JP2004098659A - Copper-clad laminate and its manufacturing process - Google Patents

Copper-clad laminate and its manufacturing process Download PDF

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JP2004098659A
JP2004098659A JP2003197909A JP2003197909A JP2004098659A JP 2004098659 A JP2004098659 A JP 2004098659A JP 2003197909 A JP2003197909 A JP 2003197909A JP 2003197909 A JP2003197909 A JP 2003197909A JP 2004098659 A JP2004098659 A JP 2004098659A
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copper
clad laminate
film
polyimide
heat
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Toshihiko Abu
Koji Narui
Noriyuki Yamamoto
山本 宣之
阿武 俊彦
鳴井 耕治
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Ube Ind Ltd
宇部興産株式会社
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Abstract

PROBLEM TO BE SOLVED: To provide a copper-clad laminate suitable for a base material of all polyimide which solves the problems of being low in adhesive strength inherent in copper-clad laminates for base material and the poor transparency of the remaining polyimide film after an etched copper foil is removed.
SOLUTION: The copper-clad laminate is formed by laminating a polyimide film and a copper foil low in degree of coarseness or a copper layer and has a light transmission rate of not less than 40% at a wavelength of 600nm on the film in either case after the etching of the copper film or after the etching of the copper layer, with haze of not more than 30%, and an adhesive strength of not less than 500N/m. The laminate has an adhesive strength of not less than 285N/m after heat treatment at 150°C for 1,000 hours.
COPYRIGHT: (C)2004,JPO

Description

【0001】 [0001]
【発明の属する技術分野】 BACKGROUND OF THE INVENTION
この発明は、銅張積層板及びその製造方法に関するものであり、さらに詳しくはポリイミドフィルムと銅箔との接着強度および銅箔をエッチング除去後の残部のポリイミドフィルムの透明性が実用可能なレベルにあり、基板材料として好適な銅張積層板及びその製造方法に関するものである。 This invention relates to copper-clad laminate and a manufacturing method thereof, and more particularly to the practical level transparency polyimide film of the remainder after adhesion strength and the copper foil removed by etching the polyimide film and the copper foil There is one of the preferred copper-clad laminate and a manufacturing method thereof as a substrate material.
【0002】 [0002]
【従来の技術】 BACKGROUND OF THE INVENTION
カメラ、パソコン、液晶ディスプレイなどの電子機器類への用途として芳香族ポリイミドフィルムは広く使用されている。 Camera, a personal computer, an aromatic polyimide film is widely used as application to electronic devices such as liquid crystal displays.
芳香族ポリイミドフィルムをフレキシブルプリント板(FPC)やテ−プ・オ−トメイティッド・ボンディング(TAB)などの基板材料として使用するためには、エポキシ樹脂などの接着剤を用いて銅箔を張り合わせる方法が採用されている。 The flexible printed circuit board of an aromatic polyimide film (FPC) Yate - flop au - for use as a substrate material, such as Tomei Incorporated bonding (TAB) is pasted copper foil using an adhesive such as an epoxy resin methods have been employed.
【0003】 [0003]
芳香族ポリイミドフィルムは耐熱性、機械的強度、電気的特性などが優れているが、接着剤の耐熱性等が劣るため、本来のポリイミドの特性を損なうことが指摘されている。 Aromatic polyimide film heat resistance, mechanical strength and the like have excellent electrical properties, for heat resistance of the adhesive is deteriorated, it is pointed out that impair the characteristics of the original polyimide.
このような問題を解決するために、接着剤を使用しないでポリイミドフィルムに銅を電気メッキしたり、銅箔にポリアミック酸溶液を塗布し、乾燥、イミド化したり、熱可塑性ポリイミドを熱圧着させたオ−ルポリイミド基材が開発されている。 To solve such a problem, or electroplating copper on a polyimide film without using an adhesive, the polyamic acid solution was applied to a copper foil, dried, or imidization, the thermoplastic polyimide was thermocompression Oh - Le polyimide substrate has been developed.
しかし、これらの方法によって得られるオ−ルポリイミドの金属箔積層体は、接着強度が小さいとか、接着強度は大きいが広幅、長尺の製品を得ることが困難であり、塗工厚みが厚い場合にイミド化に長時間を要し生産性が悪いという問題点が指摘されている。 However, these OH obtained by the method - a metal foil laminate Le polyimide Toka adhesive strength is small, the adhesive strength is large but it is difficult to obtain wide, a product of long, if the coating thickness is thick productivity takes a long time to imidization has been pointed out a problem that bad.
【0004】 [0004]
また、ポリイミドフィルムと金属箔との間にポリイミド接着剤をサンドイッチ状に接合したポリイミドラミネ−トが知られている(米国特許第4543295号)。 Polyimide La Mine bonding the polyimide adhesive sandwiched between the polyimide film and metal foil - bets are known (U.S. Pat. No. 4,543,295).
しかし、このポリイミドラミネ−トでは、低熱線膨張のビフェニルテトラカルボン酸系ポリイミドフィルムについては接着強度が小さく使用できないという問題がある。 However, the polyimide La Mine - The bets, the biphenyltetracarboxylic acid type polyimide film of low thermal linear expansion has a problem that the adhesive strength can not be used less.
【0005】 [0005]
このため、ロ−ルラミネ−ト法においてラミネ−トロ−ルの材質として特定の硬度を有する金属を使用する方法や、熱圧着性のポリイミドとして特定の芳香族ジアミンによって得られたものを使用する方法が提案されている。 Therefore, Russia - Ruramine - lamination In preparative methods - Toro - how to use and how to use a metal having a specific hardness as Le material of, those obtained by the particular aromatic diamine as a heat-bondable polyimide There has been proposed.
しかし、このポリイミドラミネ−トおよびその製法においては、接着強度の大きい銅張積層板を得るために表面粗度の大きい銅箔を使用する必要がある。 However, the polyimide La Mine - In bets and their preparation, it is necessary to use a large copper surface roughness in order to obtain a large copper-clad laminate bond strength. そして、この表面粗度の大きい銅箔の使用は、銅箔をエッチング除去後の残部のポリイミドフィルムに銅箔の表面粗さが転写されるため、透明性不良の原因となる。 The use of large copper foil of the surface roughness, the surface roughness of the copper foil is transferred to the copper foil to the polyimide film of the remainder of the post-etched and removed, causing transparency poor.
【0006】 [0006]
このため、蒸着またはスパッタ法によってあらかじめポリイミドフィルムに下地金属層を形成し銅メッキによって所定の厚さの銅メッキして得られる積層板が提案されているが、得られる銅張積層板は接着強度が小さいとか後工程の加熱時に剥離するという問題が指摘されている。 Therefore, although the laminated board obtained by copper plating of a predetermined thickness by the formed copper plating a base metal layer in advance polyimide film by vapor deposition or sputtering method has been proposed, it is obtained copper-clad laminate bond strength It has been pointed out a problem that peeling at the time of heating in the subsequent step Toka small.
【0007】 [0007]
【発明が解決しようとする課題】 [Problems that the Invention is to Solve
この発明の目的は、従来公知の基板用の銅張積層板では不可能であった接着強度が小さいこと及び銅箔をエッチング除去後の残部のポリイミドフィルムの透明性不良の問題点を解消した、基板材料として好適な銅張積層板を提供することである。 The purpose of this invention was that the adhesive strength was not possible with copper-clad laminates for conventional substrate is small and the copper foil to solve the transparency defect of the polyimide film of the remainder after etching removal, to provide a suitable copper-clad laminate as a substrate material.
【0008】 [0008]
【課題を解決するための手段】 In order to solve the problems]
すなわち、この発明は、ポリイミドフィルムと低粗度銅箔とが積層されてなり、銅箔エッチング後のフィルムの波長600nmでの光透過率が40%以上、曇価(HAZE)が30%以下であって、接着強度(T剥離強度、以下同じ)が500N/m以上である銅張積層板に関する。 That is, the present invention is made in the polyimide film and tiara degree copper foil is laminated, the light transmittance at a wavelength 600nm of the film after the copper foil etching is 40% or more, haze (HAZE) is not more than 30% there are, adhesive strength (T peel strength, the same applies hereinafter) relating to a copper-clad laminate is the 500 N / m or more.
【0009】 [0009]
また、この発明は、熱圧着性の芳香族ポリイミド層および高耐熱性の芳香族ポリイミド層からなる熱圧着性多層ポリイミドフィルムと接着性改良処理された低粗度銅箔とを加圧下に熱圧着性の芳香族ポリイミドのガラス転移温度以上で400℃以下の温度で熱圧着して積層する請求項1に記載の銅張積層板の製造方法に関する。 Further, the present invention is thermocompression bonding and low roughness copper foils adhesion improving treatment and thermocompression bonding of the aromatic polyimide layer and thermocompression-bonding multilayer polyimide film made of a high heat-resistant aromatic polyimide layer under pressure It relates to a method for producing a copper-clad laminate according to claim 1 for laminating by thermal compression bonding with sexual aromatic 400 ° C. below the temperature at or above the glass transition temperature of the polyimide.
さらに、この発明は、ポリイミドフィルムと銅層とが積層されてなり、銅層エッチング後のフィルムの波長600nmでの光透過率が40%以上、曇価(HAZE)が30%以下であって、接着強度が500N/m以上であり、150℃で1000時間の熱処理後の接着強度が285N/m以上である銅張積層板に関する。 Furthermore, the invention comprises is laminated with the polyimide film and the copper layer, the light transmittance at a wavelength 600nm of the film after the copper layer etched 40% or more, haze (HAZE) is 30% or less, adhesive strength is at 500 N / m or more, about copper-clad laminate bond strength after heat treatment for 1000 hours at 0.99 ° C. is 285N / m or more.
