200904866 九、發明說明： .【發明所屬之技術領域】 本發明係有關聚醯亞胺樹脂之表面改性方法及在經表 面改性之聚醯亞胺樹脂層上積層金屬層之覆金屬箔積層體 之製造方法。更細言之，係有關適於印刷線路基板之聚醯 亞胺樹脂之表面處理方法及覆金屬箔積層體之製造方法。 【先前技術】 一在電子裝置之電子電路中，一般使用將由絕緣材與導 電材組成之積層板進行電路加工而成之印刷線路板。印刷 ’、、良路板係在絕緣基板之表面（及内部）將按照電路設計之導 體圖案以導電性材料形成並固定而成者，且依絕緣樹脂之 種類，大致區分成板狀之剛性印刷線路板、與富有柔軟性 之柔性印刷線路板。在經常需重覆彎曲之可動部，柔性印 :::板ί成為接續用之必要零件。此外，由於柔性印刷 ^省*:此以雩曲之狀悲收藏在電子裝置内，故也可用為 之線路材料。在成為柔性印刷線路板之材料之柔 _:二邑緣樹！係一般大量使用聚醯亞胺醋或聚醮亞 大多』丨一使用I上則以具有耐熱性之聚醯亞胺樹脂佔 用銅箱面’從導電性之點來看，導電材係一般使 在柔性基板中，係有g 層)、接著劑層、鋼箱層3:戶=㈣(絕緣樹脂層之主 著劑而由基底薄膜層、“：：之積層板、與不使用接 W板不含環氧樹以丙__等耐熱性低之接 320155 5 200904866 著，層，故可靠性高，且可將電路整體予以薄膜化，其使 .用！正在增加。另一方面，從其他觀點來看，$ 了防止捲 曲產生@期盼柔性基板之基底薄膜層之熱膨騰係數低， 但由於熱膨脹係數低之聚醯亞胺樹脂之接著性不良，故當 3使用：著劑而全部為聚醯亞胺樹脂.時，必須在接著面： «又置接著性良好之聚醯亞胺樹脂層做為接著性賦予戶。此 =，也已知在兩面具有銅箱層之柔性基板，且已知^製造 單面具有鋼荡層之單面柔性基板後，叠加2片柔性基板而 ^層之方法、或在單面柔性基板疊加銅箔而積層之方法 專此&，也期盼不含接著劑層之柔性基板。 近年來’伴隨著電子農置中之高性能化'高機能化之 要求面澡，而期盼電子元件中所使用之電路基板材料之印 刷線路板之高密度化。為了使印刷線路板高密度化，而必 須將電路喊之寬度㈣隔料，亦g卩必須細節距伽㊁ =灿)化\為了使印刷線路板細節距化，而期盼使用表面粗 度低之銅治。然而，由於主二± & 而纟於表面粗度低之銅落之錨固效應 (anch〇r effeet)(亦即，對絕緣樹脂層之銅fl表面之凹凸之 到機械性接著強度’因此有對於絕緣樹 月曰之接者力會變低之問題。於是，對於提高表面粗度低之 銅落與絕緣樹脂之接著力即逐漸成為課題。 為了防止捲曲產生，而期盼基底薄膜層為埶膨脹係數 低之聚醯亞胺樹脂層，作在 …/脹係數 ^ -仁在低熱膨脹性與接著性之間係有 相反之關係。於是’為了提高 杈间接者強度，以往即有各種聚 知亞㈣之表面改性技術之報告。其中一例可舉例如經由 320155 6 200904866 電漿處理之表面改性方法。例如有··日本特開平5_2則9 ^公報（專利文獻υ、日本特開平8一 12779號公報（專利文 2)、日本特開平U — 209488號公報（專利文獻3)、日本 特開顧-5㈤號公報（專利文獻4)、日本特開厕— 咖號公報⑽!文獻5)等具體狀揭然而，現今此 4先前技術係其表面粗度低之域與㈣ 著力並非能令人滿意者。 、此外，藉由在成本面上有利之濕式钱刻之表面改性方 法也逐漸受到注目，但由於—般提高接著性之效果比起藉 由如電聚處理之乾式㈣之表面改性方法較不&，故此點 需要進-步改良。藉由如此之濕式㈣之表面改性方法可 舉例如：曰本特開平丨丨—498δ〇號公報（專利文獻6)。根據 專利文獻6揭示’在含有脂肪族—級胺之極性溶劑中處理 後之聚醯亞胺與金屬之間隔著聚醯亞胺接著劑進行熱壓接 之方法。然❼，此方法係必須設置聚隨亞胺接著劑層，而 有絕緣樹脂層會變厚之問題。 [專利文獻1]日本特開平5 —222219號公報 [專利文獻2]日本特開平8_ 12779號公報 [專利文獻3]曰本特開平η_2〇9488號公報 [專利文獻4]日本特開2〇〇4_ 51712號公報 [專利文獻5]日本特開2006— 7518號公報 [專利文獻6]日本特開平h — mmo號公報 【發明内容】 (發明欲解決的課題） 320155 7 200904866 本發明之目的係藉由將聚醯亞胺樹脂層之表面改性而 ,使接著性提高。此外，本發明之目的係將適合做為基底薄 胰^之低熱月彭脹性之聚醯亞胺樹脂狀表面改性以使接著 提高’而可省略做為接著性賦預之接著性聚醯亞胺樹 月:層或接著劑層。本發明之其他目的係提供具有極薄之接 著=之覆金屬箱積層體之製造方法，並且提供具有足夠因 應柔性基板之細節距化之接著強度之覆金屬箱積層體之 造方法。 ' (解決課題的手段） 為了達成上述目的，本發明人等在進行研究後，結果 發現若將聚醯亞胺樹脂層之表面經由特定處理而予以改 陡則可不改變聚醯亞胺樹脂層之厚度，即可得到與金屬 箔之接著強度高之經改良的聚醯亞胺樹脂層，遂完成 明。 換言之，本發明係，具備：將聚醯亞胺樹脂層之表面 側之層以下述式（1)所示之具有至少2個做為官能基之胺基 的有機處理劑進行接觸處理而形成表面接觸處理層之接觸 處理步驟、與將該表面接觸處理層進行加熱處理而形成改 性醯亞胺化層之改性醯亞胺化層形成步驟之聚醯亞胺樹脂 層之表面處理方法： h2n - ch2 - a - ch2 - nh2 ⑴ (式中，A表7F 2價有機基，且A中所含之碳原子數係2 至 18)。 在上述製造方法中，若在接觸處理步驟之前復具備進 320155 8 200904866 行電漿處理而形成電漿處理層面之電漿處理步驟，則可 高改性效果。 、 此外，本發明係’具備：在具有以上述任一方法所得 之改性聚醯亞胺化層之聚醯亞胺樹脂層之表面上疊加金屬 箔後進行熱壓接之壓接步驟之覆金屬箔積層體之製造方 法。 ° 在此，滿足金屬箔為銅箔、銅合金箔或不鏽鋼箔者、 或者、將金屬箱與改性醯亞胺化層隔著矽烷耦合劑處理層 進行熱壓接之任i者以上，可提供更優良之覆金屬箱積^ 體。 曰 進一步，本發明係具備：在具有以上述方法所得之改 性聚醯亞胺化層之聚醯亞胺樹脂層之表面’經由直接或隔 著基底金屬薄膜層蒸鍍銅而形成銅薄膜層之銅薄膜形成步 驟之覆金屬箔積層體之製造方法。 、 以下，說明關於本發明之聚醯亞胺樹脂層之表面處理 方法，其次說明關於本發明之覆金屬箔積層體之製造方 法，但共通部分係同時說明。再者，在本發明中所謂「聚 醯亞胺樹脂層」’係具有「由聚醯亞胺樹脂薄膜組成之層」 及「具有聚醯亞胺樹脂層之積層體之聚醯亞胺樹脂層」兩 者之涵義。因此，聚醯亞胺樹脂層係有為積層體之^醯亞 胺樹脂層之情形、與為聚醯亞胺樹脂薄膜之情形。 本發明中所使用之聚醯亞胺樹脂層並無特別限定，可 為由聚醯亞胺樹脂組成之薄膜（或薄片），也可為在積層於 銅箱、玻璃板、樹脂薄膜等基材上之狀態下之聚醯亞^樹 320155 9 200904866 脂層。然而，聚醯亞胺樹脂層之至少單面做為表面層。當 •表面層之兩侧為.聚醯亞胺樹脂層時，能處理其—側或兩側 之面。本發明中所得之經表面處理之聚醯亞胺樹脂層係具 有最初之聚醯亞胺化層（未改性之聚醯亞胺樹脂層）與改性 醯亞胺化層之至少2層。再者，#為積層於基材上之聚酿 亞胺樹脂層時，所謂基材，係指㈣亞胺樹.脂層所積層之 樹脂薄臈或金屬箔等材料。 形成聚醯亞胺樹脂層之聚醯亞胺樹脂，係含有所謂聚 醯亞胺樹脂，且係指聚醯胺醯亞胺、聚苯并咪唑、聚醯亞 胺酯、聚醚醯亞胺、聚矽氧烷醯亞胺等在構造中具有醯亞 胺基之耐熱j·生树脂。此外，市售之聚醯亞胺樹脂或聚醯亞 胺樹脂薄膜皆可利用。 —在聚酿亞胺樹脂層之巾，本發明<方法係尤其適於低 接者性且低熱膨脹性之聚酸亞胺樹脂層。具體而言，若應.. 用於熱線6膨脹係數在IxlG·6至3〇χ1().6(1/κ)(較佳係1χ1〇-6 至25Χ10·6(1/Κ)、更佳係15χ1〇4 25xi〇n》之低熱膨 脹性之聚醯亞胺樹脂層，則可得到报大的效果。然而，也 可應用於超過上述熱線膨脹係數之聚醢亞胺樹脂層。 •構成聚醯亞胺樹脂層之聚醯亞胺樹脂以具有通式⑺ :示之構造單元之聚醯亞胺樹脂騎。在通式（2)中，ΑΓι ⑹:式（3)或式(4)所示之4價芳香族基；ΑΓ3表示式（5)或式 乂：之2價芳香族基;R1係獨立地表示碳數1至6之i 二=或絲基；X及γ係獨立地表示單鍵或碳數！至i5 “基、從〇、8^〇,2或〇：0顺之中選出之2 320155 10 200904866 價之基，η係獨立地表 在之莫耳比’在0.1至200904866 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for modifying a surface of a polyimide resin and a metal foil layer laminated on a surface-modified polyimide layer. The manufacturing method of the body. More specifically, it relates to a surface treatment method for a polyimide film suitable for a printed circuit board and a method for producing a metal foil-clad laminate. [Prior Art] In an electronic circuit of an electronic device, a printed wiring board in which a laminate composed of an insulating material and a conductive material is circuit-processed is generally used. The printing 'and the good-duty plate are formed on the surface (and inside) of the insulating substrate by a conductive material in accordance with the circuit design, and are roughly divided into a plate-like rigid printing depending on the type of the insulating resin. Circuit board, flexible flexible printed circuit board with softness. In the movable part where the bending is often required, the flexible printing ::: board ί becomes a necessary part for the connection. In addition, since the flexible printing is saved in the electronic device, it can also be used as the wiring material. The softness of the material that becomes a flexible printed circuit board _: two rims! Generally, a large amount of polyimine vinegar or poly phthalate is used in large quantities. When using I, the heat-resistant polyimine resin occupies the copper box surface. From the point of view of conductivity, the conductive material is generally used. In the flexible substrate, the g layer), the adhesive layer, and the steel box layer 3 are: (4) (the main layer of the insulating resin layer is composed of the base film layer, ":: laminated board, and no W plate is not used. The epoxy-containing tree has a low heat resistance such as C __ and is connected to the layer 320155 5 200904866, so the reliability is high, and the whole circuit can be thinned, which is increasing. On the other hand, from other viewpoints In view of the fact, the thermal expansion coefficient of the base film layer which prevents the occurrence of curling is expected to be low, but the adhesion of the polyimide film having a low coefficient of thermal expansion is poor, so when using 3: the agent is all In the case of a polyimide resin, it is necessary to use a polyimine resin layer with good adhesion as a bonding property. This is also known as a flexible substrate having a copper box layer on both sides, and It is known that after manufacturing a single-sided flexible substrate having a steel layer on one side, two sheets of softness are superimposed. A method of laminating a substrate or a method of laminating a copper foil on a single-sided flexible substrate, and a method of laminating a flexible substrate without an adhesive layer is also expected. 'High-performance is required for facial showers, and high-density of printed circuit boards for circuit board materials used in electronic components is expected. In order to increase the density of printed circuit boards, it is necessary to shout the width of the circuit (4). Also, it is necessary to make the details of the printed circuit board in order to make the printed circuit board detailed. In addition, it is expected to use copper with a low surface roughness. However, due to the main surface roughness, the surface roughness is low. The anchoring effect of the copper drop (i.e., the mechanically subsequent strength to the unevenness of the surface of the copper fl of the insulating resin layer) has a problem that the strength of the insulator of the insulating tree is lowered. In order to prevent the occurrence of curl, it is expected that the base film layer is a polyimine resin layer having a low coefficient of expansion and is made to be inflated. Coefficient ^ - kernel in low heat expansion There is an inverse relationship between sex and susceptibility. Therefore, in order to improve the strength of 杈 indirect, there have been reports of various surface modification techniques of 聚亚亚(四). One example can be treated by, for example, 320155 6 200904866 For example, Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Special Opener-5 (5) Bulletin (Patent Document 4), Japanese Special Toilets - Coffee No. (10), Document 5) and other specifics. However, the current prior art is characterized by a low surface roughness and (4) In addition, the surface modification method by wet money engraving which is advantageous on the cost side is also attracting attention, but the effect of improving the adhesion is generally compared with the dry method by electropolymerization. (4) The surface modification method is less &amp; therefore, further improvement is required. The surface modification method of the wet type (4) can be exemplified by, for example, 曰本特开平丨丨-498δ〇 (Patent Document 6). According to Patent Document 6, a method of thermocompression bonding of a polyimide and a metal which are treated in a polar solvent containing an aliphatic-grade amine with a polyimine primer is disclosed. Then, this method is required to provide a polyimine binder layer, and there is a problem that the insulating resin layer becomes thick. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. 