TWI267442B - Flexible copper-polyimide laminate and manufacturing method thereof - Google Patents

Flexible copper-polyimide laminate and manufacturing method thereof Download PDF

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TWI267442B
TWI267442B TW94130096A TW94130096A TWI267442B TW I267442 B TWI267442 B TW I267442B TW 94130096 A TW94130096 A TW 94130096A TW 94130096 A TW94130096 A TW 94130096A TW I267442 B TWI267442 B TW I267442B
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mol
following formula
repeating unit
polyimine
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TW200624251A (en
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Sang-Kyun Kim
Jeong-Yeol Moon
Tae-Hyung Kim
Seong-Geun Kim
Chang-Beom Chung
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Kolon Inc
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    • 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
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • 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
    • C08G73/14—Polyamide-imides
    • 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
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • 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
    • 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
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles

Abstract

The present invention provides a flexible copper-polyimide laminate including a linear random block polyimide layer formed on the at least one side thereof, the linear random block polyimide layer comprising 0.25 to 90.25 mol.% of a repeating unit l represented by the formula 1, 0.25 to 90.25 mol.% of a repeating unit m represented by the formula 2, 0.25 to 90.25 mol.% of a repeating unit n represented by the formula 3, and 0.25 to 90.25 mol.% of a repeating unit o represented by the formula 4. The flexible copper-polyimide laminate having a polyimide layer is free from curls and excellent in dimensional stability, tensile property, folding endurance and resistance to flexural fatigue with low moisture content.

Description

1267442 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種撓性銅-聚醯亞胺層壓板及其製造方 法。更特定地，本發明係關於一種撓性銅-聚醯亞胺層壓 板及其製造方法’該撓性銅-聚醢亞胺層壓板具有一個聚 酿亞胺層’是從兩個二胺及兩個二酸酐聚合的聚醯胺 酉文、塗覆該聚醯胺酸在銅薄膜上並且進行醯亞胺化而製 備0 【先前技術】 近來’工業及技術的快速成長，以明顯的方式顯著地 加速與行動電話、PDP等相關電子工業的發展，並且微 小化及撓性技術對電子材料的工業已變成必不可少的並 且必需的。 克服在此領域之工業中使用黏著劑問題的許多方法已經 被提出，只解決不燃性的分解問題，但導致由於金屬及薄 φ 膜之間線性膨脹係數差異的捲曲及起皺。聚醯亞胺通常 具有高濕氣含量而導致許多問題，並且黏著劑之柔軟性 的所得惡化導致關於折疊忍受性及抗撓性疲乏的問題。 許多研究已嘗試解決那些問題。 例如：進行退火為塗覆聚醯胺醯亞胺溶液、並且乾燥該 塗層之步驟的後續製程，使之在塗覆及乾燥步驟之後減 少捲曲（曰本專利公開出版號56-23,791)。 其他方法包括一種製造層壓板的方法，藉著塗覆低熱 膨脹樹脂在金屬薄膜上（日本專利公開出版號6〇_157286 104654.doc 1267442 及1989-244841); —種製造層壓板的方法，藉著塗覆熱 塑性聚醯亞胺在聚醯亞胺薄膜的一面及耐熱聚醯亞胺在 另一面（日本號1997-148695);及一種製造層壓板的方 法，藉著塗覆聚醯亞胺共聚物（曰本號1993-245433)。 有這些所有的努力，個別的方法仍有許多問題。 如不使用黏著劑將聚醯亞胺附著在金屬薄膜上的方 法’已提出一種將經有機溶劑稀釋之聚醯胺酸塗覆在金 屬薄膜上、並且乾燥且醯亞胺化該聚醯胺酸的方法。然 而，此方法導致由於金屬及聚醯亞胺之間線性膨脹係數 之比率差異的捲曲。 聚醯亞胺在耐熱及電絕緣性質上為優良的，但是在與 金屬的黏著上為不良的，使得在一些情況下使用黏著 劑。但是，黏著劑的使用會導致由於導入濕氣的高濕氣 含量，而不保證高耐熱性。為滿足這些性質，一些方法 牵涉到合成聚醯亞胺共聚物，或混合一些聚醯胺酸並且 酸亞胺化之，而無良好結杲。 在一些情況下’聚醯亞胺薄膜被塗覆在金屬薄膜上幾 次，在該情況下，工作上有所不便。 多用於重複驅動部份的撓性銅包覆層壓板，需要具有 良好的性質，如·尺寸穩定性、張力性質、折疊忍受性 及抗撓性疲乏及類似。 習用聚醯亞胺薄膜是昂貴的，造成高單位成本，因此 其複雜的製造過程，並在高濕氣含量上也有問題。此類 撓性銅包覆層壓板主要用於重複驅動部份，並且為此理 104654.doc 1267442 由，需要良好的性質，如：張力性質、折疊忍受性、抗 撓性疲乏、尺寸穩定性及類似。 在嘗試解決問題當中，本發明之發明人發現一種銅包覆 層壓板’是製備來自兩個二胺及兩個二酸酐的聚醯胺 酸、藉著聚合及醯亞胺化該聚合溶液而製造的，經由相 當簡單的製造過程及降低價袼而滿足所需的性質，因此 完成本發明。 【發明内容】 9 因此，本發明的一個目的是提供一種撓性銅包覆層壓 板，而不使用黏著劑，該撓性鋼包覆層壓板是無捲曲的， 並且在尺寸穩定性、張力性質、折疊忍受性及抗撓性疲乏 上為優越的且具低濕氣含量。 為達到本發明的上述目的，提供一種撓性銅_聚醯亞胺 層壓板’包括在其至少一面上形成的線性無規嵌段聚醯亞 胺層，該線性無規嵌段聚醯亞胺層包含0 25至9〇25莫耳％ • 以下式1代表之重複單元，、0.25至9〇.25莫耳％以下式2代表。 之重複單元,，0.25至90.25莫耳％以下式3代表之重複單元 «及0.25至9〇.25莫耳％以下式4代表之重複單元〇。 