【0010】 [0010]
【発明の実施の形態】 DETAILED DESCRIPTION OF THE INVENTION
以下にこの発明の好ましい態様を列記ずる。 Hereinafter cunning lists the preferred embodiments of the invention.
1) ポリイミドフィルムが、熱圧着性多層ポリイミドフィルムである上記の銅張積層板。 1) a polyimide film is heat-bondable above copper-clad laminate is a multilayered polyimide film.
2)熱圧着性多層ポリイミドフィルムが、共押出−流延製膜成形法によって高耐熱性の芳香族ポリイミド層の少なくとも片面に熱圧着性の芳香族ポリイミド層を積層一体化して得られるものである上記の銅張積層板。 2) is thermocompression-bonding multilayer polyimide films, coextruded - is obtained by a least thermally bondable aromatic polyimide layer on one surface of the casting film forming method by a high heat-resistant aromatic polyimide layer integrally laminated the above copper-clad laminate.
3)150℃で1000時間の熱処理後の接着強度が285N/m以上である上記の銅張積層板。 3) The above copper-clad laminate is 150 adhesive strength after heat treatment for 1000 hours at ℃ is 285N / m or more.
4)150℃で1000時間の熱処理後でも接着強度を80%以上保持している上記の銅張積層板。 4) 0.99 ° C. The adhesive strength even after heat treatment for 1000 hours and held at least 80% in it has the above copper-clad laminate.
【0011】 [0011]
5)熱圧着が、ダブルベルトプレスによって加圧下に、熱圧着性の芳香族ポリイミドのガラス転移温度以上で400℃以下の温度で熱圧着後に冷却することによって行われる上記の銅張積層板の製造方法。 5) thermocompression bonding, under pressure by a double-belt press, the production of copper-clad laminate of the performed by cooling after thermocompression bonding at a temperature of 400 ° C. or less in the heat-bondable than the glass transition temperature of the aromatic polyimide Method.
6)接着性改良処理された低粗度銅箔が、有機処理剤による接着性改良処理されたものである上記の銅張積層板の製造方法。 6) low roughness copper foil bonded improving treatment, the above-described method for producing a copper-clad laminate in which is an adhesion improving treatment with an organic treatment agent.
7)接着性改良処理された低粗度銅箔が、1.0μm以下の表面粗さ:Rzおよび、TD(ロ−ル方向と垂直方向)310%以上、MD(ロ−ル方向)360%以上の光沢度(入射角60°)を有するものである上記の銅張積層板の製造方法。 7) low roughness copper foil bonded improving treatment, 1.0 .mu.m or less of surface roughness: Rz and, TD (B - Le and vertical) 310% or more, MD (b - Le direction) 360% production method of the above glossiness above copper-clad laminate and has a (angle of incidence 60 °).
【0012】 [0012]
この発明の銅張積層板は、好適には熱圧着性の芳香族ポリイミド層および高耐熱性の芳香族ポリイミド層からなる熱圧着性多層ポリイミドフィルムと接着性改良処理された低粗度銅箔とを加圧下に熱圧着性の芳香族ポリイミドのガラス転移温度以上で400℃以下の温度で熱圧着して積層することによって得ることができる。 CCL of this invention, preferably a low roughness copper foils adhesion improving treatment and thermocompression-bonding multilayer polyimide film comprising a heat-bondable aromatic polyimide layer and the high heat-resistant aromatic polyimide layer can be obtained by laminating by thermal compression bonding at 400 ° C. temperature below the glass transition temperature or more aromatic polyimide of the heat-bondable under pressure.
【0013】 [0013]
前記の接着性改良処理された低粗度銅箔としては、粗化処理が施された粗化処理面に接着性改良処理されたものが好ましい。 The low roughness copper foils adhesion improving treatment of said, it is preferable that roughening treatment is an adhesion improving treatment roughened surface which has been subjected. 粗化処理の一例としてはベ−ス銅箔の表面に酸化処理を施すことによって酸化被膜を形成するいわゆる黒化処理あるいは銅あるいはクロムなどのメッキ処理が挙げられる。 An example of roughening treatment base - scan plating such as so-called blackening process or a copper or chromium to form an oxide film by the oxidation treatment be applied to the surface of the copper foil and the like.
従って、銅箔または銅層とは、銅以外の金属を含むもの意味し、主として銅からなるものを意味する。 Thus, a copper foil or copper layer, means those containing a metal other than copper is one which mainly made of copper.
また、前記の接着性改良処理された低粗度銅箔としては、粗化処理面に更に有機処理剤による接着性改良処理が施されたものが好ましい。 As the low roughness copper foils adhesion improving treatment of said, it is preferable that an adhesion improving treatment further by organic treatment agent roughened surface is subjected. 前記の有機処理剤としてはシランカップリング処理剤などが挙げられる。 The organic treatment agent of the like silane coupling treatment agent.
【0014】 [0014]
前記の接着性改良処理された低粗度銅箔としては、1.0μm以下の表面粗さ:Rzおよび、TD(ロ−ル方向と垂直方向)310%以上、MD(ロ−ル方向)360%以上の光沢度(入射角60°)を有するものが好適である。 The low roughness copper foils adhesion improving treatment of the, 1.0 .mu.m or less of surface roughness: Rz and, TD (B - Le and vertical) 310% or more, MD (b - Le direction) 360 having% or more glossiness (incident angle 60 °) is preferred. また、前記の接着性改良処理された低粗度銅箔は厚みが5〜18μm、特に9〜12μmであるものがファインパタ−ン化の要求への対応が可能であり好適である。 Further, the low roughness copper foil bonded improving processing of thickness 5~18Myuemu, particularly those which are 9~12μm is fine pattern - are suitable are possible corresponding to the emission reduction requirements. 前記の銅箔が前記の表面粗さおよび光沢度であると、得られる銅張積層板から銅をエッチング除去したポリイミドフィルムの透明性が良好であり好適である。 When the copper foil of the is in surface roughness and glossiness of the transparency of the polyimide film of copper from the resulting copper clad laminate was removed by etching is preferably is good.
【0015】 [0015]
前記の接着性改良処理された低粗度銅箔の具体例としては、三井金属工業社製の低粗度銅箔(有機処理有り、厚み12μm、マット面表面粗さRz0.8μm、マット面光沢度TD319%、MD374%)、古河サ−キットフォイル社製の低粗度銅箔(有機処理有り、厚み12μm、マット面表面粗さRz0.7μm、マット面光沢度TD370%、MD393%)、日本電解社製の低粗度銅箔(有機処理有り、厚み12μm、マット面表面粗さRz0.8μm、マット面光沢度TD370%、MD393%)が挙げられる。 Specific examples of the above adhesion improving treated low roughness copper foil is Mitsui Kinzoku There low roughness foil (organic treatment Industries, Ltd., thickness 12 [mu] m, matte surface roughness Rz0.8Myuemu, matte surface gloss degrees TD319%, MD374%), Kogasa - Yes low roughness copper foil (organic treatment kit foil Co., thickness 12 [mu] m, matte surface roughness Rz0.7Myuemu, matte surface gloss TD370%, MD393%), Japan (There organic treatment, thickness 12 [mu] m, matte surface roughness Rz0.8Myuemu, matte surface gloss TD370%, MD393%) low roughness copper foil manufactured by the electrolytic Corporation and the like.
【0016】 [0016]
前記の熱圧着性多層ポリイミドフィルムは、例えば高耐熱性の芳香族ポリイミドの前駆体(ポリアミック酸ともいう)溶液乾燥膜の片面あるいは両面に熱圧着性の芳香族ポリイミドの前駆体溶液を積層した後、あるいは好ましくは、共押出し−流延製膜法によって高耐熱性の芳香族ポリイミドの前駆体溶液の片面あるいは両面に熱圧着性の芳香族ポリイミドの前駆体溶液を積層した後、乾燥、イミド化して熱圧着性多層ポリイミドフィルムを得る方法によって得ることができる。 After thermocompression-bonding multilayer polyimide film of the can by laminating, for example, highly heat-resistant aromatic polyimide precursor (also referred to as a polyamic acid) of the thermocompression-bonding of aromatic polyimide on one side or both sides of the solution dry film precursor solution , or preferably, coextrusion - after laminating the precursor solution of a heat-bondable aromatic polyimide on one side or both sides of the precursor solution of the highly heat-resistant aromatic polyimide by casting film forming method, drying, imidizing thermocompression-bonding multilayer polyimide film Te can be obtained by the method of obtaining.
【0017】 [0017]
前記の熱圧着性多層ポリイミドフィルムを構成する熱圧着性の芳香族ポリイミドとしては、300〜400℃程度の温度で熱圧着できる熱可塑性の芳香族ポリイミドであれば何でも良い。 The thermocompression bonding of the aromatic polyimide constituting the thermocompression-bonding multilayer polyimide film of the may be any thermoplastic aromatic polyimide can be thermocompression bonding at a temperature of about 300 to 400 ° C.. 好適には1,3−ビス(4−アミノフェノキシベンゼン)(以下、TPERと略記することもある。)と2,3,3',4'−ビフェニルテトラカルボン酸二無水物(以下、a−BPDAと略記することもある。)と3,3',4,4'−ビフェニルテトラカルボン酸二無水物(以下、s−BPDAと略記することもある。)とから製造される。 Preferably 1,3-bis (4-aminophenoxy benzene) (hereinafter, sometimes abbreviated as TPER.) And 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (hereinafter, a- sometimes abbreviated as BPDA.) and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (hereinafter, sometimes abbreviated as s-BPDA.) it is produced from the.
