纟積層體之 初期密合力下，提高加熱老化後(150。。，於大氣中放置168 小時後）之密合力。 鑑於上述課題，本發明提供以下之發明。 又丨）被覆有金屬之聚醯亞胺樹脂基板之製造方法，係在 聚醯亞胺樹脂膜之兩面或單面形成含有棚之無電鍛錄層， f在該表層以無電鍍鋼或電解鍍銅形成導電性被膜，於進 #上述無電鍍鎳前’施行將聚醯亞胺樹脂基板浸潰於由鹼 ( 屬氫氧化物所構成之溶液之親水化之處理、賦予觸媒處 王里及觸媒活性化處理後，將上述無電鍵鎳層之形成分成2 〔驟於第1步驟形成較第2步驟厚的無電鑛鎳層後，進 力熱處理’並且於第2步驟再次形成無電鑛錄層。 *力熱處理，可在大氣中進行。又，在對聚醯亞胺樹脂 膜進行鍍敷處理前，亦可進行乾燥脫水之處理。 並且，本發明提供： 2) 一種如上述1)所記載之被覆有金屬之聚醯亞胺樹脂 i反之製、方法，其中，第i步驟所形成之無電鍍鎳之厚 200905014 度為鐘錄層全體厚度的 % 〜80% 〇 5 5 %以上。尤其， 較佳之厚度為70 又’本發明提供： 之被覆有金屬之聚醯亞胺 電解鎳之合計厚度為0.1 3)一種如上述1)或2)所記栽 樹脂基板之製造方法，其中，無 〜1 _0〆m。200905014 IX. Description of the Invention: The present invention relates to a non-adhesive flexible laminate which is used as a material for mounting electronic components such as flexible printed substrates, TAB, COF, etc. A method for producing a metal-coated polyimide substrate having excellent heat aging resistance. [Prior Art] A metal conductor composed of copper is mainly laminated on a FCCL (Flexible Copper Clad Laminate) of a polyimide film, and is widely used as a material for a circuit board in the electronic industry. Among them, the adhesive-free flexible laminate (especially the two-layer flexible laminate) having no adhesive layer between the polyimide film and the metal layer is particularly affected by the fine pitch of the circuit wiring width. Attention. A non-adhesive flexible laminate, especially in the production of a fine-pitch, non-adhesive flexible laminate, 4 is commonly referred to as the metal spray method, ί also on the f7 S polyimine film, borrowed The metal layer is formed in advance by a dry ore method such as sputtering, cvd, or vapor deposition, and then a metal layer of the conductor layer is formed by wet plating. In order to improve the adhesion between the metal layer and the polyimide film to form a metal layer, the metal spray method is modified by electropolymerization to modify the surface of the ruthenium imide film. ', the surface of the pollutants, and improve the surface roughness (refer to the patent document 彳β Road). Although this method is extremely effective, there is a problem that the heat treatment at the time of circuit formation, the long-term reliability of the clothes, and the like are slightly lowered. 5 200905014 Further, the second method is to apply electroless nickel to the polyimide film without using an adhesive, and to plate copper thereon. In this method, nickel plating is used to prevent the copper from diffusing from the polyimide resin as a barrier, and the electroless mineral recording and the polyimide resin film have excellent adhesion properties. However, in the case where the method has a heat load, there is a problem that the strength is lowered and peeling occurs. . The reason for this is that the polyimide resin has hygroscopicity. For example, when the circuit 3 is timed, in the case of heating such as soldering, if the moisture absorbed by the polyimide resin is swelled and deformed by heat, a slight gap is formed between the polyimide film and the lock. , causing the subsequent force to decrease. As described above, if the electroless nickel method of the wet method is an unavoidable treatment step, the reduction in the strength of the subsequent one will be an unavoidable problem. Therefore, a method is proposed in which the electroless nickel plating step is divided into two steps, and in the first step, a thinner thickness is plated, and a plurality of micropores are formed between the deposited particles, and then dried to be aggregated. The water absorbed by the quinone imine resin is evaporated by a plurality of micropores between the particles, and then plated to a predetermined thickness in the second step ' (see Patent Document 3). Although electroless nickel plating is effective in two steps, it has a problem that it is not always possible to make sufficient adhesion last. The reason is that, in the second step, in the stage of thicker plating, the plurality of micropores formed in the above step (4) are generated to become the passage of the electroless nickel liquid to the polyaniline resin. Hole this phenomenon. 'Although' it is proposed that the Ni-P-based electroless forged Ni liquid is used as the electroless Ni liquid for the general use of 200905014. However, the Ni_p-based electroless ruthenium film is formed, although the resistance is good, but the remaining moment Poor, and also difficult to form a micro-pattern problem. Patent Document 1: Japanese Patent No. 317351 No. Patent Document 2: Japanese Patent Publication No. 2003-519901 (Patent Document 3) Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 5,154,895. It is to reduce the adhesion between the non-adhesive flexible layer and the initial adhesion force after heating and aging (150% after standing in the atmosphere for 168 hours). In view of the above problems, the present invention provides the following invention. Further, a method for producing a metal-coated polyimide substrate is to form an electroless forging layer containing a shed on both sides or a single side of a polyimide film, and f is electrolessly plated or electrolytically plated on the surface layer. The copper is formed into a conductive film, and the polyimide substrate is impregnated before the electroless nickel plating is applied to the treatment of the hydrophilicity of the solution composed of the