式11267442 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a flexible copper-polyimine laminate and a method of manufacturing the same. More particularly, the present invention relates to a flexible copper-polyimine laminate and a method of manufacturing the same. The flexible copper-polyimine laminate has a polyimine layer 'from two diamines and Two dianhydride polymerized polyamines, coated with polyacrylic acid on a copper film and subjected to oxime iodization to prepare 0 [Prior Art] Recently, the rapid growth of industry and technology is remarkable in an obvious manner. Accelerate the development of related electronics industries such as mobile phones, PDPs, etc., and miniaturization and flexibility technologies have become indispensable and necessary for the industry of electronic materials. Many methods for overcoming the problem of using adhesives in industries in this field have been proposed to solve only the decomposition problem of incombustibility, but cause curling and wrinkling due to the difference in linear expansion coefficient between the metal and the thin φ film. Polyimine usually has a high moisture content and causes many problems, and the resulting deterioration in the softness of the adhesive leads to problems with folding endurance and resistance to fatigue fatigue. Many studies have tried to solve those problems. For example, a subsequent process of annealing to a solution of a polyamidoxime solution and drying the coating is carried out to reduce curl after the coating and drying steps (Japanese Patent Publication No. 56-23,791). Other methods include a method of manufacturing a laminate by coating a low thermal expansion resin on a metal thin film (Japanese Patent Publication No. 6-157286 104654. doc 1267442 and 1989-244841); Coating a thermoplastic polyimide on one side of a polyimide film and a heat-resistant polyimide on the other side (JP-A-1997-148695); and a method of manufacturing a laminate by copolymerizing polyimide (曰本号 1993-245433). With all these efforts, there are still many problems with individual methods. If a method of attaching polyimine to a metal film without using an adhesive has been proposed, a polylysine diluted with an organic solvent is coated on a metal film, and dried and ruthenium iodized the polyamic acid. Methods. However, this method results in a curl due to the difference in the ratio of the linear expansion coefficients between the metal and the polyimide. Polyimine is excellent in heat resistance and electrical insulation properties, but is poor in adhesion to metal, so that an adhesive is used in some cases. However, the use of an adhesive results in a high moisture content due to the introduction of moisture, and does not guarantee high heat resistance. To satisfy these properties, some methods involve the synthesis of polyamidiene copolymers, or the mixing of some polylysines and the acid imidization without good crusting. In some cases, the polyimide film was coated on the metal film several times, in which case it was inconvenient in operation. The flexible copper clad laminate which is often used for the repeated driving portion needs to have good properties such as dimensional stability, tensile properties, folding endurance and fatigue fatigue resistance and the like. Conventional polyimine films are expensive, resulting in high unit cost, and thus have complicated manufacturing processes and problems in high moisture content. Such flexible copper clad laminates are primarily used for repetitive drive parts and for this reason 104654.doc 1267442 requires good properties such as: tensile properties, fold endurance, resistance to fatigue fatigue, dimensional stability and similar. In an attempt to solve the problem, the inventors of the present invention have found that a copper-clad laminate is prepared by preparing polyamic acid from two diamines and two dianhydrides, by polymerization and hydrazine imidization of the polymerization solution. The present invention has been completed by satisfying the required properties through a relatively simple manufacturing process and lowering the price. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a flexible copper clad laminate without the use of an adhesive which is non-crimped and which is dimensionally stable and tensile in nature. It is superior in folding endurance and resistance to fatigue and has a low moisture content. In order to achieve the above object of the present invention, there is provided a flexible copper-polyimine laminate comprising 'a linear random block polyimine layer formed on at least one side thereof, the linear random block polyimine The layer contains 0 25 to 9 〇 25 mol% • The repeating unit represented by the following formula 1, 0.25 to 9 〇.25 mol% is represented by the following formula 2. The repeating unit, 0.25 to 90.25 mol% of the repeating unit represented by the following formula 3 «and 0.25 to 9 〇.25 mol% of the repeating unit 代表 represented by the following formula 4. Formula 1