また、前記の熱圧着性の芳香族ポリイミドとしては、1,3−ビス(4−アミノフェノキシ)−2,2−ジメチルプロパン(DANPG)と4,4'−オキシジフタル酸二無水物(ODPA)とから製造される。 As examples of the thermocompression bonding of the aromatic polyimide of 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane (DANPG) and 4,4'-oxydiphthalic dianhydride (ODPA) It is produced from.
あるいは、4,4'−オキシジフタル酸二無水物(ODPA)およびピロメリット酸二無水物と1,3−ビス(4−アミノフェノキシベンゼン)とから製造される。 Or it is produced from 4,4'-oxydiphthalic dianhydride (ODPA) and pyromellitic acid dianhydride and 1,3-bis (the 4-aminophenoxy benzene).
また、1,3−ビス(3−アミノフェノキシ)ベンゼンと3,3',4,4'−ベンゾフェノンテトラカルボン酸二無水物とから、あるいは3,3'−ジアミノベンゾフェノンおよび1,3−ビス(3−アミノフェノキシ)ベンゼンと3,3',4,4'−ベンゾフェノンテトラカルボン酸二無水物とから製造される。 Further, 1,3-bis (3-aminophenoxy) benzene and 3,3 ', and a 4,4'-benzophenonetetracarboxylic acid dianhydride, or 3,3'-benzophenone and 1,3-bis ( 3-aminophenoxy) benzene and 3,3 ', is prepared from 4,4'-benzophenone tetracarboxylic dianhydride.
【0018】 [0018]
この熱圧着性の芳香族ポリイミドの物性を損なわない範囲で他のテトラカルボン酸二無水物、例えば3,3',4,4'−ビフェニルテトラカルボン酸二無水物、2,2−ビス(3、4−ジカルボキシフェニル)プロパン二無水物などで置き換えられてもよい。 Other tetracarboxylic dianhydrides within a range not to impair the physical properties of the heat-bondable aromatic polyimide, for example 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2-bis (3 , it may be replaced by such 4-dicarboxyphenyl) propane dianhydride.
また、熱圧着性の芳香族ポリイミドの物性を損なわない範囲で他のジアミン、例えば4,4'−ジアミノジフェニルエ−テル、4,4'−ジアミノベンゾフェノン、4,4'−ジアミノジフェニルメタン、2,2−ビス(4−アミノフェニル)プロパン、1,4−ビス(4−アミノフェノキシ)ベンゼン、4,4'−ビス(4−アミノフェニル)ジフェニルエ−テル、4,4'−ビス(4−アミノフェニル)ジフェニルメタン、4,4'−ビス(4−アミノフェノキシ)ジフェニルエ−テル、4,4'−ビス(4−アミノフェノキシ)ジフェニルメタン、2,2−ビス〔4−(アミノフェノキシ)フェニル〕プロパンなどの複数のベンゼン環を有する芳香族ジアミン、によって置き換えられてもよい。 Also, other diamines within a range not to impair the physical properties of the thermo-compression bonding of an aromatic polyimide, for example, 4,4'-diaminodiphenyl et - ether, 4,4'-diaminodiphenyl, 4,4'-diaminodiphenylmethane, 2, 2- bis (4-aminophenyl) propane, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenyl) diphenyl ether - ether, 4,4'-bis (4- aminophenyl) methane, 4,4'-bis (4-aminophenoxy) diphenyl ether - ether, 4,4'-bis (4-aminophenoxy) diphenylmethane, 2,2-bis [4- (aminophenoxy) phenyl] aromatic diamines having a plurality of benzene rings, such as propane, may be replaced by.
前記の熱圧着性の芳香族ポリイミドのアミン末端を封止するためにジカルボン酸類、例えば、フタル酸およびその置換体、ヘキサヒドロフタル酸およびその置換体など、特に、無水フタル酸を使用してもよい。 Dicarboxylic acids in order to seal the amine terminus of the thermocompression bonding of aromatic polyimide, for example, phthalic acid and derivatives thereof, such as hexahydrophthalic acid and its substitution products, in particular, be used phthalic anhydride good.
【0019】 [0019]
前記の熱圧着性多層ポリイミドフィルムにおける高耐熱性の芳香族ポリイミドは、好適には3,3',4,4'−ビフェニルテトラカルボン酸二無水物(以下単にs−BPDAと略記することもある。)とパラ−フェニレンジアミン(以下単にPPDと略記することもある。)と場合によりさらに4,4'−ジアミノジフェニルエ−テル(以下単にDADEと略記することもある。)および/またはピロメリット酸二無水物(以下単にPMDAと略記することもある。)とから製造される。 Highly heat-resistant aromatic polyimide in the heat bondable multilayer polyimide film of the may suitably is 3,3 ', 4,4'-biphenyl tetracarboxylic acid dianhydride (also abbreviated as s-BPDA or less .) and para -. phenylenediamine (hereinafter sometimes abbreviated as PPD) optionally further 4,4'-diaminodiphenyl d and -. sometimes abbreviated as ether (hereinafter simply DADE) and / or pyromellitic acid dianhydride (hereinafter, sometimes abbreviated as PMDA.) it is produced from the. この場合PPD/DADE(モル比)は100/0〜85/15であることが好ましい。 It is preferred in this case PPD / DADE (molar ratio) is 100 / 0-85 / 15. また、s−BPDA/PMDAは100:0〜50/50であることが好ましい。 Further, s-BPDA / PMDA is 100: is preferably 0-50 / 50.
【0020】 [0020]
また、高耐熱性の芳香族ポリイミドは、ピロメリット酸二無水物とパラフェニレンジアミンおよび4,4'−ジアミノジフェニルエ−テルとから製造される。 Further, highly heat-resistant aromatic polyimide are pyromellitic dianhydride and p-phenylenediamine and 4,4'-diaminodiphenyl et - is prepared from ether. この場合DADE/PPD(モル比)は90/10〜10/90であることが好ましい。 In this case DADE / PPD (molar ratio) is preferably 90 / 10-10 / 90.
さらに、高耐熱性の芳香族ポリイミドは、3,3',4,4'−ベンゾフェノンテトラカルボン酸二無水物(BTDA)およびピロメリット酸二無水物(PMDA)とパラフェニレンジアミン(PPD)および4,4'−ジアミノジフェニルエ−テル(DADE)とから製造される。 Furthermore, highly heat-resistant aromatic polyimide, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA) and pyromellitic dianhydride (PMDA) and paraphenylene diamine (PPD) and 4 , 4'-diamino diphenyl ether - is produced from the ether (DADE). この場合、酸二無水物中BTDAが20〜90モル%、PMDAが10〜80モル%、ジアミン中PPDが30〜90モル%、DADEが10〜70モル%であることが好ましい。 In this case, the acid dianhydride in BTDA 20 to 90 mol%, PMDA is 10 to 80 mol%, the diamine in PPD 30 to 90 mol%, it is preferable DADE is 10 to 70 mol%.
前記の高耐熱性の芳香族ポリイミドの物性を損なわない範囲で、他の種類の芳香族テトラカルボン酸二無水物や芳香族ジアミン、例えば4,4'−ジアミノジフェニルメタン等を使用してもよい。 Within a range not to impair the physical properties of the highly heat-resistant aromatic polyimide of the other types of aromatic tetracarboxylic acid dianhydrides and aromatic diamines, for example 4,4'-diaminodiphenylmethane and the like may be used.
また、前記の芳香族テトラカルボン酸二無水物や芳香族ジアミンの芳香環にフッ素基、水酸基、メチル基あるいはメトキシ基などの置換基を導入してもよい。 Further, the aromatic tetracarboxylic dianhydride and aromatic fluorine group of the aromatic diamine, a hydroxyl group, substituent groups may be introduced, such as a methyl group or a methoxy group.
【0021】 [0021]
前記の高耐熱性の芳香族ポリイミドとしては、単層のポリイミドフィルムの場合にガラス転移温度が約340℃未満程度の温度では確認不可能であるものが好ましく、特に線膨張係数(50〜200℃)(MD、TDおよびこれらの平均のいずれも)が5×10 −6 〜25×10 −6 cm/cm/℃であるものが好ましい。 The highly heat-resistant aromatic polyimide of the, preferably those which are not confirmed in the temperature of the glass transition temperature of about less than about 340 ° C. In the case of a polyimide film of a single layer, in particular a linear expansion coefficient (50 to 200 ° C. ) (MD, TD and none of the average of these) of the is is preferable 5 × 10 -6 ~25 × 10 -6 cm / cm / ℃. この高耐熱性の芳香族ポリイミドの合成は、最終的に各成分の割合が前記範囲内であればランダム重合、ブロック重合、ブレンド、あるいはあらかじめ2種類以上のポリアミック酸溶液を合成しておき各ポリアミック酸溶液を混合してポリアミック酸の再結合によって共重合体を得る、いずれの方法によっても達成される。 The synthesis of the highly heat-resistant aromatic polyimide, if the ratio of the final components is within the above range random polymerization, block polymerization, blending or each leave synthesized in advance two or more polyamic acid solution polyamic, obtaining a copolymer by the recombination of the polyamic acid by mixing an acid solution, it is also achieved by any method.