alkali hydroxide (the hydroxide is added to the catalyst) After the catalyst activation treatment, the formation of the above-mentioned electroless nickel layer is divided into 2 [the first step is to form an electroless nickel layer thicker than the second step, and the heat treatment is performed] and the electroless mineralization is formed again in the second step. The heat treatment can be carried out in the atmosphere. Further, before the plating treatment of the polyimide film, the drying and dehydration treatment can be carried out. Further, the present invention provides: 2) A method as described in 1) above The metal-coated polyimide resin is described as a method, wherein the thickness of the electroless nickel formed in the i-th step is 200905014 degrees, which is more than 80% 〇5 5 % of the total thickness of the chord layer. In particular, the thickness of the substrate is 70. The present invention provides a method for producing a resin substrate according to the above 1) or 2), wherein the metal-coated polyimide polyimide has a total thickness of 0.13. No ~1 _0〆m.
4)一種如上述！）〜3)中任 聚酿亞胺樹脂基板之製造方法 度没為90°C〜3 0〇°C。此溫度 樹脂基板蒸發之較佳條件。 又’本發明為： 一項所記載之被覆有金屬之 ’其中’係將加熱處理之溫 ，係用以使水分自聚醯亞胺 5)於上述賦予觸媒處理’亦可事先浸潰於由帶有具金 屬捕捉能力之官能基之石夕统偶合劑、與貴金屬化合物經混 合或反應所得之溶液中。上述本發明之被覆有金屬之聚酿4) One as above! ) ~3) The method of manufacturing the polyimide resin substrate is not 90 ° C ~ 3 0 ° ° C. This temperature is a preferred condition for evaporation of the resin substrate. Further, the present invention is characterized in that: the one described in the description of the metal-coated "in which the heat treatment is carried out for the purpose of allowing the water to be self-polymerized by the polyimide 5) is also impregnated in advance. It is a solution obtained by mixing or reacting with a noble metal compound having a metal-capturing functional group. The above-mentioned metal coated wine of the present invention
亞胺樹脂基板之製造方，法，可視必要使用此等，且本發明 係包含此等。 6)上述無電鍍鎳，尤以含有〇.1〜3wt%之硼之無電鍍 鎳特別有效。本發明，提供一種使用含有〇1〜3之硼 之無電鍍鎳之被覆有金屬之聚醯亞胺樹脂基板之製造方 法。此帶有硼之鎳無電鍍，可有效作為使水分自聚醯亞胺 樹脂蒸發且阻止水分再侵入聚醯亞胺樹脂之鍍敷層。又， 與一般廣泛所使用之Ni—P無電鍍鎳被膜相較之下，由於 姓刻性佳’故具有助於形成微細圖案電路等特徵。 如上述說明，係提供一種於被覆作為導體之銅之步驟 200905014 前，在對聚醯亞胺樹脂膜實施親水化處理、賦予觸媒及觸 媒活性化處理後，形成含有硼之無電鍍鎳層，且在大氣中 進行熱處理後’再次進行無電鍍鎳，以提升耐熱老化特性 之被覆有金屬之聚醯亞胺基板之製造方法，尤其是具有可 在不降低聚醯亞胺膜與金屬層間之積層後之初期密合力 下’提高老化後之密合力之優異效果。 【實施方式】 接著，說明本發明之具體例。另，以下之説明係用以 容易理解本發明者，本發明之本質並不受限於此説明。亦 即，係包含本發明所含之其他態様或變形。 本發明之被覆有金屬之聚醯亞胺樹脂基板之製造方 法，係施行將聚醯亞胺樹脂基板浸潰於由鹼金屬氫氧化物 所構成之溶液之親水化之處理、賦予觸媒處理及觸媒活性 化處理後’藉由無電鍍鎳，將含有硼之鎳層形成於該聚醯 亞胺樹脂膜之兩面或單面。另，於以下之説明中，本發明 之無電鍍鎳層，係全部為含有硼之鎳層。 於進行上述無電鍍鎳時，係將無電鍍鎳層之形成分成 2步驟’於第1步驟形成較第2步驟厚之無電鍍鎳層，接 著進行加熱處理。然後，進一步於第2步驟再次形成無電 鎖:層。 加熱處理’可在大氣中進行。又，在對聚醯亞胺樹脂 膜進行鍍敷處理前，亦可進行乾燥脫水之處理。 此處’重點在於，上述第1步驟之無電鑛錄，非為薄 的膜’而是將上述第1步驟之無電鍍鎳形成為較厚。會如 200905014 此作的理由，係由於帛2㉟之無電鑛液之水分侵入聚酿亞 胺樹脂之方式，具有取決於第〗層之厚度之傾向的緣故。 又，如後述，上述第丨步驟後之加熱處理，較佳為使相對 溫度較高來進行。 ’ 藉此，僅於上述第丨步驟之無電鍍鎳，並不進行薄的 被覆來形成複數蒸發孔，而是進行厚的被覆，來減少鍍敷 膜之孔。此具有在進行第2步驟之無電鍍鎳時，防止=自 鍍敷浴之水分侵入的功能。此係本發明之一大特徵。 此無電鍍鎳膜，由於為極薄之膜，雖然無法充分說明 其阻止水为自聚醯亞胺樹脂之蒸發、及阻止水分再侵入聚 醯亞胺樹脂之機制，但是從後述之老化後之剝離強度之實 驗數據，可確認具有該效果。尤以含有硼之無電鑛錦特別 ,极復有金屬之聚醯亞胺樹脂基板之製造方法，更佳為 形成為使帛1步驟所形成之無電鍵錄層之厚度為鑛鎳層之 全體厚度的55%以上。此係表示第1步驟所形成之無電鑛 錄層之厚度的下限值…步驟所形成之無電鍍錄層之厚 度的上限值，較佳為全體厚度之96%。 、又，本發明之被覆有金屬之聚醯亞胺樹脂基板之製造 方法，可使無電解鎳之合計厚度為〇1〜1〇”。無電解 ^合計厚度’雖然並無特別限定’但為了提升可挽性， ^佳為使上限為。然:而，此僅係表示較佳之厚度， 心了解可視製品之要求度而不受限於此厚度。 上述無電解錄或鎳合金之合計厚度的下限值，為了確 10 200905014 保與聚醯亞胺樹脂基板之接著性、及防止銅擴散入聚醯亞The production method and method of the imide resin substrate may be used as necessary, and the present invention includes these. 6) The above electroless nickel plating, particularly electroless nickel containing lanthanum of 1 to 3 wt%, is particularly effective. The present invention provides a method for producing a metal-coated polyimide film substrate using electroless nickel containing bismuth 1 to 3. The nickel with boron is electrolessly plated, and is effective as a plating layer for evaporating water from the polyimide resin and preventing moisture from re-entering the polyimide resin. Further, compared with the Ni-P electroless nickel film which is generally used in general, it is advantageous in forming a fine pattern circuit due to the good surname. As described above, before the step of coating the copper as a conductor 200905014, the electroless nickel plating layer containing boron is formed after the polyimine resin film is hydrophilized, the catalyst and the catalyst are activated. And a method of manufacturing a metal-coated polyimide substrate which is subjected to electroless nickel in the atmosphere to perform electroless nickel plating to improve heat aging resistance, in particular, without lowering between the polyimide film and the metal layer. Under the initial adhesion force after lamination, it has an excellent effect of improving the adhesion after aging. [Embodiment] Next, a specific example of the present invention will be described. In addition, the following description is for easy understanding of the inventors, and the nature of the invention is not limited by the description. That is, other states or modifications contained in the present invention are included. The method for producing a metal-coated polyimide film substrate of the present invention is a treatment for impregnating a solution of a polyamidene resin substrate with a solution of an alkali metal hydroxide, and providing a catalyst treatment. After the catalyst activation