式2 104654.doc 1267442Equation 2 104654.doc 1267442

式3Equation 3

其中Ar為 式4Where Ar is the formula 4

本發明如下更詳細地被敘述。 本發明指出一種撓性銅包覆層壓柘， ^ ^ 汉 t醯亞胺層在复上 形成，該聚醯亞胺層包括一種具有 、 有从式1代表之重複單元 、以式2代表之重複單元…乂式3代表之重複單 式4代表之重複單元0的線性無規 爲e 、，& 、^物。該聚醯亞联 層疋以製備聚醯胺酸、塗覆該樂備 表備之聚醯胺酸在銅薄膜 且然後醯亞胺化該聚醯胺酸塗層而形成。 本發明之聚醯亞胺層的形点从μ丄 成始於由兩個二胺及兩個二酿 酐製備的聚醯胺酸。該二胺白 奴包括4,4，-二胺基苯基醚（此種 104654.doc -10- 1267442 稱為"ODA")及4_胺基_N_(4_胺基苯基）苯醯胺（此後稱為 DABA )。更特定地，二胺的總含量包括χ莫耳。的及 1〇〇-χ莫耳％的DABA，其中χ滿足5.0^95.0。 二酸酐包括苯均四酸二酸酐（此後稱為npMDA”）及 3,4,3’，4’-聯苯四羧酸二酸酐（此後稱為，，3?1)八。或3,4,3，，4，_ 二苯甲酮四羧酸二酸酐（此後稱為”BTDA，，）。更特定地，二 酸酐的總含量包括$莫耳％的PMDA及1〇〇4莫耳％的bpda _ 4btda，其中 ξ滿足 5 0gs95 〇。 兩個二胺及兩個二酸酐藉著已知的聚合方法參與聚醯胺 酉文的製備，其中二胺及二酸酐的反應條件不特定限制。 因此製備之聚醯胺酸被塗覆在銅薄膜上，並且然後以如 製造撓性銅-聚醯亞胺層壓板之已知方法的相同方式，加 以醯亞胺化形成無規聚醯亞胺共聚物層，其具有5,〇〇〇至 10,000，GGG之平均重量分子量。因此形成之無規聚酿亞胺 共聚物層為具有0.25至90.25莫耳％以式}代表之重複單元 f /、0.25至90.25莫耳％以式2代表之重複單元所、〇25至 90.25莫耳％以式3代表之重複單元”及〇 25至9〇·25莫耳％以 式4代表之重複單元0的線性無規嵌段共聚物。 因此獲得之線性無規聚醯亞胺共聚物具有5,〇〇〇至 10，000,000之分子量。當分子量少於5,〇〇〇時在塗覆過程 中其薄膜形成有困難，而當分子量超過10,000,000時，聚 醯胺酸的黏度增加。 更特定地’聚酿胺酸以塗覆器或類似物塗覆在銅薄膜 上，並在50至400°c下乾燥1至8小時來醯胺化，以形成具 104654.doc 1267442 有約1 0至5 0微米之厚度的聚醯胺層。較佳地，在製程方 面’若不特定限制，在此所用之銅薄膜具有5至5〇微米之 厚度。 只從DAB Α及PMDA製備的聚醯亞胺層，在黏著性及濕 氣含量上不良；而只從0DA及BPDA製備的聚醯亞胺層具 有捲曲。 嘗試解決此問題，從DABA/PMDA製備之聚醯胺酸及從 ODA/BPDA之聚醯胺酸的混合物，被塗覆並且醯亞胺化。 但是’此方法導致合成聚醯胺酸至少兩次的不便。 為此理由，本發明是藉著使用兩個二胺及兩個二酸酐來· 製備聚醢胺酸及藉著共聚及塗覆該聚醯胺酸以形成聚醯亞 胺層而解決這些問題。根據本發明因此獲得之具有聚醯亞 胺層的撓性銅包覆層壓板係無捲曲、具低濕氣含量，並且 在尺寸穩定性、張力性質、折疊忍受性及抗撓性疲乏為優 越的。 特別地’撓性銅-聚醯亞胺層壓板可具有良好的尺寸穩 定性、具低濕氣含量，並且無關於聚醯亞胺層厚度地不捲 曲。 在本發明之撓性銅包覆層壓板中，無機顆粒可分散於聚 酉&亞胺層中。為分散無機顆粒，無機顆粒被添加到聚醯胺 酸中’並且分散’且有無機顆粒分散在其中之聚醯胺酸被 塗覆到銅；4膜上並且酿亞胺化。 在此，無機顆粒具有01至10微米之顆粒尺寸。無機顆 粒的特定實例可包括至少一個選自氧化矽、石英粉末、氧 104654.doc -12· 1267442 化鈦、氧化紹、錯英石粉末、有機黏土、氧化鎮、碳酸約 或氧化鋅。較佳地，無機顆粒使用的份量為相對於1〇〇重 量份數之聚醯胺酸總固體含量是〇 〇〇1至1〇重量份數。具 • 無機顆粒含1相對於100重量份數之聚醯胺酸總固體含量 超過1 〇重篁份數，發生分散的困難，導致不分散的顆粒， 其作用成^^酿亞胺層的缺陷。 當大於10微米時，無機顆粒從聚醯亞胺層中靜置出來， _ 影響到層壓板的外觀及物理性質。 適當尺寸之無機顆粒的分散增加聚醯亞胺層的張力係 數，並且使其可能提供在張力性質、折疊忍受性及抗撓性 疲乏上為優越的撓性銅-聚醢亞胺層壓板。 【實施方式】 進行本發明的最佳模式 此後’本發明藉著下列實例更詳細地被敘述，其不意欲 限制本發明的範蜂。 B 合成實例 根據在表1中呈現的組合物及含量，對_PDA或〇DA、 TPER及DABA為二胺及PMDA、BTDA或BPDA為二酸酐， 藉已知的方法被用來合成聚醯胺酸。在表1中的含量單位 為莫耳％。 二胺被充分地、無攪拌地溶解於溶劑（NMP，N-甲基吡 洛酮）中，並且二酸酐被添加，以莫耳比率1 : 1與二胺反 應’並且產生聚醯胺酸。因此製備之聚醯胺酸以元素分析 (EA)鑑定。在合成實例1、11、15及20中，在聚醯胺酸產 104654.doc -13 - 1267442 物上獲得的元素分析結果呈現在表2中。 表1The invention is described in more detail below. The present invention indicates a flexible copper-clad laminate, which is formed by complexing a layer comprising a repeating unit represented by Formula 1, represented by Formula 2. Repeating unit... The repeating unit represented by Equation 3 represents the linear randomness of the repeating unit 0 represented by e, , & The polybenzazole layer is formed by preparing a poly-proline, coating the poly-proline of the lyric acid on a copper film, and then yttrium-imiding the polyamic acid coating. The polyimine layer of the present invention has a shape starting from μ丄 starting from polylysine prepared from two diamines and two dianhydrides. The diamine white slave includes 4,4,-diaminophenyl ether (such 104654.doc -10- 1267442 is called "ODA") and 4_amino-_N_(4-aminophenyl)benzene Indoleamine (hereinafter referred to as DABA). More specifically, the total content of diamine includes oxime. And 1〇〇-χMole% of DABA, where χ satisfies 5.0^95.0. The dianhydride includes pyromellitic dianhydride (hereinafter referred to as npMDA) and 3,4,3',4'-biphenyltetracarboxylic dianhydride (hereinafter referred to as 3?1) VIII or 3,4 , 3, 4, benzophenone tetracarboxylic acid dianhydride (hereinafter referred to as "BTDA,"). More specifically, the total content of the dianhydride includes $ mole % of PMDA and 1 〇〇 4 mole % of bpda _ 4btda, wherein ξ satisfies 50 gs95 〇. The two diamines and the two dianhydrides are involved in the preparation of the polyamidamine by a known polymerization method, and the reaction conditions of the diamine and the dianhydride are not particularly limited. The polylysine thus prepared is coated on a copper film and then imidized to form a random polyimine in the same manner as known in the art for producing flexible copper-polyimine laminates. A copolymer layer having an average