2006-7518 [Patent Document 6] Japanese Patent Application Publication No. H-mmo Publication (Convention) The object of the present invention is 320155 7 200904866 The adhesion is improved by modifying the surface of the polyimide resin layer. Further, the object of the present invention is to modify the surface of the polyimine resin which is suitable for the low heat of the base thin pancreas so as to be subsequently improved, and may be omitted as the adhesive layer of the adhesive layer. Imine tree month: layer or adhesive layer. Another object of the present invention is to provide a method of manufacturing a metal-clad laminate having an extremely thin joint = and to provide a method of forming a metal-clad laminate having sufficient adhesion strength in accordance with the detail of the flexible substrate. (Means for Solving the Problem) In order to achieve the above object, the inventors of the present invention have found that the surface of the polyimide resin layer is not changed by the specific treatment, and the polyimine resin layer is not changed. The thickness of the modified polyimine resin layer having a high bonding strength with the metal foil can be obtained. In other words, the present invention is characterized in that the layer on the surface side of the polyimide layer is subjected to a contact treatment with an organic treatment agent having at least two amine groups as a functional group represented by the following formula (1) to form a surface. a surface treatment method of the contact treatment step of the contact treatment layer, and the polyamidimide resin layer of the modified yttrium imidization layer forming step of heat-treating the surface contact treatment layer to form a modified yttrium imide layer: h2n - ch2 - a - ch2 - nh2 (1) (wherein A is 7F a divalent organic group, and the number of carbon atoms contained in A is 2 to 18). In the above manufacturing method, if the plasma treatment step of the plasma treatment layer is formed by the plasma treatment of 320155 8 200904866 before the contact treatment step, the modification effect can be high. Further, the present invention is characterized in that: the pressure-bonding step of performing thermocompression bonding after superposing a metal foil on the surface of the polyimide-imide resin layer having the modified polyamidimide layer obtained by any of the above methods A method of manufacturing a metal foil laminate. ° Here, if the metal foil is a copper foil, a copper alloy foil or a stainless steel foil, or the metal box and the modified yttrium imide layer are thermocompression bonded via a decane coupling agent treatment layer, Provide a better metal case. Further, the present invention comprises: forming a copper thin film layer by vapor-depositing copper directly or via a base metal thin film layer on the surface of the polyimine resin layer having the modified polyamidimide layer obtained by the above method A method of producing a metal foil-clad laminate in the copper film forming step. Hereinafter, the surface treatment method of the polyimide film of the present invention will be described. Next, the method for producing the metal foil-clad laminate according to the present invention will be described, but the common portions will be described simultaneously. In the present invention, the "polyimine resin layer" has a "layer composed of a polyimide film" and a "polyimine resin layer having a laminate of a polyimide resin layer". The meaning of both. Therefore, the polyimine resin layer is in the case of a laminate of the imine resin layer and in the case of a polyimide film. The polyimine resin layer used in the present invention is not particularly limited, and may be a film (or sheet) composed of a polyimide resin, or may be laminated on a substrate such as a copper box, a glass plate, or a resin film. In the state of the 醯 醯 ^ ^ tree 320155 9 200904866 lipid layer. However, at least one side of the polyimide layer is used as a surface layer. When the surface layer is on both sides of the polyimine resin layer, it can handle the side of the side or both sides. The surface-treated polyimine resin layer obtained in the present invention has at least two layers of an initial polyimidazolium layer (unmodified polyimide phase resin layer) and a modified oxime imidization layer. Further, when # is a polyimide resin layer laminated on a substrate, the substrate refers to a material such as a resin thin layer or a metal foil in which a layer of an imide tree or a lipid layer is laminated. The polyimine resin forming the polyimine resin layer contains a so-called polyimine resin, and refers to polyamidoximine, polybenzimidazole, polyimide, polyetherimine, A polysulfoxane ylide or the like which has a quinone imine group in the structure. Further, commercially available polyimine resin or polyimide film can be used. - In the case of a layer of a polyimide resin layer, the method of the present invention is particularly suitable for a layer of a polyimide resin having a low adhesion and a low thermal expansion property. Specifically, if it is used: the expansion coefficient for the hot line 6 is IxlG·6 to 3〇χ1().6(1/κ) (preferably 1χ1〇-6 to 25Χ10·6(1/Κ), more The low thermal expansion polyimine resin layer of the fine 15χ1〇4 25xi〇n" can obtain a large effect. However, it can also be applied to a polyimine resin layer exceeding the above coefficient of thermal linear expansion. The polyimine resin of the polyimide resin layer is rodped with a polyimine resin having a structural unit of the formula (7): In the formula (2), ΑΓι (6): formula (3) or formula (4) a tetravalent aromatic group shown; ΑΓ3 represents a divalent aromatic group of the formula (5) or a formula: R1 independently represents a carbon number of 1 to 6 i = or a silk group; X and γ are independently Represents a single bond or carbon number! to i5 "base, from 〇, 8^〇, 2 or 〇: 0 顺 selected 2 320155 10 200904866 price base, η series independently in the Mobi ratio 'at 0.1 to
不0至4之整數。q表示構成單元存 1·〇(較佳係在0.5至！.〇)之範圍。 (2) Μ上單元可存在於單—聚合物中、或存在做為共 早70。當為具有複數構造單元之共聚物時，可 ^為肷&(block)共聚物、也可存在於無規㈣d_)共聚 。在具有如此之構造單元之聚醯亞胺樹脂中，可利用 之聚醯亞胺樹脂宜為非熱塑性之聚醯亞胺樹脂。 ^由於聚醯亞胺樹脂一般係由使二胺與酸野反應所製 仵，故經由說明二胺與酸酐，即可理解聚醯亞胺樹脂之具 體例。在上述通式（2)中，由於_可為二胺之殘基、柄 :為馱酐之玟基，故藉由二胺與酸酐說明較佳之聚醯亞胺 樹脂 '然巾’不限定於由此等組合所得之聚醯亞胺樹月旨。 較佳之一胺可舉例如：4,4，_二胺二苯基醚、甲氧基 4’4 _一胺基苯甲醯胺苯、I;雙（4_胺基苯氧基）苯、1，3_雙 (4-胺基苯氧基）苯、2,2’·雙[4-(4-胺基苯氧基）苯基]丙烷、 二甲基_4,4’-二胺基聯苯、3,3，-二羥基·4,4，-二胺基聯 苯、4,4’-二胺基苯曱醯胺苯等。 其他，可舉例如：2,2-雙[4-(3-胺基苯氧基）苯基]丙烷、 320155 11 200904866 雙[4-(4-胺基苯氧基）苯基]颯、雙[4-(3_胺基苯氧基）苯基] 砜、雙[4-(4-胺基苯氧基）]聯苯、雙[4-(3-胺基苯氧基）]聯 苯、雙[1-(4-胺基苯氧基）]聯苯、雙[1-(3-胺基苯氧基）]聯 苯、雙[4-(4-胺基苯氧基）苯基]甲烷、雙[4·(3-胺基苯氧基) 苯基]甲烷、雙[4-(4-胺基苯氧基）苯基]醚、雙[4-(3-胺基苯 氧基）苯基]醚、雙[4_(4_胺基苯氧基）苯基]二苯基酮、雙 [4-(3-胺基苯氧基）苯基]二苯基酮、雙[4,4'-(4·胺基苯氧基）] 本曱醯胺苯、雙[4,4'-(3-胺基苯氧基）]苯甲酿胺苯、9,9-雙 [4-(4-胺基苯氧基）苯基]苐、9,9-雙[4-(3-胺基苯氧基）苯基] 荞、2,2-雙[4-(4-胺基苯氧基）苯基]六氟丙院、2,2-雙[4-(3_ 胺基苯氧基）苯基]六氟丙烷、4,4'-亞曱基二-鄰甲苯胺、4,4'-亞甲基-2,6-二甲苯胺、4,4'-亞甲基·2,6-二乙基苯胺、4,4'_ 二胺基二苯基丙烷、3,3，·二胺基二苯基丙烷、4,4，-二胺基 二苯基乙烷、3,3，-二胺基二苯基乙烷、4,4，_二胺基二苯基 曱烷、3,3'·二胺基二苯基甲烷、4,4，_二胺基二苯基硫醚、 3,3 - 一胺基二苯基硫醚、4,4，_二胺基二苯基颯、3,3,_二胺 基二苯基颯、4,4，-二胺基二苯基醚、3,3，_二胺基二苯基醚、 3,4-一胺基二苯基醚、聯苯胺、3,3，_二胺基聯苯、二 甲基-4,4’·二胺基聯苯、3,3，_二甲氧基聯苯胺、4,4，，_二胺基 -對聯三苯、3,3”_二胺基_對聯三苯、間苯二胺、對苯二胺、 2’6-一胺基^比咬、1;4雙（4·胺基苯氧基）苯、υ•雙（心胺基 苯氧基）苯^4,4'^，4-伸苯基雙（1-甲基亞乙基）]雙苯胺、 ^-以’伸笨基雙…曱基亞乙基肢苯胺^對胺基環己 基）甲烷、雙（對胺基三級丁基苯基）醚、雙（對石_甲基- 320155 12 200904866 占·胺基戊基）苯、對-雙（2_甲基-4-胺基戊基）苯、對-雙^；^ .二甲基-5-胺基戊基）苯、i，5_二胺基萘、2,6_二胺基萘、2,‘ 雙（y5 -胺基二級丁基）甲苯、2,4_二胺基甲苯、間二甲苯 二胺、對二甲苯_2,5-二胺、間苯二甲胺、對苯二甲胺、2,6_ 一胺基吡啶、2,5_二胺基吡啶、2,5-二胺基_；[，3,4_噚二唑 (oxadiazole)、哌畊（piperazine；)等。 較佳之酸酐可舉例如：均苯四酸酐、3,3，，4,4，_聯苯四 曱酸二酐、3,3’，4,4’·二苯基砜四甲酸二酐、4,4，-氧基二酞 酸針。 其他，較佳可舉例如：2,2，，3,3，_、2,3,3,，4，•或 3,3，，4,4，_ 二苯基酮四甲酸二酐、2,3，，3,4，_聯苯四甲酸二酐、2，’2/3’3，_ 聯苯四甲酸二酐、2,3，，3,4，-二苯基醚四曱酸二酐、雙’(2’，3_ 二羧基苯基）醚二酐等。此外，也可舉例如：3,3，,，4,4|，_、 2’3,3，4 或2,2，3,3”-對聯三苯四甲酸二酐、2,2•雙（2,3_或 3,4-二叛基苯基）丙院二酐、雙（2,3_或3,4_二竣基苯基)甲烷 一針、雙（2,3-或3,4_二竣基苯基）礙三軒、匕卜雙㈤-或认 二羧基苯基）乙烷二酐、U，7,8_、^厂或菲四 甲酸二酐、2,3,6,7-f四甲酸二酐、2,2·雙（3,4·二幾基苯基） 四敦丙烷二酐、2,3,5,6-環己烷二酐、2,3,6,7_萘四甲酸二 酐、1，2,5,6-萘四曱酸二酐、1Λ5,84四曱酸二酐、4,8_二 甲基-1,2,3,5,6,7-六氫萘_1，2,5,6_四甲酸二肝、2,6-或n 二氯萘-1，4,5,8-四甲酸二酐、2,3,6,7_(或Μ，5,8_)四氯萘 -1，4,5,8-(或 2,3,6,7-)四 Ψ 酸二酐、2,3,8,9…3,4,9，1〇_: 4’5’10’11-或 5,6，11，12-茈（perylene)四甲酸二酐、環戊烷 320155 13 200904866 -1，2,3,4-四甲酸二酐、吡哄-2,3,5,6-四甲酸二酐、吡咯啶 -2,3,4,5-四甲酸二酐、噻吩（thi〇phene)_2,3,4,5_ 四甲酸二 酐、4,4-雙（2,3-二羧基苯氧基）二苯基甲烷二酐等。 二胺、酸酐可分別僅使用其〗種、也可併用2種以上 使用。此外，也可併用上述以外之二胺及酸酐，此時，上 述以外之二胺或酸酐之使用比例宜設在9〇莫耳％以下，且 以在50莫耳％以下為佳。經由選定二胺及酸酐之種類、或 虽使用2種以上之二胺或酸酐時經由選定各自之莫耳比， 即能控制熱膨脹性、接著性、玻璃轉移點（Tg)等。 製造聚醯亞胺樹脂層之方法不特別限定，有例如：在 將做為聚醯亞胺樹脂之前驅物之聚醯胺酸之樹脂溶液塗布 於基材上後進行乾煉、醯亞胺化而使聚醒亞胺樹脂層形成 於基材上之方法。將聚醯胺酸之樹脂溶液塗布於基材上之 方法不特別限制，能以逗點型刮刀（c〇mma)、模具、刀、 裂縫(rip)等塗布器塗布。 此外，乾燥、醯亞胺化之方法也不特別限制，宜採用 例如.在80至40(TC之溫度條件下加熱丨至6〇分鐘之熱 處理。由於經由進行如此之熱處理而進行聚醯胺酸之脫水 閉環，故能使聚醯亞胺樹脂層形成於基材上。使聚醯亞胺 树知層形成於基材上之聚醯亞胺樹脂層可直接做為積層體 使用、也可將樹脂層剝下等之後做為薄膜使用。 聚醯亞胺樹脂層可為僅由單層形成者或由複數層組成 者。當將聚醯亞胺樹脂層形成複數層時，能在由不同構成 成刀組成之聚醯亞胺樹脂層上將其他聚醯亞胺樹脂依序塗 320155 14 200904866 布而开/成。虽聚醯亞胺樹脂層由3層以上組成時，可使用 同工構成之聚醯亞胺樹脂2次以上。層構造最簡單之單層 在業上可有利地得到。此外，聚醯亞胺樹脂層之厚度係 在3至較佳係3至5〇//m)之範圍。 在本孓明之聚醒亞胺樹脂層之表面處理方法中，係具 備接觸處理步驟及改性醯亞胺化層形成步驟。 ' 、在接觸處理步驟中，將聚醯亞胺樹脂層之表面侧之層 =上述式⑴所示之具有至少2個做為官能基之胺基的有機 理劑（以下也稱為胺化合物）處理而形成改性處理層。在 上述式（1)中，A表示2價有機基，且A中所含之碳原 =至叫較佳係2至^、更佳係4錢）。,可為僅由碳 ” 1、氫原子所構成之2價有機基、或者也可為含有氮原 子、氧原子、硫原子或♦原子之2價有機基。在本發明中 使用之有機處理劑係.具有至少2個鍵結於末端亞甲基上之 胺基雖具有鍵結於形成環狀環或芳香族環之碳上之胺 基,、但不具有至少2個鍵結於末端亞甲基上之胺基之化合 物等係無法或甚少達到本發明之效果。 σ 西當Α為僅由碳原子與氫原子所構成之2價有機基時， 2價有機基宜為含有直鏈、分枝或環狀環之伸院基或伸苯 基·。具有如此之2價有機基之胺基化合物之具體例可舉例 ’4 一胺基丁烷、ι，5_二胺基戊烷、丨，^二胺基己烷、 2-甲基-1，5_二胺基戊烷、！，7_二胺基庚烷、胺基辛 烷13-雙（胺甲基）環己院、匕心雙（胺甲基）環己烧、 二胺基壬⑥、ι，ι〇-二胺基癸烷、U1_二胺基十一m’2_ 320155 15 200904866 二胺基十二烷等二胺基烷類；間苯二曱胺、對苯二甲胺等 .笨二T胺類。 當A為含有氮原子、氧原子、硫原子或矽原子之2價 有機基時，具有如此之2價有機基之上述胺基化合物之且 體例可舉例如：參(2_胺乙基)胺、N，N，，胺乙基 丙二胺、雙（3_胺丙基）乙二胺、1,4·雙（3-胺丙基）旅哄、二 伸乙三胺、N_甲基_2,2，_二胺基二乙基胺、3,3(_二胺基二丙 基胺、Ν,Ν-雙（3_胺丙基）甲基胺等含有氮原子之胺類；雙（3 ，丙基㈣W雙（2_胺乙氧基）乙炫、3,9_雙（3_胺丙 基）-2,4,8，10_四氧雜螺[5斗十__烧等含有氧原子之胺類； 2,2_硫雙（乙胺）等具有硫原？之胺類；u•雙胺丙基 甲基二矽氧烷等含有矽原子之胺類。 在上述式⑴所示之胺基化合物之中，A更宜為僅由碳 原子與氫原子所構成之2價煙基、或宜為含有氮原子、氧 =子或硫原子之2價有機基。在此等2價之基中，尤其依 2:二L2價烴基、氮原子之2價有機基、含有氧原子之 乂機基、接著含有硫原子之2價有機基為佳。而且， 古ft煙基之中’尤其宜為含有苯環之2價有機基’且含 效=¾之胺基化合物係易得到提高與金屬洛之接著強度之 上述之胺基化合物可單獨使用，也可併用2種以 用。此外，也能併用上述式⑴所示之胺基化合物以外之並 〇他胺基化合物，此時，上述其他胺基化合物宜設在90莫; U下’且以5〇莫耳％以下為佳、以在20莫耳％以下較 320155 16 200904866 佳。 有機處理劑以在常溫為液體或固體者為佳，其沸點係 在l〇〇°C以上，且較有利地係以在15(TC為佳。然而‘，在 300至40CTC以上之溫度中宜具有蒸氣麼、或經分解而蒸 發。當為固體時，必須溶於溶劑中。 ’·、' 有機處理劑係，只要在⑺至机附近之常溫下為液 體時，gP可直接使用，4旦由於形成之改性處理層之厚度有 變不，勻之傾向、或有機處理劑以層狀附著於改性處：層 上之量有變多之傾向’故宜使用以溶劑稀釋之溶液。