treatment, a nickel layer containing boron is formed on both sides or one side of the polyimide film by electroless nickel plating. Further, in the following description, the electroless nickel plating layer of the present invention is all a nickel layer containing boron. In the case of performing the above electroless nickel plating, the formation of the electroless nickel plating layer is divided into two steps. In the first step, an electroless nickel plating layer thicker than the second step is formed, followed by heat treatment. Then, an electric lock-free layer is formed again in the second step. The heat treatment ' can be carried out in the atmosphere. Further, the polyimine resin film may be subjected to a drying and dehydration treatment before being subjected to a plating treatment. Here, the focus is on the electroless mineral recording of the first step, which is not a thin film, but the electroless nickel in the first step is formed to be thick. For the reason of 200905014, the reason why the moisture of the electroless mineral liquid of 帛235 invades the polyimide resin has a tendency depending on the thickness of the layer. Further, as will be described later, the heat treatment after the above-described second step is preferably carried out with a relatively high relative temperature. Thus, only the electroless nickel plating in the above-described first step does not form a thin coating to form a plurality of evaporation holes, but a thick coating to reduce the pores of the plating film. This has a function of preventing the intrusion of moisture from the plating bath when the electroless nickel is subjected to the second step. This is one of the major features of the present invention. Since the electroless nickel plating film is an extremely thin film, it is not sufficient to explain the mechanism for preventing water from evaporating from the polyimide resin and preventing moisture from intruding into the polyimide resin, but it is aging after the aging described later. The experimental data of the peel strength can be confirmed to have this effect. In particular, the method for producing a polyamidide resin substrate containing a boron-containing electroless mineral ore is preferably formed so that the thickness of the electroless bond layer formed by the step 1 is the total thickness of the ore layer. More than 55%. This is the upper limit of the thickness of the electroless plating layer formed by the lower limit of the thickness of the electroless mineral layer formed in the first step, and is preferably 96% of the total thickness. Further, in the method for producing a metal-coated polyimide film of the present invention, the total thickness of the electroless nickel can be 〇1 to 1 〇". The electroless total thickness is not particularly limited, but To improve the liftability, the best is to make the upper limit. However, this only indicates the preferred thickness, and the heart knows the requirements of the visible product without being limited by the thickness. The total thickness of the above electroless recording or nickel alloy Lower limit value, in order to confirm 10 200905014 adhesion to the polyimide substrate, and to prevent copper from diffusing into the poly
胺樹脂基板，較佳為〇.1/zm。此亦僅為表示較佳之厚度， 亦可視製品之要求度來變化。 X 又，本發明之被覆有金屬之聚醯亞胺樹脂基板之製造 方法，可使加熱處理之溫度為9(rc〜 300<t。此溫度，係 用以使水分自聚醯亞胺樹脂基板蒸發之較佳條件。另一方 面，如上述，由於將第i步驟之無電鍍鎳層形成為 因此即使於鑛敷形成為粒子狀時，由於相鄰之粒子互相接 近’故即使以低溫進行加熱，亦具有閉鎖無電解鎳之微細 孔之效果。 稭此，於第2步驟之無電鍍鎳時，具有可有效阻止來 自鍍敷浴之水分侵入的功能。加熱處理時間，雖並無特別 限制，但可為1分〜60分鐘左右。 又，本發明之被覆有金屬之聚醯亞胺樹脂基板之製造 方法，於上述賦予觸媒處理，亦可事先浸潰於由帶有具金 屬捕捉能力之官能基之矽烷偶合劑、與貴金屬化合物經混 合或反應所得之溶液中。可視必要使用此等，且本發明係 包含此等。 於本發明中’雖然主要是在說明上述無電鍍，但是提 升老化後之剝離強度的方法，並不僅為此無電鑛。亦即， 亦應了解在將聚醢亞胺樹脂基板浸潰於由鹼金屬氫氧化物 所構成之溶液’施以親水化之處理、賦予觸媒處理及觸媒 活性化處理後，再進行無電鍍鎳亦為重要。 又’本發明之被覆有金屬之聚醯亞胺樹脂基板之製造 200905014 方法，係使用在上述無電鍍液含有〇 i〜3wt%之硼的無電 鏟鎳液。此帶有硼之無電鍍鎳，可有效作為使水分自聚醯 亞胺樹脂瘵發且阻止水分再侵入聚醯亞胺樹脂之鍍敷層。 若爛含量未達〇.lwt%時，則由於含有效果低’因此 較佳在O.lwt%以上，又，若硼含量超過3wt%時，則由於 老化後之剝離強度會稍微降低’因此較佳在3wt%以下。 特別有效之範圍係含有0.5〜2wt%之硼的無電鍍鎳液。 然而’此數值條件’根據所被覆之材料之種類或製造 條件，視必要，亦可使用含有上述數值條件之範圍外之硼 的無電鍍鎳液。本發明係包含此等全部。 如上述，雖然顯示使用聚醯亞胺樹脂來作為成為基板 之材料之例，但亦可使用其他的基板材料。例如，聚醚醯 亞胺（polyetherimide)、聚苯硫（polyphenylene sumde)、聚 丁烯對苯二曱酸酯（P〇lybutylene terephthalate)、環氧樹脂、 液晶聚合物等。 本發明，如上述，係施行將聚醯亞胺樹脂基板浸潰於 由驗金屬氫氧化物所構成之溶液之親水化之處理、賦予觸 媒處理及觸媒活性化處理後，再形成上述無電鍍鎳層，鹼 金屬氫氧化物，可舉氫氧化鉀、氫氧化鋰等。又，亦可使 用矽酸鈉等之矽酸化合物，可單獨使用此等或合併使用。 為了更提升鍍敷膜之密合力，亦可事先使用鉻酸、過 猛Sic 4對聚醯亞胺樹脂基板之表面進行触刻處理，且進行 使其具有因此所產生之錨定效果（anchor effect)之處理。 又，於進行鍍敷之前處理階段，亦可對聚醯亞胺樹脂基板 12 200905014 之表面以還原劑來處理。本發明，視必要可使用此。本發 明，可附加地進行此等之處理，為包含此等之處理者。 實施例 接著’根據實施例及比較例來説明。另，本實施例僅 為一例示而已，並非僅受此例所限制。亦即，亦包含本發 明所含之其他態様或變形。 (實施例1) 係將聚醯亞胺樹脂臈（DuPont股份有限公司：卡普同 150E)浸潰於25艺之100g/L之氫氧化鉀水溶液3分^作 為親水化處理，然後以純水加以洗淨。賦予觸媒步驟，係 於5(TC下事先浸潰於由帶有具金屬捕捉能力之官能基之矽 烷偶合劑、與貴金屬化合物經混合或反應所得之溶液中（日 鑛金屬股份有限公司：ΡΜ·Α)1〇分鐘，並以純水加以洗淨。 並且之後再於50 C下，浸潰於還原劑溶液（日鑛金屬股 份有限公司：ΡΜ-Β)3分鐘作為觸媒活性化處理後，以純水 加以洗淨。 第1鍍敷步驟，係使用無電解鎳一硼系鍍敷液（曰鑛金 屬電鍍股份有限公司：尼可姆ΗΒ)，如纟i所示，形成019 # m之鎳層（3有！ 6wt%硼），然後以純水加以洗淨。接著， 將水排除後’於大氣中進行15〇ΐ、1〇分鐘之熱處理。 第2鍍敷步驟，亦使用與上述相同之鍍鎳液形成〇 〇6 "m之鎳層，形成合計（第j錢敷+帛2鑛敷）ο·。〆瓜之錄 層。相對於全體之厚度，第1鎳層之厚度的比例達76%。 形成上述鍍鎳層後’使用無電解銅鍍敷液（羅門哈斯電 13 200905014 子材料股份有限公司：328)，形成無電解銅晶種層後，再以 電解鍍銅形成8 /z m之導體層’測量9〇。剝離之剝離強度。 將90 °剝離之剝離強度等之測量結果示於表1。 其結果’常態剝離強度為〇.54kN/m，於150°C、7天 老化後’為0.35kN/m，保持率（老化後/常態）達64%。 由此可清楚得知，本實施例1，其相對於全體厚度之第1 錄層之厚度的比例為75 %，保持率（老化後/常態）達64 % ’具備有良好之耐熱老化特性。 (實施例2) 使用實施例1之鍍鎳步驟中第1鍍敷步驟之無電解鎳 一棚系鑛敷液（日鑛金屬電鍍股份有限公司：尼可姆HB)， 形成0.24 // m之鎳層（含有1.4wt%硼），以純水加以洗淨。 