weight molecular weight of 5, 〇〇〇 to 10,000, GGG. Therefore, the random polyimine copolymer layer formed is a repeating unit represented by the formula: 0.25 to 90.25 mol%, 0.25 to 90.25 mol%, and 〇25 to 90.25 The linear random random block copolymer of the repeating unit represented by Formula 3 and 〇25 to 9〇·25 mol% represented by Formula 4 is a linear random random polyimine copolymer. It has a molecular weight of 5, 〇〇〇 to 10,000,000. When the molecular weight is less than 5, it is difficult to form a film during coating, and when the molecular weight exceeds 10,000,000, the viscosity of poly-lysine is increased. Specifically, polyacrylic acid is coated on a copper film with an applicator or the like and dried at 50 to 400 ° C for 1 to 8 hours to be amidated to form with 104654.doc 1267442 having about 10 The polyimide layer having a thickness of up to 50 μm. Preferably, the copper film used herein has a thickness of 5 to 5 μm in terms of process. Polyether prepared from DAB and PMDA only. Imine layer, which is poor in adhesion and moisture content; and polyimine prepared only from 0DA and BPDA The layer has a curl. Attempts to solve this problem, a mixture of polylysine prepared from DABA/PMDA and polylysine from ODA/BPDA is coated and ruthenium imidized. But this method leads to the synthesis of polyamine The acid is inconvenient at least twice. For this reason, the present invention is to prepare polylysine by using two diamines and two dianhydrides and to form a polyphthalamide by copolymerization and coating of the polyamic acid. The amine layer solves these problems. The flexible copper-clad laminate having the polyimide layer obtained according to the present invention is non-crimped, has a low moisture content, and is dimensionally stable, tensile, and tolerable. Flexibility to fatigue is superior. In particular, 'flexible copper-polyimine laminates can have good dimensional stability, have a low moisture content, and are not crimped regardless of the thickness of the polyimide layer. In the flexible copper-clad laminate of the invention, the inorganic particles may be dispersed in the polyfluorene & imine layer. To disperse the inorganic particles, the inorganic particles are added to the poly-proline to 'disperse' and the inorganic particles are dispersed in The polyproline is coated Copper; 4 film and iminolated. Here, the inorganic particles have a particle size of 01 to 10 microns. Specific examples of the inorganic particles may include at least one selected from the group consisting of cerium oxide, quartz powder, oxygen 104654.doc -12· 1267442 Titanium, oxidized, smectite powder, organic clay, oxidized town, carbonic acid or zinc oxide. Preferably, the inorganic granules are used in a portion having a total solid content of poly phthalic acid relative to 1 part by weight. 〇〇〇1 to 1 part by weight. Having an inorganic particle containing 1 relative to 100 parts by weight of the total solid content of polyamic acid exceeding 1 〇 heavy bismuth, difficulty in dispersion, resulting in non-dispersed granules, It acts as a defect in the imine layer. When it is larger than 10 μm, the inorganic particles are allowed to stand out from the polyimide layer, which affects the appearance and physical properties of the laminate. Dispersion of suitably sized inorganic particles increases the tensile modulus of the polyimide layer and makes it possible to provide flexible copper-polyimine laminates that are superior in tensile properties, folding endurance, and flex fatigue resistance. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION The present invention has been described in more detail by way of the following examples, which are not intended to limit the invention. B Synthesis Example According to the composition and content presented in Table 1, _PDA or 〇DA, TPER and DABA are diamines and PMDA, BTDA or BPDA are dianhydrides, which are used to synthesize polyamines by known methods. acid. The content in Table 1 is in mole %. The diamine was dissolved in a solvent (NMP, N-methylpyrrolidone) with sufficient agitation, and a dianhydride was added to react with the diamine at a molar ratio of 1:1 and to produce poly-proline. The polylysine thus prepared was identified by elemental analysis (EA). In Synthesis Examples 1, 11, 15, and 20, the results of elemental analysis obtained on polyglycine production 104654.doc -13 - 1267442 are shown in Table 2. Table 1

