TW201020106A - Dual-layered double-surface flexible metal laminated board and manufacturing method thereof - Google Patents

Abstract

The present invention provides a dual-layered double-surface flexible metal laminated board, which shows excellent adhesion characteristics of polyimide layer and metal layer. A double-surface dual-layered flexible metal laminated board comprises a polyimide layer interposed between metal layers. The polyimide layer can be a single layer made of non-thermoplastic polyimide resin. The metal layers and the polyimide layer have adhesion beyond 7N/cm.

Description

201020106 六、發明說明： 【發明所屬之技術領域】 本發明係關於二層雙面撓性金屬疊層板及其製造方法盥印刷 電路板。 ’、 【先前技術】 撓性金屬疊層板被廣泛應用於電子材料領域，已知有由金屬 ，與聚醢懿層及環氧翻旨層等_㈣所構成的三層撓性金屬 «層板’及由金屬層與聚醯亞胺層所構成的二層撓性金屬疊層板。 二層撓性金屬疊層板巾，又絲輕胺層的兩面有金屬層之 二層雙面撓性金屬疊層板，及聚醯亞胺層的單面有金屬 單面撓性金屬疊層板。一3 一般的二層撓性金屬疊層板的聚醯亞胺層係由含有熱可塑性 聚酿亞胺樹脂(TPI)與熱硬化性聚醯亞麟脂之錄聚酸亞胺樹 脂層所構成。 鄕f來在電子材料領域中’考慮到對自然環境或對人體的影 曰之材料的無齒素化及無錯焊錫的對應正在進展中。又，在用途 ^，電子設，的薄型·小型化及高機能化正在進展中，撓性金屬 板也由—層撓性金屬疊層板朝二層撓性金屬疊層板的轉變進 挽性金屬疊層板於用途面的高機能化的要求之―，例如在 二5 —2*安？的高溫加卫中，要求聚醯亞胺層的高耐熱化。又， $ $而。因商耐熱化和黏著性間有取捨(trade-off)關係，若欲使 ㈣缉胺層高耐熱化，雌脂會變硬，與金屬層的黏著性會降低。 取胁雙面撓性金屬疊層板的情況，上述的關係會對金屬層與 二」上胺層間的黏著性或焊錫耐熱性等的特性帶來大的影響。具 二二雖然可展現與塗佈於金屬層之聚醯亞胺層間的黏著性， +後的聚醯亞胺層表面和金屬層間以擠壓進行黏著時，會產 生無法展現黏著性的問題。 曰展 專利文獻1中’揭示了在與金屬箔接觸的聚醯亞胺層使用 3 201020106 TPI並廣泛用於撓性電路基板的金屬箔疊層板。 了 〜文獻2巾，揭示了於與金屬箱相接的絕緣樹脂層使用 同耐熱性聚醯亞胺樹脂的金屬箔疊層板。201020106 VI. Description of the Invention: [Technical Field] The present invention relates to a two-layer double-sided flexible metal laminate and a method of manufacturing the same, and a printed circuit board. ', [Prior Art] Flexible metal laminates are widely used in the field of electronic materials, and there are known three layers of flexible metal «layers composed of metal, polyfluorene layer and epoxy layer. a plate' and a two-layer flexible metal laminate composed of a metal layer and a polyimide layer. A two-layer flexible metal laminate sheet, a two-layer double-sided flexible metal laminate having a metal layer on both sides of the light amine layer, and a metal single-sided flexible metal laminate on one side of the polyimide layer board. The polyimine layer of a general two-layer flexible metal laminate is composed of a layer of a polyacrylamide resin containing a thermoplastic polyimine resin (TPI) and a thermosetting polysulfide resin. .鄕f is in the field of electronic materials' The correspondence between the dentate-free and error-free soldering of materials that affect the natural environment or the human body is progressing. In addition, in the development of thin-film, miniaturization, and high-performance, the flexible metal plate is also transitioned from a flexible metal laminate to a two-layer flexible metal laminate. The requirements for the high functionalization of metal laminates on the application surface, for example in two 5-2*? In the high temperature curing, the high heat resistance of the polyimide layer is required. Again, $ $ instead. Due to the trade-off relationship between the heat resistance and the adhesiveness, if the (4) guanamine layer is to be highly heat-resistant, the female fat will become hard and the adhesion to the metal layer will be lowered. In the case of the double-sided flexible metal laminate, the above-described relationship greatly affects the properties such as adhesion between the metal layer and the upper amine layer, and solder heat resistance. Although the adhesiveness between the polyimide and the polyimide layer coated on the metal layer is exhibited, when the surface of the polyimide layer and the metal layer are adhered by extrusion, the problem of inability to exhibit adhesion is caused.曰 Patent Document 1 discloses a metal foil laminated board widely used for a flexible circuit board in which a polyimide layer in contact with a metal foil is used in 201020106 TPI. The document 2 towel discloses that a metal foil laminate of a heat-resistant polyimide resin is used for the insulating resin layer that is in contact with the metal case.

你勒if$獻3中’揭示了介由可熱壓接之聚醯亞胺系的黏著: 箔i層體。生多層聚酿亞胺薄膜與金屬箱疊層一體化後的撓性金J 成的獻4中’揭示了域壓接性多層聚醯亞胺薄獅 面金巾，揭柏乡層的非射雛聚醯麵構成之雙 ί醯;胺層為兩層以上，且塗佈面側的聚醯亞胺： 基’壓接_的聚醯亞胺翻旨末稿上述以外末“如 【專利文獻1】日本特開2004_209680號公報 ^專利文獻2】國際公開第〇2/〇85616號小冊子 【專利文獻3】曰本特開2〇〇5_131919號公報 ^專利文獻4】日本特開2〇〇7_216688號公報 ^專利文獻5】日本特開2〇〇7_118477號公報 【專利文獻6】日本特公平7_19939號公報 【發明内容】 [發明所欲解決的問題] 、而，專利文獻1及2中所揭示的金屬箔愚 層中二使用了熱可塑__，高溫加自==奴亞胺 亞胺^^ 、^^^香族聚疏 也因=用===壓接性多層聚™中， 201020106 又，專利文獻4中的背景技術揭示了塗佈了聚醯胺酸溶液的 全部聚醯亞胺基材無法展現與銅箔的黏著性。 田如專利文獻5所揭示，僅以某一層的聚醯亞胺製得雙面金屬 疊層板的情況，恐有與塗佈侧、壓接侧的任一侧的金屬箔間盔法 展現黏著性之虞。 ^ 、又，專利文獻6的圖5中，雖然揭示了由一層的線狀塑膠構 成的雙面金屬箔疊層板之結構，然而此結構的具體製法並未揭 示，又，，為作為線狀塑膠用的樹脂，其醚基、羰基等的彎曲部 位多，又胺基為m_配位，被認為是熱可塑性聚醯亞胺樹脂。再者， 因為線狀塑膠的Tg為150〜260°C，恐有在需高溫、高壓加工之 ❿ aiipOnFilm(COF)等的表面安裝性不佳之虞。 再者，以專利文獻6中所揭示的方法擠壓，即使將塗佈後的 聚醯亞胺層與銅箔面進行壓接後仍無法發現十足的黏著力。 甘制本發明所欲解決的問題，係提供一種二層雙面撓性金屬板及 /、ϋ"方法其改善以彺為問題的高溫加工性，直即使不使用 ΤΡΙ，金屬層與聚醯亞胺層間也有良好的黏著性。 [解決課題之手段] 航發明人等為解決上述問題，努力研究後發現’藉由使聚 胺層為㈣熱可塑性聚醯亞雌脂構成之單層，經二階段於 ❹卜溫度_亞胺化後所製成的二層雙面撓性金屬疊層板 決上述問題，並完成本發明。 胛 ^即’本發曰月提供如以下的二層雙面撓性金屬叠層板及 造方法，與印刷電路板。 穴衣 [1] 拉一種二層雙面撓性金屬疊層板，係聚醯亞胺層由金屬層所夾 & ，亡，聚醯亞胺層係由非熱可塑性聚醯亞胺樹脂構成之單 g，且金屬層及聚醯亞胺層間的黏著性皆為以上。 ’上述^^酸亞胺層的 如[1]之二層雙面撓性金屬疊層板，其中 線膨脹係數為25xl〇_VC以下。 5 201020106 [3] 如[1]或[2]之二面雙層撓性金屬疊層板，其中，上述聚醯亞胺 層的玻璃轉移溫度為300〜400¾。 [4] 如[1]至[3]中任一項之二層雙面撓性金屬疊層板，其中，上述 非熱可塑性聚醯亞胺樹脂係由至少一種選自3,4,3，4，·聯苯四羧 酸二酐、2,3,3’，4’ ·聯苯四羧酸二酐、2,3,2’，3，-聯苯四羧酸二 酐、均苯四酸二酐、2,3,6,7-萘四羧酸二酐及ι，4,5,8-萘四羧酸二酐 的酸二酐，與 由至少兩種選自2,2，-二甲基-4,4，-二胺基聯苯、對苯二胺、 ^3-雙(3_胺基苯氧基)苯、1,3_雙(4_胺基苯氧基)苯、3,3，_二胺基聯 苯喊、3,4’-二胺基聯苯醚及4,4，-二胺基聯苯醚的二胺成分，進行 聚合而得。 [5] 如[4]的二層雙面撓性金屬疊層板，其中， 上述酸二酐成分係由 (A) 至少一種選自3,4,3,4，-聯苯四羧酸二酐、2,3,3，，4, _聯苯四 繞酸一酐、2,3,2’，3’-聯苯四羧酸二酐的聯苯四羧酸二酐，與 (B) 至少一種選自均苯四酸二酐、2,3,6,7-萘四羧酸二酐及 1，4,5,8-萘四羧酸二酐的剛性酸二酐構成。 [6] 如[4]或[5]之二層雙面撓性金屬疊層板，其中， 上述二胺成分係由 (C) 至少一種選自2,2’ _二甲基-4,4，-二胺基聯苯、對苯二胺的 剛性二胺成分，與 (D) 至少一種選自1，3_雙(3_胺基苯氧基)苯、1，3_雙(4_胺基苯氧 基)苯、3,3’ -二胺基聯苯醚、3,4’ _二胺基聯苯醚的二胺成分構成。 [7] 如[5]或是[6]之二層雙面撓性金屬疊層板，其中，上述(A)為 70〜100莫耳％，上述(b)為〇〜3〇莫耳〇/0。 201020106 [8] 如[6]或[7]中任一項之聚醯胺酸，其中，上述(C)為50〜95簟 耳％，上述(D)為5〜5〇莫耳。 、 [9] ' 如[6]〜[8]中任—項之聚醯胺酸，其中，上述(c 〇/〇，上述(D)為5〜4〇莫耳％。 