JP2015141094A - Polyimide film dimension stability evaluation method - Google Patents

Polyimide film dimension stability evaluation method Download PDF

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JP2015141094A
JP2015141094A JP2014013797A JP2014013797A JP2015141094A JP 2015141094 A JP2015141094 A JP 2015141094A JP 2014013797 A JP2014013797 A JP 2014013797A JP 2014013797 A JP2014013797 A JP 2014013797A JP 2015141094 A JP2015141094 A JP 2015141094A
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polyimide film
test piece
dimensional change
temperature
film
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JP6153088B2 (en
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恭子 宮内
Kyoko Miyauchi
恭子 宮内
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Sumitomo Metal Mining Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a method for accurately and easily evaluating a dimension change ratio of a polyimide film used as an electronic component base film in a transport direction (MD direction) and width direction (TD direction) of the polyimide film, by reducing affection of a moisture absorption state of the film.SOLUTION: There is provided the polyimide film dimension stability evaluation method for calculating a dimension change ratio from testing piece length of a polyimide film measured in accordance with a temperature profile set by using a constant load tension measurement mode of a thermal mechanic analyzer (TMA), and comparing and evaluating the dimension change ratio by the calculated dimension change ratio.

Description

本発明は、フレキシブルプリント配線板用銅張積層板などの電子部品の基板に用いられるポリイミドフィルムの寸法安定性を評価する方法に関し、更に詳しくは、ポリイミドフィルムを熱機械分析装置（ＴＭＡ、Ｔｈｅｒｍｏ Ｍｅｃｈａｎｉｃａｌ Ａｎａｌｙｚｅｒ）を用いてフィルムの延伸方向に対して平行並びに垂直にフィルム試験片を設置して引張モードにて、温度プロファイルによる寸法変化を測定して、その寸法安定性を評価する方法に関する。   The present invention relates to a method for evaluating the dimensional stability of a polyimide film used for a substrate of an electronic component such as a copper-clad laminate for a flexible printed wiring board. More specifically, the present invention relates to a thermomechanical analyzer (TMA, Thermo Mechanical). The present invention relates to a method for evaluating the dimensional stability by installing a film specimen in parallel and perpendicular to the stretching direction of the film using Analyzer and measuring the dimensional change due to the temperature profile in the tensile mode.

ポリイミドフィルムは優れた耐熱性を有している上、機械的特性、電気的特性、および化学的特性において、他のプラスチック材料と比べて遜色ない特性を有することから、例えばプリント配線板（ＰＷＢ）、フレキシブルプリント配線板（ＦＰＣ）、テープ自動ボンディング用テープ（ＴＡＢ）、チップオンフィルム（ＣＯＦ）等の電子部品用の絶縁基板材料として一般的に使用されている。通常、ＰＷＢ、ＦＰＣ、ＴＡＢ、及びＣＯＦは、ポリイミドフィルムの少なくとも片面に金属導体層として銅を被覆して銅被覆ポリイミド基板を形成した後、この基板をパターニング加工することによって作製することができる。   Polyimide film has excellent heat resistance and mechanical properties, electrical properties, and chemical properties that are comparable to other plastic materials. For example, printed wiring board (PWB) It is generally used as an insulating substrate material for electronic parts such as flexible printed wiring boards (FPC), tape automatic bonding tapes (TAB), and chip-on-film (COF). Usually, PWB, FPC, TAB, and COF can be prepared by coating copper as a metal conductor layer on at least one surface of a polyimide film to form a copper-coated polyimide substrate, and then patterning the substrate.

近年、携帯電子機器などの電子装置の小型化・薄型化に伴い、上記ＴＡＢやＣＯＦの配線ピッチ（配線幅及びスペース幅）も益々狭くなっており、これに対応できるように高密度で精密なパターンで配線加工が可能なものが求められている。
このような状況の下、導体層（銅層）の厚みを薄くでき、且つ厚みを自由にコントロールできる２層めっき基板が注目されている。この２層めっき基板は、ポリイミドフィルムの片面に金属層をめっきして形成されるが、より高密度で精密な配線加工が可能になるように、その基板のベースフィルムの寸法変化率をできる限り小さくすることが要件になっている。 In recent years, with the miniaturization and thinning of electronic devices such as portable electronic devices, the wiring pitch (wiring width and space width) of the TAB and COF has been increasingly narrowed. There is a demand for wiring patterns that can be processed.
Under such circumstances, a two-layer plated substrate that can reduce the thickness of the conductor layer (copper layer) and can control the thickness freely has been attracting attention. This two-layer plated substrate is formed by plating a metal layer on one side of a polyimide film, but the dimensional change rate of the base film of the substrate is made as much as possible so that higher-density and precise wiring processing is possible. It is a requirement to make it smaller.

従来から、フレキシブルプリント配線板用銅張積層板用ベースフィルムに関しては、例えば非特許文献１にはフレキシブルプリント配線板用銅張積層板の試験方法としてスクリーン印刷によって設けた評点パターン（ａ、ｂ、ｃ、ｄ）間の距離を、積層された銅層をエッチング後に測定し、ＭＤ方向（フィルムの搬送方向）の寸法変化率ｄＬｍ（％）及びＴＤ方向（フィルムの幅方向）の寸法変化率ｄＬｔ（％）を算出する手法が記載されている。 Conventionally, regarding a base film for a copper-clad laminate for a flexible printed wiring board, for example, in Non-Patent Document 1, as a test method for a copper-clad laminate for a flexible printed wiring board, a rating pattern (a, b, The distance between c and d) is measured after etching the laminated copper layer, and the dimensional change rate dL m (%) in the MD direction (film transport direction) and the dimensional change rate in the TD direction (film width direction). A method for calculating dL t (%) is described.

また、非特許文献２においては、プリント配線板用銅張積層板の試験方法として、寸法変化率の測定手法が記載されており、全面銅箔をエッチングにより除去した後、プラスチックフィルムに穴を開け、試験前後での穴間隔（常態：ｌ０、エッチング後：ｌ１、加熱処理後：ｌ２）を測定して寸法変化率を算出する手法が記載されている。 Non-Patent Document 2 describes a method for measuring a dimensional change rate as a test method for a copper-clad laminate for a printed wiring board. After removing the entire copper foil by etching, a hole is made in a plastic film. , And a method of calculating a dimensional change rate by measuring a hole interval before and after the test (normal state: l 0 , after etching: l 1 , after heat treatment: l 2 ).

しかし、試料寸法に関し、非特許文献１では２４０×３００ｍｍ、非特許文献２では長さ３００ｍｍ×幅３００ｍｍと明記されており、いずれの方法でも幅方向に対する詳細な寸法特性を評価することが難しいという問題があった。   However, regarding sample dimensions, Non-Patent Document 1 specifies 240 × 300 mm and Non-Patent Document 2 specifies length 300 mm × width 300 mm, and it is difficult to evaluate detailed dimensional characteristics in the width direction by either method. There was a problem.

また、非特許文献１及び２では、寸法測定時の温湿度条件が規定されておらず、例えばその分子鎖に親水基であるカルボニル基を持つポリイミドフィルムを測定する場合、フィルム自体の吸水性が高い為に吸湿による寸法変化の影響が大きく、正確な寸法変化率を得ることが難しいという問題があった。   Further, in Non-Patent Documents 1 and 2, the temperature and humidity conditions at the time of dimension measurement are not stipulated. For example, when measuring a polyimide film having a carbonyl group that is a hydrophilic group in its molecular chain, the film itself has water absorption. Due to its high size, the effect of dimensional change due to moisture absorption is large, and it is difficult to obtain an accurate dimensional change rate.

