TWI635136B - Polyimine film - Google Patents

Polyimine film Download PDF

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TWI635136B
TWI635136B TW103121966A TW103121966A TWI635136B TW I635136 B TWI635136 B TW I635136B TW 103121966 A TW103121966 A TW 103121966A TW 103121966 A TW103121966 A TW 103121966A TW I635136 B TWI635136 B TW I635136B
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film
polyimine
dimensional change
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polyimide
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TW201510080A (en
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秋山聰
戶井田紀子
大場大史
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東麗 杜邦股份有限公司
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Abstract

本發明提供一種可抑制對角線方向之尺寸變化之產生之接著膜、及貼合金屬箔而獲得之軟性金屬積層板。 The present invention provides an adhesive film which can suppress the occurrence of dimensional change in the diagonal direction and a soft metal laminate obtained by bonding a metal foil.

本發明係一種聚醯亞胺膜，其特徵在於：製膜寬度為1m以上，且對以膜之機械搬送方向(MD)作為基準，膜之配向角度(θ)為45°與135°下之超音波脈衝之傳播速度V測定時的式1所表示之各向異性指數(Anisotoropy Index：AI)涵蓋全寬為12以下，於全寬上對角線(45°、135°)方向之軟性金屬積層板之蝕刻處理前後之對角線方向之尺寸變化率均為-0.05~0.05%，且於至少單面具有厚度為0.5~20μm之熱塑性聚醯亞胺層。 The present invention relates to a polyimide film having a film width of 1 m or more and a film alignment angle (θ) of 45° and 135° with respect to a film transport direction (MD). The anisotropy index (AI) expressed by Equation 1 at the time of measuring the propagation velocity V of the ultrasonic pulse covers a soft metal having a full width of 12 or less and a diagonal (45°, 135°) in full width. The dimensional change rate in the diagonal direction before and after the etching treatment of the laminate is -0.05 to 0.05%, and has a thermoplastic polyimide layer having a thickness of 0.5 to 20 μm on at least one side.

AI(45、135)=|(V45ˆ2-V135ˆ2)/((V45ˆ2+V135ˆ2)/2)×100 | (式1) AI(45,135)=|(V45ˆ2-V135ˆ2)/((V45ˆ2+V135ˆ2)/2)×100 | (Equation 1)

Description

聚醯亞胺膜 Polyimine film

本發明係關於一種聚醯亞胺膜。進而關於一種於聚醯亞胺膜之至少單面具有熱塑性聚醯亞胺之接著膜。進而關於一種對該接著膜貼合金屬箔而獲得之軟性金屬積層板。 This invention relates to a polyimide film. Further, it relates to an adhesive film having a thermoplastic polyimine on at least one side of a polyimide film. Further, a soft metal laminate obtained by laminating a metal foil to the adhesive film is used.

軟性印刷配線板(FPC：Flexible printed circuits)一般由各種絕緣材料所形成，其係藉由將具有柔軟性之絕緣性膜作為基板並於該基板之表面經由各種接著材料將金屬箔藉由加熱、壓接而貼合的方法而製造。作為上述絕緣性膜，可較佳地使用耐熱性、電氣絕緣性優異之聚醯亞胺膜。作為上述接著材料，一般使用環氧系、丙烯酸系等之熱硬化性接著劑(以下，將使用該等熱硬化性接著劑之FPC亦稱為三層FPC)。 FPC (Flexible printed circuits) are generally formed of various insulating materials by heating a metal foil with a flexible insulating film as a substrate and on the surface of the substrate via various bonding materials. It is manufactured by a method of crimping and bonding. As the insulating film, a polyimide film excellent in heat resistance and electrical insulating properties can be preferably used. As the above-mentioned adhesive material, a thermosetting adhesive such as an epoxy resin or an acrylic resin is generally used (hereinafter, FPC using these thermosetting adhesives is also referred to as a three-layer FPC).

熱硬化性接著劑具有可於相對低溫下進行接著之優點。然而，認為今後隨著耐熱性、彎曲性、電氣可靠性等要求特性日趨嚴格，亦會出現難以使用利用熱硬化性接著劑之三層FPC之用途。對此，業界提出於絕緣性膜上直接設置金屬層、或使用熱塑性聚醯亞胺作為接著層之FPC(以下，亦稱為兩層FPC)，期待該兩層FPC於今後需求不斷增長。 The thermosetting adhesive has the advantage that it can be carried out at a relatively low temperature. However, it is considered that in the future, as the required characteristics such as heat resistance, flexibility, and electrical reliability become stricter, there is a possibility that it is difficult to use a three-layer FPC using a thermosetting adhesive. On the other hand, the industry has proposed to provide a metal layer directly on an insulating film or an FPC (hereinafter also referred to as a two-layer FPC) using a thermoplastic polyimide as an adhesive layer, and it is expected that the demand for the two-layer FPC will continue to increase in the future.

作為用於兩層FPC之軟性金屬積層板之製作方法，可列舉：於金屬箔上流延、塗佈作為聚醯亞胺之前驅物之聚醯胺酸後進行醯亞胺化之澆鑄法；藉由濺鍍、鍍敷於聚醯亞胺膜上直接設置金屬層之金屬 噴敷法；經由熱塑性聚醯亞胺將聚醯亞胺膜與金屬箔貼合之層壓法。其中，層壓法就可適應之金屬箔之厚度範圍較澆鑄法廣且裝置成本較金屬噴敷法低之方面而言優異。作為進行層壓之裝置，使用一面捲出捲筒狀之材料一面連續進行層壓之熱輥層壓裝置或雙履帶裝置等。上述中，從生產性方面看，可更佳地使用熱輥層壓法。 As a method for producing a soft metal laminate for use in a two-layer FPC, a casting method in which a ruthenium imidization is carried out by casting a metal ruthenium as a precursor of a polyimide precursor; a metal that is directly provided with a metal layer by sputtering or plating on a polyimide film Spray coating method; a lamination method in which a polyimide film is bonded to a metal foil via a thermoplastic polyimide. Among them, the thickness of the metal foil which can be adapted by the lamination method is superior to that of the casting method and the device cost is lower than that of the metal spraying method. As the apparatus for laminating, a hot roll laminating apparatus or a double crawler apparatus which continuously laminates while rolling out a roll-shaped material is used. Among the above, the hot roll lamination method can be more preferably used from the viewpoint of productivity.

於利用層壓法製作先前之三層FPC時，由於使用了熱硬化性樹脂作為接著層，故而可於層壓溫度未達200℃下進行(專利文獻1)。相對於此，由於兩層FPC係使用熱塑性聚醯亞胺作為接著層，故而為了表現熱融黏性而必須施加200℃以上、視情形接近400℃之高溫。因此，於經層壓而獲得之軟性金屬積層板產生殘留應變，於進行蝕刻形成配線時以及為了安裝零件而進行回焊時表現為尺寸變化。 When the conventional three-layer FPC is produced by the lamination method, since the thermosetting resin is used as the adhesive layer, the lamination temperature is less than 200 ° C (Patent Document 1). On the other hand, since the two-layer FPC uses a thermoplastic polyimide as the adhesive layer, it is necessary to apply a high temperature of 200 ° C or higher and, as the case may be, 400 ° C in order to exhibit hot melt adhesiveness. Therefore, the soft metal laminated board obtained by lamination generates residual strain, and exhibits dimensional change when etching is performed to form wiring and when reflowing is performed for mounting a part.

尤其是若列舉層壓法之一例，則有於聚醯亞胺膜上設置含有熱塑性聚醯亞胺之接著層時，於流延、塗佈作為熱塑性聚醯亞胺之前驅物之聚醯胺酸後連續加熱進行醯亞胺化，並貼合金屬箔的方法，但由於不僅於醯亞胺化步驟，於貼合金屬層時亦連續進行加熱加壓，故而材料多在被施加張力之狀態下置於加熱環境下。其結果為，多數情況下自軟性金屬積層板蝕刻金屬箔時及通過回焊進行加熱時該應變被解除，而於該等步驟前後表現為尺寸變化。 In particular, when an example of a lamination method is used, when a polyimide layer containing a thermoplastic polyimide is provided on a polyimide film, the polyamine which is a precursor of the thermoplastic polyimide may be cast and coated. After the acid is continuously heated, the ruthenium is imidized and the metal foil is bonded. However, since the metal layer is continuously heated and pressurized not only in the ruthenium imidization step, the material is often subjected to tension. Placed under heating. As a result, in many cases, the strain is released when the metal foil is etched from the soft metal laminate and when it is heated by reflow, and the dimensional change occurs before and after the steps.

近年來，為了達成電子設備之小型化、輕量化，而推進設置於基板之配線之微細化，安裝之零件亦搭載小型化、高密度化者。因此，若形成微細之配線後之尺寸變化變大，則會產生自設計階段中之零件搭載位置偏移，而零件與基板無法良好地連接之問題。因此，對聚醯亞胺膜之要求事項亦增多，例如作為聚醯亞胺膜之物性要求具有與金屬同等程度之線膨脹係數、進一步減小尺寸變化。 In recent years, in order to reduce the size and weight of electronic devices, the wiring provided on the substrate has been miniaturized, and the components to be mounted have been reduced in size and density. Therefore, if the dimensional change after the formation of the fine wiring becomes large, there is a problem that the component mounting position is shifted from the design stage, and the component and the substrate are not well connected. Therefore, the requirements for the polyimide film are also increased. For example, the physical properties of the polyimide film are required to have a linear expansion coefficient equivalent to that of the metal, and the dimensional change is further reduced.

到目前為止，對於軟性金屬積層板之尺寸變化僅重視膜之機械搬送方向(MD方向)與膜寬度方向(TD方向)，隨著配線之微細化、配 線板之高積層化之發展，不僅對於MD、TD方向，對於自MD向左右45°之方向亦逐漸要求軟性金屬積層板之尺寸變化，業界期待滿足該等之軟性金屬積層板。 Up to now, only the mechanical transfer direction (MD direction) and the film width direction (TD direction) of the film have been emphasized for the dimensional change of the flexible metal laminate, and the wiring has been miniaturized and matched. The development of the high-layer stratification of the wire board is not only for the MD and TD directions, but also for the size change of the flexible metal laminate from the MD to the left and right 45°, and the industry is expected to satisfy these soft metal laminates.

專利文獻2中揭示自MD方向向左右45°之方向上之250℃/30分鐘之條件下之尺寸變化率在-0.10~+0.10%之範圍內較佳，但近年來要求更微細配線，250℃/30分鐘之條件下之尺寸變化率為-0.10~+0.10%並不充分。較理想為於300℃/30分鐘之條件下為-0.10~+0.10%。專利文獻3中雖然對降低聚醯亞胺膜之各向異性之方法有所記載，但並未考慮到由拉幅除冷步驟中之殘留應力之影響所致之膜應變之影響，對於改善軟性金屬積層板之對角線方向尺寸變化並不充分。 Patent Document 2 discloses that the dimensional change ratio under the condition of 250 ° C / 30 minutes from the MD direction to the right and left 45 ° is preferably in the range of -0.10 to +0.10%, but in recent years, finer wiring is required, 250 The dimensional change rate under the condition of °C/30 minutes is not sufficient -0.10~+0.10%. It is preferably -0.10 to +0.10% at 300 ° C / 30 minutes. Although the method of reducing the anisotropy of the polyimide film is described in Patent Document 3, the influence of the film strain due to the influence of the residual stress in the tentering and cooling step is not considered, and the softness is improved. The dimensional change in the diagonal direction of the metal laminate is not sufficient.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特開平9-199830號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 9-199830

[專利文獻2]日本專利特開2007-91947號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-91947

[專利文獻3]日本專利特開2008-12276號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-12276

本發明係鑒於上述問題而完成者，其目的在於提供一種抑制對角線方向之尺寸變化之產生之接著膜、及貼合金屬箔而獲得之軟性金屬積層板。 The present invention has been made in view of the above problems, and an object thereof is to provide an adhesive film which suppresses the occurrence of dimensional change in the diagonal direction and a flexible metal laminate obtained by bonding a metal foil.

本發明者等人為了解決上述問題而反覆進行努力研究，結果發現：於滿足以膜之機械搬送方向(MD)作為基準，膜之配向角度(θ)為45°與135°下之式1所表示之各向異性指數AI(45、135)值涵蓋全寬為12以下，進而300℃/30分鐘之條件下之45°與135°下之尺寸變化率 差涵蓋全寬為-0.05~0.05%之情形時，可抑制FCCL(Flexible Copper Clad Laminate，軟性覆銅板)及FPC之製造步驟中所產生之尺寸變化，尤其可抑制膜之斜向之尺寸變化。本發明者等人基於該見解進一步進行研究，從而完成本發明。 In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that the alignment angle (θ) of the film is 45° and 135° in accordance with the mechanical transport direction (MD) of the film. The anisotropy index AI (45, 135) value is expressed as the full width is less than 12, and the dimensional change rate at 45 ° and 135 ° under 300 ° C / 30 minutes When the difference covers a full width of -0.05 to 0.05%, the dimensional change generated in the manufacturing steps of the FCCL (Flexible Copper Clad Laminate) and the FPC can be suppressed, and in particular, the dimensional change of the film in the oblique direction can be suppressed. The present inventors further studied based on this finding, thereby completing the present invention.

即，本發明係關於以下之發明。 That is, the present invention relates to the following invention.

[1]一種聚醯亞胺膜，其特徵在於：製膜寬度為1m以上，且以膜之機械搬送方向(MD)作為基準，膜之配向角度(θ)為45°與135°下之式1所表示之各向異性指數AI(45、135)值涵蓋全寬為12以下，於全寬上對角線(45°、135°)方向之軟性金屬積層板之蝕刻處理前後之尺寸變化率均為-0.05~0.05%，且於至少單面具有厚度為0.5~20μm之熱塑性聚醯亞胺層，AI(45、135)=|(V45ˆ2-V135ˆ2)/((V45ˆ2+V135ˆ2)/2)×100|(式1)。 [1] A polyimide film having a film width of 1 m or more and a film orientation angle (θ) of 45° and 135° based on a mechanical transfer direction (MD) of the film. The anisotropy index AI (45, 135) value indicated by 1 covers the dimensional change rate before and after the etching treatment of the soft metal laminate in the diagonal (45°, 135°) direction with a full width of 12 or less. Both are -0.05~0.05%, and have a thermoplastic polyimide layer with a thickness of 0.5~20μm on at least one side, AI(45,135)=|(V45ˆ2-V135ˆ2)/((V45ˆ2+V135ˆ2)/2) ×100|(Formula 1).

[2]如上述[1]之聚醯亞胺膜，其特徵在於：於與膜之機械搬送方向(MD)垂直之方向之直線上選擇自製膜寬度兩端進入200mm內側之2點，於連接該2點之直線之範圍內，選擇包含該2點之直線上之中央部±200mm以內之1點，進而選擇任意2點，於至少該等5點之全部，各向異性指數為12以下。 [2] The polyimine film according to the above [1], characterized in that: on the straight line perpendicular to the mechanical transport direction (MD) of the film, two ends of the width of the self-made film are entered into the inner side of 200 mm, and are connected. In the range of the straight line of the two points, one point within ±200 mm of the central portion on the straight line including the two points is selected, and any two points are selected, and at least the five points are at least the anisotropy index of 12 or less.

[3]如上述[1]或[2]之聚醯亞胺膜，其特徵在於：其係藉由如下方式製造，且製膜寬度為1m以上且厚度為3~50μm：製作將作為聚醯亞胺前驅物之聚醯胺酸溶液流延塗佈於支持體上並使其部分地乾燥及/或硬化而成之具有自持性的凝膠膜，使該凝膠膜通過具備至少2個以上之加熱爐之拉幅加熱爐，一面將該凝膠膜之寬度方向兩端固持一面進行乾燥及/或熱處理。 [3] The polyimine film according to [1] or [2] above, which is produced by the method of forming a film having a width of 1 m or more and a thickness of 3 to 50 μm: The polyamine acid solution of the imine precursor is cast on the support and partially dried and/or hardened to form a self-sustaining gel film, and the gel film is provided with at least two or more The tenter heating furnace of the heating furnace is dried and/or heat-treated while holding the both ends of the gel film in the width direction.