並且’將水排除後’於大氣中進行15(TC、1〇分鐘之熱處 理。 接著’第2鑛敷步驟’係使用與上述相同之鍍鎳液形 成之鎳層，形成合計（第1鍍敷+第2鍍敷）0·25 "m之鎳層。相對於全體之厚度，第丨鎳層之厚度的比例 達 96% 〇 其他係與實施例1相同之步驟。同樣地，將9〇。剝離 之剝離強度等測量結果示於表i。 其結果’常態剝離強度為〇 54kN/m，i5〇〇c、7天老 化後，為0.34kN/m，保持率（老化後〆常態）達63%。由 此可β楚得知，本實施例2，其相對於全體厚度之第丨鎳 層之厚度的比例為96% ’保持率（老化後/常態）達⑽， 14 200905014 具備有良好之耐熱老化特性。 [表1] 處理條件 剝 (k 離驗 N/m) 保持率 Μ鱗度 βνα 第1層 Ni#"m 第1層 含有物 :MS% 熱處理 條件。C分 常態 150。(：、7天 老嫌 老似灸 /常態 實施例1 0.25 0.19 76% 棚 1.6wt% 150°C 10分 0.54 0.35 64% 實施例2 0.25 0.24 96% 硼 1.4wt% 150。。 10分 0.54 0.34 63% 實施例3 0.25 0.14 56% 棚 1.6wt% 150°C 10分 0.57 0.32 56% 實施例4 0.25 0.15 60% 硼 1.6wt% 150。。 10分 0.56 0.33 59% 實施例5 0.25 0.16 64% 碼 1.6wt% 150。。 10分 0.53 0.33 62% 實施例6 0.25 0.18 12% 删 1.6wt% 150°C 10分 0.54 0.34 63% 實施例7 0.25 0.20 80% 硼 1.5wt% 150°C 10分 0.52 0.34 65% 實施例8 0.25 0.21 84% 硼 1.4wt% 150°C 10分 0.55 0.33 60% 實施例9 0.25 0.22 88% 觸 1.5wt% 150。。 10分 0.53 0.32 60% 比較例1 0.25 0.12 48% 刪 1.6wt% 150°C 10分 0.56 0.26 46% 比較例2 0.25 0.19 76% 删 1.6wt% 60°C 10分 0.54 0.27 50% 比較例3 0.25 0.25 100% 棚 1.2wt% 無 0.52 0.26 50% 比較例4 0.25 0.19 76% 蝴 7.4wt% 150°C 10分 0.45 0.21 47% (實施例3) 15 200905014 使用實施例1之鍍鎳步驟中第1鍍敷步驟之無電解鎳 —硼系鍍敷液（日鑛金屬電鍍股份有限公司：尼可姆HB)， 形成0·14μιη之鎳層（含有l.6wt%硼），以純水加以洗淨。 並且，將水排除後’於大氣中進行l5(rc、分鐘之熱處 理。 接著，第2鍍敷步驟，係使用與上述相同之鍍鎳液形 成〇.ll/zm之鎳層，形成合計（第！鍍敷+第2鍍敷）〇·25 之鎳層。相對於全體之厚度，第丨鎳層之厚度的比例 達 56% 〇 其他係與實施例1相同之步驟。同様地，將9(Γ剝離 之剝離強度等測量結果示於表1。 (實施例4) 形 並 理 使用實施例1之鑛錄步驟中第i鍵敷步驟之無 硼系鍍敷液（日鑛金屬電鍍股份有限公司：尼 *、 』姆Η B)， 成0_15"m之鎳層（含有i.6wt%爛），以紬 峴水加以洗淨。 且’將水排除後’於大氣中進行1 5 〇它、 。 〇分鐘之熱處 接著，第2鍍敷步驟，係使用與上述相同之 成Ο.ΙΟμιη之鎳層，形成合計（第丨錄敷+第2鎳液％ "m之鎳層。相對於全體之厚度，第！鎳 鍍敷）〇.25 達60%。 厚度的比例 其他係與實施例1相同之步驟。同様地， 。 之剝離強度等測量結果示於表丨。 ：9(Γ制離 (實施例5) 16 200905014 使用實施例1之錢鎳步驟中第！鑛敷步驟之無電解錄 —硼系鍍敷液（日鑛金屬電鍍股份有限公司：尼可姆HB)， 形成之鎳層（含有硼），以純水加以洗淨。 並且，將水排除後，於大氣中進行15〇t、1〇分鐘之熱處 理。 接著，帛2鑛敷步驟，係使用與上述相同之鑛錄液形 成0.09/zm之鎳層，形成合計（第i鍍敷+ / 一層。相對於全體之厚度，第丨錦層第之厚=⑽ 達 64%。 其他係與實施例1相同之步驟。同様地，將9〇。剝離 之剝離強度等測量結果示於表1。 (實施例6) 使用實施例1之鍍鎳步驟中第丨鍍敷步驟之無電解鎳 —硼系鍍敷液（日鑛金屬電鍍股份有限公司：尼可姆hb)， 形成〇.18/zm之錄層（含有1.6wt%硼），以純水加以洗淨。 \ 並且，將水排除後，於大氣中進行150t：、1〇分鐘之熱處 理。 接著，第2鍍敷步驟，係使用與上述相同之鍍鎳液形 成〇.〇7#m之鎳層，形成合計（第！鍍敷+第2鍍敷）〇·乃 之鎳層。相對於全體之厚度，第丨鎳層之厚度的比例 達72%。 又 ' 其他係與實施例1相同之步驟。同様地，將9〇。剝離 之剝離強度等測量結果示於表1。 (實施例7) 17 200905014 使用實施例1之鑛錄步驟φ银，力办由l 7鄉中第1鍍敷步驟之無電解鎳 —侧系鍵敷液（日鑛金屬電鐘股 喊股伤有限公司：尼可姆HB)， 形成0.20/zm之錄層（含有1 ς +0/ V ’ h5wt%硼），以純水加以洗淨。 並且，將水排除後，於大氣中進行 理0 150°C、1〇分鐘之熱處 接著，第2鍍敷步驟，係使用與上述相同之鑛錄液形 成〇.〇5,m之鎳層，形成合計(第【鏡敷…鍍敷)〇25 …錄層。相對於全體之厚度，第1鎳層之厚度的比例 達 80%。 同様地，將90。剝離 其他係與實施例1相同之步称 之剝離強度等測量結果示於表1。 (實施例8) 使用實施例1之鑛錄步驟中第i鑛敷步驟之無電解錄 —硼系鍍敷液（曰鑛金屬電鍍股份有限公司：尼可姆Η”， 形成〇.2Wm之錄層（含有14^硼），以純水加以洗淨。 並且，將水排除後，於大氣中進行15〇。〇、ι〇分鐘之熱處 接著，帛2鍍敷步驟，係使用與上述相同之锻鎮液形 成〇_〇4#m之鎳廣，形成合計（第1鍍敷+第2鍍敷爪25The amine resin substrate is preferably 〇.1/zm. This also only indicates a preferred thickness, and may also vary depending on the requirements of the article. Further, in the method for producing a metal-coated polyimide resin substrate of the present invention, the temperature of the heat treatment can be set to 9 (rc to 300 < t. This temperature is used to make the moisture from the polyimide substrate. On the other hand, as described above, since the electroless nickel layer of the i-th step is formed so that even if the mineral deposit is formed into a particulate shape, since the adjacent particles are close to each other, heating is performed even at a low temperature. It also has the effect of blocking the micropores of the electroless nickel. In the second step, the electroless nickel plating has a function of effectively preventing moisture from entering from the plating bath. The heat treatment time is not particularly limited. However, the method for producing a metal-coated polyimide film substrate coated with the present invention may be impregnated with a metal-trapping property in advance. a functional decane coupling agent, a solution obtained by mixing or reacting with a noble metal compound, which may be used as necessary, and the present invention includes such a. In the present invention, although mainly explained The method of electroless plating, but improving the peel strength after aging, is not only for the purpose of no electromineralization. That is, it should also be understood that the polyimine resin substrate is impregnated into a solution composed of an alkali metal hydroxide. It is also important to carry out electroless nickel plating after hydrophilization treatment, catalyst treatment, and catalyst activation treatment. Further, the production of the metal-coated polyimide resin substrate of the present invention 200905014 is used in The above electroless plating solution contains 〇i~3wt% boron of the electroless shovel nickel liquid. The boron-free electroless nickel can effectively serve as a moisture elongating from the polyimide resin and prevent moisture from intruding into the polyimide resin. If the rot content is less than l.lwt%, it is preferably at least 0.1% by weight because it has a low effect, and if the boron content exceeds 3% by weight, the peel strength after aging Slightly lower' is therefore preferably less than 3% by weight. A particularly effective range is an electroless nickel solution containing 0.5 to 2% by weight of boron. However, 'this numerical condition' depends on the type of material to be coated or the manufacturing conditions, if necessary, Can be used The electroless nickel plating liquid of boron outside the range of the numerical conditions. The