溶^ 係’只要為與有機處理劑混合者或溶解者則不特別限定: 但以使用極性溶劑較有利。極性溶劑可舉例如：水；戋甲 醇、乙醇、丙醇、丁醇等醇類；或是丙嗣、二甲基嗣5 基乙基酮等酮類’·四氫呋喃等醚類；或者N•甲基吡 酮、N，N-二甲基乙醯胺、二？基？醯胺等3級胺類；二甲 基亞石風等，且以N-甲其叫· σ交/ χτ χτ /+ Τ基比各疋酮、Ν，Ν-二甲基乙醯胺為 仏。可併用此等1種或2種以卜蚀田 ㈣2種以上使用’更可-部分使用如 甲本、甲本之芳香族烴。溶劑之滞點宜較有機處理劑者 為低’且以在2001：以下為佳。 含有有機處理劑之溶液之濃度係宜使用濃度00〇〇1 :至5莫耳/L)(較佳係_至遣、更佳係㈣ 至1M)之溶液。 以有機處理劑處理之方法係，只要為有機處理劑或有 松處理劑之溶液能接觸聚醯亞胺樹脂層之表面側 法，則不特別限定，可利用已周知之方法，但以均；地使 320155 17 200904866 印、吏用例如:浸漬法、喷灑法、刷塗或者 即可。(車又佳係在1〇至4(rc之常溫) m左右之一定厚度。之-液塗布成10至100# 進仃使有機處理劑或有機處理劑溶 脂層之表面側之声而裉士主二以 致卿本酿亞叙树 ^ ,^ θ /成表面接觸處理層之接觸處理步 :二=處理步驟中係將有機處理劑或有機處理劑溶 ==Γ層之表面層之内部而形成表面接觸 2層纟面接觸處理層之厚度係能藉由接觸時間或溫度 調整’但以在聚醯亞胺樹脂層厚度之1/100至1/1〇左右為 佳，從其他觀點來看以在(U至5/zm之範圍為佳。〜 其次’將此表面接觸處理層進行加熱處理。加熱處理 係經由在有機處理劑與聚醯亞胺樹脂之間使至少一部分反 應產生而使醯胺基生成，然後在此醯胺基醯亞胺化之溫度 維持預定時間而進行。當制有機處理狀溶液進行接觸 處理步驟時，以在加熱處理步驟之前段進行乾燥為佳。 用以生成醯胺基之加熱處理條件宜在溫度100至200 °C下處理1至60分鐘，且以在120°C至l8〇t下處理2至 20分鐘為更佳。用以進行醯亞胺化時之加熱處理條件宜在 溫度130至420°C下處理1至300分鐘，且以在18〇。〇至 380 C下處理3至30分鐘為佳。在加熱處理時，可以階段 性地提高溫度而進行之分批（batch)式，也可以連續提高、、θ 度而進行之連續硬化式，其方法不限定。此外，用以生成 醯胺基之加熱處理及用以醯亞胺化之加熱處理可連續或同 320155 18 200904866 9 時進行。 可認為在100至200°c之溫度中主要產生有機處理劑 之胺基與存在於聚醯亞胺樹脂層中（特別是在表面上;)之醯 亞胺基進行親核取代反應而生成醯胺基之醯胺反應。此 時’也可一併進行乾燥及將過量之有機處理劑之一部分蒸 發。並且’在130C以上之溫度也可並行地產生使醯胺基 之一部分生成醯亞胺基之醯亞胺化反應。此醯亞胺化反應 係通常在300至420。(：結束。其中，若有未反應之有機處 理劑’則其一部分會參與醯胺反應及醯亞胺化反應而一部 分會蒸發。因此，因經由此加熱處理使聚醯亞胺樹脂之表 層部醯胺化，從而降低分子量，其後再予以醯亞胺化，結 果會使聚醯亞胺樹脂層之接著性提高。 進行醯亞胺化時，如同上述藉由加熱之醯亞胺化、或 利用觸媒之化學性醯亞胺化之中之任一皆可，不特別限 定，但當上述藉由加熱之醯亞胺化不完全時，可併用藉由 觸媒之化學性醯亞胺化。 在本發明之聚醯亞胺樹脂層之表面處理方法中，在改 性處理步驟之前也可具備電漿處理步驟。經由此電漿處理 而形成電漿處理層面，藉此能使聚醯亞胺樹脂層之表面侧 之層粗化、或使表面側之層之化學構造改變。藉此，該表 面側之層之濕潤性提高，且與有機處理劑之親和性提高Λ : 特別有利此電漿處理之有機處理劑可舉例如··在至 °C之常溫下呈固體之態樣之胺基化合物（例如：間笨二、甲 胺、對苯二甲胺等），—經由具備電衆處理步驟，而能均勻地 320155 19 200904866 φ 形成改性醯亞胺化層面。 電漿係使用例如大氣壓方式之電漿處理裝置，在真空 處理室内使氬氣、氦氣、氮氣或此等之混合氣體之電漿= 成。此時以令處理壓力在5000至2〇〇〇〇〇Pa之範圍内處 理温度在10至贼之範圍内、高頻（或者微波）輸出在％ 至400W之範圍内為佳。 本發明之覆金屬箔積層體之製造方法係具備：準備具 有依上述任一方法進行表面處理後之改性醯亞胺化層之聚 醯亞胺樹脂層，在聚醯亞胺樹脂層之表面之改性醯亞胺化 層上疊加金屬箔後進行熱壓接（therm〇c〇mpressi()n bQnding) 之壓接步驟。 熱壓接之方法不特別限制，能適當採用周知之方法。 將金屬泊貼合之方法可舉例如：_般之液壓㈣卿代叫、 真空式之液壓、高壓釜加壓式真空壓接、連續式熱積層等。 從可得到足夠之施壓壓力，且也能容易進行殘留揮發成分 之去除，並進一步能防止金屬箔之氧化之觀點來看，在將 金屬猪貼合之方法中，尤以使用真空液壓、連續式熱積層 為佳。 此外，熱壓接以一面加熱至150至450。(：之範圍内一 面將金屬謂壓接為佳。以加熱至15〇至·。c之範圍内較 佳並且以加熱至15〇至38〇£)(：之範圍内更佳。從其他觀 點=看，宜為聚醯亞胺樹脂層或改性醯亞胺化層之玻璃轉 移溫度以上之溫度。此外’關於施避壓力，係依使用之壓 接機之種類而異，但通常宜在1至50MPa左右。 320155 20 200904866 - 金屬箔以銅箔、銅合金 鋼箔之例可直你丨‘ * 鐘鋼括為佳。金屬笮為 使用於此用途時之銅言：=板用途之情形。 為佳，且以在5至3〇// ;度以在3至5〇心之範圍 、“ 之範圍較佳，作要臾y 途中所使用之覆銅簿積声 —要求細即距之用 A主屮八 、θ 、且使用薄的鋼落（含右w細 為主成分之銅合金蕩），此時 （3有以銅 佳。此外，在本發明之製造方法二/⑼心之範圍為 小之銅箔也可得到對於樹即使使用表面粗度 用表面叔度小之使 點平均粗度在(U i 之=^之表面粗度以十 Φ #之乾圍為佳。特別是，對於在 要求細郎距之用途中所使用 主& ±产 在 V使用之銅泊，表面粗度以十點平均 粗度在0.1至1.0# m為佳。 金屬落為不鏽鋼落之例可舉例如：使用於搭载於硬碟 令之懸置（suspension)(以下稱為HDD懸置）用途之情形。做 為此用途使用時之不鏽鋼箔之厚度以在10至100# m之範 圍為佳，且以在15至70#m之範圍較佳、以在15至5〇 # m之範圍更佳。 金屬箔可在與改性醯亞胺化層接觸之面上施行矽烷耦 合劑處理。矽烷耦合劑以具有胺基或毓基等官能基之矽烷 耦合劑為佳，且以具有胺基之矽烷耦合劑較佳。具體例可 舉例如：3-胺丙基三甲氧基矽烷、3_胺丙基三乙氧基矽烷、 2-胺丙基三甲氧基矽烷、2-胺丙基三乙氧基矽烷、Ν_(2·胺 乙基）-3-胺丙基三Τ氧基矽烷、ν-(2-胺乙基）-3-胺丙基三乙 氧基矽烷、N-(2-胺乙基）-3-胺丙基甲基二甲氧基矽烷等。 21 320155 200904866 "其中尤以從3_胺丙基三乙氧基矽烷、3-胺丙基三甲氧基矽 烷、N-(2-胺乙基）-3-胺丙基三甲氧基矽烷、N_(2_胺乙基）·3· 胺丙基甲基二甲氧基矽烷、3_三乙氧基矽烷基_Ν_(ι，3-二甲 基亞丁基）丙胺及Ν-苯基_3_胺丙基三甲氧基石夕燒之中選出 之至少1種為佳。特別是，以從3_胺丙基三乙氧基石夕炫、 3-胺丙基三甲氧基矽烷之中選出之至少j種為佳。 矽烧叙合劑係做為極性溶劑之溶液使用。極性溶叫以 水或含有水之極性有機溶劑為佳。極性有機溶劑係，二要 為具有與水之親和性之極性液體，則不特別限定。如此之 極性有機溶劑可舉例如：甲醇、乙醇、丙醇、異丙醇 酮、四虱吱喃、二甲基甲醯胺、二甲基乙酿胺等。石夕 合劑溶液宜為濃度在〇.〇1至5重量％ (較佳係在〇 重量％、更佳係在〇.5U.〇重量％)之溶液。 關於石夕燒輕合劑處理要為 極性溶劑m夕士 + 、要為接觸各有石夕燒輕合劑之 才选今狀4之方法，則不特職定，可利用周知 。可利關如：浸潰法、魏法 溫度係〇至i〇(rc@祜尨a i剕去4。 (較佳係在10至4〇°c附近之常溫）即可。Not an integer from 0 to 4. q denotes a range in which the constituent unit stores 1·〇 (preferably in the range of 0.5 to !.〇). (2) The supra-unit may be present in the mono-polymer or present as a total of 70. When it is a copolymer having a plurality of structural units, it may be a 肷 & (block) copolymer, or may be present in a random (d) d_) copolymer. In the polyimine resin having such a structural unit, the polyimine resin which can be used is preferably a non-thermoplastic polyimide resin. Since the polyimine resin is generally produced by reacting a diamine with an acid field, a specific example of the polyimide resin can be understood by explaining the diamine and the acid anhydride. In the above formula (2), since _ may be a residue of a diamine and a stalk: a sulfhydryl group of phthalic anhydride, the preferred polyimine resin 'detailed' by a diamine and an acid anhydride is not limited to The resulting polyimine tree is thus combined. Preferred examples of the amine include, for example, 4,4,-diamine diphenyl ether, methoxy 4'4-monoaminobenzamide, I; bis(4-aminophenoxy)benzene, 1,3_bis(4-aminophenoxy)benzene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, dimethyl-4,4'-diamine A phenyl group, a 3,3,-dihydroxy-4,4,-diaminobiphenyl, a 4,4'-diaminobenzoquinone benzene or the like. Other examples include 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 320155 11 200904866 bis[4-(4-aminophenoxy)phenyl]indole, double [4-(3-Aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)]biphenyl, bis[4-(3-aminophenoxy)]biphenyl , bis[1-(4-aminophenoxy)]biphenyl, bis[1-(3-aminophenoxy)]biphenyl, bis[4-(4-aminophenoxy)phenyl Methane, bis[4.(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy) Phenyl]ether, bis[4-(4-aminophenoxy)phenyl]diphenyl ketone, bis[4-(3-aminophenoxy)phenyl]diphenyl ketone, bis[ 4,4'-(4.Aminophenoxy)]benzamide, bis[4,4'-(3-aminophenoxy)]benzamide, 9,9-double [ 4-(4-Aminophenoxy)phenyl]anthracene, 9,9-bis[4-(3-aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4-amine Phenyloxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 4,4'-arylene di-o-toluidine, 4,4'-methylene-2,6-xylyleneamine, 4,4'-methylene-2,6-diethylaniline, 4,4'_ Aminodiphenylpropane, 3,3,diaminodiphenylpropane, 4,4,-diaminodiphenylethane, 3,3,-diaminodiphenylethane, 4, 4,-Diaminodiphenylnonane, 3,3'-diaminodiphenylmethane, 4,4,-diaminodiphenyl sulfide, 3,3-aminoaminodiphenyl sulfide Ether, 4,4,-diaminodiphenylphosphonium, 3,3,-diaminodiphenylphosphonium, 4,4,-diaminodiphenyl ether, 3,3,-diaminodiyl Phenyl ether, 3,4-aminodiphenyl ether, benzidine, 3,3,-diaminobiphenyl, dimethyl-4,4'-diaminobiphenyl, 3,3,_ Dimethoxybenzidine, 4,4,,diamino-para-triphenyl, 3,3"-diamino-p-terphenyl, m-phenylenediamine, p-phenylenediamine, 2'6-monoamine Base, bite, 1; 4 bis(4.aminophenoxy)benzene, bismuth(cardamoylphenoxy)benzene^4,4'^, 4-phenylene bis(1-methyl Ethylene)] bisaniline, ^- to 'extended base bis(indenyl imino) aniline oxime to aminocyclohexyl) methane, bis(p-aminotributyl phenyl) ether, double (pair _methyl-320155 12 200904866 octa-aminopentyl) benzene, p-bis(2-methyl-4-aminopentyl) Benzene, p-bis^;^. dimethyl-5-aminopentyl)benzene, i,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,' bis(y5-amino group II Butyl)toluene, 2,4-diaminotoluene, m-xylenediamine, p-xylene-2,5-diamine, m-xylylenediamine, p-xylylenediamine, 2,6-monoamine Pyridine, 2,5-diaminopyridine, 2,5-diamino-[;3,4-oxadiazole, piperazine; and the like. Preferred acid anhydrides are, for example, pyromellitic anhydride, 3,3,4,4,4-biphenyltetracarboxylic dianhydride, 3,3',4,4'diphenylsulfone tetracarboxylic dianhydride, 4 , 4,-oxydicarboxylic acid needle. Others, preferably, for example, 2, 2, 3, 3, _, 2, 3, 3, 4, or 3, 3, 4, 4, _ diphenyl ketone tetracarboxylic dianhydride, 2 ,3,,3,4,_biphenyltetracarboxylic dianhydride, 2,'2/3'3,_biphenyltetracarboxylic dianhydride, 2,3,,3,4,-diphenyl ether tetradecanoic acid Di-anhydride, bis'(2',3-dicarboxyphenyl)ether dianhydride, and the like. In addition, for example, 3, 3,,, 4, 4|, _, 2'3, 3, 4 or 2, 2, 3, 3"-paired triphenyltetracarboxylic dianhydride, 2, 2 • double (2,3_ or 3,4-di-nepiphenyl) propylene dianhydride, bis(2,3_ or 3,4-diphenylphenyl)methane, a needle (2, 3- or 3) , 4_didecylphenyl) shangxuan, 匕bs(5)- or bis-carboxyphenyl)ethane dianhydride, U,7,8_,^ plant or phenanthrenecarboxylic acid dianhydride, 2,3,6 , 7-f tetracarboxylic dianhydride, 2,2·bis(3,4·diylphenyl) tetrahydropropane dianhydride, 2,3,5,6-cyclohexane dianhydride, 2,3,6 , 7_naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalene tetraphthalic acid dianhydride, 1Λ5,84 tetradecanoic acid dianhydride, 4,8-dimethyl-1,2,3,5,6 ,7-hexahydronaphthalene_1,2,5,6-tetracarboxylic acid di-hepatic, 2,6- or n-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7_ (or Μ, 5,8_) tetrachloronaphthalene-1,4,5,8-(or 2,3,6,7-)tetradecanoic acid dianhydride, 2,3,8,9...3,4,9 , 1〇_: 4'5'10'11- or 5,6,11,12-茈(perylene) tetracarboxylic dianhydride, cyclopentane 320155 13 200904866 -1,2,3,4-tetracarboxylic dianhydride , pyridin-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiene (thi〇phene)_2,3,4,5_tetracarboxylic acid An anhydride, 4,4-bis(2,3-dicarboxyphenoxy)diphenylmethane dianhydride, etc. The diamine and the acid anhydride may be used singly or in combination of two or more kinds. In addition, the diamine and the acid anhydride other than the above may be used. In this case, the use ratio of the diamine or the acid anhydride other than the above is preferably 9 〇 mol% or less, and preferably 50 mol% or less. When the two or more kinds of diamines or acid anhydrides are used, the thermal expansion property, the adhesion property, the glass transition point (Tg), and the like can be controlled by selecting the respective molar ratios. The method for producing the polyimide resin layer is not particularly For example, a resin solution of poly-proline which is used as a precursor of a polyimide resin is applied onto a substrate, and then dried and yttrium-imided to form a layer of the polyimide resin layer. The method of coating the polyacetic acid resin solution on the substrate is not particularly limited, and can be applied by a coater such as a squeegee blade, a