合成實例 二胺（100莫耳％) 二酸朝 F (100 莫耳％) 對-PDA(1) oda(2) tper(3) daba(4) pmda(5) BTDA ⑹ BPDA ⑺ 1 - 20 - 80 10 90 • · 2 - 20 - 80 50 50 - 3 . - 20 80 90 10 - 4 - 20 - 80 10 - 90 5 - 20 - 80 50 - 50 6 - 20 - 80 90 - 10 7 - 50 - 50 10 90 - 8 - 50 - 50 50 50 - 9 - 50 - 50 90 10 - 10 - 50 - 50 10 - 90 11 - 50 - 50 50 - 50 12 - 50 - 50 90 - 10 13 - 90 - 10 10 90 - 14 - 90 - 10 50 50 - 15 - 90 - 10 90 10 - 16 - 90 - 10 10 - 90 17 - 90 - 10 50 - 50 18 - 90 - 10 90 - 10 19 - 100 - - 100 - - 20 100 - - - 100 - - 21 - 50 50 - - 100 - 22 - 50 50 - 100 - - 23 - - - 100 - - 100 24 - 100 - - - 100 - 25 - - 100 - 50 50 - 26 100 - - - - 50 50 (註） (1)對-PDA :對-伸苯基二胺（2)00入：4,4’-二胺基苯基醚 (3) TPER ·· 1,3-雙(4-胺基苯氧基)苯 (4) DABA : 4-胺基-ΛΚ4-胺基苯基)苯醯胺 (5) PMDA :苯均四酸二酸酐 ⑹BTDA : 3,4,3’，4’-二苯曱酮四羧酸二酸酐 ⑺BPDA : 3,4,3’，斗聯苯基四羧酸二酸酐_ 表2 C (%) 〇(%) N (%) H(%) 合成實例1 65.47 23.69 7.41 3.40 合成實例11 64.96 24.03 7.48 3.49 合成實例15 63.38 26.35 6.87 3.36 合成實例20 58.87 29.46 8.58 3.05 實例1至18 104654.doc -14- 1267442 在合成實例1至18中製備的各聚醯胺酸，以塗覆器被塗 覆在12微米厚度的銅（商業上可自Furukawa公司獲得）上， 並在80°C下乾燥2小時、200°C下2小時及350°C下一小時， 來酿亞胺化’以製備具有厚度25微米之聚醯亞胺層的撓性 銅包覆層壓板。 比較例1至8 在合成實例19至26中製備的各聚醯胺酸，以塗覆器被塗 _ 覆在12被米厚度的銅（商業上可自Frukawa公司獲得）上，並 在80 C下乾燥2小時、200°C下2小時及35〇°C下一小時，來 酿亞胺化，以製備具有厚度25微米之聚醯亞胺層的撓性銅 包覆層壓板。 實例19至21 以100重量份數之聚醯胺酸固體含量為基礎，添加重 里伤數之Si〇2顆粒（Gasil 35M，由Crossfield公司供應）至丨j在 合成實例2、7及15中製備的各聚醯胺酸中，並且以均質器 _ (T25基本型，由iKALaboratechnik公司供應）在每分鐘95〇〇 轉下分散5分鐘。 因此製備之溶液被塗覆在12微米厚度的銅（商業上可自 Frukawa公司獲得）上，並在80°C下乾燥2小時、2〇〇〇c下2 小時及350°C下一小時，來醯亞胺化，以製備具有厚度25 微米之聚醯亞胺層的撓性銅-聚醯亞胺層壓板。 實例22至24 以100重量份數之聚醯胺酸固體含量為基礎，添加5〇重 量份數之Ti〇2顆粒（R700，由杜邦（DuPont)公司供應）到在 104654.doc -15- 1267442 合成實例2、7及1 5中製備的各聚醯胺酸中，並且以均質器 (T25基本型，由IKALaboratechnik公司供應）在每分鐘9500 轉下分散5分鐘。 因此製備之溶液被塗覆在12微米厚度的銅（商業上可自 Furukawa公司獲得）上，並在80°C下乾燥2小時、200°C下2 小時及35〇°C下一小時，來醯亞胺化，以製備具有厚度25 微米之聚醯亞胺層的撓性銅包覆層壓板。 在實例及比較例中製造的各撓性銅包覆層壓板，根據表 3的方法，對捲曲、濕氣含量、尺寸穩定性、張力性質、 折疊忍受性、抗撓性疲乏及重量平均分子量分析。測量的 結果呈現於表4中。 表3 項目 測量方法 測量設備 捲曲 巨觀觀察 - 濕氣含量 IPC-TM-650, 2.6.2 JEIO TECH 0-25 烘箱，Mattler尺規 尺寸穩定性 IPC-TM-650, 2.2.4 無接觸3維測試機器 (EG40600，由 VIMTEC供應） 張力性質 IPC-TM-650, 2.4.19 UTM (INSTRON4303,由INSTRON供應） 抗撓性疲乏 IPC-TM-650, 2A3 抗撓性疲乏測試 (由Kyungsung測試機公司 (Kyungsung Tester Company)供應） 折疊忍受性 JIS C6471，8.2 折疊忍受測試機 (MIT-D) 重量平均分子量 沖提液： NMP/THF=9G/1()(體積 / 體積) 10毫莫耳濃度LiBr， ίο毫莫耳濃度h3po4 GPC Waters Styragel HR 5E+HR4E 管柱溫度:4(TC，RI偵測器 -16- 104654.doc 1267442 表4Synthesis example diamine (100 mol%) diacid toward F (100 mol%) p-PDA(1) oda(2) tper(3) daba(4) pmda(5) BTDA (6) BPDA (7) 1 - 20 - 80 10 90 • · 2 - 20 - 80 50 50 - 3 . - 20 80 90 10 - 4 - 20 - 80 10 - 90 5 - 20 - 80 50 - 50 6 - 20 - 80 90 - 10 7 - 50 - 50 10 90 - 8 - 50 - 50 50 50 - 9 - 50 - 50 90 10 - 10 - 50 - 50 10 - 90 11 - 50 - 50 50 - 50 12 - 50 - 50 90 - 10 13 - 90 - 10 10 90 - 14 - 90 - 10 50 50 - 15 - 90 - 10 90 10 - 16 - 90 - 10 10 - 90 17 - 90 - 10 50 - 50 18 - 90 - 10 90 - 10 19 - 100 - - 100 - - 20 100 - - - 100 - - 21 - 50 50 - - 100 - 22 - 50 50 - 100 - - 23 - - - 100 - - 100 24 - 100 - - - 100 - 25 - - 100 - 50 50 - 26 100 - - - - 50 50 (Note) (1) p-PDA: p-phenylenediamine (2) 00: 4,4'-diaminophenyl ether (3) TPER ·· 1,3-double (4-Aminophenoxy)benzene (4) DABA : 4-Amino-indole 4-aminophenyl)benzamide (5) PMDA : Pyromellitic dianhydride (6) BTDA : 3,4,3', 4'-diphenyl fluorenone tetracarboxylic acid dianhydride (7) BPDA : 3,4,3', piperidinyl tetracarboxylic acid II Anhydride _ Table 2 C (%) 〇 (%) N (%) H (%) Synthesis Example 1 65.47 23.69 7.41 3.40 Synthesis Example 11 64.96 24.03 7.48 3.49 Synthesis Example 15 63.38 26.35 6.87 3.36 Synthesis Example 20 58.87 29.46 8.58 3.05 Example 1 To 18 104654.doc -14- 1267442 each of the polylysines prepared in Synthesis Examples 1 to 18 was coated on a 12 micron thick copper (commercially available from Furukawa) as an applicator, and Drying at 80 ° C for 2 hours, 200 ° C for 2 hours, and 350 ° C for one hour to brew imidization 'to prepare a flexible copper-clad laminate having a 25 μm thick polyimide layer. Comparative Examples 1 to 8 Each of the polylysines prepared in Synthesis Examples 19 to 26 was coated with an applicator on 12 meters of copper (commercially available from Frukawa