JP4525338B2 - Slippery metal laminate - Google Patents
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- JP4525338B2 JP4525338B2 JP2004375850A JP2004375850A JP4525338B2 JP 4525338 B2 JP4525338 B2 JP 4525338B2 JP 2004375850 A JP2004375850 A JP 2004375850A JP 2004375850 A JP2004375850 A JP 2004375850A JP 4525338 B2 JP4525338 B2 JP 4525338B2
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Description
本発明は、スジ状の凹凸を有することにより、易滑性に優れ、多層基板を結んでいるヒンジ部の離型性を良好にすることができる易滑性金属積層体に関する。 The present invention relates to a slidable metal laminate having excellent slipperiness and having good releasability of a hinge part connecting a multilayer substrate by having streak-like irregularities.
ポリイミドフィルムは、絶縁性、耐熱性、電気特性、機械的特性に優れていることから、例えば銅箔などの金属箔と積層したフレキシブル回路基板用のベースフィルムなどの用途に幅広く利用されている。 Polyimide films are widely used in applications such as base films for flexible circuit boards laminated with a metal foil such as a copper foil because they are excellent in insulation, heat resistance, electrical properties, and mechanical properties.
そして、ポリイミドフィルムがこれらの用途に用いられる際の重要な要求特性の一つとして、フィルム表面の易滑性が挙げられる。フィルム表面が完全に平滑なポリイミドフィルムは滑り性が悪く、フィルム加工工程において、搬送時の支持体（例えばロールなど）との摩擦係数が大きく、しわが入ったり、ロールに巻き付いたりするため、例えばフレキシブルプリント基板を生産する際に、銅箔とのラミネートができないといったトラブルが生じることがある。 And one of the important required characteristics when a polyimide film is used for these uses is the slipperiness of the film surface. Polyimide film with a completely smooth film surface has poor slipperiness and has a large coefficient of friction with a support (for example, a roll) during transportation in the film processing process, causing wrinkles or winding around the roll. When producing a flexible printed circuit board, troubles such as inability to laminate with copper foil may occur.
さらには、多層の基板をボンディングシートを用いて加熱プレスにより積層した際に基板同士を接合する役目をになっているヒンジ部にも熱プレスの影響を受けフィルム同士が密着し合ってしまい、それらを剥がす手間が生じるほか、擦れ有って「音鳴り」を起こしてしまうといった不具合が生じることがある。 Furthermore, when a multilayer substrate is laminated by a hot press using a bonding sheet, the films are in close contact with each other under the influence of the hot press on the hinge part that serves to bond the substrates together. In addition to the trouble of peeling off, there may be problems such as “sounding” due to rubbing.
従来、ポリイミドフィルム表面に易滑性を付与する方法として表面の粗面化が挙げられ様々な方法が存在してきた。例えばポリイミドフィルムにリン酸カルシウムなどのフィラーを混合し、フィルム表面に微細な突起を生じさせることにより易滑性を付与する方法（例えば、特許文献１および特許文献２参照）が知られていた。また、ポリイミドがアルカリに溶解性があることを利用し、ポリイミドフィルム表面をアルカリ性溶液で処理して、表面を粗面化させることにより易滑性を付与する方法（例えば、特許文献３参照）が知られていた。これらの方法によってフィルム加工工程の搬送時に生じていた銅箔とのラミネートができないなどのトラブルは解消されたが、ヒンジ部におけるフィルム同士が密着し合うといった不具合、「音鳴り」などの不具合は生じたままであり、さらなるフィルム表面の粗面化が必要であった。
本発明は、上述した従来技術における問題点の解決を課題として検討した結果達成されたものである。 The present invention has been achieved as a result of studying the solution of the problems in the prior art described above as an issue.
したがって、本発明の目的は、多層の基板を加熱プレスにより積層した際のヒンジ部におけるフィルム同士の密着を低減し、フィルム同士が擦れあっての「音鳴り」トラブルを解消することのできる易滑性に優れたポリイミドフィルムを基材とした金属積層体を提供することにある。 Therefore, the object of the present invention is to reduce the adhesion between films at the hinge part when a multilayer substrate is laminated by a hot press, and to easily solve the “sounding” trouble caused by the films rubbing each other. It is providing the metal laminated body which made the base material the polyimide film excellent in the property.
上記の目標を達成するために、本発明の易滑性金属積層体は、フィルム表面に、フィルムの機械送り方向に平行なスジ状の凹凸を有し、ＪＩＳ Ｋ−７１２５に準じて測定したフィルム表面同士の静摩擦係数が０．１〜０．７であるポリイミドフィルムを基材とし、このポリイミドフィルムのスジ状の凹凸を付与していない面に金属が積層されていることを特徴とする。
To achieve the above objectives, lubricity metal laminate of the present invention, the film surface has a parallel stripe-like unevenness in the machine feed direction of the film was measured according to JIS K-7125 film A polyimide film having a coefficient of static friction between surfaces of 0.1 to 0.7 is used as a base material, and a metal is laminated on a surface of the polyimide film not provided with streak-like irregularities .
