TW201233715A - Method for producing co-extruded multi-layer polyimide film - Google Patents

Method for producing co-extruded multi-layer polyimide film Download PDF

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Publication number
TW201233715A
TW201233715A TW100145667A TW100145667A TW201233715A TW 201233715 A TW201233715 A TW 201233715A TW 100145667 A TW100145667 A TW 100145667A TW 100145667 A TW100145667 A TW 100145667A TW 201233715 A TW201233715 A TW 201233715A
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Taiwan
Prior art keywords
thermoplastic
multilayer
thermoplastic polyimide
layer
polyimine
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TW100145667A
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Chinese (zh)
Inventor
Teruo Matsutani
Yasutaka Kondo
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Kaneka Corp
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Publication of TW201233715A publication Critical patent/TW201233715A/en

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
    • B29K2079/08—PI, i.e. polyimides or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
    • B29K2079/08—PI, i.e. polyimides or derivatives thereof
    • B29K2079/085—Thermoplastic polyimides, e.g. polyesterimides, PEI, i.e. polyetherimides, or polyamideimides; Derivatives thereof
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0129—Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic polymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Laminated Bodies (AREA)
  • Moulding By Coating Moulds (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

Provided is a method for producing multilayered co-extruded polyimide film, with which the partial sticking of a polyimide layer onto a substrate that occurs when a polyamide acid solution is cast by multilayered co-extrusion onto the substrate in order to produce a multilayered polyimide film by multilayered co-extrusion is prevented by adding an imidation catalyst to only the polyamide acid solution that comes into direct contact with the substrate.

Description

201233715 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種可較佳地用於可撓性印刷配線板之多 層共擠壓聚醯亞胺膜之製造方法。 . 【先前技術】 . 近年來，隨著電子產品之輕量化、小型化及高密度化， 各種印刷基板之需求正在擴大，其中，可撓性積層板（亦 稱為3撓性印刷配線板（Fpc，Flexible Print Circuit)等）之 需求尤為擴大。可撓性積層板具有於聚醯亞胺膜等絕緣性 膜上形成有包含金屬層之電路之構造。 成為上述可撓性配線板之基材之可撓性覆金屬積層板一 般可係藉由如下方法製造：以由各種絕緣材料形成且具有 柔軟性之絕緣性膜作為基板，於該基板之表面介隔各種接 者材料對金屬箱進行加熱、壓接而使其貼合。作為上述絕 緣性臈，可較佳i也使用$醯亞胺膜等。作為上述接著材 料’一般使用環氧系、丙烯酸系等熱硬化性接著劑，雖然 熱硬化性接著劑具有可於相對低溫下進行接著之優點，但 由於料熱性、撓曲性、電可靠㈣特性之要求日益嚴 ' & ’認為使用熱硬化性接著劑製作三層FPC變得困難。因 &，提出有於絕緣性膜上直接設置金屬層，或於接著層使 用熱塑性聚醯亞胺之二層Fpc。該二層Fpc具有比三層π。 更優異之特性，期待其今後需求擴大。 作為二㈣⑶多層聚醯亞胺膜，雖可列舉於聚醒亞胺 膜之表面塗佈聚酿胺酸溶液並使其乾燥(醯亞胺化），從而 160742.doc 201233715 製造多層聚醯亞胺膜之方法，但其需要製造聚醯亞胺膜之 步驟，於聚醯亞胺膜之表面塗佈聚醯胺酸溶液並使其乾燥 (醯亞胺化）之步驟’使步驟成為複數，有使成本增加之情 況（例如，參照專利文獻1)。 又’作為二層FPC用多層聚醯亞胺膜，可列舉使複數層 聚醯胺酸溶液同時流延至支持體上，於乾燥後自支持體剝 離並進行熱處理而製造多層聚醯亞胺膜之方法，但存在直 接接觸支持體上之聚酿亞胺層部分性地貼附於支持體上而 殘留於支持體上之問題（例如，參照專利文獻2〜3)。 [先前技術文獻] [專利文獻] [專利文獻1 ]曰本公開專利公報「特開平11 6254號公報 (1997年5月2日公開）」 [專利文獻2 ]日本公開專利公報「特開平7 _ 214 6 3 7號公報 (1995年8月15日公開）」 [專利文獻3]日本公開專利公報「特開平1 〇_丨3 8318號公 報（1998年5月26曰公開）」 【發明内容】 [發明欲解決之問題] 本發明係鑒於上述课題而成者’其目的在於提供一種於 藉由多層共擠壓使聚醯胺酸溶液流延至支持體上時，聚酿 亞胺層不會部分性地貼附於支持體上的多層共擠壓聚醯亞 胺膜之製造方法。 [解決問題之技術手段] 160742.doc 201233715 本發明者等人鑒 本發明。 於上述課題而進行努力 研究，結果完成 :月係關於帛多層共擠壓聚醯亞胺膜之製造方法， 政在⑨藉由多層共擠愿使複數之聚醯胺酸溶液流延 至支持體上，而费i生你$ a 於至夕含有非熱塑性聚醯亞胺之非熱 塑性聚酿亞胺層之至少罩而卜接麻士^I人 夕早面上積層有至少含有熱塑性聚醯 胺-塑!·生聚醯亞胺層的多層聚醯亞胺膜；並且於上述 複數之聚醯胺St溶液之中，僅使直接接觸上述支持體之聚 醯胺酸溶液中含有醯亞胺化觸媒。 [發明之效果] 根據本發明，可提供一種於藉由多層共擠壓使聚醯胺酸 冷液流延至支持體上時，聚醯亞胺層不會部分性地貼附於 支持體上的多層共擠壓聚醯亞胺膜之製造方法。 根據本發明，可提供一種於自支持體剝離聚醯亞胺層 時’不會於支持體上殘留聚醯亞胺層之片段（剝離殘渣）之 多層共擠壓聚醯亞胺膜之製造方法。 【實施方式】 以下對本發明之一個實施形態進行說明。 本發明係關於一種多層共擠壓聚醯亞胺膜之製造方法， 其特徵在於：藉由多層共擠壓使複數之聚醯胺酸溶液流延 至支持體上，而製造於至少含有非熱塑性聚醯亞胺之非熱 塑性聚醯亞胺層之至少單面上積層有至少含有熱塑性聚醯 亞胺之熱塑性聚醯亞胺層的多層聚醯亞胺膜；並且於上述 複數之聚醯胺酸溶液之中，僅使直接接觸上述支持體之聚 160742.doc 201233715 醯胺酸溶液中含有醯亞胺化觸媒。 本發明中之非熱塑性聚醯亞胺通常係指經加熱亦不顯示 軟化或接著性之聚酿亞胺。於本發明中，係指即使對於將 非熱塑性聚醯亞胺單獨製膜而獲得之膜於45(rc加熱1分 鐘，亦不產生皺褶或伸長而保持形狀之聚醯亞胺；或於 DSC(示差掃描熱量測定，Differential Scanning Calorimetry) 中實質上不具有玻璃轉移溫度之聚醯亞胺。 又，所謂熱塑性聚醯亞胺通常係指於DSC(示差掃描熱 量測疋）中具有玻璃轉移溫度之聚醯亞胺。本發明中之熱 塑性聚酿亞胺係指上述玻璃轉移溫度為15 〇 5 〇它者。 作為多層聚醯亞胺膜之非熱塑性聚醯亞胺層所含有之非 熱塑性聚醯亞胺之原料而使用之芳香族酸二酐，並無特別 限定’可列舉均苯四甲酸二酐、2,3,6,7_萘四甲酸二酐、 3,3’，4,4’-聯苯四曱酸二酐、萘四甲酸二酐、 2,2’，3,3’-聯苯四曱酸二野、3,3'，4,4'-二苯甲_四甲酸二 酐、2,2-雙（3，4-二叛基笨基）丙烧二針、3，4,9,10-茈四甲酸 二酐、雙（3,4-二缓基苯基）丙烧二酐、1，1_雙（2,3_二叛基苯 基）乙烷二酐、1，1-雙（3,4-二羧基苯基）乙烷二酐、雙（2,3_ 二叛基苯基）曱烷二酐、雙（3,4-二羧基苯基）乙烷二酐、氧 雙鄰苯二甲酸二酐、雙（3,4_二羧基笨基）砜二酐、對伸苯 基雙（偏苯三曱酸單酯酸酐）、伸乙基雙（偏苯三甲酸單酿酸 酐）、雙酚A雙（偏笨三曱酸單酯酸酐）及該等之衍生物，該 等可較佳地單獨使用’或較佳地使用以任意之比例混合而 成之混合物。 160742.doc 201233715 其中’較佳為選自由均苯四甲酸二酐、3,3，，4,4，-聯苯四 甲酸一酐、3,3’，4,4,_二苯甲酮四甲酸二酐所組成之群中至 少1種酸二酐，就製造時之溶劑溶解性之觀點而言，進而 較佳為均苯四曱酸二酐、3,3’，4,4，_二苯甲酮四甲酸二酐。 作為多層聚醯亞胺膜之非熱塑性聚醯亞胺層所含有之非 熱塑性聚醯亞胺之原料而使用之芳香族二胺並無特別限 制，可列舉2,2-雙[4-(4-胺基苯氧基）苯基]丙烷、4,4,_二胺 基二苯醚、3,4'-二胺基二苯醚、丨’弘雙㈠―胺基苯氧基）苯、 1，4-雙（4-胺基苯氧基）苯、對伸苯基二胺、4,4，-二胺基二笨 基丙烷、4,4’-二胺基二苯基曱烷、聯苯胺、3,3,_二氣聯苯 胺、4,4'-二胺基二苯基硫醚、3,3，_二胺基二苯基硬、4,4，_ 一胺基二苯基硬、4,4'-二胺基二苯鱗、3,3'-二胺基二笨 謎、3,4’-二胺基二苯醚、ls5_二胺基萘、4,4,_二胺基二笨 基二乙基矽烷、4,4’-二胺基二苯基矽烷、4,4'-二胺基二苯 基乙基氧化膦、4,4'-二胺基二苯基甲基胺、4,4'-二胺基 二苯基N-苯胺、1，4-二胺基苯（對伸苯基二胺）、I] —二胺基 苯、1，2-二胺基苯、2,2-雙[4-(4-胺基苯氧基）苯基]丙烷及 該等之衍生物等，該等可較佳地單獨使用，或較佳地使用 以任意之比例混合而成之混合物。 其中，作為構成非熱塑性聚醯亞胺之二胺，就形成熱塑 性嵌段之觀點而言，較佳為使用2,2-雙[4-(4-胺基苯氧基） 苯基]丙烷’就控制線膨脹係數及強度之觀點而言，較佳 為使用對伸苯基二胺、4,4，-二胺基二苯醚。 再者，就可提高非熱塑性聚醯亞胺與熱塑性聚醢亞胺之 160742.doc 201233715 密著性點之觀點而言，較佳為非熱塑性聚醯亞胺含有熱塑 性I段成分’即，成為非熱塑性聚醯亞胺層之聚醯胺酸係 於分子中具有熱塑性嵌段成分之非熱塑性聚醢亞胺之前驅 物者。 作為多層聚醯亞胺膜之熱塑性聚醯亞胺層所含有之熱塑 性聚酿亞胺之原料而使用之芳香族酸二酐，並無特別限 定’可列舉均笨四甲酸二酐、2,3,6,7_萘四甲酸二酐、 3’3’，4,4’·聯苯四甲酸二酐、ι，2,5,6-萘四甲酸二酐、 2,2’，3,3’-聯苯四曱酸二酐、3,3，，4,4，_二苯曱酮四甲酸二 酐、2,2-雙（3,4-二羧基苯基）丙烷二酐、3,4,9,1〇_茈四甲酸 一酐、雙（3,4-二羧基笨基）丙烷二酐、丨，卜雙（2,3·二羧基苯 基）乙烷二酐、1，1_雙（3,4_二羧基苯基）乙烷二酐、雙（2,3_ 二羧基苯基）甲烷二酐、雙（3,4_二羧基苯基）乙烷二酐、氧 雙鄰苯二曱酸二酐、雙（3,4-二羧基苯基）砜二酐、對伸苯 基雙（偏笨三甲酸單酯酸酐）、伸乙基雙（偏苯三甲酸單酯酸 酐）、雙酚A雙（偏笨三甲酸單酯酸酐）及該等之衍生物，該 等可較佳地單獨使用，或較佳地使用以任意之比例混合而 成之混合物。 其中’較佳為選自由均苯四曱酸二酐、3,3，，4,4，-聯苯四 曱西义一針3,3 ,4,4 -二苯曱酮四曱酸二針所組成之群中至 少1種酸二酐，就提高可撓性覆金屬積層板之銅箔剝離強 度之觀點而言’較佳為使用3,3,，4,4，_聯苯四曱酸二酐，就 面提问可撓性覆金屬積層板之銅箱剝離強度，_面提高 焊錫财熱性之觀點而言，較佳為併用均苯四曱酸二 160742.doc 201233715 3,3|，4,4'-聯苯四甲酸二酐。 作為多層ί^酿亞胺膜之熱塑性聚酿亞胺層所含有之熱塑 性聚醯亞胺之原料而使用之芳香族二胺並無特別限制，可 列舉2,2-雙[4-(4·胺基苯氧基）苯基]丙烷、4,4，_二胺基二苯 醚、3,4'-二胺基二苯醚、1，3_雙（4_胺基苯氧基）苯、丨,4-雙 (4-胺基苯氧基）苯、對伸苯基二胺、4,4，-二胺基二苯基丙 烷、4,4'-二胺基二苯基曱烷、聯苯胺、3,3，_二氯聯苯胺、 4,4'-二胺基二苯基硫醚、3,3’-二胺基二苯基碟、4,4'-二胺 基二苯基颯、4,4'-二胺基二苯醚、3,3，_二胺基二苯醚、 3,4'-二胺基二苯醚、l，5-二胺基萘、4,4·-二胺基二苯基二 乙基石夕燒、4,4’-二胺基二苯基矽烷、4,4，-二胺基二苯基乙 基氧化膦、4,4'-二胺基二苯基曱基胺、4,4'-二胺基二苯 基Ν-苯胺、1，4-二胺基苯（對伸苯基二胺）、ι，3_二胺基苯、 1，2-二胺基苯、2,2-雙[4-(4-胺基笨氧基）苯基]丙烷及該等 之衍生物等’該等可較佳地單獨使用，或較佳地使用以任 意之比例混合而成之混合物。 其中，構成熱塑性聚醯亞胺之2,2-雙[4-(4-胺基苯氧基） 笨基]丙烧就可提高覆金屬箔積層板之金屬箔之剝離強度 之觀點而言較佳。 多層聚醯亞胺膜係於非熱塑性聚醯亞胺層之至少單面形 成有熱塑性聚醯亞胺層者，但就可製作兩面覆金屬積層 板’並可實現可撓性印刷配線板之輕量化、小型化、高密 度化之觀點而言’較佳為於非熱塑性聚醯亞胺層之兩面上 形成有熱塑性聚醯亞胺層之多層聚醯亞胺膜。 160742.doc 201233715 作為多層聚㈣胺膜之製造方法，係藉由多層共擠壓使 多層聚酿胺酸同時流延至支持體上而製造多層聚酿亞胺 膜。此時’僅使直接接觸支持體之聚酿胺酸溶液中含有酿 亞胺化觸媒。藉由含有酿亞胺化觸媒，使直接接觸支持體 上之聚酿胺酸進行醯亞胺化而顯；見自我支撐性，使膜強度 提高且不於支持體上殘留部分性貼附（剝離殘渣卜可將多 層凝膠膜自支持體剥離。又，若進行醯亞胺化反應，則由 於聚醯胺酸與聚醯亞胺之溶劑溶解度之差而使溶劑滲出， 使多層凝膠膜變得容易自支持體剝離。因此，使直接接觸 支持體之聚醯胺酸溶液中含有醯亞胺化觸媒有用。進而， 直接接觸支持體上之聚醯胺酸中之醯亞胺化觸媒係於加熱 時向厚度方向逃逸者，此時，藉由該醯亞胺化觸媒使其他 聚醯胺酸溶液亦進行醯亞胺化反應，而可使反應效率良好 地進行。再者，藉由併用醯亞胺化觸媒與化學脫水劑，可 使反應效率更佳地進行。 雖然無論直接接觸支持體之聚醢胺酸溶液為非熱塑性聚 醯亞胺層之聚醯胺酸溶液或熱塑性聚醯亞胺層之聚醯胺酸 溶液’均可表現同樣之效果’但於熱塑性聚醯亞胺層之聚 醯胺酸溶液直接接觸支持體之情形時，效果表現得尤其顯 著。 關於藉由多層共擠壓使熱塑性聚醯亞胺層之聚醯胺酸溶 液流延至支持體上，並使該聚醯胺酸溶液於支持體上乾燥 而獲得之多層凝膠膜，即使支持體上之乾燥溫度係低於熱 塑性聚醯亞胺之玻璃轉移溫度者，只要聚醯胺酸骨架部分 160742.doc •10- 201233715 性地殘留，則玻璃轉移溫度便會降低，雖亦取決於多層凝 膠膜之殘溶劑量’但仍變得容易軟化。藉此，若僅於支持 體上乾燥，則於多層凝膠膜中至少部分性地無法顯現可耐 丈自支持體剝離之強度，導致熱塑性聚醯亞胺之多層凝膠 膜仍部分性地貼附於支持體上。另一方面，於熱塑性聚醯 亞胺層之聚醯胺酸溶液直接接觸支持體之情形時，藉由使 成為熱塑性聚醯亞胺層之聚醯胺酸溶液中含有醯亞胺化觸 媒，可使熱塑性聚醯亞胺之多層凝膠膜顯現強度，並減少 自支持體剝離時熱塑性聚醯亞胺之多層凝膠膜貼附支持體 之情況。又，藉由併用醯亞胺化觸媒與化學脫水劑，可使 醯亞胺化反應變得更容易進行，並可進而提高多層凝膠膜 之強度。 直接接觸支持體上之聚醯胺酸溶液之醯亞胺化觸媒之含 量相對於含有醯亞胺化觸媒之溶液所含有之聚醯胺酸中之 酿胺酸單元1莫耳，較佳為0.05〜2.0莫耳，進而較佳為 〇.05 1.〇莫耳，就保持自支持體剝離時凝膠膜之強度、及 自支持體之剝離性之平衡之觀點而言，特佳為^〜㈣莫 耳。 化冬脫水劑之含量相對於含有化學脫水劑及醯亞胺 化觸媒之，谷液所含有之聚醯胺酸中之醯胺酸單元1莫耳， 較佳為0.5〜4.5莫彳’就保持自支持體剝離時凝膠膜之強 度及自支持體之剝離性之平衡之觀點而言，進而較佳為 1.0〜4.0莫耳。 關於醯亞胺化時間’只要使用充分之時間使醯亞胺化及 160742.doc 201233715 乾燥實質上完成便可，並無單一之限定，通常，於採用使 用化學脫水劑之化學固化法之情形時，可於^600秒左右 適當地設定，於採用不使用化學脫水劑之熱固化法之情形 時，可於60〜1800秒之範圍内適當地設定。 作為進行醯亞胺化時對於聚醯亞胺層所施加之張力，較 佳為設為1 kg/m〜15 kg/m之範圍内，特佳為設為5 kg/m〜1〇 kg/m之範圍内。於張力小於上述範圍之情形時可能產生 於搬送膜時產生鬆弛或蜿蜒而於捲取時形成皺褶或無法均 勻地捲取等問題。相反地，於大於上述範圍之情形時，因 於施加有較強之張力之狀態下進行高溫加熱，故而存在使 用覆金屬積層板用基材而製作之覆金屬積層板之尺寸特性 變差之情況。 作為多層聚醯亞胺膜之厚度，較佳為75 μηι以上、125 μιη以下。多層聚醯亞胺膜中之非熱塑性聚醯亞胺層之至 少單面的熱塑性聚醯亞胺層之厚度較佳為17 μιη以上、35 pm以下，進而較佳為1>7 μ〇1以上、1〇 μπι以下，特佳為1 7 μιη以上、8 μιη以下。若未滿丨.7 μηι，則存在對銅箔之密著 性變差之情況，雖然其亦取決於金屬箔表面之粗度。又， 於厚於35 μιη之情形時，存在蝕刻覆金屬箔積層板之金屬 箱後之尺寸變化率於負方向上變大之情況。 其次，對構成多層聚醯亞胺膜之熱塑性聚醯亞胺層與非 熱塑性聚酿亞胺層之密著性進行說明。 於熱塑性聚醯亞胺之結構與非熱塑性聚醯亞胺之結構不 同之情形時’例如’於構成熱塑性聚醯亞胺之酸二酐單體 160742.doc •12- 201233715 及二胺單體之合計莫耳數之内的未滿6〇%係與構成非熱塑 性聚醯亞胺之酸二酐單體及二胺單體相同之單體之情形 時’熱塑性聚醯亞胺之多層凝膠膜變得容易自非熱塑性聚 醯亞胺之多層凝膠膜剝離，導致熱塑性聚醢亞胺之多層凝 膠膜仍部分性地貼附於支持體上。認為其原因在於：非熱 塑性聚醢亞胺層之聚醯胺酸之醢亞胺化速度大於熱塑性聚 醯亞胺層之聚醢胺酸之醯亞胺化速度。但，藉由使直接接 觸支持體之熱塑性聚醯亞胺之聚醯胺酸溶液含有醯亞胺化 觸媒，使得非熱塑性聚醯亞胺之聚醯胺酸之醯亞胺化速度 接近熱塑性聚醯亞胺之聚醯胺酸之醯亞胺化速度，提高非 熱塑性聚醯亞胺層與熱塑性聚醯亞胺層之密著性，並減少 熱塑性聚醢亞胺之凝膠膜部分性地貼附支持體之情況。藉 由併用醯亞胺化觸媒及化學脫水劑，使得醯亞胺化速度更 接近’且可進而減少熱塑性聚醯亞胺之凝膠膜貼附支持體 之情況。 於熱塑性聚醯亞胺之結構與非熱塑性聚醯亞胺之結構類 似之情形時’例如，於構成熱塑性聚醯亞胺之酸二酐單體 及二胺單體之合計莫耳數之60%以上係與構成非熱塑性聚 醯亞胺之酸二酐單體及二胺單體相同之單體之情形時，由 於結構類似，故而原本非熱塑性聚醯亞胺之聚醯胺酸之醯 亞胺化速度與熱塑性聚醯亞胺之聚醯胺酸之醯亞胺化速度 之差便較小，並且熱塑性聚醯亞胺之凝膠膜部分不易貼附 支持體，但若為提高生產效率而提高線速，則存在熱塑性 聚醯亞胺之凝膠膜部分部分性地貼附支持體之情況。但， 160742.doc •13· 201233715 藉由使直接接觸支持體之熱塑性聚醯亞胺之聚醯胺酸溶液 含有醯亞胺化觸媒，可使得熱塑性聚醯亞胺之聚醯胺酸之 醯亞胺化速度提高，並且溶劑於支持體與多層凝膠膜之間 滲出而使多層凝膠膜平滑地自支持體剝離，減少熱塑性聚 醯亞胺之凝膠膜部分貼附支持體之情況，藉由併用醯亞胺 化觸媒與化學脫水劑，可使醯亞胺化速度更接近，進而減 少熱塑性聚醯亞胺之凝膠膜貼附支持體之情況。 又’於構成熱塑性聚醯亞胺之酸二酐單體及二胺單體之 合計莫耳數之60%以上係與構成非熱塑性聚醯亞胺之酸二 酐單體及二胺單體相同之單體之情形時，熱塑性聚醯亞胺 層與非熱塑性聚醯亞胺層之密著性提高且焊錫耐熱性提 南。此處’為顯現製成覆金屬箔積層板之情形時之銅箔剝 離強度’需要熱塑性聚醯亞胺層具有熱塑性。 此處’所謂構成熱塑性聚醯亞胺之酸二酐單體及二胺單 體之合計莫耳數之60%以上係與構成非熱塑性聚醯亞胺之 酸二針單體及二胺單體相同之單體’係指以構成熱塑性聚 醯亞胺之酸一酐單體及二胺單體之合計莫耳數（總莫耳數） 為基準’該合計莫耳數之60。/。以上係與構成形成非熱塑性 聚醯亞胺層之聚醯胺酸之酸二酐單體及二胺單體相同的單 體。而且，上述數值係根據（同類莫耳數）/(總莫耳數）之算 式而算出。 若構成上述熱塑性聚醯亞胺之酸二酐單體及二胺單體之 同類莫耳數之比率為總莫耳數之60%以上，則會減少熱塑 性聚醯亞胺之多層凝膠膜貼附支持體之情況，該數值較佳 160742.doc -14- 201233715 為70%以上，進而較佳為8〇%以上。&，比率之上限較佳 為"A以下，繼而較佳為98°/。以下。 本發明之多層聚醯亞胺膜之製造方法係藉由多層共擠壓 使聚醯胺S文溶液同時供給至二層以上之多層模具中，自上 述模，之排出口製成至少二層以上之薄膜狀體並流延至滾 筒環帶等支持體上，於支持體上以6〇^〜15〇。〔加熱後， 將多層凝膠膜自支持體剝離，於15G°C以上之高溫下進行 加熱，而製造於非熱塑性聚醯亞胺層之至少單面上積層有 熱塑性聚醢亞胺層之多層聚醯亞胺膜之方法。層之數目只 要為y 2層以上則不存在問題，但為抑制所獲得之多層 聚酿亞胺膜之捲曲，較佳為3層。於3層之情料，各層之 具體構成並無特別限定’例如，可於非熱塑性聚醯亞胺之 兩面上積層熱塑性聚酿亞胺層，亦可於非熱塑性聚醯亞胺 層之一側之面上積層熱塑性聚醯亞胺層，並且於另一側之 面上積層非熱塑性聚醯亞胺層。於該情形時，於非熱塑性 聚醯亞胺層之單側之面上形成的熱塑性聚醯亞胺層及非熱 塑性聚醯亞胺層各自可為1層亦可為多層。又，多層共擠 壓就生產性之觀點而言較佳，就吸濕焊錫耐熱性之觀點而 言亦較佳。隨未確認，但推測其原因在於：由於同時擠壓 非熱塑性聚醯亞胺層之聚醯胺酸與熱塑性聚醯亞胺層之聚 醯胺酸，使得界面中雙方之聚醯胺酸大量混合，使非熱塑 性聚酿亞胺層與熱塑性聚醯亞胺層之一體性提高。 以下，對藉由多層共擠壓製造多層聚醯亞胺膜之方法進 行說明。 160742.doc 201233715 若對通常所使用之方法進行說明，則係將自二層以上之 多層模，、擠塵而成之上述溶液連續地擠出至平滑之支持體 、藉由使上述支持體上之多層之薄膜狀體的溶劑 ^邛刀昇華而獲得具有自我支撐性之多層凝膠膜。 較佳為使支持體上之多層聚醯胺酸於最高溫度 100〜200°c下進行加熱。 進而，將該多層凝膠膜自上述支持體上剝離，最後，藉 由將該多層凝膠膜於高溫（25G_6⑽。c)下充分進行加熱處理 而面實質上除去溶劑，一面使醯亞胺化完全地進行而可 獲得多層聚醯亞胺膜。自支持體剝離之多層凝膠膜處於自 聚醯胺酸向聚醯亞胺之硬化的t間階段，並具有自我支撐 性，自式（1) (A-B)xl〇〇/B · · · ·式（1) 於式（1)中’ A、B表示以下内容。 A:多層膜之重量 B :將多層膜於450。(：下加熱20分鐘後之重量 算出之揮發分含量為5〜2〇〇重量％之範圍，較佳為1〇〜1〇〇 重量％，更佳為30〜80重量％之範圍。適合使用該範圍之多 層凝膠膜，就可抑制煅燒過程中之膜之斷裂、乾燥不均所 導致之膜之色調不均、特性不均勻等異常之觀點而言較 佳。又，為了提高熱塑性聚醯亞胺層之熔融流動性，亦可 有意地使醯亞胺化率降低及/或使溶劑殘留。 本發明之支持體係使自多層模具擠壓而成之多層液膜對 其流延者，且係於該支持體上對多層液膜加熱乾燥而對於 I60742.doc .16- 201233715 5層液膜賦予自我支推性者。該支持體之形狀並無特別要 求’若考慮接著膜之生產性，則較佳為筒狀或帶狀。又， 支寺體之材質亦無特別要求，可列舉金屬、塑膠、玻 陶瓷等，較佳為金屬，更佳為耐腐蝕性優異之SUS(不 鑛鋼，STEEL USESTAINLESS)材料。又，亦可對支持體 進行Cr、Ni、Sn等金屬電鍍。 可使用各種構造之模具作為上述多層模具，例如可使用 製&複數層之膜用之τ模具等。又，可較佳地使用先前已 知之所有構造之模具，但作為可尤其較佳地使用者，可例 示進料模組Τ模具或多歧管τ模具。 於本發明中’用以合成聚醯胺酸之較佳之溶劑只要是溶 解聚醯胺酸之溶劑則可任意使用，可例示酿胺系溶劑，即 Ν’Ν_-甲基甲醯胺、Ν，Ν-二甲基乙醯胺、Ν·甲基-2-吡咯 烷綱等。