さらに、非特許文献１ではスクリーン印刷による評点パターンの形成が必要であり、また非特許文献２では穴あけ機による測定対象の穴形成が必要である為に、測定者による差異が発現しやすく、高い精度を保つことが難しいという問題もあった。   Further, in Non-Patent Document 1, it is necessary to form a score pattern by screen printing, and in Non-Patent Document 2, since it is necessary to form a hole to be measured by a punching machine, a difference due to a measurer is likely to occur and is high. There was also a problem that it was difficult to maintain accuracy.

以上のような種々の問題があるため、フレキシブルプリント配線板用銅張積層板用基板のベースフィルムとして一般的に採用されるポリイミドフィルムの寸法変化率を、湿度の影響を抑え、精度よくかつ簡便に評価できる方法が望まれている。   Due to the various problems described above, the dimensional change rate of polyimide film generally used as a base film for copper-clad laminates for flexible printed wiring boards can be controlled accurately and easily with reduced humidity. Therefore, a method that can be evaluated is desired.

ＪＩＳ Ｃ ６４７１ フレキシブルプリント配線板用銅張積層板試験方法JIS C 6471 Test method for copper-clad laminates for flexible printed wiring boards ＪＩＳ Ｃ ６４８１ プリント配線板用銅張積層板試験方法JIS C 6481 Test method for copper-clad laminates for printed wiring boards

本発明の目的は、フレキシブルプリント配線板用銅張積層板用ベースフィルムとして使用するポリイミドフィルムの寸法安定性を評価するために、熱機械分析装置（ＴＭＡ）を用いて寸法変化率を算出する評価方法であって、フィルムの搬送方向（ＭＤ方向）及びフィルムの幅方向（ＴＤ方向）の寸法変化率を、フィルムの吸湿状態の影響を低減して、精度よく、かつ簡便に評価できる方法を提供することにある。   An object of the present invention is to evaluate the dimensional change rate using a thermomechanical analyzer (TMA) in order to evaluate the dimensional stability of a polyimide film used as a base film for a copper-clad laminate for a flexible printed wiring board. A method that can accurately and easily evaluate the dimensional change rate in the film transport direction (MD direction) and the film width direction (TD direction) by reducing the influence of the moisture absorption state of the film. There is to do.

本発明が提供するポリイミドフィルムの評価方法の第１の発明は、ポリイミドフィルムの寸法安定性評価方法であって、熱機械分析装置（ＴＭＡ：Ｔｈｅｒｍｏ Ｍｅｃｈａｎｉｃａｌ Ａｎａｌｙｚｅｒ）の定荷重引張測定モードを用い、下記試験条件下で測定した前記ポリイミドフィルムの試験片長から、下記式（１）から（３）を用いて寸法変化率を算出し、算出した寸法変化率を下記評価手順により比較、評価することを特徴とするポリイミドフィルムの寸法安定性評価方法である。   1st invention of the evaluation method of the polyimide film which this invention provides is a dimensional stability evaluation method of a polyimide film, Comprising: Using the constant load tension measurement mode of a thermomechanical analyzer (TMA: Thermo Mechanical Analyzer), the following From the test piece length of the polyimide film measured under test conditions, the dimensional change rate is calculated using the following formulas (1) to (3), and the calculated dimensional change rate is compared and evaluated by the following evaluation procedure. This is a method for evaluating the dimensional stability of a polyimide film.

［試験条件］
（ａ）．試験片は、短冊状で、ポリイミドフィルムのＴＤ方向を、試験片の幅方向とする試験片Ｍ系列と、ポリイミドフィルムのＭＤ方向を、試験片の幅方向とする試験片Ｔ系列を、ポリイミドフィルムの幅方向における中心線位置、及び前記中心線位置から幅方向に等間隔の複数位置からサンプリングする。
（ｂ）．雰囲気は不活性雰囲気。
（ｃ）．試験片に与える温度プロファイルは、第１段階で一旦基準点となる室温ｔ０から１００℃以上、２００℃以下の温度に達した後に冷却して温度ｔ１（但し、ｔ１＝２５±２℃）とし、続いて第２段階として、温度ｔ１から温度ｔ２（但し、ｔ２＝１５０±２℃）まで昇温、保持し、その後、第３段階として、冷却して温度ｔ３（但し、ｔ３＝２５±２℃）にて保持する。
（ｄ）．試験片長の測定は、試験片毎に、温度ｔ０、ｔ１、ｔ２、ｔ３における標点間距離ｐ０、ｐ１、ｐ２、ｐ３の値を測定する。
（ｅ）．寸法変化率の算出は、（ｄ）で得た各試験片毎のｐ０〜ｐ３の値を、下記式（１）〜（３）に代入して各試験片毎の寸法変化率ｄＬ０、ｄＬ１、ｄＬ２、ｄＬ３を算出する。 [Test conditions]
(A). The test piece is strip-shaped, and a test piece M series in which the TD direction of the polyimide film is the width direction of the test piece and a test piece T series in which the MD direction of the polyimide film is the width direction of the test piece are polyimide films. Are sampled from the center line position in the width direction and a plurality of positions equidistant from the center line position in the width direction.
(B). The atmosphere is inert.
(C). The temperature profile given to the test piece is a temperature t 1 (however, t 1 = 25 ± 2 ° C.) after reaching a temperature of 100 ° C. or more and 200 ° C. or less once from the room temperature t 0 which is a reference point in the first stage. Then, as the second stage, the temperature is raised and maintained from the temperature t 1 to the temperature t 2 (where t 2 = 150 ± 2 ° C.), and then the third stage is cooled to the temperature t 3 (however, , T 3 = 25 ± 2 ° C.).
(D). The test piece length is measured by measuring the distances between the gauge points p 0 , p 1 , p 2 , and p 3 at temperatures t 0 , t 1 , t 2 , and t 3 for each test piece.
(E). The dimensional change rate is calculated by substituting the values of p 0 to p 3 for each test piece obtained in (d) into the following formulas (1) to (3), and the dimensional change rate dL 0 for each test piece. , DL 1 , dL 2 , dL 3 are calculated.

［評価手順］
（イ）．試験片Ｍ系列及び試験片Ｔ系列における寸法変化の基準位置を、測定に供したポリイミドフィルムの幅方向における中心線位置から採られた試験片とする。
（ロ）．試験片Ｍ系列毎、及び試験片Ｔ系列毎に、前記基準位置の試験片における寸法変化率ｄＬ３と、フィルムの幅方向の最外側に位置する試験片における寸法変化率ｄＬ３を比較し、寸法変化安定性を評価する。 [Evaluation procedure]
(I). The reference position of the dimensional change in the test piece M series and the test piece T series is a test piece taken from the center line position in the width direction of the polyimide film subjected to the measurement.
(B). For each specimen M series and each specimen T series, the dimensional change rate dL 3 in the test piece at the reference position is compared with the dimensional change ratio dL 3 in the test piece located on the outermost side in the width direction of the film, Evaluate dimensional change stability.

Figure 2015141094
Figure 2015141094

本発明の第２の発明は、第１の発明における熱機械分析装置（ＴＭＡ）の定荷重引張測定モードにおける定荷重が、ポリイミドフィルムの弾性限内の荷重であることを特徴とするポリイミドフィルムの寸法安定性評価方法である。   According to a second aspect of the present invention, there is provided a polyimide film characterized in that the constant load in the constant load tensile measurement mode of the thermomechanical analyzer (TMA) in the first aspect is a load within the elastic limit of the polyimide film. This is a dimensional stability evaluation method.

本発明の第３の発明は、第１及び第２の発明のけるポリイミドフィルムが、電子部品の基板用ポリイミドフィルムであることを特徴とするポリイミドフィルムの寸法安定性評価方法である。   A third invention of the present invention is a method for evaluating the dimensional stability of a polyimide film, wherein the polyimide film according to the first and second inventions is a polyimide film for a substrate of an electronic component.