【0022】 [0022]
前記のポリアミック酸を得るために使用する有機溶媒は、高耐熱性の芳香族ポリイミドおよび熱圧着性の芳香族ポリイミドのいずれに対しても、N−メチル−2−ピロリドン、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N,N−ジエチルアセトアミド、ジメチルスルホキシド、ヘキサメチルホスホルアミド、N−メチルカプロラクタム、クレゾ−ル類などが挙げられる。 The organic solvent used to obtain the polyamic acid of above, for any highly heat-resistant aromatic polyimide and thermocompression bonding of the aromatic polyimide, N- methyl-2-pyrrolidone, N, N- dimethylformamide , N, N- dimethylacetamide, N, N- diethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, N- methyl caprolactam, cresol - such as Le acids and the like. これらの有機溶媒は単独で用いてもよく、2種以上を併用してもよい。 These organic solvents may be used alone or in combination of two or more thereof.
【0023】 [0023]
また、ポリアミック酸のゲル化を制限する目的でリン系安定剤、例えば亜リン酸トリフェニル、リン酸トリフェニル等をポリアミック酸重合時に固形分(ポリマ−)濃度に対して0.01〜1%の範囲で添加することができる。 Also, phosphorus-based stabilizer for the purpose of limiting gelation of the polyamic acid, for example triphenyl phosphite, solid triphenyl phosphate or the like during the polyamic acid polymerization (polymer -) 0.01% to 1% relative to the concentration it can be added in the range of. また、イミド化促進の目的で、ド−プ液中に塩基性有機化合物系触媒を添加することができる。 Further, for the purpose to promote imidization, de - a basic organic compound catalyst can be added to the flop solution. 例えば、イミダゾ−ル、2−イミダゾ−ル、1,2−ジメチルイミダゾ−ル、2−フェニルイミダゾ−ルなどをポリアミック酸(固形分)に対して0.01〜20重量%、特に0.5〜10重量%の割合で使用することができる。 For example, imidazo - Le, 2-imidazo - le, 1,2-dimethylimidazolidinone - methylphenol, 2-phenyl-imidazo - 0.01 to 20% by weight relative to the Le such a polyamic acid (solids), in particular 0.5 it can be used in a proportion of 10% by weight. これらは比較的低温でポリイミドフィルムを形成するため、イミド化が不十分となることを避けるために使用する。 These relatively to form a polyimide film at a low temperature, is used to avoid insufficient imidization.
【0024】 [0024]
前記の熱圧着性多層ポリイミドフィルムの製造においては、好適には共押出し−流延製膜法、例えば上記の高耐熱性の芳香族ポリイミドを与えるポリアミック酸溶液の片面あるいは両面に熱圧着性の芳香族ポリイミドを与えるポリアミック酸溶液を共押出して、これをステンレス鏡面、ベルト面等の支持体面上に流延塗布し、100〜200℃で半硬化状態またはそれ以前の乾燥状態とする方法が採用できる。 In the production of thermal bondable multilayer polyimide film of the is preferably coextrusion - casting film forming method, such as the above-mentioned highly heat-resistant thermal bondable aromatic on one side or both sides of the polyamic acid solution to give an aromatic polyimide the polyamic acid solution which gives a family polyimide coextruding, which stainless steel mirror was cast coated on a support surface of the belt surface or the like, can process for a semi-cured state or a dried state before the adoption at 100 to 200 ° C. . 200℃を越えた高い温度で流延フィルムを処理すると、熱圧着性多層ポリイミドフィルムの製造において、接着性の低下などの欠陥を来す傾向にある。 Treatment of cast film at a high temperature in excess of 200 ° C., in the production of thermal bondable multilayer polyimide film tends to cause defects such as a decrease in adhesiveness. この半硬化状態またはそれ以前の状態とは、加熱および/または化学イミド化によって自己支持性の状態にあることを意味する。 The semi-cured state or the state before the means in a self-supporting state by heating and / or chemical imidization.
【0025】 [0025]
前記高耐熱性の芳香族ポリイミドを与えるポリアミック酸の溶液と熱圧着性の芳香族ポリイミドを与えるポリアミック酸の溶液との共押出しは、例えば特開平3−180343号公報(特公平7−102661号公報)に記載の共押出法によって二層あるいは三層の押出し成形用ダイスに供給し、支持体上にキャストしておこなうことができる。 Coextrusion, for example, JP-A 3-180343 JP (Kokoku Patent Publication No. H07-102661 of a solution of the polyamic acid to give the high heat resistance of the solution and heat bondable aromatic polyimide of the polyamic acid to give an aromatic polyimide ) by co-extrusion method according to supplied to an extrusion die for two-layer or three-layer, can be carried out by casting onto a support.
前記の高耐熱性の芳香族ポリイミドを与える押出し物層の片面あるいは両面に、熱圧着性の芳香族ポリイミドを与えるポリアミック酸溶液を積層して多層フィルム状物を形成して乾燥後、熱圧着性の芳香族ポリイミドのガラス転移温度(Tg)以上で劣化が生じる温度以下の温度、好適には300〜500℃の温度(表面温度計で測定した表面温度)まで加熱して(好適にはこの温度で1〜60分間加熱して)乾燥およびイミド化して、高耐熱性(基体層)の芳香族奥ポリイミドの片面あるいは両面に熱圧着性の芳香族ポリイミドを有する熱圧着性多層ポリイミドフィルムを製造することができる。 On one side or both sides of the extrudate layer that provides a highly heat-resistant aromatic polyimide of the after a polyamic acid solution which gives a heat-bondable aromatic polyimide laminated dried to form a multilayered film material, heat bondable aromatic glass transition temperature (Tg) of more than deteriorates temperature below the temperature of polyimide, preferably by heating to (surface temperature measured by surface thermometer) temperature of 300 to 500 ° C. (preferably at this temperature in heated 1 to 60 minutes) with drying and imidization, to produce a heat-bondable multilayer polyimide film having high heat resistance (aromatic thermocompression bonding of aromatic polyimide on one side or both sides of the inner polyimide substrate layer) be able to.
【0026】 [0026]
前記の熱圧着性多層ポリイミドを構成する熱圧着性の芳香族ポリイミドは、前記の酸成分とジアミン成分とを使用することによって、ガラス転移温度が180〜275℃、特に200〜275℃であって、好適には前記の条件で乾燥・イミド化して熱圧着性の芳香族ポリイミドのゲル化を実質的に起こさせないことによって得られる、ガラス転移温度以上で300℃以下の範囲内の温度で液状化せず、かつ弾性率が、通常275℃での弾性率が室温付近の温度(50℃)での弾性率の0.0002〜0.2倍程度を保持しているものが好ましい。 Thermocompression bonding of the aromatic polyimide constituting the heat bondable multilayer polyimide, by using the above-mentioned acid component and the diamine component, the glass transition temperature of 180-275 ° C., in particular two hundred to two hundred and seventy-five ° C. , preferably obtained by not substantially cause gelation of an aromatic polyimide of the heat-bondable drying and imidization above conditions, liquid at temperatures in the range of 300 ° C. at a temperature above the glass transition temperature without and elastic modulus, which elastic modulus at ordinary 275 ° C. holds a 0.0002 to 0.2 times the modulus at temperatures near room temperature (50 ° C.) are preferred.
【0027】 [0027]
前記の熱圧着性多層ポリイミドを構成する熱圧着性の芳香族ポリイミド層の厚みは各々0.5〜10μm、特に1〜8μm程度が好ましい。 The thickness of the heat-bondable aromatic polyimide layer constituting the heat bondable multilayer polyimide each 0.5 to 10 [mu] m, particularly about 1~8μm are preferred. 0.5μm未満では接着性能が低下し、10μmを超えても使用可能であるが特に効果はなく、むしろ銅張積層板の耐熱性が低下する。 If it is less than 0.5μm reduces the bonding performance, no particular but can be used even exceed 10μm effect, heat resistance of the copper clad laminate is reduced rather.
また、前記の熱圧着性多層ポリイミドを構成する高耐熱性の(基体層)ポリイミド層の厚さは5〜50μm、特に5〜40μmであることが好ましい。 Further, high heat resistance (base layer) thickness of the polyimide layer constituting the heat bondable multilayer polyimide 5 to 50 [mu] m, it is particularly preferably 5 to 40 m. 5μm未満では作成した熱圧着性多層ポリイミドフィルムの機械的強度、寸法安定性に問題が生じる。 The mechanical strength of the thermocompression-bonding multilayer polyimide film prepared, a problem in dimensional stability occurring at less than 5 [mu] m.
また、熱圧着性多層ポリイミドフィルムは厚みが7〜50μm、特に7〜約40μmであることが好ましい。 The heat-bonding multilayer polyimide film has a thickness 7~50Myuemu, it is particularly preferably 7 to about 40 [mu] m. 7μm未満では作成したフィルムの取り扱いが難しく、50μmより厚くなるとファインパタ−ン化に不利である。 Difficult to handle the created film is less than 7 [mu] m, is thicker than 50μm when the fine pattern - which is disadvantageous for emissions reduction.
【0028】 [0028]
前記の共押出し−流延製膜法によれば、高耐熱性の芳香族ポリイミド層とその片面あるいは両面の熱圧着性の芳香族ポリイミドとを比較的低温度でキュアして熱圧着性の芳香族ポリイミドの劣化を来すことなく、自己支持性フィルムのイミド化、乾燥を完了させることができ、良好な電気特性および接着強度を有する熱圧着性多層ポリイミドフィルムを得ることができる。 Coextrusion of the - according to the casting film forming method, highly heat-resistant aromatic polyimide layer and cured to thermocompression bonding of the aroma and its one side or both sides of the heat-bondable aromatic polyimide at a relatively low temperature without causing the deterioration of the family polyimide imidization of self-supporting film, it is possible to complete the drying, it is possible to obtain a heat-bondable multilayer polyimide film having good electrical properties and adhesive strength.