其中，可特佳地使用ν，ν-二甲基甲酿胺、Ν，Ν-二 甲基乙醯胺。 於本發明中，針對非熱塑性聚酿胺酸之聚合可使用任意 方法添加單體。作為代表性的聚合方法可列舉如下； 法。即， 1)使芳香族一胺溶解至有機極性溶劑中，並與實質上與其 等莫耳之芳香族四幾酸二針進行反應而使芳香族二胺與芳 香族四羧酸二酐聚合之方法； 敬芳香族四叛酸二肝及對其過小莫耳量之芳香族二胺化 合物於有機極性溶劑中反應，並獲得於兩末端具有酸肝基 之預聚物。繼而，以於所有步驟中芳香族四鲮酸二酐與芳 I60742.doc -17- 201233715 香族二胺化合物成為實質上等莫耳之方式使用芳香族 化合物使上述預聚物聚合之方法； 3)使芳香族四叛酸二酐與對其過剩莫耳量之芳香族二胺化 合物於有機極性溶财反應，並獲得於兩末端具有胺基之 預聚物。繼而於此追加添加芳香族二胺化合物後，以於所 有步驟中芳香族四幾酸二針與芳香族二胺化合物成為實質 上專莫耳之方式使用芳香族四缓酸二肝使上述預聚物聚合 之方法； 4) 於使芳香族四㈣二酐於有機極性溶劑中溶解及/或分散 後’以成為實質上等莫耳之方式使用芳香族二胺化合物使 方香族四幾酸二酐與芳香族二胺化合物聚合之方法，· 5) 使實質上等莫耳之芳香族四缓酸二酐與芳香族二胺之混 合物於有機極性溶劑令反應，而使芳香族四幾酸二肝與芳 香族二胺化合物聚合之方法； 等方法。該等方法可單獨使用，亦可部分性地組合使用。 其辛’非熱塑性聚醯亞胺層之聚醯胺酸較佳為藉由下述 之步驟（a)〜(c)而獲得。 ⑷使芳香族酸二酐與對其過剩莫耳量之芳香族二胺於有 機極性溶劑中反應，並獲得於兩末端具有胺基之預聚物’ (b)繼而，於此追加添加芳香族二胺， ⑷進而’以所有步财之料錢二酐與芳㈣二胺成 為實質上等莫耳之方式添加芳香族酸二奸，使預聚物聚合 而獲得聚醯胺酸溶液。 I60742.doc 201233715 上述方法之中，較佳為（a)所獲得之預聚物成為熱塑性欲 段成分。其次’針對判斷預聚物是否為熱塑性嵌段成分之 方法進行說明。 (熱塑性嵌段成分之判定方法） 將於製造預聚物時使用之酸二酐與二胺修正為等莫耳量 (於所使用之酸_一 sf為複數種之情形時，使其比率固定， 並且於使用之二胺為複數種之情形時，亦使其比率固定） 而獲得聚醯胺酸溶液，並利用刮刀式塗佈機使其流延至鋁 4上，以130。(： X 1 00秒進行加熱後，自鋁箔剝離自我支撐 性之凝膠膜並固定於金屬框上。其後，於以3〇〇〇c χ2〇秒、 45〇C><l分進行熱處理後，於膜發生軟化或熔融而外觀變 形之情形時，判定酸二酐及二胺含有熱塑性嵌段成分。 可成為熱塑性嵌段成分之酸二酐及二胺並無特別限制， 作為酸二酐，較佳為使用3,3，，4,41_聯苯四甲酸二酐、 3,3'，4,4'-二苯曱酮四曱酸二酐作為必需成分。又，作為二 胺，較佳為使用2,2-雙[4-(4-胺基苯氧基）苯基]丙烷作為必 需成分。 熱塑性聚醯亞胺之熱塑性聚醯胺酸之製造方法較佳為（a) 使芳香族酸二酐與對其過剩莫耳量之芳香族二胺於有機極 性洛劑中反應，並獲得於兩末端具有胺基之預聚物之步 驟，（b)繼而，以所有步驟中之芳香族酸二酐與芳香族二胺 之比成為既定之比的方式添加芳香族酸二酐，並使預聚物 聚合。（b)中，作為添加芳香族酸二酐之方法，有放入粉末 之方法，或放入預先使酸二酐溶解至有機極性溶劑而成之 I60742.doc -19· 201233715 酸溶液之方法等，就容易使反應均勻地進行之觀點而言， 較佳為放入酸溶液之方法。 聚合時之固形物成分濃度較佳為1〇〜3〇重量％。固形物 成分濃度可藉由聚合速度、聚合黏度決定。聚合黏度可根 據將熱塑性聚醯亞胺之聚醯胺酸溶液塗佈至支持體膜上之 情形，或與非熱塑性聚醯亞胺共擠壓之情形而進行設定， 於塗佈之情形時，例如，較佳為固形物成分濃度14重量％ 之聚合黏度為1〇〇 poise以下。又，於進行共擠壓之情形 時，例如’較佳為固形物成分濃度14重量％之聚合黏度為 1〇〇 poise〜1200 p〇ise，就可使所獲得之多層聚醯亞胺膜之 膜厚均勻之觀點而言’較佳為15〇 poise〜8〇〇 p〇ise。可考 慮多層聚醯亞胺膜之特性及生產性而改變順序使用上述說 明之芳香族酸二酐與芳香族二胺。 又’為了改善滑動性、熱傳導性、導電性、耐電暈性等 膜之諸特性，亦可添加填充料。作為填充料並無特別限 制’作為較佳之例’可列舉：矽土、氧化鈦、氧化鋁、氮 化矽、氮化硼、磷酸氫鈣、磷酸鈣、雲母等。 於為了改善膜之滑動性而添加填充料之情形時，填充料 之粒徑為0.1〜ίο μιη，較佳為（Md μιη。若粒徑為該範圍 以下’則難以顯現改善滑動性之效果，若為該範圍以上， 則有難以製成高精細之佈線圖案之傾向。又，於添加填充 料之情形時’填充料之分散狀態亦較為重要，較佳為使具 有20 μιη以上之平均直徑之填充料之凝集物為5〇個/^以 下，較佳為40個/m2以下。若具有20 μιη以上之平均直徑之 160742.doc -20- 201233715 填充料凝集物多於該範圍，則有於塗佈接著劑時排斥接著 劑，或於製作高精細佈線圖案時導致接著面積減少而降低 可挽性印刷基板自身之絕緣可靠性之傾向。 - 填充料之添加可使用例如， (1) 於聚合前或途中向聚合反應液中添加填充料之方法 (2) 於聚合結束後，利用三輥研磨機等混練填充料之方 法 (3) 準備含有填充料之分散液並將其混合至聚醯胺酸有 機溶劑溶液中之方法 (4) 利用珠磨機等使填充料分散之方法 等任—方法，但就可於填充料對生產線之污染最低的情 況下π成之觀點而言，較佳為將含有填充料之分散液混合 至聚醯胺酸溶液中之方&，尤纟是於即將製膜之前混合之 方法。 於準備含有填充料之分散液之情形時，作為該分散液， 較佳為使用與I醯胺酸之聚合溶劑相同之溶劑者。又，為 使填充料良好地分散，並且使分散狀態穩定化，可於不影 響膜的物性之範圍内使用分散劑、增黏劑等。 聚醯亞胺係自聚醯亞胺之前驅物、即聚醯胺酸藉由脫水 轉化反應而獲得，作為進行該轉化反應之方法，最廣為人 知的有僅藉由熱而進行之熱固化法，及使用化學脫水劑之 化學固化法這2種方法。然而，就生產性優異之觀點而 5 ，更佳為採用化學固化法。於熱固化法及化學固化法 中，就可使醯亞胺化反應較快進行之觀點而言，較佳為使 160742.doc .21 · 201233715 用醯亞胺化觸媒。 所謂化學脫水劑係指對於聚醯胺酸之脫水閉環劑，作為 其主成分’可較佳地使用脂肪族酸酐、芳香族酸軒、 N，N’-二烷醯氧基硼、低級脂肪族齒化物、南化低級脂肪 族酸酐、芳基磺酸二鹵化物、亞硫醯_化物或該等2種以 上之混合物。其中尤其是脂肪族酸酐及芳香族酸酐可良好 地發揮作用。又’所謂醯亞胺化觸媒係指具有促進硬化劑 對於聚醯胺酸之脫水閉環作用之效果之成分，例如，可使 用脂肪族3級胺、芳香族3級胺、雜環式3級胺。其中，較 佳為咪唑、苯并咪唑、異喹啉、喹啉或卜甲基吡啶等含氮 雜環化合物《進而，亦可適當選擇向由化學脫水劑及醯亞 胺化觸媒所構成之溶液中導入有機極性溶劑之方式。 本發明之可撓性覆金屬積層板之製造方法較佳為含有於 上述多層聚酿亞胺膜上貼合金屬箔之步驟。關於可橈性金 屬積層板中所使用之金屬箔（例如，銅箔），可使用卜25 μιη之厚度，並可使用壓延銅箔、電解銅箔之任一者。 作為將多層聚醯亞胺膜與金屬箔貼合之方法，例如，可 使用藉由具有一對以上金屬輥之熱輥層壓裝置、或雙帶式 壓製機（DBP ’ double belt press)之連續處理。其中，就裝 置構成單純且於維護成本方面有利之觀點而言，較佳為使 用具有一對以上金屬輥之熱輥層壓裝置。 此處所謂「具有一對以上金屬輥之熱輥層壓裝置」係 才a ’只要疋具有用以對材料加熱加壓之金屬報之裝置便 可’其具體之裝置構成並無特別限定。 160742.doc •22- 201233715 再者，以下將藉由熱層壓使多層聚醯亞胺膜與金屬箔貼 合之步驟稱作「熱層壓步驟」。 實知•上述熱層壓步驟之機構（以下亦稱作「熱層壓機 構」）之具體構成並無特聽$，為使所獲得之積層板之 外觀良好，較佳為於加壓面與金屬羯之間配置保護材料。 作為上述保護材料，可列舉可耐受熱層壓步驟之加熱溫 度之材料，例如：非熱塑性聚醯亞胺膜等耐熱性塑膠，銅 '、銘荡、su㈣等金屬羯等。其中，就对熱性、再使用 !·生等之平衡優異之觀點而言，可較佳地使用非熱塑性聚醯 亞胺膜，或由玻璃轉移溫度（Tg)高於層壓溫度5〇它以上之 熱塑性聚醯亞胺所構成之膜。於使用熱塑性聚ϋ亞胺之情 形時’可藉由選擇滿足上述條件者而防止熱塑性聚醯亞胺 對輥之附著。 又’若保護材料之厚度較薄，則變得無法充分地發揮層 壓時之緩衝及保護之作用’故而非熱塑性聚醯亞胺膜之厚 度較佳為75 μιη以上。 又，該保護材料並非必須為丨層，亦可為具有不同特性 之2層以上之多層構造（例如，三層構造）。 又’於層壓溫度為高溫之情形時，若直接將保護材料用 於層遂’則有由於急遽之熱膨脹導致可撓性覆金屬積層板 之外觀或尺寸穩定性不充分之情況。因此，較佳為於層壓 前對保護材料實施預加熱。如此，於進行保護材料之預加 熱後進行層壓之情形時，由於保護材料之熱膨脹結束，故 而可抑制對可撓性覆金屬積層板之外觀或尺寸特性所造成 160742.doc •23· 201233715 之影響。 等=:::之:方:，。可列舉使保護 、 作為接觸時間，較佳為1秒鐘以 上’進而較佳為3秒鐘 η 矽鉍以上。於接觸時間短於上述之情形 則於保指料之熱膨脹未結束之情況下進行層塵，故 而有於層料引起保護材料之急遽熱膨脹，使所獲狀可 撓性覆金屬積層板之外觀或尺寸特性產生變差之情況。關 於使保4材料保持於加熱輥上之距離，並無特別限定，可 根據加熱輥之徑與上述接觸時間而適當調整。 上述熱層壓機構中之被積層材料之加熱方式並無特別限 定，例如，可使用採用熱循環方式、熱風加熱方式、感應 加熱方式等可以特定之溫度加熱之先前公知的方式之加熱 機構。同樣地，上述熱層壓機構中之被積層材料之加壓方 式亦無特別限制，例如，可使用採用油壓方式、氣壓方 式、隙間壓力方式等可施加特定之壓力之先前公知的方式 之加壓機構。 上述熱層壓步驟中之加熱溫度、即層壓溫度較佳為多層 聚酿亞胺膜之熱塑性聚醯亞胺層所含有之熱塑性聚醯亞胺 的玻璃轉移溫度（Tg)+5(TC以上之溫度，更佳為多層聚醯 亞胺膜之熱塑性聚醯亞胺層所含有之熱塑性聚醯亞胺之玻 璃轉移溫度（Tg)+ioo°c以上。若為Tg+5(rc以上之溫度， 則可將多層聚醯亞胺膜與金屬箔較佳地熱層壓。又，若為 Tg+100°C以上，則可提高層壓速度並進一步提高可撓性覆 金屬積層板之生產性。 160742.doc -24· 201233715 尤其是，較佳為作為本發明之多層聚醯亞胺膜之核心使 用的聚醯亞胺膜係設計為於進行層壓之情形時可有效發揮 緩和熱應力之作用，則可生產性良好地獲得尺寸穩定性優 異之可撓性覆金屬積層板。 可撓性覆金屬積層板與加熱輥之接觸時間較佳為〇 .丨秒 鐘以上，更佳為0.2秒鐘以上，特佳為〇 5秒鐘以上。於接 觸時間短於上述範圍之情形時，有無法充分產生緩和效果 之it形。接觸時間之上限較佳為5秒鐘以下。即使使其接 觸長於5秒鐘，緩和效果亦不會更大，因使層壓速度之低 下或對於生產線之處理產生制約故而不佳。 又，有即使於層壓後使可撓性覆金屬積層板接觸加熱輥 而進行緩冷’可撓性覆金屬積層板與室溫之差依然較大之 情形，又，有無法完全使殘留畸變緩和之情形。因此，較 佳為使接觸加熱報並緩冷後之可繞性覆金屬積層板於仍配 置有保護材料之狀態下進行後期加熱步驟。較佳為將此時 之張力設為1〜10 N/cm之範圍。又，較佳為將後期加熱之 環境溫度設為（溫度-200t )〜(層壓溫度+ 1〇〇t )之範圍。 此處所謂「環境溫度」係指密著於可撓性覆金屬積層板 之兩面之保護材料的外表面溫度。雖然實際之可撓性覆金 屬積層板之溫度會根據保護材料之厚度而梢微變化，但只 要將保護材料表面之溫度設為上述範圍内，便可顯現後期 加熱之效果。保護材料之外表面溫度測定可利用熱電偶或 溫度計等進行。 上述熱層壓步驟甲之層壓速度較佳為〇·5 m/議以上，更 I60742.doc •25- 201233715 佳為1.0 m/min以上。若為〇 5 m/min以上，則可充分地熱 層壓，進而，若為1〇 m/min以上則可更進一步提高生產 性。 上述熱層壓步驟中之壓力、即層壓壓力具有壓力越高則 可使層壓溫度越低且層壓速度越快之優點，但一般而言， :¾層CC力過面，則有所獲得之積層板之尺寸變化變差之 傾向。相反地，若層壓壓力過低，則所獲得之積層板之金 屬箔之接著強度變低。因此，層壓壓力較佳為49〜490 N/Cm(5〜50 kgf/cm)之範圍内，更佳為98〜294 N/Cm(10〜30 kgf/cm)之範圍内。若為該範圍内，則可使層壓溫度、層壓 速度及層壓塵力這三個條件良好，並可更進一步提高生產 性。 上述層壓步驟中之接著膜張力較佳為〇〇i〜4 N/cm之範 圍内’更佳為0.02〜2.5 N/cm之範圍π，特佳為〇 Μ— 5 N/cm之範圍内。若張力為上述範圍以下，則於層壓之搬送 時產生鬆他或蜿蜒而無法均勻地送入加熱輕令，故而有時 難以獲得外觀良好之可繞性覆金屬積層板。相反地，若為 上述範圍以上，則有時張力之影響變強以至藉由控制接著 層之Tg與儲存彈性·亦無法緩和，使尺寸穩定性變差。 為獲得本發明之可撓性覆金屬積層板，較佳為使用一面 連續地加熱被積層材料面進行壓接之熱層壓裝置。進 而’於該熱層Μ裝置令’亦可於熱層壓機構之前段設置抽 出被積層材料之被積層材料抽出機構，亦可於熱層壓機構 之後段設置捲取被積層材料之被積層材料捲取機構。藉由 160742.doc -26- 201233715 設置該等機構，可更進一步提高上述熱層壓裝置之生產 性。 上述被積層材料抽出機構及被積層材料捲取機構之具體 構成並無特別限定，例如可列舉可捲取接著膜、金屬箱或 所獲得之積層板之公知的輥狀捲取機等。 . 進而，右设置可捲取或抽出保護材料之保護材料捲取機 構或保護材料抽出機構，則更佳。若具備該等保護材料捲 取機構、保護材料抽出機構，則可藉由於熱層壓步驟中將 使用過一次之保護材料捲取並於抽出側再次設置而重複使 用保護材料。 又，為於捲取保護材料時使保護材料之兩端部對齊，亦 可設置端部位置檢測機構及捲取位置修正機構。藉此，由 於可面精度地將保護材料之端部對齊並捲取，故而可提高 再使用之效率。再者，該等保護材料捲取機構、保護材料 抽出機構、端部位置檢測機構及捲取位置修正機構之具體 構成並無特別限定，可使用先前公知之各種裝置。 可撓性覆金屬積層板之多層聚醯亞胺膜與金屬箔之剝離 強度較佳為10 N/cm以上。 '本發明亦可如下構成。 •於上述多層共擠壓聚醯亞胺膜之製造方法中，較佳為於 上述複數之聚醯胺酸溶液之中，僅於直接接觸支持體之聚 醯胺酸溶液中含有化學脫水劑及醯亞胺化觸媒。 又，較佳為於上述複數之聚醯胺酸溶液之中，直接接觸 上述支持體之聚醯胺酸溶液係成為熱塑性聚酸亞胺層之聚 160742.doc •27· 201233715 醯胺酸溶液。 又’較佳為構成上述熱塑性聚醯亞胺之酸二酐單體及二 胺單體之合計莫耳數之60%以上係與構成上述非熱塑性聚 醯亞胺之酸二酐單體及二胺單體相同之單體。 又’較佳為構成上述熱塑性聚醯亞胺之二胺以2,2-雙[4-(4-胺基苯氧基）苯基]丙烷作為必需成分。 又’較佳為成為上述非熱塑性聚醯亞胺層之聚醯胺酸係 於分子中具有熱塑性嵌段成分之非熱塑性聚醯亞胺之前驅 物者。 又’較佳為於上述非熱塑性聚醢亞胺層之兩面上積層上 述熱塑性聚醯亞胺層。 [實施例] 以下利用實施例具體地說明本發明，但本發明並不僅限 於該等實施例。再者’合成例、實施例及比較例中之多層 聚醯亞胺膜與金屬之剝離強度及焊錫耐熱性之評價方法 如下。 (覆金屬積層板之製作方法） 於多層聚酿亞胺膜之兩面配置厚度為18 μιη之壓延銅落 (ΒΗΥ-22Β-Τ ;日礦金屬製造），進而於其兩側配置保護材 料（Apical 125ΝΡΙ ; Kaneka製造），利用熱親層壓機，以層 壓溫度380°C、層壓壓力294 N/cm(30 kgf/cm)、層壓速度 1 ·0 m/min之條件連續地進行熱層壓而製作可撓性覆金屬積 層板。 (金屬箔之剝離強度） 160742.doc -28- 201233715 根據JIS C6471之「6.5剝離強度」製作樣本，於％ mm/min之條件下將3 mm寬之金屬落部分以ΐ8〇度之剝離角 度剝離，並測定其荷重。 (焊錫耐熱性評價） 自可撓性覆金屬積層板切出3 cmx3 cm之試片，實施常 態時與吸濕時之焊錫耐熱性評價。於常態時，將試片於 23 C /55%RH下調整24小時後，利用經加溫之焊錫浴以浮 法放置3 0秒。其後，對接觸焊錫浴侧之銅箔進行钱刻，並 確認有無鼓起。將無鼓起之焊錫浴之溫度記載於表丨〜2。 又，於吸濕時’將試片K85t/85%RH下調整24小時後， 利用經加溫之焊錫浴以浮法放置3〇秒。其後，對接觸焊錫 浴側之銅箔進行蝕刻，並確認有無鼓起。將無鼓起之焊錫 浴之溫度記載於表1〜2。 以下表示合成例中使用之單體之縮寫。 DMF : N，N-二甲基甲醯胺 BAPP: 2,2·雙[4-(4-胺基苯氧基）苯基]丙烷 ODA : 4,4’-二胺基二苯醚 PDA :對伸苯基二胺 BPDA : 3,3'，4,4·-聯苯四甲酸二酐 BTDA : 3,3',4,4'-二苯甲酮四曱酸二酐 PMDA :均苯四甲酸二酐 以下表示聚醯胺酸溶液之合成例。 (合成例1) 於冷卻至 l〇t 之DMF(1173.5 g)中溶解BAPP(57.3 g: 160742.doc -29- 201233715 0.140 mol)、〇DA(18.6 g : 0.093 mol)。向其中添加 BTDA(30.0 g : 0.093 mol)、PMDA(25.4 g : 0.116 mol)，均 勻攪拌30分鐘而獲得預聚物。 於該溶液中溶解PDA(25.2 g: 0.233 mol)後，溶解PMDA (46·9 g : 0.215 mol) ’並小心地添加另外製備之pMDA之 7.2重量 ％ DMF溶液 115.1 g(PMDA : 0.038 mol)，於黏度達 到2500 poise左右時停止添加。進行1小時攪拌而獲得23°C 下之旋轉黏度為2600 poise之聚酿胺酸溶液。 再者，利用刮刀式塗佈機使將製造預聚物時所使用之酸 二奸與二胺設為等莫耳量而合成之聚醞胺酸溶液流延至銘 箔上’以130°C X100秒進行加熱後，自鋁箔剝離自我支撐 性之凝膠膜並固定於金屬框上。其後，以3〇〇°c χ20秒、 450°C X 1分鐘進行熱處理後’因膜發生炫融且外觀變形， 故而判定本合成例1之嵌段成分為熱塑性嵌段成分。 (合成例2) 於N，N-二曱基甲醯胺（DMF)937.6 g中添加BPDA(85.6 g: 0.291 mol)後，添加 BAPP(118.6 g: 0.289 mol)而獲得 固形物成分濃度約17%且黏度於23t下為800 poise之聚醯 胺酸溶液。其後’添加DMF而獲得固形物成分濃度14重量 °/〇之聚醯胺酸溶液。 (合成例3) 於N，N-二曱基曱醯胺（DMF)843.4 g中溶解BAPP(118.6 g : 0.289 mol)。向其中放入BPDA(12.7 g : 0.043 mol)並加 熱至 50°C 後，冷卻至 10°C，添加PMDA(48.6 g : 0.223 mol) 160742.doc • 30 - 201233715 而獲得預聚物。 其後’小心地添加另外製備之PMDA之7重量％DMF溶液 65.4 g(PMDA:0.021 mol) ’獲得固形物成分濃度約17〇/〇且 黏度於23°C下為800 poise之聚醯胺酸溶液。其後，添加 DMF而獲得固形物成分濃度14重量。之聚醯胺酸溶液。 (實施例1) 利用開幅200 mm之多歧管式之3層共擠壓三層模具將合 成例2所獲得之聚醯胺酸溶液/合成例1所獲得之聚醯胺酸 溶液/合成例2所獲得之聚醯胺酸溶液之順序之3層構造擠 壓並流延至鋁箔上。其次，將該三層膜以1 5〇艺χ丨〇〇秒加 熱後’剝離具有自我支撐性之三層凝膠膜而固定於金屬框 上，以 25(TC Χ40秒、300°c Χ60秒、35〇t Χ60秒、37(TC Χ30 秒進行乾燥、醯亞胺化，獲得熱塑性聚醯亞胺層/非熱塑 性聚醯亞胺層/熱塑性聚醯亞胺層之厚度為2 7 μιη/12 6 μηι/2·7 μιη之三層聚醯亞胺膜。 此種情形時，針對合成例2所獲得之聚醯胺酸溶液，僅 於直接接觸支持體上之面之聚酿胺酸溶液即將放入三層模 具之前’相對於該聚醯胺酸溶液1〇〇 g添加由乙酸針/異啥 琳/DMF(重量比33.0 g/8.3 g/58,6 g)所構成之硬化劑（化學 脫水劑及醯亞胺化觸媒）20 g並以混合器進行混合。 於使用三層聚醯亞胺膜製作覆金屬積層板後，測定金屬 箔之剝離強度與焊錫耐熱性。將結果整理於表丨~2。再 者，表中’將直接接觸支持體上之面之熱塑性聚酿亞胺層 作為B面，將相反侧之熱塑性聚醯亞胺層作為a面記載。 160742.doc •31- 201233715 (比較例1) 除未於合成例2之聚醯胺酸溶液（直接接觸支持體上之面 (B面）之聚醯胺酸溶液）中添加化學脫水劑及醯亞胺化觸媒 以外，與實施例1同樣實施。 直接接觸支持體上之B面之熱塑性聚醯亞胺層存在部分 剝離之痕跡。於使用三層聚醯亞胺膜製作覆金屬積層板 後，測疋金屬箔之剥離強度與焊錫财熱性。將結果整理於 表1〜2 〇 (實施例2) 利用開幅200 mm之多歧管式之3層共擠壓三層模具將合 成例3所獲得之聚醯胺酸溶液/合成例1所獲得之聚醯胺酸 溶液/合成例3所獲得之聚醯胺酸溶液之順序之3層構造擠 壓並/，IL延至铭殆上。其次，將該三層膜以i 5〇艺χ 1 〇〇秒加 熱後，剝離具有自我支撐性之三層凝膠膜而固定於金屬框 上，以25〇Cx40秒、300(^x60秒、350°C><60秒、370°C><30 秒進行乾燥、醯亞胺化，獲得熱塑性聚醯亞胺層/非熱塑 性聚醯亞胺層/熱塑性聚醯亞胺層之厚度為2.7 12 6 μηι/2.7 μιη之三層聚醯亞胺膜。 此種情形時，針對合成例3所獲得之聚醯胺酸溶液，僅 於直接接觸支持體上之面之聚醯胺酸溶液即將放入三層模 具之前’相對於該聚醯胺酸溶液1〇〇 g添加由乙酸酐/異唾 淋/DMF(重量比33.〇 g/8.3 g/58.6 g)所構成之硬化劑（化學 脫水劑及醯亞胺化觸媒）20 g並以混合器進行混合。 於使用三層聚酿亞胺膜製作覆金屬積層板後，測定金屬 160742.doc -32- 201233715 箔之剝離強度與焊錫耐熱性。將結果整理於表丨~2。 (比較例2) 除未於合成例3之聚醯胺酸溶液中添加化學脫水劑及醯 亞胺化觸媒以外，與實施例1JS]樣實施4使用三層聚酿 亞胺膜製作覆金屬積層板後’測定金屬箔之剝離強度與焊 錫耐熱性。將結果整理於表卜2。直接接觸支持體上之6面 之熱塑性聚醯亞胺層上存在剝離之痕跡。 (實施例3) 除針對合成例2之聚醯胺酸溶液（直接接觸支持體上之面 (B面）之聚醯胺酸溶液），於即將放入三層模具之前，相對 於s亥聚醯胺酸溶液1 〇〇 g添加由異喹啉/DMF(重量比8 3 g/58.6 g)所構成之硬化劑（僅醯亞胺化觸媒）14 g並以混合 器進行混合以外’與實施例1同樣實施。 於使用三層聚醯亞胺膜製作覆金屬積層板後，測定金屬 箔之剝離強度與焊錫耐熱性。將結果整理於表丨〜2。 (實施例4) 針對合成例3之聚醯胺酸溶液（直接接觸支持體上之面（b 面）之聚醯胺酸溶液），於即將放入三層模具之前，相對於 該聚醯胺酸溶液100 g添加由異喹啉/DMF(重量比8 3 g/58 6 g)所構成之硬化劑（僅醯亞胺化觸媒）14 g並以混合器進行 混合以外，與實施例1同樣實施。 於使用三層聚醯亞胺膜製作覆金屬積層板後，測定金屬 箔之剝離強度與焊錫耐熱性。將結果整理於表丨〜2。 160742.doc •33- 201233715 [表i] 實施例1 比較例1 實施例2 比較例2 金屬箔剝離 強度(N/cm) Α面/Β面 14/14 14/14 14/14 14/14 B面剝離 無 有 無 有 焊錫耐熱性(°C) 常態時 300 300 350 350 吸濕時 250 250 300 300 厚度構成(μηι) 熱塑性聚醯 亞胺層(A面） 2.7 2.7 2.7 2.7 非熱塑性聚 醯亞胺層 12.6 12.6 12.6 12.6 熱塑性聚醯 亞胺層(B面） 2.7 2.7 2.7 2.7 與於非熱塑性聚醯亞胺1Μ吏用之 酸二酐及二胺同類之熱塑性聚醯 亞胺中之酸二酐及二胺之比例(％) 50 50 93 93 [表2] 實施例3 實施例4 金屬箔剝離 強度(N/cm) Α面/Β面 14/14 14/14 B面剝離 無 無 焊錫耐熱性(°C) 常態時 300 350 吸濕時 250 300 厚度構成(μιη) 熱塑性聚醯亞胺層(A面） 2.7 2.7 非熱塑性聚醖亞胺層 1 12.6 12.6 熱塑性聚醯亞胺層(B面） 2.7 2.7 與於非熱塑性聚醯亞胺中使用之酸 二酐及二胺同類之熱塑性聚醞亞胺 中之酸二酐及二胺之比例(％) 50 93 [產業上之可利用性] 本發明可用於可撓性印刷配線板之製造等。 -34- 160742.doc201233715 VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing a multi-layer co-extruded polyimine film which can be preferably used for a flexible printed wiring board. [Prior Art] In recent years, with the light weight, miniaturization, and high density of electronic products, the demand for various printed substrates has been expanding. Among them, flexible laminates (also known as 3 flexible printed wiring boards ( The demand for Fpc, Flexible Print Circuit, etc.) is particularly broadened. The flexible laminate has a structure in which a circuit including a metal layer is formed on an insulating film such as a polyimide film. The flexible metal-clad laminate which is the substrate of the flexible wiring board can be generally produced by using an insulating film formed of various insulating materials and having flexibility as a substrate on the surface of the substrate. The metal case is heated and crimped to be attached to each other by various materials. As the above-mentioned insulating enthalpy, it is preferable to use a ruthenium imine film or the like. As the above-mentioned adhesive material, a thermosetting adhesive such as an epoxy resin or an acrylic resin is generally used. Although the thermosetting adhesive has the advantage of being able to be carried out at a relatively low temperature, it is characterized by heat, flexibility, and electrical reliability. The demand is becoming more and more '&' It is considered difficult to make a three-layer FPC using a thermosetting adhesive. For &, a two-layer Fpc having a metal layer directly on the insulating film or a thermoplastic polyimide is used in the adhesive layer. The two-layer Fpc has a ratio of three layers π. More excellent characteristics, and look forward to expanding its future demand. As a two (four) (3) multi-layered polyimide film, a polylactoic acid solution is coated on the surface of the polyamidimide film and dried (醯i-imidized), thereby producing a multilayer polyimine of 160742.doc 201233715 Membrane method, but it requires a step of producing a polyimide film, a step of coating a polyphthalic acid solution on the surface of the polyimide film and drying it (醯imination) step to make the step plural, The case where the cost is increased (for example, refer to Patent Document 1). Further, as a multilayer polyimide film for a two-layer FPC, a plurality of polyamic acid solutions are simultaneously cast onto a support, and after drying, the support is peeled off and heat-treated to produce a multilayer polyimide film. However, there is a problem in that the polyimine layer directly contacting the support is partially attached to the support and remains on the support (for example, refer to Patent Documents 2 to 3). [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei 11 6254 (published on May 2, 1997). [Patent Document 3] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. Hei. No. 8-8318 (published May 26, 1998). [Problem to be Solved by the Invention] The present invention has been made in view of the above problems, and an object thereof is to provide a polyanilin layer which is not formed when a polyamic acid solution is cast onto a support by multilayer co-extrusion. A method of producing a multilayer coextruded polyimine film partially attached to a support. [Technical means for solving the problem] 160742.doc 201233715 The present inventors have examined the present invention. Efforts have been made to study the above problems, and the results have been completed: a method for manufacturing a multilayer multi-layer co-extruded polyimine film, which is desired to multiply a plurality of polyamine liquid solutions onto a support by multi-layer coextrusion. And the fee i have you at least a non-thermoplastic polyimine layer containing non-thermoplastic polyimine layer at least until the cover of the aspergillus ^I people on the early morning layer has at least a thermoplastic polyamine - a multi-layered polyimide film having a polyimine layer; and among the above polyamines St solutions, only the polyaminic acid solution directly contacting the above support contains a ruthenium Media. [Effects of the Invention] According to the present invention, it is possible to provide a polyimine layer which is not partially attached to a support when the polyamic acid cold liquid is cast onto the support by multilayer co-extrusion. A method of producing a multilayer co-extruded polyimine film. According to the present invention, there is provided a method for producing a multilayer co-extruded polyimine film which does not leave a fragment of a polyimide layer on a support (peeling residue) when the polyimide layer is peeled off from the support . [Embodiment] Hereinafter, an embodiment of the present invention will be described. The present invention relates to a method for producing a multilayer co-extruded polyimine film, characterized in that a plurality of polyamic acid solutions are cast onto a support by multilayer co-extrusion, and at least a non-thermoplastic polymer is produced. a multi-layered polyimide film having at least one layer of a thermoplastic polyimide layer containing at least a thermoplastic polyimide, at least one side of the non-thermoplastic polyimide layer of the quinone imine; and the above poly-proline solution Among them, only the poly-160742.doc 201233715 proline solution containing the support is directly contacted with a ruthenium-catalyzed catalyst. The non-thermoplastic polyimine in the present invention generally means a poly-imine which is heated or does not exhibit softening or adhesion. In the present invention, it is meant that the film obtained by separately forming a film of a non-thermoplastic polyimide is maintained at 45 (rc heated for 1 minute without wrinkles or elongation to maintain the shape of the polyimine); or in DSC (Differential Scanning Calorimetry) A polyimine that does not substantially have a glass transition temperature. Further, the term "thermoplastic polyimide" generally means a glass transition temperature in DSC (differential scanning calorimetry). Polyimine. The thermoplastic polyimine in the present invention refers to the above glass transition temperature of 15 〇 5 。. The non-thermoplastic poly-polymer layer contained in the non-thermoplastic polyimide layer of the multilayer polyimide film The aromatic acid dianhydride used for the raw material of ruthenium is not particularly limited, and examples thereof include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 3,3',4,4. '-Biphenyltetradecanoic acid dianhydride, naphthalene tetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetradecanoic acid di野,3,3',4,4'-diphenylmethyltetracarboxylic acid Dianhydride, 2,2-bis(3,4-di-t-stupyl)-propanone two-needle, 3,4,9,10-decanetetracarboxylic dianhydride, bis(3,4-di-hydroxyphenyl) Burning dianhydride, 1,1_bis(2,3_bis-phenylidenephenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, double (2,3_ Direylphenyl)decane dianhydride, bis(3,4-dicarboxyphenyl)ethane dianhydride, oxydiphthalic dianhydride, bis(3,4-dicarboxyphenyl) sulfone dianhydride , p-phenylene bis(p-benzoic acid monoester anhydride), ethyl bis(trimellitic acid mono-anhydride), bisphenol A bis (powdered tribasic acid monoester anhydride) and derivatives thereof Preferably, these may be used alone or preferably in a mixture of any ratio. 160742.doc 201233715 wherein 'preferably selected from pyromellitic dianhydride, 3, 3, 4 From the viewpoint of solvent solubility in the production of at least one acid dianhydride composed of 4,-biphenyltetracarboxylic acid monoanhydride and 3,3',4,4, benzophenone tetracarboxylic dianhydride Further, it is preferably pyromellitic dianhydride or 3,3',4,4, benzophenone tetracarboxylic dianhydride. As a non-thermoplastic polyimide layer of a multilayer polyimide film An aromatic diamine used in the raw material of a non-thermoplastic polyimine There is no particular limitation, and examples thereof include 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4,-diaminodiphenyl ether, and 3,4'-diaminodiphenyl. Ether, 丨'hongshuang(1)-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, p-phenylenediamine, 4,4,-diaminodiphenyl Propane, 4,4'-diaminodiphenyl decane, benzidine, 3,3,_di-diphenylaniline, 4,4'-diaminodiphenyl sulfide, 3,3,-diamine Diphenyl hard, 4,4,-aminodiphenyl hard, 4,4'-diaminodiphenyl scale, 3,3'-diamino 2, 4', diamine Diphenyl ether, ls5_diaminonaphthalene, 4,4,-diaminodiphenyldiethyldecane, 4,4'-diaminodiphenylnonane, 4,4'-diaminodiyl Phenylethylphosphine oxide, 4,4'-diaminodiphenylmethylamine, 4,4'-diaminodiphenyl N-aniline, 1,4-diaminobenzene (p-phenylene) Diamine), I]-diaminobenzene, 1,2-diaminobenzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and the like, These may preferably be used singly or as a mixture of any mixture in any ratio. Among them, as the diamine constituting the non-thermoplastic polyimine, from the viewpoint of forming a thermoplastic block, it is preferred to use 2,2-bis[4-(4-aminophenoxy)phenyl]propane. From the viewpoint of controlling the coefficient of linear expansion and strength, it is preferred to use p-phenylenediamine and 4,4,-diaminodiphenyl ether. Further, from the viewpoint of improving the adhesion point of the non-thermoplastic polyimide and the thermoplastic polyimide, the non-thermoplastic polyimide contains the thermoplastic component I. The polyaminic acid of the non-thermoplastic polyimide layer is a non-thermoplastic polyimine precursor having a thermoplastic block component in the molecule. The aromatic acid dianhydride used as a raw material of the thermoplastic polyiminoimine contained in the thermoplastic polyimide layer of the multilayer polyimide film is not particularly limited, and examples thereof include tetrabasic tetracarboxylic dianhydride and 2,3. , 6,7-naphthalenetetracarboxylic dianhydride, 3'3', 4,4'-biphenyltetracarboxylic dianhydride, iota, 2,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3 '-Biphenyltetradecanoic dianhydride, 3,3,,4,4,-dibenzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 3, 4,9,1〇_茈tetracarboxylic acid monoanhydride, bis(3,4-dicarboxyphenyl)propane dianhydride, hydrazine, bis(2,3·dicarboxyphenyl)ethane dianhydride, 1,1 _bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ethane dianhydride, oxygen double neighbor Benzoyl phthalic anhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, p-phenylene bis(powdered tricarboxylic acid monoester anhydride), ethyl bis(trimellitic acid monoester anhydride) , bisphenol A bis (partial tricarboxylic acid monoester anhydride) and such derivatives, which may preferably be used singly or preferably in any ratio Mix and mix. Wherein 'preferably selected from the group consisting of pyromellitic dianhydride, 3,3,4,4,-biphenyltetrazine and a pin 3,3,4,4-dibenzophenone tetradecanoate At least one acid dianhydride in the group is preferably '3,3,4,4,4-biphenyltetradecanoic acid from the viewpoint of improving the peeling strength of the copper foil of the flexible metal-clad laminate. The dianhydride is used to ask the copper box peel strength of the flexible metal-clad laminate, and it is preferable to use the pyromellitic acid two 160742.doc 201233715 3,3|,4 from the viewpoint of improving the soldering heat of the surface. , 4'-biphenyltetracarboxylic dianhydride. The aromatic diamine used as a raw material of the thermoplastic polyimine contained in the thermoplastic polyimide layer of the multilayer imide film is not particularly limited, and examples thereof include 2,2-bis[4-(4· Aminophenoxy)phenyl]propane, 4,4,-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,3_bis(4-aminophenoxy)benzene , hydrazine, 4-bis(4-aminophenoxy)benzene, p-phenylenediamine, 4,4,-diaminodiphenylpropane, 4,4'-diaminodiphenylnonane , benzidine, 3,3,-dichlorobenzidine, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl dish, 4,4'-diamino group Phenylhydrazine, 4,4'-diaminodiphenyl ether, 3,3,-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 4 , 4·-Diaminodiphenyldiethylcarbazide, 4,4′-diaminodiphenylnonane, 4,4,-diaminodiphenylethylphosphine oxide, 4,4′- Diaminodiphenyldecylamine, 4,4'-diaminodiphenylanthracene-aniline, 1,4-diaminobenzene (p-phenylenediamine), iota, 3-diaminobenzene 1,2-diaminobenzene, 2,2-bis[4-(4-aminophenyloxy)phenyl]propane and the derivatives thereof Etc. 