[4]如上述[3]之聚醯亞胺膜，其特徵在於：其係進而於機械搬送方向(MD)上在低張力下實施加熱處理而成。 [4] The polyimine film according to [3] above, which is further subjected to heat treatment under low tension in a machine transport direction (MD).

[5]如上述[1]至[4]中任一項之聚醯亞胺膜，其特徵在於：聚醯亞胺膜係使用選自由對苯二胺、4,4'-二胺基二苯醚及3,4'-二胺基二苯醚所組成之群中之1種以上芳香族二胺成分與選自由均苯四甲酸二酐及3,3’-4,4’-聯苯四羧酸二酐所組成之群中之1種以上酸酐成分而製造。 [5] The polyimine film according to any one of the above [1] to [4] wherein the polyimine film is selected from the group consisting of p-phenylenediamine and 4,4'-diamino group. One or more aromatic diamine components in a group consisting of phenyl ether and 3,4'-diaminodiphenyl ether and selected from pyromellitic dianhydride and 3,3'-4,4'-biphenyl It is produced by using one or more acid anhydride components in a group consisting of tetracarboxylic dianhydride.

[6]一種如上述[1]至[5]中任一項之聚醯亞胺膜之製造方法，其特徵在於：包括如下步驟，且控制拉幅加熱爐內之乾燥速度，該步驟係製作將作為聚醯亞胺前驅物之聚醯胺酸溶液流延塗佈於支持體上並使其部分地乾燥及/或硬化而成之具有自持性的凝膠膜，使該凝膠膜通過具備至少2個以上之加熱爐之拉幅加熱爐，一面將該凝膠膜之寬度方向兩端固持一面進行乾燥及/或熱處理。 [6] A method for producing a polyimide film according to any one of the above [1] to [5], comprising the steps of: controlling a drying speed in a tenter heating furnace, the step of producing a gelatin film having a self-sustaining gel film which is cast-coated on a support and partially dried and/or hardened as a polyamidamine precursor, and the gel film is passed through The tenter heating furnace of at least two or more furnaces is dried and/or heat-treated while holding the both ends of the gel film in the width direction.

[7]如上述[6]之聚醯亞胺膜之製造方法，其特徵在於：包括對利用如上述[6]之製造方法所獲得之聚醯亞胺膜進而進行強熱處理之步驟，且上述強熱處理之溫度為250℃以上且500℃以下。 [7] The method for producing a polyimine film according to the above [6], which comprises the step of performing a strong heat treatment on the polyimide film obtained by the production method of the above [6], and the above The temperature of the strong heat treatment is 250 ° C or more and 500 ° C or less.

[8]一種軟性金屬積層板，其特徵在於：其係對如上述[1]至[5]中任一項之聚醯亞胺膜貼合金屬箔而獲得。 [8] A flexible metal laminate obtained by laminating a metal foil of the polyimine film according to any one of the above [1] to [5].

本發明之聚醯亞胺膜及軟性金屬積層板可抑制尺寸變化之產生，尤其亦可有效地抑制層壓法中之尺寸變化之產生。具體而言，關於去除金屬箔前後之尺寸變化率，可減小自膜之機械搬送方向(MD方向)向左右45°之方向各自之尺寸變化率，並且可減小自MD方向向右45°方向與向左45°方向之尺寸變化之差異，可設為0.05%以下之範圍。因此，亦可較佳地用於形成有微細配線之FPC等，可改善位置偏移等問題。尤其於連續生產之寬度為1m以上之接著膜之情形時，發揮不僅上述尺寸變化率較小，而且膜於全寬上之尺寸變化率亦穩定之效果。 The polyimine film and the soft metal laminate of the present invention can suppress the occurrence of dimensional change, and in particular, can effectively suppress the occurrence of dimensional change in the lamination method. Specifically, regarding the dimensional change rate before and after the removal of the metal foil, the dimensional change rate of each of the mechanical transfer directions (MD direction) from the film to the left and right 45° can be reduced, and the 45° to the right from the MD direction can be reduced. The difference in the dimensional change between the direction and the 45° direction to the left can be set to a range of 0.05% or less. Therefore, it can also be preferably used for an FPC or the like in which fine wiring is formed, and problems such as positional shift can be improved. In particular, in the case of continuously producing a film having a width of 1 m or more, the effect of not only the dimensional change rate but also the dimensional change rate of the film over the full width is exhibited.

A‧‧‧聚醯亞胺膜之製膜寬度 Film width of A‧‧‧ polyimine film

B‧‧‧自製膜寬度端進入200mm內側之點 B‧‧‧The point where the width of the homemade film enters the inner side of 200mm

b'‧‧‧自製膜寬度端進入200mm內側之點 b'‧‧‧The point at which the width of the self-made film enters the inner side of 200mm

c‧‧‧製膜寬度之中央部±200mm以內之點 C‧‧‧ points within ±200mm of the central part of the film width

d‧‧‧連接b與b'之直線上之任意點 D‧‧‧any point on the line connecting b and b'

d'‧‧‧連接b與b'之直線上之任意點 D'‧‧‧any point on the line connecting b and b'

e‧‧‧聚醯亞胺膜 e‧‧‧Polyimide film

f‧‧‧配向角度測定之中心值 f‧‧‧Center value of alignment angle measurement

g‧‧‧配向軸 g‧‧‧Alignment axis

h‧‧‧配向角度(θ) h‧‧‧Alignment angle (θ)

i‧‧‧各角度下之超音波速度 I‧‧‧ Ultrasonic speeds from all angles

圖1表示AI(45、135)與尺寸變化率之關係。 Figure 1 shows the relationship between AI (45, 135) and dimensional change rate.

圖2係表示配向軸與配向角度(θ)之概略圖。中空箭頭表示膜之機械搬送方向(MD)及寬度方向(TD)。 Fig. 2 is a schematic view showing an alignment axis and an alignment angle (θ). The hollow arrows indicate the mechanical transport direction (MD) and the width direction (TD) of the film.

圖3係將各角度下之超音波速度雷達圖化，自其引出配向軸，作為配向角度(θ)而求出。中空箭頭表示膜之機械搬送方向(MD)。 Fig. 3 is a graph in which the ultrasonic velocity at each angle is radarized, and the alignment axis is extracted therefrom to obtain the alignment angle (θ). The hollow arrow indicates the mechanical transport direction (MD) of the film.

圖4係表示本發明之聚醯亞胺膜之AI(45、135)之測定位置的概略圖。中空箭頭表示膜之機械搬送方向(MD)。 Fig. 4 is a schematic view showing the measurement position of AI (45, 135) of the polyimide film of the present invention. The hollow arrow indicates the mechanical transport direction (MD) of the film.

圖5表示對在實施有通常熱處理或強熱處理(退火處理)之軟性金屬積層板之銅箔蝕刻後頂點之位置偏移多少，僅於寬度方向上進行評價所得的結果。上述通常熱處理意指150~200℃之熱處理。 Fig. 5 shows the results of the evaluation of the positional deviation of the apex after etching the copper foil of the soft metal laminate having the usual heat treatment or the strong heat treatment (annealing treatment), and evaluated only in the width direction. The above usual heat treatment means heat treatment at 150 to 200 °C.

以下，對本發明進行具體說明。本發明之聚醯亞胺膜之特徵在於：製膜寬度為1m以上，且對以膜之機械搬送方向(MD)作為基準，膜之配向角度(θ)為45°與135°下之超音波脈衝之傳播速度V進行測定時的式1所表示之各向異性指數(Anisotoropy Index：AI)涵蓋全寬為12以下，於全寬上對角線(45°、135°)方向之軟性金屬積層板之蝕刻處理前後之尺寸變化率均為-0.05~0.05%，且於至少單面具有厚度為0.5~20μm之熱塑性聚醯亞胺層。 Hereinafter, the present invention will be specifically described. The polyimine film of the present invention is characterized in that the film width is 1 m or more, and the alignment angle (θ) of the film is 45° and 135° with respect to the mechanical transfer direction (MD) of the film. The anisotropy index (AI) expressed by Formula 1 when the propagation velocity V of the pulse is measured covers a soft metal layer having a full width of 12 or less and a diagonal (45°, 135°) in full width. The dimensional change rate of the plate before and after the etching treatment is -0.05 to 0.05%, and the thermoplastic polyimide layer having a thickness of 0.5 to 20 μm is formed on at least one side.

AI(45、135)=|(V45ˆ2-V135ˆ2)/((V45ˆ2+V135ˆ2)/2)×100|(式1) AI(45, 135)=|(V45ˆ2-V135ˆ2)/((V45ˆ2+V135ˆ2)/2)×100|(Formula 1)

本發明之式1中之超音波脈衝之傳播速度(亦稱為超音波速度)V係使用野村商事製造之SST-2500(Sonic Sheet Tester)進行測定。若使用SST-2500，則對膜之面方向0~180°(0°與MD方向平行)每隔11.25°自動測定16方向之超音波速度。根據所獲得之各方向之速度中以MD方向作為基準為45°與135°下之超音波速度V45、V135而求出式1所表示之各向異性指數(Anisotoropy Index：AI)。 The propagation velocity (also referred to as ultrasonic velocity) V of the ultrasonic pulse in the first embodiment of the present invention is measured using SST-2500 (Sonic Sheet Tester) manufactured by Nomura Corporation. When the SST-2500 is used, the ultrasonic velocity in the 16 directions is automatically measured at 11.25° for the surface direction of the film from 0 to 180° (0° parallel to the MD direction). An anisotropy index (AI) expressed by Formula 1 is obtained from the ultrasonic speeds V45 and V135 at 45° and 135° with reference to the MD direction based on the obtained speed in each direction.

(式1)AI(45、135)=|(V45ˆ2-V135ˆ2)/((V45ˆ2+V135ˆ2)/2)×100| (Formula 1) AI(45, 135)=|(V45ˆ2-V135ˆ2)/((V45ˆ2+V135ˆ2)/2)×100|

所獲得之AI(45、135)之值越小，表示對角線上之各向異性越小之膜。於本發明中，上述各向異性指數為12以下，就可進一步抑制尺寸變化之產生之方面而言，更佳為11以下，進而較佳為8以下，尤佳為6以下。 The smaller the value of the obtained AI (45, 135), the smaller the anisotropy on the diagonal line. In the present invention, the anisotropy index is 12 or less, and more preferably 11 or less, further preferably 8 or less, and particularly preferably 6 or less, from the viewpoint of further suppressing the occurrence of dimensional change.

本發明者等人進行了努力研究，結果發現：膜之AI(45、135)與使用該接著膜之軟性金屬積層板之尺寸變化率如圖1所示般顯示相關，具體而言，若膜之AI(45、135)值增大，則使用該接著膜之軟性金屬積層板之尺寸變化亦增大。 The inventors of the present invention conducted diligent research and found that the dimensional change rate of the AI (45, 135) of the film and the soft metal laminate using the adhesive film is shown in Fig. 1, specifically, if the film When the value of AI (45, 135) is increased, the dimensional change of the flexible metal laminate using the adhesive film is also increased.

本發明中之配向角度係使用野村商事製造之SST-2500(Sonic Sheet Tester)進行測定。本發明中之所謂配向角度(θ)意指配向軸之方向，如圖2所示將膜之機械搬送方向(MD)作為基準線設為零度，以使基準線向順時針方向旋轉之側之角度來表示。若使用SST-2500，則對膜之面方向0~180°(0°與MD平行)每隔11.25°自動測定16方向之超音波速度。藉由將所獲得之各方向之速度雷達圖化(使用Microsoft Excel之圖表功能)，而繪出如圖3所示之模式圖。自圓中心向該模式圖之鼓出最多之部分引出之線為配向軸(g)，以MD作為基準線，測定配向軸距該基準線之角度(θ)，將其作為配向角度而求出。 The alignment angle in the present invention was measured using SST-2500 (Sonic Sheet Tester) manufactured by Nomura Corporation. The alignment angle (θ) in the present invention means the direction of the alignment axis, and the mechanical transport direction (MD) of the film is set to zero as a reference line as shown in FIG. 2 so that the reference line is rotated clockwise. Expressed by angle. When the SST-2500 is used, the ultrasonic velocity in the 16 directions is automatically measured every 11.25° in the direction of the film from 0 to 180° (0° in parallel with the MD). By patterning the obtained speeds in all directions (using the chart function of Microsoft Excel), a pattern diagram as shown in Fig. 3 is drawn. The line leading from the center of the circle to the most bulging part of the pattern is the alignment axis (g), and MD is used as the reference line, and the angle (θ) of the alignment wheel from the reference line is measured, and this is obtained as the alignment angle. .

本發明中之尺寸變化率係利用下述實施例中記載之方法所測得之值。 The dimensional change rate in the present invention is a value measured by the method described in the following examples.

本發明者等人進行了努力研究，結果發現：利用烘箱之低張力下之加熱處理溫度對使用該接著膜之軟性金屬積層板之尺寸變化率顯示如圖5所示之相關，加熱處理會對使用該接著膜之軟性金屬積層板之尺寸變化之降低產生影響。 The inventors of the present invention conducted diligent research and found that the temperature change rate under the low tension of the oven is related to the dimensional change rate of the flexible metal laminate using the adhesive film as shown in FIG. 5, and the heat treatment will be performed. The reduction in dimensional change of the flexible metal laminate using the adhesive film has an effect.

關於使用本發明之聚醯亞胺膜而獲得之軟性金屬積層板，去除金屬箔前後之尺寸變化率較佳為自MD方向右45°方向及左45°方向均在-0.05%~+0.05%之範圍內，更佳為在-0.045%~+0.045%之範圍內，尤佳為在-0.025%~+0.025%之範圍內。 Regarding the soft metal laminate obtained by using the polyimide film of the present invention, the dimensional change rate before and after the removal of the metal foil is preferably from -0.05% to +0.05% in the right 45° direction from the MD direction and from the left 45° direction. The range is preferably in the range of -0.045% to +0.045%, and more preferably in the range of -0.025% to +0.025%.

進而，右45°方向及左45°方向之尺寸變化率之差較佳為0.01%以下，較佳為0.005%以下。去除金屬箔前後之尺寸變化率係以蝕刻步驟前之軟性金屬積層板之特定尺寸及蝕刻步驟後之特定尺寸之差量與上述蝕刻步驟前之特定尺寸的比來表示。 Further, the difference in dimensional change ratio between the right 45° direction and the left 45° direction is preferably 0.01% or less, preferably 0.005% or less. The dimensional change rate before and after the removal of the metal foil is represented by the ratio of the difference between the specific size of the flexible metal laminate before the etching step and the specific size after the etching step to the specific size before the etching step.

若尺寸變化率超出該範圍內，則對於軟性金屬積層板，有形成微細配線後及搭載零件時之尺寸變化變大，而自設計階段中之零件搭載位置偏移之情形。其結果有安裝之零件與基板無法良好地連接之虞。換言之，若尺寸變化率為上述範圍內，則可視為於零件搭載方面無障礙。 When the dimensional change rate is outside the range, the dimensional change of the soft metal laminated board after the formation of the fine wiring and the mounting of the component is increased, and the component mounting position in the design stage is shifted. As a result, there is a problem that the mounted component and the substrate are not well connected. In other words, if the dimensional change rate is within the above range, it can be considered that the component mounting is unobstructed.

上述尺寸變化率之測定方法並無特別限定，只要為可對軟性金屬積層板測定蝕刻或加熱步驟前後所產生之尺寸之增減之方法，則先前公知之任何方法均可使用。 The method for measuring the dimensional change rate is not particularly limited, and any method known in the art can be used as long as it can measure the increase or decrease in the size of the soft metal laminate before and after the etching or heating step.