mold, a knife, or a rip. The method of drying and hydrazine imidization is also not particularly limited, and it is preferably used, for example, at 80 to 40. (The heat treatment of heating the crucible to a temperature of TC for 6 minutes. The dehydration ring closure of the polyamic acid by performing such heat treatment enables the polyimine resin layer to be formed on the substrate. The polyimine resin layer formed on the substrate by the amine tree layer can be used as a laminate directly, or can be used as a film after peeling off the resin layer. The polyimide layer of the polyimide may be composed of only a single layer or a plurality of layers. When the polyimine resin layer is formed into a plurality of layers, the other polyimide resin can be sequentially coated on the polyimide resin layer composed of different knives and formed into a film of 320155 14 200904866. When the polyimine resin layer is composed of three or more layers, the polyamidene resin having the same composition can be used twice or more. The simplest single layer of layer construction is advantageously available. Further, the thickness of the polyimide film layer is in the range of 3 to preferably 3 to 5 Å/m. In the surface treatment method of the waking imine resin layer of the present invention, a contact treatment step and a modified quinone imidization layer forming step are provided. In the contact treatment step, the layer on the surface side of the polyimide resin layer = a mechanism agent having at least two amine groups as a functional group represented by the above formula (1) (hereinafter also referred to as an amine compound) The treatment forms a modified treatment layer. In the above formula (1), A represents a divalent organic group, and the carbonogen contained in A = to be preferably 2 to 2, more preferably 4). It may be a divalent organic group composed only of carbon "1", a hydrogen atom, or a divalent organic group containing a nitrogen atom, an oxygen atom, a sulfur atom or a ♦ atom. The organic treating agent used in the present invention An amine group having at least 2 bonded to a terminal methylene group having an amine group bonded to a carbon forming a cyclic ring or an aromatic ring, but having no at least 2 bonded to the terminal end group The compound of the amine group on the base cannot or rarely achieve the effect of the present invention. When σ Α Α is a divalent organic group composed only of a carbon atom and a hydrogen atom, the divalent organic group preferably contains a linear chain. a compound of a branched or cyclic ring or a phenyl group. Specific examples of the amine compound having such a divalent organic group can be exemplified by '4 monoaminobutane, iota-5-diaminopentane,丨, ^ diamino hexane, 2-methyl-1,5-diaminopentane, !, 7-diaminoheptane, aminooctane 13-bis (aminomethyl) ring,匕 bis (aminomethyl) cyclohexane, diamino hydrazine 6, ι, ι〇-diamino decane, U1_diamine y1 m'2_ 320155 15 200904866 diaminododecane, etc. Aminoalkyl a class of diphenylamines, p-xylylenediamine, etc. stupid diamines. When A is a divalent organic group containing a nitrogen atom, an oxygen atom, a sulfur atom or a ruthenium atom, it has such a divalent organic group. Examples of the above-mentioned amine compound include gin(2-aminoethyl)amine, N,N, amine ethyl propylenediamine, bis(3-aminopropyl)ethylenediamine, 1,4·. Bis(3-Aminopropyl) ruthenium, diethylenetriamine, N-methyl-2,2,-diaminodiethylamine, 3,3 (diaminodipropylamine, hydrazine, An amine containing a nitrogen atom such as bis-bis(3-aminopropyl)methylamine; bis(3,propyl(tetra)Wbis(2-aminoethoxy)ethanol, 3,9-bis(3-amine C) Base, -2,4,8,10_tetraoxaspiro[5 bucket ten __-burning amines containing oxygen atoms; 2,2-sulfenyl (ethylamine) and other amines having sulfurogen; An amine containing a halogen atom such as bisaminopropylmethyldioxane. Among the amine compounds represented by the above formula (1), A is preferably a divalent tobacco group composed only of a carbon atom and a hydrogen atom. Or preferably a divalent organic group containing a nitrogen atom, an oxygen group or a sulfur atom. Among these divalent groups, especially 2: two L2 valent hydrocarbon groups, nitrogen atoms The divalent organic group, the halogen group containing an oxygen atom, and the divalent organic group containing a sulfur atom are preferred. Moreover, among the ancient ft tobacco groups, 'especially preferably a divalent organic group containing a benzene ring' is effective. The amine compound of the above formula (1) can be used alone or in combination of two or more kinds of the amine compound represented by the above formula (1). Further, the other amino group compound is preferably set at 90 mol; U lower' and preferably 5 〇 mol% or less, and 20 mol% or less is better than 320155 16 200904866. The agent is preferably a liquid or a solid at normal temperature, and has a boiling point of 10 ° C or more, and more preferably 15 (TC is preferred). However, it is desirable to have a vapor at a temperature of 300 to 40 CTC or more, or to decompose and evaporate. When it is a solid, it must be dissolved in a solvent. '·,' Organic treatment agent, as long as it is liquid at room temperature (7) to the vicinity of the machine, gP can be used directly, 4 denier due to the thickness of the modified treatment layer formed, uniform tendency, or organic treatment agent The layer is attached to the modification: the amount on the layer tends to increase. Therefore, it is preferable to use a solution diluted with a solvent. The solvent is not particularly limited as long as it is mixed with or dissolved in the organic treatment agent: However, it is advantageous to use a polar solvent. Examples of the polar solvent include water; alcohols such as methanol, ethanol, propanol, and butanol; and ethers such as ketones such as propyl hydrazine and dimethyl sulfonium 5-ethyl ketone, such as tetrahydrofuran; Kepirone, N,N-dimethylacetamide, two? base? a class 3 amine such as guanamine; a dimethyl sulphate, etc., and N-methyl, σ / / χτ χτ / + Τ base ratio of each fluorenone, hydrazine, hydrazine-dimethyl acetamide . One or two of these may be used in combination with the etched field (four) or two or more types of the aromatic hydrocarbons such as A and A. The stagnation point of the solvent is preferably lower than that of the organic treating agent and is preferably in the following 2001:. The concentration of the solution containing the organic treating agent is preferably a solution having a concentration of 00 〇〇 1 : to 5 mol / L) (preferably, to a better, (4) to 1 M). The method of treating with an organic treatment agent is not particularly limited as long as it is a surface side method in which a solution of an organic treatment agent or a release treatment agent can be contacted with the polyimide resin layer, and a well-known method can be used, but For 320155 17 200904866, use, for example, dipping, spraying, brushing or just. (The car is also in a certain thickness from 1〇 to 4 (the normal temperature of rc) m. The liquid is coated into 10 to 100#, so that the surface of the organic treatment agent or the organic treatment agent is on the surface side.士主二以致卿本亚亚亚树 ^ , ^ θ / contact surface treatment layer contact treatment step: two = treatment step is the organic treatment agent or organic treatment agent == Γ layer of the surface layer inside The thickness of the surface contact two-layered surface contact treatment layer can be adjusted by contact time or temperature 'but preferably from 1/100 to 1/1 厚度 of the thickness of the polyimide layer, from other viewpoints Preferably, the surface contact treatment layer is heat-treated in a range of (U to 5/zm.). The heat treatment is carried out by causing at least a part of the reaction between the organic treatment agent and the polyimide resin. The formation of an amine group is then carried out at a temperature at which the amidoxime imidization is maintained for a predetermined period of time. When the organically treated solution is subjected to a contact treatment step, it is preferred to carry out the drying before the heat treatment step. Amine based heat treatment conditions should be at a temperature of 100 to 200 ° It is more preferably treated at C for 1 to 60 minutes, and more preferably treated at 120 ° C to 18 ° C for 2 to 20 minutes. The heat treatment conditions for the hydrazine imidization are preferably treated at a temperature of 130 to 420 ° C. 1 to 300 minutes, and it is preferably treated at 18 〇 to 380 C for 3 to 30 minutes. In the case of heat treatment, the batch can be gradually increased in temperature, and the batch can be continuously improved. The method of continuously curing the θ degree is not limited. Further, the heat treatment for forming the guanamine group and the heat treatment for hydrazine imidation may be carried out continuously or at the same time as 320155 18 200904866 9. An amine group mainly producing an organic treating agent at a temperature of 100 to 200 ° C is subjected to a nucleophilic substitution reaction with a quinone imine group present in the polyimide layer (especially on the surface) to form a guanamine group. The guanamine reaction. At this time, it is also possible to dry and partially evaporate one part of the excess organic treatment agent, and 'the temperature at 130C or higher can also produce a ruthenium group which is a part of the sulfhydryl group. Amination reaction. This ruthenium reaction system is usually between 300 and 42 0. (: End. Among them, if there is an unreacted organic treating agent', part of it will participate in the indoleamine reaction and the oxime imidization reaction, and a part will evaporate. Therefore, the polyimine resin is subjected to heat treatment by this heat treatment. The surface layer is amidated to lower the molecular weight, and then the ruthenium imidization results in an increase in the adhesion of the polyimide layer. As a result of the imidization, the imidization is carried out by heating as described above. Or any one of the chemical ruthenium imidizations of the catalyst may be used, and is not particularly limited, but when the above imidization by heating is incomplete, the chemical chemistry by the catalyst may be used in combination. In the surface treatment method of the polyimine resin layer of the present invention, a plasma treatment step may be provided before the modification treatment step. The plasma treatment layer is formed by the plasma treatment, whereby the layer on the surface side of the polyimide layer can be roughened or the chemical structure of the layer on the surface side can be changed. Thereby, the wettability of the layer on the surface side is improved, and the affinity with the organic treatment agent is improved. 