'these may preferably be used alone, or preferably a mixture of an arbitrary ratio to the mixed. Among them, the 2,2-bis[4-(4-aminophenoxy)phenyl]propane which constitutes the thermoplastic polyimine can improve the peel strength of the metal foil of the metal foil-clad laminate. good. The multi-layered polyimide film is formed by forming a thermoplastic polyimide layer on at least one side of the non-thermoplastic polyimide layer, but a double-sided metal-clad laminate can be fabricated and the flexible printed wiring board can be made light. From the viewpoint of quantification, miniaturization, and high density, it is preferable to form a multilayer polyimide film having a thermoplastic polyimide layer on both sides of the non-thermoplastic polyimide layer. 160742.doc 201233715 As a method for producing a multilayer poly(tetra)amine film, a multilayered polyiminoimide film is produced by simultaneously casting a plurality of layers of polyacrylic acid onto a support by multilayer co-extrusion. At this time, only the polyamidonic acid solution directly contacting the support contains the brewing catalyst. By containing a brewing imidizing catalyst, the poly-amic acid on the direct contact support is yttrium-imided; see self-supporting, which increases the strength of the film and does not adhere to the partial adhesion on the support ( The peeling residue can peel the multilayer gel film from the support. Further, if the oxime imidization reaction is carried out, the solvent is oozing out due to the difference in solvent solubility of the polyaminic acid and the polyimine, and the multilayer gel film is obtained. It becomes easy to peel off from the support. Therefore, it is useful to contain a ruthenium-imiding catalyst in a poly-proline solution directly contacting the support. Further, it is directly contacted with the ruthenium imide in the poly-proline on the support. When the medium escapes in the thickness direction during heating, the other polyamic acid solution is also subjected to a ruthenium imidization reaction by the ruthenium imidization catalyst, whereby the reaction proceeds efficiently. The reaction efficiency can be further improved by using a ruthenium-imiding catalyst and a chemical dehydrating agent. Although the poly-proline solution in which the support is directly contacted with the support is a non-thermoplastic polyimide layer or Polyamide of thermoplastic polyimide layer The acid solution 'can exhibit the same effect', but the effect is particularly remarkable when the polyamic acid solution of the thermoplastic polyimide layer is directly contacted with the support. About the thermoplastic polysiloxane by multilayer co-extrusion a multilayer gel film obtained by casting a polyamic acid solution of an amine layer onto a support and drying the polyamic acid solution on a support, even if the drying temperature on the support is lower than that of the thermoplastic polyimide For the glass transfer temperature, as long as the polyacetic acid skeleton portion 160742.doc •10-201233715 remains, the glass transition temperature will decrease, although it depends on the residual solvent amount of the multilayer gel film' but it is still easy. Softening. Therefore, if it is only dried on the support, the strength of the self-supporting body peeling off at least partially cannot be exhibited in the multilayer gel film, resulting in the multilayer gel film of the thermoplastic polyimide. Attached to the support. On the other hand, when the polyamic acid solution of the thermoplastic polyimide layer is directly contacted with the support, the polyaminic acid solution which becomes the thermoplastic polyimide layer is obtained. The ruthenium-containing catalyst can be used to exhibit the strength of the multilayered gel film of the thermoplastic polyimide, and to reduce the adhesion of the multilayered gel film of the thermoplastic polyimide to the support when the support is peeled off. By using a ruthenium iodide catalyst and a chemical dehydrating agent, the ruthenium imidization reaction can be made easier, and the strength of the multilayer gel film can be further improved. Direct contact with the polyamine solvent solution on the support The content of the imidization catalyst is preferably 0.05 to 2.0 moles, more preferably 〇., per mole of the tyrosine acid unit in the polyamido acid contained in the solution containing the ruthenium-catalyzed catalyst. 05 1. In terms of the balance between the strength of the gel film and the peelability of the self-supporting body when the support is peeled off, it is particularly preferable that it is ^~(4) Moer. The content of the winter dehydrating agent is relatively In the case of a chemical dehydrating agent and a ruthenium-containing catalyst, the lysine unit 1 mol of the polylysine contained in the trough, preferably 0.5 to 4.5 彳, keeps the coagulation from the support. It is further preferred from the viewpoint of the balance between the strength of the film and the peelability of the support. 1.0~4.0 mole. Regarding the hydrazine imidization time, as long as sufficient time is used for the imidization and the drying of 160742.doc 201233715 is substantially complete, there is no single limitation, usually in the case of chemical curing using a chemical dehydrating agent. It can be appropriately set in about 600 seconds, and can be appropriately set in the range of 60 to 1800 seconds in the case of using a heat curing method which does not use a chemical dehydrating agent. The tension applied to the polyimide layer in the imidization of the ruthenium is preferably in the range of 1 kg/m to 15 kg/m, and particularly preferably set to 5 kg/m to 1 〇 kg/ Within the range of m. When the tension is less than the above range, there may be a problem that slack or squeak occurs when the film is conveyed, wrinkles are formed at the time of winding, or it is not uniformly wound up. On the other hand, when it is larger than the above range, high-temperature heating is performed in a state where a strong tension is applied, and thus the dimensional characteristics of the metal-clad laminate produced by using the substrate for a metal-clad laminate are deteriorated. . The thickness of the multilayer polyimide film is preferably 75 μη or more and 125 μηη or less. The thickness of the at least one-sided thermoplastic polyimide layer of the non-thermoplastic polyimide layer in the multilayer polyimide film is preferably 17 μm or more and 35 pm or less, and more preferably 1 > 7 μ〇 or more. , 1 〇μπι or less, particularly preferably 1 7 μηη or more and 8 μιη or less. If it is less than .7 μηι, there is a case where the adhesion to the copper foil is deteriorated, although it also depends on the thickness of the surface of the metal foil. Further, when the thickness is 35 μm, there is a case where the dimensional change rate after etching the metal foil-clad laminate is increased in the negative direction. Next, the adhesion between the thermoplastic polyimide layer constituting the multilayer polyimide film and the non-thermoplastic polyimide layer will be described. In the case where the structure of the thermoplastic polyimide is different from the structure of the non-thermoplastic polyimide, for example, the acid dianhydride monomer constituting the thermoplastic polyimine 160742.doc •12-201233715 and the diamine monomer When the total amount of 〇% in the molar number is the same as the monomer constituting the acid dianhydride monomer and the diamine monomer of the non-thermoplastic polyimine, the multilayer gel film of the thermoplastic polyimide. It becomes easy to peel off from the multi-layered gel film of the non-thermoplastic polyimide, and the multilayered gel film of the thermoplastic polyimide is still partially attached to the support. The reason for this is considered to be that the rate of ruthenium imidization of the polyaminic acid layer of the non-thermoplastic polyimine layer is greater than the rate of hydrazide imidation of the polyamic acid of the thermoplastic polyimide layer. However, by allowing the polyaminic acid solution of the thermoplastic polyimine directly contacting the support to contain a ruthenium-based catalyst, the rate of ruthenium imidization of the non-thermoplastic polyimine is close to that of the thermoplastic polymer. The imidization speed of the ruthenium polyamine, the adhesion of the non-thermoplastic polyimide layer to the thermoplastic polyimide layer, and the partial reduction of the gel film of the thermoplastic polyimide With the support case. By using a ruthenium-imiding catalyst and a chemical dehydrating agent, the ruthenium imidization speed is closer to ' and the gelatin film-attached support of the thermoplastic polyimide may be further reduced. When the structure of the thermoplastic polyimide is similar to that of the non-thermoplastic polyimide, 'for example, 60% of the total number of moles of the acid dianhydride monomer and the diamine monomer constituting the thermoplastic polyimide. In the case where the above is the same as the acid dianhydride monomer and the diamine monomer constituting the non-thermoplastic polyimine, since the structure is similar, the non-thermoplastic polyimide of the polyimine is the imine. The difference between the tempering rate and the imidization speed of the polyimide of the thermoplastic polyimine is small, and the gel film portion of the thermoplastic polyimide is not easily attached to the support, but is improved for improving production efficiency. At the line speed, there is a case where the gel film portion of the thermoplastic polyimide is partially attached to the support. However, 160742.doc •13· 201233715 The polyamido acid of the thermoplastic polyimine can be made by the polyaminic acid solution of the thermoplastic polyimine directly contacting the support containing the ruthenium catalyzed catalyst. The imidization rate is increased, and the solvent oozes between the support and the multilayer gel film to smoothly peel the multilayer gel film from the support, thereby reducing the adhesion of the gel film portion of the thermoplastic polyimide to the support. By using a ruthenium-imiding catalyst and a chemical dehydrating agent, the ruthenium imidization speed can be made closer, and the gel film-attached support of the thermoplastic polyimide can be reduced. Further, 60% or more of the total number of moles of the acid dianhydride monomer and the diamine monomer constituting the thermoplastic polyimide is the same as the acid dianhydride monomer and the diamine monomer constituting the non-thermoplastic polyimide. In the case