さらに、本発明易滑性金属積層体は下記（１）〜（５）を併せ持つことが好ましい。
（１）スジ状の凹凸を有し、ＪＩＳ Ｂ−０６０１に準じて測定したフィルム表面粗さＲｚが０．８〜３．０μｍであるポリイミドフィルムを基材とすること。
（２）スジ状の凹凸の高低差が０．０５〜４．００μｍの範囲にあるポリイミドフィルムを基材とすること。
（３）スジ状の凹凸の幅が０．１〜１０μｍの範囲であるポリイミドフィルムを基材とすること。
（４）スジ状の凹凸が、０．１〜１０００本／ｍｍの範囲であるポリイミドフィルムを基材とすること。
（５）金属が銅であること。
Furthermore, the slippery metal laminate of the present invention preferably has the following (1) to (5).
(1) A polyimide film having streak-like irregularities and having a film surface roughness Rz of 0.8 to 3.0 μm measured according to JIS B-0601 is used as a base material.
(2) The base material is a polyimide film in which the height difference of the stripe-shaped unevenness is in the range of 0.05 to 4.00 μm.
(3) A polyimide film having a stripe-shaped unevenness in the range of 0.1 to 10 μm is used as a base material.
(4) A polyimide film having streaky irregularities in the range of 0.1 to 1000 pieces / mm is used as a base material.
(5) The metal is copper.
本発明の易滑性金属積層体は、スジ状の凹凸を有することによって易滑性を高めたポリイミドフィルムを基材とすることにより、その結果フィルム同士の密着が無くなり、折り曲げ時のフィルムの擦れ合いも無くなり、フレキシブルプリント基板のヒンジ部へ好適に用いることができる。 The slidable metal laminate of the present invention is based on a polyimide film having improved slidability by having streak-like irregularities. As a result, there is no adhesion between the films, and the film rubs when folded. There is no match, and it can be suitably used for the hinge part of the flexible printed circuit board.
以下本発明について詳細に説明する。 The present invention will be described in detail below.
本発明の易滑性金属積層体の基材として使用されるポリイミドフィルムは、ＪＩＳ Ｋ−７１２５に準じて測定したフィルム表面同士の静摩擦係数が０．１〜０．７であることが好ましく、０．２〜０．６がさらに好ましい。また、これに加えてＪＩＳ Ｂ−０６０１に準じて測定したフィルム表面粗さＲｚが０．８〜３．０μｍであることが好ましく、１．０〜２．５μｍがさらに好ましい。これらの特性は、フィルム表面上に特定のスジ状の凹凸を付与することによって得ることができる。 The polyimide film used as the base material of the slippery metal laminate of the present invention preferably has a coefficient of static friction between the film surfaces measured according to JIS K-7125 of 0.1 to 0.7. .2 to 0.6 is more preferable. In addition to this, the film surface roughness Rz measured according to JIS B-0601 is preferably 0.8 to 3.0 μm, and more preferably 1.0 to 2.5 μm . Characteristics of these can be obtained by applying a specific streaky irregularities on the film surface.
ポリイミドフィルムへのスジ状の凹凸を付与する方法としては、例えば図１あるいは図２のように、ポリイミドフィルムに研磨テープを接触させて走行させることによって得ることができる。 For example, as shown in FIG. 1 or FIG. 2, the polyimide film can be obtained by causing the polyimide film to contact with a polishing tape and causing the polyimide film to run.
図１において、ポリイミドフィルムは巻出しロール１から送り出され、走行方向に対して逆方向に回転している研磨ロール３の表面を擦過しながら巻取りロール２に巻き取られる。図２では、巻出しロール１を出たポリイミドフィルムは逆方向に回転している研磨ロール３と押さえロール４との間を擦過しながら通り、巻取りロール２に巻き取られる。この時の面圧は１〜１０ｋｇ／５００ｍｍが好ましい。
In FIG. 1, the polyimide film is fed from an
図１あるいは図２のような方式でフィルムの片面処理することができるが、図２の方が研磨固定ロールをフィルムに接触させる時の圧力をコントロールでき、効率的に凹凸を付与できるので好ましい。これらの処理をする際にフィルムに与える張力としては１０〜５０Ｎ／ｍの範囲で調整することが好ましく、また処理速度は５〜４０ｍ／ｍｉｎの範囲で調整することが好ましい。 The film can be processed on one side by the method shown in FIG. 1 or FIG. 2, but FIG. 2 is preferable because the pressure when the polishing fixing roll is brought into contact with the film can be controlled and the unevenness can be efficiently imparted. The tension applied to the film during these treatments is preferably adjusted in the range of 10 to 50 N / m, and the treatment speed is preferably adjusted in the range of 5 to 40 m / min.