本発明のポリイミドフィルムの評価方法によれば、精度よく、かつ簡便にポリイミドフィルムの寸法安定性を、汎用的に使用される熱機械分析装置（ＴＭＡ）を用いて評価できる。   According to the method for evaluating a polyimide film of the present invention, the dimensional stability of the polyimide film can be accurately and easily evaluated using a general-purpose thermomechanical analyzer (TMA).

さらに、フレキシブルプリント配線板における高密度、且つ精密な配線加工を可能とするためには、その基板のベースフィルムの寸法変化率をできる限り小さくすることが必要であり、従って、この寸法変化率を精度よく評価して、高密度、且つ精密な配線加工に適するフィルムの選別を簡便にできるようにするため、本発明が特定する条件でＴＭＡを用いて、その寸法変化率を測定することで、０．０１μｍの高い精度で寸法変化率を算出することが可能となり、工業上顕著な効果を奏するものである。   Furthermore, in order to enable high-density and precise wiring processing in a flexible printed wiring board, it is necessary to make the dimensional change rate of the base film of the substrate as small as possible. In order to evaluate accurately and enable easy selection of a film suitable for high-density and precise wiring processing, by measuring the dimensional change rate using TMA under the conditions specified by the present invention, It becomes possible to calculate the dimensional change rate with a high accuracy of 0.01 μm, which has a remarkable industrial effect.

本発明に係る試験片のサンプリング法を示す図で、（ａ）はサンプリング箇所を示す図、（ｂ）は試験片の形状を示す図である。It is a figure which shows the sampling method of the test piece which concerns on this invention, (a) is a figure which shows a sampling location, (b) is a figure which shows the shape of a test piece. 本発明に係るＴＭＡ装置による寸法測定における説明図で、（ａ）は測定チャックに両端を把持、固定された試験片で構成される測定サンプルを示し、（ｂ）は寸法測定におけるＴＭＡ装置の測定部を示す図である。It is explanatory drawing in the dimension measurement by the TMA apparatus which concerns on this invention, (a) shows the measurement sample comprised by the test piece which hold | gripped both ends to the measurement chuck | zipper, (b) measured the TMA apparatus in dimension measurement FIG. 本発明にかかるＴＭＡ測定の温度プロファイルである。It is a temperature profile of TMA measurement concerning the present invention. 実施例におけるポリイミドフィルムの測定データの一例である。It is an example of the measurement data of the polyimide film in an Example.

以下に、本発明について具体的に説明する。
本発明のフレキシブルプリント配線板用銅張積層板用ポリイミドフィルムの評価方法の特徴とする所は、フレキシブルプリント配線板用銅張積層板などの電子部品の基板に用いられるポリイミドフィルムの寸法安定性を、熱機械分析装置（ＴＭＡ、Ｔｈｅｒｍｏ Ｍｅｃｈａｎｉｃａｌ Ａｎａｌｙｚｅｒ）を用い、フィルム試験片を定荷重引張モードにて試験、評価する方法である。 The present invention will be specifically described below.
The feature of the evaluation method of the polyimide film for copper-clad laminates for flexible printed wiring boards of the present invention is that the dimensional stability of the polyimide film used for substrates of electronic components such as copper-clad laminates for flexible printed wiring boards is increased. In this method, a film test piece is tested and evaluated in a constant load tension mode using a thermomechanical analyzer (TMA, Thermo Mechanical Analyzer).

その試験条件について説明する。
（ａ）．試験片
使用する試験片は、図１（ａ）に示すようなポリイミドフィルム１のＴＤ方向を、試験片の幅方向とする試験片Ｍ系列と、ポリイミドフィルム１のＭＤ方向を、試験片の幅方向とする試験片Ｔ系列を、ポリイミドフィルムの幅方向における中心線位置Ｃ、及び前記中心線位置Ｃから幅方向に等間隔ｄの複数位置ＣＭ Ｒ、ＣＯ Ｒ、ＣＭ Ｌ、ＣＯ Ｌからサンプリングした図１（ｂ）に示す短冊状試験片Ｓである。
なお、サンプリングする位置は、少なくとも、基準点となる中心線位置Ｃを含んで、少なくとも２か所以上とする。実施例では片側３か所の場合（試料１Ａ〜１Ｅ、２Ａ〜２Ｅ）を示しているが、幅方向の両側からサンプリングしても良い。
試験片Ｍ系列と試験片Ｔ系列は、図１（ａ）に示すように対比する位置関係でのサンプリングが望ましい。 The test conditions will be described.
(A). Test piece The test piece used is a test piece M series in which the TD direction of the polyimide film 1 as shown in FIG. 1A is the width direction of the test piece, and the MD direction of the polyimide film 1 is the width of the test piece. The test piece T series to be oriented is a center line position C in the width direction of the polyimide film, and a plurality of positions C M R , C O R , C M L , C O at equal intervals d from the center line position C in the width direction. a strip specimen S shown in FIG. 1 (b) sampled from L.
The sampling positions include at least two or more locations including the center line position C as a reference point. In the embodiment, the case of three places on one side (samples 1A to 1E, 2A to 2E) is shown, but sampling may be performed from both sides in the width direction.
The test piece M series and the test piece T series are preferably sampled in a positional relationship as shown in FIG.

試験片の厚みは、ポリイミドフィルムが使用される用途によって変わるが０．２〜１ｍｍの範囲で良好な測定が可能で、その幅は、通常２〜６ｍｍである。さらに、長さは幅の数倍程度とし、通常２０〜５０ｍｍ程度とすればよい。
この評価に供する試料を複数枚、同一形状で採取して評価測定し、その結果を比較解析することにより、フィルムの面内のバラつきや寸法安定性の傾向など、従来のＪＩＳ法では得られなかった詳細な情報を得ることができる。 Although the thickness of a test piece changes with uses in which a polyimide film is used, a favorable measurement is possible in the range of 0.2-1 mm, and the width | variety is 2-6 mm normally. Furthermore, the length is about several times the width, and usually about 20 to 50 mm.
Samples to be used for this evaluation are collected in the same shape, measured and evaluated, and the results are compared and analyzed, which cannot be obtained by conventional JIS methods such as in-plane variations in film and dimensional stability. Detailed information can be obtained.

（ｂ）．試験時の雰囲気
試験時における試料回りの雰囲気は不活性雰囲気が良く、窒素ガス、アルゴンガスなどを使用して試験雰囲気を形成する。これらのガスを使用する際には、ガス中の水分を除去した乾燥ガスとして使用する。 (B). Atmosphere at the time of testing The atmosphere around the sample at the time of testing is preferably an inert atmosphere, and a test atmosphere is formed using nitrogen gas, argon gas, or the like. When these gases are used, they are used as a dry gas from which moisture in the gas has been removed.

（ｃ）．試験片に与える温度プロファイル
本発明では、電子部品のベースフィルムに用いられるポリイミドフィルムの寸法変化率を評価する目的で、プリント配線板の製造時の温度プロファイルとしている。その温度プロファイルを図３に図示して示す。なお、この温度プロファイルは、対象とする用途に合わせた条件とすることも可能である。 (C). Temperature profile given to test piece In the present invention, for the purpose of evaluating the dimensional change rate of a polyimide film used for a base film of an electronic component, a temperature profile at the time of manufacturing a printed wiring board is used. The temperature profile is shown in FIG. Note that this temperature profile can also be set according to the intended application.