of a monomer, the adhesion between the thermoplastic polyimide layer and the non-thermoplastic polyimide layer is improved and the solder heat resistance is increased. Here, the peeling strength of the copper foil in the case where the metal foil-clad laminate is formed is required to have a thermoplastic polyimide layer having thermoplasticity. Here, the so-called 60% or more of the total number of moles of the acid dianhydride monomer and the diamine monomer constituting the thermoplastic polyimide is related to the acid two-needle monomer and the diamine monomer constituting the non-thermoplastic polyimide. The same monomer' means 60 of the total number of moles based on the total number of moles (total moles) of the mono- and monoamine monomers constituting the thermoplastic polyimide. /. The above is the same monomer as the acid dianhydride monomer and the diamine monomer constituting the polyaminic acid forming the non-thermoplastic polyimide layer. Further, the above numerical values are calculated based on the equation of (the same molar number) / (total molar number). If the ratio of the molar ratio of the acid dianhydride monomer and the diamine monomer constituting the thermoplastic polyimide is 60% or more of the total mole number, the multilayered gel film of the thermoplastic polyimide may be reduced. In the case of a support, the value is preferably 160742.doc -14 - 201233715 is 70% or more, and further preferably 8% or more. The upper limit of the & ratio is preferably "A or less, and then preferably 98°/. the following. The method for producing the multilayer polyimine film of the present invention is to simultaneously supply the polyamidamine S solution to a multilayer mold of two or more layers by multi-layer co-extrusion, and at least two layers are formed from the discharge port of the mold. The film-like body is cast onto a support such as a drum loop, and is 6 〇 15 15 15 。 on the support. [After heating, the multilayer gel film is peeled off from the support and heated at a high temperature of 15 G ° C or higher, and a multilayer of a thermoplastic polyimide layer is laminated on at least one side of the non-thermoplastic polyimide layer. A method of polyimine film. The number of layers is only y 2 or more, and there is no problem, but in order to suppress the curl of the obtained multilayered polyimide film, it is preferably 3 layers. In the case of the three layers, the specific constitution of each layer is not particularly limited. For example, a thermoplastic polyimide layer may be laminated on both sides of the non-thermoplastic polyimide, or on one side of the non-thermoplastic polyimide layer. A layer of thermoplastic polyimide is laminated on the surface and a layer of non-thermoplastic polyimide is laminated on the other side. In this case, the thermoplastic polyimide layer and the non-thermoplastic polyimide layer formed on one side of the non-thermoplastic polyimide layer may each be one layer or multiple layers. Further, the multilayer co-extrusion is preferable from the viewpoint of productivity, and is also preferable from the viewpoint of moisture resistance of the solder. It is unconfirmed, but it is presumed that the reason is that, due to the simultaneous extrusion of the polyaminic acid of the non-thermoplastic polyimide layer and the polyamic acid of the thermoplastic polyimide layer, the polyamic acid in the interface is mixed in a large amount. The physical properties of the non-thermoplastic polyimide layer and the thermoplastic polyimide layer are improved. Hereinafter, a method of producing a multilayer polyimide film by multilayer co-extrusion will be described. 160742.doc 201233715 If the method generally used is described, the above-mentioned solution which is squeezed from a multilayer mold of two or more layers is continuously extruded to a smooth support by using the above support. The solvent of the multi-layered film is sublimated to obtain a self-supporting multilayer gel film. Preferably, the poly-polyglycolic acid on the support is heated at a maximum temperature of 100 to 200 ° C. Further, the multilayer gel film is peeled off from the support, and finally, the multilayer gel film is sufficiently heat-treated at a high temperature (25G_6(10).c) to substantially remove the solvent, thereby iodizing the ruthenium. A multilayer polyimide film can be obtained completely. The multi-layer gel film stripped from the support is in the t-stage of hardening from poly-proline to polyimine and is self-supporting, from the formula (1) (AB) xl 〇〇 / B · · · · In the formula (1), 'A, B' represents the following. A: Weight of the multilayer film B: The multilayer film was at 450. (The content of the volatile matter calculated by weight after heating for 20 minutes is in the range of 5 to 2% by weight, preferably 1% to 1% by weight, more preferably 30 to 80% by weight. The multi-layered gel film of this range is preferable in terms of suppressing abnormalities such as rupture of the film during the calcination process, uneven color tone of the film due to uneven drying, and unevenness in characteristics, and the like. The melt fluidity of the imine layer may also intentionally lower the ruthenium imidization rate and/or leave the solvent. The support system of the present invention allows the multilayer liquid film extruded from the multilayer mold to be cast, and The multi-layer liquid film is heated and dried on the support, and the self-supporting property is imparted to the liquid film of I60742.doc.16-201233715. The shape of the support is not particularly required. It is preferably a tubular shape or a belt shape. Further, there is no special requirement for the material of the temple body, and examples thereof include metal, plastic, glass ceramics, etc., preferably metal, and more excellent SUS (non-mineral steel) with excellent corrosion resistance. , STEEL USESTAINLESS) material. Also, support Metal plating such as Cr, Ni, or Sn is performed. A mold having various structures can be used as the multilayer mold, and for example, a τ mold for a film of a plurality of layers can be used. Further, all of the previously known configurations can be preferably used. Mold, but as a particularly preferable user, a feed module Τ mold or a multi-manifold τ mold can be exemplified. In the present invention, a preferred solvent for synthesizing polyamic acid is as long as it dissolves poly-proline. The solvent may be used arbitrarily, and examples thereof include a brewing amine solvent, that is, Ν'Ν_-methylformamide, hydrazine, hydrazine-dimethylacetamide, hydrazine-methyl-2-pyrrolidine, and the like. It is particularly preferable to use ν,ν-dimethylacetamide, hydrazine, hydrazine-dimethylacetamide. In the present invention, for the polymerization of the non-thermoplastic polyamic acid, the monomer may be added by any method. A typical polymerization method is exemplified by the following method: 1) dissolving an aromatic monoamine in an organic polar solvent, and reacting it with two moles of an aromatic tetrachaic acid substantially Method for polymerizing amine and aromatic tetracarboxylic dianhydride; Acid and its liver is too small molar amounts of aromatic diamine compound in an organic polar solvent in the reaction, is obtained at both ends and having an acid group of the prepolymer liver. Then, in all the steps, the aromatic tetraphthalic acid dianhydride and the aromatic I60742.doc -17-201233715 scented diamine compound are substantially homogenized to use an aromatic compound to polymerize the above prepolymer; The aromatic tetra-retensive dianhydride is reacted with an excess of the molar amount of the aromatic diamine compound in an organic polar solvent, and a prepolymer having an amine group at both terminals is obtained. Then, after the addition of the aromatic diamine compound, the above-mentioned prepolymerization is carried out by using the aromatic tetrazoic acid dihepatic in a manner in which the aromatic tetracarboxylic acid two-needle and the aromatic diamine compound are substantially exclusively used in all the steps. Method for polymerizing a polymer; 4) After dissolving and/or dispersing the aromatic tetrakis(di) dianhydride in an organic polar solvent, the aromatic diamine compound is used in such a manner as to be substantially monomolar. a method for polymerizing an anhydride and an aromatic diamine compound, 5) allowing a mixture of substantially a molar amount of an aromatic tetrazoic acid dianhydride and an aromatic diamine to react in an organic polar solvent to cause an aromatic tetraacid a method of polymerizing liver and an aromatic diamine compound; and the like. These methods may be used singly or in combination. The polyamic acid of the octanomeric non-thermoplastic polyimide layer is preferably obtained by the following steps (a) to (c). (4) Aromatic acid dianhydride is reacted with an excess amount of aromatic diamine in an organic polar solvent to obtain a prepolymer having an amine group at both ends' (b), and then an aromatic is additionally added thereto. The diamine, (4) Further, the aromatic acid is added in such a manner that the dianhydride and the aryl (tetra)diamine are substantially in a molar manner, and the prepolymer is polymerized to obtain a polyaminic acid solution. I60742.doc 201233715 Among the above methods, it is preferred that the prepolymer obtained in (a) is a thermoplastic component. Next, a method for judging whether or not the prepolymer is a thermoplastic block component will be described. (Method for Determining Thermoplastic Block Component) The acid dianhydride and diamine used in the production of the prepolymer are corrected to the same molar amount (when the acid _ sf used is plural), the ratio is fixed. And when the diamine used is plural, the ratio is also fixed to obtain a polyamic acid solution, and it is cast onto the aluminum 4 by a knife coater to 130. (: After X 1 00 seconds of heating, the self-supporting gel film was peeled off from the aluminum foil and fixed on the metal frame. Thereafter, at 3 〇〇〇 c χ 2 〇 second, 45 〇 C ><1 After the heat treatment, when the film is softened or melted and the appearance is deformed, it is judged that the acid dianhydride and the diamine contain the thermoplastic block component. The acid dianhydride and the diamine which can be a thermoplastic block component are not particularly limited, and as the acid dianhydride, 3,3,4,41-biphenyltetracarboxylic dianhydride, 3,3', 4 is preferably used. 4'-dibenzophenone tetradecanoic acid dianhydride is an essential component. Further, as the diamine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane is preferably used as a necessary component. The method for producing a thermoplastic polyimine acid of a thermoplastic polyimine is preferably (a) reacting an aromatic acid dianhydride with an excess amount of an aromatic diamine in an organic polar agent, and obtaining two a step of having a prepolymer having an amine group at the end, (b) then adding an aromatic acid dianhydride in such a manner that the ratio of the aromatic acid dianhydride to the aromatic diamine in all steps is a predetermined ratio, and prepolymerizing