研磨固定ロールは表面が硬く、粗い状態のものであればよいが、テープに研磨剤をコーティングした研磨テープを通常のロールに貼り付けたものも使用可能である。研磨テープとしては、例えばＰＥＴフィルムをベースとし、その上に研磨材がコーティングされている形式のものが挙げられる。そのベースとなるＰＥＴフィルムの厚みは２５〜７５μｍの範囲にあると取り扱いやすいので好ましい。研磨材は炭化ケイ素、酸化アルミニウム、酸化クロム、酸化セリウム、ダイヤモンドなどが挙げられ、研磨材の粒度は粗面化したい程度に応じて０．１〜１００μｍの範囲にあることが好ましく、より好ましくは１〜５０μｍの範囲にあることである。この範囲より粒度が大きいとフィルムを荒らしすぎて強度などの機械特性を損ねる恐れがあり、この範囲より粒度が小さいとフィルムの易滑性を付与する効果が低くなるので好ましくない。 The polishing fixing roll may have a hard surface and a rough state, but a polishing tape obtained by coating a tape with an abrasive may be used. Examples of the abrasive tape include a tape having a PET film as a base and an abrasive coated thereon. The thickness of the PET film as the base is preferably in the range of 25 to 75 μm because it is easy to handle. Examples of the abrasive include silicon carbide, aluminum oxide, chromium oxide, cerium oxide, and diamond. The particle size of the abrasive is preferably in the range of 0.1 to 100 μm depending on the degree of roughening, more preferably It exists in the range of 1-50 micrometers. If the particle size is larger than this range, the film may be too rough, and mechanical properties such as strength may be impaired. If the particle size is smaller than this range, the effect of imparting the slipperiness of the film is lowered, which is not preferable.
これらの条件を種々変えることによって、フィルム表面に付与させるスジ状の凹凸における、スジの高低差を０．０５〜４．００μｍの範囲に調整させることが好ましく、さらにはスジ状の凹凸の幅が０．１〜１０μｍの範囲に調整させることがより好ましい。また、スジ状の凹凸の密度は０．１〜１０００本／ｍｍ幅、好ましくは１０〜８００本／ｍｍ幅、より好ましくは１００〜５００本／ｍｍ幅の範囲に調整させることがより好ましい。これによってフィルムへの易滑性を付与することができ、フレキシブルプリント基板のヒンジ部を形成した後、熱プレスの影響を受けてもフィルム同士が密着し合わず、音鳴りなどの不具合を防ぐことができる。 By changing these conditions variously, it is preferable to adjust the level difference of the stripes in the stripe-like unevenness to be imparted to the film surface to a range of 0.05 to 4.00 μm, and further, the width of the stripe-like unevenness is It is more preferable to adjust in the range of 0.1 to 10 μm. Further, the density of the stripe-shaped unevenness is more preferably adjusted to a range of 0.1 to 1000 / mm width, preferably 10 to 800 / mm width, more preferably 100 to 500 / mm width. This makes it easy to slip on the film, and after forming the hinge part of the flexible printed circuit board, the films do not adhere to each other even under the influence of heat press, preventing problems such as noise. Can do.
スジ状の凹凸の方向は、フィルムの機械送り方向（ＭＤ）に平行に沿って付与させることが必要であり、図１〜２に示すような装置を用いてフィルムの機械送り方向（ＭＤ）に平行に沿って付与させる方法が、最も工程的に簡易にできるので好ましい。 Direction of streaky irregularities, it is necessary to impart along parallel to the machine feed direction (MD) of the film in the machine feed direction (MD) of the film using a device UNA by FIG 1-2 A method of imparting along the parallel is preferable because it can be simplified most in the process.
このようにして得られたポリイミドフィルムのスジ状凹凸を付与させていない方の面上に、ポリエステルベース、アクリルベース、エポキシベースあるいはポリイミドベース等の接着剤を介して導電性の金属を積層させることによって易滑性金属積層体を得ることができる。また未処理のポリイミドフィルムの一方の面上に、接着剤を介して導電性の金属を積層させ金属積層体を形成させた後に、金属積層面とは反対の面を図１あるいは図２のように研磨テープで処理してスジ状凹凸を付与させることも可能である。 A conductive metal is laminated on the surface of the polyimide film obtained in this way, which has not been provided with streak-like irregularities, with an adhesive such as polyester base, acrylic base, epoxy base or polyimide base. Thus, a slippery metal laminate can be obtained. Further, after a conductive metal is laminated on one surface of an untreated polyimide film via an adhesive to form a metal laminate, the surface opposite to the metal laminate surface is as shown in FIG. 1 or FIG. It is also possible to apply streak-like irregularities by treating with a polishing tape.
ポリイミドフィルムに積層する金属としては銅、アルミニウム、鉄、などが挙げられるが、回路の形成しやすさや導電性から銅が使用されるのが好ましい。 Examples of the metal to be laminated on the polyimide film include copper, aluminum, iron, etc., but copper is preferably used from the viewpoint of ease of circuit formation and conductivity.