再者，測定尺寸變化率時之蝕刻步驟之具體條件並無特別限定。即，由於蝕刻條件根據金屬箔之種類或所形成之圖案配線之形狀等而異，故而本發明中測定尺寸變化率時之蝕刻步驟之條件可為先前公知之任何條件。 Further, the specific conditions of the etching step in measuring the dimensional change rate are not particularly limited. That is, since the etching conditions vary depending on the type of the metal foil or the shape of the patterned wiring formed, etc., the conditions of the etching step in the measurement of the dimensional change ratio in the present invention may be any previously known conditions.

進而，本發明之聚醯亞胺膜之配向角度(θ)較佳為以機械搬送方向(MD)作為基準在90°±23°之範圍內，更佳為在90°±12°之範圍內。此處，配向角度90°係配向軸朝向與膜寬度方向(TD)平行之方向。即，配向角度於上述範圍內表示涵蓋膜全寬配向軸朝向TD方向且差異較小。因此，不論選取任何位置，膜之物性值均近似，TD之尺寸穩定性變高，故而較佳。若配向角度(θ)超過90±23°，則膜之TD配 向紊亂而物性亦改變，故而欠佳。 Further, the alignment angle (θ) of the polyimide film of the present invention is preferably in the range of 90°±23°, more preferably in the range of 90°±12°, based on the mechanical transport direction (MD). . Here, the alignment angle is 90°, and the alignment axis is oriented in a direction parallel to the film width direction (TD). That is, the alignment angle within the above range means that the full width alignment axis of the covering film faces the TD direction and the difference is small. Therefore, regardless of the position selected, the physical property values of the film are approximate, and the dimensional stability of TD becomes high, so that it is preferable. If the alignment angle (θ) exceeds 90±23°, the TD of the film The physical properties are also changed to disorder, so it is not good.

本發明之聚醯亞胺膜之製造方法並無特別限定，以下表示製造方法之詳情。製造方法之第一態樣例如可包括：(1)使芳香族二胺成分與酸酐成分於有機溶劑中聚合而獲得聚醯胺酸溶液的步驟；(2)使上述步驟(1)中獲得之聚醯胺酸溶液進行環化反應而獲得凝膠膜的步驟；(3)對上述步驟(2)中獲得之凝膠膜進行MD之延伸(以下亦稱為縱延伸)為2階段延伸且TD之延伸倍率為MD之總延伸倍率之1.10倍以上且1.50倍以下之MD與TD之雙軸延伸處理的步驟。 The method for producing the polyimide film of the present invention is not particularly limited, and the details of the production method are shown below. The first aspect of the production method may include, for example, the steps of: (1) polymerizing an aromatic diamine component and an acid anhydride component in an organic solvent to obtain a polyaminic acid solution; and (2) obtaining the above step (1). a step of obtaining a gel film by a cyclization reaction of a polyaminic acid solution; (3) performing MD extension (hereinafter also referred to as longitudinal stretching) on the gel film obtained in the above step (2) as a 2-stage extension and TD The stretching ratio is a step of biaxial stretching treatment of MD and TD of 1.10 times or more and 1.50 times or less of the total stretching ratio of MD.

步驟(1)係藉由使芳香族二胺成分與酸酐成分於有機溶劑中聚合而獲得聚醯胺酸溶液的步驟。 The step (1) is a step of obtaining a polyaminic acid solution by polymerizing an aromatic diamine component and an acid anhydride component in an organic solvent.

作為上述芳香族二胺之具體例，只要不阻礙本發明之效果，則無特別限定，可列舉對苯二胺、間苯二胺、聯苯胺、對苯二甲胺、4,4'-二胺基二苯醚、3,4'-二胺基二苯醚、4,4'-二胺基二苯甲烷、4,4'-二胺基二苯基碸、3,3'-二甲基-4,4'-二胺基二苯甲烷、1,5-二胺基萘、3,3'-二甲氧基聯苯胺、1,4-雙(3-甲基-5-胺基苯基)苯或該等之醯胺形成性衍生物。較佳為調整其中具有提高膜之拉伸彈性模數之效果之對苯二胺、3,4'-二胺基二苯醚等二胺之量，使最終獲得之聚醯亞胺膜之拉伸彈性模數成為4.0GPa以上。該等芳香族二胺可單獨使用或混合2種以上而使用。於該等芳香族二胺中，較佳為對苯二胺、4,4'-二胺基二苯醚、3,4'-二胺基二苯醚。芳香族二胺之使用量並無特別限定，於併用對苯二胺與4,4'-二胺基二苯醚及/或3,4'-二胺基二苯醚之情形時，更佳為以69/31~90/10(莫耳比)使用(i)4,4'-二胺基二苯醚及/或3,4'-二胺基二苯醚與(ii)對苯二胺，特佳為以70/30~85/15(莫耳比)使用。 Specific examples of the aromatic diamine are not particularly limited as long as the effects of the present invention are not inhibited, and examples thereof include p-phenylenediamine, m-phenylenediamine, benzidine, p-xylylenediamine, and 4,4'-di. Aminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylanthracene, 3,3'-dimethyl 4-,4'-diaminodiphenylmethane, 1,5-diaminonaphthalene, 3,3'-dimethoxybenzidine, 1,4-bis(3-methyl-5-amino group Phenyl) benzene or such guanamine forming derivatives. Preferably, the amount of the diamine such as p-phenylenediamine or 3,4'-diaminodiphenyl ether having an effect of increasing the tensile modulus of the film is adjusted to obtain the finally obtained polyimide film. The tensile modulus is 4.0 GPa or more. These aromatic diamines can be used alone or in combination of two or more. Among these aromatic diamines, p-phenylenediamine, 4,4'-diaminodiphenyl ether, and 3,4'-diaminodiphenyl ether are preferred. The amount of the aromatic diamine to be used is not particularly limited, and it is more preferable when p-phenylenediamine and 4,4'-diaminodiphenyl ether and/or 3,4'-diaminodiphenyl ether are used in combination. To use (i) 4,4'-diaminodiphenyl ether and/or 3,4'-diaminodiphenyl ether and (ii) p-phenylene with 69/31~90/10 (mole ratio) Amine, especially preferably used at 70/30~85/15 (Morbi).

作為上述酸酐成分之具體例，只要不阻礙本發明之效果，則無特別限定，可列舉均苯四甲酸、3,3',4,4'-聯苯四羧酸、2,3',3,4'-聯苯 四羧酸、3,3',4,4'-二苯甲酮四羧酸、2,3,6,7-萘四羧酸、2,2-雙(3,4-二羧基苯基)醚、吡啶-2,3,5,6-四羧酸、或該等之醯胺形成性衍生物等之酸酐，較佳為芳香族四羧酸之酸二酐，尤佳為均苯四甲酸二酐及/或3,3',4,4'-聯苯四羧酸二酐。該等酸酐成分可單獨使用或混合2種以上而使用。酸酐成分之使用量並無特別限定，於併用均苯四甲酸二酐與3,3',4,4'-聯苯四羧酸二酐之情形時，更佳為以80/20~60/40(莫耳比)使用均苯四甲酸二酐與3,3',4,4'-聯苯四羧酸二酐，特佳為以75/25~65/35(莫耳比)使用。 Specific examples of the acid anhydride component are not particularly limited as long as the effects of the present invention are not inhibited, and examples thereof include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, and 2,3',3. , 4'-biphenyl Tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl) An acid anhydride such as an ether, a pyridine-2,3,5,6-tetracarboxylic acid, or a guanamine-forming derivative thereof, preferably an acid dianhydride of an aromatic tetracarboxylic acid, and more preferably a pyromellitic acid. Dihydride and/or 3,3',4,4'-biphenyltetracarboxylic dianhydride. These acid anhydride components can be used singly or in combination of two or more. The amount of the acid anhydride component to be used is not particularly limited. When pyromellitic dianhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride are used in combination, it is more preferably 80/20 to 60/. 40 (mole ratio) uses pyromellitic dianhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride, particularly preferably 75/25 to 65/35 (mole ratio).

於本發明中，作為用於形成聚醯胺酸溶液之有機溶劑並無特別限定，例如可列舉：二甲亞碸、二乙亞碸等亞碸系溶劑；N,N-二甲基甲醯胺、N,N-二乙基甲醯胺等甲醯胺系溶劑；N,N-二甲基乙醯胺、N,N-二乙基乙醯胺等乙醯胺系溶劑；N-甲基-2-吡咯啶酮、N-乙烯基-2-吡咯啶酮等吡咯啶酮系溶劑；苯酚、鄰甲酚、間甲酚、或對甲酚、二甲苯酚、鹵化苯酚、鄰苯二酚等酚系溶劑；或六甲基磷醯胺、γ-丁內酯等非質子性極性溶劑，該等較理想為單獨使用或以混合物之形式使用2種以上，進而亦可使用二甲苯、甲苯等芳香族烴。 In the present invention, the organic solvent used to form the polyaminic acid solution is not particularly limited, and examples thereof include an anthraquinone solvent such as dimethyl hydrazine or diethyl hydrazine; and N,N-dimethylformamidine. A carbamide solvent such as an amine or N,N-diethylformamide; an acetamide solvent such as N,N-dimethylacetamide or N,N-diethylacetamide; N-A Pyrrolidone-based solvent such as phenyl-2-pyrrolidone or N-vinyl-2-pyrrolidone; phenol, o-cresol, m-cresol, or p-cresol, xylenol, halogenated phenol, ortho-benzene a phenolic solvent such as a phenol; or an aprotic polar solvent such as hexamethylphosphonium or γ-butyrolactone, and it is preferred to use two or more kinds thereof in a single form or in a mixture, and further, xylene may be used. An aromatic hydrocarbon such as toluene.

聚合方法可利用公知之任一方法進行，並無特別限定，例如可列舉如下方法等：(i)先將芳香族二胺成分之全部量添加至有機溶劑中，其後以與芳香族二胺成分之全部量成為當量之方式添加酸酐成分進行聚合；(ii)先將酸酐成分之全部量添加至溶劑中，其後以與酸酐成分成為當量之方式添加芳香族二胺成分進行聚合；(iii)將一芳香族二胺成分(a1)添加至溶劑中後，以使酸酐成分(b1)相對於反應成分成為95~105莫耳%之比率混合反應所需之時間，其後添加另一芳香族二胺成分(a2)，繼而以全部芳香族二胺成分與酸酐成分成為大致當量之方式添加酸酐成分(b2)進行聚合；(iv)將一酸酐成分(b1)添加至溶劑中後，以使一芳香族二胺成分(a1)相對於反應成分成為95~105莫耳 %之比率混合反應所需之時間，其後添加酸酐成分(b2)，繼而以全部芳香族二胺成分與全部酸酐成分成為大致當量之方式添加另一芳香族二胺成分(a2)進行聚合；(v)於溶劑中使一芳香族二胺成分與酸酐成分以任一者成為過量之方式反應而製備聚醯胺酸溶液(A)，於另一溶劑中使另一芳香族二胺成分與酸酐成分以任一者成為過量之方式反應而製備聚醯胺酸溶液(B)，其次，將所獲得之各聚醯胺酸溶液(A)與(B)混合而完成聚合；(vi)於(v)中，於製備聚醯胺酸溶液(A)時芳香族二胺成分過量之情形時，於聚醯胺酸溶液(B)中使酸酐成分過量，又，於聚醯胺酸溶液(A)中酸酐成分過量之情形時，於聚醯胺酸溶液(B)中使芳香族二胺成分過量，將聚醯胺酸溶液(A)與(B)混合，以該等反應所使用之全部芳香族二胺成分與酸酐成分成為大致當量之方式進行製備。 The polymerization method can be carried out by any known method, and is not particularly limited, and examples thereof include the following methods: (i) adding the entire amount of the aromatic diamine component to the organic solvent, followed by the aromatic diamine (i) adding the entire amount of the acid anhydride component to the solvent, and then adding the aromatic diamine component to form an equivalent of the acid anhydride component, and then polymerizing; After the aromatic diamine component (a1) is added to the solvent, the time required for the reaction of the acid anhydride component (b1) to be 95 to 105 mol% with respect to the reaction component is added, and then another fragrance is added. The group diamine component (a2) is then polymerized by adding the acid anhydride component (b2) such that the entire aromatic diamine component and the acid anhydride component are substantially equivalent; (iv) the monoanhydride component (b1) is added to the solvent, and then The aromatic diamine component (a1) is made 95 to 105 moles relative to the reaction component. a ratio of % to the time required for the reaction to be mixed, followed by addition of the acid anhydride component (b2), followed by addition of another aromatic diamine component (a2) so that all of the aromatic diamine component and the entire acid anhydride component are substantially equivalent; (v) preparing a polyaminic acid solution (A) by reacting one aromatic diamine component and an acid anhydride component in an excess amount in a solvent, and allowing another aromatic diamine component in another solvent The acid anhydride component is reacted in an excess amount to prepare a polyamic acid solution (B), and secondly, each of the obtained polyaminic acid solutions (A) and (B) is mixed to complete polymerization; (vi) In the case of (v), when the polydiamine acid solution (A) is prepared in an excess amount of the aromatic diamine component, the acid anhydride component is excessively present in the polyaminic acid solution (B), and further, in the polyaminic acid solution ( A) When the amount of the acid anhydride component is excessive, the aromatic diamine component is excessively mixed in the polyaminic acid solution (B), and the polyamic acid solution (A) and (B) are mixed and used for the reaction. The preparation is carried out in such a manner that all of the aromatic diamine component and the acid anhydride component are substantially equivalent.

如此獲得之聚醯胺酸溶液通常含有5~40重量%之固形物成分，較佳為含有10~30重量%之固形物成分。又，聚醯胺酸溶液之黏度係依據JIS K6726_1994，利用使用布氏黏度計之旋轉黏度計法所得之測定值，並無特別限定，通常為10~2000Pa‧s(100~20000 poise)，為了實現穩定之送液，較佳為100~1000Pa‧s(1000~10000 poise)。又，有機溶劑溶液中之聚醯胺酸亦可部分經醯亞胺化。 The polyamic acid solution thus obtained usually contains 5 to 40% by weight of a solid content component, preferably 10 to 30% by weight of a solid content component. Further, the viscosity of the polyaminic acid solution is not particularly limited as measured by a rotational viscometer method using a Brookfield viscometer according to JIS K6726_1994, and is usually 10 to 2000 Pa‧s (100 to 20000 poise), in order to To achieve stable liquid delivery, preferably 100~1000Pa‧s (1000~10000 poise). Further, the polyamine acid in the organic solvent solution may also be partially imidized by hydrazine.

本發明之聚醯胺酸溶液亦可為了獲得膜之易滑性而視需要含有氧化鈦、微細二氧化矽、碳酸鈣、磷酸鈣、磷酸氫鈣、聚醯亞胺填料等化學上呈惰性之有機填料或無機填料等。 The polyaminic acid solution of the present invention may also contain chemically inert, such as titanium oxide, fine cerium oxide, calcium carbonate, calcium phosphate, calcium hydrogen phosphate, polythenimine filler, etc., in order to obtain the smoothness of the film. Organic filler or inorganic filler.

本發明所使用之無機填料(無機粒子)並無特別限定，較佳為全部粒子之粒徑為0.005μm以上且2.0μm以下之無機填料，更佳為全部粒子之粒徑為0.01μm以上且1.5μm以下之無機填料。關於粒度分佈(體積基準)並無特別限定，較佳為粒徑為0.10μm以上且0.90μm以下之粒子於全部粒子中占80體積%以上之無機填料，就易滑性更 優異之方面而言，更佳為粒徑為0.10μm以上且0.75μm以下之粒子於全部粒子中占80體積%以上之無機填料。若平均粒徑成為0.05μm以下，則膜之易滑性效果降低，故而欠佳，若成為1.0μm以上，則局部地成為較大之粒子而存在，故而欠佳。上述粒度分佈、平均粒徑及粒徑範圍可使用堀場製作所之雷射繞射/散射式粒度分佈測定裝置LA-910進行測定。上述平均粒徑係指體積平均粒徑。 The inorganic filler (inorganic particles) used in the present invention is not particularly limited, and is preferably an inorganic filler having a particle diameter of 0.005 μm or more and 2.0 μm or less, and more preferably a particle diameter of all particles of 0.01 μm or more and 1.5. An inorganic filler of less than μm. The particle size distribution (volume basis) is not particularly limited, and it is preferably an inorganic filler having a particle diameter of 0.10 μm or more and 0.90 μm or less, which accounts for 80% by volume or more of all particles, and is more slippery. In an excellent aspect, it is more preferable that the particles having a particle diameter of 0.10 μm or more and 0.75 μm or less account for 80% by volume or more of the total filler. When the average particle diameter is 0.05 μm or less, the effect of the film slipperiness is lowered, which is not preferable, and when it is 1.0 μm or more, it is locally large particles, which is not preferable. The above particle size distribution, average particle size, and particle size range can be measured using a laser diffraction/scattering particle size distribution measuring apparatus LA-910 manufactured by Horiba. The above average particle diameter means a volume average particle diameter.