特别: It is particularly advantageous for the organic treatment agent for the plasma treatment to be, for example, a solid state at a normal temperature to °C. The amine-based compound (for example, succinimide, methylamine, p-xylylenediamine, etc.) can form a modified oxime imidization layer uniformly by 320155 19 200904866 φ by having a power treatment step. The plasma is a plasma treatment apparatus such as an atmospheric pressure type in which a plasma of argon gas, helium gas, nitrogen gas or the like is mixed in a vacuum processing chamber. At this time, it is preferred that the treatment pressure be in the range of 5,000 to 2 〇〇〇〇〇 Pa in the range of 10 to the thief, and the high frequency (or microwave) output be in the range of % to 400 W. The method for producing a metal foil-clad laminate according to the present invention comprises: preparing a polyimide film having a modified yttrium imidization layer surface-treated by any of the above methods, on the surface of the polyimide layer The pressure-bonding step of thermocompression bonding (therm〇c〇mpressi()n bQnding) is performed after the metal foil is superimposed on the modified yttrium imide layer. The method of thermocompression bonding is not particularly limited, and a well-known method can be suitably employed. The method of attaching the metal poise can be exemplified by: _like hydraulic (four) Qing dynasty, vacuum type hydraulic pressure, autoclave pressure type vacuum pressure bonding, continuous heat accumulation layer, and the like. From the viewpoint of obtaining sufficient pressure of pressure, and also facilitating the removal of residual volatile components and further preventing oxidation of the metal foil, in the method of bonding metal pigs, vacuum hydraulic pressure and continuous use are particularly used. Thermal laminates are preferred. In addition, the thermocompression is heated to 150 to 450 on one side. (In the range of: the metal is preferably crimped on one side. It is preferably heated within the range of 15 〇 to · c and heated to 15 〇 to 38 )). = Look, it should be the temperature above the glass transition temperature of the polyimide or imide layer. In addition, the pressure on the application varies depending on the type of crimping machine used, but it is usually appropriate. Between 1 and 50 MPa. 320155 20 200904866 - Metal foil with copper foil and copper alloy steel foil can be straightforward. * Bell steel is better. Metal enamel is used for this purpose: = board use case It is better, and in the range of 5 to 3 〇 / / ; in the range of 3 to 5 、 heart, "the range is better, the copper-clad book sound used on the way to 臾 y - requires fine spacing Use A main 屮8, θ, and use a thin steel drop (including the right w fine copper alloy as the main component), at this time (3 is better with copper. In addition, in the manufacturing method of the present invention 2 / (9) heart The range of small copper foil can also be obtained for the tree even if the surface roughness is small, the surface roughness is small, and the average roughness of the point is (U i = ^ surface roughness) It is better to use the dry circumference of ten Φ #. In particular, for the copper used in the use of the main & ± used in the application of the fine lang distance, the surface roughness is 10 points average thickness of 0.1 to 1.0# For example, it is used in the case of a suspension mounted on a hard disk (hereinafter referred to as HDD suspension), and the stainless steel foil is used for this purpose. The thickness is preferably in the range of 10 to 100 #m, and more preferably in the range of 15 to 70 #m, more preferably in the range of 15 to 5 Å #m. The metal foil can be imidized with the modified oxime. The surface of the layer contact is treated with a decane coupling agent. The decane coupling agent is preferably a decane coupling agent having a functional group such as an amine group or a fluorenyl group, and is preferably a decane coupling agent having an amine group. Specific examples include, for example, 3 -Aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, Ν_(2.Amineethyl)- 3-aminopropyltrimethoxy decane, ν-(2-aminoethyl)-3-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldi Methoxy oxime Alkane, etc. 21 320155 200904866 " Among them, especially from 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxynonane, N-(2-aminoethyl)-3-aminopropyltrimethoxy Baseline, N_(2-aminoethyl)·3·aminopropylmethyldimethoxydecane, 3-triethoxydecyl-Ν-(ι,3-dimethylbutylidene)propylamine and hydrazine- It is preferred to select at least one selected from the group consisting of phenyl-3-aminopropyltrimethoxy zeoxime. In particular, it is derived from 3-aminopropyltriethoxylate, 3-aminopropyltrimethoxydecane. At least j of the selected ones are preferred. The simmering sulphur mixture is used as a solution of a polar solvent. The polar solution is preferably water or a polar organic solvent containing water. The polar organic solvent is not particularly limited as long as it is a polar liquid having affinity with water. Examples of such a polar organic solvent include methanol, ethanol, propanol, isopropanol, tetradecyl, dimethylformamide, dimethyletheneamine and the like. The solution solution of Shi Xi is preferably a solution having a concentration of from 1 to 5% by weight (preferably in 〇% by weight, more preferably 〇.5U. 〇% by weight). Regarding the treatment of Shi Xi-burn light mixture, it is necessary to use the method of selecting the current solvent 4 for the polar solvent m s +, and the method for the contact with each of them. Keliguan such as: dipping method, Weifa temperature system to i〇 (rc@祜尨a i剕 to 4. (preferably at room temperature around 10 to 4 ° °c).
此外，當應用浸清、土 口士 士， } r JIn addition, when applying immersion, earthenmouth, } r J
/ τ，有效之浸潰時間係處理1 〇秒至J 小時’且以30秒至〗s八供*丛上 办主1 方法丨〜 5刀鐘為佳。處理後進行乾燥。乾烊 焊γ 士限疋’可使用自然乾燥、藉由空氣搶嘖吹之r 燥、或藉由烘笳少私π姑 ^ ^j岛貝人之乾 1¾ I 、s A 、 心’專。乾燥條件亦依極性溶劑之# ^ 而異，通常在10至15〇。 W之種類 至W下處理]Ω ,下處理5秒至6〇分鐘，以在25 …〗 3〇分鐘為佳、尤以在3〇至120。「 下處理1分鐘至1〇分鐘更佳。 主u〇c 320155 22 200904866 依本發明之覆金屬箔積層體之製造方法所得之積層體 ，聚醯亞胺樹脂層之單面或兩面具有金屬箱之積層體。 f早面具有金屬0之積層體可經由在依本發明之聚釀亞胺 樹脂層之表面處理方法所得之改性醯亞胺化層之表面上積 層金屬^而得到。當表面處理聚醯亞胺樹脂層積層於玻 璃、樹脂薄膜等基材上時，宜在積層金屬箔前或積層後將 基材制離。當基材為銅箱等金屬落時，能經由在此聚醒亞 胺樹脂層側積層金屬ϋ形成兩面覆金屬荡積層體。此外， 兩面具有金屬箔之覆金屬箔積層體係除了上述方法以外， 其他可經由在聚醯亞胺膜之兩面形成改性醯亞胺化層後， 在此兩面積層金屬箔而得到。並且，在製得單面具有金屬 箔之單面覆金屬箔積層體後，也能依對於至少i片單面覆 金屬浴積層體在聚酿亞胺樹脂·層之表面侧之層上形成上述 改性醯亞胺化層後，疊加2片單面覆金屬箔積層體之聚醯 亞胺層後進行熱壓接之方法製造。 本發明之覆金屬箔積層體之第二製造方法係具備：準 備具有依上述表面處理方法所處理之改性醯亞胺化層之聚 酿亞胺樹脂層，經由在改性醯亞胺化層之表面直接或隔著 基底金屬薄膜層蒸鑛銅而形成銅薄膜層之銅薄膜形成步 此銅薄膜層係經由蒸鑛銅而形成，但此時，可將使接 著性更加提高之基底金屬薄膜層設置於改性醯亞胺化層， 且也可在其上設置銅薄膜層。基底金屬薄膜層係有鎳、鉻 或此等之合金層。當設置基底金屬薄膜層時，其厚度係宜 23 320155 200904866 \ 3薄膜層厚度之1/2以下（較佳係在1/5以下），且宜 ‘度在！至50腿左右。此基底金屬薄膜層宜依蒸錢法而形 成。 _ 用於形成銅薄膜層之蒸鍍法可採用周知 r« ,, 〜乃》ί：。可储 用例如：真空蒸鐘法、賤鍍法、電子束蒸锻法、離子 法，特別是，以雜法為佳。關於依贿法形成銅薄^層 之條件，宜為在例如：使用氬氣做為濺鍍氣體，壓力以 以1〇2至心為佳、以在5><10-2至5><1〇_11)3較佳，賤鍵電 力密度宜在1至l00Wcm-2、更宜在i至5〇Wc 二 下進行之方法。 —所使用之銅可為-部分含有其他金屬之合金銅。經由 瘵鍍所形成之銅或銅合金以含銅率在9〇質量％以上者為 佳，且以含銅率在95質量％以上者特佳。銅可含有之金屬 係鉻、鍅、鎳、石夕、鋅、鈹等。此外，可為含有此等金屬 2種以上之銅合金薄膜。 在銅薄膜形纟步驟中㈣成之銅薄膜層之厚度宜在 0·0〇1至l.〇#m之範圍，且以在〇 〇1至〇 5#m之範圍為 以在0.05至〇.5/z m較佳、以在〇」至〇 瓜更佳。 田欲使銅薄膜層變的更厚時，可經由非電錢或電鐘形成 膜。 (發明的效果） 根據本發明’能經由簡便之表面處理使聚醯亞胺層之 :大巾田提同。由於即使在適於形成細節距之低粗度銅 白之清形也迠使接著力提高，故能以低成本製造高密度印 24 320155 200904866 刷線路板中所使用之覆銅箔積層板，此外，由於也可利用 於HDD懸置用途，故其工業價值相當高。 【實施方式】 以下，藉由實施例更詳細說明本發明，但本發明並非 受實施例所限定。再者，在以下之實施例中，只要未特別 說明，各種評估即依下述進行。 [接著強度之測定] 關於接著強度之測定，係對於所得之覆金屬箔積層體 使用壓接機切成寬度1mm之矩形，並使用TENSILON測 試機（東洋精機製作所公司製）在室溫測定90°、1mm剝離 強度。 [線性熱膨脹係數之測定] 線性熱膨脹係數之測定係使用熱機械分析儀（Seiko Instruments(股）製），以20°C/分鐘之速度升溫至255°C，並 在該溫度保持10分鐘後，再以5°C/分鐘之固定速度冷卻。 計算從240°C冷卻至l〇〇°C時之平均熱膨脹係數，以此做為 線性熱膨脹係數。 其次，按照實施例具體說明本發明，但本發明不受實 施例所限定。 (製作例1) 在5OOmL之分離式燒瓶中，一面擾拌一面使4,4'-二胺 基-2'-甲氧基笨甲醯胺苯20.7g(0.08莫耳）溶於N，N-二曱基 乙醯胺343g中。其次，在氮氣流中在該溶液中加入均苯四 酸酐28.5g(0.13莫耳）及4,4匕二胺基二苯基醚10.3g(0.05 25 320155 200904866 莫耳）。之後，持續攪拌約3小時進行聚合反應，而得到黏 稠之聚醯胺酸溶液A。將此所得之聚醯胺酸溶液A塗布於 基板上，並在130 C乾燥5分鐘，之後費時15分鐘升溫至 360 C後，結束醯亞胺化，去除基板而得到聚醯亞胺膜a。 測疋所得之聚醯亞胺膜A之線性熱膨脹係數後，結果為B xlO_6/K。再者，聚醯亞胺膜a之厚度係1〇#m。 (製作例2) 將製作们巾所得之聚醯亞胺膜A f過注入氨氣 7I7mln、氦虱3L/mm及氮氣〇 3L/min之混合氣體之室中， 在常壓下’輸入施加電壓3.2kv、功率謂之電力進行 ^漿放=30移、’將聚醯亞胺膜A之樹脂層侧進行電聚處 理’而得到聚醯亞胺膜B。 (製作例3) 合並甲氧基· 5"醇5,及水2.5" 之2! 調製㈣合劑溶液。將預先經水满 ΤΑ 白1(新日本製鐵股份有限&WSUS304 H- ^為〇度8二=樹脂層侧之表面粗度：十點平均粗度 後，先取出貝於錢麵合劑溶液（液溫約2〇。〇30秒 空之溶液。