present invention includes all of the above. As described above, although the polyimide resin is used as an example of a material to be a substrate, other substrate materials may be used. For example, polyetherimide, polyphenylene sumde, polybutylene terephthalate, epoxy resin, liquid crystal polymer, etc. The present invention, as described above The method of impregnating a polyimine resin substrate with a hydrophilicity of a solution composed of a metal hydroxide, a catalyst treatment, and a catalyst activation treatment, and then forming the electroless nickel layer and the alkali The metal hydroxide may, for example, be potassium hydroxide or lithium hydroxide. Further, a citric acid compound such as sodium citrate may be used, and these may be used singly or in combination. In order to further improve the adhesion of the plating film, the surface of the polyimide film substrate may be subjected to a etch treatment using chromic acid or Sic 4 in advance, and the anchor effect (occusation effect) thus produced may be performed. ) processing. Further, the surface of the polyimide film substrate 12 200905014 may be treated with a reducing agent at a stage before the plating. The present invention can be used as necessary. The present invention can additionally perform such processing as a processor including such. EXAMPLES Next, the description will be made based on examples and comparative examples. In addition, this embodiment is merely an example, and is not limited only by this example. That is, other states or variations contained in the present invention are also included. (Example 1) A polyimine resin ruthenium (DuPont Co., Ltd.: Kaputong 150E) was impregnated into a 25 g aqueous solution of 100 g/L of potassium hydroxide for 3 minutes as a hydrophilization treatment, followed by pure water. Wash it. The catalyst-providing step is carried out in a solution of 5 or less (under TC) in a solution obtained by mixing or reacting a decane coupling agent having a metal-capturing functional group with a noble metal compound (Nippon Mining Co., Ltd.: ΡΜ ·Α) 1 minute, and washed with pure water. Then, at 50 C, immersed in a reducing agent solution (Nippon Mining Co., Ltd.: ΡΜ-Β) for 3 minutes as a catalyst activation treatment. Washed with pure water. The first plating step uses an electroless nickel-boron plating solution (Nippon Metal Electroplating Co., Ltd.: Nikko), as shown by 纟i, forming 019 # m The nickel layer (3 has! 6wt% boron), and then washed with pure water. Then, after the water is removed, it is heat treated in the atmosphere for 15 〇ΐ, 1 〇 minutes. The second plating step is also used. The same nickel plating liquid is formed into a nickel layer of 〇〇6 "m, and a total of (the jth money coating + 帛2 mineral deposit) is formed. ο. The recording layer of the squash. The thickness of the first nickel layer is relative to the thickness of the whole The ratio of the thickness is 76%. After the formation of the above nickel plating layer, 'Using electroless copper plating solution (Rohmaha) Electric 13 200905014 Sub-materials Co., Ltd.: 328), after forming an electroless copper seed layer, and then electroplating copper to form a conductor layer of 8 / zm 'measured 9 〇. Peel strength of peeling. Peel strength of 90 ° peeling The measurement results are shown in Table 1. The results were 'normal peel strength 〇.54 kN/m, 'at 0.35 kN/m after aging at 150 ° C, and retention rate (post-aging/normal) of 64%. From this, it is clear that in the first embodiment, the ratio of the thickness of the first recording layer to the entire thickness is 75%, and the retention ratio (post-aging/normal state) is 64%, which has good heat aging characteristics. (Example 2) An electroless nickel-plated ore dressing liquid (Nippon Mining Electroplating Co., Ltd.: Nikom HB) of the first plating step in the nickel plating step of Example 1 was used to form 0.24 // m Nickel layer (containing 1.4% by weight of boron), washed with pure water, and 'removed water' in the atmosphere for 15 (TC, 1 minute heat treatment. Then '2nd mineralization step' is used and above Nickel layer formed by the same nickel plating solution to form a total (first plating + second plating) 0·25 "m The ratio of the thickness of the second nickel layer was 96% with respect to the thickness of the entire layer. The other steps were the same as those of the first embodiment. Similarly, the measurement results of the peel strength and the like of the peeling were shown in Table i. RESULTS: The normal peel strength was 〇54kN/m, i5〇〇c, after aging for 7 days, it was 0.34kN/m, and the retention rate (after aging was normal) reached 63%. 2. The ratio of the thickness of the ruthenium nickel layer to the entire thickness is 96% 'retention rate (post-aging/normal state) up to (10), 14 200905014 has good heat aging characteristics. [Table 1] Treatment conditions Peeling (k test N/m) Retention rate Μ Scaling degree βνα Tier 1 Ni#" m No. 1 Content: MS% Heat treatment conditions. C minutes Normal 150. (:, 7 days old like moxibustion / normal embodiment 1 0.25 0.19 76% shed 1.6wt% 150 ° C 10 points 0.54 0.35 64% Example 2 0.25 0.24 96% boron 1.4wt% 150. 10 points 0.54 0.34 63% Example 3 0.25 0.14 56% shed 1.6 wt% 150 ° C 10 points 0.57 0.32 56% Example 4 0.25 0.15 60% boron 1.6 wt% 150. 