前記の熱圧着性多層ポリイミドフィルムは、熱線膨張係数(50〜200℃)(MD、TDの平均)が10×10 −6 〜25×10 −6 cm/cm/℃であるものが好ましい。 Thermocompression-bonding multilayer polyimide film of said linear thermal expansion coefficient (50~200 ℃) (MD, average TD) are those preferably 10 × 10 -6 ~25 × 10 -6 cm / cm / ℃.
【0029】 [0029]
この発明の方法においては、前記の熱圧着性多層ポリイミドフィルムと接着性改良処理された低粗度銅箔とを加圧下に熱圧着性の芳香族ポリイミドのガラス転移温度以上で400℃以下の温度で熱圧着して積層することによって、ポリイミドフィルムと銅箔との接着強度および銅箔をエッチング除去後の残部のポリイミドフィルムの透明性が実用可能なレベルにあり、基板材料として好適な銅張積層板を得ることができる。 In the method of the present invention, the thermocompression bonding multilayer polyimide film and the adhesive improving treatment, low roughness copper foil and a temperature of 400 ° C. or less at or above the glass transition temperature of the aromatic polyimide of the thermocompression-bonding under pressure in by laminating by thermal compression bonding, there the adhesive strength and the copper foil with the polyimide film and copper foil transparency practical level of the polyimide film of the remainder after etching removal, suitable copper-clad laminate as a substrate material it is possible to obtain a plate.
【0030】 [0030]
前記の方法において、熱圧着性多層ポリイミドフィルムと接着性改良処理された低粗度銅箔とをダブルベルトプレスに導入し、好適には導入する直前のインラインで150〜250℃程度に予熱して、加圧下に高温加熱−冷却して積層一体化して、銅張積層板を得ることが好ましい。 In the above method, and a low roughness copper foils adhesion improving treatment and thermocompression-bonding multilayer polyimide film was introduced into a double belt press, preferably preheated to approximately 150 to 250 ° C. immediately before the line to be introduced , elevated temperature under pressure heating - laminated integrally by cooling, it is preferable to obtain a copper-clad laminate.
【0031】 [0031]
また、ダブルベルトプレスの加熱圧着ゾ−ンの温度が熱圧着性の芳香族ポリイミドのガラス転移温度より20℃以上高く400℃以下の温度、特にガラス転移温度より30℃以上高く400℃以下の温度で加圧下に熱圧着し、引き続いて冷却ゾ−ンで加圧下に冷却して、好適には熱圧着性ポリイミドのガラス転移温度より20℃以上低い温度、特に30℃以上低い温度まで冷却して、銅張積層板を得ることが好ましい。 Furthermore, thermocompression bonding zone of the double belt press - down of temperature thermocompression bonding of aromatic glass transition temperature of from 20 ° C. or higher high 400 ° C. below the temperature of the polyimide, the following temperature particularly high 400 ° C. 30 ° C. or higher than the glass transition temperature in under pressure in thermocompression bonding, followed by cooling zone - was cooled under pressure in emissions, preferably a glass transition temperature below 20 ° C. or more lower temperature of the heat-bondable polyimide, in particular cooled down to low temperature 30 ° C. or higher it is preferable to obtain a copper-clad laminate.
【0032】 [0032]
前記の方法において、3層構造の熱圧着性多層ポリイミドフィルムを使用して接着性改良処理された低粗度銅箔1層と積層する場合には、剥離容易な高耐熱性フィルム、例えばRzが1.0μm未満の高耐熱性フィルム、好適にはポリイミドフィルム(宇部興産社製、ユ−ピレックスS)やフッ素樹脂フィルムなどの高耐熱性樹脂フィルムや圧延銅箔などであって表面粗さが小さく表面平滑性の良好な金属箔を保護材として、巻き取り時に熱圧着性ポリイミド層と他の耐熱性キャリア付き極薄銅箔の耐熱性キャリア面との間に介在させてもよい。 In the above method, when using a heat-bondable multilayer polyimide film having a three-layer structure laminated with the adhesion improving treated low roughness foil one layer, easy-peeling highly heat-resistant film, for example, Rz is high heat-resistant film of less than 1.0 .mu.m, preferably a polyimide film (manufactured by Ube Industries, Ltd., Yu - Pirekkusu S) or fluororesin film highly heat-resistant resin film and a rolled copper foil and the like surface roughness, such as small the surface smoothness of the good metal foil as a protective material may be interposed between the heat-bondable polyimide layer and another heat resistant refractory carrier surface of the carrier with ultra-thin copper foil during winding. この保護材は積層後、積層体から除いて巻き取っても良く、保護材を積層したままで巻き取って使用時に取り除いてもよい。 After the protective material laminated, may be wound up except a laminate may be removed during use and wound while stacking a protective material.
【0033】 [0033]
前記の方法において、接着性改良処理された低粗度銅箔と熱圧着性多層ポリイミドフィルムとを好適にはダブルベルトプレスによって加圧下に、熱圧着性の芳香族ポリイミドのガラス転移温度以上で400℃以下の温度で熱圧着−冷却して積層することによって、銅箔エッチング後のフィルムの波長600nmでの光透過率が40%以上、曇価(HAZE)が30%以下であって、接着強度が500N/m以上である銅張積層板を得ることができる。 In the above method, at the pressure preferably by double belt press a low roughness copper foil is an adhesion improving treatment and the thermocompression-bonding multilayer polyimide film, the thermocompression bonding of the aromatic polyimide glass transition temperature or higher 400 ℃ thermocompression bonding at a temperature below - by laminating and cooling, the light transmittance at a wavelength 600nm of the film after the copper foil etching is 40% or more, haze (hAZE) is not more than 30%, the adhesive strength There can be obtained a copper-clad laminate is 500 N / m or more.
また、前記の方法によれば、ポリイミドフィルムと銅層とが積層されてなり、銅層エッチング後のフィルムの波長600nmでの光透過率が40%以上、曇価(HAZE)が30%以下であって、接着強度が500N/m以上であり、150℃で1000時間の熱処理後の接着強度が285N/m以上、好適には400N/m以上である銅張積層板を得ることができる。 Further, according to the aforementioned method, it is laminated with the polyimide film and the copper layer, the light transmittance at a wavelength 600nm of the film after the copper layer etched 40% or more, haze (HAZE) is not more than 30% there are, it is the adhesive strength is 500 N / m or more, can be adhesion strength after heat treatment for 1000 hours at 0.99 ° C. is 285N / m or more, preferably to obtain a copper-clad laminate is 400 N / m or more.
この発明の銅張積層板には、長尺状のものだけでなく前記のように長尺状のものを所定の大きさに切断したものも含まれる。 The copper-clad laminate of the invention also include those taken as the not only elongated ones elongated to a predetermined size.
【0034】 [0034]
この発明の銅張積層板は、そのままあるいはロ−ル巻き、エッチング、および場合によりカ−ル戻し等の各処理を行った後、必要ならば所定の大きさに切断して、電子部品用基板として使用できる。 CCL of this invention, as such or b - Le winding, mosquitoes by etching, and if - after Le returns the processing such as, and cut into a predetermined size, if necessary, a substrate for electronic components It can be used as.
例えば、FPC、TAB、多層FPC、フレックスリジッド基板の基板として好適に使用することができる。 For example, it FPC, TAB, multilayer FPC, be suitably used as a substrate for flex-rigid substrate.
【0035】 [0035]
また、片面銅箔積層体から、エポキシ系接着剤あるいは熱可塑性ポリイミドや熱可塑性ポリアミドイミドあるいはポリイミドシロキサン−エポキシ系などの耐熱性ポリイミド系接着剤から選ばれる耐熱性接着剤(厚み5〜50μm、好ましくは5〜15μm、特に7〜12μm)で複数の銅箔積層体を接着することによって銅箔積層体が2〜10層で、高耐熱性・低吸水・低誘電率・高電気特性を満足する多層基板を好適に得ることができる。 Further, the single-sided copper foil laminate, epoxy adhesive or a thermoplastic polyimide, thermoplastic polyamide-imide or polyimide siloxane - heat-resistant adhesive agent selected from heat-resistant polyimide adhesive such as an epoxy (thickness 5 to 50 [mu] m, preferably is 5 to 15 [mu] m, a copper foil laminate in 2-10 layers, to satisfy the high heat resistance, low water absorption, low dielectric constant and high electrical characteristics particularly by bonding a plurality of copper foil laminate 7~12Myuemu) it is possible to obtain a multilayer substrate suitably.
【0036】 [0036]
この発明の銅張積層板には、耐熱性キャリアを剥離してそれ自体公知のエッチング工程および加熱工程の逐次処理を加えて、回路基板として使用される。 The copper-clad laminate of the invention, in addition to sequential processing known per se to peeling off the heat-resistant carrier etching step and the heating step, is used as a circuit board.
前記のエッチング工程としては、例えば銅張積層板の銅箔を常温で塩化第二鉄水溶液などのエッチング処理液によってエッチング処理する方法が挙げられる。 As the etching process, a method of etching by etching solution, such as aqueous ferric chloride for example a copper foil of the copper-clad laminate at room temperature. また、前記の加熱工程としては、例えば耐熱性キャリアを剥離した銅張積層板を280℃の半田浴に10秒間程度浸漬する半田処理や、他の銅張積層板と耐熱性接着剤によって積層して多層基板とする加熱圧着が挙げられる。 Further, as the heating step, for example, soldering or immersing about 10 seconds in a solder bath at a copper-clad laminate was peeled heat-resistant carrier 280 ° C., layered with other copper-clad laminate and heat-resistant adhesive It includes thermocompression bonding a multilayer substrate Te.