図３から、本発明における温度プロファイルは、先ず第１段階で一旦基準点となる室温ｔ０（厳密に測定する際には、ｔ１と同じく２５℃±２℃とする）から１００℃以上、２００℃以下の温度に達した後に冷却して温度ｔ１（但し、ｔ１＝２５±２℃）とし、続いて第２段階として、温度ｔ１から温度ｔ２（但し、ｔ２＝１５０±２℃）まで昇温、保持し、その後、第３段階として、冷却して温度ｔ３（但し、ｔ３＝２５±２℃）にて保持する。 From FIG. 3, the temperature profile in the present invention is first from the room temperature t 0 (25 ° C. ± 2 ° C. as in t 1 when measured strictly), which is once a reference point in the first stage, to 100 ° C. or more. After reaching a temperature of 200 ° C. or lower, the system is cooled to a temperature t 1 (where t 1 = 25 ± 2 ° C.). Subsequently, as a second stage, the temperature t 1 is changed to a temperature t 2 (where t 2 = 150 ±). The temperature is raised to 2 ° C. and held, and then cooled and held at a temperature t 3 (where t 3 = 25 ± 2 ° C.) as a third stage.

測定における温度プロファイルを与える昇降温速度については、毎分３℃以上、１０℃以下、特に毎分５℃を条件とした測定が望ましい。
毎分３℃未満ではＴＭＡ装置での温度制御が難しく、毎分１０℃を超えると測定対象フィルムが設定温度に至るのに充分な時間ではなく測定感度が低下するため好ましくない。
なお、図３中の符号ＰＩは、試験片に用いた「ポリイミドフィルム」を意味するものである。 About the temperature rising / falling speed which gives the temperature profile in a measurement, the measurement on condition of 3 degreeC / min or more and 10 degrees C / min, especially 5 degreeC / min is desirable.
If the temperature is less than 3 ° C. per minute, it is difficult to control the temperature with the TMA apparatus. If the temperature exceeds 10 ° C. per minute, it is not preferable because the measurement sensitivity is not sufficient for the film to be measured to reach the set temperature.
In addition, the code | symbol PI in FIG. 3 means the "polyimide film" used for the test piece.

（ｄ）．試験片長の測定
図４は、図３の温度プロファイルに伴って変化した試験片長挙動を示す測定データの一例を表す曲線で、試験片毎に、温度ｔ０、ｔ１、ｔ２、ｔ３における試験片長（標点間距離：ＧＬ）ｐ０、ｐ１、ｐ２、ｐ３の値を試験片長として測定する。 (D). Measurement of Specimen Length FIG. 4 is a curve showing an example of measurement data showing the behavior of the specimen length changed with the temperature profile of FIG. 3, and the temperature at each of the specimens at temperatures t 0 , t 1 , t 2 , t 3 is shown. Test piece length (distance between gauge points: GL) The values of p 0 , p 1 , p 2 , and p 3 are measured as test piece lengths.

（ｅ）．寸法変化率の算出
前記（ｄ）で得た各試験片毎のｐ０〜ｐ３の値を、下記式（１）〜（３）に代入して各試験片毎の寸法変化率ｄＬ０、ｄＬ１、ｄＬ２、ｄＬ３を算出する。 (E). Calculation of dimensional change rate The value of p 0 to p 3 for each test piece obtained in (d) above is substituted into the following formulas (1) to (3), and the dimensional change rate dL 0 for each test piece. dL 1 , dL 2 , dL 3 are calculated.

Figure 2015141094
Figure 2015141094

（ｆ）．試験片長測定条件
図２は、ＴＭＡ装置による寸法測定における説明図で、図２（ａ）は測定サンプルを示し、図２（ｂ）は寸法測定におけるＴＭＡ装置の測定部を示す図である。
ＴＭＡ装置を用いて、（ｄ）の試験片長を測定する際に試験片Ｓを、図２（ａ）に示すように測定チャック３、３により両端を把持、固定された測定サンプル２に形成する。
その測定サンプル２は、図２（ｂ）に示すようにＴＭＡ装置の引張モード用治具１０、１１で構成する測定位置に取り付けられる。その際、測定位置に保持する荷重については、ポリイミドフィルムの弾性限内で試験片の保持が可能な程度の荷重が望ましく、上記本発明の試験片の形態においては、３ｇ以上、７ｇ未満、特に５ｇでの測定が望ましい。３ｇ未満の場合はフィルムの保持が不十分で測定データに振動によるノイズが加わりやすく、７ｇを超えるとフィルムに外力が加わってしまう為精度が高い測定ができない。 (F). Test Specimen Length Measurement Conditions FIG. 2 is an explanatory diagram in dimension measurement by a TMA apparatus, FIG. 2 (a) shows a measurement sample, and FIG. 2 (b) shows a measurement unit of the TMA apparatus in dimension measurement.
Using the TMA apparatus, when measuring the length of the test piece (d), the test piece S is formed into a measurement sample 2 held and fixed at both ends by the measurement chucks 3 and 3 as shown in FIG. .
The measurement sample 2 is attached to a measurement position constituted by the tensile mode jigs 10 and 11 of the TMA apparatus as shown in FIG. At that time, the load held at the measurement position is preferably a load that can hold the test piece within the elastic limit of the polyimide film. In the test piece form of the present invention, the load is 3 g or more and less than 7 g. Measurement at 5 g is desirable. If it is less than 3 g, the film is not sufficiently held, and noise due to vibration is likely to be added to the measurement data. If it exceeds 7 g, an external force is applied to the film, so high-precision measurement cannot be performed.

すなわち、本発明に係る評価方法における寸法変化率の測定では、室温（ｔ０）から昇温させて１００℃以上、２００℃以下の設定温度に達した後に２５±２℃（ｔ１）まで冷却し保持する第１段階と、その後ポリイミドフィルムをベースフィルムとした場合において２５±２℃（ｔ１）から１５０±２℃（ｔ２）まで昇温、保持した後２５±２℃（ｔ３）に保持する第２段階を連続して不活性ガス雰囲気中で測定することで、測定中に大気雰囲気中の水分を吸湿することなく、寸法変化を精度よく測定することができる。 That is, in the measurement of the dimensional change rate in the evaluation method according to the present invention, the temperature is raised from room temperature (t 0 ), and after reaching a set temperature of 100 ° C. or higher and 200 ° C. or lower, cooling to 25 ± 2 ° C. (t 1 ). In the case where a polyimide film is used as a base film, the temperature is raised from 25 ± 2 ° C. (t 1 ) to 150 ± 2 ° C. (t 2 ), and then held 25 ± 2 ° C. (t 3 ). By continuously measuring the second stage held in the inert gas atmosphere, the dimensional change can be accurately measured without absorbing moisture in the air atmosphere during the measurement.

［評価手順］
上記（ａ）から（ｆ）により求めた寸法変化率を用いた寸法安定性の評価を下記に示す。
（イ）．試験片Ｔ系列、及び試験片Ｍ系列における寸法変化の基準位置を、測定に供したポリイミドフィルムの幅方向における中心線位置Ｃから採られた試験片（図１（ａ）における試験片１Ａ及び試験片２Ａ）とする。 [Evaluation procedure]
Evaluation of dimensional stability using the dimensional change rate obtained from (a) to (f) above is shown below.
(I). The test piece taken from the center line position C in the width direction of the polyimide film subjected to the measurement was used as the reference position of the dimensional change in the test piece T series and the test piece M series (test piece 1A and test in FIG. 1A). Let's say piece 2A)

（ロ）．試験片Ｍ系列毎、及び試験片Ｔ系列毎に、前記基準位置の試験片における寸法変化率ｄＬ３と、フィルムの幅方向の最外側に位置する試験片（図１（ａ）における試験片１Ｄ、１Ｅ及び試験片２Ｄ、２Ｅ）における寸法変化率ｄＬ３を比較し、寸法変化安定性を評価する。 (B). For each specimen M series and each specimen T series, the dimensional change rate dL 3 in the specimen at the reference position, and the specimen located on the outermost side in the width direction of the film (the specimen 1D in FIG. 1A). , 1E and specimen 2D, to compare the dimensional change rate dL 3 in 2E), to evaluate the dimensional change stability.