本發明所使用之無機填料並無特別限定，較佳為以相對於聚醯胺酸溶液之重量為0.03重量%以上且未達1.0重量%之比率均勻地分散於膜中，就易滑性效果之方面而言，更佳為0.30重量%以上且0.80重量%以下之比率。若為1.0重量%以上，則可見機械強度之降低，若為0.03重量%以下，則無法看到充分之易滑性效果，故而欠佳。 The inorganic filler used in the present invention is not particularly limited, and is preferably uniformly dispersed in a film at a ratio of 0.03 wt% or more to less than 1.0 wt% based on the weight of the polyaminic acid solution, and the slipperiness effect is obtained. In terms of the ratio, the ratio is preferably 0.30% by weight or more and 0.80% by weight or less. When it is 1.0% by weight or more, the mechanical strength is lowered, and when it is 0.03% by weight or less, a sufficient slipperiness effect cannot be seen, which is not preferable.

步驟(2)係使上述步驟(1)中獲得之聚醯胺酸溶液進行環化反應而獲得凝膠膜的步驟。使上述聚醯胺酸溶液進行環化反應之方法並無特別限定，具體而言，可列舉：(i)將上述聚醯胺酸溶液澆鑄成膜狀，以熱方式使其脫水環化而獲得凝膠膜的方法(熱閉環法)；或(ii)於上述聚醯胺酸溶液中混合環化觸媒及轉化劑以化學方式使其脫環化而製作凝膠膜，並藉由加熱而獲得凝膠膜的方法(化學閉環法)等，關於所獲得之聚醯亞胺膜，就可藉由與其他構成要件之組合而均勻地抑制尺寸變化之方面而言，較佳為後者之方法。上述聚醯胺酸溶液可含有凝膠化延遲劑等。作為凝膠化延遲劑並無特別限定，可使用乙醯丙酮等。 The step (2) is a step of subjecting the polyamic acid solution obtained in the above step (1) to a cyclization reaction to obtain a gel film. The method for carrying out the cyclization reaction of the polyamic acid solution is not particularly limited, and specific examples thereof include (i) casting the polyamic acid solution into a film form and dehydrating and cyclizing it by heat. a method of a gel film (thermal closed loop method); or (ii) mixing a cyclization catalyst and a conversion agent in the polyamic acid solution to chemically de-cyclize the gel film to form a gel film, and heating A method of obtaining a gel film (chemical ring closure method) or the like, and the obtained polyimide film can be uniformly suppressed in size by a combination with other constituent elements, preferably the latter method . The polyamic acid solution may contain a gelation retarder or the like. The gelation retarder is not particularly limited, and acetonitrile or the like can be used.

作為上述環化觸媒並無特別限定，例如可列舉：三甲基胺、三伸乙基二胺等脂肪族三級胺；二甲基苯胺等芳香族三級胺；異喹啉、吡啶、β-甲基吡啶等雜環三級胺等，較佳為選自由異喹啉、吡啶及β-甲基吡啶所組成之群中之1種以上雜環式三級胺。作為上述轉化劑並無特別限定，例如可列舉：乙酸酐、丙酸酐、丁酸酐等脂肪族羧酸酐；苯甲酸酐等芳香族羧酸酐等，較佳為乙酸酐及/或苯甲酸酐。該 等環化觸媒及轉化劑之含量並無特別限定，相對於聚醯胺酸溶液100重量%，分別較佳為10~40重量%左右，更佳為15~30重量%左右。 The cyclization catalyst is not particularly limited, and examples thereof include aliphatic tertiary amines such as trimethylamine and tri-ethylenediamine; aromatic tertiary amines such as dimethylaniline; and isoquinoline and pyridine. A heterocyclic tertiary amine such as β-picoline or the like is preferably one or more heterocyclic tertiary amines selected from the group consisting of isoquinoline, pyridine and β-methylpyridine. The above-mentioned conversion agent is not particularly limited, and examples thereof include an aliphatic carboxylic acid anhydride such as acetic anhydride, propionic anhydride, and butyric anhydride; and an aromatic carboxylic anhydride such as benzoic anhydride; and acetic anhydride and/or benzoic anhydride are preferable. The The content of the cyclization catalyst and the conversion agent is not particularly limited, and is preferably about 10 to 40% by weight, and more preferably about 15 to 30% by weight, based on 100% by weight of the polyaminic acid solution.

上述凝膠膜可藉由如下方式獲得：將上述聚醯胺酸溶液或於聚醯胺酸溶液中混合環化觸媒及轉化劑而成之混合溶液自附有狹縫之噴嘴流延於支持體上而成型為膜狀，藉由來自支持體之受熱、來自熱風或電加熱器等熱源之受熱而將其加熱進行閉環反應，並使游離之有機溶劑等揮發分乾燥，藉此製成具有自持性之凝膠膜後，將其自支持體剝離。 The above gel film can be obtained by mixing the above polyamic acid solution or a mixed solution of a cyclization catalyst and a conversion agent in a polyaminic acid solution from a nozzle with a slit to support Formed into a film shape on the body, heated by a heat source from a support, heated by a heat source such as hot air or an electric heater, and subjected to a ring closure reaction, and the volatile matter such as a free organic solvent is dried, thereby having After the self-sustaining gel film, it is peeled off from the support.

作為上述支持體並無特別限定，作為例子可列舉金屬(例如不鏽鋼)製之轉筒、環帶等，支持體之溫度係藉由(i)液體或氣體之熱介質、(ii)電加熱器等之輻射熱等而控制，並無特別限定，例如可為30~200℃，較佳為40~150℃。 The support is not particularly limited, and examples thereof include a drum made of a metal (for example, stainless steel), an endless belt, etc., and the temperature of the support is by (i) a heat medium of a liquid or a gas, and (ii) an electric heater. The radiant heat or the like is not particularly limited, and may be, for example, 30 to 200 ° C, preferably 40 to 150 ° C.

步驟(3)係對上述步驟(2)中獲得之凝膠膜進行MD之延伸為2階段延伸且TD之延伸倍率為MD之總延伸倍率之1.10倍以上且1.50倍以下之向MD與TD之雙軸延伸處理的步驟。 Step (3) is to extend the MD of the gel film obtained in the above step (2) to a 2-stage extension and the stretching ratio of TD is 1.10 times or more and 1.50 times or less to the total stretching ratio of MD to MD and TD. The step of the biaxial extension process.

對於自上述支持體剝離之凝膠膜，一面藉由旋轉輥限制移行速度一面向移行方向(MD)延伸。旋轉輥需要限制凝膠膜之移行速度所需之固持力，作為旋轉輥，較佳為使用將金屬輥與橡膠輥組合而成之夾輥、真空輥、多段張力削減輥或減壓抽吸方式之吸輥等。 The gel film peeled from the support is stretched toward the traveling direction (MD) by the rotating roller to restrict the traveling speed. The rotating roller needs to have a holding force required to limit the moving speed of the gel film. As the rotating roller, it is preferable to use a nip roller which combines a metal roller and a rubber roller, a vacuum roller, a multi-stage tension reducing roller or a vacuum suction method. The suction roller and the like.

於步驟(3)中，進行雙軸延伸處理。上述雙軸延伸處理之順序並無特別限定，較佳為於進行機械搬送方向(MD)之延伸(縱延伸)後進行寬度方向(TD)之延伸(以下亦稱為橫延伸)。又，就可藉由與其他構成要件之組合而均勻地抑制尺寸變化之方面而言，更佳為進行縱延伸繼而進行加熱處理後進行橫延伸之步驟、或進行縱延伸繼而與加熱處理同時進行橫延伸之步驟。 In the step (3), a biaxial stretching process is performed. The order of the biaxial stretching treatment is not particularly limited, and it is preferably extended in the width direction (TD) after extending (longitudinal extension) in the machine transport direction (MD) (hereinafter also referred to as lateral extension). Further, in terms of uniformly suppressing the dimensional change by the combination with other constituent elements, it is more preferable to perform the longitudinal stretching followed by the heat treatment followed by the lateral stretching step, or the longitudinal stretching followed by the heating treatment. The step of horizontal extension.

關於上述雙軸延伸處理中之MD之延伸(縱延伸)，對於聚醯亞胺膜，為了藉由與其他構成要件之組合而抑制尺寸變化，而分為2階段進行。於向MD之2階段延伸中，第1階段之延伸倍率(以下亦稱為縱延伸率)並無特別限定，較佳為1.02倍以上且1.3倍以下，就可均勻地抑制尺寸變化之方面而言，更佳為1.04倍以上且1.1倍以下。第2階段之MD之延伸倍率較佳為1.02倍以上且1.3倍以下，就可藉由與其他構成要件之組合而均勻地抑制尺寸變化之方面而言，更佳為1.04倍以上且1.1倍以下。又，於本發明中，關於第1階段之延伸之延伸倍率相對於MD之總延伸倍率之比率，就可藉由與其他構成要件之組合而均勻地抑制尺寸變化之方面而言，較佳為MD之總延伸倍率之40%以上，就可進一步抑制尺寸變化之方面而言，更佳為50%以上且80%以下。此處，第1階段之延伸之延伸倍率相對於MD之總延伸倍率之比率之算出方法如下述式2所示。 Regarding the extension (longitudinal extension) of the MD in the above biaxial stretching treatment, the polyimide film is divided into two stages in order to suppress the dimensional change by combining with other constituent elements. In the two-stage extension of the MD, the stretching ratio of the first stage (hereinafter also referred to as the longitudinal elongation) is not particularly limited, and is preferably 1.02 times or more and 1.3 times or less, so that the dimensional change can be uniformly suppressed. More preferably, it is 1.04 times or more and 1.1 times or less. In the second stage, the MD stretching ratio is preferably 1.02 times or more and 1.3 times or less, and more preferably 1.04 times or more and 1.1 times or less from the viewpoint of uniformly suppressing dimensional change by combination with other constituent elements. . Further, in the present invention, the ratio of the stretching ratio of the extension of the first stage to the total stretching ratio of the MD can be uniformly suppressed by the combination with other constituent elements, and is preferably The 40% or more of the total stretching ratio of the MD is more preferably 50% or more and 80% or less in terms of further suppressing the dimensional change. Here, the method of calculating the ratio of the stretching ratio of the extension of the first stage to the total stretching ratio of the MD is as shown in the following formula 2.

例如所謂延伸倍率1.1倍係指相對於基本長度(延伸前之長度)1延伸0.1倍之狀態。因此，自延伸倍率減去1而算出。MD之總延伸倍率並無特別限定，較佳為1.04倍以上且1.4倍以下，更佳為1.05倍以上且1.3倍以下。MD之延伸溫度並無特別限定，較佳為60~100℃左右，更佳為65~90℃左右。MD之延伸速度並無特別限定，於進行2階段延伸之情形時，就可藉由與其他構成要件之組合而均勻地抑制尺寸變化之方面而言，該2階段延伸之第1階段之延伸速度較佳為1%/分鐘~20%/分鐘左右，更佳為2%/分鐘~10%/分鐘左右。該2階段延伸之第2階段之延伸速度較佳為1%/分鐘~20%/分鐘左右，更佳為2%/分鐘~10%/分鐘左右。於向MD之2階段延伸中，各階段 之延伸時間並無特別限定，為5秒~5分鐘左右，較佳為10秒~3分鐘。作為上述縱延伸之模式，可列舉自延伸倍率1一次延伸至上述延伸倍率之方法、逐次延伸之方法、以不定率之倍率逐漸延伸之方法、以定率之倍率逐漸延伸之方法、或將該等組合複數種而成之方法等，尤佳為以固定倍率逐漸延伸之方法。 For example, the extension magnification of 1.1 times means a state in which the basic length (length before stretching) 1 is extended by 0.1 times. Therefore, it is calculated by subtracting 1 from the stretching ratio. The total stretching ratio of MD is not particularly limited, but is preferably 1.04 times or more and 1.4 times or less, more preferably 1.05 times or more and 1.3 times or less. The extension temperature of the MD is not particularly limited, but is preferably about 60 to 100 ° C, more preferably about 65 to 90 ° C. The extension speed of the MD is not particularly limited, and in the case of performing the two-stage extension, the extension speed of the first stage of the two-stage extension can be uniformly suppressed by the combination with other constituent elements. It is preferably from about 1%/minute to about 20%/minute, more preferably from about 2%/minute to about 10%/minute. The extension speed of the second stage of the two-stage extension is preferably from about 1%/minute to about 20%/minute, more preferably from about 2%/minute to about 10%/minute. In the 2 stage extension of MD, each stage The extension time is not particularly limited and is about 5 seconds to 5 minutes, preferably 10 seconds to 3 minutes. Examples of the longitudinal stretching mode include a method of extending from the stretching ratio 1 to the stretching ratio at one time, a method of successively stretching, a method of gradually extending at a magnification of an indefinite rate, a method of gradually extending at a magnification of a constant rate, or the like. A method in which a plurality of kinds are combined, and the like is preferably a method of gradually extending at a fixed magnification.

於進行上述MD之延伸後進行加熱處理之情形時，加熱溫度並無特別限定，較佳為高於MD之延伸時之溫度的溫度，通常為80~550℃左右，較佳為180~500℃左右，更佳為200~450℃左右。若未達80℃而開始延伸，則有膜較硬且較脆之情形，而有難以延伸之虞。加熱處理時間較佳為30秒~20分鐘，更佳為50秒~10分鐘。又，加熱處理亦可以不同之溫度多階段地(2階段、3階段等)進行。例如以多階段進行加熱處理之情形時之第1階段之加熱溫度並無特別限定，為了充分地去除溶劑，較佳為80℃以上且300℃以下，更佳為100℃以上且290℃以下，進而較佳為120℃以上且285℃以下。以多階段進行加熱處理之情形時之最終階段之加熱溫度只要為高於第1階段之加熱溫度之溫度，且與第1階段之加熱溫度之設定不同，則無特別限定，例如較佳為大於300℃且550℃以下，更佳為320℃以上且500℃以下，進而較佳為350℃以上且450℃以下。若第1階段之加熱溫度高於最終階段之加熱溫度，則溶劑急遽蒸發，所獲得之膜變脆，而不實用。多階段加熱處理之情形時之各階段之處理時間與上述相同。於加熱處理時，可使用具有溫度不同之複數個區塊(區域)之澆鑄爐或加熱爐等加熱裝置等。加熱處理較佳為藉由銷式拉幅裝置、夾式拉幅裝置、夾頭等將膜之兩端固定而進行。藉由該加熱處理，可去除溶劑。拉幅裝置較佳為具有至少2個以上之加熱爐者。 In the case where the heat treatment is performed after the extension of the MD, the heating temperature is not particularly limited, and is preferably a temperature higher than the temperature at which the MD is extended, and is usually about 80 to 550 ° C, preferably 180 to 500 ° C. Left and right, more preferably around 200~450 °C. If the elongation starts less than 80 ° C, there is a case where the film is hard and brittle, and there is a difficulty in stretching. The heat treatment time is preferably from 30 seconds to 20 minutes, more preferably from 50 seconds to 10 minutes. Further, the heat treatment may be carried out in multiple stages (two stages, three stages, etc.) at different temperatures. For example, the heating temperature in the first step in the case where the heat treatment is performed in multiple stages is not particularly limited, and in order to sufficiently remove the solvent, it is preferably 80° C. or higher and 300° C. or lower, more preferably 100° C. or higher and 290° C. or lower. Further, it is preferably 120 ° C or more and 285 ° C or less. The heating temperature in the final stage when the heat treatment is performed in multiple stages is not particularly limited as long as it is higher than the heating temperature of the first stage, and is not particularly limited, for example, preferably larger than the heating temperature of the first stage. 300 ° C and 550 ° C or less, more preferably 320 ° C or more and 500 ° C or less, further preferably 350 ° C or more and 450 ° C or less. If the heating temperature of the first stage is higher than the heating temperature of the final stage, the solvent evaporates rapidly, and the obtained film becomes brittle and is not practical. The processing time of each stage in the case of multi-stage heat treatment is the same as described above. In the heat treatment, a heating device such as a casting furnace or a heating furnace having a plurality of blocks (regions) having different temperatures may be used. The heat treatment is preferably carried out by fixing both ends of the film by a pin tenter, a clip-on tenter, a chuck, or the like. By this heat treatment, the solvent can be removed. The tenter device preferably has at least two or more heaters.