、鬥 吴耳 [10]You are able to reveal the adhesion of a thermo-compressive polyimine system: a foil i-layer. The flexible gold J which is integrated with the multi-layered polyimide film and the metal box is integrated into the '4' to reveal the domain pressure-bonded multi-layered polyimine thin lion face gold towel, the non-shooting of the Jiebai town layer The polythene layer is composed of two layers; the amine layer is two or more layers, and the polyimide surface of the coated surface side: the base 'pressure-bonded polyimine is turned out to be the end of the above-mentioned "such as [Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-209680 (Patent Document 2) International Publication No. 2/〇85616 pamphlet [Patent Document 3] 曰本特开2〇〇5_131919号 Patent Document 4] Japanese Special Opening 2〇〇7_216688 [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei 7-118477 (Patent Document 6) Japanese Patent Publication No. Hei 7-19939 [Patent Document] [Problems to be Solved by the Invention] Patent Documents 1 and 2 In the metal foil layer, the second uses the thermoplastic __, the high temperature is added from the == sulphide imine ^^, ^^^ scented polyglycolate = use === crimping multilayer poly-TM, 201020106 The background art in Patent Document 4 discloses that all polyimide substrates coated with a polyaminic acid solution cannot exhibit copper Adhesiveness As disclosed in Patent Document 5, when a double-sided metal laminated plate is produced only by a certain layer of polyimide, there is a fear that there is a metal foil on either side of the coated side and the pressure-bonded side. The helmet method exhibits adhesiveness. ^ Further, in Fig. 5 of Patent Document 6, although a structure of a double-sided metal foil laminate composed of a layer of linear plastic is disclosed, the specific method of the structure is not disclosed. Further, in order to use a resin for a linear plastic, the ether group, the carbonyl group and the like have many bent portions, and the amine group is m_coordinated, and is considered to be a thermoplastic polyimine resin. The Tg of the plastic is 150 to 260 ° C, and there is a fear of poor surface mountability such as aiipOnFilm (COF) after high-temperature processing and high-pressure processing. Further, it is extruded by the method disclosed in Patent Document 6, even if After the coated polyimine layer is pressed against the copper foil surface, the adhesive force is still not found. The problem to be solved by the present invention is to provide a two-layer double-sided flexible metal plate and/or ϋ&quot Method to improve the high temperature processability with 彺 as a problem, even if not used ΡΙ, there is also good adhesion between the metal layer and the polyimide layer. [Means for Solving the Problem] In order to solve the above problems, the inventor of the ship has tried to find out that 'by making the polyamine layer (4) thermoplasticity The single layer composed of the fat, the two-layer double-sided flexible metal laminate prepared by the second-stage temperature-imidization is used to solve the above problems, and the present invention has been completed. Such as the following two-layer double-sided flexible metal laminate and manufacturing method, and printed circuit board. The hole [1] pulls a two-layer double-sided flexible metal laminate, the polyimine layer is made of metal layer The clip & dying, polyimine layer is a single g composed of a non-thermoplastic polyimine resin, and the adhesion between the metal layer and the polyimide layer is above. A two-layer double-sided flexible metal laminate such as the above [1], wherein the coefficient of linear expansion is 25 x 1 〇_VC or less. 5 201020106 [3] A double-sided flexible metal laminate according to [1] or [2], wherein the polyimine layer has a glass transition temperature of 300 to 4003⁄4. [4] The two-layer double-sided flexible metal laminate according to any one of [1] to [3] wherein the non-thermoplastic polyimide resin is at least one selected from the group consisting of 3, 4, 3, 4, ·biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,2',3,-biphenyltetracarboxylic dianhydride, benzene tetra Acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride and acid dianhydride of iota, 4,5,8-naphthalenetetracarboxylic dianhydride, and at least two selected from 2, 2,- Dimethyl-4,4,-diaminobiphenyl, p-phenylenediamine, ^3-bis(3-aminophenoxy)benzene, 1,3_bis(4-aminophenoxy)benzene The diamine component of 3,3,-diaminobiphenyl, 3,4'-diaminodiphenyl ether and 4,4,-diaminodiphenyl ether is obtained by polymerization. [5] The two-layer double-sided flexible metal laminate according to [4], wherein the acid dianhydride component is (A) at least one selected from the group consisting of 3,4,3,4,-biphenyltetracarboxylic acid Anhydride, 2,3,3,,4, _biphenyltetracarboxylic acid anhydride, 2,3,2',3'-biphenyltetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and (B) At least one selected from the group consisting of pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 1,4,5,8-naphthalenetetracarboxylic dianhydride is a rigid acid dianhydride. [6] The two-layer double-sided flexible metal laminate according to [4] or [5], wherein the diamine component is (C) at least one selected from the group consisting of 2,2'-dimethyl-4,4 , a diamine biphenyl, a rigid diamine component of p-phenylenediamine, and (D) at least one selected from the group consisting of 1,3_bis(3-aminophenoxy)benzene, 1,3_bis (4_ A diamine component of an aminophenoxy)benzene, a 3,3'-diaminodiphenyl ether, and a 3,4'-diaminodiphenyl ether. [7] The two-layer double-sided flexible metal laminate according to [5] or [6], wherein the above (A) is 70 to 100 mol%, and the above (b) is 〇~3〇莫耳〇 /0. The polyamino acid of any one of [6] or [7], wherein the above (C) is 50 to 95% by mole, and the above (D) is 5 to 5 moles. [9] ' Polyamines as in [6]~[8], wherein, (c 〇 / 〇, the above (D) is 5 to 4 〇 mol%. 10]