接著喷吹壓縮/ τ, the effective immersion time is 1 sec to J hr' and 30 sec to s s ‧ 丛 丛 办 1 1 丨 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Dry after treatment. Dry 烊 γ 士 士 疋 可 can be used to dry naturally, by air rushing to blow dry, or by drying less private π ^ ^ ^ ^ island of people dry 13⁄4 I, s A, heart 'special. Drying conditions also vary depending on the polarity of the solvent, usually between 10 and 15 Torr. Type of W to the next processing] Ω, the next processing 5 seconds to 6 〇 minutes, to 25 〗 3 〇 minutes, especially in the range of 3 〇 to 120. "It is more preferable to process from 1 minute to 1 minute. Mainly 〇c 320155 22 200904866 The laminate obtained by the method for producing a metal foil-clad laminate according to the present invention, the polyimide layer has a metal case on one side or both sides The laminated body having the metal 0 in the early face can be obtained by laminating a metal on the surface of the modified yttrium imidizing layer obtained by the surface treatment method of the polyimide resin layer of the present invention. When the polyimide polyimide resin layer is laminated on a substrate such as glass or a resin film, it is preferable to separate the substrate before or after laminating the metal foil. When the substrate is a metal such as a copper box, it can be gathered there. The metal ruthenium layer on the side of the imide resin layer is formed to form a double-sided metal-clad layer. Further, the metal foil-clad laminate system having metal foil on both sides may be modified on the both sides of the polyimide film by the above method. After the amination layer, the metal foil is obtained in the two-layer layer, and after the single-sided metal foil-clad laminate having the metal foil on one side is obtained, it can also be laminated on the at least one-side metal-clad laminate. Brewed imine tree After the modified yttrium imide layer is formed on the layer on the surface side of the layer, the polyimine layer of the two-sided metal foil-clad laminate is laminated and then subjected to thermocompression bonding. The metal foil of the present invention is produced. The second manufacturing method of the laminated body comprises: preparing a polyanilin resin layer having a modified sulfimine layer treated by the above surface treatment method, directly or via a surface of the modified ruthenium layer The copper thin film layer is formed by vaporizing copper in the base metal film layer to form a copper thin film layer. The copper thin film layer is formed by steaming copper. However, in this case, the underlying metal thin film layer having improved adhesion can be disposed on the modified germanium. An imidization layer, and a copper film layer may also be disposed thereon. The base metal film layer is made of nickel, chromium or alloy layers thereof. When the base metal film layer is provided, the thickness thereof is preferably 23 320155 200904866 \ 3 film The thickness of the layer is less than 1/2 (preferably below 1/5), and is preferably in the range of ~! to about 50. The base metal film layer should be formed by the steaming method. _ used to form a copper film layer The vapor deposition method can be known as r« , , , For storage, for example, vacuum steaming method, ruthenium plating method, electron beam steaming method, ion method, in particular, it is preferable to use a hybrid method. The condition for forming a copper thin layer by the bribe method is preferably used, for example: Argon gas is used as the sputtering gas, and the pressure is preferably from 1 〇 2 to the core, and is preferably 5 Ω _ _ _ _ _ _ _ 11 l00Wcm-2, more preferably carried out under i to 5 〇Wc. - The copper used may be - part of alloy copper containing other metals. The copper or copper alloy formed by yttrium plating has a copper content of 9 5% by mass or more, and particularly preferably 95% by mass or more. Copper may contain metals such as chromium, ruthenium, nickel, shi, zinc, ruthenium, etc. Further, these metals may be contained Two or more kinds of copper alloy films. In the copper film-shaped enthalpy step, the thickness of the copper film layer is preferably in the range of 0·0〇1 to 1.〇#m, and is in the range of 〇〇1 to 〇5#m to 0.05 to 〇. .5/zm is better, and it is better to use it. When Tian wants to make the copper film layer thicker, it can form a film through non-electric money or electric clock. (Effects of the Invention) According to the present invention, the polyimine layer can be made by a simple surface treatment. Since the adhesion is improved even in the shape of the low-thickness copper-white which is suitable for forming the fine pitch, the copper-clad laminate used in the high-density printing 24 320155 200904866 brush circuit board can be manufactured at low cost, in addition, It can also be used for HDD suspension applications, so its industrial value is quite high. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited by the examples. Further, in the following examples, various evaluations were carried out as follows unless otherwise specified. [Measurement of the strength] The obtained metal foil laminate was cut into a rectangular shape having a width of 1 mm using a crimping machine, and the TENSILON tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used to measure 90° at room temperature. , 1mm peel strength. [Measurement of linear thermal expansion coefficient] The linear thermal expansion coefficient was measured by using a thermomechanical analyzer (manufactured by Seiko Instruments Co., Ltd.), and the temperature was raised to 255 ° C at a rate of 20 ° C / min, and after maintaining the temperature for 10 minutes, It was then cooled at a fixed rate of 5 ° C / min. Calculate the average coefficient of thermal expansion from 240 ° C to l ° ° C as the linear thermal expansion coefficient. Next, the invention will be specifically described by way of examples, but the invention is not limited by the examples. (Production Example 1) In a 500 mL-separated flask, 20.7 g (0.08 mol) of 4,4'-diamino-2'-methoxybenzamide was dissolved in N, N while being disturbed. - Dimercaptoacetamide in 343g. Next, 28.5 g (0.13 mol) of pyromellitic anhydride and 10.3 g of 4,4 decyldiaminodiphenyl ether (0.05 25 320155 200904866 mol) were added to the solution in a nitrogen stream. Thereafter, the polymerization was continued by stirring for about 3 hours to obtain a viscous polyamic acid solution A. The obtained polyamic acid solution A was applied onto a substrate, dried at 130 C for 5 minutes, and then heated to 360 C in 15 minutes, and then the oxime imidization was completed to remove the substrate to obtain a polyimide film a. After measuring the linear thermal expansion coefficient of the obtained polyimide film A, the result was B xlO_6/K. Further, the thickness of the polyimide film a is 1 〇 #m. (Production Example 2) The polyimine film A f obtained by making the towel was injected into a chamber of a mixed gas of ammonia gas 7I7 mln, 氦虱3 L/mm, and nitrogen gas 〇3 L/min, and the input voltage was input at normal pressure. 3.2kv, power is said to be electric power, slurry discharge = 30 shift, 'the resin layer side of the polyimide film A is subjected to electropolymerization treatment' to obtain a polyimide film B. (Production Example 3) Combine methoxy 5 "alcohol 5, and water 2.5" 2! Modulate (4) mixture solution. It will be pre-exposed with water and white 1 (Nippon Steel Co., Ltd. & WSUS304 H-^ is the temperature of 8 2 = surface roughness of the resin layer side: 10 points of average thickness, first take out the shell in the surface of the mixture (The liquid temperature is about 2 〇. 〇 30 seconds of empty solution. Then blow compression
分鐘，而尸 ’、 麦在11〇C進行加熱處理3C (製作例4錢輕合劑處理之不鏽鋼们。 320155 26 200904866 之銅V白1(厚度18# m、樹脂層側之表面粗度：十點平均粗 '度Rz為Ο.8#111)/完潰於矽烷耦合劑溶液（液溫約20。〇30 私後先取出置於大氣中，滴乾多餘之溶液。接著喷吹壓 縮空氣約15秒進行乾燥。之後，在ncrc進行加熱處理30 分鐘，而得到經矽烷耦合劑處理之銅箔4。 (實施例1) 製作在N，N-—甲基乙醯胺1〇mL中溶有間苯二甲胺 之有機處理劑之溶液。於製作例2中所得之 聚醯亞胺膜B上將此溶液塗布成厚度，且在13代 加熱2分鐘，並升溫至⑽t料乾燥後，費時15分鐘升 溫至36代後，結束酿亞胺化，而得到具有改性酿亞胺化 層之聚醯亞胺膜。在所得之聚醯亞胺膜之改性酿亞胺化層 之表面上疊加不_ i，並以高性能高溫真_機： =〇C、20MPa、！分鐘之條件下進行壓接，而製得覆金屬 落積層體。聚醯亞胺膜與不鏽鋼箱之接著強度係〇.嶋心 (實施例2) 除了使用製作例3中所得之不鏽鋼箱3取代不錄鋼箱 1以外’係與實施例i同樣進行，而製得覆金屬落積層體。 聚醯亞胺膜與不鏽鋼箔之接著強度係〇 9kN/m。 (實施例3) 除了使用銅落2(三井金屬製NS—VLp箱，鋼荡厚" ㈣，樹脂層側之表面粗度：G.8//m)取代不鏽㈣！以^ 係與實施例1同樣進行，而製得覆金屬落積層體。 胺膜與銅箔之接著強度係0.9kN/m。 、 320155 27 200904866 (實施例4) 除了使用製作例4中所得之銅箔4取 外，係與實施例丨同樣進行，而製得覆^不鏽鋼羯1以 醯亞胺膜與銅箔之接著強度係UkN/m。 篮 ^ (實施例5) 除了使用對苯二曱胺⑶奶⑻酬）取代間^ 1.36g(10mmol)以外，係與實施例1同樣 J银進仃，而得到且有 改性酿亞胺化層之聚醯亞胺膜，接著，势费 、 ^ 衣作覆金屬箔積層 體。接著強度係0.6kN/m。 、 (實施例6) 除了使用對苯二甲胺1.36§(10随〇1)取代間苯二甲胺 1.36g(1 Ommol)、以及使用製作例3中所得之不鏽鋼荡3取 代不鏽鋼箔1以外，係與實施例1同樣進行，而得到具有 改性醯亞胺化層之聚醯亞胺膜，接著，製作覆金屬箔積層 體。接著強度係〇.8kN/m。 ' 9 (實施例7) 除了使用參（2-胺乙基）胺1.46g(l Ommol)取代間苯一 甲胺1.36g(10mmol)、以及使用製作例1中所得之聚酿亞 胺膜A取代聚醯亞胺膜B以外，係與實施例1同樣進行， 而得到具有改性醯亞胺化層之聚醯亞胺膜，接著，紫作覆 金屬箔積層體。接著強度係〇.5kN/m。 (實施例8) 除了使用參（2-胺乙基）胺1.46g(10mmol)取代間笨_ 甲胺1.36g(10mmol)以外，係與實施例1同樣進行，而得 320155 28 200904866 到具有改性醯亞胺化層之聚醯亞胺膜，接著，製作覆金屬 落積層體。接著強度係0.5kN/ln。 设 (實施例9) 除了使用參（2·胺乙基）胺取代間苯二 :胺1.36g(1〇mmc)1)、以及使用製作例3中所得之不^ 洎3取代不鏽鋼箔1以外，係與實施例丨同樣進行，而得 到具有改性醯亞胺化層之聚醯亞胺膜，接著，製作覆金: 箱積層體。接著強度係0.6kN/jn。 1 (實施例10) 除了使用參（2-胺乙基）胺i.46g(l〇mm〇1)取代間苯二 甲胺1.36g(10mmol)、使用製作例i中所得之聚酿亞賴: 取代聚醯亞胺膜B、以及使用不鏽鋼落3取代 :外:係與實施例Μ樣進行，而得到具有改性酿亞胺化 θ之聚I亞胺膜，接著，製作覆金屬箱積層體 係〇.6kN/m。 者強度 (實施例11) 笨一：了使用雙(3_胺丙基)乙二胺—取代間 :::胺咖―、使用製作们中所得之聚酿亞 代聚醯亞胺膜B、以及使用不_们取代不鑛 =^外，係與實施例！同樣進行，而得到具有改性酿 =二層之聚酸亞胺膜’接著’製作覆金屬箱積層體。接 者強度係〇.6kN/m。 (實施例12) 除了使用雙（3-胺丙基）四甲基石夕氧烧2构 320155 29 200904866 (lOnrnoi)取代間苯二甲胺136g(1〇mm〇i)、使用製作例1 ，所得之聚酿亞胺膜八取代聚酿亞胺膜B、以及使用不鑛 =箱3取代不鏽㈣〗以外，係與實施例〗同樣進行，而 传到具有改性醯亞胺化層之聚醯亞胺膜，接著，製作覆金 屬箔積層體。接著強度係0 5kN/m。 (實施例13) —除了使用14-雙（3-胺丙基）哌畊2.00g〇〇mm〇1)取代間 苯二M L36g(10mm〇1)、使用製作例i中所得之聚酿亞 胺膜A取代聚酸亞胺膜B、以及使用不鏽鋼箱3取代不鐵 鋼泊1以外，係與實施例丨同樣進行，而得到具有改性醯 亞胺化層之聚醯亞胺膜，接著，製作覆金屬箔積層體。接 著強度係0.4kN/m。 (實施例14) 製作在N，N-二甲基乙醯胺10mL中溶有間苯二甲胺 1.36g(10mmol)之有機處理劑之溶液後，於製作例2中所得 之聚醯亞胺膜B上將此處理液塗布成厚度5〇#m，且在13〇 C加熱2分鐘，並升溫至16〇它進行乾燥後，費時〗5分鐘 升溫至360°C後，結束醯亞胺化，而得到具有改性醯亞胺 化層之聚醯亞胺膜。為了使銅原料成臈於所得之具有改性 醯亞胺化層之聚醯亞胺膜之改性醯亞胺化層之表面上，而 設置於RF磁控濺鍍（magnetron sputtering)裝置，形成銅薄 膜層。設置有聚醯亞胺膜之槽内係在減壓至3xl〇-4Pa後， 導入氬氣使真空度成為2x10'Aa，並以RF電源產生電漿。 籍由此電漿成膜至聚醯亞胺膜使鎳絡之合金層（比例8: 2， 30 320155 200904866 99.9重量％，以下稱為鎳鉻合金層或第一濺鍍層）之膜厚達 3 Onm。將此鎳鉻合金層成膜後，在同一環境中，於此錄鉻 合金層上進一步經由濺鍍，將銅（99.99重量％ )成膜0.2# m，而形成第二濺鑛層。 接著，以上述銅濺鍍膜（第二濺鍍層）做為電極藉由電 鍍浴形成8 // m厚之銅鍍層。電鍍浴係使用硫酸銅浴（硫酸 銅100g/L、硫酸220g/L、氯40mg/L、陽極係含磷銅），以 電流密度2.OA/dm2形成電鍍膜。在電鍍後以蒸餾水充分洗 淨並進行乾燥。如此進行而製得由聚醯亞胺膜/鎳鉻合金層 /銅濺鍍層/電鍍銅層所構成之覆金屬箔積層體。聚醯亞胺 膜與銅之接著力係0.6kN/m。 (比較例1) 在製作例1中所製得之聚醯亞胺膜A之表面上疊加不 鏽鋼箔1，且以高性能高溫真空壓接機，在370°C、20MPa、 1分鐘之條件下進行壓接，而製得覆金屬箔積層體。聚醯 亞胺膜與不鏽鋼箔之接著強度係未達0.1kN/m。 (比較例2) 在製作例2中所製得之聚醯亞胺膜B之表面上疊加不 鏽鋼箔1，且以高性能高溫真空壓接機，在370°C、20MPa、 1分鐘之條件下進行壓接，而製得覆金屬箔積層體。聚醯 亞胺膜與不鏽鋼箔之接著強度係未達0.1kN/m。 (比較例3) 在製作例1中所製得之聚醯亞胺膜A之表面上疊加銅 箔2，且以高性能高溫真空壓接機，在370°C、20MPa、1 31 320155 200904866 分鐘之條件下進行壓接，而製得覆金屬箔積層體。聚醯亞 胺膜與銅箔之接著強度係未達0.1kN/m。 (比較例4) 在製作例1中所製得之聚醯亞胺膜A之表面上疊加製 作例4中所得之銅箔4，且以高性能高溫真空壓接機，在 370°C、20MPa、1分鐘之條件下進行壓接，而製得覆金屬 箔積層體。接著強度係未達O.lkN/m。 (比較例5) 除了使用4,4'-亞曱基雙（環己胺）2.10§(1〇111111〇1)取代 間苯二甲胺1.36g(10mmol)以外，係與實施例1同樣進行， 而得到經表面處理之聚醯亞胺膜（對照具有改性醯亞胺化 層之聚醯亞胺膜，在以下之比較例中皆同），接著，製作覆 金屬箔積層體。聚醯亞胺膜與不鏽鋼箔之接著強度係 0.2kN/m。 (比較例6) 除 了使用 1,4-二氮雜雙環[2.2.2]辛烷1.12§(1〇111111〇1) 取代間苯二甲胺1.36g(10mmol)以外，係與實施例1同樣 進行，而得到經表面處理之聚醯亞胺膜，接著，製作覆金 屬箔積層體。聚醢亞胺膜與不鏽鋼箔之接著強度係 0.2kN/m 〇 (比較例7) 除了使用1,8-二氮雜雙環[5.4.0]十一烯-7 1.52g (lOmmol)取代間苯二甲胺1.36g(10mmol)以外，係與實施 例1同樣進行，而得到經表面處理之聚醯亞胺膜，接著， 32 320155 200904866 製作覆金屬名積層體。聚醯亞胺膜與不鏽鋼箱之接著強度 係 0.1kN/m。 又 (比較例8) 製作在N，N-二曱基乙醯胺1〇mL中溶有乙醇胺 1.61g(l〇mm〇l)之有機處理劑之溶液後，於製作例1中所得 。之聚醯亞胺膜A上將此處理液塗布成厚度5〇“m，且在⑽ C加熱2分鐘，並升溫至160〇C進行乾燥後，費時15分鐘 升溫至360 C，而得到經表面處理之聚醯亞胺膜。在所得 之絰表面處理之聚醯亞胺膜之處理面上疊加不鏽鋼箔1， 且以高性能高溫真空壓接機，在37〇它、2〇MPa、工分鐘之 條件下進行壓接，而製得覆金屬箔積層體。聚醯亞胺膜與 不鏽鋼箔之接著強度係未達〇 lkN/m。 (比較例9) ’為了使銅原料成膜於製作例1.中所得之聚醯亞胺膜A 之表面上，而δ又置於RJ?磁控濺鍍裝置，形成銅薄膜層。 汉置有聚醯亞胺膜之槽内係在減壓至3><1〇-41^後，導入氬 氣使真空度成為SxlO-^a，並以RF電源產生電漿。藉由 此電漿成膜至聚醯亞胺膜使鎳鉻之合金層（比例8: 2, 99.9 重量％ ，以下稱為鎳鉻合金層或第一濺鍍層）之膜厚達 fnm。將此鎳鉻合金層成膜後，在同一環境中，於此鎳鉻 口金層上進一步經由濺鍍，將銅（99 99重量％ )成膜Ο ] # m，而形成第二濺鍍層。 接著，以上述銅濺鍍膜（第二濺鍍層）做為電極藉由電 鍍浴形成8/zm厚之銅鍍層。電鍍浴係使用硫酸銅浴（硫酸 320155 33 200904866 銅100g/L、硫酸220g/L、氯40mg/L、陽極係含磷銅），以 '電流密度2.OA/dm2形成電鍍膜。在電鍍後以蒸餾水充分洗 « 淨並進行乾燥。如此進行而製得由聚醯亞胺膜/鎳鉻合金層 /銅濺鍍層/電鍍銅層所構成之覆金屬箔積層體。聚醯亞胺 膜與銅之接著力係未達0.1kN/m。 整理上述之結果如表1所示。再者，表中之記號係表 示以下之化合物。 MXDA :間苯二甲胺 PXDA :對苯二曱胺 TAEA :參（2-胺乙基）胺 ΒΑΡΕΑ:雙（3-胺丙基）乙二胺 BAPTS: 1，3-雙（3-胺丙基）四曱基矽氧烷 BAPPy: 1,4-雙（3-胺丙基）哌哄 MBCHA : 4,4’-亞甲基雙（環己.胺） DABCO ： ^ DBU: 1,8-二氮雜雙環[5.4.0]十一烯-7 EA :乙醇胺 34 320155 200904866 [表i] 金屬層之 形成方法 金屬箔 聚醯亞胺膜 有機處理劑 接著強度 (kN/m) 實施例1 熱壓接 不鐘鋼羯1 B MXDA 0.6 實施例2 熱壓接 不鑛鋼羯3 B MXDA 0.9 實施例3 熱壓接 銅箱2 B MXDA 0.9 實施例4 熱壓接 銅绪4 B MXDA 1.1 實施例5 熱壓接 不鐘鋼箱1 B PXDA 0.6 實施例6 熱壓接 不鏽鋼箔3 B PXDA 0.8 實施例7 熱壓接 不鑛鋼箱1 A TAEA 0.5 實施例8 熱壓接 不鑛鋼猪1 B TAEA 0.5 實施例9 熱壓接 不鏽鋼箔3 B TAEA 0.6 實施例10 熱壓接 不鏽鋼箔3 A TAEA 0.6 實施例11 熱壓接 不鑛鋼箱3 A ΒΑΡΕΑ 0.6 實施例12 熱壓接 不鏽鋼箔3 A BAPTS 0.5 實施例13 熱壓接 不鐵鋼猪3 A BAPPy 0.4 實施例14 濺鍍+電鍍 — B MXDA 0.6 比較例1 熱壓接 不鑛鋼绪1 A — <0.1 比較例2 熱壓接 不鑛鋼箱1 B _ <0.1 比較例3 熱壓接 銅落2 A — <0.1 比較例4 熱壓接 銅箱4 A _ <0.1 比較例5 熱壓接 不鑛鋼1¾ 1 B MBCHA 0.2 比較例6 熱壓接 不鏽鋼箔1 B DABCO 0.2 比較例7 熱壓接 不鐘鋼猪1 B DBU 0.1 比較例8 熱壓接 不鑛鋼箱1 A EA <0,1 比較例9 濺鍍+電鍍 — A — <0.1 【圖式簡單說明】 無 【主要元件符號說明】 無 35 320155Minutes, while the corpse ', mai at 11 〇 C for heat treatment 3C (production example 4 money light mixture treatment of stainless steel. 320155 26 200904866 copper V white 1 (thickness 18 # m, resin layer side surface roughness: ten The average point of the crude 'degree Rz is Ο.8#111)/completed in the decane coupling agent solution (the liquid temperature is about 20. 〇30, after taking it out, it is taken out in the atmosphere, and the excess solution is dripped. Then the compressed air is sprayed. After drying for 15 seconds, heat treatment was carried out in ncrc for 30 minutes to obtain a copper foil 4 treated with a decane coupling agent. (Example 1) Preparation was carried out in N,N-methylethylamine 1 mL a solution of an organic treating agent of m-xylylenediamine. The solution was applied to a thickness of the polyimine film B obtained in Preparation Example 2, and heated in 13 passages for 2 minutes, and heated to (10) after drying the material, which took time. After heating to 36 generations in 15 minutes, the imidization was terminated to obtain a polyimine film having a modified brewed imidization layer on the surface of the modified brewed imidization layer of the obtained polyimide film. Superimposed not _ i, and the high-performance high-temperature true _ machine: = 〇 C, 20MPa, ! minutes under the conditions of crimping, and the preparation of gold The falling layer body. The adhesive strength of the polyimide film and the stainless steel box was the same. (Example 2) The same procedure as in Example i except that the stainless steel box 3 obtained in Production Example 3 was used instead of the unrecorded steel box 1. The metal-coated falling layer body was obtained, and the adhesive strength of the polyimide film and the stainless steel foil was k9 kN/m. (Example 3) In addition to the use of the copper drop 2 (the NS-VLp box made of Mitsui Metals, the steel thickness was thickened). < (4), the surface roughness of the resin layer side: G.8 / / m) instead of stainless (four)! In the same manner as in Example 1, to obtain a metal-covered layer. The amine film and the copper foil The strength was 0.9 kN/m., 320155 27 200904866 (Example 4) The same procedure as in Example 丨 was carried out except that the copper foil 4 obtained in Production Example 4 was used, and a stainless steel crucible was prepared. The bonding strength between the film and the copper foil was UkN/m. Basket ^ (Example 5) The same procedure as in Example 1 except that p-benzoic acid (3) milk (8) was used instead of 1.36 g (10 mmol).仃, and obtain a polyimine film with a modified brewed imidization layer, followed by a coating, a metal foil laminate, followed by a strength system 0.6 kN/m. (Example 6) In addition to the use of p-xylylenediamine 1.36 § (10 with 〇 1), 1.36 g (1 Ommol) of m-xylylenediamine was substituted, and the stainless steel obtained in Production Example 3 was used. In the same manner as in Example 1, except that the stainless steel foil 1 was used, a polyimide film having a modified sulfimine layer was obtained, and then a metal foil-clad laminate was produced. The strength was then 〇8 kN/m. 9 (Example 7) In place of 1.46 g (10 mmol) of stilbene monomethylamine, 1.46 g (10 mmol) of hydrazine (2-aminoethyl)amine was used, and the polyamine film A obtained in Preparation Example 1 was used instead. In the same manner as in Example 1, except for the polyimide film B, a polyimide film having a modified quinon imide layer was obtained, followed by a purple metal foil-clad laminate. Then the strength system is 55 kN/m. (Example 8) The same procedure as in Example 1 was carried out except that 1.46 g (10 mmol) of stilbene (2-aminoethyl)amine was used instead of 1.66 g (10 mmol) of m-methylamine, and 320155 28 200904866 was obtained. The polyimide film of the sulfonium imide layer is followed by the formation of a metal-clad layer. The strength is then 0.5 kN/ln. (Example 9) In addition to the use of stilbene (2. Aminoethyl)amine in place of isophthalic acid: 1.36 g (1 〇 mmc) 1), and the use of the stainless steel foil 1 obtained in the production example 3 instead of stainless steel foil 1 This was carried out in the same manner as in Example , to obtain a polyimine film having a modified quinone imidization layer, followed by preparation of a gold-clad: box laminate. The intensity is then 0.6 kN/jn. 1 (Example 10) In addition to the use of ginseng (2-aminoethyl)amine i.46 g (10 〇mm〇1), 1.36 g (10 mmol) of m-xylylenediamine was used, and the granules obtained in Preparation Example i were used. : Substituting polyimine film B, and using stainless steel falling 3 substitution: external: is carried out in the same manner as in the example, to obtain a polyimine film having modified brewing ianization θ, followed by making a metal-clad laminate The system is 〇.6kN/m. Strength (Example 11) Stupid one: using bis(3_aminopropyl)ethylenediamine-substituted:::amine coffee-, using the polyaluminum polyimide film B obtained in the production, And use not to replace the non-mine = ^, the system and the embodiment! In the same manner, a polyimide film having a modified brew = two layers was obtained, and then a metal-clad laminate was produced. The receiver strength is 66 kN/m. (Example 12) The use of bis(3-aminopropyl)tetramethyl oxalate 2, 320155 29 200904866 (lOnrnoi) was substituted for m-xylylenediamine 136 g (1 〇 mm〇i), and Production Example 1 was used. The obtained polyaniline film octasubstituted polyimide film B and the use of non-mine = box 3 in place of stainless (four), were carried out in the same manner as in the examples, and passed to a modified yttrium-imiding layer. A polyimide film was laminated, followed by a metal foil-clad laminate. The strength is then 0 5 kN/m. (Example 13) - In addition to the use of 14-bis(3-aminopropyl) pipedtin 2.00 g 〇〇mm〇1) in place of m-phenylene M L36g (10 mm 〇1), the granule obtained in Preparation Example i was used. The amine film A was replaced with the polyimide film B, and the stainless steel tank 3 was used instead of the non-ferrous steel poise 1, and the same procedure as in Example , was carried out to obtain a polyimine film having a modified quinon imide layer, followed by , making a metal foil laminated body. The strength is then 0.4 