將向MD延伸後之凝膠膜導入至具備加熱爐之拉幅裝置(拉幅加熱爐)中，將寬度方向兩端部固持於拉幅夾，一面與拉幅夾一同移 行，一面向寬度方向(TD)延伸。作為TD之延伸倍率(以下亦稱為橫延伸率)並無特別限定，較佳為1.35倍以上且2.0倍以下，就可藉由與其他構成要件之組合而均勻地抑制尺寸變化之方面而言，更佳為1.40倍以上且1.8倍以下。上述TD之延伸倍率意指實施例中之橫延伸率。TD之延伸倍率(橫延伸率)必須設定為高於MD之延伸倍率(縱延伸率)，具體而言，通常為MD之總延伸倍率之1.10倍以上且1.50倍以下，就可藉由與其他構成要件之組合而均勻地抑制尺寸變化之方面而言，較佳為1.15倍以上且1.45倍以下。MD之延伸為上述2階段延伸，且與膜之MD之延伸倍率相比較高地設定TD之延伸倍率，可獲得藉由與其他構成要件之組合而抑制尺寸變化之膜。TD之延伸可於上述加熱處理後進行，亦可於上述加熱處理前進行，就可更均勻地抑制尺寸變化之方面而言，較佳為與上述加熱處理同時進行。TD之延伸之延伸時間並無特別限定，為5秒~10分鐘左右，較佳為10秒~5分鐘。作為上述橫延伸之模式，可列舉自延伸倍率1一次延伸至上述橫延伸倍率之方法、逐次延伸之方法、以不定率之倍率逐漸延伸之方法、以定率之倍率逐漸延伸之方法、或將該等組合複數種而成之方法等。尤其於同時進行橫延伸與多階段加熱處理之情形時，較佳為於第1階段之加熱處理時，以TD之延伸倍率成為最大延伸率之方式進行設定，並逐漸降低延伸倍率。又，亦較佳為於第1階段之加熱處理後亦進而逐漸提高TD之延伸倍率，於第2階段或最終階段之加熱處理時以TD之延伸倍率成為最大延伸率之方式進行設定。 The gel film extending to the MD is introduced into a tenter device (later heating furnace) equipped with a heating furnace, and both ends in the width direction are held by the tenter clip, and are moved together with the tenter clip. Line, one facing the width direction (TD) extension. The stretching ratio of TD (hereinafter also referred to as lateral elongation) is not particularly limited, and is preferably 1.35 times or more and 2.0 times or less, and it is possible to uniformly suppress the dimensional change by combining with other constituent elements. More preferably, it is 1.40 times or more and 1.8 times or less. The extension ratio of the above TD means the lateral elongation in the examples. The stretching ratio (transverse elongation) of TD must be set to be higher than the stretching ratio (longitudinal elongation) of MD. Specifically, it is usually 1.10 times or more and 1.50 times or less of the total stretching ratio of MD, and It is preferably 1.15 times or more and 1.45 times or less in terms of a combination of constituent elements and uniform suppression of dimensional change. The extension of the MD is the above-described two-stage stretching, and the stretching ratio of TD is set higher than the stretching ratio of the MD of the film, and a film which suppresses dimensional change by combination with other constituent elements can be obtained. The extension of the TD may be performed after the above heat treatment, or may be performed before the heat treatment, and the dimensional change may be more uniformly suppressed, and it is preferably carried out simultaneously with the heat treatment. The extension time of the extension of TD is not particularly limited, and is about 5 seconds to 10 minutes, preferably 10 seconds to 5 minutes. Examples of the mode of the lateral stretching include a method of extending from the stretching ratio 1 to the lateral stretching ratio at one time, a method of successively stretching, a method of gradually extending at a magnification of an indefinite rate, a method of gradually extending at a magnification of a constant rate, or a method of gradually extending the ratio Such as the combination of a plurality of methods and the like. In particular, in the case where the lateral stretching and the multi-stage heat treatment are simultaneously performed, it is preferable to set the stretching ratio of the TD to the maximum elongation in the first-stage heat treatment, and gradually reduce the stretching ratio. Moreover, it is also preferable to gradually increase the stretching ratio of TD after the heat treatment in the first stage, and to set the stretching ratio of TD to the maximum elongation in the heat treatment in the second stage or the final stage.

於使導入至上述拉幅加熱爐內之凝膠膜乾燥時，就可藉由與其他構成要件之組合而均勻地抑制尺寸變化之方面而言，較佳為控制乾燥速度。此種效果並無特別限定，可藉由膜之製膜速度與乾燥速度之最佳之組合而達成。於將製膜速度設為固定之情形時，若乾燥速度大於製膜速度，則膜相對於製膜行進方向於外側配向，反之，若乾燥速 度小於製膜速度，則膜相對於行進方向於內側配向。然而，藉由適當正確地控制製膜速度與乾燥速度可獲得均勻地抑制相對於製膜行進方向向斜向之尺寸變化之膜。乾燥係藉由經加熱器加熱之熱風進行，乾燥速度之控制可藉由熱風之流量進行，亦可藉由熱風之溫度進行，將該等組合亦可獲得相同之結果。製膜速度可藉由原料聚合物之噴出速度(例如100~1000kg/小時)、製作凝膠膜時之支持體之溫度、環化觸媒及轉化劑之含量、殘留揮發成分之量等而調整。為了抑制對角線方向之尺寸變化，較佳為膜之配向角度(θ)以機械搬送方向(MD)作為基準為90°±23°之範圍。 When the gel film introduced into the tenter heating furnace is dried, it is preferable to control the drying speed in terms of uniformly suppressing dimensional change by combination with other constituent elements. Such an effect is not particularly limited and can be achieved by an optimum combination of the film forming speed of the film and the drying speed. When the film forming speed is set to be fixed, if the drying speed is greater than the film forming speed, the film is aligned to the outside with respect to the film forming traveling direction, and vice versa. If the degree is less than the film forming speed, the film is aligned on the inner side with respect to the traveling direction. However, by appropriately controlling the film forming speed and the drying speed, it is possible to obtain a film which uniformly suppresses the dimensional change in the oblique direction with respect to the film forming traveling direction. The drying is carried out by hot air heated by a heater, and the drying speed can be controlled by the flow rate of the hot air or by the temperature of the hot air, and the combination can also obtain the same result. The film forming speed can be adjusted by the ejection speed of the base polymer (for example, 100 to 1000 kg/hr), the temperature of the support when the gel film is formed, the content of the cyclization catalyst and the conversion agent, and the amount of residual volatile components. . In order to suppress the dimensional change in the diagonal direction, it is preferable that the alignment angle (θ) of the film is in the range of 90° ± 23° with respect to the mechanical transport direction (MD).

進而對於製造於全寬上具有所需之尺寸變化率，且於膜寬度方向具有均勻之對角線方向尺寸變化率差的聚醯亞胺膜，將膜進行TD延伸時之溶劑殘留率會產生影響。若於過度去除溶劑之情況或溶劑之去除不充分之情況下使膜向TD方向延伸，則因向TD方向之延伸與向MD方向之乾燥收縮力而於膜之端部向斜向配向，於將使聚醯胺酸溶液進行環化反應而獲得凝膠膜之步驟中之凝膠膜所含有之溶劑量設為100%時，若於乾燥步驟中之溶劑殘留率為50~90%時進行向寬度方向(TD)之延伸，則向MD方向之張力由膜本身緩和，可製造於全寬上具有均勻之尺寸變化率之聚醯亞胺膜。進而，就進一步抑制尺寸變化率之差異之方面而言，橫延伸率為50%時之溶劑殘留率更佳為50~90%，進而較佳為75~90%。又，橫延伸率為80%時之溶劑殘留率更佳為50~90%，進而較佳為55~75%。該等溶劑殘留率亦可組合，例如可於橫延伸為50%時溶劑殘留率為60~90%，且於橫延伸率為80%時溶劑殘留率為50~70%。上述尺寸變化率之差異之測定例如係於圖4所示之位置進行。具體而言，於製膜寬度為1m以上之情形時，於與膜之機械搬送方向(MD)垂直之方向之直線上選擇自製膜寬度兩端進入200mm內側之2點，於連接該2點之直線之範圍內，選 擇包含該2點之直線上之中央部±200mm以內之1點，進而選擇任意2點，可列舉至少該等5點。 Further, in the case of a polyimide film having a desired dimensional change ratio over the entire width and having a uniform difference in dimensional change in the diagonal direction in the film width direction, the solvent residual ratio in the TD extension of the film is generated. influences. When the solvent is excessively removed or the solvent is removed insufficiently, the film is extended in the TD direction, and the film is obliquely aligned at the end portion of the film due to the stretching in the TD direction and the drying contraction force in the MD direction. When the amount of the solvent contained in the gel film in the step of obtaining the gel film by the cyclization reaction of the polyamic acid solution is 100%, the solvent remaining ratio in the drying step is 50 to 90%. When extending in the width direction (TD), the tension in the MD direction is moderated by the film itself, and a polyimide film having a uniform dimensional change ratio over the entire width can be produced. Further, in terms of further suppressing the difference in dimensional change ratio, the solvent residual ratio at a transverse elongation of 50% is more preferably from 50 to 90%, still more preferably from 75 to 90%. Further, the solvent residual ratio at a transverse elongation of 80% is more preferably from 50 to 90%, still more preferably from 55 to 75%. These solvent residual ratios may be combined, for example, when the lateral elongation is 50%, the solvent residual ratio is 60 to 90%, and when the lateral elongation is 80%, the solvent residual ratio is 50 to 70%. The measurement of the difference in the dimensional change rate described above is performed, for example, at the position shown in FIG. Specifically, when the film width is 1 m or more, the two sides of the width of the self-made film enter the inner side of 200 mm on the straight line perpendicular to the mechanical transfer direction (MD) of the film, and the two points are connected. Within the range of the line One point within ±200 mm of the central portion on the straight line including the two points is selected, and any two points are selected, and at least these five points are exemplified.

其次，以下對本發明之聚醯亞胺膜之製造方法之第二態樣進行詳細說明。製造方法之第二態樣例如可包括：(1)使芳香族二胺成分與酸酐成分於有機溶劑中聚合而獲得聚醯胺酸溶液的步驟；(2)使上述步驟(1)中獲得之聚醯胺酸溶液進行環化反應而獲得凝膠膜的步驟；(3)對上述步驟(2)中獲得之凝膠膜進行MD之延伸(以下亦稱為縱延伸)為3階段以上之多階段延伸且TD之延伸倍率為MD之總延伸倍率之1.10倍以上且1.50倍以下之MD與TD之雙軸延伸處理的步驟。 Next, the second aspect of the method for producing a polyimide film of the present invention will be described in detail below. The second aspect of the production method may include, for example, the steps of: (1) polymerizing an aromatic diamine component and an acid anhydride component in an organic solvent to obtain a polyaminic acid solution; and (2) obtaining the above step (1). a step of obtaining a gel film by a cyclization reaction of a polyaminic acid solution; (3) performing an extension of MD (hereinafter also referred to as a longitudinal extension) of the gel film obtained in the above step (2) to a maximum of three stages or more The step of extending and the stretching ratio of TD is a step of biaxial stretching processing of MD and TD of 1.10 times or more and 1.50 times or less of the total stretching magnification of MD.

於第二製造態樣中，步驟(3)係對上述步驟(2)中獲得之凝膠膜進行MD之延伸為3階段以上之多階段延伸且TD之延伸倍率為MD之總延伸倍率之1.10倍以上且1.50倍以下之向MD與TD之雙軸延伸處理的步驟。 In the second aspect of the invention, the step (3) is performed by extending the MD of the gel film obtained in the above step (2) to a multi-stage extension of three stages or more and the stretching ratio of the TD is 1.10 of the total stretching ratio of the MD. The step of biaxial stretching processing of MD and TD is more than twice and 1.50 times or less.

對於上述步驟(2)中之自支持體剝離之凝膠膜，一面藉由旋轉輥限制移行速度一面向移行方向(MD)延伸。旋轉輥需要限制凝膠膜之移行速度所需之固持力，作為旋轉輥，較佳為使用將金屬輥與橡膠輥組合而成之夾輥、真空輥、多段張力削減輥、或減壓抽吸方式之吸輥等。 The gel film peeled from the support in the above step (2) is stretched toward the traveling direction (MD) by the rotating roller to restrict the traveling speed. The rotating roller needs to have a holding force required to limit the moving speed of the gel film. As the rotating roller, it is preferable to use a nip roll which combines a metal roll and a rubber roll, a vacuum roll, a multi-stage tension reducing roll, or a vacuum suction. The suction roller of the method.

於步驟(3)中，進行雙軸延伸處理。上述雙軸延伸處理之順序可以與上述第一製造態樣同樣之方式進行。 In the step (3), a biaxial stretching process is performed. The order of the above biaxial stretching process can be performed in the same manner as the first manufacturing aspect described above.

於上述第二製造態樣中，上述雙軸延伸處理中之MD之延伸(縱延伸)係分為3階段以上之多階段進行。MD之延伸(縱延伸)只要為3階段以上，則無特別限定，可以3階段、4階段、5階段等進行，就所獲得之膜之線熱膨脹係數之均一性較高之方面而言，較佳為3階段延伸。 In the second manufacturing aspect described above, the extension (longitudinal extension) of the MD in the biaxial stretching treatment is performed in a plurality of stages of three or more stages. The MD extension (longitudinal extension) is not particularly limited as long as it is three or more stages, and can be carried out in three stages, four stages, five stages, etc., and the uniformity of the linear thermal expansion coefficient of the obtained film is higher. Good for the 3 stage extension.

MD之各階段之延伸倍率並無特別限定，例如於3階段延伸之情形時，第1階段之延伸倍率並無特別限定，較佳為1.02倍以上且1.3倍以下，更佳為1.04倍以上且1.1倍以下。第2階段之MD之延伸倍率較佳為1.005倍以上且1.4倍以下，更佳為1.01倍以上且1.3倍以下。第3階段之MD之延伸倍率較佳為1.02倍以上且1.3倍以下，更佳為1.04倍以上且1.1倍以下。又，於本發明中，第1階段之延伸之延伸倍率相對於MD之總延伸倍率之比率較佳為40%以上，更佳為設為50%以上且80%以下。又，第2階段之延伸倍率相對於MD之總延伸倍率之比率較佳為5%以上，更佳為8%以上且30%以下。MD之總延伸倍率並無特別限定，較佳為1.04倍以上且1.4倍以下，更佳為1.05倍以上且1.3倍以下。關於各MD延伸之延伸倍率相對於MD之總延伸倍率之比率之算出方法如上述第一態樣中所述。 The stretching ratio at each stage of the MD is not particularly limited. For example, in the case of the three-stage stretching, the stretching ratio of the first stage is not particularly limited, but is preferably 1.02 times or more and 1.3 times or less, more preferably 1.04 times or more. 1.1 times or less. The MD stretching ratio in the second stage is preferably 1.005 times or more and 1.4 times or less, more preferably 1.01 times or more and 1.3 times or less. The stretching ratio of the MD in the third stage is preferably 1.02 times or more and 1.3 times or less, more preferably 1.04 times or more and 1.1 times or less. Further, in the present invention, the ratio of the stretching ratio of the extension of the first stage to the total stretching ratio of the MD is preferably 40% or more, and more preferably 50% or more and 80% or less. Further, the ratio of the stretching ratio in the second stage to the total stretching ratio in MD is preferably 5% or more, more preferably 8% or more and 30% or less. The total stretching ratio of MD is not particularly limited, but is preferably 1.04 times or more and 1.4 times or less, more preferably 1.05 times or more and 1.3 times or less. The method for calculating the ratio of the stretching ratio of each MD extension to the total stretching ratio of MD is as described in the first aspect above.