了種二層雙面撓性金屬疊層板之製造方法，該二面雙層撓性 金屬疊層板係將單層的聚醯亞胺層由金屬層所夾持，金屬層I 醯亞胺層間的黏著性皆為TjWcm#上者， /、 包含以下步驟： (1) 將非熱可塑性聚醯亞胺樹脂的前驅樹脂塗佈於第一金 層； (2) 將已塗佈於第一金屬層的上述前驅樹脂以28〇。〇〜(上述非 熱可塑性聚醯亞胺樹脂的玻璃轉移溫度朽的它的範 胺化後，得到二層單面撓㈣層板； (3) 將第二金屬層擠壓於上述二層單面撓性金屬疊層板； (4) 於(上述非熱可塑性聚醯亞胺樹脂的玻璃轉移溫度)它以 上，進行二次醯亞胺化。 [11] 如[10]之二層雙面撓性金屬疊層板之製造方法，其中，上述 前驅樹脂含有溶劑，於上述步驟(1)後，包含將上述前驅樹脂 乾燥之步驟。 j [12] 如[11]之二層雙面撓性金屬疊層板之製造方法，其中，上求 溶劑係選自由Ν,Ν-二甲基乙醯胺及N_曱基_2_吡咯烷/萌構成^ 組中至少一種。 [13] 如[11]或[12]之二層雙面撓性金屬疊層板之製造方法，其中， 上述二面單層撓性金屬的一次醯亞胺化後之聚醯亞胺層的溶'劑揮 7 201020106 發成分量，於200〜300°C為1質量％以下。 [14] 、 一種二層雙面撓性金屬疊層板，係藉由[10]〜[13]之二層雙面 撓性金屬疊層板之製造方法所得。 [15] 一種印刷電路板’係由上述[1]〜[9]及[14]中任一項之二層雙面 撓性金屬疊層板構成。 [發明之效果] 藉由本發明，可提供一種二層雙面撓性金屬疊層板及其製造 方法’改善高溫加工性’再者即使不使用TH、使用由聚醯亞胺 樹脂所構成之單層的聚醯亞胺層，金屬層與聚醯亞胺層間也有良 好的黏著性。 【實施方式】 [實施發明的最佳形態] '以下，詳細記載實施本發明之最佳形態。又，本發明並不限 於以下為實施發明之最佳職，可在在該要旨的細内進行各種 變更後實施。 [二層雙面撓性金屬疊層板] 本發明的二層雙面撓性金屬疊層板，係聚醯亞胺層由金屬層 所夾持者，上述聚醯亞胺層為由非熱可塑性聚酿亞胺樹脂構 且金屬層及聚醯亞胺層間的黏著性皆為7N/cm以上。 本發明中，聚醯亞胺層由金屬層所夾持，係指具有金屬層一 4醯亞胺層一金屬層的層構造。 發明的—層雙面撓性金屬疊層板，藉由使金屬層與聚酿亞 ^層間_紐為7N/em社，在雜亞胺層的鑄造面及擠壓 h ίί層與聚醯亞胺制醜著性良好。又，於加工時及最終 裏如狀態，無金屬電路的剝離，可提升製品的壽命。 ^發日种，黏著性係指第—金屬層與聚醯亞胺層之禱造面的 ,占者性，及不_第—金屬層的第二金騎與聚麵胺間之擠壓 201020106 面的黏著性。 例所法雜雜賴_難可以下實施 本發明中’「非熱可塑性聚酿亞胺控 ， (¾^上加熱仍不會軟化，彈神會緩慢降低的^_移，皿度 本發明中，「熱可塑性聚醯亞胺樹脂係 樹脂Γ _曰為在Tg以上加熱則軟化，為有軟化點溫度的 ❿ 本1x月中，熱硬化性樹月旨」係指在玻璃轉移溫度以 熱則硬化，彈性率不會降低的樹脂。 油=祕黏彈性_，可確認其為非熱可塑性樹脂。 22，圖1所示’因為熱可塑性樹脂隨著溫度上升的同時 極端地降低’相對於此，非熱可塑性樹酬為彈性率 緩地降低，、因此，可確認其域可紐樹脂鱗熱可塑性樹脂。 又，因為熱硬化性樹脂隨溫度上升彈性率並不會降低， 可確認其為熱硬化性樹脂或非熱可塑性樹脂。 在此，圖1所示DMA為使用Rheometric Scientific公 =動絲彈性測定裝置RSAII，以l〇t：/min升溫時所測定的彈性 竿。 本發_二巧面撓性金屬疊層板中，聚醯亞胺層之線膨服 係數(CTE)為25x10 /°C以下較佳，24xl〇_Vt以下更佳。 因為當CTE為25><1〇-6/。〇以下時，銅箔的CTE 18xlO_/°C，聚醯亞胺層與金屬層的CTE顯示為近似值，由、二^ 雙面撓性金屬疊層板之尺寸安定性的觀點而言為較佳。一曰 本發明中，CTE可利用以下的實施例所記載的方法進行測定。 本發明的二層雙面撓性金屬疊層板中，聚醯亞胺層的 移溫度(Tg)以300〜400¾較佳。 夕在本發明中，Tg係指二次醯亞胺化後的聚醯亞胺層的破璃轉 移溫度。 201020106 m3(x)〜4(xrc ’可在高溫下加工，可在短時間内製品化。 $發明中，Tg可利用以下的實施例所記載的方法測定。 [一層雙面撓性金屬疊層板的製造方法] 本發明的二層雙面撓性金屬疊層板之製 白為7N/cm以上的二層雙面撓性金屬疊層板， 包含以下步驟： 層 .⑴將非熱可雜雜亞胺樹脂的前驅樹脂塗佈於第—金屬 =)將塗佈於第一金屬層的上述前驅樹脂以2贼〜(上述 亞，脂的玻璃轉移溫度+3G)°C的範圍内一次醯亞月ΐ 化後付到—層早面撓性疊層板； 壓；（3)將第二金屬層擠壓於上述二層單面挽性金屬疊層板擠 上，胺樹脂的玻補移溫度忙以 [步驟1] -全二將^ T塑性聚酸亞胺樹脂的前驅樹脂塗佈於第 角伽魏_式塗佈餘~)、缺 進行^ C〇mma C〇ater)、模具塗佈機(die coater)等的塗佈機來 的情、况，肝vL， 吕’以㈣等較佳。又，使用金屬箔 面撓層2前驅樹脂’一次醯亞胺化後的二層單 金屬讀板中，形成作絲難胺與第—金之界面的 性聚生聚釀亞胺之前驅體，係含有非熱可塑 性祕亞驅斷聚__樹脂。 201020106 本發明中的聚酸胺酸，皋 而得的聚醯胺酸。 吏馱二酐成分與二胺成分聚合A method for manufacturing a two-layer double-sided flexible metal laminated board, wherein the single-layered polyimide layer is sandwiched by a metal layer, and the metal layer is imine The adhesion between the layers is TjWcm#, /, including the following steps: (1) Applying the precursor resin of the non-thermoplastic polyimine resin to the first gold layer; (2) Applying to the first layer The above precursor resin of the metal layer was 28 Å. 〇~(The above-mentioned non-thermoplastic polyimine resin has a glass transition temperature decayed after it is aminated, and a two-layer single-sided flex (four) layer is obtained; (3) the second metal layer is extruded on the above-mentioned two-layer single a flexible metal laminate; (4) above (the glass transition temperature of the non-thermoplastic polyimide resin) above, for secondary imidization. [11] Two layers of double layer as [10] In the method for producing a flexible metal laminate, the precursor resin contains a solvent, and after the step (1), a step of drying the precursor resin is included. j [12] Two-layer double-sided flexibility as in [11] A method for producing a metal laminated plate, wherein the solvent is selected from at least one selected from the group consisting of ruthenium, osmium-dimethylacetamide, and N-fluorenyl-2-pyrrolidine/emolecule. [13] [11] The method for producing a two-layer double-sided flexible metal laminate according to [12], wherein the disintegrating agent of the polyimine layer after the primary hydrazide of the two-sided single-layer flexible metal 201020106 The amount of the component is 1% by mass or less at 200 to 300 ° C. [14] A two-layer double-sided flexible metal laminate is a two-layer double-sided layer of [10] to [13] [15] A printed circuit board comprising the two-layer double-sided flexible metal laminate of any one of the above [1] to [9] and [14]. Advantageous Effects of Invention According to the present invention, it is possible to provide a two-layer double-sided flexible metal laminate and a method for producing the same, which are capable of improving high-temperature workability. Further, even if TH is not used, a single layer composed of polyimide resin is used. The polyimine layer has a good adhesion between the metal layer and the polyimide layer. [Embodiment] [Best Mode for Carrying Out the Invention] The following describes in detail the best mode for carrying out the invention. The present invention is not limited to the following, and can be carried out in various ways within the scope of the gist of the invention. [Two-layer double-sided flexible metal laminate] The two-layer double-sided flexible metal laminate of the present invention The plate, the polyimine layer is held by a metal layer, the polyimine layer is made of a non-thermoplastic polyaniline resin and the adhesion between the metal layer and the polyimide layer is 7 N/cm. In the present invention, the polyimine layer is sandwiched by a metal layer, which means that it has gold. Layer-by-layer 4-imine layer-metal layer layer structure. The invention-layer double-sided flexible metal laminate plate, by making the metal layer and the poly-branze layer__7N/em, in the imine The casting surface of the layer and the extrusion h ίί layer and the polyimide are ugly. In addition, during the processing and in the final state, the stripping of the metal-free circuit can improve the life of the product. Sex refers to the praying surface of the first metal layer and the polyimine layer, and the adhesion of the surface between the second gold riding and the polyamine of the non-first metal layer 201020106. The method of the invention is difficult to implement the "non-thermoplastic polystyrene control" in the present invention, (3⁄4^ heating does not soften, and the spring will slowly decrease), in the present invention, "The thermoplastic polyimine resin-based resin Γ _ 软化 is softened when heated above Tg, and is ❿ which has a softening point temperature. In the 1x month, the thermosetting tree is used to heat hard at the glass transition temperature. The resin whose modulus of elasticity does not decrease. Oil = secret viscoelasticity _, which can be confirmed as a non-thermoplastic resin. 22, as shown in Fig. 1 'Because the thermoplastic resin is extremely lowered as the temperature rises', the non-thermoplasticity is slowly reduced as the elastic modulus, and therefore, the thermodynamic plasticity of the domain can be confirmed. Resin. Further, since the thermosetting resin does not decrease in modulus with temperature, it is confirmed to be a thermosetting resin or a non-thermoplastic resin. Here, the DMA shown in Fig. 1 is an elastic enthalpy measured at a temperature of l〇t:/min using a Rheometric Scientific male-wire elastic measuring device RSAII. In the present invention, the linear expansion coefficient (CTE) of the polyimine layer is preferably 25x10 / °C or less, and more preferably 24xl 〇 _Vt or less. Because when the CTE is 25><1〇-6/. In the following, the CTE of the copper foil is 18x10_°C, and the CTE of the polyimide layer and the metal layer are approximated, which is preferable from the viewpoint of dimensional stability of the double-sided flexible metal laminate. . In the present invention, the CTE can be measured by the method described in the following examples. In the two-layer double-sided flexible metal laminate of the present invention, the migration temperature (Tg) of the polyimide layer is preferably from 300 to 4003⁄4. In the present invention, Tg means the glass transition temperature of the polyimide layer after the secondary hydrazine imidization. 201020106 m3 (x) to 4 (xrc ' can be processed at a high temperature and can be produced in a short time. In the invention, Tg can be measured by the method described in the following examples. [One layer of double-sided flexible metal laminate Method for manufacturing a plate] A two-layer double-sided flexible metal laminate having a whitening of 7 N/cm or more of the two-layer double-sided flexible metal laminate of the present invention comprises the following steps: (1) Non-thermally miscible The precursor resin of the hybrid imine resin is coated on the first metal =) the above-mentioned precursor resin applied to the first metal layer is once in the range of 2 thief~ (the above-mentioned sub-lipid glass transition temperature + 3G) °C After the uterus is added, the layer is laminated to the early flexible laminate; (3) the second metal layer is extruded on the two-layer single-sided metal laminate, and the glass resin is removed by the amine resin. The temperature is busy [Step 1] - All two will apply the precursor resin of the T plastic poly imide resin to the first angle of the weiwei _ type coating residue ~), the lack of ^ C〇mma C〇ater), mold coating The condition of the coater such as a die coater, liver vL, LV's (four), etc. are preferred. Further, in the two-layer single metal reading plate after the primary ytterbium imitation of the metal foil face layer 2 precursor resin, a precursor of the polyglycolide which forms the interface between the wire and the gold is formed. It contains non-thermoplastic micro-driver __ resin. 201020106 The polyamic acid of the present invention, a polylysine obtained by hydrazine. Polymerization of azelaic anhydride component and diamine component