kN/m. (Example 14) A solution of the organic treating agent in which 1.36 g (10 mmol) of m-xylylenediamine was dissolved in 10 mL of N,N-dimethylacetamide was prepared, and the polyimine obtained in Production Example 2 was prepared. On the film B, the treatment liquid was applied to a thickness of 5 〇 #m, and heated at 13 ° C for 2 minutes, and heated to 16 Torr. After drying, it took time to heat up to 360 ° C for 5 minutes, and then the oxime imidization was completed. A polyimine film having a modified quinon imide layer was obtained. In order to form a copper raw material on the surface of the modified yttrium imide layer of the obtained polyimine film having a modified ruthenium imidization layer, it is provided in an RF magnetron sputtering apparatus to form Copper film layer. The inside of the tank provided with the polyimide film was depressurized to 3x1 〇 -4 Pa, and argon gas was introduced to make the degree of vacuum 2x10'Aa, and plasma was generated by the RF power source. The film thickness of the alloy layer (ratio 8: 2, 30 320155 200904866 99.9 wt%, hereinafter referred to as nickel-chromium alloy layer or first sputter layer) of the nickel-based alloy film formed by the plasma to the polyimide film is 3 Onm. After the nickel-chromium alloy layer was formed into a film, copper (99.99% by weight) was further formed into a film of 0.2 #m by sputtering on the chrome-plated alloy layer in the same environment to form a second sputtering layer. Next, a copper plating layer of 8 // m thick was formed by using the above-mentioned copper sputtering film (second sputtering layer) as an electrode by an electroplating bath. In the electroplating bath, a copper sulfate bath (100 g/L of copper sulfate, 220 g/L of sulfuric acid, 40 mg/L of chlorine, and phosphorus-containing copper of an anode) was used, and a plating film was formed at a current density of 2.OA/dm2. After electroplating, it was sufficiently washed with distilled water and dried. In this manner, a metal foil-clad laminate composed of a polyimide film/nickel-chromium alloy layer/copper sputter layer/electroplated copper layer was obtained. The adhesion of the polyimide film to copper is 0.6 kN/m. (Comparative Example 1) The stainless steel foil 1 was superposed on the surface of the polyimide film A prepared in Production Example 1, and was subjected to a high-performance high-temperature vacuum crimping machine at 370 ° C, 20 MPa, 1 minute. A metal foil-clad laminate was produced by crimping. The adhesion strength between the polyimide film and the stainless steel foil was less than 0.1 kN/m. (Comparative Example 2) The stainless steel foil 1 was superposed on the surface of the polyimide film B prepared in Production Example 2, and was subjected to a high-performance high-temperature vacuum crimping machine at 370 ° C, 20 MPa, 1 minute. A metal foil-clad laminate was produced by crimping. The adhesion strength between the polyimide film and the stainless steel foil was less than 0.1 kN/m. (Comparative Example 3) The copper foil 2 was superposed on the surface of the polyimide film A prepared in Production Example 1, and was subjected to a high-performance high-temperature vacuum crimping machine at 370 ° C, 20 MPa, 1 31 320155 200904866 minutes. Under the conditions of the pressure bonding, a metal foil-clad laminate was obtained. The adhesion strength of the polyimide film to the copper foil was less than 0.1 kN/m. (Comparative Example 4) The copper foil 4 obtained in Preparation Example 4 was superposed on the surface of the polyimide film A prepared in Production Example 1, and was subjected to a high-performance high-temperature vacuum crimping machine at 370 ° C, 20 MPa. The pressure-bonding was carried out for 1 minute to obtain a metal foil-clad laminate. Then the strength system did not reach O.lkN/m. (Comparative Example 5) The same procedure as in Example 1 was carried out except that 4,4'-fluorenylene bis(cyclohexylamine) 2.10 § (1〇111111〇1) was used instead of m-xylylenediamine 1.36 g (10 mmol). On the other hand, a surface-treated polyimine film (the polyimine film having a modified yttrium imide layer was used, which is the same in the following comparative examples), and then a metal foil-clad laminate was produced. The adhesion strength between the polyimide film and the stainless steel foil was 0.2 kN/m. (Comparative Example 6) The same procedure as in Example 1 except that 1,4-diazabicyclo[2.2.2]octane 1.12 § (1〇111111〇1) was used instead of m-xylylenediamine 1.36 g (10 mmol). The surface-treated polyimide film was obtained, and then a metal foil-clad laminate was produced. The adhesion strength between the polyimide film and the stainless steel foil was 0.2 kN/m 〇 (Comparative Example 7) except that 1,8-diazabicyclo [5.4.0] undecene-7 1.52 g (10 mmol) was used for the substitution of m-benzene. A surface-treated polyimine film was obtained in the same manner as in Example 1 except that 1.36 g (10 mmol) of dimethylamine was used, and then a metal-clad laminate was produced by 32 320155 200904866. The adhesion strength between the polyimide film and the stainless steel tank was 0.1 kN/m. Further, (Comparative Example 8) A solution obtained by dissolving an organic treating agent of 1.61 g (100 μm) of ethanolamine in 1 mL of N,N-dimercaptoacetamide was prepared in Production Example 1. The treatment liquid on the polyimide film A was applied to a thickness of 5 〇 "m, and heated at (10) C for 2 minutes, and heated to 160 ° C for drying, and then heated to 360 C for 15 minutes to obtain a surface. The treated polyimide film is superimposed on the treated surface of the obtained fluorene-treated polyimine film, and is superhigh-temperature vacuum crimping machine at 37 〇, 2 〇 MPa, minutes Under the conditions of the pressure bonding, a metal foil-clad laminate was obtained. The adhesive strength of the polyimide film and the stainless steel foil was less than 〇lkN/m. (Comparative Example 9) 'In order to form a copper raw material into a production example 1. The surface of the polyimine film A obtained in the film, and δ is placed in the RJ? magnetron sputtering device to form a copper film layer. The groove of the polyimide film with the polyimide film is reduced to 3> After <1〇-41^, argon gas is introduced to make the degree of vacuum SxlO-^a, and plasma is generated by RF power source, thereby forming a film of nickel-chromium alloy by plasma formation onto the polyimide film ( a ratio of 8: 2, 99.9 wt%, hereinafter referred to as a nickel-chromium alloy layer or a first sputter layer, to a film thickness of fnm. After forming the nickel-chromium alloy layer, in the same environment On the nickel-chromium-plated gold layer, copper (99 99% by weight) is further formed into a film by sputtering, and a second sputtering layer is formed. Next, the copper sputtering film (second sputtering layer) is used as the The electrode is formed into a 8/zm thick copper plating layer by an electroplating bath. The electroplating bath is a copper sulfate bath (sulfuric acid 320155 33 200904866 copper 100 g/L, sulfuric acid 220 g/L, chlorine 40 mg/L, anode-containing phosphorus copper), A current density of 2.OA/dm2 forms a plating film. After electroplating, it is thoroughly washed with distilled water and dried. This is carried out by a polyimide film/nickel-chromium layer/copper sputter layer/electroplated copper layer. The metal foil-clad laminate has a bonding strength of less than 0.1 kN/m. The results of the above are shown in Table 1. In addition, the symbols in the table indicate the following compounds: MXDA: M-xylylenediamine PXDA: p-benzoic acid amine TAEA: gin(2-aminoethyl)amine hydrazine: bis(3-aminopropyl)ethylenediamine BAPTS: 1,3-bis(3-aminopropyl) Tetramethyl oxetane BAPPy: 1,4-bis(3-aminopropyl)piperidin MBCHA : 4,4'-methylenebis(cyclohexylamine) DABCO : ^ DBU: 1,8-diaza Miscellaneous Ring [5.4.0] undecene-7 EA: ethanolamine 34 320155 200904866 [Table i] Method for forming metal layer Metal foil polyimide film organic treatment agent strength (kN/m) Example 1 Thermocompression bonding钟钢羯1 B MXDA 0.6 Example 2 Hot-pressed stainless steel 羯3 B MXDA 0.9 Example 3 Hot-pressed copper box 2 B MXDA 0.9 Example 4 Hot-pressed copper 4 B MXDA 1.1 Example 5 Hot pressing Steel box 1 B PXDA 0.6 Example 6 Hot-pressed stainless steel foil 3 B PXDA 0.8 Example 7 Hot-pressed non-mineral steel box 1 A TAEA 0.5 Example 8 Hot-pressed non-mineral steel pig 1 B TAEA 0.5 Implementation Example 9 Thermocompression bonding stainless steel foil 3 B TAEA 0.6 Example 10 Thermocompression bonding stainless steel foil 3 A TAEA 0.6 Example 11 Thermocompression bonding steel box 3 A ΒΑΡΕΑ 0.6 Example 12 Thermocompression bonding stainless steel foil 3 A BAPTS 0.5 Implementation Example 13 Hot-pressed stainless steel pig 3 A BAPPy 0.4 Example 14 Sputtering + plating - B MXDA 0.6 Comparative Example 1 Hot-pressed non-mineral steel 1 A - <0.1 Comparative Example 2 Hot-pressed non-mine steel box 1 B _ <0.1 Comparative Example 3 Thermocompression bonding copper 2 A — <0.1 Comparative Example 4 Thermocompression bonding copper box 4 A _ <0.1 Comparative Example 5 Thermocompression bonded steel 13⁄4 1 B MBCHA 0.2 Comparative Example 6 Thermocompression stainless steel foil 1 B DABCO 0.2 Comparative Example 7 Hot crimping not steel pig 1 B DBU 0.1 Comparative example 8 Hot crimping non-mine steel box 1 A EA <0,1 Comparative Example 9 Sputtering + Plating - A - <0.1 [Simple description of the drawing] No [Main component symbol description] None 35 320155