MD之延伸溫度可以與上述第一製造態樣同樣之方式進行。MD之延伸速度只要適當選擇可獲得目標線熱膨脹係數之條件即可，並無特別限定，於進行3階段延伸之情形時，該3階段延伸之第1階段之延伸速度較佳為1%/分鐘~20%/分鐘左右，更佳為2%/分鐘~10%/分鐘左右。該3階段延伸之第2階段之延伸速度較佳為1%/分鐘~20%/分鐘左右，更佳為2%/分鐘~10%/分鐘左右。該3階段延伸之第3階段之延伸速度較佳為1%/分鐘~20%/分鐘左右，更佳為2%/分鐘~10%/分鐘左右。於向MD之3階段延伸中，各階段之延伸時間並無特別限定，為2秒~5分鐘左右，較佳為5秒~3分鐘。縱延伸及橫延伸之模式可以與第一製造態樣同樣之方式進行。 The extension temperature of the MD can be carried out in the same manner as the first manufacturing aspect described above. The extension speed of the MD is not particularly limited as long as the condition for obtaining the thermal expansion coefficient of the target line is appropriately selected. When the three-stage extension is performed, the extension speed of the first stage of the three-stage extension is preferably 1%/minute. ~20% / minute or so, more preferably 2% / minute ~ 10% / minute. The extension speed of the second stage of the three-stage extension is preferably from about 1%/minute to about 20%/minute, more preferably from about 2%/minute to about 10%/minute. The extension speed of the third stage of the three-stage extension is preferably from about 1%/minute to about 20%/minute, more preferably from about 2%/minute to about 10%/minute. In the 3-stage extension to the MD, the extension time of each stage is not particularly limited, and is about 2 seconds to 5 minutes, preferably 5 seconds to 3 minutes. The mode of longitudinal extension and lateral extension can be performed in the same manner as the first manufacturing aspect.

MD之延伸後之加熱處理及TD之延伸可以與第一製造態樣同樣之方式進行。藉由於該等範圍內調整延伸倍率，並且調整溶劑殘留率，可製造具有所需之各向異性指數，且可藉由與其他構成要件之組合而均勻地抑制尺寸變化的膜。 The heat treatment after the extension of the MD and the extension of the TD can be carried out in the same manner as in the first manufacturing aspect. By adjusting the stretching ratio within the ranges and adjusting the solvent residual ratio, a film having a desired anisotropy index and uniformly suppressing dimensional change by combination with other constituent elements can be produced.

本發明之聚醯亞胺膜之厚度並無特別限定，較佳為設為1μm以上且100μm以下之範圍，更佳為設為3μm以上且50μm以下之範圍。本發明之聚醯亞胺膜之製膜寬度並無特別限定，較佳為1m以上。作為本發明之聚醯亞胺膜，例如可列舉製膜寬度為1m以上且厚度為3~50μm者。 The thickness of the polyimide film of the present invention is not particularly limited, but is preferably in the range of 1 μm or more and 100 μm or less, and more preferably in the range of 3 μm or more and 50 μm or less. The film formation width of the polyimide film of the present invention is not particularly limited, but is preferably 1 m or more. The polyimine film of the present invention may, for example, be a film having a film width of 1 m or more and a thickness of 3 to 50 μm.

本發明者等人進行了努力研究，結果發現：即便控制TD延伸時之溶劑殘留量來控制膜端部之向斜向之配向，因熱處理後之緩冷步驟中產生之收縮而引起之向斜向之殘留應力亦會影響對角線方向之尺寸變化率差。對於由第一製造態樣或第二製造態樣所獲得之聚醯亞胺膜，為了解除該應力，必須於特定之溫度下進行強熱處理(退火處理)。由於膜兩端部被銷式拉幅裝置、夾式拉幅裝置、夾頭等固定，故而因向TD方向之膜之固定及由冷卻所引起之膜之收縮而產生斜向之尺寸變化率差，對尺寸變化造成影響。可藉由退火處理產生膜之熱鬆弛而將加熱收縮率抑制為較小，除此以外，亦可改善兩端部之斜向之尺寸變化差。作為退火處理之溫度並無特別限定，較佳為250℃以上且500℃以下，更佳為270℃以上且370℃以下，尤佳為300℃以上且350℃以下。於本發明之聚醯亞胺膜之製法中由於膜向TD之配向較強，故而有TD上之加熱收縮率變高之傾向，但可藉由起因於退火處理之熱鬆弛而將200℃下之加熱收縮率於膜之MD、TD均抑制為0.05%以下，因此尺寸精度進一步變高，故而較佳。具體而言，較佳為於250℃以上且500℃以下、較佳為270℃以上且370℃以下、尤佳為300℃以上且350℃以下之爐中使膜向機械搬送方向於低張力下移行，而進行退火處理。膜在爐中滯留之時間成為處理時間，藉由改變移行速度而進行控制，較佳為30秒~5分鐘之處理時間。若處理時間短於該處理時間，則熱未充分傳導至膜，若長於該處理時間，則變得略微過熱而損害平面性，故而欠佳。又，移行時之膜張力較佳為 10~50N/m，更佳為15~30N/m。若張力低於該範圍，則膜之移行性變差，若張力高於該範圍，則所獲得之膜之移行方向之熱收縮率變高，故而欠佳。如圖5所示般藉由強熱處理而扭轉得到改善。圖5係對於進行通常熱處理(150~200℃)或強熱處理(300℃)時之軟性金屬積層板之銅箔蝕刻後頂點之位置偏移多少，僅於寬度方向上進行評價所得者。由圖5明確，藉由對相同之批次、相同之選取位置者(於同一熱處理之情形時顯示相同之扭轉行為)將熱處理由通常熱處理變更為強熱處理，會使扭轉改善。橫軸表示進行通常熱處理時之扭轉，縱軸表示進行強熱處理時之扭轉。 The inventors of the present invention conducted diligent research and found that even if the amount of solvent remaining in the TD extension is controlled to control the orientation of the film in the oblique direction, the skew caused by the shrinkage in the slow cooling step after the heat treatment is caused. The residual stress to the residual force also affects the dimensional change rate difference in the diagonal direction. For the polyimine film obtained from the first manufacturing aspect or the second manufacturing aspect, in order to relieve the stress, a strong heat treatment (annealing treatment) must be performed at a specific temperature. Since both ends of the film are fixed by a pin tenter, a clip-on tenter, a chuck, etc., the dimensional change rate difference in the oblique direction is caused by the fixation of the film in the TD direction and the shrinkage of the film caused by the cooling. , affecting dimensional changes. The heat shrinkage of the film can be suppressed by the annealing treatment to suppress the heat shrinkage rate to be small, and in addition to this, the difference in dimensional change between the both ends can be improved. The temperature of the annealing treatment is not particularly limited, but is preferably 250 ° C or more and 500 ° C or less, more preferably 270 ° C or more and 370 ° C or less, and particularly preferably 300 ° C or more and 350 ° C or less. In the method for producing a polyimide film of the present invention, since the film has a strong alignment to TD, the heating shrinkage ratio in TD tends to be high, but it can be 200 ° C by thermal relaxation caused by annealing treatment. Since the heat shrinkage ratio is suppressed to 0.05% or less in both MD and TD of the film, the dimensional accuracy is further increased, which is preferable. Specifically, it is preferred to subject the film to a mechanical transfer direction under a low tension in a furnace of 250 ° C or more and 500 ° C or less, preferably 270 ° C or more and 370 ° C or less, and more preferably 300 ° C or more and 350 ° C or less. Transfer and perform annealing treatment. The time during which the film stays in the furnace becomes the processing time, and is controlled by changing the moving speed, and is preferably a processing time of 30 seconds to 5 minutes. If the treatment time is shorter than the treatment time, the heat is not sufficiently conducted to the membrane, and if it is longer than the treatment time, it becomes slightly overheated to impair the planarity, which is not preferable. Moreover, the film tension at the time of migration is preferably 10~50N/m, more preferably 15~30N/m. When the tension is less than the above range, the film transition property is deteriorated, and if the tension is higher than the range, the heat shrinkage rate in the traveling direction of the obtained film becomes high, which is not preferable. The torsion is improved by a strong heat treatment as shown in FIG. Fig. 5 is a graph showing the positional deviation of the apex after etching of the copper foil of the soft metal laminate in the usual heat treatment (150 to 200 ° C) or the strong heat treatment (300 ° C), and evaluation was performed only in the width direction. As is clear from Fig. 5, the torsion is improved by changing the heat treatment from the usual heat treatment to the strong heat treatment for the same batch and the same selected position (showing the same torsional behavior in the case of the same heat treatment). The horizontal axis represents the torsion when the normal heat treatment is performed, and the vertical axis represents the torsion when the heat treatment is performed.

為了使所獲得之聚醯亞胺膜具有接著性，亦可對膜表面進行如電暈處理或電漿處理之電處理或如噴砂處理之物理處理。進行電漿處理之氣氛之壓力並無特別限定，通常為13.3~1330kPa之範圍，較佳為13.3~133kPa(100~1000Torr)之範圍，更佳為80.0~120kPa(600~900Torr)之範圍。 In order to impart adhesion to the obtained polyimide film, the surface of the film may be subjected to electrical treatment such as corona treatment or plasma treatment or physical treatment such as sand blasting. The pressure of the atmosphere to be subjected to the plasma treatment is not particularly limited, but is usually in the range of 13.3 to 1330 kPa, preferably in the range of 13.3 to 133 kPa (100 to 1000 Torr), and more preferably in the range of 80.0 to 120 kPa (600 to 900 Torr).

進行電漿處理之氣氛係含有至少20莫耳%之惰性氣體者，較佳為含有50莫耳%以上之惰性氣體者，更佳為含有80莫耳%以上者，最佳為含有90莫耳%以上者。上述惰性氣體包含He、Ar、Kr、Xe、Ne、Rn、N2及該等之2種以上之混合物。尤佳之惰性氣體為Ar。進而，亦可對上述惰性氣體混合氧、空氣、一氧化碳、二氧化碳、四氯化碳、氯仿、氫、氨、四氟甲烷(四氟化碳)、三氯氟乙烷、三氟甲烷等。關於用作本發明之電漿處理之氣氛之較佳之混合氣體之組合，可列舉：氬/氧、氬/氨、氬/氦/氧、氬/二氧化碳、氬/氮/二氧化碳、氬/氦/氮、氬/氦/氮/二氧化碳、氬/氦、氦/空氣、氬/氦/甲矽烷、氬/氦/二矽烷等。 The atmosphere in which the plasma treatment is carried out contains at least 20 mol% of an inert gas, preferably 50 mol% or more of an inert gas, more preferably 80 mol% or more, and most preferably 90 mol%. More than %. The inert gas contains He, Ar, Kr, Xe, Ne, Rn, N 2 and a mixture of two or more of these. The preferred inert gas is Ar. Further, the inert gas may be mixed with oxygen, air, carbon monoxide, carbon dioxide, carbon tetrachloride, chloroform, hydrogen, ammonia, tetrafluoromethane (carbon tetrafluoride), trichlorofluoroethane, trifluoromethane or the like. As a preferable combination of the mixed gas used as the atmosphere for plasma treatment of the present invention, argon/oxygen, argon/ammonia, argon/helium/oxygen, argon/carbon dioxide, argon/nitrogen/carbon dioxide, argon/helium/ Nitrogen, argon/helium/nitrogen/carbon dioxide, argon/argon, helium/air, argon/krypton/formane, argon/helium/dioxane, and the like.

實施電漿處理時之處理電力密度並無特別限定，較佳為200W‧min/m2以上，更佳為500W‧min/m2以上，最佳為1000W‧min/m2 以上。進行電漿處理之電漿照射時間較佳為1秒~10分鐘。藉由將電漿照射時間設定為該範圍內，可於不伴隨膜之劣化之情況下充分地發揮電漿處理之效果。電漿處理之氣體種類、氣壓、處理密度並不限定於上述條件，亦可於大氣中進行。 The plasma processing process embodiment the power density is not particularly limited, but is preferably 200W‧min / m 2 or more, more preferably 500W‧min / m 2 or more, most preferably 1000W‧min / m 2 or more. The plasma irradiation time for performing the plasma treatment is preferably from 1 second to 10 minutes. By setting the plasma irradiation time within this range, the effect of the plasma treatment can be sufficiently exhibited without causing deterioration of the film. The gas type, gas pressure, and treatment density of the plasma treatment are not limited to the above conditions, and may be carried out in the atmosphere.

本發明所使用之熱塑性聚醯亞胺可藉由將作為前驅物之聚醯胺酸進行醯亞胺化而獲得。對於熱塑性聚醯亞胺之前驅物亦無特別限定，可使用公知之所有聚醯胺酸。又，關於其製造，亦可使用公知之原料或反應條件等。又，亦可視需要添加無機或有機物之填料。 The thermoplastic polyimine used in the present invention can be obtained by ruthenium imidization of a polylysine as a precursor. The thermoplastic polyimine precursor is also not particularly limited, and all known polylysines can be used. Moreover, well-known raw materials, reaction conditions, etc. can also be used for manufacture. Further, a filler of an inorganic or organic substance may be added as needed.

熱塑性聚醯亞胺之玻璃轉移溫度只要為150℃~350℃之範圍，則無特別限定。 The glass transition temperature of the thermoplastic polyimide is not particularly limited as long as it is in the range of 150 ° C to 350 ° C.

本發明之接著膜可藉由於上述連續生產之特定之聚醯亞胺膜之至少單面設置含有熱塑性聚醯亞胺之接著層而獲得。作為其具體之製造方法，可較佳地例示於成為基材膜之聚醯亞胺膜上形成接著層之方法、或將接著層成形為片狀並將其貼合於上述聚醯亞胺膜之方法等。其中，於採用前者之方法之情形時，若使接著層中所含有之熱塑性聚醯亞胺之前驅物即聚醯胺酸完全醯亞胺化，則有於有機溶劑中之溶解性降低之情形，因此有難以於聚醯亞胺膜上設置上述接著層之情形。因此，就上述觀點而言，更佳為採用如下順序：製備含有作為熱塑性聚醯亞胺之前驅物之聚醯胺酸之溶液，並將其塗佈於基材膜，繼而進行醯亞胺化。 The adhesive film of the present invention can be obtained by providing an adhesive layer containing a thermoplastic polyimide at least on one side of the above-mentioned continuously produced specific polyimide film. As a specific production method, a method of forming an adhesive layer on a polyimide film which is a base film, or forming a laminate into a sheet shape and bonding it to the above polyimide film can be preferably exemplified. Method and so on. In the case where the former method is employed, if the polyacrylamide precursor, which is a precursor of the thermoplastic polyimine contained in the adhesive layer, is completely imidized, the solubility in the organic solvent is lowered. Therefore, it is difficult to provide the above-mentioned adhesive layer on the polyimide film. Therefore, in view of the above, it is more preferable to adopt a procedure of preparing a solution containing a poly-proline which is a precursor of a thermoplastic polyimide, and applying it to a substrate film, followed by ruthenium imidization. .