10 points 0.56 0.33 59% Example 5 0.25 0.16 64% code 1.6wt% 150. 10 points 0.53 0.33 62% Example 6 0.25 0.18 12% Cut 1.6wt% 150°C 10 minutes 0.54 0.34 63% Example 7 0.25 0.20 80% Boron 1.5wt% 150°C 10 minutes 0.52 0.34 65% Example 8 0.25 0.21 84% Boron 1.4 wt% 150 ° C 10 min 0.55 0.33 60% Example 9 0.25 0.22 88% touch 1.5 wt% 150. 10 min 0.53 0.32 60% Comparative Example 1 0.25 0.12 48% Delete 1.6wt% 150°C 10 points 0.56 0.26 46% Comparative Example 2 0.25 0.19 76% Delete 1.6wt% 60°C 10 points 0.54 0.27 50% Comparative Example 3 0.25 0.25 100% Shed 1.2wt% None 0.52 0.26 50% Comparative Example 4 0.25 0.19 76% 7.4 wt% 150 ° C 10 minutes 0.45 0.21 47% (Example 3) 15 200905014 Electroless nickel-boron plating solution using the first plating step in the nickel plating step of Example 1 ( Nippon Mining Metal Plating Co., Ltd.: Nikom HB), forming a nickel layer of 0·14μηη (containing 1.6% by weight of boron), washed with pure water, and after removing water, 'l5 in the atmosphere (rc, minute) Next, in the second plating step, a nickel layer of 〇.ll/zm is formed using the same nickel plating liquid as described above to form a nickel layer of a total of (the first plating + the second plating) 〇·25. The ratio of the thickness of the second nickel layer was 56% with respect to the entire thickness. The other steps were the same as in Example 1. Similarly, the measurement results of 9 (peel peeling peel strength, etc.) are shown in Table 1. (Examples) 4) Forming and using the boron-free plating solution of the ith bonding step in the mineral recording step of the first embodiment (Nippon Mining Metal Electroplating Co., Ltd.: Nie*, ΗmΗ B), into 0_15"m nickel The layer (containing i.6wt% rotten) was washed with water. And 'after the water is removed', it is carried out in the atmosphere for 1 5 、. In the second plating step, the nickel layer of the same layer as the above is used to form a total of (the second layer of the nickel liquid % " m nickel layer. Relative to the whole The thickness, the first! Nickel plating) 〇.25 up to 60%. The ratio of the thickness is the same as that of the first embodiment. At the same time, . The measurement results such as peel strength are shown in Table 丨. :9 (Γ制离 (Example 5) 16 200905014 The electroless recording of the No. mineralization step in the nickel step of Example 1 - Boron-based plating solution (Nippon Mining Metal Co., Ltd.: Nikom HB The formed nickel layer (containing boron) is washed with pure water. After the water is removed, it is heat-treated in the atmosphere for 15 〇t and 1 〇. Next, the 帛2 mineralization step is used. The above-mentioned same mineral recording liquid forms a nickel layer of 0.09/zm to form a total (i-th plating + / one layer. The thickness of the third layer of the third layer is (%) is 64% relative to the thickness of the whole layer. Other systems and examples 1 The same procedure was carried out. Similarly, the measurement results of peeling strength and the like of the peeling were shown in Table 1. (Example 6) Electroless nickel-boron plating using the first plating step in the nickel plating step of Example 1. Dressing liquid (Nippon Metal Electroplating Co., Ltd.: Nikko hb), forming a layer of 〇18/zm (containing 1.6% by weight of boron), washed with pure water. \ And, after the water is removed, Heat treatment at 150t:, 1 minute in the atmosphere. Next, the second plating step uses the same plating as described above. The nickel liquid forms a nickel layer of 〇.〇7#m, and forms a total of (the first plating + the second plating) of the nickel layer. The ratio of the thickness of the second nickel layer is 72% with respect to the entire thickness. The other steps are the same as those in the first embodiment. Similarly, the measurement results of the peel strength and the like of the peeling are shown in Table 1. (Example 7) 17 200905014 The mineral recording step φ silver of Example 1 was used. The electroless nickel-side system of the first plating step in the township of the 7th township (Nikkei Metal Electric Clock Co., Ltd.: Nikom HB) was formed to form a recording layer of 0.20/zm (including 1 ς +0/ V 'h5wt% boron), washed with pure water. After removing the water, it is treated in the atmosphere at a temperature of 150 ° C for 1 minute, followed by a second plating step. The nickel layer of 〇.〇5,m is formed using the same mineral recording liquid as described above to form a total (the first [...] coating] 〇25 ... recording layer. The thickness of the first nickel layer is relative to the thickness of the whole The ratio was 80%. In the same manner, the peeling strength and the like of the same step as in Example 1 were measured and shown in Table 1. (Example 8) Using Example 1 The electroless recording of the i-th mineral deposit step in the mineral recording step - boron-based plating solution (Strontium Metal Electroplating Co., Ltd.: Nikko Η), forming a recording layer of 〇.2Wm (containing 14^ boron), pure The water is washed. Further, after the water is removed, it is carried out in the atmosphere for 15 〇. 热, 〇 〇 minutes of heat, and then 帛 2 plating step, using the same forging liquid as above to form 〇_〇4# The nickel of m is wide, and the total is formed (first plating + second plating claw 25