Polymerization. (b) In the method of adding an aromatic acid dianhydride, there is a method of adding a powder, or a method of dissolving an acid dianhydride in an organic polar solvent to form an I60742.doc -19·201233715 acid solution. From the viewpoint of easily allowing the reaction to proceed uniformly, a method of placing an acid solution is preferred. The solid content concentration at the time of polymerization is preferably from 1 〇 to 3 〇 by weight. The concentration of the solids component can be determined by the polymerization rate and the polymerization viscosity. The polymerization viscosity can be set according to the case where the polyamido acid solution of the thermoplastic polyimide is applied to the support film or the co-extruded with the non-thermoplastic polyimide, in the case of coating, For example, it is preferred that the polymer component having a solid content concentration of 14% by weight has a polymerization viscosity of 1 〇〇 poise or less. Further, in the case of co-extrusion, for example, it is preferable that the polymerization viscosity of the solid content concentration of 14% by weight is from 1 〇〇poise to 1200 p〇ise, and the obtained multilayer polyimide film can be obtained. From the viewpoint of uniform film thickness, 'preferably 15 〇 poise 〜 8 〇〇 p〇ise. The aromatic acid dianhydride and the aromatic diamine described above may be used in consideration of the characteristics and productivity of the multilayer polyimide film. Further, in order to improve the properties of the film such as slidability, thermal conductivity, electrical conductivity, and corona resistance, a filler may be added. The filler is not particularly limited. As a preferred example, alumina, titanium oxide, aluminum oxide, cerium nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica or the like can be given. In the case where a filler is added to improve the slidability of the film, the particle diameter of the filler is 0.1 to ίο μηη, preferably (Md μηη. If the particle diameter is below the range), it is difficult to exhibit an effect of improving the slidability. If it is more than this range, it is difficult to form a high-definition wiring pattern. Further, in the case of adding a filler, the dispersion state of the filler is also important, and it is preferable to have an average diameter of 20 μm or more. The agglomerate of the filler is 5 / / / or less, preferably 40 / m 2 or less. If the average diameter of the above is 160 742.doc -20 - 201233715, the filler agglomerate is more than the range, When the adhesive is applied, the adhesive is repelled, or when the high-definition wiring pattern is formed, the adhesion area is reduced to lower the insulation reliability of the printable printed circuit board itself. - Addition of the filler can be used, for example, (1) for polymerization. Method for adding a filler to a polymerization reaction liquid before or during the process (2) After the completion of the polymerization, a method of kneading a filler by a three-roll mill or the like (3) preparing a dispersion containing a filler and mixing the same The method of using the polyacetic acid organic solvent solution (4) the method of dispersing the filler by a bead mill or the like, but the method can be used in the case where the filler has the lowest pollution to the production line. Preferably, the mixture containing the filler is mixed into the polyamic acid solution, and is especially a method of mixing just before the film formation. When preparing the dispersion containing the filler, The dispersion liquid is preferably one which is the same as the polymerization solvent of the imine acid. Further, in order to disperse the filler well and stabilize the dispersion state, the dispersant can be used without affecting the physical properties of the film. , a tackifier, etc. Polyimide is obtained from a polyimine precursor, that is, polyglycine by a dehydration conversion reaction, and as a method for carrying out the conversion reaction, the most widely known is only by heat. Two methods of performing the heat curing method and the chemical curing method using a chemical dehydrating agent. However, from the viewpoint of excellent productivity, 5, it is more preferable to use a chemical curing method. In the heat curing method and the chemical curing method, Can make From the viewpoint that the ruthenium imidization reaction proceeds relatively quickly, it is preferred to use a ruthenium imidization catalyst for 160742.doc.21 · 201233715. The so-called chemical dehydration agent refers to a dehydration ring-closing agent for poly-proline. The main component 'is preferably used as an aliphatic acid anhydride, an aromatic acid oxime, N,N'-dialkyl decyloxy boron, a lower aliphatic dentate, a southern fatty acid anhydride, an aryl sulfonic acid dihalide, a sulfite-based compound or a mixture of two or more of them. Among them, an aliphatic acid anhydride and an aromatic acid anhydride particularly function well. Further, the term "sodium ruthenium-based catalyst" means having a promoting hardening agent for poly-proline As a component of the effect of the dehydration ring-closing action, for example, an aliphatic tertiary amine, an aromatic tertiary amine, or a heterocyclic tertiary amine can be used. Among them, a nitrogen-containing heterocyclic compound such as imidazole, benzimidazole, isoquinoline, quinoline or pyridylpyridine is preferred. Further, it may be appropriately selected from a solution consisting of a chemical dehydrating agent and a ruthenium-catalyzed catalyst. The way to introduce organic polar solvents. The method for producing a flexible metal-clad laminate according to the present invention preferably comprises the step of laminating a metal foil on the multilayered polyimide film. As the metal foil (for example, copper foil) used in the sturdy metal laminate, a thickness of 25 μm can be used, and either a rolled copper foil or an electrolytic copper foil can be used. As a method of bonding a multilayer polyimide film to a metal foil, for example, a continuous roll laminating apparatus having a pair of metal rolls or a double belt press (DBP 'double belt press) can be used. deal with. Among them, in view of the fact that the apparatus is simple and advantageous in terms of maintenance cost, it is preferable to use a hot roll laminating apparatus having one or more metal rolls. Here, the "heat roll laminating apparatus having one or more metal rolls" is not limited as long as it has a means for heating and pressurizing the material. The specific device configuration is not particularly limited. 160742.doc • 22-201233715 Further, the step of bonding a multilayer polyimide film to a metal foil by thermal lamination is hereinafter referred to as a "thermal lamination step". It is known that the specific structure of the above-mentioned thermal lamination step (hereinafter also referred to as "hot lamination mechanism") is not specifically listened to, and in order to obtain a good appearance of the laminated sheet obtained, it is preferable to use the pressing surface and Protective materials are placed between the metal crucibles. Examples of the protective material include materials which can withstand the heating temperature of the thermal lamination step, for example, heat-resistant plastics such as non-thermoplastic polyimide membranes, and metal ruthenium such as copper ', yin, and su (four). Among them, a non-thermoplastic polyimide film can be preferably used from the viewpoint of excellent balance of heat, reuse, and the like, or the glass transition temperature (Tg) is higher than the lamination temperature of 5 〇 or more. a film composed of a thermoplastic polyimine. In the case of using a thermoplastic polyimine, the adhesion of the thermoplastic polyimide to the roll can be prevented by selecting those satisfying the above conditions. Further, if the thickness of the protective material is thin, the effect of buffering and protection at the time of lamination is not sufficiently exhibited. Therefore, the thickness of the non-thermoplastic polyimide film is preferably 75 μm or more. Further, the protective material is not necessarily a layer of tantalum, and may have a multilayer structure of two or more layers having different characteristics (for example, a three-layer structure). Further, when the laminating temperature is high, if the protective material is directly applied to the layer 遂, the appearance or dimensional stability of the flexible metal-clad laminate may be insufficient due to rapid thermal expansion. Therefore, it is preferred to pre-heat the protective material prior to lamination. Thus, in the case where the pre-heating of the protective material is carried out, the thermal expansion of the protective material is completed, so that the appearance or dimensional characteristics of the flexible metal-clad laminate can be suppressed from being caused by 160742.doc •23·201233715 influences. Etc. =:::: Party:,. The protection and the contact time are preferably 1 second or more and more preferably 3 seconds η 矽铋 or more. When the contact time is shorter than the above, the dust is carried out under the condition that the thermal expansion of the filler material is not finished, so that the layer material causes rapid thermal expansion of the protective material, so that the appearance or size of the obtained flexible metal-clad laminate is obtained. The characteristic produces a situation of deterioration. The distance for holding the material of the protective material 4 on the heating roller is not particularly limited, and can be appropriately adjusted depending on the diameter of the heating roller and the above contact time. The heating method of the laminated material in the heat laminating mechanism is not particularly limited. For example, a heating mechanism of a conventionally known method which can be heated at a specific temperature such as a thermal cycle method, a hot air heating method or an induction heating method can be used. Similarly, the method of pressurizing the laminated material in the above-described thermal lamination mechanism is not particularly limited. For example, a previously known method in which a specific pressure can be applied, such as a hydraulic method, a pneumatic method, or an interstitial pressure method, can be used. Pressure mechanism. The heating temperature, that is, the laminating temperature in the above thermal lamination step is preferably a glass transition temperature (Tg) + 5 (TC or more) of the thermoplastic polyimine contained in the thermoplastic polyimide layer of the multilayered polyimine film. The temperature is preferably more than the glass transition temperature (Tg) + ioo ° c of the thermoplastic polyimine contained in the thermoplastic polyimide layer of the multilayer polyimide film. If it is Tg + 5 (temperature above rc Further, the multilayer polyimide film and the metal foil can be preferably thermally laminated, and if it is Tg + 100 ° C or more, the laminating speed can be increased and the productivity of the flexible metal-clad laminate can be further improved. 