關於將聚醯胺酸溶液流延、塗佈於聚醯亞胺膜之方法並無特別限定，可使用模具塗佈機、反向塗佈機、刮刀塗佈機等既有之方法。於連續地形成接著層之情形時，發明之效果變得顯著。即為如下方法：將以上述方式獲得之聚醯亞胺膜捲取，將其捲出，並連續地塗佈含有作為熱塑性聚醯亞胺之前驅物之聚醯胺酸之溶液。又，於上述聚醯胺酸溶液中，亦可根據用途而含有例如填料之類的其他材料。又， 關於耐熱性接著膜各層之厚度構成，只要以成為適合用途之總厚度之方式適當調整即可。 The method of casting and coating the polyaminic acid solution on the polyimide film is not particularly limited, and a conventional method such as a die coater, a reverse coater, or a knife coater can be used. The effect of the invention becomes remarkable in the case where the subsequent layer is continuously formed. That is, the method is as follows: the polyimine film obtained in the above manner is taken up, rolled up, and a solution containing polyamic acid as a precursor of the thermoplastic polyimide. Further, in the polyamic acid solution, other materials such as a filler may be contained depending on the application. also, The thickness of each layer of the heat-resistant adhesive film may be appropriately adjusted so as to be a total thickness suitable for the application.

作為醯亞胺化之方法，可使用加熱醯亞胺化法或化學醯亞胺化法之任一者。於採用任一醯亞胺化順序之情形時，均為了高效率地進行醯亞胺化而進行加熱，此時之溫度較佳為設定為(熱塑性聚醯亞胺之玻璃轉移溫度-100℃)~(玻璃轉移溫度+200℃)之範圍內，更佳為設定為(熱塑性聚醯亞胺之玻璃轉移溫度-50℃)~(玻璃轉移溫度+150℃)之範圍內。由於加熱溫度較高者容易引起醯亞胺化，故而可加快醯亞胺化速度，於生產性方面較佳。但是，若過高，則有熱塑性聚醯亞胺發生熱分解之情形。另一方面，若加熱溫度過低，則即便化學醯亞胺化亦難以進行醯亞胺化，而醯亞胺化步驟所需之時間變長。 As a method of ruthenium imidation, either a heated hydrazine imidation method or a chemical hydrazine imidation method can be used. In the case of using any of the ruthenium imidization sequences, the ruthenium imidization is carried out with high efficiency, and the temperature is preferably set to (the glass transition temperature of the thermoplastic polyimide) - 100 ° C) In the range of ~ (glass transition temperature + 200 ° C), it is more preferably set within the range of (glass transition temperature of thermoplastic polyimide) - (glass transition temperature + 150 ° C). Since the heating temperature is high, the ruthenium imidization is likely to occur, so that the hydrazine imidization speed can be accelerated, which is preferable in terms of productivity. However, if it is too high, there is a case where the thermoplastic polyimine is thermally decomposed. On the other hand, if the heating temperature is too low, it is difficult to carry out the imidization by chemical imidization, and the time required for the oxime imidization step becomes long.

關於醯亞胺化時間，只要採取實質上醯亞胺化及乾燥完成所充分之時間即可，並無特別限定。 The hydrazine imidization time is not particularly limited as long as it takes a sufficient period of time for substantially purifying imidization and drying.

熱塑性聚醯亞胺之厚度較佳為0.1μm以上且30μm以下，更佳為0.5μm以上且20μm以下。 The thickness of the thermoplastic polyimide is preferably 0.1 μm or more and 30 μm or less, more preferably 0.5 μm or more and 20 μm or less.

本發明所使用之金屬之種類並無特別限定，作為例子可列舉銅及銅合金、不鏽鋼及其合金、鎳及鎳合金(亦包含42合金)、鋁及鋁合金等。較佳為銅及銅合金。又，亦可利用於該等金屬表面形成有防銹層或耐熱層(例如鉻、鋅等之鍍敷處理)、矽烷偶合劑等者。較佳為銅及/或包含鎳、鋅、鐵、鉻、鈷、鉬、鎢、釩、鈹、鈦、錫、錳、鋁、磷、矽等中之至少1種以上之成分與銅之銅合金，該等於電路加工方面較佳而被使用。尤其理想之金屬箔為藉由壓延或電鍍法而形成之銅箔，其厚度較佳為3~150μm，更佳為3~35μm。 The type of the metal used in the present invention is not particularly limited, and examples thereof include copper and a copper alloy, stainless steel and an alloy thereof, nickel and a nickel alloy (including a 42 alloy), aluminum, and an aluminum alloy. Copper and copper alloys are preferred. Further, it is also possible to form a rustproof layer or a heat-resistant layer (for example, a plating treatment such as chromium or zinc) or a decane coupling agent on the surface of the metal. Preferably, it is copper and/or contains at least one of nickel, zinc, iron, chromium, cobalt, molybdenum, tungsten, vanadium, niobium, titanium, tin, manganese, aluminum, phosphorus, antimony, etc. The alloy, which is equivalent to the circuit processing, is preferably used. Particularly preferably, the metal foil is a copper foil formed by calendering or electroplating, and has a thickness of preferably from 3 to 150 μm, more preferably from 3 to 35 μm.

該金屬箔可於兩面均未實施任何粗化處理，亦可於單面或兩面實施有粗化處理。 The metal foil may be subjected to any roughening treatment on both sides, or may be roughened on one side or both sides.

作為非熱塑性聚醯亞胺與金屬之加熱壓接方法，有如下方法： 於非熱塑性聚醯亞胺膜上塗佈熱塑性聚醯亞胺之前驅物之聚醯胺酸及/或聚醯亞胺溶液並使其乾燥後，與金屬貼合，或者先利用同樣之方法於金屬上形成熱塑性聚醯亞胺後，再與非熱塑性聚醯亞胺膜貼合，貼合時可使用加熱壓製法及/或連續層壓法。作為加熱壓製法，例如可藉由將切成壓製機之特定尺寸之金屬箔與聚醯亞胺重合，並利用加熱壓製進行熱壓接而製造。 As a method of heating and crimping a non-thermoplastic polyimide and a metal, there are the following methods: Coating the polyaminic acid and/or polyimine solution of the thermoplastic polyimine precursor onto the non-thermoplastic polyimide film and drying it, bonding with the metal, or using the same method first After the thermoplastic polyimide is formed on the metal, it is bonded to the non-thermoplastic polyimide film, and a heat pressing method and/or a continuous lamination method can be used for bonding. As the heat pressing method, for example, it can be produced by superposing a metal foil of a specific size cut into a press machine with polyimine and thermocompression bonding by heat pressing.

作為連續層壓法並無特別限制，例如有夾入輥與輥之間進行貼合之方法。該輥可利用金屬輥、橡膠輥等。材質並無限制，作為金屬輥，可使用鋼材或不鏽鋼材料。較佳為使用表面為硬鉻鍍敷、碳化鎢等之提高了表面硬度之處理輥。作為橡膠輥，較佳為於金屬輥之表面使用具有耐熱性之矽橡膠、氟系橡膠。 The continuous lamination method is not particularly limited, and for example, there is a method in which a pinch roll and a roll are bonded together. The roller can utilize a metal roll, a rubber roll, or the like. The material is not limited. As the metal roll, steel or stainless steel can be used. It is preferable to use a treatment roll whose surface hardness is hard chrome plating, tungsten carbide or the like which improves the surface hardness. As the rubber roller, it is preferable to use a heat-resistant ruthenium rubber or a fluorine-based rubber on the surface of the metal roll.

又，亦可藉由被稱為帶式層壓之如下方式進行連續層壓：將上下2根金屬輥設為1組，於將其1組以上串列配置之上下輥間，將上下2個無縫之不鏽鋼帶配置於其間，藉由金屬輥對該帶進行加壓，進而藉由金屬輥或其他熱源進行加熱。 Further, it is also possible to carry out continuous lamination by a method called belt lamination: one set of the upper and lower metal rolls is set to one set, and one or more sets are arranged in series between the upper and lower rolls, and two upper and lower sides are arranged. A seamless stainless steel strip is disposed therebetween, which is pressurized by a metal roll and heated by a metal roll or other heat source.

作為層壓溫度，較佳為200~400℃之溫度範圍。亦較佳為於加熱壓製及/或連續層壓後進行加熱退火。 The lamination temperature is preferably in the range of 200 to 400 °C. It is also preferred to carry out heat annealing after heat pressing and/or continuous lamination.

藉由本發明之製造方法而獲得之軟性金屬積層板如上所述，若對金屬箔進行蝕刻而形成所需之圖案配線，則可用作安裝有各種小型化、高密度化之零件之軟性配線板。當然，本發明之用途並不限定於此，只要為包含金屬箔之積層體，則當然可用於各種用途。 As described above, the flexible metal laminate obtained by the production method of the present invention can be used as a flexible wiring board in which various miniaturized and high-density components are mounted by etching a metal foil to form a desired pattern wiring. . Needless to say, the use of the present invention is not limited thereto, and it is of course applicable to various uses as long as it is a laminate including a metal foil.

本發明只要發揮本發明之效果，則於本發明之技術範圍內包含將上述構成各種組合而成之態樣。 In the present invention, as long as the effects of the present invention are exerted, the above-described configurations are combined in various aspects.

[實施例] [Examples]

其次，列舉實施例進而具體地說明本發明，但本發明並不受該等實施例任何限定，於該領域具有通常之知識者可於本發明之技術思 想內進行多種變化。 In the following, the present invention will be specifically described by way of examples, but the present invention is not limited by the examples, and those skilled in the art can think of the present invention. I want to make a variety of changes.

以下對本發明中之各種特性之測定方法進行說明。 Hereinafter, a method of measuring various characteristics in the present invention will be described.

(1)AI(45、135) (1) AI (45, 135)

本發明中之超音波脈衝之傳播速度V係使用野村商事製造之SST-2500(Sonic Sheet Tester)進行測定。若使用SST-2500，則對膜之面方向0~180度(0度與MD方向平行)每隔11.25°自動測定16方向之超音波速度。根據所獲得之各方向之速度中以MD方向作為基準為45°與135°下之超音波速度V45、V135而求出式1所表示之各向異性指數(Anisotoropy Index：AI)。使用藉由下述實施例及比較例而獲得之膜，於圖3所示之位置分別進行測定。 The propagation velocity V of the ultrasonic pulse in the present invention is measured using SST-2500 (Sonic Sheet Tester) manufactured by Nomura Corporation. When the SST-2500 is used, the ultrasonic velocity in the 16 directions is automatically measured every 11.25° from 0 to 180 degrees (0 degrees parallel to the MD direction). An anisotropy index (AI) expressed by Formula 1 is obtained from the ultrasonic speeds V45 and V135 at 45° and 135° with reference to the MD direction based on the obtained speed in each direction. The film obtained by the following examples and comparative examples was measured at the position shown in FIG.

(式1)：AI(45、135)=|(V45ˆ2-V135ˆ2)/((V45ˆ2+V135ˆ2)/2)×100| (Formula 1): AI(45, 135)=|(V45ˆ2-V135ˆ2)/((V45ˆ2+V135ˆ2)/2)×100|

(2)配向角度 (2) Alignment angle

本發明中之配向角度係使用野村商事製造之SST-2500(Sonic Sheet Tester)進行測定。若使用SST-2500，則對膜之面方向0~180°(0°與MD方向平行)每隔11.25°自動測定16方向之超音波速度。藉由將所獲得之各方向之速度雷達圖化(使用Microsoft Excel之圖表功能)，而繪出如圖3所示之模式圖。自圓中心向該模式圖之鼓出最多之部分引出之線為配向軸(g)，以MD方向作為基準線，測定配向軸距該基準線之角度(θ)，將其作為配向角度而求出。 The alignment angle in the present invention was measured using SST-2500 (Sonic Sheet Tester) manufactured by Nomura Corporation. When the SST-2500 is used, the ultrasonic velocity in the 16 directions is automatically measured at 11.25° for the surface direction of the film from 0 to 180° (0° parallel to the MD direction). By patterning the obtained speeds in all directions (using the chart function of Microsoft Excel), a pattern diagram as shown in Fig. 3 is drawn. The line leading from the center of the circle to the most bulging part of the pattern is the alignment axis (g), and the MD direction is used as the reference line, and the angle (θ) of the alignment wheel from the reference line is measured, and this is obtained as the alignment angle. Out.

(3)尺寸變化率 (3) Dimensional change rate

根據JIS C6481 5.16，於試樣之接著膜之中心及對角線上形成4個孔，並測定各孔距中心部之各自之距離。其次，於350℃/30分鐘之條件下貼附銅箔，並實施蝕刻步驟自軟性金屬積層板去除金屬箔後，再次以與蝕刻步驟前同樣之方式測定上述4個孔距中心部之各自之距離。將去除金屬箔前之各孔之距離之測定值設為D1，將去除金 屬箔後之各孔之距離之測定值設為D2，藉由下式求出蝕刻前後之尺寸變化率。 According to JIS C6481 5.16, four holes were formed in the center and diagonal lines of the film of the sample, and the respective distances of the holes from the center portion were measured. Next, the copper foil was attached at 350 ° C / 30 minutes, and the etching step was performed to remove the metal foil from the flexible metal laminate. Then, the respective four pitches of the center portion were measured in the same manner as before the etching step. distance. The measured value of the distance between the holes before removing the metal foil is set to D1, and the gold is removed. The measured value of the distance between the respective holes after the foil was D2, and the dimensional change rate before and after the etching was obtained by the following formula.

尺寸變化率(%)={(D2-D1)/D1}×100 Dimensional change rate (%) = {(D2-D1) / D1} × 100

又，求出右45°、左45°之尺寸變化率之差。 Further, the difference in dimensional change ratio between the right 45° and the left 45° was obtained.

[聚醯亞胺合成例1] [Polyimine Synthesis Example 1]

以莫耳比計為80/20/75/25之比率準備均苯四甲酸二酐(分子量218.12)/3,3',4,4'-聯苯四羧酸二酐(分子量294.22)/4,4'-二胺基二苯醚(分子量200.24)/對苯二胺(分子量108.14)，於DMAc(N,N-二甲基乙醯胺)中製成20重量%溶液並進行聚合，而獲得3500 poise之聚醯胺酸溶液。 Preparation of pyromellitic dianhydride (molecular weight 218.12) / 3,3',4,4'-biphenyltetracarboxylic dianhydride (molecular weight 294.22) / 4 in molar ratio of 80/20/75/25 , 4'-diaminodiphenyl ether (molecular weight 200.24) / p-phenylenediamine (molecular weight 108.14), made a 20% by weight solution in DMAc (N, N-dimethylacetamide) and polymerized, and A 3500 poise polyamine solution was obtained.

[聚醯亞胺合成例2] [Polyimine Synthesis Example 2]

以莫耳比計為65/35/80/20之比率準備均苯四甲酸二酐(分子量218.12)/3,3',4,4'-聯苯四羧酸二酐(分子量294.22)/4,4'-二胺基二苯醚(分子量200.24)/對苯二胺(分子量108.14)，於DMAc(N,N-二甲基乙醯胺)中製成20重量%溶液並進行聚合，而獲得3500 poise之聚醯胺酸溶液。 Preparation of pyromellitic dianhydride (molecular weight 218.12) / 3,3',4,4'-biphenyltetracarboxylic dianhydride (molecular weight 294.22) / 4 in molar ratio of 65/35/80/20 , 4'-diaminodiphenyl ether (molecular weight 200.24) / p-phenylenediamine (molecular weight 108.14), made a 20% by weight solution in DMAc (N, N-dimethylacetamide) and polymerized, and A 3500 poise polyamine solution was obtained.