本発明で使用されるポリイミドフィルムの例としては、ピロメリット酸二無水物および４，４’−ジアミノジフェニルエーテルから得られるポリアミド酸から製造されたポリイミドフィルム、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、ピロメリット酸二無水物、ｐ−フェニレンジアミン、４，４’−ジアミノジフェニルエーテルの４成分から得られるポリアミド酸から製造されたポリイミドフィルム、ピロメリット酸二無水物、４，４’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルエーテルの３成分から得られるポリアミド酸から製造されたポリイミドフィルム、ピロメリット酸二無水物、４，４’−ジアミノジフェニルエーテル、ｐ−フェニレンジアミンの３成分から得られるポリアミド酸から製造されたポリイミドフィルム、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物およびｐ−フェニレンジアミンから得られるポリアミド酸から製造されたポリイミドフィルム、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物および４，４’−オキシジアニリンから得られるポリアミド酸から製造されたポリイミドフィルム、等が挙げられる。ポリアミド酸からポリイミドへの脱環化は化学的閉環法、熱的閉環法のいずれでも構わない。また加工性改善などを目的として１０重量％以下の無機質または有機質の添加物を含有することも可能である。 As an example of the polyimide film used in the present invention, a polyimide film produced from polymellitic acid obtained from pyromellitic dianhydride and 4,4′-diaminodiphenyl ether, 3,3 ′, 4,4′-biphenyl Polyimide film produced from polyamic acid obtained from four components of tetracarboxylic dianhydride, pyromellitic dianhydride, p-phenylenediamine and 4,4′-diaminodiphenyl ether, pyromellitic dianhydride, 4, Polyimide film produced from 3 components of 4′-diaminodiphenyl ether and 3,4′-diaminodiphenyl ether, 3 components of pyromellitic dianhydride, 4,4′-diaminodiphenyl ether and p-phenylenediamine Manufactured from polyamic acid obtained from Polyimide film prepared from polyamic acid obtained from 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and p-phenylenediamine, 3,3 ′, 4,4′-biphenyl And a polyimide film produced from a polyamic acid obtained from tetracarboxylic dianhydride and 4,4′-oxydianiline. The decyclization of polyamic acid to polyimide may be either a chemical ring closure method or a thermal ring closure method. Further, for the purpose of improving workability, it is possible to contain 10% by weight or less of an inorganic or organic additive.
本発明に使用されるポリイミドフィルムの厚みは３〜２００μｍであることが望ましい。すなわち、厚みが３μｍ未満では形状を保持することが困難となり、また２００μｍを越えると屈曲性に欠けるため、フレキシブル回路基板用途には不向きである。またポリイミドフィルムの寸法安定性を向上させるために、アニール処理等により低熱収縮化させることや、接着性を向上させるためにプラズマ処理等を行っても良い。 The thickness of the polyimide film used in the present invention is desirably 3 to 200 μm. That is, if the thickness is less than 3 μm, it is difficult to maintain the shape, and if it exceeds 200 μm, the flexibility is insufficient, so that it is not suitable for flexible circuit board applications. In order to improve the dimensional stability of the polyimide film, it may be subjected to low heat shrinkage by annealing treatment or the like, or plasma treatment or the like may be performed to improve the adhesiveness.
かくして、易滑性に優れ、多層フレキシブル板を結んでいるヒンジ部の離型性を良好にすることができる易滑性金属積層体を提供することができる。 Thus, it is possible to provide a slippery metal laminate that is excellent in slipperiness and that can improve the releasability of the hinge portion connecting the multilayer flexible plates.
以下に実施例を挙げて、本発明をさらに具体的に説明する。なお、実施例中の各特性は、以下の方法により測定した値である。 The present invention will be described more specifically with reference to the following examples. In addition, each characteristic in an Example is the value measured with the following method.
［摩擦係数（静摩擦係数）］
ＪＩＳ Ｋ−７１２５に準じて測定した。すなわち、スベリ係数測定装置Ｓｌｉｐ Ｔｅｓｔｅｒ（株式会社テクノニーズ製）を使用し、フィルム処理面同士を重ね合わせて、その上に２００ｇのおもりを載せ、フィルムの一方を固定、もう一方を１００ｍｍ／分で引っ張り、摩擦係数を測定した。
[Friction coefficient (Static friction coefficient)]
It measured according to JIS K-7125. That is, using a slip coefficient measuring apparatus Slip Tester (manufactured by Technonez Co., Ltd.), the film processing surfaces are overlapped with each other, a 200 g weight is placed thereon, one side of the film is fixed, and the other side is fixed at 100 mm / min. Tensile and friction coefficients were measured.
［フィルムの表面粗さＲｚの測定］
ＪＩＳ Ｂ−０６０１「表面粗さ」に基づき、レーザー顕微鏡により測定した。すなわちレーザーテック（株）製走査型レーザー顕微鏡「１ＬＭ１５Ｗ」にて、ニコン製５０倍レンズ（ＣＦ Ｐｌａｎ Ａｐｏ ５０×／０．９５ ∞／０ ＥＰＩ）を用いて、「ＳＵＲＦＡＣＥ２」モードにてフィルム表面を撮影後、三谷商事（株）製ＳＡＬＴにて、粗さ曲線を作成する時のカットオフ値を０．０２５ｍｍに設定して、拡張表面粗さ０．０１ｍｍ２以上の面積を解析し、Ｒｚ（十点平均粗さ）の値を読み取った。
[Measurement of surface roughness Rz of film]
Based on JIS B-0601 “Surface roughness”, measurement was performed with a laser microscope. That is, the surface of the film was photographed in the “SURFACE2” mode using a scanning laser microscope “1LM15W” manufactured by Lasertec Co., Ltd. and using a Nikon 50 × lens (CF Plan Apo 50 × / 0.95∞ / 0 EPI). After that, in SALT manufactured by Mitani Shoji Co., Ltd., the cut-off value when creating the roughness curve was set to 0.025 mm, and an area with an extended surface roughness of 0.01 mm 2 or more was analyzed. The value of (point average roughness) was read.