160742.doc -24· 201233715 In particular, it is preferred that the polyimine film used as the core of the multilayer polyimide film of the present invention is designed to effectively exert the effect of mitigating thermal stress in the case of lamination. The flexible metal-clad laminate having excellent dimensional stability can be obtained with good productivity. The contact time between the flexible metal-clad laminate and the heating roller is preferably 〇.丨 second or more, more preferably 0.2 second. Above, it is particularly good for 〇 5 seconds or more. The contact time is shorter than In the case of the above range, there is a shape in which the relaxation effect cannot be sufficiently obtained. The upper limit of the contact time is preferably 5 seconds or less. Even if the contact is made longer than 5 seconds, the relaxation effect is not greater because of the lamination speed. The lowering or the handling of the production line is not preferable. Moreover, even after the lamination, the flexible metal-clad laminate is brought into contact with the heating roller to perform the slow cooling. The difference between the flexible metal-clad laminate and the room temperature is still In the larger case, there is a case where the residual distortion cannot be completely alleviated. Therefore, it is preferable to carry out the post-heating of the wrap-around metal-clad laminate which is subjected to the contact heating and slow cooling while still being provided with the protective material. Preferably, the tension at this time is set to a range of 1 to 10 N/cm. Further, it is preferable to set the ambient temperature of the late heating to (temperature - 200 t) to (lamination temperature + 1 〇〇t) The term "ambient temperature" as used herein refers to the outer surface temperature of the protective material adhered to both sides of the flexible metal-clad laminate. Although the actual temperature of the flexible metal-clad laminate is based on the thickness of the protective material. Tip micro However, as long as the temperature of the surface of the protective material is within the above range, the effect of late heating can be exhibited. The surface temperature measurement of the protective material can be performed by using a thermocouple or a thermometer, etc. The lamination speed of the above thermal lamination step Preferably, it is 〇·5 m/above, and I60742.doc •25-201233715 is preferably 1.0 m/min or more. If it is 〇5 m/min or more, it can be sufficiently thermally laminated, and further, if it is 1 〇m More than /min can further improve the productivity. The pressure in the above thermal lamination step, that is, the lamination pressure has a higher pressure, the lower the lamination temperature and the faster the lamination speed, but in general, : 3⁄4 layer CC force over the surface, there is a tendency that the dimensional change of the obtained laminate is deteriorated. On the contrary, if the lamination pressure is too low, the subsequent strength of the metal foil of the obtained laminate becomes low. Therefore, the laminating pressure is preferably in the range of 49 to 490 N/cm (5 to 50 kgf/cm), more preferably in the range of 98 to 294 N/cm (10 to 30 kgf/cm). If it is within this range, the three conditions of lamination temperature, lamination speed, and lamination dust force can be made good, and productivity can be further improved. The film tension in the above laminating step is preferably in the range of 〇〇i to 4 N/cm, more preferably in the range of 0.02 to 2.5 N/cm, and particularly preferably in the range of 〇Μ-5 N/cm. . When the tension is less than or equal to the above range, loosening or squeezing occurs during lamination and the heating is not uniformly applied. Therefore, it is difficult to obtain a wrap-around metal-clad laminate having a good appearance. On the other hand, when it is at least the above range, the influence of the tension is so strong that the Tg and the storage elasticity of the adhesive layer are not moderated, and the dimensional stability is deteriorated. In order to obtain the flexible metal-clad laminate of the present invention, it is preferred to use a heat laminating apparatus which continuously heats the surface of the laminated material to be pressure-bonded. Furthermore, the layered material extraction mechanism for extracting the laminated material may be disposed in the front portion of the thermal lamination mechanism, or the laminated material for winding the laminated material may be disposed in the subsequent stage of the thermal lamination mechanism. Coiling mechanism. The establishment of these mechanisms by 160742.doc -26- 201233715 can further improve the productivity of the above thermal lamination apparatus. The specific configuration of the laminated material extracting means and the laminated material take-up means is not particularly limited, and examples thereof include a known roll-shaped winder which can take up an adhesive film, a metal case, or a obtained laminated board. Further, it is more preferable to provide a protective material take-up mechanism or a protective material take-up mechanism which can take up or take out the protective material to the right. If the protective material take-up mechanism and the protective material extracting mechanism are provided, the protective material can be repeatedly used by winding up the protective material once used in the thermal lamination step and re-setting it on the drawing side. Further, in order to align the both end portions of the protective material when the protective material is wound up, an end position detecting mechanism and a take-up position correcting mechanism may be provided. Thereby, since the ends of the protective material are aligned and wound with high precision, the efficiency of reuse can be improved. Further, the specific configuration of the protective material take-up mechanism, the protective material extracting mechanism, the end position detecting mechanism, and the take-up position correcting mechanism is not particularly limited, and various conventionally known devices can be used. The peeling strength of the multilayer polyimide film of the flexible metal-clad laminate and the metal foil is preferably 10 N/cm or more. The present invention can also be configured as follows. In the above method for producing a multilayer co-extruded polyimine film, preferably, in the plurality of polyamic acid solutions, the polyhydrazide solution directly contacting the support contains a chemical dehydrating agent and Amidoxime catalyst. Further, preferably, in the plurality of polyamic acid solutions, the polyamic acid solution directly contacting the support is a polyamic acid layer of a thermoplastic polyimide layer. Further, it is preferable that 60% or more of the total number of moles of the acid dianhydride monomer and the diamine monomer constituting the thermoplastic polyimide is related to the acid dianhydride monomer and the second non-thermoplastic polyimide. The same monomer as the amine monomer. Further, it is preferred that the diamine constituting the above thermoplastic polyimine has 2,2-bis[4-(4-aminophenoxy)phenyl]propane as an essential component. Further, it is preferred that the polyamic acid which is the non-thermoplastic polyimide layer is a precursor of a non-thermoplastic polyimide which has a thermoplastic block component in the molecule. Further, it is preferred that the thermoplastic polyimide layer is laminated on both sides of the non-thermoplastic polyimide layer. [Examples] Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited to the Examples. Further, the evaluation methods of the peeling strength and solder heat resistance of the multilayer polyimide film and the metal in the synthesis examples, the examples, and the comparative examples are as follows. (Manufacturing method of metal-clad laminate) A rolled copper drop (ΒΗΥ-22Β-Τ; manufactured by Nippon Minerals Co., Ltd.) having a thickness of 18 μm is disposed on both sides of the multilayered polyimide film, and a protective material is disposed on both sides thereof (Apical) 125ΝΡΙ; manufactured by Kaneka), using a thermal pro-layer laminator, continuously heats at a laminating temperature of 380 ° C, a lamination pressure of 294 N/cm (30 kgf/cm), and a laminating speed of 1.0 mm/min. A flexible metal clad laminate is produced by lamination. (Peel strength of metal foil) 160742.doc -28- 201233715 A sample was prepared according to "6.5 Peel Strength" of JIS C6471, and the metal drop portion of 3 mm width was peeled off at a peel angle of 〇8 于 under % mm/min. And measure its load. (Evaluation of Solder Heat Resistance) A test piece of 3 cm x 3 cm was cut out from a flexible metal-clad laminate to evaluate the solder heat resistance during normal and moisture absorption. In the normal state, the test piece was adjusted at 23 C /55% RH for 24 hours, and then floated for 30 seconds using a heated solder bath. Thereafter, the copper foil on the side of the solder bath was burned and it was confirmed whether or not there was a bulge. The temperature of the solder bath without bulging is described in Table 丨2. Further, at the time of moisture absorption, the test piece K85t/85% RH was adjusted for 24 hours, and then placed in a float bath for 3 seconds using a heated solder bath. Thereafter, the copper foil on the side of the solder bath was etched to confirm the presence or absence of bulging. The temperatures of the solder bath without bulging are shown in Tables 1 and 2. The abbreviations of the monomers used in the synthesis examples are shown below. DMF : N,N-dimethylformamide BAPP: 2,2·bis[4-(4-aminophenoxy)phenyl]propane ODA : 4,4'-diaminodiphenyl ether PDA: P-phenylenediamine BPDA : 3,3',4,4·-biphenyltetracarboxylic dianhydride BTDA : 3,3',4,4'-benzophenone tetradecanoic acid dianhydride PMDA : benzene tetra The formic acid dianhydride below represents a synthesis example of a polyamic acid solution. (Synthesis Example 1) BAPP (57.3 g: 160742.doc -29-201233715 0.140 mol) and 〇DA (18.6 g: 0.093 mol) were dissolved in DMF (1173.5 g) cooled to 1 Torr. BTDA (30.0 g: 0.093 mol) and PMDA (25.4 g: 0.116 mol) were added thereto, and the mixture was uniformly stirred for 30 minutes to obtain a prepolymer. After dissolving PDA (25.2 g: 0.233 mol) in the solution, PMDA (46·9 g: 0.215 mol) was dissolved, and 115.1 g (PMDA: 0.038 mol) of a 7.2 wt% DMF solution of separately prepared pMDA was carefully added. Stop adding when the viscosity reaches 2500 poise. The mixture was stirred for 1 hour to obtain a polyamic acid solution having a rotational viscosity of 2600 poise at 23 °C. Further, a poly-proline solution synthesized by using a smear-type coater and a diamine used in the production of a prepolymer is cast on a foil by a doctor blade coater at 130 ° C. After heating for two seconds, the self-supporting gel film was peeled off from the aluminum foil and fixed on the metal frame. Thereafter, the heat treatment was carried out at 3 ° C c for 20 seconds and 450 ° C for 1 minute, and the block component of the synthesis example 1 was determined to be a thermoplastic block component because the film was fused