【0037】 [0037]
この発明の銅張積層板は、銅箔とポリイミドフィルムとの接着強度が大きくしかも銅箔をエッチング除去後のポリイミドフィルムの透明性が良好であり、従来のボンディングマシンによるTAB実装が可能である。 CCL of this invention, the transparency of the polyimide film after the adhesive strength is increased moreover the copper foil removed by etching the copper foil and the polyimide film is good, it is possible TAB mounting by conventional bonding machine.
【0038】 [0038]
【実施例】 【Example】
以下、この発明を実施例によりさらに詳細に説明する。 It will now be described in detail with the invention examples.
以下の各例において、物性評価は以下の方法に従って行った。 In the examples, evaluations of physical properties were carried out according to the following methods.
表面粗さ(Rz):JIS B0601に従って測定した。 Surface roughness (Rz): measured in accordance with JIS B0601.
光沢度:JIS Z8741に従って測定した。 Gloss was measured in accordance with JIS Z8741. 平均値を表示する。 To display the average value.
熱線膨張係数:TMA法、50−200℃平均、昇温速度5℃/分で測定(TD、MDの平均値)、cm/cm/℃ Coefficient of linear thermal expansion: TMA method, 50-200 ° C. The average Atsushi Nobori rate of 5 ° C. / measured in minutes (TD, the average value of MD), cm / cm / ℃
ガラス転移温度(Tg):動的粘弾装置を用い、損失正接ピ−ク温度よりより測定。 Glass transition temperature (Tg): Using a dynamic viscoelasticity device, loss tangent peak - more measurements than peak temperature.
【0039】 [0039]
接着強度:銅張積層板から切り取った10mm幅の試料について、図1に示すT剥離治具を用い、JIS C6471に記載された方法により、MD方向、クロスヘッド速度50mm/分にてT剥離強度を測定した。 Bonding strength: Samples of 10mm width were cut from the copper-clad laminate, using a T-peel jig shown in FIG. 1, according to the method described in JIS C6471, MD direction, T peel strength at a crosshead speed of 50 mm / min It was measured.
光透過率:フィルムまたは積層板の場合は銅箔を全面エッチング後のフィルムを使用して、光透過法により波長600nmで試料面に対して90°入射での透過率を、島津製作所社製のUV−2100型にて測定した。 Light transmittance: The case of a film or laminate using the film after etching the entire surface of the copper foil, the transmission at 90 ° incidence to the sample surface at a wavelength 600nm by light transmission method, manufactured by Shimadzu Corporation It was measured by a UV-2100 type.
【0040】 [0040]
曇度(HAZE):フィルムまたは銅箔を全面エッチング後のフィルムを使用して、JIS−K6714に従って、スガ試験機、直流ヘッドコンピュ−タ−、HGM−2DPにて測定した。 Haze (HAZE): a film or a copper foil using a film after etching the entire surface, in accordance with JIS-K6714, manufactured by Suga Test Instruments, DC head computer - data - was measured by HGM-2DP.
曇度(HAZE)=(Td/Tt)×100% Haze (HAZE) = (Td / Tt) × 100%
Td:散乱光透過率、Tt:全光線透過率【0041】 Td: scattered light transmittance, Tt: total light transmittance [0041]
アライメントマ−ク視認性:銅箔を全面エッチング後のフィルムを使用して、実装時のアライメントマ−ク視認性を新川社製インナ−リ−ドボンダ−ILT−110を用いてデモ用パタ−ンの視認性を目視評価し、視認可能なものを可能、視認不可能なものを不可能と各々表示する。 Alignment mark - click visibility: a copper foil using a film after etching the entire surface, at the time of mounting alignment mark - click visibility Shinkawa Corporation inner - Li - demonstration pattern with Dobonda -ILT-110 - down the visibility was visually evaluated, allow those visible to impossible with each display what invisible.
150℃加熱処理後の接着強度:JIS C6471に記載された方法により、150℃の空気循環式恒温槽内に1000時間置いた試料について、クロスヘッド速度50mm/分にてT剥離強度を測定し、常態での測定値と比較した。 Adhesion strength after 0.99 ° C. heat treatment: By the method described in JIS C6471, for 1000 hours at a sample to 0.99 ° C. air circulation type thermostatic oven, measuring the T-peel strength at a crosshead speed of 50 mm / min, It was compared with the measured values ​​in the normal state.
総合評価:以下の4ランクで表示する。 Overall rating: to display the following four ranks.
◎:秀、○:良、△:やや不良、×:不良【0042】 ◎: Xiu, ○: good, △: Slightly poor, ×: poor [0042]
高耐熱性の芳香族ポリイミド製造用ド−プの合成例1 Highly heat-resistant aromatic polyimide prepared for de - Synthesis of flops Example 1
攪拌機、窒素導入管を備えた反応容器に、N−メチル−2−ピロリドンを加え、さらに、パラフェニレンジアミンと3,3',4,4'−ビフェニルテトラカルボン酸二無水物とを1000:998のモル比でモノマ−濃度が18%(重量%、以下同じ)になるように加えた。 Stirrer, a reaction vessel equipped with a nitrogen inlet tube, N- methyl-2-pyrrolidone was added, further, p-phenylenediamine and 3,3 ', and 4,4'-biphenyltetracarboxylic dianhydride 1000: 998 monomer in a molar ratio - concentration of 18% (wt%, hereinafter the same) was added to a. 添加終了後50℃を保ったまま3時間反応を続けた。 Adding was continued for 3 hours while maintaining 50 ° C. After completion. 得られたポリアミック酸溶液は褐色粘調液体であり、25℃における溶液粘度は約1500ポイズであった。 The resulting polyamic acid solution was a brown viscous liquid, a solution viscosity at 25 ° C. was about 1500 poise. この溶液をド−プとして使用した。 It was used as a flop - This solution soil.
【0043】 [0043]
熱圧着性の芳香族ポリイミド製造用ド−プの合成攪拌機、窒素導入管を備えた反応容器に、N−メチル−2−ピロリドンを加え、さらに、1,3−ビス(4−アミノフェノキシ)ベンゼンと2,3,3',4'−ビフェニルテトラカルボン酸二無水物と3,3',4,4'−ビフェニルテトラカルボン酸二無水物とを100:20:80のモル比でモノマ−濃度が18%になるように、またトリフェニルホスフェ−トをモノマ−重量に対して0.1%加えた。 Thermocompression bonding of the aromatic polyimide prepared for de - Synthesis stirrer flops, into a reaction vessel equipped with a nitrogen inlet tube, N- methyl-2-pyrrolidone was added, further, 1,3-bis (4-aminophenoxy) benzene When 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride and 3,3', 4,4'-biphenyltetracarboxylic dianhydride and 100: 20: 80 monomer in a molar ratio of - concentration There so that 18%, also triphenyl Fe - plus 0.1% by weight - bets monomer. 添加終了後25℃を保ったまま1時間反応を続けた。 Added while maintaining 25 ° C. After completion was continued for 1 hour. このポリアミック酸溶液は、25℃における溶液粘度が約1100ポイズであった。 The polyamic acid solution, a solution viscosity at 25 ° C. was about 1100 poise. この溶液をド−プとして使用した。 It was used as a flop - This solution soil.
【0044】 [0044]
参考例1 Reference Example 1
上記の高耐熱性の芳香族ポリイミド用ド−プと熱圧着性の芳香族ポリイミド製造用ド−プとを三層押出し成形用ダイス(マルチマニホ−ルド型ダイス)を設けた製膜装置を使用し、ダイスの厚みを変え、金属製支持体上に流延し、140℃の熱風で連続的に乾燥し、固化フィルムを形成した。 The above highly heat-resistant aromatic polyimide for de - using film forming apparatus provided with - (field-die Maruchimaniho) - flops and thermocompression bonding of the aromatic polyimide prepared for de-flop and a three-layer extrusion die , changing the thickness of the die was cast on a metal support, continuously dried with hot air at 140 ° C., to form a solid film. この固化フィルムを支持体から剥離した後加熱炉で200℃から320℃まで徐々に昇温して溶媒の除去、イミド化を行って、次の二種類の熱圧着性三層押出しポリイミドフィルムを巻き取りロ−ルに巻き取った。 The solidified film was gradually heated from 200 ° C. to 320 ° C. in a heating furnace after peeling from the support removal of the solvent, performing imidization, winding the following two types of heat-bondable three layer extruded polyimide film It was wound up in Le - take Russia.
この熱圧着性三層押出しポリイミドフィルムは、次のような物性を示した。 The heat-bondable three layer extruded polyimide film exhibited the following physical properties.
【0045】 [0045]
1)熱圧着性多層ポリイミドフィルムA 1) thermocompression-bonding multilayer polyimide film A
厚み構成:5μm/28μm/5μm(合計38μm) Thickness configuration: 5μm / 28μm / 5μm (total 38μm)
薄層の熱圧着性の芳香族ポリイミドのTg:240℃ Thermocompression bonding of the aromatic polyimide thin layer Tg: 240 ° C.