［スジの高低差］
レーザーテック（株）製走査型レーザー顕微鏡「１ＬＭ１５Ｗ」にて、ニコン製５０倍レンズ（ＣＦ Ｐｌａｎ Ａｐｏ ５０×／０．９５ ∞／０ ＥＰＩ）を用いて、「ＳＵＲＦＡＣＥ１」モードにてフィルム表面を撮影・解析し得られたチャートから各スジの高低差を読み取った。代表値としては無作為に選んだ５点の平均値とし、最大値としては、「ＳＵＲＦＡＣＥ２」モードで撮影後のＳＡＬＴでの拡張表面粗さ０．０１ｍｍ２以上の面積での解析による最大高さＲｙで確認した。
[Difference in stripes]
Using the scanning laser microscope “1LM15W” manufactured by Lasertec Co., Ltd., using Nikon 50 × lens (CF Plan Apo 50 × / 0.95∞ / 0 EPI), the film surface was photographed in “SURFACE1” mode. The height difference of each streak was read from the chart obtained by analysis. The representative value is the average value of 5 points selected at random, and the maximum value is the maximum height by analysis with an area of 0.01 mm 2 or more of the extended surface roughness in SALT after shooting in “SURFACE2” mode. Confirmed with Ry.
［スジ状凹凸の幅］
レーザーテック（株）製走査型レーザー顕微鏡「１ＬＭ１５Ｗ」にて、ニコン製５０倍レンズ（ＣＦ Ｐｌａｎ Ａｐｏ ５０×／０．９５ ∞／０ ＥＰＩ）を用いて、「ＳＵＲＦＡＣＥ１」モードにてフィルム表面を撮影・解析し、各スジにＬキー（左）とＲキー（右）を定めてスジ幅を読み取った。この視野で見える中で最大幅のスジを代表値とした。
[Striped uneven width]
Using the scanning laser microscope “1LM15W” manufactured by Lasertec Co., Ltd., using Nikon 50 × lens (CF Plan Apo 50 × / 0.95∞ / 0 EPI), the film surface was photographed in “SURFACE1” mode. Analysis was performed, and the L key (left) and R key (right) were determined for each streak, and the streak width was read. The maximum width streak that can be seen in this field of view was used as a representative value.
［スジ状凹凸の数］
レーザーテック（株）製走査型レーザー顕微鏡「１ＬＭ１５Ｗ」にて、ニコン製５０倍レンズ（ＣＦ Ｐｌａｎ Ａｐｏ ５０×／０．９５ ∞／０ ＥＰＩ）を用いて、「ＳＵＲＦＡＣＥ１」モードにてフィルム表面を撮影し、観察されているスジの数をカウントした。
[Number of stripe-shaped irregularities]
The surface of the film was photographed in “SURFACE1” mode using a scanning laser microscope “1LM15W” manufactured by Lasertec Co., Ltd. and using a Nikon 50 × lens (CF Plan Apo 50 × / 0.95∞ / 0 EPI). The number of streaks that were observed was counted.
［プレス後の剥離性評価］
２組の銅張積層体についてフィルム面同士を合わせて、１８０℃×１時間、１０ＭＰａの圧力で加熱プレスし、プレス後に２組の銅張積層体が剥離されるかどうかを評価した。手に持って軽く振っても剥離されず密着しているものをＮＧ、取り出して既に剥離しているもの、軽く振ることで簡単に剥離するものをＯＫとした。
[Evaluation of peelability after pressing]
The film surfaces of the two sets of copper-clad laminates were combined and heated and pressed at 180 ° C. for 1 hour at a pressure of 10 MPa, and whether the two sets of copper-clad laminates were peeled after pressing was evaluated. Those that were not peeled even when shaken lightly and held in close contact were judged as NG, those that had already been peeled off after being taken out, and those that peeled off easily by shaking lightly were judged as OK.