Sic -一針成分例如至少—籍4登ώι。j 2,3,3，，4, ·聯苯_酸二酐、2 3 t4,3’4，·聯苯讀酸二酐、 酐、2,3,6,7·萘吨酸二狀’M 本;^酸二酐、均苯四酸二 s , #，，5,8_萘四羧酸二酐的酸二酐成分。 苯二胺、㈣3·胺基苯氧基)苯、丨本， 二胺基聯苯醚、3,4，-二胺基聯笨㈣以，（胺基本乳基)本，-分。 土唧本鰱及4,4，-二胺基聯苯醚的二胺成 與二後利用習知的方法，將㈣成分 耳的ϊ聚製造方絲言’例何料在溶射，將等莫 耳的酸二酐成分與二胺成分混合來製造。 ^_巧二胺成分後’在轉蚊錄的祕，—邊慢慢 -酐成》邊進行重合也可以，於溶液添加酸二針成分 後，在溶解献分散離s ’-邊慢慢添加二 進行 聚合也可以。 在本發明中，使二胺成分和酸二酐成分於溶劑中進行反應， 可知到聚醯胺酸。彳于到的反應溶液因為含有聚醯胺酸與溶劑，適 Φ 合做為前驅樹脂使用。又，溶劑的量，相對於前驅樹脂的全量， 可在80〜90質量％的範圍内，考慮塗佈性後適當設定。 本發明中’溶劑列舉例如Ν,Ν-二甲基乙醯"胺、N_曱基冬吡咯 烷酮、γ-丁内酯等非質子性極性溶劑。 溶劑係至少一種選自Ν,Ν-二曱基乙醯胺、Ν_甲基_2_吡咯烷酮 所組成的群組的溶劑較佳。 溶液可使用一種’也可使用二種以上的混合溶劑。 製造聚醯胺酸時，也可添加由11比咬等的三級胺、醋酸酐等的 酸針作為代表的醯亞胺化促進劑、界面活性劑等的均塗劑、填料。 製造聚醯胺酸時的反應溫度，在-1〇。匚〜溶劑的沸點之範圍内 較佳，反應時間，以30分鐘以上較佳。 11 201020106 於第一金屬層塗佈前驅樹脂的步驟中’可吉 製造溶液使用於塗佈步驟作為前驅樹脂，也 溶劑中稀釋後所得的樹脂作為前驅樹脂。將—於 ，發日种，動咖旨巾所含料溶劑的量， 的全I，以80〜90質量〇/〇較佳。 、刖驅樹月曰 度。藉由溶劑的量為80〜90質量％，可成為塗佈性優異的清漆黏 純在本發财，「_樹脂的全量」係指前驅翻旨巾©體物和、容 論的質量的合計。「_物」係制體本身 以 溶劑將固體物溶解後，成為溶解狀態的物f。解物」係才日以 量)Xl^=(ft%)可以(溶綱_/(前卿旨的全量的質 驟非熱可塑性聚輕胺細旨㈣驅樹脂 ίϊ ίΐ ί後，於步驟(2)的—次酿㈣化前，包含將雜 於第一孟屬層的如驅樹脂進行乾燥的步驟較佳。 ^包含乾燥麵’可除去前驅樹脂的過_溶劑成分。 中’將塗佈於第—金屬層的非熱可塑性聚輕胺樹脂 的則驅樹月曰進打乾燥的步驟，藉由於80〜15(rc進行卜30分j 佳0 全量，保持 [步驟⑺] t發明中’將塗佈於第一金屬層的前驅樹脂，在·C〜(上 述非,、、、可塑性聚醯亞職脂的玻璃轉移溫度+3眼的範圍内進行 j亞胺化以獲％—層單面撓性金屬疊層板的步驟，係以在氮Sic - a needle component such as at least - 4 ώ ι. j 2,3,3,,4, ·biphenyl-acid dianhydride, 2 3 t4,3'4, ·biphenyl read acid dianhydride, anhydride, 2,3,6,7-naphthoic acid dimorphic' M;; acid dianhydride, pyromellitic acid s, #,, 5,8-naphthalene tetracarboxylic dianhydride acid dianhydride component. Phenylenediamine, (tetra)-3-aminophenoxy)benzene, hydrazine, diaminodiphenyl ether, 3,4,-diamine-based (tetra), (amine-based base), and -. The diamines of the earthworms and the 4,4,-diaminodiphenyl ethers are formed by the conventional method, and the (4) components of the ear are condensed to produce a square wire. The acid dianhydride component of the ear is mixed with the diamine component to produce. ^_ Qiao diamine component after the 'secret in the mosquito record, - slowly - anhydride into the side" can also be overlapped, after adding the acid two-needle ingredients in the solution, slowly dissolved in the dissolution of the s '- side Second, it is also possible to carry out polymerization. In the present invention, polyamine acid is known by reacting a diamine component and an acid dianhydride component in a solvent. The reaction solution obtained is used as a precursor resin because it contains polyamic acid and a solvent. In addition, the amount of the solvent can be appropriately set in consideration of the coatability in the range of 80 to 90% by mass based on the total amount of the precursor resin. In the present invention, the solvent includes, for example, an aprotic polar solvent such as hydrazine, hydrazine-dimethylacetamidine, amine, N-mercapto-pyrrolidone or γ-butyrolactone. The solvent is preferably a solvent selected from the group consisting of ruthenium, osmium-dimercaptoacetamide and hydrazine-methyl-2-pyrrolidone. The solution may be used in the form of a mixture of two or more kinds. In the case of producing a poly-proline, a soy-based imidization accelerator such as a tertiary amine such as a bite or an acid needle such as acetic anhydride, or a leveling agent or a filler such as a surfactant may be added. The reaction temperature at the time of producing poly-proline is -1 Torr. Preferably, the boiling point of the solvent is preferably in the range of 30 minutes or more. 11 201020106 In the step of coating the precursor resin in the first metal layer, the 'Keiki production solution is used as a precursor resin in the coating step, and the resin obtained after dilution in a solvent is used as a precursor resin. It is preferable to use the amount of the solvent contained in the coffee-making towel, and the total amount of the solvent is preferably 80 to 90% by weight.刖 树 树 树 树 树. By the amount of the solvent of 80 to 90% by mass, it is possible to obtain a varnish which is excellent in applicability, and it is a good thing in the present invention. "The total amount of resin" refers to the total mass of the body and the quality of the precursor. . The "_" system itself dissolves the solid matter in a solvent, and becomes a substance f in a dissolved state. The solution is based on the amount of Xl^=(ft%). (Solution _/(The full amount of the non-thermoplastic polylight amine for the purpose of the pre-Qing dynasty (4) drive the resin ϊ ϊ ΐ ί , 2) Before the second brewing, the step of drying the resin such as the driving resin mixed with the first Meng layer is preferably used. ^ The dry surface is included to remove the solvent component of the precursor resin. In the first-metal layer of the non-thermoplastic poly-light amine resin, the step of drying the tree into the drying process, by 80~15 (rc is 30 minutes, j is good, the whole amount is maintained, [step (7)] t in the invention' The precursor resin applied to the first metal layer is subjected to i-imidization in a range of +C~(the above-mentioned non-,,, plasticized polythene resin glass transition temperature + 3 eyes to obtain a %-layer single Surface flexible metal laminate step, in nitrogen