さらに、本発明では以下に示すポリイミドフィルムの特性を評価することも可能である。
（ハ）試験片毎の寸法変化率ｄＬ１の評価は、使用したポリイミドフィルムの含有水分量について推定することができる。
例えば、ｄＬ１が負の値となった場合には、含有水分の除去によってフィルムが収縮したと考えられる。 Furthermore, in this invention, it is also possible to evaluate the characteristic of the polyimide film shown below.
(C) The evaluation of the dimensional change rate dL 1 for each test piece can be estimated for the moisture content of the polyimide film used.
For example, when dL 1 becomes a negative value, it is considered that the film contracted due to the removal of the contained water.

（ニ）試験片毎の寸法変化率ｄＬ２の評価は、加熱処理によるポリイミドフィルムの伸張傾向を推定することができる。
例えばｄＬ２がより大きな値を示す場合はポリイミドフィルムの膨張係数が高いと推定でき、さらに３０分間の温度保持の間での寸法変化挙動についても評価が可能である。 (D) Evaluation of dimensional change dL 2 specimens per can estimate the expansion tendency of the polyimide film by heat treatment.
For example, when showing the dL 2 Gayori larger value can be estimated with high expansion coefficient of the polyimide film, it is possible to further evaluation for dimensional change behavior among the temperature hold of 30 minutes.

（ホ）試験片毎の寸法変化率ｄＬ３の評価は、加熱処理後の寸法安定性を推定することができる。
例えば、ｄＬ３が正の値の場合は加熱処理後に伸張したと推定でき、ｄＬ３が負の値の場合は加熱処理後に収縮したと推定できる。さらに２５±２℃（ｔ３）に１時間以上保った後に測定するため、加熱処置後の寸法安定性についても評価が可能である。 (E) Evaluation of the dimensional change rate dL 3 for each test piece can estimate the dimensional stability after the heat treatment.
For example, when dL 3 is a positive value, it can be estimated that the film has expanded after the heat treatment, and when dL 3 is a negative value, it can be estimated that the film has contracted after the heat treatment. Furthermore, since the measurement is performed after maintaining at 25 ± 2 ° C. (t 3 ) for 1 hour or longer, it is possible to evaluate the dimensional stability after the heat treatment.

以下に本発明の実施例、比較例を示して詳細に説明するが、本発明は以下の実施例により何ら制限されることはない。
測定用試料として、Ａ社及びＢ社の２種類のポリイミドフィルムＡ、Ｂを用いた。
測定装置及び測定条件は、ＴＭＡ装置にブルカー・エイエックス株式会社製「ＴＭＡ−４０３０ＳＡ」を使用し、窒素雰囲気下において昇温・冷却速度を毎分５℃に設定し、荷重を５ｇとして、測定を行った。 EXAMPLES Hereinafter, examples and comparative examples of the present invention will be described in detail, but the present invention is not limited by the following examples.
Two types of polyimide films A and B from Company A and Company B were used as measurement samples.
Measurement equipment and measurement conditions were measured using a Bruker Ax Co., Ltd. “TMA-4030SA” as the TMA equipment, setting the heating / cooling rate to 5 ° C./min in a nitrogen atmosphere, and setting the load to 5 g. Went.

評価用ポリイミドフィルムとして、幅５２４ｍｍのポリイミドフィルムＡを使用し、図１（ａ）に示すようにフィルムの中心と中心から間隔ｄを１００ｍｍごとにそれぞれ２枚で合計５枚とし、試料の長手方向がフィルムの搬送方向と垂直（ＴＤ）になるような試験片Ｔ系列の試験片１Ａ〜１Ｅを、幅５ｍｍ×長さ約３０ｍｍの短冊状の測定サンプル（図１（ｂ）参照）として採取した。   As a polyimide film for evaluation, a polyimide film A having a width of 524 mm was used, and as shown in FIG. 1A, the distance d from the center of the film was 2 for each 100 mm, for a total of 5 sheets. Test specimens 1A to 1E of T series, which are perpendicular to the film transport direction (TD), were collected as strip-shaped measurement samples (see FIG. 1B) having a width of 5 mm and a length of about 30 mm. .

［試料１Ａ］
ＴＭＡ装置の測定チャック３、３に試料１Ａ（図２（ａ）、符号Ｓ）を把持、固定して測定サンプル２（図２（ａ）参照）を形成し、図２（ｂ）に示す引張モード用治具１０、１１で構成する測定位置に取り付け、ＴＤ方向に５ｇの荷重が付加した。次いで引張モード用治具１０、１１間の距離（標点間距離ＧＬ）ｐ０（１Ａ）を測長したところ、ｐ０（１Ａ）＝２３．２０００ｍｍであった。
測定は、まず室温から１０５℃まで昇温させた後、一旦２５℃（ｔ１）まで冷却した後、３０分間保持した。この保持時の試料寸法ｐ１（１Ａ）＝２３．１８５６ｍｍであった。次に引き続き２５℃（ｔ１）から１５０℃（ｔ２）まで昇温し、３０分間保持した。その保持時の試料寸法ｐ２（１Ａ）＝２３．２２５８ｍｍであった。続いて２５℃（ｔ３）まで冷した後、９０分間保持し、この保持後の試料寸法ｐ３（１Ａ）＝２３．１８４９ｍｍであった。 [Sample 1A]
A sample 1A (FIG. 2A, symbol S) is held and fixed on the measurement chucks 3 and 3 of the TMA apparatus to form a measurement sample 2 (see FIG. 2A), and the tension shown in FIG. It was attached to the measurement position constituted by the mode jigs 10 and 11, and a load of 5 g was applied in the TD direction. Next, when the distance between the tensile mode jigs 10 and 11 (distance GL between the gauge points) p 0 (1A) was measured, it was p 0 (1A) = 23.2000 mm.
In the measurement, the temperature was first raised from room temperature to 105 ° C., then cooled to 25 ° C. (t 1 ), and held for 30 minutes. The sample size p 1 (1A) at the time of holding was 23.1856 mm. Next, the temperature was raised from 25 ° C. (t 1 ) to 150 ° C. (t 2 ) and held for 30 minutes. The sample size p 2 (1A) at the time of holding was 23.2258 mm. Subsequently, after cooling to 25 ° C. (t 3 ), the sample was held for 90 minutes, and the sample size p 3 (1A) after this holding was 23.1849 mm.

試料１Ａの測定点ｔ１（ＲＴ−１０５℃−２５℃）における寸法変化率は、ｄＬ１（１Ａ）は−０．０６２％と、フィルムは収縮していたことがわかる。原因として、フィルムが水分を吸湿したものと推定される。
他の測定点における寸法変化率は、測定点ｔ２（２５℃−１５０℃）では寸法変化率ｄＬ２（１Ａ）は０．１７３％、測定点ｔ３（１５０℃−２５℃）では寸法変化率ｄＬ３（１Ａ）は−０．００３％であった。 The dimensional change rate at the measurement point t 1 (RT-105 ° C.-25 ° C.) of the sample 1A was −0.062% for dL 1 (1A), indicating that the film was contracted. The cause is presumed that the film absorbed moisture.
Dimensional change at the other measurement points, the measurement point t 2 (25 ℃ -150 ℃) the dimensional change dL 2 (1A) is 0.173%, the dimensional change in the measurement point t 3 (150 ℃ -25 ℃) The rate dL 3 (1A) was −0.003%.