Co., Ltd.) at 80 C. It was dried for 2 hours, 2 hours at 200 ° C, and 1 hour at 35 ° C for the imidization to prepare a flexible copper-clad laminate having a polyimide layer having a thickness of 25 μm. Examples 19 to 21 Si/2 pellets (Gasil 35M, supplied by Crossfield) were added to a solid content of polyglycolic acid in an amount of 100 parts by weight to prepare in Synthesis Examples 2, 7, and 15. Each of the polylysines was dispersed in a homogenizer (T25 basic type, supplied by iKA Laboratechnik Co., Ltd.) at 95 rpm for 5 minutes. The prepared solution was thus coated on a 12 micron thick copper (commercially available from Frukawa) and dried at 80 ° C for 2 hours, 2 ° C for 2 hours and 350 ° C for one hour. The imidization was carried out to prepare a flexible copper-polyimine laminate having a layer of polyimide having a thickness of 25 μm. Examples 22 to 24 Add 5 parts by weight of Ti〇2 particles (R700, supplied by DuPont) to 104654.doc -15-1267442 based on 100 parts by weight of the polyglycolic acid solids content. Each of the polylysines prepared in Examples 2, 7 and 15 was synthesized, and dispersed in a homogenizer (T25 basic type, supplied by IKA Laboratechnik Co., Ltd.) at 9,500 rpm for 5 minutes. The prepared solution was thus coated on a 12 micron thick copper (commercially available from Furukawa) and dried at 80 ° C for 2 hours, 200 ° C for 2 hours and 35 ° C for one hour. The oxime is imidized to prepare a flexible copper clad laminate having a layer of polyimide having a thickness of 25 microns. Each of the flexible copper-clad laminates produced in the examples and comparative examples was analyzed for curl, moisture content, dimensional stability, tensile properties, folding endurance, flex fatigue resistance, and weight average molecular weight according to the method of Table 3. . The results of the measurements are presented in Table 4. Table 3 Project Measurement Method Measurement Equipment Curl Giant View - Moisture Content IPC-TM-650, 2.6.2 JEIO TECH 0-25 Oven, Mattler Ruler Dimensional Stability IPC-TM-650, 2.2.4 Contactless 3D Test machine (EG40600, supplied by VIMTEC) Tension properties IPC-TM-650, 2.4.19 UTM (INSTRON4303, supplied by INSTRON) Anti-flexibility fatigue IPC-TM-650, 2A3 Flexibility fatigue test (by Kyungsung Tester) (Kyungsung Tester Company) supply) Folding tolerance JIS C6471, 8.2 Folding Endurance Tester (MIT-D) Weight average molecular weight extract: NMP/THF=9G/1() (vol/vol) 10 millimolar concentration LiBr , ίο millimolar concentration h3po4 GPC Waters Styragel HR 5E+HR4E Column temperature: 4 (TC, RI detector-16-104654.doc 1267442 Table 4

測試 捲曲 濕氣 含量 尺寸禾 1定性 張力性質 抗彎 曲性 抗撓性 疲乏 Mw(3) MD⑴ TD(2) 張力 強度 延長性 張力 係數 - % % % 百萬巴 斯卡 (MPa) % 百萬巴 斯卡 次數 次數 道耳頓 (Dalton) 氺 1 無 0.1 -0.024 -0.025 202.5 21.2 8620 24800 7500 182261 2 無 0.1 -0.025 -0.025 203.4 21.8 8710 24900 7650 161842 3 無 0.2 -0.023 -0.024 204.8 22.4 8790 25100 7710 159233 4 無 0.1 -0.026 -0.026 201.2 20.4 8580 24900 7610 158086 5 無 0.2 -0.025 -0.026 202.9 21.1 8690 25000 7700 167272 6 無 0.2 -0.023 -0.027 203.6 22.1 8760 25200 7730 166473 7 無 0.2 -0.024 -0.026 205.7 23.4 8850 25000 7680 111271 8 無 0.1 -0.025 -0.026 206.4 23.8 8910 25100 7700 122371 9 無 0.2 -0.023 -0.026 207.3 24.6 8980 25300 7740 127048 10 無 0.1 -0.022 -0.024 204.9 23.1 8810 25200 7710 151640 11 無 0.1 -0.024 -0.026 205.6 23.9 8930 25300 7730 157009 12 無 0.1 -0.025 -0.025 206.1 24.2 8960 25500 7760 157060 13 無 0.1 -0.022 -0.025 206.8 24.4 8970 25400 7750 151960 14 無 0.2 -0.025 -0.027 207.5 24.9 9010 25500 7770 126258 15 無 0.2 -0.024 -0.024 208.6 25.2 9040 25700 7780 116549 16 無 0.1 -0.023 -0.026 205.4 23.6 8910 25300 7710 117675 17 無 0.2 -0.026 -0.027 206.5 24.3 8960 25400 7730 108927 18 無 0.2 -0.024 -0.025 207.9 25.1 9020 25500 7740 113019 19 無 0.2 -0.029 -0.031 215.7 26.2 9760 26000 7790 144019 20 無 0.3 -0.028 -0.029 216.8 27.1 9790 25900 7790 121552 21 無 0.3 -0.027 -0.028 218.4 28.1 9850 26100 7800 156454 22 無 0.2 -0.026 -0.029 217.2 27.1 9840 25800 7800 129255 24 無 0.2 -0.028 -0.030 219.2 27.8 9870 26200 7910 115782 25 無 0.3 -0.027 -0.029 220.3 28.4 9920 26100 7880 127669 氺 氺 1 許多 1.2 -0.042 -0.045 185.7 11.5 7810 20800 6590 130685 2 許多 1.4 -0.031 -0.035 190.5 9.6 10360 22100 6820 152295 3 許多 1.1 -0.046 -0.048 167.8 16.4 6890 19800 5840 158680 4 許多 1.0 •0.048 -0.050 154.2 18.2 5960 19900 5950 154389 5 許多 1.4 -0.039 -0.041 174.1 14.6 7520 20400 6730 150235 6 許多 1.1 -0.042 -0.044 170.9 13.2 7450 20100 6570 145803 7 許多 1.2 -0.038 -0.040 192.5 10.2 9860 21800 6390 148899 8 許多 1.3 -0.047 -0.048 160.5 12.7 8560 20500 6230 129255 (註） _ * :實例號碼，-:比較實例號碼，-(1) MD :機械方向 -(2):橫斷方向，-(3)Mw :重量平均分子量_ 104654.doc -17- 1267442 如伙表4中所見’以塗覆從兩個二胺及兩個二酸哥製傷 之聚醯胺酸在銅薄膜上所製造的本發明撓性銅-聚醯亞胺 層壓板，與使用從ODA為二胺及BTDA為二酸針製備之聚 醯胺酸的比較例5、及使用非本發明所用那些之兩個二胺 及兩個二酸酐之的比較例3、6及7的那些比較，其無捲曲 並且在張力性質、折疊忍受性、抗撓性疲乏、具良好濕氣 含1及南尺寸穩定性上為優越的。