Hf氣體氛圍下，或是在真空下經由階段性地升溫過程 進行者加熱較佳。 升溫速度係在25°c/小時以下的速度進行者較佳 。藉由25°C/ 小時以=升^度，可抑制醢亞胺化反應劇烈進行及樹脂中分 子鏈的配向不良，能使CTE減小。 12 201020106 在本發明中’一次贐亞胺化係指製成二層單面撓性金屬疊層 板時，將前驅樹脂縮合的步驟。 曰 藉由在280°C以上進行一次醯亞胺化，可抑制第二金屬層的 擠壓時孔隙的產生。 又’藉由在(非熱可塑性聚醯亞胺樹脂的玻璃轉移溫度+3〇)。〇 以下進行一次醯亞胺化，擠壓面可得到十足的黏著性。 本發明中，非熱可塑性聚醯亞胺樹脂的玻璃轉移溫度係指前 述Tg。 魯 魯 在本發明中，一次醯亞胺化溫度為非熱可塑性聚蕴亞胺樹脂 的玻璃轉移溫度+30。(：以下’係指一次醯亞胺化後的非熱可塑性聚 醯亞胺樹脂的彈性率E，變為〇.15GPa以上的溫度。… Λ 〜本發明中，藉由在Ε’為〇.15GPa以上的溫1進行一次醯亞 胺化，一次醯亞胺化後的聚醯亞胺層的高溫區域的柔軟性不會降 ，二於一次醯亞胺化後的聚醯亞胺層擠壓第二金屬層時，可▲成 ，一金屬層與聚酸亞胺層間具有優異黏著性的二層雙面撓性金屬 ^層板。亦即，藉由在E’為〇.15GPa以上的溫度進行一次酿亞 月女化丄可製成在二層雙面撓性金屬疊層板的聚醯亞胺層的柔軟性 及黏著性，與聚醯亞胺層的硬化的相反性質方面，有優異 ^^酿亞胺層。 μ资本發明中，一次醯亞胺化後的非熱可塑性聚醯亞胺樹脂的彈 Ε ，可利用以下實施例中所記載的方法測定。 西明ί ’二層單面撓性金屬疊層板之一次醯亞胺化後的聚 之洛液揮發成分量在2〇〇〜3〇〇t：，為1質量％以下較佳。 第-ίϊϊϊϊ成分量在2GG〜3啊為1 f量％以下，可抑制將 ti 於二層單面撓性金屬疊層板的聚醯亞胺層面時發 孔可1成點著性良好的二層雙面撓性金屬疊層板。 測定 巾，溶劑揮發成分量可㈣下實施射所記載的方法 人而雜可雖雜亞贿脂，舰上述》胺酸縮 口而件的雜可塑性魏亞麟脂，在—次醢亞胺化步驟== 13 201020106 聚醯胺_前轉麟合而絲熱可雜雜亞胺樹脂。 明巾發現：在第—金屬層和雜亞胺制之鑄造面的優 ίίΓΓ可藉由酸二酐成分和二胺成分聚合而得的聚醯亞胺樹 月曰為非熱可塑性聚醯亞胺樹脂而達成。 it本發明中’認為藉由在非熱可塑性聚醯亞麟脂的玻璃 轉=溫i以上進行二次醯亞胺化，可緩和施加在非熱可塑性聚醯 亞胺樹脂的應力，未反應的聚醯亞胺樹脂也會進行反應 面的黏著性變佳。 〜 ’ 本，發明中的非熱可塑性聚醯亞胺樹脂，係由至少一種選自 ^4,3’4’-聯苯四羧酸二酐、2,3,3，，4,-聯苯四羧酸二酐、2,3,2，，3，_聯 笨四竣酸一酐、均苯四酸二酐、2,3,6,7-萘四羧酸二酐及ι,4,5,8-萘 四羧酸二酐的酸二酐成分，與 由至少兩種選自2,2’-二甲基-4,4'-二胺基聯苯、對苯二胺、χ，3_ $(3-胺基苯氧基)苯、ι，3-雙(4-胺基苯氧基)苯、3,3，_二胺基聯苯 醚二3,4’-二胺基聯苯醚及4,4’-二胺基聯苯醚中的二胺成分所聚合 而得的非熱可塑性聚醯亞胺樹脂較佳。 本發明中，酸二酐成分係由 (A) 至少一種選自 3,4,3 4 -聯苯四叛酸二酐、;2,3,3’，4，_聯苯四叛酸二酐、 2,3,2 ，3’ -聯苯四竣酸二肝的聯苯四幾酸二肝與 (B) 至少一種選自均苯四酸二酐、2,3,6,7_萘四羧酸二酐及 1，4,5,8-萘四羧酸二酐的剛性酸二酐 構成者’因含有剛性成分，使CTE變小者故較佳。 本發明中’酸二酐成分僅由(A)成分所構成的情況，非熱可塑 性t酿亞胺樹脂的前驅樹脂的聚合反應也可均一地進行，使非熱 可塑性聚醯亞胺樹脂的前驅樹脂的黏度控制變容易，就提高加工 性而言較佳。 (A)成分的酸二酐單體，可單獨使用，也可以兩種以上的混合 .物的形式使用。 (A)成分在高黏著性、容易取得的觀點方面，以3,4,3’ 4’ - 201020106 聯苯四羧酸二酐較佳。 物的酸二_ ’可單_，也可以_上的混合 針較^)成”在祕者性、取得容易性峨點方面，明苯四酸二 在本發明中，二胺成分係由 中的2,2’ 零4,4，_二細苯及對苯二胺 美戌(D)3^ -二H自Λ3·雙(3_胺基苯氧基)苯、以雙(4_胺基苯氧 聯苯醚的二赋佳3f _二胺基聯細及4,4’ -二胺基 的形的—^體’可單敏用’也可以兩種以上的混合物 (C)成分在咼耐熱性的觀點方面，以對苯二胺較佳。 的形分的"胺單體，可翔，也可㈣翻上的混合物 雙(4-^^=性_方面，以Μ，·二絲聯苯鍵、以 本發明之雜可紐聚酿亞賴脂，於兼具冑 CTE之觀點而言，酸二酐=係^ 成刀為70〜1〇〇莫耳％、（B)成分在〇〜3〇莫耳％較佳二胺 (〇：)成^為50〜95莫耳％且(〇)成分在5〜50莫耳％較佳。 藉由使(B)成分的含量相對於酸二酐成分為3〇莫耳％以 非熱可塑性1酸亞胺樹脂具優異的柔軟性，故可製成盘 的黏著性優频二層雙面撓性金層板。 U屬治間 ^ ’藉由使(A)成分的含量相對於酸二酐成分為7〇〜1〇〇莫 %的曰，圍内，非熱可塑性聚醯亞胺樹脂本身的柔敕性增加，黏著 性提高。 ’ 本發明中，（A)成分為70〜95莫耳％，（B)成分為5〜3〇莫 較佳。 、^~ 〇 15 201020106 莫耳ίΐ和=軒的莫耳數’可以(A)成分的莫耳數_成分的 心f 成分的含量相對於二胺成分為5莫耳％以上，可製 層表面與金屬層間的黏著性優異的二層雙面撓性ϋ ί 莫耳％以下，則非熱可塑性聚醯亞胺樹脂中的彎曲 誠内，可製成耐熱性優異的二層雙面撓性ί屬 ❹ r m t使(C)成分的含量相對於二胺成分為5G〜95莫耳％的 熱性提且因鱗熱可雜親亞胺_本身的CTE 接近於金屬箱的CTE，故尺寸安定性提高。 ♦利I比 。/ f 匕’ (C)成分為60〜95莫耳％，⑻成分為5,莫耳 〜9G莫耳％，⑼成分為1G〜4G料％又更佳 數Ιχίοϋ二的3置可以[(C)成分的莫耳數]/[二胺成分的莫耳 分的含量可以[⑼成分的莫刪 二胺‘分 Ο 的莫ΐί之分的莫耳數，可以(C)成分的莫耳數與(D)成分 數，成分、(戰分、（〇成分及_分的莫耳 成八圍較雖無特別限制，⑷成分、⑻成分、（C) 知的莫耳數各為相等時製成的非熱可塑性樹月旨亦為 [步驟(3)] 牛驟本’將第二金屬層播壓於二層單面撓性金屬疊層板的 擠顧力在替w上進行較佳。Heating in a Hf gas atmosphere or under a vacuum in a stepwise heating process is preferred. The rate of temperature rise is preferably at a rate of 25 ° C / h or less. By the use of 25 ° C / hr in terms of liters, it is possible to suppress the ruthenium imidization reaction and the misorientation of the molecular chain in the resin, thereby reducing the CTE. 12 201020106 In the present invention, the term "primary ruthenium imidization" refers to a step of condensing a precursor resin when a two-layer single-sided flexible metal laminate is produced.藉 By performing hydrazine imidization at 280 ° C or higher, the generation of voids during extrusion of the second metal layer can be suppressed. Further, by (the glass transition temperature of the non-thermoplastic polyimide resin + 3 〇). 〇 The following oxime imidization is carried out, and the extruded surface can be fully adhesive. In the present invention, the glass transition temperature of the non-thermoplastic polyimide resin refers to the above Tg. Lulu In the present invention, the primary hydrazide temperature is a glass transition temperature of +30 for the non-thermoplastic polyimine resin. (: "The following" refers to the elastic modulus E of the non-thermoplastic polyimide resin after primary imidization, and becomes a temperature of 〇15 GPa or more. Λ ～ In the present invention, Ε' is 〇. At a temperature of 15 GPa or more, the yttrium imidization is carried out, and the softness of the high-temperature region of the polyamidimide layer after the primary hydrazide is not lowered, and the polyimine layer extrusion after the primary imidization In the case of the second metal layer, a two-layer double-sided flexible metal layer having excellent adhesion between the metal layer and the polyimide layer can be formed, that is, by a temperature of 〇.15 GPa or more at E'. The flexibility and adhesion of the polyimide layer on the two-layer double-sided flexible metal laminate can be made once, and it is excellent in the opposite nature of the hardening of the polyimide layer. ^^ The imine layer. In the μ capital invention, the impeller of the non-thermoplastic polyimine resin after the primary imidization can be determined by the method described in the following examples. The amount of volatile components of the polysodium sulphide after the primary yttrium imitation of the surface flexible metal laminate is 2〇〇~3〇〇t:, 1 It is preferable that the mass % is less than or equal to 1. The amount of the - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - A two-layer double-sided flexible metal laminate with good adhesion. The amount of volatile components in the solvent can be measured by (4) the method described in the shooting method, but the miscellaneous can be used to make the above-mentioned amino acid shrinkage. The heterogeneous plasticity of Wei Yalin, in the sub-imidization step == 13 201020106 Polyamide _ former lining and silk heat can be mixed imine resin. Ming towel found: in the metal layer and the imine The preferred aspect of the casting surface can be achieved by polymerizing the dianhydride tree and the diamine component to form a non-thermoplastic polyimide resin. In the present invention, Glass transition of non-thermoplastic polyphthalocyanine = secondary iridization of temperature i or above, which can alleviate the stress applied to the non-thermoplastic polyimide resin, and the unreacted polyimine resin also reacts. The adhesion of the surface is better. ~ 'This, the non-thermoplastic polyimine resin in the invention And at least one selected from the group consisting of ^4,3'4'-biphenyltetracarboxylic dianhydride, 2,3,3,4,-biphenyltetracarboxylic dianhydride, 2,3,2,,3,_ An acid dianhydride component of bis, tetradecanoic acid anhydride, pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and iota, 4,5,8-naphthalenetetracarboxylic dianhydride, And at least two selected from the group consisting of 2,2'-dimethyl-4,4'-diaminobiphenyl, p-phenylenediamine, anthracene, 3_$(3-aminophenoxy)benzene, iota, 3 - bis(4-aminophenoxy)benzene, 3,3,-diaminobiphenyl ether 3,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl ether The non-thermoplastic polyimine resin obtained by polymerizing the diamine component is preferred. In the present invention, the acid dianhydride component is (A) at least one selected from the group consisting of 3,4,3 4 -biphenyltetrahydro acid dianhydride. , 2,3,3',4,_biphenyltetrahydro acid dianhydride, 2,3,2,3'-biphenyltetradecanoic acid diphenyl biphenyl tetraacid dihydrate and (B) at least one A rigid acid dianhydride composed of pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 1,4,5,8-naphthalenetetracarboxylic dianhydride It is better to make the CTE smaller. In the present invention, when the acid dianhydride component is composed only of the component (A), the polymerization reaction of the precursor resin of the non-thermoplastic t-imine resin can be uniformly performed to make the precursor of the non-thermoplastic polyimide resin. The viscosity control of the resin becomes easy, and it is preferable in terms of improving workability. The acid dianhydride monomer of the component (A) may be used singly or in the form of a mixture of two or more. The component (A) is preferably 3,4,3' 4' - 201020106 biphenyltetracarboxylic dianhydride from the viewpoint of high adhesion and easy availability. The acid _ ' can be a single _, can also be _ on the mixed needle compared to ^) into "in the secret, easy to obtain points, pyromellitic acid two in the present invention, the diamine component is from 2,2' zero 4,4,_diphenyl and p-phenylenediamine (D)3^-diH from Λ3·bis(3_aminophenoxy)benzene, with bis(4-amine The bisphenanthrene of the phenoxy phenoxyphenyl ether and the 4,4'-diamine group may be mono- sensible or may be a mixture of two or more (C) components. From the viewpoint of heat resistance, the preferred embodiment of p-phenylenediamine is an amine monomer which can be condensed or (iv) turned over by a mixture of double (4-^^=sexuality, in terms of Μ, · The di-biphenyl bond, the heterogeneous yam-yield of the present invention, in terms of the enthalpy of CTE, the acid dianhydride = system ^ is 70~1 〇〇 mol%, (B) The content of the component (B) is preferably from 50 to 95 mol% and the (〇) component is from 5 to 50 mol%, preferably from 〇~3〇mol%, preferably from 50 to 95 mol%. The non-thermoplastic 1 acid imine resin has excellent flexibility with respect to the acid dianhydride component of 3 〇 mol%, so that the adhesiveness of the disk can be made excellent. Two-layer double-sided flexible gold laminate. U belongs to the treatment zone. ' By making the content of the component (A) relative to the acid dianhydride component 7〇~1〇〇%%, surrounded by non-thermoplastic polymer The flexibility of the quinone imine resin itself is increased, and the adhesion is improved. In the present invention, the component (A) is 70 to 95 mol%, and the component (B) is preferably 5 to 3 Å. ^, ~ 15 201020106 Moer's and Mox's Moir number can be a molar amount of (A) component _ component of the heart f component is 5 mol% or more relative to the diamine component, and the adhesion between the surface of the layer and the metal layer can be made. Excellent two-layer double-sided flexible ϋ ί 摩尔% or less, the bending in the non-thermoplastic polyimide resin can be made into a two-layer double-sided flexible rmt with excellent heat resistance ( The content of the component C) is 5G to 95% by mole relative to the diamine component, and the CTE of the scaly heat-mixable parent imine is close to the CTE of the metal case, so the dimensional stability is improved. / f 匕 ' (C) component is 60~95 mol%, (8) component is 5, mol ~ 9G mol%, (9) component is 1G~4G material% and better number Ιχίοϋ2 of 3 The content of the molar content of the [(C) component] / [the content of the molar component of the diamine component may be the molar number of the molybdenum of the [(9) component of the molybdenum diamine], and the component (C) may be used. Moole number and (D) component number, composition, (war score, (〇 component and _ point of the molars are not particularly limited, (4) component, (8) component, (C) know the number of moles are The non-thermoplastic tree made at the same time is also [Step (3)]. The squeezing force of the second metal layer on the two-layer single-sided flexible metal laminate is performed on the w Preferably.