［試料１Ｂ］
試料１Ａ同様の条件で測定を行った結果、その寸法変化率は、ｄＬ１（１Ｂ）は−０．０８８％、ｄＬ２（１Ｂ）は０．１７４％、ｄＬ３（１Ｂ）は−０．００３％であった。 [Sample 1B]
Sample 1A 1 was measured under the same conditions, the dimensional change rate, dL 1 (1B) is -0.088%, dL 2 (1B) is 0.174%, dL 3 (1B) is -0. It was 003%.

［試料１Ｃ］
試料１Ａ同様の条件で測定を行った結果、その寸法変化率は、ｄＬ１（１Ｃ）は−０．０９５％、ｄＬ２（１Ｃ）は０．１７８％、ｄＬ３（１Ｃ）は−０．００２％であった。 [Sample 1C]
Sample 1A 1 was measured under the same conditions, the dimensional change rate, dL 1 (1C) is -0.095%, dL 2 (1C) is 0.178%, dL 3 (1C) -0. It was 002%.

［試料１Ｄ］
試料１Ａ同様の条件で測定を行った結果、その寸法変化率は、ｄＬ１（１Ｄ）は−０．０６０％、ｄＬ２（１Ｄ）は０．１７２％、ｄＬ３（１Ｄ）は−０．００４％であった。 [Sample 1D]
As a result of the measurement under the same conditions as the sample 1A, the dimensional change rate was -0.060% for dL 1 (1D), 0.172% for dL 2 (1D), and -0.0.d for dL 3 (1D). It was 004%.

［試料１Ｅ］
試料１Ａ同様の条件で測定を行った結果、その寸法変化率は、ｄＬ１（１Ｅ）は−０．０５５％、ｄＬ２（１Ｅ）は０．１７５％、ｄＬ３（１Ｅ）は−０．００３％であった。 [Sample 1E]
Sample 1A 1 was measured under the same conditions, the dimensional change rate, dL 1 (1E) is -0.055%, dL 2 (1E) is 0.175%, dL 3 (1E) -0. It was 003%.

以上の試料１Ａ〜１Ｅの寸法変化率の測定結果から、ｄＬ１はいずれもマイナスの数値で収縮状態にあり、フィルム全体において、吸湿していたことがわかる。またポリイミドフィルムの幅（ＴＤ）方向の寸法変化率ｄＬ３は−０．００２〜−０．００３％であると算定され、ポリイミドフィルムＡの加熱処理後のＴＤ方向の寸法変化率ｄＬ３は極めて小さく安定しており、フレキシブルプリント配線板用銅張積層板用ベースフィルムとして良好な寸法安定性を有していると評価できた。 From the measurement results of the dimensional change rates of the above samples 1A to 1E, it can be seen that dL 1 is in a contracted state with a negative value, and the entire film has absorbed moisture. The dimensional change rate dL 3 in the width (TD) direction of the polyimide film is calculated to be −0.002 to −0.003%, and the dimensional change rate dL 3 in the TD direction after the heat treatment of the polyimide film A is extremely high. It was small and stable and could be evaluated as having good dimensional stability as a base film for copper-clad laminates for flexible printed wiring boards.

評価用ポリイミドフィルムとして、実施例１と同じフィルムを使用し、フィルムの中心と中心から間隔を１００ｍｍごとにそれぞれ２枚で合計５枚とし、試料の長手方向がフィルムの搬送方向と平行（ＭＤ）になるようにフィルム幅５ｍｍ×長さ約２３ｍｍの短冊状の測定サンプルとして２Ａ〜２Ｅの５枚の試料を採取した。   As the polyimide film for evaluation, the same film as in Example 1 is used, and the distance from the center of the film is 2 for each 100 mm, for a total of 5 sheets, and the longitudinal direction of the sample is parallel to the film transport direction (MD) Thus, five samples 2A to 2E were collected as strip-shaped measurement samples having a film width of 5 mm and a length of about 23 mm.

［試料２Ａ］
測定チャックに試料２Ａを取り付け、実施例1と同様にして評価した。測定用治具間の距離ｐ０（２Ａ）は２３．４３００ｍｍであった。２５℃（ｔ１）まで冷却した後の試料寸法ｐ１（２Ａ）は２３．４１８２ｍｍであった。次に引き続き２５℃（ｔ１）から１５０℃（ｔ２）まで昇温し、３０分間保持した後の試料寸法ｐ２（２Ａ）は２３．４６２６ｍｍであった。最後に２５℃（ｔ３）まで冷した後の試料寸法ｐ３（２Ａ）は２３．４１７６ｍｍであった。 [Sample 2A]
Sample 2A was attached to the measurement chuck and evaluated in the same manner as in Example 1. The distance p 0 (2A) between the measuring jigs was 23.4300 mm. The sample dimension p 1 (2A) after cooling to 25 ° C. (t 1 ) was 23.4182 mm. Next, the sample size p 2 (2A) after the temperature was raised from 25 ° C. (t 1 ) to 150 ° C. (t 2 ) and held for 30 minutes was 23.4626 mm. The sample size p 3 (2A) after finally cooling to 25 ° C. (t 3 ) was 23.4176 mm.

この場合のｄＬ１（２Ａ）は−０．０５０％とフィルムが収縮したことから、吸湿していたと推定できる。ｄＬ２（２Ａ）は０．１４０％、ｄＬ３（２Ａ）は−０．００３％であった。
実施例１と同様に、測定した。 In this case, dL 1 (2A) was −0.050%, and it was estimated that moisture was absorbed because the film contracted. dL 2 (2A) was 0.140% and dL 3 (2A) was −0.003%.
Measurement was performed in the same manner as in Example 1.

試料２Ｂ〜試料２Ｅについても試料２Ａと同様の条件で測定を行った結果、試料２Ｂでは、ｄＬ１（２Ｂ）は−０．０５１％、ｄＬ２（２Ｂ）は０．１８０％、ｄＬ３（２Ｂ）は−０．００８％であった。
試料２Ｃでは、ｄＬ１（２Ｃ）は−０．０４２％、ｄＬ２（２Ｃ）は０．１８８％、ｄＬ３（２Ｃ）は−０．００９％であった。
試料２Ｄでは、ｄＬ１（２Ｄ）は−０．０４３％、ｄＬ２（２Ｄ）は０．１５２％、ｄＬ３（２Ｄ）は−０．００８％であった。
試料２Ｅでは、ｄＬ１（２Ｅ）は−０．０４９％、ｄＬ２（２Ｅ）は０．１６５％、ｄＬ３（２Ｅ）は−０．００６％であった。 As a result of measuring Sample 2B to Sample 2E under the same conditions as Sample 2A, dL 1 (2B) is −0.051%, dL 2 (2B) is 0.180%, dL 3 ( 2B) was -0.008%.
In sample 2C, dL 1 (2C) was −0.042%, dL 2 (2C) was 0.188%, and dL 3 (2C) was −0.009%.
In sample 2D, dL 1 (2D) was −0.043%, dL 2 (2D) was 0.152%, and dL 3 (2D) was −0.008%.
In sample 2E, dL 1 (2E) was −0.049%, dL 2 (2E) was 0.165%, and dL 3 (2E) was −0.006%.

以上の試料２Ａ〜２Ｅの寸法変化率の測定結果から、幅（ＭＤ）方向の寸法変化率ｄＬ３は−０．００３〜−０．００９％であると算定され、ポリイミドフィルムＡの加熱処理後の幅（ＭＤ）方向の寸法変化率は小さく安定しており、フレキシブルプリント配線板用銅張積層板用ベースフィルムとして良好な寸法安定性を有していると評価できた。 From the measurement result of the dimensional change rate of the above samples 2A to 2E, the dimensional change rate dL 3 in the width (MD) direction is calculated to be −0.003 to −0.009%, and after the heat treatment of the polyimide film A The rate of dimensional change in the width (MD) direction was small and stable, and could be evaluated as having good dimensional stability as a base film for copper-clad laminates for flexible printed wiring boards.