特別地，如實例19至24 • 中顯示，分散於聚醯亞胺層之無機顆粒的使用大大增進張 力性質、折疊忍受性及抗撓性疲乏。 如上述，具有從ODA及DABA為二胺及PMDA及 — BPDA/BTDA為二酸酐製備之線性無規嵌段聚醯胺酸、塗 覆該溶液在銅上並且醯亞胺化而形成之聚醯亞胺層的撓性 銅-聚醯亞胺層壓板，其無捲曲並且在尺寸穩定性、張力 性質、折疊忍受性及抗撓性疲乏、具低濕氣含量上為優越 的。 藝 當本發明與具體實施例相關聯地被敘述時，為習知此藝 者所了解的是：本發明不限於所揭示的具體實施例，但相 反地，意欲涵蓋各種改變及相當的安排。 104654.doc -18-Test Curl Moisture Content Size He 1 Qualitative Tensile Properties Flexibility Flexibility Fatigue Mw (3) MD(1) TD(2) Tensile Strength Extension Tension Coefficient - % % % Million Baska (MPa) % Millass Number of times of the card Dalton 氺1 No 0.1 -0.024 -0.025 202.5 21.2 8620 24800 7500 182261 2 None 0.1 -0.025 -0.025 203.4 21.8 8710 24900 7650 161842 3 None 0.2 -0.023 -0.024 204.8 22.4 8790 25100 7710 159233 4 None 0.1 -0.026 -0.026 201.2 20.4 8580 24900 7610 158086 5 None 0.2 -0.025 -0.026 202.9 21.1 8690 25000 7700 167272 6 None 0.2 -0.023 -0.027 203.6 22.1 8760 25200 7730 166473 7 None 0.2 -0.024 -0.026 205.7 23.4 8850 25000 7680 111271 8 None 0.1 -0.025 -0.026 206.4 23.8 8910 25100 7700 122371 9 None 0.2 -0.023 -0.026 207.3 24.6 8980 25300 7740 127048 10 None 0.1 -0.022 -0.024 204.9 23.1 8810 25200 7710 151640 11 None 0.1 -0.024 -0.026 205.6 23.9 8930 25300 7730 157009 12 None 0.1 -0.025 -0.025 206.1 24.2 8960 25500 7760 157060 13 None 0.1 -0.022 -0.025 206.8 24.4 8970 25400 7750 151960 14 None 0.2 -0.025 -0.027 207.5 24.9 9010 25500 7770 126258 15 None 0.2 -0.024 -0.024 208.6 25.2 9040 25700 7780 116549 16 None 0.1 -0.023 -0.026 205.4 23.6 8910 25300 7710 117675 17 None 0.2 -0.026 -0.027 206.5 24.3 8960 25400 7730 108927 18 None 0.2 -0.024 -0.025 207.9 25.1 9020 25500 7740 113019 19 None 0.2 -0.029 -0.031 215.7 26.2 9760 26000 7790 144019 20 None 0.3 -0.028 -0.029 216.8 27.1 9790 25900 7790 121552 21 None 0.3 -0.027 -0.028 218.4 28.1 9850 26100 7800 156454 22 None 0.2 -0.026 -0.029 217.2 27.1 9840 25800 7800 129255 24 None 0.2 -0.028 -0.030 219.2 27.8 9870 26200 7910 115782 25 None 0.3 -0.027 -0.029 220.3 28.4 9920 26100 7880 127669 氺氺1 Many 1.2 - 0.042 -0.045 185.7 11.5 7810 20800 6590 130685 2 Many 1.4 -0.031 -0.035 190.5 9.6 10360 22100 6820 152295 3 Many 1.1 -0.046 -0.048 167.8 16.4 6890 19800 5840 158680 4 Many 1.0 •0.048 -0.050 154.2 18.2 5960 19900 5950 154389 5 Many 1.4 -0.039 -0.041 174.1 14.6 7520 20400 6730 150235 6 Many 1.1 -0.042 -0.044 170.9 13.2 7450 20100 6570 145803 7 Many 1.2 -0.038 -0.040 192.5 10.2 9860 21800 6390 148899 8 Many 1.3 -0.047 -0.048 160.5 12.7 8560 20500 6230 129255 (Note) _ * : Example number, -:Comparative example number , -(1) MD : mechanical direction - (2): transverse direction, - (3) Mw : weight average molecular weight _ 104654.doc -17 - 1267442 as seen in Table 4 'to coat from two diamines And the flexible copper-polyimine laminate of the present invention produced on the copper film by two polyacids produced by the diacid, and the polyfluorene prepared by using the diamine from ODA and the diacid needle from BTDA. Comparative Example 5 of the amine acid, and those of Comparative Examples 3, 6 and 7 using two diamines and two dianhydrides other than those used in the present invention, which were free from curl and were in tensile properties, folding endurance, and resistance. It is excellent in flexibility, good moisture content, and south dimensional stability. In particular, as shown in Examples 19 to 24, the use of inorganic particles dispersed in the polyimide layer greatly enhances tensile properties, folding endurance, and resistance to fatigue fatigue. As described above, a linear random block polyaminic acid prepared from ODA and DABA as a diamine and PMDA and - BPDA/BTDA as a dianhydride, coated on the copper and iodized to form a polyfluorene The flexible copper-polyimine laminate of the imine layer is non-crimped and is superior in dimensional stability, tensile properties, folding endurance and resistance to fatigue, and low moisture content. While the present invention has been described in connection with the specific embodiments thereof, it is understood that the invention is not limited to the specific embodiments disclosed, but rather, various modifications and equivalent arrangements are intended. 104654.doc -18-