本卷明中，第二金屬層舉例如銅 UIn the present invention, the second metal layer is, for example, copper U

電性、電路加工性_朗言，贿鮮絲金U 16 201020106 •的情況’可施以鑛鋅、鐵鉻等 山叮#、，a 烧偶f解進行的:t機表鱗ί讀錢表面處理，也可施以石夕 亞胺於二層單面撓性金屬疊層板，二次酿 二金屬層，蝴雜亞胺層與第 也可=日种’第二金屬層的材質’可與第-金屬層的材質相同， [步驟(4)] 以卜在(非熱可塑性聚醯亞胺樹脂的玻璃轉移溫度)°c ❿下^胺化的步驟’細在氮鮮的不活性氣體氛圍 下’或疋在真工下經階段性地升溫過程進行加熱者較佳。 ，係在25°c/小時以下的速度進行較佳。當升溫速度在 25 C/小時以下，可展現良好的黏著性。 在本發明中，二次醯亞胺化係指將第二金屬層擠壓於二声 .?撓性，疊層板後，使聚醯亞胺層與第-及第二金屬層^黏 者性提尚，而製成二層雙面金屬疊層板的步驟。 — 少_藉由在(非熱可塑性聚醯亞胺樹脂的玻璃轉移溫度)°C以上進 行二次醯亞胺化，鑄造面及擠壓面可得到十足的黏著性。 一利用本發明之二層雙面撓性金屬疊層板的製造方法所得到的 ❹一層雙面撓性金屬登層板’可製成在金屬層與聚酿亞胺層的黏 面，黏著性皆為7N/cm以上者。 ” 本發明的—層雙面撓性金屬疊層板的聚酿亞胺層的厚度在 2〜50 //m較佳，5〜30 # m更佳。金屬層的厚度在2〜35^ m較^， 8〜18/zm更佳。 本發明之二層雙面撓性金屬疊層板，藉由使聚醯亞胺層由聚 胺酸縮合後的非熱可塑性聚醯亞胺樹脂構成，尺寸安定性良好， 在加工時及最終製品狀態，金屬電路等的剝離減少，故製=壽合 提升。 。口可p 又’因為非熱可塑性聚醯亞胺樹脂具有耐熱性，即使加工溫 度為高溫也可對應，不必降低溫度即可進行加工。藉此，加工$ 17 201020106 間的減短變得可能。再者，可製成電路形成、半導體元件安裝等 的加·^性、產量提高的二層雙面撓性金屬疊層板。 、 —，藉由將本發明之二層雙面撓性金屬疊層板的金屬層蝕刻為既 疋形狀，可製成印刷電路板，將钱刻後得到的蚀刻面以金屬層電 路被覆材被覆後，可得到被覆完成的電路。 金屬層電路被覆材方面，只要是可被覆金屬層電路的物質即 可，並無限定，舉例如使用了聚醯亞胺薄膜的表覆膜、液狀抗银 劑、乾膜抗敍劑等。 【實施例】 以下’利用實施例及比較例更加具體地說明本發明，但本發 明並不僅限於此等實施例。 ❹ ，用於實施例及比較例的酸二酐成分、二胺成分及溶劑如以 下。實施例及比較例中的評價方法及測定方法如以下。 (A)成分 · s_BPDA : 3,4,3’，4’聯苯四羧酸二酐(宇部興產製造） . ⑻成分 PMDA :均苯四酸酐(大赛璐化學工業製造） (C) 成分 p-PDA :對苯二胺(關東化學製造） m-TB : 2,2’ -二曱基_4,4’ -二胺基聯苯(和歌山精化製造） 〇 (D) 成分 TPE-Ri l，3-雙(4-胺基苯氧基)苯（和歌山精化製造） 4,4’ -DPE:4,4，二胺基聯苯醚(和歌山精化製造） 溶劑 NMP : N-曱基-2-吡啶烷酮(關東化學製造） (l)E’測定 使用將一次醯亞胺化後的二層單面撓性金屬疊層板的銅箔經 餘刻後所得的膜狀試樣(僅聚醯亞胺層），利用拙e〇metric Scientific 公司製造的動態黏彈彳生測定裝置RSAII，從以〗(fc/min升溫後的 動態黏彈性求得一次醯亞胺化後之非熱可塑性聚醯亞胺樹脂的 18 201020106 E’ 。 (2) 溶劑揮發成分量 π ，用將—次醯亞胺化後的二層單面撓性金屬疊層板經蝕刻所 知的薄膜狀s式樣’利用精工儀器(&也〇 )製造的差示熱 熱，量同時測定裝置TG/DTA6200，在氮氣氛圍下，從以1 〇。(：/min 升溫後的重量減少求得200〜30(TC時溶劑揮發成分量。 (3) CTE測定 &使用將實施例及比較例中得到的二層雙面撓性金屬疊層板的 銅猪進行餘刻所得之薄膜狀試樣。 ，使用島津製作所製造的熱機械分析儀TMA-60，樣本 大1、定為寬度5随、長度15mm ’從以負荷5g，於1G°C/min的 升温速度加熱時由1〇〇芄至200。(：為止的尺寸變化求得。 ⑷Tg測定 使用將實施例及比較例中得到的二層雙面撓性金屬疊層板的 銅治進行韻刻所得之薄膜狀試樣。 姑使用SdentiflC公司製造的動態黏彈性測定 f SAII ’測定以1(rc/min升溫時的動態黏彈性，從她 極大值求得Tg。 (5)黏著性 參 笔以中所得到的二層雙面撓性金屬疊層板的銅 ΪΐΞ:為覓度3mm後所得試樣，依據nS C 6471的8.1 ，用島津製作所製造的EZ_TEST，在常溫下 度度椒編及輸—剝離，並 ⑹膨脹 外觀檢ΐίίϊΐίΐ謝所制的二騎峨_疊層板的 X卜觀/又有產生直徑2mm以上的膨脹者定為〇，產生膨脹者定為Electrical, circuit processing _ lang, bribe fresh silk gold U 16 201020106 • The situation 'can be applied to mine zinc, iron chrome and other mountains #,, a squirt f solution: t machine scale ί reading Surface treatment, can also be applied to the two layers of single-sided flexible metal laminates, secondary brewing of two metal layers, the imide imine layer and the third can also be the 'material of the second metal layer' It can be the same as the material of the first metal layer, [Step (4)] The step of amination of the non-thermoplastic polyimide resin at the glass transition temperature of the non-thermoplastic polyimine resin It is preferred to heat under a gas atmosphere or to perform heating under a period of normal temperature. It is preferred to carry out the speed at 25 ° C / hour or less. When the heating rate is below 25 C/hour, good adhesion can be exhibited. In the present invention, the secondary hydrazine imidization means that the second metal layer is extruded to the second sound. The flexible layer is laminated, and the polyimide layer and the first and second metal layers are adhered. The step of making a two-layer double-sided metal laminate. — Less _ By the secondary hydrazine imidization (above the glass transition temperature of the non-thermoplastic polyimide resin) °C, the casting surface and the extrusion surface can be fully adhesive. A double-sided flexible metal cladding board obtained by the method for manufacturing a two-layer double-sided flexible metal laminate of the present invention can be made into a bonding surface between a metal layer and a polyaniline layer, and adhesiveness All are 7N/cm or more. The thickness of the polyaniline layer of the double-layer flexible metal laminate of the present invention is preferably 2 to 50 // m, more preferably 5 to 30 # m. The thickness of the metal layer is 2 to 35 μm. More preferably, it is more preferably 8 to 18/zm. The two-layer double-sided flexible metal laminate of the present invention is composed of a non-thermoplastic polyimide resin obtained by condensing a polyimide layer with a polyamine. The dimensional stability is good, and the peeling of the metal circuit or the like is reduced during processing and the final product state, so the system is improved. The mouth can be p' because the non-thermoplastic polyimine resin has heat resistance even if the processing temperature is High-temperature processing is also possible, and processing can be performed without lowering the temperature. This shortens the processing between $17 and 201020106. In addition, it can be used for circuit formation, semiconductor component mounting, etc. A two-layer double-sided flexible metal laminated board, which can be made into a printed circuit board by etching a metal layer of the two-layer double-sided flexible metal laminated board of the present invention into a printed circuit board After the obtained etched surface is covered with the metal layer circuit covering material, the coated circuit can be obtained. The metal layer circuit covering material is not particularly limited as long as it can coat the metal layer circuit, and for example, a surface film of a polyimide film, a liquid silver anti-silver agent, a dry film anti-synthesis agent, or the like can be used. EXAMPLES Hereinafter, the present invention will be more specifically described by way of Examples and Comparative Examples, but the present invention is not limited to the examples. ❹ The acid dianhydride component, the diamine component and the solvent used in the examples and the comparative examples. The evaluation methods and measurement methods in the examples and the comparative examples are as follows. (A) Component · s_BPDA: 3,4,3', 4'biphenyltetracarboxylic dianhydride (manufactured by Ube Industries) (8) Ingredients PMDA: pyromellitic anhydride (manufactured by Daicel Chemical Industries) (C) Component p-PDA: p-phenylenediamine (manufactured by Kanto Chemical Co., Ltd.) m-TB : 2,2'-dimercapto-4,4'-diamine Biphenyl (made by Wakayama Seiki Co., Ltd.) 〇 (D) Component TPE-Ri l, 3-bis(4-aminophenoxy)benzene (made by Wakayama Seiki) 4,4' -DPE: 4,4, 2 Aminobiphenyl ether (manufactured by Wakayama Seiki Co., Ltd.) Solvent NMP: N-mercapto-2-pyridinone (manufactured by Kanto Chemical Co., Ltd.) (1) E' measurement using imidization of primary oxime A film-like sample (polyimine layer only) obtained by etching a copper foil of a two-layer single-sided flexible metal laminate, using a dynamic viscoelastic test device RSAII manufactured by 拙e〇metric Scientific From the dynamic viscoelasticity after heating at fc/min, the non-thermoplastic polyimine resin after the primary imidization is obtained. 18 201020106 E' (2) The solvent volatile component π, used The film-like s-like pattern of the two-layered single-sided flexible metal laminate after yttrium imidation is etched by a precision instrument (& TG/DTA6200, manufactured by Seiko Instruments) Under a nitrogen atmosphere, from 1 〇. (:/min The weight reduction after heating was 200 to 30 (the amount of solvent volatile component at TC. (3) CTE measurement & using the two-layer double-sided flexible metal laminate obtained in the examples and the comparative examples The copper pig was subjected to the film sample obtained in the past. The thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation was used. The sample size was 1. The width was 5 and the length was 15 mm. 'From the load 5g, at 1G °C/min. The temperature rise rate was heated from 1 〇〇芄 to 200. (: The dimensional change was determined. (4) The Tg measurement was performed using the copper rule of the two-layer double-sided flexible metal laminated plate obtained in the examples and the comparative examples. The obtained film-form sample was measured by dynamic viscoelasticity measurement f SAII' manufactured by SdentiflC Co., Ltd., and the dynamic viscoelasticity at 1 rc/min was measured, and Tg was obtained from her maximum value. (5) Adhesive ginseng was The copper ruthenium of the two-layer double-sided flexible metal laminated plate obtained in the middle is a sample obtained after the twist of 3 mm, and the EZ_TEST manufactured by Shimadzu Corporation is used according to 8.1 of nS C 6471, and the pepper is woven and transferred at room temperature. - peeling, and (6) inflated appearance inspection ΐ ίίϊΐί ΐ 所 所 所 所 峨 叠X Concept Bu plate / have a diameter of 2mm or more generated by expansion as square, as generated by the expansion