評価用ポリイミドフィルムとして、幅５２４ｍｍのポリイミドフィルムＢを使用して、実施例１と同様にサンプリングを行い、試料の長手方向がフィルムの搬送方向と垂直（ＴＤ）になるような試験片Ｔ系列の試験片３Ａ〜３Ｅの５枚の試料を採取した。   As a polyimide film for evaluation, using a polyimide film B having a width of 524 mm, sampling was performed in the same manner as in Example 1, and a test piece T series in which the longitudinal direction of the sample was perpendicular (TD) to the transport direction of the film. Five samples of test pieces 3A to 3E were collected.

［試料３Ａ］
実施例１と同条件で測定を行った結果、測定用治具間の距離ｐ０（３Ａ）＝２３．５２００ｍｍ、試料寸法ｐ１（３Ａ）は２３．４８３２ｍｍ、ｐ２（３Ａ）は２３．５２２５ｍｍ、ｐ３（３Ａ）は２３．４８１４ｍｍであった。
この場合のｄＬ１（３Ａ）は−０．１５６％とフィルムが収縮したことから吸湿していたと推定できる。また、実施例１のポリイミドフィルムＡと比較して、より吸湿していたフィルムと推定できる。ｄＬ２（３Ａ）は０．１６７％、ｄＬ３（３Ａ）は−０．００８％であった。 [Sample 3A]
As a result of measurement under the same conditions as in Example 1, the distance between the measurement jigs p 0 (3A) = 23.5200 mm, the sample size p 1 (3A) was 23.4832 mm, and p 2 (3A) was 23. 5225 mm and p 3 (3A) were 23.4814 mm.
In this case, dL 1 (3A) was −0.156%, and it can be estimated that moisture was absorbed because the film contracted. Moreover, it can be presumed that the film absorbs more moisture than the polyimide film A of Example 1. dL 2 (3A) is 0.167%, dL 3 (3A) was -0.008%.

実施例１と同様に、試料３Ｂ〜試料３Ｅについて、測定した。
試料３Ａ同様の条件で測定を行った結果、試料３Ｂでは、ｄＬ１（３Ｂ）は−０．１４０％、ｄＬ２（３Ｂ）は０．１６５％、ｄＬ３（３Ｂ）は−０．００３％であった。
試料３Ｃでは、ｄＬ１（３Ｃ）は−０．０７３％、ｄＬ２（３Ｃ）は０．１６６％、ｄＬ３（３Ｃ）は−０．００８％であった。
試料３Ｄでは、ｄＬ１（３Ｄ）は−０．０５６％、ｄＬ２（３Ｄ）は０．１６６％、ｄＬ３（３Ｄ）は−０．０１０％であった。
試料３Ｅでは、ｄＬ１（３Ｅ）は−０．１３２％、ｄＬ２（３Ｅ）は０．１５８％、ｄＬ３（３Ｅ）は−０．０２２％であった。 In the same manner as in Example 1, measurement was performed on Sample 3B to Sample 3E.
As a result of measurement under the same conditions as Sample 3A, in Sample 3B, dL 1 (3B) was −0.140%, dL 2 (3B) was 0.165%, and dL 3 (3B) was −0.003%. Met.
In sample 3C, dL 1 (3C) was −0.073%, dL 2 (3C) was 0.166%, and dL 3 (3C) was −0.008%.
In sample 3D, dL 1 (3D) was −0.056%, dL 2 (3D) was 0.166%, and dL 3 (3D) was −0.010%.
In sample 3E, dL 1 (3E) was −0.132%, dL 2 (3E) was 0.158%, and dL 3 (3E) was −0.022%.

試料３Ａ〜３Ｅの寸法変化率から、ポリイミドフィルムＢの幅（ＴＤ）方向の寸法変化率ｄＬ３は−０．００３〜−０．０２２％であると算定され、このポリイミドフィルムＢの加熱処理後の幅（ＭＤ）方向の寸法変化率は、比較的小さく、フレキシブルプリント配線板用銅張積層板用ベースフィルムとして良好な寸法安定性を有し十分使用することはできるが、ポリイミドフィルムＡと比較すると幅（ＴＤ）方向で寸法変化が増加する傾向があることがわかった。 From the dimensional change rate of the samples 3A to 3E, the dimensional change rate dL 3 in the width (TD) direction of the polyimide film B is calculated to be −0.003 to −0.022%. The dimensional change rate in the width (MD) direction is relatively small and can be used sufficiently as a base film for copper-clad laminates for flexible printed wiring boards, but it can be used sufficiently. Compared with polyimide film A Then, it turned out that a dimensional change tends to increase in the width (TD) direction.

（比較例１）
実施例１で評価した幅５２４ｍｍのポリイミドフィルムＡを、「ＪＩＳ Ｃ ６４８１」の手法に準拠して３００×３００ｍｍに切り出し、０．８〜１．２ｍｍの穴をあけた。
試料を温度２０±２℃、相対湿度６０〜７０％の室内に２４時間放置し、ＴＤ方向の穴間隔を測定し、常態の試料寸法ｌ０とした。その後１５０℃、３０分間の加熱処理を行い、ＴＤ方向の穴間隔を測定し、加熱処理後の寸法ｌ２とした。但し、銅張積層基板ではない為、エッチング処置及びエッチング後の寸法l1は測定しないこととした。
加熱処理後の寸法変化率ＤＳ２を下記式（４）にて算出したところ、寸法変化率ＤＳ２＝０．０４７％であった。 (Comparative Example 1)
The polyimide film A having a width of 524 mm evaluated in Example 1 was cut into a size of 300 × 300 mm according to the method of “JIS C 6481”, and a 0.8 to 1.2 mm hole was formed.
The sample was left in a room at a temperature of 20 ± 2 ° C. and a relative humidity of 60 to 70% for 24 hours, and the hole interval in the TD direction was measured to obtain a normal sample size 10 . Then 0.99 ° C., subjected to a heat treatment of 30 minutes, to measure the hole spacing in the TD direction, and the dimensions l 2 after the heat treatment. However, since it is not a copper clad laminated substrate, the etching treatment and the dimension l 1 after etching were not measured.
When the dimensional change rate DS 2 after the heat treatment was calculated by the following formula (4), the dimensional change rate DS 2 = 0.047%.

Figure 2015141094
Figure 2015141094

（比較例２）
比較例１で評価した３００×３００ｍｍに切り出したポリイミドフィルムＡについて、「ＪＩＳ Ｃ ６４８１」の手法に準拠してＭＤ方向の常態試料寸法ｌ０、１５０℃、３０分間の加熱処理後のＭＤ方向の寸法ｌ２を測定した。加熱処理後の寸法変化率ＤＳ２は−０．００２％であった。 (Comparative Example 2)
About the polyimide film A cut out to 300 × 300 mm evaluated in Comparative Example 1, the normal sample size l 0 in the MD direction in accordance with the method of “JIS C 6481”, 150 ° C., the MD direction after the heat treatment for 30 minutes. The dimension l 2 was measured. Dimensional change DS 2 after the heat treatment was -0.002%.