［実施例１］
ピロメリット酸二無水物７０モル％、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物３０モル％と４，４’−ジアミノジフェニルエーテル８０モル％、パラフェニレンジアミン２０モル％とから得られるポリアミド酸に平均粒径１μｍのリン酸水素カルシウムを約０．１重量％混入させ、製造された厚さ２５μｍのポリイミドフィルムに、粒度２０μｍの炭化ケイ素を研磨材として用いた研磨テープを使用して、図１の要領にて走行速度１０ｍ／ｍｉｎで処理して、フィルム上にスジ状の凹凸を付与させた。次にスジ状凹凸の付与させていない方の面上に、接着剤Ｐｙｒａｌｕｘ ＬＦ１００（デュポン社製）を介して３４μｍ厚の圧延銅箔（日鉱マテリアルズ社製）を１８０℃×７０ＭＰａで６０分間プレスして積層させた。得られた銅張積層体のフィルム面の静摩擦係数は０．３０、表面粗さＲｚは、１．２５μｍであり、フィルム表面上に付与されたスジ状凹凸の高低差は０．７２μｍ、最大高低差Ｒｙは１．３８μｍ、スジ状凹凸の最大幅は１．７μｍ、スジ状凹凸の数は２２５本／ｍｍ幅であった。プレス後の剥離性評価については、２組の銅張積層体は剥離しておりＯＫであった。
[Example 1]
From 70 mol% of pyromellitic dianhydride, 30 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 80 mol% of 4,4′-diaminodiphenyl ether, and 20 mol% of paraphenylenediamine. About 0.1% by weight of calcium hydrogen phosphate having an average particle size of 1 μm is mixed with the resulting polyamic acid, and a polishing tape using a silicon carbide with a particle size of 20 μm as an abrasive material is used for the manufactured polyimide film with a thickness of 25 μm. Then, processing was performed at a traveling speed of 10 m / min in the manner shown in FIG. 1 to give stripe-shaped irregularities on the film. Next, 34 μm-thick rolled copper foil (manufactured by Nikko Materials) is pressed at 180 ° C. × 70 MPa for 60 minutes through the adhesive Pyralux LF100 (manufactured by DuPont) on the surface not provided with streak-like irregularities. And laminated. The resulting copper-clad laminate has a coefficient of static friction on the film surface of 0.30, a surface roughness Rz of 1.25 μm, and the height difference of the stripe-shaped irregularities imparted on the film surface is 0.72 μm, the maximum height The difference Ry was 1.38 μm, the maximum width of the stripe-shaped unevenness was 1.7 μm, and the number of stripe-shaped unevenness was 225 / mm width. Regarding evaluation of peelability after pressing, the two sets of copper-clad laminates were peeled off and were OK.
［実施例２］
図２の要領にて走行速度１０ｍ／ｍｉｎ、処理面圧３ｋｇ／５００ｍｍで処理した以外は実施例１と同様にした結果、得られた銅張積層体のフィルム面の静摩擦係数は０．２９、表面粗さＲｚは、１．６８μｍであり、フィルム表面上に付与されたスジ状凹凸の高低差は１．０９μｍ、最大高低差Ｒｙは２．０５μｍ、スジ状凹凸の最大幅は５．９μｍ、スジ状凹凸の数は２１３本／ｍｍ幅であった。プレス後の剥離性評価については、２組の銅張積層体は剥離しておりＯＫであった。
[Example 2]
The static friction coefficient of the film surface of the obtained copper-clad laminate was 0.29 as a result of the same as in Example 1 except that the treatment was performed at a traveling speed of 10 m / min and a treatment surface pressure of 3 kg / 500 mm as shown in FIG. The surface roughness Rz is 1.68 μm, the height difference of the stripe-shaped unevenness imparted on the film surface is 1.09 μm, the maximum height difference Ry is 2.05 μm, the maximum width of the stripe-shaped unevenness is 5.9 μm, The number of stripe-shaped irregularities was 213 / mm width. Regarding evaluation of peelability after pressing, the two sets of copper-clad laminates were peeled off and were OK.
［実施例３］
厚さ１２．５μｍのポリイミドフィルムを使用した以外は実施例１と同様にした結果、得られた銅張積層体のフィルム面の静摩擦係数は０．３５、表面粗さＲｚは、１．１５μｍであり、フィルム表面上に付与されたスジ状凹凸の高低差は０．６６μｍ、最大高低差Ｒｙは１．３９μｍ、スジ状凹凸の最大幅は１．５μｍ、スジ状凹凸の数は２２５本／ｍｍ幅であった。プレス後の剥離性評価については、２組の銅張積層体は剥離しておりＯＫであった。
[Example 3]
As a result of carrying out similarly to Example 1 except having used the polyimide film of thickness 12.5 micrometers, the static friction coefficient of the film surface of the obtained copper clad laminated body is 0.35, and surface roughness Rz is 1.15 micrometers. Yes, the height difference of the stripe-shaped unevenness provided on the film surface is 0.66 μm, the maximum height difference Ry is 1.39 μm, the maximum width of the stripe-shaped unevenness is 1.5 μm, and the number of the stripe-shaped unevenness is 225 / mm. It was wide. Regarding evaluation of peelability after pressing, the two sets of copper-clad laminates were peeled off and were OK.
［実施例４］
厚さ１２．５μｍのポリイミドフィルムを使用し、図２の要領にて走行速度１０ｍ／ｍｉｎ、処理面圧３ｋｇ／５００ｍｍで処理した以外は、実施例１と同様にした結果、得られた銅張積層体のフィルム面の静摩擦係数は０．３１、表面粗さＲｚは、１．８２μｍであり、フィルム表面上に付与されたスジ状凹凸の高低差は１．２１μｍ、最大高低差Ｒｙは２．２５μｍ、スジ状凹凸の最大幅は６．４μｍ、スジ状凹凸の数は２１８本／ｍｍ幅であった。プレス後の剥離性評価については、２組の銅張積層体は剥離しておりＯＫであった。
[Example 4]
As a result of the same operation as in Example 1 except that a polyimide film having a thickness of 12.5 μm was used, and processing was performed at a traveling speed of 10 m / min and a processing surface pressure of 3 kg / 500 mm as shown in FIG. The static friction coefficient of the film surface of the laminate is 0.31, the surface roughness Rz is 1.82 μm, the height difference of the stripe-shaped unevenness imparted on the film surface is 1.21 μm, and the maximum height difference Ry is 2. The maximum width of the stripe-shaped unevenness was 6.4 μm, and the number of the stripe-shaped unevenness was 218 / mm width. Regarding evaluation of peelability after pressing, the two sets of copper-clad laminates were peeled off and were OK.