Am之鎳層。相對於全體之厚度，第 矛i歸層之厚度的比例 達 84% 〇 其他係與實施例1相同之步驟。同様地，將9〇。剝離 之剝離強度等測量結果示於表1。 (實施例9) 200905014 使用實施例1之錢鎳步驟中第1鍍敷步驟之無電解鎳 —硼系鍍敷液（日鑛金屬電鍍股份有限公司：尼可姆HB)， 形成0.22〆m之鎳層（含有1 5wt%硼），以純水加以洗淨。 並且，將水排除後，於大氣中進行15CTC、10分鐘之熱處 理。 接著’第2鑛敷步驟’係使用與上述相同之鍍鎳液形 成〇·03" m之鎳層，形成合計（第1鍍敷+第2鍍敷）0.25 以m之鎳層。相對於全體之厚度，第1鎳層之厚度的比例 達 88%。 其他係與實施例1相同之步驟。同様地，將9〇。剝離 之剝離強度等測量結果示於表i。 (比較例1) 使用實施例1之鑛鎳步驟中第1鍍敷步驟之無電解鎳 —硼系鍍敷液（日鑛金屬電鍍股份有限公司：尼可姆HB)， 形成0· 12 // m之鎳層（含有i 6wt%硼），以純水加以洗淨， 將水排除後，於大氣中進行15(rc、1〇分鐘之熱處理，第 2鍍敷步驟，係使用與上述相同之鍍鎳液形成〇13#m之 鎳層，形成合計（第1鍍敷+第2鍍敷）〇 25〆m之鎳層。 相對於全體之厚度，第i鎳層之厚度的比例為48%。 其他係與實施例1相同之步驟。同樣地，將9 〇。剝離 之剝離強度等測量結果示於表1。 其結果，常態剝離強度為〇.56kN/m，於150〇c、7天 老化後，為0.26kN/m，保持率（老化後/常態）達46%。 由此可清楚得知，本比較例丨，其相對於全體厚度之第1 200905014 錄層之厚度的比例為50%，保持率（老化後/常態）為46 % ’可知耐熱老化特性不佳。 (比較例2) 使用實施例1之鍍鎳步驟中第1鍍敷步驟之無電解鎳 —棚系鍛敷液（日鑛金屬電鍍股份有限公司：尼可姆hB)， 形成〇.19#m之錄層（含有i.6wt%硼），以純水加以洗淨， 將水排除後，於大氣中進行6{rc、丨〇分鐘之熱處理，第2 鍵敷步驟’係使用與上述相同之鍍鎳液形成〇〇6 # m之鎳 層，形成合計（第1鍍敷+第2鍍敷）〇 25" m之鎳層。相 對於全體之厚度’第！鎳層之厚度的比例為76%。其中， 如上述，為60C、1〇分鐘之熱處理。 其他係與實施例1相同之步驟。同様地，將9〇。剝離 之剝離強度等測量結果示於表1。 其結果，常態剝離強度為〇.54kN/m，於15〇。(：、7天 老化後’為0.27kN/m ’保持率（老化後/常態）達50%。 由此可清楚得知，本比較例2，其相對於全體厚度之第i 鎳層之厚度的比例為75%，由於加熱處理溫度低，因此保 持率（老化後/常態）僅有50%，可知耐熱老化特性不佳。 (比較例3) 使用實施例1之鍍鎳步驟中第1鍍敷步驟之無電解鎳 〜蝴系鍵敷液（日鑛金屬電鍍股份有限公司：尼可姆HB)， 形成0.25 m之鎳層（含有i.2wt%硼），熱處理及第2鍍敷 步驟則不進行。相對於全體之厚度’第1鎳層之厚度的比 例為100%。 20 200905014 其他係與實施例1相同之步驟。同様地，將9〇。剝離 之剝離強度專測量結果示於表1。 其結果’常態剝離強度為〇 52kN/m，於150。。、7天 老化後，為0.26kN/m，保持率（老化後/常態）為5〇%。 由此可清楚得知’本比較例3，其相對於全體厚度之第i 錄層之厚度的比例為100%，由於未進行加熱處理，因此 保持率（老化後/常態）僅有50%，可知耐熱老化特性不佳。 (比較例4) 使用實施例1之鍍鎳步驟中第丨鍍敷步驟之無電解錄 -填系鍍敷液（日鑛金屬電鍍股份有限公司：KG530F)，形 成〇.19"m之錄層（含有7.4wt% P)，以純水加以洗淨，將 水排除後’於大氣中進行i 50°C、丨〇分鐘之熱處理，第2 鐘敷步驟’係使用與上述相同之鍍鎳液形成〇 〇6以m之鎳 層’形成合計（第1鍍敷+第2鍍敷）0.25// m之鎳層《相 對於全體之厚度，第1鎳層之厚度的比例為76%。 其他係與實施例1相同之步驟。同様地，將90。剝離 之剝離強度等測量結果示於表1。 其結果’常態剝離強度為〇.45kN/m，於15〇t、7天 老化後’為〇_21kN/m，保持率（老化後/常態）為47%。 由此可清楚得知，本比較例4，由於無電解鎳液係使用鎳 —填系’因此保持率（老化後/常態）僅有47%，可知耐熱 老化特性不佳。且可知即使是相同Ni系合金之無電鍍， 使用無電解鎳—磷系亦無法得到充分之特性。 從以上實施例與比較例之比較可清楚得知，形成含有 21 200905014 硼之無電鍍鎳層之情形，於第1步驟形成較第2步驟厚的 無電鑛鎳層後，再進行加熱處理，並且於第2步驟再次形 成無電鍍鎳層，可提供耐熱老化特性優異之被覆有金屬之 聚醯亞胺樹脂基板。當第1步驟之無電鍍鎳層之形成不充 分，且僅有1層之無電鍍鎳層時，耐熱老化特性並不充分。 又’可知即使是通常所使用之含有P之無電鍍鎳層，同樣 地耐熱老化特性亦不佳。 於上述實施例1〜9中，硼的含量係在1·4〜I.6wt%的 範圍内實施，但是若為含有〇」〜3wt%之硼的無電鍍鎳層， 則可確認可得到與上述實施例1〜9幾乎相同的結果。 產業上之利用可能性 本發明’係提供一種於被覆作為導體之銅之步驟前， 在對聚醯亞胺樹脂膜實施親水化處理、賦予觸媒及觸媒活 性化處理後，形成無電鍍鎳層，且在大氣中進行熱處理後， 再次進行無電鍍鎳，以提升耐熱老化特性之被覆有金屬之 聚醢亞胺基板之製造方》，尤其具有可提升聚醯亞胺膜與 金屬層間之積層後之初期密合力，並提高老化後之密合 力’且有助於形成微細圖案之效果，因此適合作為可撓性 ㈣基板、TAB、C〇F等電子零件之構裝材料所使用之無 接著劑可撓性積層#，特別是耐熱老化特性優異之被覆有 金屬之聚醯亞胺樹脂基板。 【圖式簡單說明】 益 ”》、 【主要元件符號說明】 22 200905014Am nickel layer. The ratio of the thickness of the first spear i to the layer is 84% with respect to the thickness of the whole. 〇 The other steps are the same as in the first embodiment. At the same time, 9 will be. The measurement results of the peeling strength and the like are shown in Table 1. (Example 9) 200905014 The electroless nickel-boron plating solution (Nippon Mining Electroplating Co., Ltd.: Nikom HB) of the first plating step in the nickel nickel step of Example 1 was used to form 0.22 μm. A nickel layer (containing 15% by weight of boron) was washed with pure water. Further, after the water was removed, 15 CTC and 10 minutes of heat treatment were carried out in the atmosphere. Next, the 'second mineral depositing step' is performed by forming a nickel layer of 〇·03" m using the same nickel plating liquid as described above to form a nickel layer of 0.25 m in total (first plating + second plating). The ratio of the thickness of the first nickel layer was 88% with respect to the entire thickness. Other steps are the same as in the first embodiment. At the same time, 9 will be. The measurement results of peeling peel strength and the like are shown in Table i. (Comparative Example 1) The electroless nickel-boron plating solution (Nippon Mining Electroplating Co., Ltd.: Nikom HB) of the first plating step in the mineral nickel step of Example 1 was used to form 0·12 // The nickel layer of m (containing i 6wt% boron) is washed with pure water, and after the water is removed, it is subjected to 15 (rc, 1 minute heat treatment in the atmosphere, and the second plating step is the same as above). The nickel plating liquid forms a nickel layer of 〇13#m, and forms a total of (first plating + second plating) 镍25 〆m nickel layer. The ratio of the thickness of the ith nickel layer is 48% with respect to the entire thickness. The other steps were the same as in Example 1. Similarly, the measurement results of peeling strength such as peeling were shown in Table 1. As a result, the normal peel strength was 〇.56 kN/m at 150 ° C, 7 days. After aging, it is 0.26 kN/m, and the retention ratio (post-aging/normal state) is 46%. From this, it can be clearly seen that the ratio of the thickness of the first layer 200905014 of the entire thickness is 50. %, retention ratio (post-aging/normal state) was 46% 'The heat-resistant aging characteristics were poor. (Comparative Example 2) The first plating in the nickel plating step of Example 1 was used. The electroless nickel-shed forging solution (Nippon Mining & Metal Co., Ltd.: Nikom hB) is applied to form a recording layer of 〇.19#m (containing i.6wt% boron), which is washed with pure water. After the water is removed, 6{rc, 丨〇 minute heat treatment is performed in the atmosphere, and the second bonding step is to form a nickel layer of 〇〇6 #m using the same nickel plating liquid as above to form a total (the first 1 plating + second plating) 〇25" m nickel layer. The ratio of the thickness of the whole layer 'the thickness of the nickel layer is 76%. Here, as described above, the heat treatment is 60 C, 1 minute. The procedure was the same as in Example 1. Similarly, the measurement results of the peel strength and the like of peeling were shown in Table 1. As a result, the normal peel strength was 〇54 kN/m at 15 Å. (:, 7 days) After aging, the retention rate of 0.27 kN/m (after aging/normal state) was 50%. It is thus clear that in Comparative Example 2, the ratio of the thickness of the ith nickel layer to the entire thickness is 75%. Since the heat treatment temperature is low, the retention ratio (post-aging/normal state) is only 50%, and it is understood that the heat aging resistance is not good. (Comparative Example 3) Using the electroless nickel-female keying solution (Nippon Mining Electroplating Co., Ltd.: Nikom HB) of the first plating step in the nickel plating step of Example 1, a nickel layer of 0.25 m was formed (containing i.2wt) % boron), heat treatment and second plating step are not performed. The ratio of the thickness of the first nickel layer to the entire thickness is 100%. 20 200905014 Other steps are the same as in the first embodiment. 〇. The peeling strength specific measurement results are shown in Table 1. The result was 'normal peel strength 〇52 kN/m at 150. . After 7 days of aging, it was 0.26 kN/m, and the retention rate (post-aging/normal state) was 5〇%. From this, it can be clearly understood that 'this comparative example 3 has a ratio of the thickness of the i-th recording layer of the entire thickness to 100%, and since the heat treatment is not performed, the retention ratio (post-aging/normal state) is only 50%. It is known that heat aging characteristics are not good. (Comparative Example 4) The electroless recording-filling plating solution (Nippon Mining Electroplating Co., Ltd.: KG530F) of the first plating step in the nickel plating step of Example 1 was used to form a recording layer of 〇.19" (containing 7.4 wt% P), washed with pure water, after the water is removed, 'heat treatment at 50 ° C for 丨〇 minutes in the atmosphere, and the second step is the same as using the nickel plating solution described above. The formation of the nickel layer of 〇〇6 in a total of (the first plating + the second plating) of 0.25//m of the nickel layer "the thickness of the first nickel layer is 76% with respect to the entire thickness." Other steps are the same as in the first embodiment. At the same time, it will be 90. The measurement results of the peeling strength and the like are shown in Table 1. As a result, the normal peel strength was 〇45 kN/m, and after 15 〇t, 7 days of aging, it was 〇21 kN/m, and the retention ratio (post-aging/normal state) was 47%. From this, it can be clearly seen that in Comparative Example 4, since the nickel-filled system was used for the electroless nickel liquid, the retention ratio (post-aging/normal state) was only 47%, and it was found that the heat-resistant aging characteristics were not good. Further, it is understood that even if electroless plating of the same Ni-based alloy is used, sufficient characteristics cannot be obtained by using an electroless nickel-phosphorus system. It can be clearly seen from the comparison between the above examples and the comparative examples that in the case of forming an electroless nickel layer containing 21 200905014 boron, after the electroless nickel layer of the second step is formed in the first step, heat treatment is performed, and The electroless nickel plating layer is formed again in the second step, and a metal-coated polyimide film substrate excellent in heat aging resistance can be provided. When the formation of the electroless nickel layer in the first step is insufficient, and only one layer of the electroless nickel layer is formed, the heat aging resistance is not sufficient. Further, it is understood that even in the electroless nickel plating layer containing P which is usually used, the heat aging resistance is also inferior. In the above Examples 1 to 9, the boron content is carried out in the range of from 1-4 to 1.6% by weight, but if it is an electroless nickel layer containing bismuth to 3% by weight of boron, it can be confirmed that The above Examples 1 to 9 have almost the same results. INDUSTRIAL APPLICABILITY The present invention provides a method of forming an electroless nickel after performing a hydrophilization treatment on a polyimide film, a catalyst, and a catalyst activation treatment before coating a copper as a conductor. a layer, and after heat treatment in the atmosphere, re-electroplating nickel to improve the heat-resistant aging characteristics of the metal-coated polyimide substrate, especially to enhance the laminate between the polyimide film and the metal layer After the initial adhesion, and improve the adhesion after aging, and contribute to the effect of forming a fine pattern, it is suitable for use as a flexible material (4) substrate, TAB, C〇F and other electronic components. The flexible laminate layer #, in particular, a metal-coated polyimide substrate having excellent heat aging resistance. [Simple description of the schema] Benefits", [Key component symbol description] 22 200905014