コア層の高耐熱性の芳香族ポリイミドのTg:340℃以上光透過率(波長600nm):57% Of highly heat-resistant aromatic polyimide core layer Tg: 340 ° C. or higher light transmittance (wavelength 600 nm): 57%
HAZE:6% HAZE: 6%
熱線膨張係数(50〜200℃):18×10 −6 ×cm/cm/℃ Coefficient of linear thermal expansion (50~200 ℃): 18 × 10 -6 × cm / cm / ℃
体積抵抗:3×10 16 Ω・cm Volume resistivity: 3 × 10 16 Ω · cm
【0046】 [0046]
2)熱圧着性多層ポリイミドフィルムB 2) thermocompression-bonding multilayer polyimide film B
厚み構成:4μm/17μm/4μm(合計25μm) Thickness configuration: 4μm / 17μm / 4μm (total 25μm)
薄層の熱圧着性の芳香族ポリイミドのTg:240℃ Thermocompression bonding of the aromatic polyimide thin layer Tg: 240 ° C.
コア層の高耐熱性の芳香族ポリイミドのTg:340℃以上光透過率(波長600nm):69% Of highly heat-resistant aromatic polyimide core layer Tg: 340 ° C. or higher light transmittance (wavelength 600 nm): 69%
HAZE:4% HAZE: 4%
熱線膨張係数(50〜200℃):18×10 −6 ×cm/cm/℃ Coefficient of linear thermal expansion (50~200 ℃): 18 × 10 -6 × cm / cm / ℃
体積抵抗:3×10 16 Ω・cm Volume resistivity: 3 × 10 16 Ω · cm
【0047】 [0047]
実施例1 Example 1
熱圧着性三層押出しポリイミドフィルムAと三井金属工業社製の低粗度銅箔(有機処理有り、厚み12μm、マット面表面粗さRz0.8μm、マット面光沢度TD319%、MD374%)と保護材(ユ−ピレックス25S)とを、ダブルベルトプレスに連続的に供給し、予熱後、加熱ゾ−ンの温度(最高加熱温度)330℃(設定)、冷却ゾ−ンの温度(最低冷却温度)117℃)、圧着圧力40kg/cm 、圧着時間2分で、連続的に加圧下に熱圧着−冷却して積層し、銅張積層板(幅:約530mm、以下同じ)であるロ−ル巻状物を得た。 (There organic treatment, thickness 12 [mu] m, matte surface roughness Rz0.8Myuemu, matte surface gloss TD319%, MD374%) low roughness foil made of heat-bondable three layer extruded polyimide film A and Mitsui Mining Industry Co. and protection Material - the (Yu Pirekkusu 25S) and was continuously fed into a double belt press, after preheating, heating zone - down temperature (maximum heating temperature) 330 ° C. (setting), the cooling zone - down temperature (minimum cooling temperature ) 117 ° C.), crimping pressure 40 kg / cm 2, pressure bonding time 2 minutes, thermocompression bonding continuously under pressure - laminated cooled, copper-clad laminate (width: about 530mm, hereinafter the same) b - was obtained Le wound like material.
【0048】 [0048]
得られた銅張積層板についての評価結果を次に示す。 Following the evaluation results of the obtained copper-clad laminate.
接着強度:1290N/m Adhesive strength: 1290N / m
光透過率(波長600nm):44% Light transmittance (wavelength 600 nm): 44%
HAZE:27% HAZE: 27%
アライメントマ−ク視認性:可能150℃×1000時間加熱処理後の接着強度保持率:94% Alignment mark - click visibility: it allows 0.99 ° C. × 1000 hours of heat treatment after the bonding strength retention rate: 94%
総合評価:◎ Overall Evaluation: ◎
【0049】 [0049]
実施例2 Example 2
銅箔として日本電解社性の低粗度銅箔(有機処理有り、厚み12μm、マット面表面粗さRz0.8μm、マット面光沢度TD370%、MD393%)を使用した他は実施例1と同様にして、銅張積層板(幅:約530mm、以下同じ)であるロ−ル巻状物を得た。 Nippon electrolytic Inc. of (with organic treatment, thickness 12 [mu] m, matte surface roughness Rz0.8Myuemu, matte surface gloss TD370%, MD393%) low roughness foil as foil other using the same manner as in Example 1 a manner, copper-clad laminate (width: about 530mm, hereinafter the same) is a b - was obtained Le wound like material.
得られた銅張積層板についての評価結果を次に示す。 Following the evaluation results of the obtained copper-clad laminate.
接着強度:710N/m Adhesive strength: 710N / m
光透過率(波長600nm):43% Light transmittance (wavelength 600 nm): 43%
HAZE:28% HAZE: 28%
アライメントマ−ク視認性:可能150℃×1000時間加熱処理後の接着強度保持率:82% Alignment mark - click visibility: it allows 0.99 ° C. × 1000 hours of heat treatment after the bonding strength retention rate: 82%
総合評価:◎ Overall Evaluation: ◎
【0050】 [0050]
実施例3 Example 3
銅箔として古河サ−キットフォイル社製の低粗度銅箔(有機処理有り、厚み12μm、マット面表面粗さRz0.7μm、マット面光沢度TD370%、MD393%)を使用した他は実施例1と同様にして、銅張積層板(幅:約530mm、以下同じ)であるロ−ル巻状物を得た。 Furukawa service as copper - (with organic treatment, thickness 12 [mu] m, matte surface roughness Rz0.7Myuemu, matte surface gloss TD370%, MD393%) kit Foil Co. of low roughness foil other using the embodiment 1 were used to give a copper-clad laminate (width: about 530mm, hereinafter the same) is a b - was obtained Le wound like material.
得られた銅張積層板についての評価結果を次に示す。 Following the evaluation results of the obtained copper-clad laminate.
接着強度:540N/m Adhesive strength: 540N / m
光透過率(波長600nm):48% Light transmittance (wavelength 600 nm): 48%
HAZE:20% HAZE: 20%
アライメントマ−ク視認性:可能150℃×1000時間加熱処理後の接着強度保持率:64% Alignment mark - click visibility: it allows 0.99 ° C. × 1000 hours of heat treatment after the bonding strength retention rate: 64%
総合評価:○ Overall rating: ○
【0051】 [0051]
実施例4 Example 4
熱圧着性三層押出しポリイミドフィルムBと三井金属工業社製の低粗度銅箔(NA−VLP、有機処理有り、厚み12μm、マット面表面粗さRz0.6μm、マット面光沢度TD339%、MD410%)とを使用した他は実施例1と同様にして、銅張積層板(幅:約530mm、以下同じ)であるロ−ル巻状物を得た。 Thermocompression-bonding a three-layer extruded polyimide film B and Mitsui Kinzoku Kogyo low roughness copper foil (NA-VLP, there organically treated, thickness 12 [mu] m, matte surface roughness Rz0.6Myuemu, matte surface gloss TD339%, MD410 %) of the other using the same manner as in example 1, a copper-clad laminate (width: about 530mm, hereinafter the same) is a b - was obtained Le wound like material.
得られた銅張積層板についての評価結果を次に示す。 Following the evaluation results of the obtained copper-clad laminate.
接着強度:610N/m Adhesive strength: 610N / m
光透過率(波長600nm):54% Light transmittance (wavelength 600 nm): 54%
HAZE:22% HAZE: 22%
アライメントマ−ク視認性:可能150℃×1000時間加熱処理後の接着強度保持率:106% Alignment mark - click visibility: it allows 0.99 ° C. × 1000 hours of heat treatment after the bonding strength retention rate: 6%
総合評価:◎ Overall Evaluation: ◎
【0052】 [0052]
実施例5 Example 5
銅箔として日本電解社性の低粗度銅箔(HLS、有機処理有り、厚み9μm、マット面表面粗さRz0.8μm、マット面光沢度TD339%、MD410%)を使用した他は実施例1と同様にして、銅張積層板(幅:約530mm、以下同じ)であるロ−ル巻状物を得た。 Nippon electrolytic Corporation of low roughness foil as foil (HLS, there organically treated, thickness 9 .mu.m, matte surface roughness Rz0.8Myuemu, matte surface gloss TD339%, MD410%) Other embodiments using 1 in the same manner as, copper-clad laminate (width: about 530mm, hereinafter the same) is a b - was obtained Le wound like material.
得られた銅張積層板についての評価結果を次に示す。 Following the evaluation results of the obtained copper-clad laminate.
接着強度:816N/m Adhesive strength: 816N / m
光透過率(波長600nm):43% Light transmittance (wavelength 600 nm): 43%
HAZE:28% HAZE: 28%
アライメントマ−ク視認性:可能150℃×1000時間加熱処理後の接着強度保持率:77% Alignment mark - click visibility: it allows 0.99 ° C. × 1000 hours of heat treatment after the bonding strength retention rate: 77%
総合評価:◎ Overall Evaluation: ◎
【0053】 [0053]
実施例6 Example 6
銅箔として古河サ−キットフォイル社製の低粗度銅箔(F0−WS、有機処理有り、厚み12μm、マット面表面粗さRz0.7μm、マット面表面TD392%、MD403%)を使用した他は実施例4と同様にして、銅張積層板(幅:約530mm、以下同じ)であるロ−ル巻状物を得た。 Furukawa service as copper - Kits Foil Co. low roughness copper foil (F0-WS, there organically treated, thickness 12 [mu] m, matte surface roughness Rz0.7Myuemu, matte surface TD392%, MD403%) other Using in the same manner as in example 4, copper clad laminate (width: about 530mm, hereinafter the same) is a b - was obtained Le wound like material.
得られた銅張積層板についての評価結果を次に示す。 Following the evaluation results of the obtained copper-clad laminate.