［実施例５］
厚さ１２．５μｍのポリイミドフィルムを使用し、粒度９μｍの炭化ケイ素を研磨材として用いた研磨テープを使用して、図２の要領にて走行速度１０ｍ／ｍｉｎ、処理面圧３ｋｇ／５００ｍｍで処理した以外は、実施例１と同様にした結果、得られた銅張積層体のフィルム面の静摩擦係数は０．２６、表面粗さＲｚは、１．７７μｍであり、フィルム表面上に付与されたスジ状凹凸の高低差は１．３７μｍ、最大高低差Ｒｙは２．２２μｍ、スジ状凹凸の最大幅は６．０μｍ、スジ状凹凸の数は３２７本／ｍｍ幅であった。プレス後の剥離性評価については、２組の銅張積層体は剥離しておりＯＫであった。
[Example 5]
Using a polyimide film with a thickness of 12.5 μm and a polishing tape using silicon carbide with a grain size of 9 μm as an abrasive, processing at a running speed of 10 m / min and a processing surface pressure of 3 kg / 500 mm as shown in FIG. Except for the above, the same results as in Example 1 were obtained. As a result, the static friction coefficient of the film surface of the obtained copper-clad laminate was 0.26, and the surface roughness Rz was 1.77 μm, which was applied on the film surface. The height difference of the stripe unevenness was 1.37 μm, the maximum height difference Ry was 2.22 μm, the maximum width of the stripe unevenness was 6.0 μm, and the number of stripe unevenness was 327 / mm width. Regarding evaluation of peelability after pressing, the two sets of copper-clad laminates were peeled off and were OK.
［実施例６］
ピロメリット酸二無水物と４，４’−ジアミノジフェニルエーテルから得られるポリアミド酸に平均粒径１μｍのリン酸水素カルシウムを約０．１重量％混入させ、製造された厚さ２５μｍのポリイミドフィルムに、粒度２０μｍの炭化ケイ素を研磨材として用いた研磨テープを使用して、図１の要領にて走行速度１０ｍ／ｍｉｎで処理した。その後は実施例１と同様にした結果、得られた銅張積層体のフィルム面の静摩擦係数は０．３７、表面粗さＲｚは、１．１４μｍであり、フィルム表面上に付与されたスジ状凹凸の高低差は０．５４μｍ、最大高低差Ｒｙは１．２７μｍ、スジ状凹凸の最大幅は１．５μｍ、スジ状凹凸の数は２１９本／ｍｍ幅であった。プレス後の剥離性評価については、２組の銅張積層体は剥離しておりＯＫであった。
[Example 6]
A polyamic acid obtained from pyromellitic dianhydride and 4,4′-diaminodiphenyl ether was mixed with about 0.1% by weight of calcium hydrogen phosphate having an average particle size of 1 μm, and a polyimide film having a thickness of 25 μm was manufactured. A polishing tape using silicon carbide having a particle size of 20 μm as an abrasive was used and processed at a running speed of 10 m / min as shown in FIG. Thereafter, the same results as in Example 1 were obtained. As a result, the static coefficient of friction of the film surface of the obtained copper-clad laminate was 0.37, the surface roughness Rz was 1.14 μm, and the streak shape provided on the film surface The height difference of the unevenness was 0.54 μm, the maximum height difference Ry was 1.27 μm, the maximum width of the stripe-shaped unevenness was 1.5 μm, and the number of the stripe-shaped unevenness was 219 / mm width. Regarding evaluation of peelability after pressing, the two sets of copper-clad laminates were peeled off and were OK.
［比較例１］
ピロメリット酸二無水物７０モル％、３，３‘，４，４’−ビフェニルテトラカルボン酸二無水物３０モル％と４，４’−ジアミノジフェニルエーテル８０モル％、パラフェニレンジアミン２０モル％とから得られるポリアミド酸から製造された厚さ２５μｍのポリイミドフィルムを研磨テープで処理することなく片側の面を接着剤Ｐｙｒａｌｕｘ ＬＦ１００（デュポン社製）を介して３４μｍ厚の圧延銅箔（日鉱マテリアルズ社製）を１８０℃×７０ＭＰａで６０分間プレスして積層させた。得られた銅張積層体のフィルム面の各種特性を測定した。スジ状の凹凸は無く、静摩擦係数は２．３３、表面粗さＲｚは、０．１１μｍであった。プレス後の剥離性評価については、２組の銅張積層体は完全に密着してしまい手で振っても剥離せずＮＧであった。
[Comparative Example 1]
From 70 mol% of pyromellitic dianhydride, 30 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 80 mol% of 4,4′-diaminodiphenyl ether, and 20 mol% of paraphenylenediamine. Rolled copper foil of 34 μm thickness (manufactured by Nikko Materials Co., Ltd.) through the adhesive Pyralux LF100 (manufactured by DuPont) without treating the 25 μm-thick polyimide film produced from the resulting polyamic acid with an abrasive tape ) Was pressed at 180 ° C. × 70 MPa for 60 minutes for lamination. Various characteristics of the film surface of the obtained copper-clad laminate were measured. There were no stripe-shaped unevenness | corrugations, the static friction coefficient was 2.33, and surface roughness Rz was 0.11 micrometer. Regarding the evaluation of peelability after pressing, the two sets of copper clad laminates were in close contact and were not peeled even when shaken by hand, and were NG.