[熱塑性聚醯亞胺之合成例A] [Synthesis Example A of Thermoplastic Polyimine]

將1,3-雙-(4-胺基苯氧基)苯添加至溶劑二甲基乙醯胺中，並進行攪拌直至溶解。其後，添加4,4'-二氧基二鄰苯二甲酸酐進行攪拌，而獲得聚醯胺酸溶液。二甲基乙醯胺中之固形物成分為15%，Tg為217℃。 1,3-bis-(4-aminophenoxy)benzene was added to the solvent dimethylacetamide and stirred until dissolved. Thereafter, 4,4'-dioxydiphthalic anhydride was added and stirred to obtain a polyamidonic acid solution. The solid content of dimethylacetamide was 15% and the Tg was 217 °C.

[實施例1] [Example 1]

將利用雷射繞射/散射式粒度分佈測定裝置LA-910(堀場製作所製造)所測得之全部粒子之粒徑控制為0.01μm以上且1.5μm以下、平均粒徑(體積平均粒徑)為0.42μm、關於粒度分佈(體積基準)粒徑為0.15~0.60μm之粒子於全部粒子中占89.9體積%的二氧化矽之N,N- 二甲基乙醯胺漿料以相對於樹脂重量為0.4重量%添加至合成例1中獲得之聚醯胺酸溶液中，並充分地攪拌、分散。於該聚醯胺酸溶液中將乙酸酐(分子量102.09)與β-甲基吡啶以相對於聚醯胺酸溶液分別為17重量%、17重量%之比率混合並攪拌。將所獲得之混合物澆鑄於藉由T型狹縫式模具進行旋轉之75℃之不鏽鋼製轉筒上，而獲得殘留揮發成分為55重量%且厚度約為0.05mm之具有自持性之凝膠膜。將該凝膠膜自轉筒剝離，經過2組夾輥進行搬送。此時藉由改變不鏽鋼製轉筒(R1)、最初之夾輥(R2)、第2組夾輥(R3)之各者之旋轉速度而以2階段進行縱延伸，以各延伸率成為下述表1中記載之值之方式於65℃下進行縱延伸。於縱延伸後，將膜之兩端固持，於加熱爐中以250℃×50秒、400℃×75秒進行處理，而獲得寬度2.2m、厚度20μm之聚醯亞胺膜。橫延伸係以於通過去除溶劑之加熱爐時(250℃×50秒)成為最大之方式設定。將上述通過加熱爐時之延伸倍率設為最大延伸率，於通過加熱爐後，橫延伸倍率逐漸降低。橫延伸率係作為最大橫延伸率之膜寬度除以自轉筒剝離後之凝膠膜寬度所得之值而求出。 The particle diameter of all the particles measured by the laser diffraction/scattering type particle size distribution measuring apparatus LA-910 (manufactured by Horiba, Ltd.) is controlled to be 0.01 μm or more and 1.5 μm or less, and the average particle diameter (volume average particle diameter) is 0.42 μm, the particle size distribution (volume basis) particle size of 0.15 ~ 0.60 μm particles accounted for 89.9% by volume of all particles of N, N- The dimethylacetamide slurry was added to the polyamic acid solution obtained in Synthesis Example 1 at 0.4% by weight based on the weight of the resin, and sufficiently stirred and dispersed. In the polyamic acid solution, acetic anhydride (molecular weight: 102.09) and β-picoline were mixed and stirred at a ratio of 17% by weight to 17% by weight based on the polyamic acid solution, respectively. The obtained mixture was cast on a stainless steel drum rotated at 75 ° C by a T-slit die to obtain a self-sustaining gel film having a residual volatile component of 55 wt% and a thickness of about 0.05 mm. . The gel film was peeled off from the drum and conveyed through two sets of nip rolls. At this time, the rotation speed of each of the stainless steel drum (R1), the first nip roller (R2), and the second group nip roller (R3) is changed in the longitudinal direction in two stages, and the respective elongations are as follows. The manner of the values described in Table 1 was carried out longitudinally at 65 °C. After the longitudinal stretching, both ends of the film were held and treated in a heating furnace at 250 ° C × 50 seconds and 400 ° C × 75 seconds to obtain a polyimide film having a width of 2.2 m and a thickness of 20 μm. The lateral extension is set so as to be maximized by the furnace in which the solvent is removed (250 ° C × 50 seconds). The stretching ratio when passing through the heating furnace described above is set as the maximum elongation, and the transverse stretching ratio is gradually lowered after passing through the heating furnace. The transverse elongation was determined as a value obtained by dividing the film width of the maximum transverse elongation by the width of the gel film after peeling from the drum.

對所獲得之膜於可利用熱風與加熱器連續加熱之烘箱中以張力20N/m進行300℃/30秒之退火處理。將橫延伸率示於下述表1。針對所獲得之聚醯亞胺膜，對圖4所示之5點(b、b'、c、d、d')求出AI(45、135)，並示於下述表2。 The obtained film was annealed at 300 ° C / 30 seconds at a tension of 20 N/m in an oven which was continuously heated by hot air and a heater. The lateral elongation is shown in Table 1 below. With respect to the obtained polyimide film, AI (45, 135) was obtained for 5 points (b, b', c, d, d') shown in Fig. 4, and is shown in Table 2 below.

[熱塑性聚醯亞胺、軟性金屬積層板之製造方法] [Method for Producing Thermoplastic Polyimine and Soft Metal Laminate]

於實施例1中製作之膜上以乾燥後之厚度成為2μm之方式塗佈合成例A之熱塑性聚醯亞胺之聚醯胺酸溶液，並於150℃下熱醯亞胺化10分鐘，於350℃下熱醯亞胺化1分鐘(接著膜之製作)。其後，於熱塑性聚醯亞胺側以350℃/30分鐘貼合銅箔，而製作軟性金屬積層板。測定軟性金屬積層板製作前後之尺寸變化率。將尺寸變化率示於 下述表2。 The polyimine solution of the thermoplastic polyimine of Synthesis Example A was applied to the film prepared in Example 1 so as to have a thickness of 2 μm after drying, and was thermally imidized at 150 ° C for 10 minutes. Hot iodization at 350 ° C for 1 minute (following the production of the film). Thereafter, a copper foil was bonded to the thermoplastic polyimide side at 350 ° C for 30 minutes to prepare a flexible metal laminate. The dimensional change rate before and after the production of the flexible metal laminate was measured. Show the dimensional change rate at Table 2 below.

[實施例2~4] [Examples 2 to 4]

分別如表1所示般設定所使用之聚醯胺酸溶液、縱延伸率、橫延伸率、乾燥溫度、聚醯亞胺膜膜厚，除此以外，以與實施例1同樣之方式獲得各聚醯亞胺膜，針對所獲得之各聚醯亞胺膜，以與實施例1同樣之方式製成接著膜後，製作軟性金屬積層板，並求出尺寸變化率，示於下述表2。 In the same manner as in Example 1, except that the polyaminic acid solution, the longitudinal elongation, the lateral elongation, the drying temperature, and the film thickness of the polyimide film were used as shown in Table 1, respectively. A polyimide film was formed on the polyimine film obtained in the same manner as in Example 1 to prepare a film of a flexible metal laminate, and a dimensional change ratio was obtained, which is shown in Table 2 below. .

[比較例1、2] [Comparative Examples 1, 2]

分別如表1所示般設定所使用之聚醯胺酸溶液、縱延伸率、橫延伸率、乾燥溫度、聚醯亞胺膜膜厚，除此以外，以與實施例1同樣之方式獲得各聚醯亞胺膜，針對所獲得之各聚醯亞胺膜，以與實施例1同樣之方式製成接著膜後，製作軟性金屬積層板，並求出尺寸變化率，示於下述表2。 In the same manner as in Example 1, except that the polyaminic acid solution, the longitudinal elongation, the lateral elongation, the drying temperature, and the film thickness of the polyimide film were used as shown in Table 1, respectively. A polyimide film was formed on the polyimine film obtained in the same manner as in Example 1 to prepare a film of a flexible metal laminate, and a dimensional change ratio was obtained, which is shown in Table 2 below. .

[比較例3] [Comparative Example 3]

分別如表1所示般設定所使用之聚醯胺酸溶液、縱延伸率、橫延伸率、乾燥溫度、聚醯亞胺膜膜厚，除此以外，以與實施例1同樣之方式獲得聚醯亞胺膜，對於所獲得之聚醯亞胺膜，於200℃下加熱30秒(退火處理)後製成接著膜，製作軟性金屬積層板，並求出尺寸變化率，示於下述表2。 The poly-phthalic acid solution, the longitudinal elongation, the lateral elongation, the drying temperature, and the film thickness of the polyimide film were set as shown in Table 1, except that the polymerization was obtained in the same manner as in Example 1. The yttrium imide film was heated at 200 ° C for 30 seconds (annealing) to obtain a film, and a flexible metal laminate was produced, and the dimensional change rate was determined. 2.

根據上述結果可確認，本發明之聚醯亞胺膜可抑制尺寸變化，亦可降低由膜之位置所引起之尺寸變化率之差異。另一方面，於比較例1~3中，無法如本發明之聚醯亞胺膜般抑制尺寸變化，亦可見由膜之位置所引起之尺寸變化率之差異。 From the above results, it was confirmed that the polyimide film of the present invention can suppress dimensional change and also reduce the difference in dimensional change rate caused by the position of the film. On the other hand, in Comparative Examples 1 to 3, the dimensional change was not suppressed as in the case of the polyimide film of the present invention, and the difference in the dimensional change rate caused by the position of the film was also observed.

[產業上之可利用性] [Industrial availability]

本發明之聚醯亞胺膜對軟性印刷配線板有用。 The polyimide film of the present invention is useful for a flexible printed wiring board.

Claims (10)

一種聚醯亞胺膜，其特徵在於：製膜寬度為1m以上，且以膜之機械搬送方向(MD)作為基準，膜之配向角度(θ)為45°與135°下之式1所表示之各向異性指數AI(45、135)值涵蓋全寬為12以下，於全寬上對角線(45°、135°)方向之軟性金屬積層板之蝕刻處理前後之尺寸變化率均為-0.05~0.05%，且於至少單面具有厚度為0.5~20μm之熱塑性聚醯亞胺層，AI(45、135)=|(V45ˆ2-V135ˆ2)/((V45ˆ2+V135ˆ2)/2)×100| (式1)。 A polyimide film having a film width of 1 m or more and a film-oriented mechanical direction (MD) as a reference, wherein the film has an alignment angle (θ) of 45° and 135° The anisotropy index AI (45, 135) value covers a full width of 12 or less, and the dimensional change rate before and after the etching treatment of the soft metal laminate in the diagonal (45°, 135°) direction on the full width is - 0.05~0.05%, and having a thermoplastic polyimide layer having a thickness of 0.5-20 μm on at least one side, AI(45, 135)=|(V45ˆ2-V135ˆ2)/((V45ˆ2+V135ˆ2)/2)×100| (Formula 1). 如請求項1之聚醯亞胺膜，其中於與膜之機械搬送方向(MD)垂直之方向之直線上選擇自製膜寬度兩端進入200mm內側之2點，於連接該2點之直線之範圍內，選擇包含該2點之直線上之中央部±200mm以內之1點，進而選擇任意2點，於至少該等5點之全部，各向異性指數為12以下。 The polyimine film of claim 1, wherein the two sides of the width of the self-made film enter the inner side of 200 mm on a straight line perpendicular to the mechanical transfer direction (MD) of the film, and the range of the line connecting the two points is Then, one point within ±200 mm of the central portion on the straight line including the two points is selected, and any two points are selected, and at least the five points are at least the anisotropy index of 12 or less. 如請求項1之聚醯亞胺膜，其係藉由如下方式製造，且製膜寬度為1m以上且厚度為3~50μm：製作將作為聚醯亞胺前驅物之聚醯胺酸溶液流延塗佈於支持體上並使其部分地乾燥及/或硬化而成之具有自持性的凝膠膜，使該凝膠膜通過具備至少2個以上之加熱爐之拉幅加熱爐，一面將該凝膠膜之寬度方向兩端固持一面進行乾燥及/或熱處理。 The polyimine film according to claim 1, which is produced by the method of forming a film having a width of 1 m or more and a thickness of 3 to 50 μm: casting a polyamic acid solution as a polyimide precursor a self-sustaining gel film which is applied to a support and partially dried and/or cured, and the gel film is passed through a tenter heating furnace having at least two or more heating furnaces. The both sides of the gel film are held in one side in the width direction to be dried and/or heat-treated. 如請求項2之聚醯亞胺膜，其係藉由如下方式製造，且製膜寬度為1m以上且厚度為3~50μm：製作將作為聚醯亞胺前驅物之聚醯胺酸溶液流延塗佈於支持體上並使其部分地乾燥及/或硬化而成之具有自持性的凝膠膜，使該凝膠膜通過具備至少2個以上之加熱爐之拉幅加熱爐，一面將該凝膠膜之寬度方向兩端 固持一面進行乾燥及/或熱處理。 The polyimine film according to claim 2, which is produced by the method of forming a film having a width of 1 m or more and a thickness of 3 to 50 μm: casting a polyamic acid solution as a polyimide precursor a self-sustaining gel film which is applied to a support and partially dried and/or cured, and the gel film is passed through a tenter heating furnace having at least two or more heating furnaces. Both ends of the gel film in the width direction The holding side is dried and/or heat treated. 如請求項3之聚醯亞胺膜，其係進而於機械搬送方向(MD)上在低張力下實施加熱處理而成。 The polyimine film of claim 3 is further subjected to heat treatment under low tension in a machine transport direction (MD). 如請求項4之聚醯亞胺膜，其係進而於機械搬送方向(MD)上在低張力下實施加熱處理而成。 The polyimine film of claim 4 is further subjected to heat treatment under low tension in a machine transport direction (MD). 如請求項1至6中任一項之聚醯亞胺膜，其中聚醯亞胺膜係使用選自由對苯二胺、4,4'-二胺基二苯醚及3,4'-二胺基二苯醚所組成之群中之1種以上芳香族二胺成分與選自由均苯四甲酸二酐及3,3’-4,4’-聯苯四羧酸二酐所組成之群中之1種以上酸酐成分而製造。 The polyimine film according to any one of claims 1 to 6, wherein the polyimine film is selected from the group consisting of p-phenylenediamine, 4,4'-diaminodiphenyl ether, and 3,4'-di One or more aromatic diamine components in the group consisting of aminodiphenyl ethers and a group selected from the group consisting of pyromellitic dianhydride and 3,3'-4,4'-biphenyltetracarboxylic dianhydride It is produced by using one or more kinds of acid anhydride components. 一種如請求項1至7中任一項之聚醯亞胺膜之製造方法，其特徵在於：包括如下步驟，且控制拉幅加熱爐內之乾燥速度，該步驟係製作將作為聚醯亞胺前驅物之聚醯胺酸溶液流延塗佈於支持體上並使其部分地乾燥及/或硬化而成之具有自持性的凝膠膜，使該凝膠膜通過具備至少2個以上之加熱爐之拉幅加熱爐，一面將該凝膠膜之寬度方向兩端固持一面進行乾燥及/或熱處理。 A method for producing a polyimide film according to any one of claims 1 to 7, characterized by comprising the steps of: controlling the drying speed in the tenter heating furnace, the step of producing a polyimine The polyamic acid solution of the precursor is cast on the support and partially dried and/or hardened to form a self-sustaining gel film, and the gel film is heated by at least two or more. The tenter heating furnace of the furnace is subjected to drying and/or heat treatment while holding the both ends of the gel film in the width direction. 如請求項8之聚醯亞胺膜之製造方法，其包括對利用如請求項8之製造方法所獲得之聚醯亞胺膜進而進行強熱處理之步驟，且上述強熱處理之溫度為250℃以上且500℃以下。 The method for producing a polyimide film according to claim 8, which comprises the step of subjecting the polyimine film obtained by the production method of claim 8 to a strong heat treatment, and the temperature of the above strong heat treatment is 250 ° C or higher And below 500 ° C. 一種軟性金屬積層板，其特徵在於：其係對如請求項1至7中任一項之聚醯亞胺膜貼合金屬箔而獲得。 A flexible metal laminate obtained by laminating a metal foil of the polyimide film according to any one of claims 1 to 7.
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