(7)DMA 19 201020106 ，用將實施例與比較例中得到的二層雙面撓性金屬疊層板的 銅=進行蝕刻後所得的薄膜狀試樣，利用公 Ϊ ΐ的動態黏彈性測定裝置RSAI1，測定以1叱驗升溫時的彈 广。，定結果如圖1所示。實施例i為祕可塑性輯亞胺樹 月曰，比較例9為熱硬化性聚醯亞胺樹脂，比較例1〇為熱可塑性聚 亞胺樹脂。 [實施例1] 於500mL的燒瓶中加入255g的NMp。添加作為二胺成分的 p_PDA 9‘5g (a〇88mol)及 TPE-R 6.3g (0.022mol)後，於 30°C 攪拌使 其溶解。 於得到的溶液中慢慢地添加作為酸二酐成分的s_BPDA25 7g 〇 (0.087mol)及 PMDA4.8g (0.022mol)。 之後’藉由在室溫下攪拌1〇小時’得到聚醯胺酸溶液。 將得到的聚醯胺酸溶液以塗佈棒塗佈於銅箔（日礦金屬製造 . 的BH^22B-T-18/zm)的粗縫化處理面，使二次酸亞胺化後的樹脂. 層厚度此成為25/zm，使其於130°C乾燥1〇分鐘，得到殘存溶劍 量為50質量％以下的塗佈•乾燥樣本。 子 。將塗佈•乾燥樣本以升溫速度251/小時進行加熱至 315 C(物體溫度）’在315°C維持3小時後(一次醯亞胺化溫度），自 然冷卻至室溫，得到一次醯亞胺化的樣本。 ◎ 於360°C將銅箔（日礦金屬製造的BHY-22B-T-18//m)的粗糙 化處理面擠壓於一次醯亞胺化樣本的聚醢亞胺面，得到擠壓樣本。 將擠壓樣本以升溫速度25。(：/小時加熱至37(TC(物體溫度）， 於370°C維持3小時後(二次醯亞胺化溫度），自然冷卻至室溫， 到二層雙面撓性金屬疊層板。 上述(1)〜(6)的結果如表1所示。 [實施例2-10] 成分及製造條件變更如表1所示，除此之外，與實施例^以 相同的方法處理後’得到二層雙面撓性金屬疊層板。上述(1) 的結果如表1所示。 20 201020106 [比較例1] 製造條件變更如表2所示，除此之外，與實施例1以相同的 方法處理後’得到二層雙面挽性金屬疊層板。 上述(1)〜(6)的結果如表2所示。 [比較例2-9] 成分及製造條件變更如表2所示，除此之外，與比較例1以 相同的方法處理後，得到二層撓性金屬疊層板。 上述(1)〜(6)的結果如表丨所示。 隙)，Ϊ法二撓性金屬疊層板本身發生膨脹(空 【表1】(7) DMA 19 201020106, a film-form sample obtained by etching copper of a two-layer double-sided flexible metal laminated plate obtained in the examples and the comparative examples, and a dynamic viscoelasticity measuring apparatus using a public ΐ RSAI1 measures the width of the bullet when it is heated up by 1 叱. The results are shown in Figure 1. Example i is a cosmetic plastic imide tree. The comparative example 9 is a thermosetting polyimide resin, and Comparative Example 1 is a thermoplastic polyimide resin. [Example 1] 255 g of NMp was placed in a 500 mL flask. After adding p_PDA 9 '5 g (a 〇 88 mol) and TPE-R 6.3 g (0.022 mol) as a diamine component, the mixture was dissolved at 30 ° C to dissolve. s_BPDA25 7 g 0.0 (0.087 mol) and PMDA 4.8 g (0.022 mol) as an acid dianhydride component were slowly added to the obtained solution. Thereafter, a polyaminic acid solution was obtained by stirring at room temperature for 1 hour. The obtained polyaminic acid solution was applied to a rough-treated surface of a copper foil (BH^22B-T-18/zm manufactured by Nippon Mining Co., Ltd.) by a coating bar to imidize the secondary acid. Resin. The layer thickness was 25/zm, and it was dried at 130 ° C for 1 minute to obtain a coated/dried sample having a residual sizing amount of 50% by mass or less. Child. The coated and dried samples were heated to 315 C (object temperature) at a heating rate of 251 / hour 'after 3 hours at 315 ° C (primary hydrazine imidization temperature), and naturally cooled to room temperature to obtain a quinone imine. Sample. ◎ The roughened surface of copper foil (BHY-22B-T-18//m made from Nippon Mining & Metals) was extruded at 360 ° C on the polyimide surface of the yttrium imidized sample to obtain an extruded sample. . The sample will be squeezed at a ramp rate of 25. (: / hour heated to 37 (TC (object temperature), after maintaining at 370 ° C for 3 hours (secondary imidization temperature), naturally cooled to room temperature, to a two-layer double-sided flexible metal laminate. The results of the above (1) to (6) are shown in Table 1. [Example 2-10] The components and the manufacturing conditions were changed as shown in Table 1, except that they were treated in the same manner as in Example 2. A two-layer double-sided flexible metal laminate was obtained. The results of the above (1) are shown in Table 1. 20 201020106 [Comparative Example 1] The manufacturing conditions were changed as shown in Table 2, except that, in addition to Example 1, After the same method, a two-layer double-sided metal-clad laminate was obtained. The results of the above (1) to (6) are shown in Table 2. [Comparative Example 2-9] The composition and manufacturing conditions were changed as shown in Table 2. In the same manner as in Comparative Example 1, a two-layer flexible metal laminate was obtained. The results of the above (1) to (6) are shown in Table 。. The flexible metal laminate itself expands (empty [Table 1]

21 201020106 實施例9 〇 § IT) 〇〇 (N 324 00 ο 340 370 325 On o 〇 實施例8 〇 Η § m 1 卜 ο o m wo 370 325 OO as 〇 實施例7 ο ϊ-Η 〇 〇 cn m 330 in o CTi l〇 370 WO CO cn o 〇 實施例6 § 〇 320 317 MD Ο § cn 寸 330 300 〇 r—H 〇 實施例5 〇 m 1 in Ο o m 380 卜 340 OO 卜 〇 實施例4 § 320 1 in S u~) 370 t-j 330 0's ON 〇 實施例3 § § ΓΟ 325 o § cn in 370 C\ 320 OO On 〇 實施例2 § 310 320 卜 o S cn 370 〇\ 320 OO OO 〇 實施例1 § cn 326 o § cn i〇 370 〇\ 320 OO 〇 s-BPDA PMDA p-PDA m-TB TPE-R W (¾. 9 樊 饍 1 E’成為0_15GPa之溫度(°C) N ,P ♦1 o 唿7 僉〇 % q rsr* vO 概 姨 ®H ’、概 擠壓溫度(°c) 1 擠壓壓力(MPa) /·—s P 樊 饍 Ί 〇 S Η U Tg(°C) 鑄造面 擠壓面 膨脹 黏著性(N/cm) 成分 (莫耳％) 製造條件 特性 201020106 【CN<】 比較例10 〇 Η o t-H 250 252 寸· 280 m o cn cn o <N (N r—H X 比較例9 〇 〇 1—Η m 1 ο 360 〇 cn m H m 卜 (N 〇 比車交例8 〇 § § (N 1 rn 340 〇 cn 宕 <N m o T—H 1 X 比較例7 g O 00 〇 S rn <Τ) s r〇 〇 cn oo ·»—H 〇 cn cn H 1 X 比較例6 g (N S cn <Ν 360 o CO G\ r—H 宕 m o 1 X 比較例5 § g 〇 1 οο 300 to 300 On r—H 320 寸 (N 〇 比較例4 § § 〇 CO 1 00 ο 360 1-H 320 m 卜 〇 比較例3 § § 300 1 οο 360 in o m ON i—H CO 寸 卜 〇 比較例2 § § Ο cn 1 οο o CO m 〇 (Π On r—H cn o r~H 寸 〇 比較例1 § ο m 360 r—Η 360 iTi 370 〇\ T—H 宕 cn o r-H CN 〇 s-BPDA PMDA <ί Q Ph m-TB TPE-R 4,4'-DPE 一次醯亞胺化溫度(°c) E成為0.15GPa之溫度(°C) 溶劑揮發殘量 (質量％/200〜300°c) 奪 擠壓壓力(MPa) 二次醯亞胺化溫度(°C) CTE(10_6/°C) /*—-N P 禱造面 擠壓面 膨脹 黏著性 (N/cm) 成分 (莫耳％) 製造條件 特性 201020106 [產業上利用性] 面撓性轉性良好的二層雙 有產業利祕。 7作料刷電路板等，在f子材料領域具 【圖式簡單說明】 在圖f 1表示實施例1、比較例9及比較例10的DMA的結果 Θ中，縱軸表示彈性率，橫軸表示溫度。 ^主要元件符號說明】 無021 201020106 Example 9 〇§ IT) 〇〇 (N 324 00 ο 340 370 325 On o 〇 Example 8 § § m 1 卜 om wo 370 325 OO as 〇 Example 7 ο ϊ-Η 〇〇cn m 330 in o CTi l〇370 WO CO cn o 〇Example 6 § 〇320 317 MD § § inch 330 300 〇r-H 〇Example 5 〇m 1 in Ο om 380 340 OO 〇 〇 Example 4 § 320 1 in S u~) 370 tj 330 0's ON 〇 Example 3 § § ΓΟ 325 o § cn in 370 C\ 320 OO On 〇 Example 2 § 310 320 卜 o S cn 370 〇 \ 320 OO OO 〇 Example 1 § cn 326 o § cn i〇370 〇\ 320 OO 〇s-BPDA PMDA p-PDA m-TB TPE-R W (3⁄4. 9 Fan Shi 1 E' becomes 0_15GPa temperature (°C) N ,P ♦ 1 o 唿7 佥〇% q rsr* vO 姨®H', approximate extrusion temperature (°c) 1 extrusion pressure (MPa) /·-s P Fan Ί 〇S Η U Tg(°C) casting Surface Extrusion Surface Expansion Adhesion (N/cm) Composition (Mole%) Manufacturing Condition Characteristics 201020106 [CN<] Comparative Example 10 〇Η o tH 250 252 inch · 280 mo cn cn o <N (N r-HXComparative Example 9 〇〇1—Η m 1 ο 360 〇cn m H m 卜 (N 〇比车交例8 〇§ § (N 1 rn 340 〇cn 宕<N mo T-H 1 X Comparative Example 7 g O 00 〇S rn <Τ) sr〇〇cn oo ·»—H 〇cn cn H 1 X Comparative Example 6 g (NS cn <Ν 360 o CO G\ r-H 宕mo 1 X Comparative Example 5 § g 〇1 οο 300 to 300 On r—H 320 inches (N 〇Comparative Example 4 § § 〇CO 1 00 ο 360 1-H 320 m Divination Comparative Example 3 § § 300 1 οο 360 in om ON i-H CO寸 〇 Comparative Example 2 § § Ο cn 1 οο o CO m 〇 (Π On r—H cn or~H 〇 〇 Comparative Example 1 § ο m 360 r—Η 360 iTi 370 〇\ T—H 宕cn o rH CN 〇s-BPDA PMDA <ί Q Ph m-TB TPE-R 4,4'-DPE Primary oxime imidization temperature (°c) E becomes 0.15GPa temperature (°C) Solvent residue (% by mass) /200~300°c) Extrusion pressure (MPa) Secondary bismuth imidization temperature (°C) CTE(10_6/°C) /*—-NP Prayer surface extrusion surface expansion adhesion (N/cm ) Component (mol%) Manufacturing condition characteristics 201020106 [Industrial use] Good surface flexibility The second floor double has industry secrets. 7 as a brush circuit board, etc., in the field of f sub-materials, a brief description of the drawings. In Fig. f1, the results of DMA of Example 1, Comparative Example 9, and Comparative Example 10 show that the vertical axis represents the elastic modulus and the horizontal axis. Indicates the temperature. ^Main component symbol description] No 0