Claims (1)

1267442 、申請專利範圍： 一種撓性銅-聚醯亞胺層壓板，包括在其至少一面上形成 的線性無規嵌段聚醯亞胺層，該線性無規嵌段聚酿亞胺 層包含0·25至9〇·25莫耳％以下式 —莫耳⑽下式2代表之= 9〇.25莫耳％以下式3代表之重複m _重设早U、〇.25至 %以下式4代表之重複單元〇 ·早7°乃及〇·25至90.25莫耳 式11267442, Patent Application Range: A flexible copper-polyimine laminate comprising a linear random block polyimine layer formed on at least one side thereof, the linear random block polyimine layer comprising 0 · 25 to 9 〇 · 25 mol % of the following formula - Moer (10) The following formula 2 represents = 9 〇. 25 mol % The following formula 3 represents the repetition of m _ reset early U, 〇. 25 to % below Repetitive unit of the representative 〇·7°I and 〇25~90.25 Moer 1 104654.doc 1267442104654.doc 1267442 其中Ar為 y >+、 或 2 ·如晴求項1的撓性鋼-聚 山 取醞亞胺層壓板，其中該線性無規 嵌段聚醯亞胺層包括分散在其中的無機顆粒。 月求員2的撓性銅_聚醯亞胺層壓板’其中該無機顆粒 包括至少-種選自氧化石夕、石英粉末、氧化欽、氧化 紹、錯英石粉末、有機黏土、氧㈣、碳_或氧化辞 之顆粒’該無機·具有OUH)微米之顆粒尺寸。 (-種製造撓性鋼.聚醯亞胺層麼板的方法，該方法包括的 v驟為聚0 一胺及二酸野來製備聚酿胺酸，將該聚醯 胺酸塗覆在銅上，光Θ，往f it且進订醯亞胺化作用，以形成聚醯 亞胺層； 該一胺包括％莫耳％的4,4, 一二胺基苯基鍵及ι〇〇1莫耳％ 的4-胺基_N_(4_胺基苯基）苯醯胺，其中χ滿足 5.0<χ<95.0 ； 口亥一 s文酐包括€莫耳％的苯均四酸二酐及ι〇〇4莫耳％的 3,4,3，4 -聯苯基四羧酸二酐或3,4,3，，4，-二苯甲酮四羧酸 二酐，其中ξ滿足5.0$ξ$95.0 ; 該聚醯亞胺層包含〇·25至9〇·25莫耳％以下式丨代表之重 複單兀/、0.25至90.25莫耳％以下式2代表之重複單元所、 0.25至90·25莫耳％以下式3代表之重複單元"及〇 25至 90.25莫耳％以下式4代表之重複單元〇 : 式1 104654.doc 1267442Wherein Ar is y >+, or 2. A flexible steel-polyamidene laminate such as Clearance 1, wherein the linear random block polyimine layer comprises inorganic particles dispersed therein. The flexible copper-polyimine laminate of the applicant 2, wherein the inorganic particles include at least one selected from the group consisting of oxidized stone, quartz powder, oxidized chin, oxidized sulphur, stray powder, organic clay, oxygen (four), Carbon- or oxidized particles 'this inorganic · has OUH) micron particle size. (a method for producing a flexible steel. Polyimine layer, the method comprising the steps of preparing poly-monoamine and diacid field to prepare poly-brenic acid, and coating the poly-proline to copper Upper, optically, to fi and imidize the imidization to form a polyimine layer; the monoamine includes % mol% of 4,4, monodiaminophenyl bond and ι〇〇1 Mole% of 4-amino-N_(4-aminophenyl)benzoquinone, wherein χ satisfies 5.0 < χ <95.0; 亥 一 s s dianhydride includes € mol% of pyromellitic dianhydride And ι〇〇4 mol% of 3,4,3,4-diphenyltetracarboxylic dianhydride or 3,4,3,,4,-benzophenonetetracarboxylic dianhydride, wherein ξ meets 5.0 $ξ$95.0 ; The polyimine layer contains 〇·25 to 9〇·25 mol% of the following formula 丨 represents a repeating unit 兀, 0.25 to 90.25 mol %, and the repeating unit represented by the following formula 2, 0.25 to 90 · 25 mol% of the repeating unit represented by the following formula 3 " and 〇25 to 90.25 mol%. The repeating unit represented by the following formula 4: Formula 1 104654.doc 1267442 式4Equation 4 5. 如請求項4的方法，其進一步包含的步驟為，在製備聚醯 胺酸及將聚醯胺酸塗覆在銅上的步驟前，將無機顆粒分 散在聚醯胺酸中。 6. 如請求項5的方法，其中該無機顆粒包括至少一種選自 氧化矽、石英粉末、氧化鈦、氧化鋁、锆英石粉末、有 104654.doc 12674425. The method of claim 4, further comprising the step of dispersing the inorganic particles in the polyamic acid prior to the step of preparing the polyamic acid and coating the polylysine on the copper. 6. The method of claim 5, wherein the inorganic particles comprise at least one selected from the group consisting of cerium oxide, quartz powder, titanium oxide, aluminum oxide, zircon powder, having 104654.doc 1267442 機黏土、氧化鎂、碳酸鈣或氧化鋅之顆粒，該無機顆粒 具有0.1至10微米之顆粒尺寸，無機顆粒被分散的份量， 以100重量份數之聚醯胺酸總固體含量計，為0.001至10 重量份數。 104654.doca particle of machine clay, magnesia, calcium carbonate or zinc oxide having a particle size of 0.1 to 10 μm and a fraction of the inorganic particles dispersed in an amount of 0.001 based on 100 parts by weight of the total solid content of polyamic acid Up to 10 parts by weight. 104654.doc
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