and the appearance was deformed. (Synthesis Example 2) After adding BPDA (85.6 g: 0.291 mol) to 937.6 g of N,N-dimercaptocarbamide (DMF), BAPP (118.6 g: 0.289 mol) was added to obtain a solid content concentration of about 17 % and a viscosity of 800 poise of polyamic acid solution at 23t. Thereafter, DMF was added to obtain a polyaminic acid solution having a solid content concentration of 14% by weight. (Synthesis Example 3) BAPP (118.6 g: 0.289 mol) was dissolved in N,N-dimercaptodecylamine (DMF) 843.4 g. After BPDA (12.7 g: 0.043 mol) was placed therein and heated to 50 ° C, it was cooled to 10 ° C, and PMDA (48.6 g: 0.223 mol) 160742.doc • 30 - 201233715 was added to obtain a prepolymer. Thereafter, '7 wt% DMF solution of additionally prepared PMDA was carefully added 65.4 g (PMDA: 0.021 mol)' to obtain a polylysine having a solid content concentration of about 17 〇/〇 and a viscosity of 800 poise at 23 ° C. Solution. Thereafter, DMF was added to obtain a solid content concentration of 14% by weight. Poly-proline solution. (Example 1) Polylysine solution obtained in Synthesis Example 2 / Polylysine solution obtained in Synthesis Example 1 / Synthesis using a three-layer co-extruded three-layer mold having a width of 200 mm The three-layer structure of the polyamic acid solution obtained in Example 2 was extruded and cast onto an aluminum foil. Next, the three-layer film was heated at 15 χ丨〇〇 χ丨〇〇 后, and then the self-supporting three-layer gel film was peeled off and fixed on the metal frame to 25 (TC Χ 40 sec, 300 ° c Χ 60 sec. , 35 〇t Χ 60 seconds, 37 (TC Χ 30 seconds for drying, hydrazine imidization, obtaining a thermoplastic polyimide layer / non-thermoplastic polyimide layer / thermoplastic polyimide layer thickness of 2 7 μηη / 12 a three-layer polyimine film of 6 μηι/2·7 μιη. In this case, the polyamic acid solution obtained in Synthesis Example 2 is only about to be directly contacted with the polyamic acid solution on the surface of the support. Adding a hardener consisting of acetic acid needle/isoindene/DMF (weight ratio 33.0 g/8.3 g/58,6 g) to 1 〇〇g of the polyaminic acid solution before being placed in the three-layer mold (chemistry) 20 g of a dehydrating agent and a ruthenium-based catalyst were mixed by a mixer. After a metal-clad laminate was produced using a three-layer polyimide film, the peel strength and solder heat resistance of the metal foil were measured. Table 丨~2. In addition, the table will directly contact the thermoplastic polyimide layer on the support surface as the B side, the opposite side The thermoplastic polyimide layer is described as a surface. 160742.doc • 31-201233715 (Comparative Example 1) The polyphosphonic acid solution (the surface directly contacting the support (B surface)) of the synthesis example 2 was not used. A chemical dehydrating agent and a ruthenium-imiding catalyst were added to the amine acid solution, and the same procedure as in Example 1 was carried out. The thermoplastic polyimide layer having a B-face on the support was directly contacted with a trace of partial peeling. After the metal-clad laminate was fabricated on the polyimide film, the peel strength of the metal foil and the heat of the solder were measured. The results were summarized in Tables 1 to 2 (Example 2) Using a multi-manifold type of 200 mm. The layer was co-extruded into a three-layer mold, and the poly-proline solution obtained in Synthesis Example 3 / the poly-proline solution obtained in Synthesis Example 1 / the poly-proline solution obtained in Synthesis Example 3 was extruded in three layers. Press and /, IL is extended to the name. Secondly, after heating the three-layer film with i 5 〇 χ 1 〇〇 second, the self-supporting three-layer gel film is peeled off and fixed on the metal frame to 25 〇Cx40 seconds, 300 (^x60 seconds, 350 °C) <60 seconds, 370 ° C><30 seconds drying, hydrazine imidation, obtaining a thermoplastic polyimide layer/non-thermoplastic polyimide layer/thermoplastic polyimide layer having a thickness of 2.7 12 6 μηι/2.7 μηη Amine film. In this case, for the polyaminic acid solution obtained in Synthesis Example 3, only the polyamic acid solution directly contacting the surface of the support is placed in the three-layer mold before 'relative to the polyamic acid solution 1 〇〇g added 20 g of a hardener (chemical dehydrating agent and ruthenium amide) consisting of acetic anhydride/isopropion/DMF (weight ratio 33.〇g/8.3 g/58.6 g) and used as a mixer Mix. After the metal-clad laminate was produced using a three-layered polyimide film, the peel strength and solder heat resistance of the metal 160742.doc -32-201233715 foil were measured. Organize the results in Table 丨~2. (Comparative Example 2) Except that the chemical dehydrating agent and the ruthenium-imiding catalyst were not added to the polyamic acid solution of Synthesis Example 3, the same procedure as in Example 1JS was carried out. After laminating the sheet, the peel strength of the metal foil and the heat resistance of the solder were measured. Organize the results in Table 2. There are traces of peeling on the thermoplastic polyimide layer of the 6 faces directly contacting the support. (Example 3) Except for the polyaminic acid solution of Synthesis Example 2 (poly-proline solution directly contacting the surface (B side) of the support), before being placed in the three-layer mold, it was compared with s醯g acid solution 1 〇〇g added 14 g of hardener (only ruthenium-imiding catalyst) composed of isoquinoline/DMF (weight ratio 8 3 g/58.6 g) and mixed with a mixer Example 1 was carried out in the same manner. After a metal-clad laminate was produced using a three-layer polyimide film, the peel strength and solder heat resistance of the metal foil were measured. Organize the results in Table 丨~2. (Example 4) The polylysine solution of Synthesis Example 3 (polylysine solution directly contacting the face (b face) on the support) was applied to the polyamine before being placed in the three-layer mold. 100 g of an acid solution was added with 14 g of a hardener (only ruthenium-imiding catalyst) composed of isoquinoline/DMF (weight ratio of 8 3 g/58 6 g) and mixed by a mixer, and Example 1 The same implementation. After a metal-clad laminate was produced using a three-layer polyimide film, the peel strength and solder heat resistance of the metal foil were measured. Organize the results in Table 丨~2. 160742.doc •33-201233715 [Table i] Example 1 Comparative Example 1 Example 2 Comparative Example 2 Peeling strength of metal foil (N/cm) Noodles/face 14/14 14/14 14/14 14/14 B Surface peeling without solder heat resistance (°C) Normal 300 300 350 350 Water absorption 250 250 300 300 Thickness composition (μηι) Thermoplastic polyimide layer (A side) 2.7 2.7 2.7 2.7 Non-thermoplastic polyimine Layer 12.6 12.6 12.6 12.6 Thermoplastic polyimide layer (B side) 2.7 2.7 2.7 2.7 Acid dianhydride in thermoplastic polyimine and non-thermoplastic polyimides and diamines Ratio of diamine (%) 50 50 93 93 [Table 2] Example 3 Example 4 Peel strength of metal foil (N/cm) Noodles/Β 14/14 14/14 B-side peeling without solder heat resistance ( °C) 300 350 in normal state 250 300 in moisture absorption (μιη) Thermoplastic polyimide layer (A side) 2.7 2.7 Non-thermoplastic polyimide layer 1 12.6 12.6 Thermoplastic polyimide layer (B side) 2.7 2.7 Ratio of acid dianhydride and diamine in thermoplastic polyimine similar to acid dianhydride and diamine used in non-thermoplastic polyimide Example (%) 50 93 [Industrial Applicability] The present invention can be applied to the production of a flexible printed wiring board. -34- 160742.doc

Claims (1)

201233715 七、申請專利範園： 1· 一種多層共擠壓聚醯亞胺膜之製造方法，其特徵在於： 藉由多層共擠壓使複數之聚醯胺酸溶液流延至支持體 上，而製造於至少含有非熱塑性聚醯亞胺之非熱塑性聚 酿亞胺層之至少I面上積層有至少含有熱塑性聚酿亞胺 之熱塑性聚醯亞胺層的多層聚醯亞胺膜；並且 於上述複數之聚醢胺酸溶液之中，僅使直接接觸上述 支持體之聚醢胺酸溶液中含有醯亞胺化觸媒。 2·如請求項1之多層共擠壓聚醯亞胺膜之製造方法，其中 於上述複數之聚醯胺酸溶液之中，僅使直接接觸上述支 持體之聚醯胺酸溶液中含有化學脫水劑及醯亞胺化觸 媒。 3. 如请求項1之多層共擠壓聚醯亞胺膜之製造方法，其中 於上述複數之聚醯胺酸溶液之中，直接接觸上述支持體 之聚醯胺酸溶液係成為熱塑性聚醯亞胺層者。 4. 如請求項1之多層共擠壓聚醯亞胺膜之製造方法，其中 構成上述熱塑性聚醯亞胺之酸二酐單體及二胺單體之合 計莫耳數之60。/。以上係與構成上述非熱塑性聚醯亞胺之 酸二酐單體及二胺單體相同之單體。 5. 如請求項1之多層共擠壓聚醯亞胺膜之製造方法，其中 構成上述熱塑性聚醯亞胺之二胺以2,2-雙[4-(4-胺基苯氧 基）苯基]丙烷作為必需成分。 6. 如請求項1之多層共擠壓聚醯亞胺膜之製造方法，其中 成為上述非熱塑性聚醯亞胺層之聚醯胺酸係作為於分子 160742.doc 201233715 中具有熱塑性嵌段成分之非熱塑性聚醯亞胺之前驅物 者。 7.如請求項1至6中任一項之多層共擠壓聚醯亞胺膜之製造 方法，其中於上述非熱塑性聚醯亞胺層之兩面上積層上 述熱塑性聚醯亞胺層。 160742.doc 201233715 四、指定代表圖： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件符號簡單說明： 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： (無） 160742.doc201233715 VII. Application for Patent Park: 1· A method for manufacturing a multilayer co-extruded polyimine film, which is characterized in that: a plurality of poly-proline solutions are cast onto a support by multi-layer co-extrusion a multilayer polyimine film having a thermoplastic polyimide layer containing at least a thermoplastic polyimine layer laminated on at least one side of a non-thermoplastic polyimide layer containing at least a non-thermoplastic polyimide; Among the polyamic acid solutions, only the ruthenium-catalyzed catalyst is contained in the polyamic acid solution directly contacting the support. 2. The method for producing a multilayer co-extruded polyimine film according to claim 1, wherein in the plurality of polyamic acid solutions, only the polyamine acid solution directly contacting the support contains chemical dehydration And bismuth imidization catalyst. 3. The method for producing a multilayer co-extruded polyimine film according to claim 1, wherein in the plurality of polyamic acid solutions, the polyamic acid solution directly contacting the support is a thermoplastic polysiloxane. Amine layer. 4. The method for producing a multilayer co-extruded polyimine film according to claim 1, wherein the total number of moles of the acid dianhydride monomer and the diamine monomer constituting the thermoplastic polyimide is 60. /. The above is the same as the acid dianhydride monomer and the diamine monomer constituting the above non-thermoplastic polyimide. 5. The method for producing a multilayer co-extruded polyimine film according to claim 1, wherein the diamine constituting the above thermoplastic polyimine is 2,2-bis[4-(4-aminophenoxy)benzene Base] propane as an essential component. 6. The method for producing a multilayer co-extruded polyimine film according to claim 1, wherein the polyamic acid which is the non-thermoplastic polyimide layer is a thermoplastic block component in the molecule 160742.doc 201233715. Non-thermoplastic polyimine precursors. The method of producing a multilayer co-extruded polyimide film according to any one of claims 1 to 6, wherein the thermoplastic polyimide layer is laminated on both sides of the non-thermoplastic polyimide layer. 160742.doc 201233715 IV. Designation of the representative representative: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: (none) 160742.doc
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US10798826B2 (en) 2015-03-31 2020-10-06 Kaneka Corporation Polyimide laminate film, method for manufacturing polyimide laminate film, method for manufacturing thermoplastic polyimide, and method for manufacturing flexible metal-clad laminate
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