（比較例３）
幅５２４ｍｍのポリイミドフィルムＢを、比較例１と同様に「ＪＩＳ Ｃ ６４８１」の手法に準拠して３００×３００ｍｍに切り出し、０．８〜１．２ｍｍの穴をあけた。
ＴＤ方向の常態試料寸法ｌ０、１５０℃、３０分間の加熱処理後のＭＤ方向の寸法ｌ２を測定した。加熱処理後の寸法変化率ＤＳ２は、０．０１１％であった。 (Comparative Example 3)
A polyimide film B having a width of 524 mm was cut into a size of 300 × 300 mm in accordance with the method of “JIS C 6481” in the same manner as in Comparative Example 1, and a hole of 0.8 to 1.2 mm was formed.
A normal sample dimension l 0 in the TD direction, a dimension l 2 in the MD direction after heat treatment at 150 ° C. for 30 minutes was measured. Dimensional change DS 2 after the heat treatment was 0.011%.

上記のように、比較例１〜３の従来法である「ＪＩＳ Ｃ ６４８１」の手法に準拠した評価方法では、本発明のようなフィルムの面内ばらつきなど詳細な情報が得られず、また得られた寸法変化率の数値も精度に問題のある数値であり、正確な評価が困難であることがわかり、本発明の評価方法によれば、フィルムの吸湿性の影響を抑え、精度よくかつ簡便に測定でき、フィルムの面内ばらつきの情報が得られる。   As described above, the evaluation method based on the method of “JIS C 6481” which is the conventional method of Comparative Examples 1 to 3 cannot obtain detailed information such as in-plane variation of the film as in the present invention. The numerical value of the obtained dimensional change rate is also a numerical value having a problem in accuracy, and it is found that accurate evaluation is difficult. According to the evaluation method of the present invention, the influence of the hygroscopicity of the film is suppressed, and it is accurate and simple. And information on in-plane variation of the film can be obtained.

１ ポリイミドフィルム
２ 測定サンプル
３ 測定チャック
１０、１１ 引張モード用治具
Ｓ 試験片 DESCRIPTION OF SYMBOLS 1 Polyimide film 2 Measurement sample 3 Measurement chucks 10 and 11 Tensile mode jig S Test piece

Claims (3)

ポリイミドフィルムの寸法安定性評価方法であって、
熱機械分析装置（Ｔｈｅｒｍｏ Ｍｅｃｈａｎｉｃａｌ Ａｎａｌｙｚｅｒ，ＴＭＡ）の定荷重引張測定モードを用い、
下記試験条件下で測定した前記ポリイミドフィルムの試験片長から、下記式（１）から（３）を用いて寸法変化率を算出し、算出した寸法変化率を下記評価手順により比較、評価することを特徴とするポリイミドフィルムの寸法安定性評価方法。

（記）
［試験条件］
（ａ）．試験片は短冊状で、
前記ポリイミドフィルムのＴＤ方向を、試験片の幅方向とする試験片Ｍ系列と、
前記ポリイミドフィルムのＭＤ方向を、試験片の幅方向とする試験片Ｔ系列を、
前記ポリイミドフィルムの幅方向における中心線位置、及び前記中心線位置から幅方向に等間隔の複数位置からサンプリングする。
（ｂ）．雰囲気は不活性雰囲気。
（ｃ）．試験片に与える温度プロファイルは、
第１段階で一旦基準点となる室温ｔ０から１００℃以上、２００℃以下の温度に達した後に冷却して温度ｔ１（但し、ｔ１＝２５±２℃）とし、続いて第２段階として、温度ｔ１から温度ｔ２（但し、ｔ２＝１５０±２℃）まで昇温、保持し、その後、第３段階として、冷却して温度ｔ３（但し、ｔ３＝２５±２℃）にて保持する。
（ｄ）．試験片長の測定は、試験片毎に、
温度ｔ０、ｔ１、ｔ２、ｔ３における標点間距離ｐ０、ｐ１、ｐ２、ｐ３の値を測定する。
（ｅ）．寸法変化率の算出は、
前記（ｄ）で得た試験片毎のｐ０〜ｐ３の値を、下記式（１）〜（３）に代入して各試験片毎の寸法変化率ｄＬ０、ｄＬ１、ｄＬ２、ｄＬ３を算出する。

［評価手順］
（イ）．前記試験片Ｍ系列及び試験片Ｔ系列における寸法変化の基準位置を、測定に供したポリイミドフィルムの幅方向における中心線位置から採られた試験片とする。
（ロ）．試験片Ｍ系列毎、及び試験片Ｔ系列毎に、前記基準位置の試験片における寸法変化率ｄＬ３と、フィルムの幅方向の最外側に位置する試験片における寸法変化率ｄＬ３を比較し、寸法変化安定性を評価する。
Figure 2015141094
 A method for evaluating the dimensional stability of a polyimide film,
Using the constant load tensile measurement mode of the thermomechanical analyzer (Thermo Mechanical Analyzer, TMA)
From the test piece length of the polyimide film measured under the following test conditions, the dimensional change rate is calculated using the following formulas (1) to (3), and the calculated dimensional change rate is compared and evaluated by the following evaluation procedure. A method for evaluating the dimensional stability of a polyimide film.

(Record)
[Test conditions]
(A). The specimen is strip-shaped,
A test piece M series in which the TD direction of the polyimide film is the width direction of the test piece,
A test piece T series in which the MD direction of the polyimide film is the width direction of the test piece,
Sampling is performed from a center line position in the width direction of the polyimide film and a plurality of positions at equal intervals in the width direction from the center line position.
(B). The atmosphere is inert.
(C). The temperature profile given to the specimen is
In the first stage, the temperature reaches a temperature of t 1 (where t 1 = 25 ± 2 ° C.) after reaching a temperature of 100 ° C. or more and 200 ° C. or less from room temperature t 0 which is a reference point, and then the second step. The temperature is raised and maintained from the temperature t 1 to the temperature t 2 (where t 2 = 150 ± 2 ° C.), and then cooled and the temperature t 3 (where t 3 = 25 ± 2 ° C.) as the third stage. ).
(D). The test piece length is measured for each test piece.
The values of the distances p 0 , p 1 , p 2 , and p 3 between the gauge points at the temperatures t 0 , t 1 , t 2 , and t 3 are measured.
(E). The calculation of the dimensional change rate is
By substituting the values of p 0 to p 3 for each test piece obtained in (d) into the following formulas (1) to (3), the dimensional change rates dL 0 , dL 1 , dL 2 for each test piece, to calculate the dL 3.

[Evaluation procedure]
(I). The reference position of the dimensional change in the test piece M series and the test piece T series is a test piece taken from the center line position in the width direction of the polyimide film subjected to the measurement.
(B). For each specimen M series and each specimen T series, the dimensional change rate dL 3 in the test piece at the reference position is compared with the dimensional change ratio dL 3 in the test piece located on the outermost side in the width direction of the film, Evaluate dimensional change stability.
Figure 2015141094
 前記熱機械分析装置（ＴＭＡ）の定荷重引張測定モードにおける定荷重が、前記ポリイミドフィルムの弾性限内の荷重であることを特徴とする請求項１記載のポリイミドフィルムの寸法安定性評価方法。   The method for evaluating dimensional stability of a polyimide film according to claim 1, wherein the constant load in the constant load tensile measurement mode of the thermomechanical analyzer (TMA) is a load within an elastic limit of the polyimide film. 前記ポリイミドフィルムが、電子部品の基板用ポリイミドフィルムであることを特徴とする請求項１又は２に記載のポリイミドフィルムの寸法安定性評価方法。   The polyimide film dimensional stability evaluation method according to claim 1, wherein the polyimide film is a polyimide film for a substrate of an electronic component.
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CN112394029B (en) * 2019-08-13 2023-03-17 宝山钢铁股份有限公司 Simulation liquid for evaluating film binding force on surface of coated iron and evaluation method thereof

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