24twenty four

Claims (1)

201020106 七、申請專利範圍.： 1. 一種二層雙面撓性金屬疊層板’係聚醯亞胺層由金屬層所爽持 者，該聚醯亞胺層為由非熱可塑性聚醯亞胺樹脂構成的單層，且 金屬層與聚醯亞胺層的黏著性皆為7N/cm以上。 曰 2. 如專利申請範圍第1項之二層雙面撓性金屬疊層板，其中，該聚 醯亞胺層的線膨脹係數為25xl〇-6/°C以下。 3. 如專利申請範圍第1項之二層雙面撓性金屬疊層板，其中，該聚 醯亞胺層的玻璃轉移溫度為300〜400°C。 乂 4·如專利申請範圍第1項之二層雙面撓性金屬疊層板，其中， 該非熱可塑性聚醯亞胺樹脂係使 ® 至少一種選自3,4,3,4，-聯苯四羧酸二酐、2,3,3，，4，-聯笨四缓酸二 酐、2,3,2，，3，-聯苯四羧酸二酐、均苯四酸二酐、2,3,6,7_萘四繞酸二 酐及1,4,5,8-萘四羧酸二酐的酸二酐成分，與 ' 至少兩種選自2,2，-二甲基-4,4'-二胺基聯苯、對苯二胺、 , 雙(3_胺基苯氧基)苯、U-雙(4-胺基苯氧基)苯、3,3，-二胺基聯’苯 _、3,4’-二胺基聯苯醚及4,4’-二胺基聯苯喊的二胺成分進行聚合 而獲得。 Λ 口 5. 如專利申請範圍第4項之二層雙面撓性金屬疊層板，其中， 酸二酐成分係由 φ (Α)至少一種選自3,4,3’4’-聯苯四羧酸二酐、2,3,3，，4,-聯苯四 羧酸二酐、2,3,2，，3，-聯苯四羧酸二酐的聯苯四羧酸二酐，與 (Β)至少一種選自（Β)均苯四酸二酐、2,3,6,7-萘四羧酸二酐及 1，4,5,8-萘四羧酸二酐的剛性酸二酐構成。 6. 如專利申請範圍第4項之二層雙面撓性金屬疊層板， 其中，二胺成分係由 (C)至少一種選自2,2’-二甲基-4,4’-二胺基聯苯及對苯二胺的 剛性二胺成分，與 ⑼由至少一種選自(D)l，3-雙(3_胺基苯氧基)苯、雙(4_胺 基苯氧基)苯、3,3’-二胺基聯苯醚、3,4’-二胺基聯苯醚的二胺成分 構成。 25 201020106 專範圍第5項之二層雙面撓性金屬疊層板，其中，該(A) 為70〜100莫耳％，該(B)為0〜30莫耳％。 範圍第6項之二層雙面撓性金屬疊層板，其中，該(C) 為50〜95莫耳％，該⑼為5〜50莫耳％。 8項之二層雙面金屬疊層板，其中，該⑹為 60〜95莫耳/ί> ’該(d)為5〜40莫耳％。 1 凰面撓性金屬4層板讀造雜，該二層雙面撓性金 板係早層的聚醯亞胺層為金屬層所夾持，且金屬層與聚醯 亞胺層之黏著性皆為7N/cin以上， 包含以下步驟：201020106 VII. Scope of application for patents: 1. A two-layer double-sided flexible metal laminate plate is a layer of polyimine which is held by a metal layer. The polyimide layer is made of non-thermoplastic polyimide. A single layer composed of an amine resin, and the adhesion between the metal layer and the polyimide layer is 7 N/cm or more. 2. The two-layer double-sided flexible metal laminate according to item 1 of the patent application, wherein the polyimine layer has a coefficient of linear expansion of 25 x 1 〇 -6 / ° C or less. 3. The two-layer double-sided flexible metal laminate according to the first aspect of the patent application, wherein the polyimide layer has a glass transition temperature of 300 to 400 °C.乂4. The two-layer double-sided flexible metal laminate of claim 1, wherein the non-thermoplastic polyimide resin is at least one selected from the group consisting of 3, 4, 3, 4, and biphenyl. Tetracarboxylic dianhydride, 2,3,3,,4,-biphenyl tetra-acid dianhydride, 2,3,2,3,-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 2 , 3,6,7-naphthalene tetracarboxylic acid dianhydride and 1,4,5,8-naphthalenetetracarboxylic dianhydride acid dianhydride component, and 'at least two selected from 2,2,-dimethyl- 4,4'-diaminobiphenyl, p-phenylenediamine, bis(3-aminophenoxy)benzene, U-bis(4-aminophenoxy)benzene, 3,3,-diamine The bis-benzene-, 3,4'-diaminobiphenyl ether and the 4,4'-diaminobiphenyl fluorene diamine component are obtained by polymerization. 5. A two-layer double-sided flexible metal laminate according to item 4 of the patent application, wherein the acid dianhydride component is composed of at least one selected from the group consisting of 3,4,3'4'-biphenyl. Tetracarboxylic dianhydride, 2,3,3,4,4-biphenyltetracarboxylic dianhydride, 2,3,2,3,2-biphenyltetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, And (Β) at least one rigid acid selected from the group consisting of pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 1,4,5,8-naphthalenetetracarboxylic dianhydride The dianhydride composition. 6. The two-layer double-sided flexible metal laminate according to item 4 of the patent application, wherein the diamine component is (C) at least one selected from the group consisting of 2,2'-dimethyl-4,4'-di a rigid diamine component of an aminobiphenyl and p-phenylenediamine, and (9) from at least one selected from the group consisting of (D) 1,3-bis(3-aminophenoxy)benzene, bis(4-aminophenoxy) a diamine component of benzene, 3,3'-diaminodiphenyl ether, and 3,4'-diaminodiphenyl ether. 25 201020106 The second layer of the double-sided flexible metal laminate of the fifth item, wherein the (A) is 70 to 100 mol%, and the (B) is 0 to 30 mol%. The two-layer double-sided flexible metal laminate of the sixth aspect, wherein the (C) is 50 to 95% by mole, and the (9) is 5 to 50% by mole. A two-layer double-sided metal laminate of 8 items, wherein the (6) is 60 to 95 m / ί > and the (d) is 5 to 40 mol%. 1 phoenix flexible metal 4-layer board read and write, the two-layer double-sided flexible gold plate is an early layer of polyimine layer sandwiched by a metal layer, and the adhesion of the metal layer to the polyimide layer Both are above 7N/cin and include the following steps: (ι)將非熱可塑性聚醯亞胺樹脂的前驅樹脂塗佈於第一金屬 層； (2) 將已塗佈於第一金屬層的該前驅樹脂於280〇C〜(該非熱可 ^性聚醯亞峨脂的綱轉移溫度+30。〇的翻崎行-次醢亞 胺化，得到二層單面撓性金屬疊層板； (3) 將第二金屬層擠壓於該二層單面撓性金屬疊層板； (4) 於(該非熱可塑性聚醯亞胺樹脂的玻璃轉移溫度)它以上進 行二次醯亞胺化。(1) applying a precursor resin of the non-thermoplastic polyimide resin to the first metal layer; (2) applying the precursor resin which has been applied to the first metal layer to 280 〇C~ (the non-heatable property) The transfer temperature of the polyruthenium resin is +30. The ruthenium of the ruthenium is sub-imided to obtain a two-layer single-sided flexible metal laminate; (3) the second metal layer is extruded on the second layer Single-sided flexible metal laminate; (4) It is subjected to secondary oxime imidization above (the glass transition temperature of the non-thermoplastic polyimide resin). 如ί利申請範圍第1〇項之二層雙面撓性金屬疊層板之製造方 〉’ /、中，該前驅樹脂含有溶劑’且於該步驟(1)後，包含將該前 驅樹脂乾燥之步驟。 如甘專利申魏圍帛11項之二層雙面撓性金屬疊層板之製造方 ”中’該溶劑係選自由Ν,Ν-二曱基乙醯胺及N-曱基-2-吡咯烷 酮構成的群組中至少一種。 |3.如專利申請範圍第11項之二層雙面撓性金屬疊層板之製造方 法二其中’該二層單面撓性金屬疊層板的一次醯亞胺化後的聚醯 亞胺層的溶液揮發成分量，於200〜30(TC為1質量％以下。 14.=利申請範圍第12項之二層雙面撓性金屬疊層板之製造方 法二其中’該二層單面撓性金屬疊層板的一次醯亞胺化後的聚醯 亞胺層的溶液揮發成分量，於200~300。(：，為1質量％以下。 26 201020106 is.—種二層雙面撓性金屬疊層板，係藉由專利申請範圍第10〜14 項中任一項之'一層雙面繞性金屬疊層板之製造方法所製得。 16. —種印刷電路板’係由專利申請範圍第1—9項之二層雙面撓性 金屬疊層板構成。 17. —種印刷電路板’係由專利申請範圍15項之二層雙面撓性金屬 疊層板構成。 八、圖式· 〇-❹ 27The manufacturing method of the two-layer double-sided flexible metal laminate according to the first aspect of the application is as follows: '/, the precursor resin contains a solvent' and after the step (1), the precursor resin is dried. The steps. For example, the manufacturer of the two-layer double-sided flexible metal laminate of the 11th patent of Weiwei Weiwei is in the solvent selected from the group consisting of ruthenium, Ν-dimercaptoacetamide and N-mercapto-2-pyrrolidone. At least one of the group consisting of. 3. A method for manufacturing a two-layer double-sided flexible metal laminate according to claim 11 of the patent application, wherein the second layer of the single-sided flexible metal laminate is The amount of the volatile component of the solution of the aminated polyimide layer is from 200 to 30 (TC is 1% by mass or less. 14. The method for producing the two-layer double-sided flexible metal laminate of item 12 of the application application range 2. The amount of the solution volatile component of the polyamidimide layer after the primary hydrazide of the two-layer single-sided flexible metal laminate is 200 to 300. (:, 1% by mass or less. 26 201020106 is The two-layer double-sided flexible metal laminate is produced by the method for manufacturing a double-sidedly wound metal laminate according to any one of the patent applications of the above-mentioned items 10 to 14. 16. A printed circuit board is composed of a two-layer double-sided flexible metal laminate of the first to ninth patent application. 17. A printed circuit board is composed of Patent Application Layer range sided flexible metal laminate 15 constitutes Eight, FIG formula-square-❹ 27