［比較例２］
ピロメリット酸二無水物７０モル％、３，３‘，４，４’−ビフェニルテトラカルボン酸二無水物３０モル％と４，４’−ジアミノジフェニルエーテル８０モル％、パラフェニレンジアミン２０モル％とから得られるポリアミド酸に平均粒径１μｍのリン酸水素カルシウムを約０．１重量％混入させ、製造された厚さ２５μｍのポリイミドフィルムを研磨テープで処理することなく片側の面を接着剤Ｐｙｒａｌｕｘ ＬＦ１００（デュポン社製）を介して３４μｍ厚の圧延銅箔（日鉱マテリアルズ社製）を１８０℃×７０ＭＰａで６０分間プレスして積層させた。得られた銅張積層体のフィルム面の各種特性を測定した。スジ状の凹凸は無く、静摩擦係数は０．７５、表面粗さＲｚは、０．６２μｍであった。プレス後の剥離性評価については、２組の銅張積層体は完全に密着してしまい手で振っても剥離せずＮＧであった。
[Comparative Example 2]
From 70 mol% of pyromellitic dianhydride, 30 mol% of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 80 mol% of 4,4′-diaminodiphenyl ether, and 20 mol% of paraphenylenediamine. About 0.1% by weight of calcium hydrogen phosphate having an average particle diameter of 1 μm is mixed in the obtained polyamic acid, and the produced polyimide film having a thickness of 25 μm is treated with an adhesive Pyralux LF100 (without adhesive tape). A rolled copper foil (manufactured by Nikko Materials Co., Ltd.) having a thickness of 34 μm was pressed at 180 ° C. × 70 MPa for 60 minutes and laminated. Various characteristics of the film surface of the obtained copper-clad laminate were measured. There were no streak-like irregularities, the coefficient of static friction was 0.75, and the surface roughness Rz was 0.62 μm. Regarding the evaluation of peelability after pressing, the two sets of copper clad laminates were in close contact and were not peeled even when shaken by hand, and were NG.
本発明の易滑性金属積層体は易滑性に優れていることから、フレキシブル回路基板用の積層体として好ましく利用できる。 Since the slippery metal laminate of the present invention is excellent in slipperiness, it can be preferably used as a laminate for a flexible circuit board.
１：巻出しロール、２：巻取りロール、３：研磨ロール、４：押さえロール 1: Unwinding roll, 2: Winding roll, 3: Polishing roll, 4: Pressing roll
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| JP2004375850A JP4525338B2 (en) | 2004-12-27 | 2004-12-27 | Slippery metal laminate |
| TW95123065A TW200800602A (en) | 2004-12-27 | 2006-06-27 | Labile metal laminate and process thereof |
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| WO2007148395A1 (en) * | 2006-06-22 | 2007-12-27 | Du Pont-Toray Company, Ltd. | Slippery metal laminate and process for producing the same |
| WO2007148394A1 (en) * | 2006-06-22 | 2007-12-27 | Du Pont-Toray Company, Ltd. | Polyimide film and process for producing the same |
| JP4845705B2 (en) * | 2006-12-19 | 2011-12-28 | 日東電工株式会社 | Printed wiring board, manufacturing method thereof, and electronic device |
| US8383230B2 (en) | 2007-05-24 | 2013-02-26 | Arisawa Mfg. Co., Ltd. | Flexible printed wiring board, multilayered flexible printed wiring board, and mobile telephone terminal employing multilayered flexible printed wiring board |
| JP4954111B2 (en) * | 2008-02-18 | 2012-06-13 | 株式会社有沢製作所 | Flexible printed wiring board, metal-clad laminate, and coverlay used for flexible printed wiring board |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07196826A (en) * | 1993-12-28 | 1995-08-01 | Kuraray Co Ltd | Improving method for friction resistance of liquid crystal polymer film |
| JP2002256085A (en) * | 2000-12-27 | 2002-09-11 | Du Pont Toray Co Ltd | Easily slidable polyimide film and its production method |
| JP2003165905A (en) * | 2001-11-29 | 2003-06-10 | Du Pont Toray Co Ltd | Aromatic polyimide film, manufacturing method therefor, and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07196826A (en) * | 1993-12-28 | 1995-08-01 | Kuraray Co Ltd | Improving method for friction resistance of liquid crystal polymer film |
| JP2002256085A (en) * | 2000-12-27 | 2002-09-11 | Du Pont Toray Co Ltd | Easily slidable polyimide film and its production method |
| JP2003165905A (en) * | 2001-11-29 | 2003-06-10 | Du Pont Toray Co Ltd | Aromatic polyimide film, manufacturing method therefor, and use thereof |
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