接着強度:560N/m Adhesive strength: 560N / m
光透過率(波長600nm):61% Light transmittance (wavelength 600 nm): 61%
HAZE:14% HAZE: 14%
アライメントマ−ク視認性:可能150℃×1000時間加熱処理後の接着強度保持率:67% Alignment mark - click visibility: it allows 0.99 ° C. × 1000 hours of heat treatment after the bonding strength retention rate: 67%
総合評価:○ Overall rating: ○
【0054】 [0054]
比較例1 Comparative Example 1
銅箔として三井金属鉱業社製の銅箔(有機処理有り、厚み9μm、表面粗さRz2.0μm)を使用した他は実施例1と同様にして、銅張積層板(幅:約530mm、以下同じ)であるロ−ル巻状物を得た。 (There organic treatment, thickness 9 .mu.m, the surface roughness Rz2.0Myuemu) Mitsui Mining & Smelting Co., Ltd. of the copper foil as the copper foil other using in the same manner as in Example 1, a copper-clad laminate (width: about 530mm, or less b is the same) - was obtained Le wound like material.
得られた銅張積層板についての評価結果を次に示す。 Following the evaluation results of the obtained copper-clad laminate.
接着強度:780N/m Adhesive strength: 780N / m
光透過率(波長600nm):10% Light transmittance (wavelength 600 nm): 10%
HAZE:76% HAZE: 76%
アライメントマ−ク視認性:不可能総合評価:× Alignment mark - click visibility: Impossible Overall rating: ×
【0055】 [0055]
比較例2 Comparative Example 2
銅箔として古河サ−キットフォイル社製の銅箔(有機処理有り、厚み9μm、表面粗さRz1.9μm)を使用した他は実施例1と同様にして、銅張積層板(幅:約530mm、以下同じ)であるロ−ル巻状物を得た。 Furukawa service as copper - (with organic treatment, thickness 9 .mu.m, the surface roughness Rz1.9Myuemu) kit Foil Co. copper foil other using in the same manner as in Example 1, a copper-clad laminate (width: about 530mm a hereinafter) b - was obtained Le wound like material.
得られた銅張積層板についての評価結果を次に示す。 Following the evaluation results of the obtained copper-clad laminate.
接着強度:740N/m Adhesive strength: 740N / m
光透過率(波長600nm):10% Light transmittance (wavelength 600 nm): 10%
HAZE:76% HAZE: 76%
アライメントマ−ク視認性:不可能総合評価:× Alignment mark - click visibility: Impossible Overall rating: ×
【0056】 [0056]
比較例3 Comparative Example 3
新日鐵化学社製の銅張積層板であるエスパネックス(SC12−25−00AE)について同様に測定した。 Was measured similarly for Espanex (SC12-25-00AE) is manufactured by Nippon Steel Chemical Co., Ltd. of copper-clad laminate.
得られた結果を次に示す。 Following the results obtained.
光透過率(波長600nm):2% Light transmittance (wavelength 600 nm): 2%
アライメントマ−ク視認性:不可能総合評価:× Alignment mark - click visibility: Impossible Overall rating: ×
【0057】 [0057]
【発明の効果】 【Effect of the invention】
この発明によれば、以上のような構成を有しているため、次のような効果を奏する。 According to the present invention, since it has a structure as described above, the following effects can be obtained.
この発明によれば、ポリイミドフィルムと低粗度銅箔との接着強度(常態)が十分大きく、銅箔エッチング後のポリイミドフィルムの透明性が良好な銅張積層板を得ることができる。 According to the present invention, the adhesive strength between the polyimide film and the tiara of copper foil (normal) is sufficiently large, it is possible transparency of the polyimide film after the copper foil etching to obtain a good copper-clad laminate.
特に、この発明によれば、実装時のアライメントマ−ク視認性も十分可能である。 In particular, according to the present invention, during mounting of the alignment mark - click visibility is sufficiently possible.
また、この発明によれば、上記の銅張積層板を容易に得ることができる。 Further, according to the present invention, it is possible to easily obtain the above copper-clad laminate.
【図面の簡単な説明】 BRIEF DESCRIPTION OF THE DRAWINGS
【図1】図1は、T剥離強度測定のための試料取り付け方法を示す概略図である。 [1] Figure 1 is a schematic diagram illustrating a sample method of mounting for T peel strength measurement.
【符号の説明】 DESCRIPTION OF SYMBOLS
1 T型剥離治具2 銅箔3 ポリイミドフィルム4 クランプ4' クランプ 1 T-peel jig 2 copper foil 3 polyimide film 4 clamp 4 'Clamp

Claims (10)

  1. ポリイミドフィルムと低粗度銅箔とが積層されてなり、銅箔エッチング後のフィルムの波長600nmでの光透過率が40%以上、曇価(HAZE)が30%以下であって、接着強度が500N/m以上である銅張積層板。 Will be a polyimide film and a tiara of copper foil is laminated, the light transmittance at a wavelength 600nm of the film after the copper foil etching is 40% or more, haze (HAZE) is not more than 30%, the adhesive strength 500 N / m or more at a copper-clad laminate.
  2. ポリイミドフィルムが、熱圧着性多層ポリイミドフィルムである請求項1に記載の銅張積層板。 Polyimide film, copper-clad laminate according to claim 1 which is heat-bondable multilayer polyimide film.
  3. 熱圧着性多層ポリイミドフィルムが、共押出−流延製膜成形法によって高耐熱性の芳香族ポリイミド層の少なくとも片面に熱圧着性の芳香族ポリイミド層を積層一体化して得られるものである請求項2に記載の銅張積層板。 Claim in which the thermocompression bonding aromatic polyimide layer on at least one surface of the casting film forming method by a high heat-resistant aromatic polyimide layer obtained by laminating and integrating - thermocompression-bonding multilayer polyimide film, co-extruded copper-clad laminate according to 2.
  4. 150℃で1000時間の熱処理後の接着強度が285N/m以上である請求項1に記載の銅張積層板。 Copper-clad laminate according to claim 1 adhesion strength after heat treatment for 1000 hours at 0.99 ° C. is 285N / m or more.
  5. 150℃で1000時間の熱処理後でも接着強度を80%以上保持している請求項1に記載の銅張積層板。 Copper-clad laminate according to claim 1, the adhesion strength even after heat treatment for 1000 hours at 0.99 ° C. retains 80% or more.
  6. 熱圧着性の芳香族ポリイミド層および高耐熱性の芳香族ポリイミド層からなる熱圧着性多層ポリイミドフィルムと接着性改良処理された低粗度銅箔とを加圧下に熱圧着性の芳香族ポリイミドのガラス転移温度以上で400℃以下の温度で熱圧着して積層する請求項1に記載の銅張積層板の製造方法。 Thermocompression bonding of the aromatic polyimide layer and the high heat resistance of the heat-bonding multilayer polyimide film and the adhesion improving treated low roughness copper and foil under pressure of thermocompression bonding aromatic polyimide comprising an aromatic polyimide layer method for producing a copper-clad laminate according to claim 1 for laminating by thermal compression bonding at 400 ° C. below the temperature at or above the glass transition temperature.
  7. 熱圧着が、ダブルベルトプレスによって加圧下に、熱圧着性の芳香族ポリイミドのガラス転移温度以上で400℃以下の温度で熱圧着後に冷却することによって行われる請求項6に記載の銅張積層板の製造方法。 Thermocompression bonding, under pressure by a double-belt press, the copper-clad laminate according to claim 6 at a temperature of 400 ° C. or less in the heat-bondable than the glass transition temperature of the aromatic polyimide is carried out by cooling after thermocompression the method of production.
  8. 接着性改良処理された低粗度銅箔が、有機処理剤による接着性改良処理されたものである請求項6に記載の銅張積層板の製造方法。 Low roughness copper foil bonded improving processing method for producing a copper-clad laminate according to claim 6 in which is an adhesion improving treatment with an organic treatment agent.
  9. 接着性改良処理された低粗度銅箔が、1.0μm以下の表面粗さ:Rzおよび、TD(ロ−ル方向と垂直方向)310%以上、MD(ロ−ル方向)360%以上の光沢度(入射角60°)を有するものである請求項6に記載の銅張積層板の製造方法。 Low roughness copper foil bonded improving treatment, 1.0 .mu.m or less of surface roughness: Rz and, TD (B - Le and vertical) 310% or more, MD (b - Le direction) of more than 360% method for producing a copper-clad laminate according to claim 6 are those having glossiness (incident angle of 60 °).
  10. ポリイミドフィルムと銅層とが積層されてなり、銅層エッチング後のフィルムの波長600nmでの光透過率が40%以上、曇価(HAZE)が30%以下であって、接着強度が500N/m以上であり、150℃で1000時間の熱処理後の接着強度が285N/m以上である銅張積層板。 Will be a polyimide film and a copper layer are laminated, the light transmittance at a wavelength 600nm of the film after the copper layer etched 40% or more, haze (HAZE) is not more than 30%, the adhesive strength is 500 N / m above, and the copper-clad laminate is the adhesive strength after heat treatment for 1000 hours at 0.99 ° C. is 285N / m or more.
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JP2014112682A (en) * 2013-12-05 2014-06-19 Nippon Steel & Sumikin Chemical Co Ltd Coverlay film and circuit board
KR20160086377A (en) 2013-12-10 2016-07-19 제이엑스금속주식회사 Treated surface copper foil, copper-clad laminate, printed wiring board, electronic device, and printed wiring board manufacturing method
KR20160086378A (en) 2013-12-10 2016-07-19 제이엑스금속주식회사 Treated surface copper foil, copper-clad laminate, printed wiring board, electronic device, and printed wiring board manufacturing method
JP2016204706A (en) * 2015-04-22 2016-12-08 福田金属箔粉工業株式会社 Electrolytic copper foil for printed wiring board and copper-clad laminate using electrolytic copper foil

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