JP2009057556A - Polyimide film - Google Patents
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- JP2009057556A JP2009057556A JP2008216536A JP2008216536A JP2009057556A JP 2009057556 A JP2009057556 A JP 2009057556A JP 2008216536 A JP2008216536 A JP 2008216536A JP 2008216536 A JP2008216536 A JP 2008216536A JP 2009057556 A JP2009057556 A JP 2009057556A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
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Abstract
Description
本発明は、ポリイミドフィルムに関する。 The present invention relates to a polyimide film.
ポリイミドフィルムは、耐熱性、絶縁性、耐溶剤性及び耐低温性などを備え、コンピュータ及びＩＣ制御の電気・電子機器の部品材料として広く用いられているが、例えばフレキシブルプリント配線板、ＴＡＢ用キャリアテープのベースフィルム、航空機などの電線被覆剤、磁気記録用テープのベースフィルム、超伝導コイルの線材被覆材などを挙げることができる。これらの各種用途には、それぞれの用途に適したポリイミドフィルムが適宜選択される。 Polyimide films have heat resistance, insulation, solvent resistance, and low temperature resistance, and are widely used as component materials for computers and IC-controlled electrical and electronic equipment. For example, flexible printed wiring boards and TAB carriers Examples thereof include a tape base film, an electric wire coating agent for aircraft, a magnetic recording tape base film, a superconducting coil wire covering material, and the like. For these various uses, a polyimide film suitable for each use is appropriately selected.
このようにポリイミドフィルムに対する需要は更に増大しており、優れた品質を有するポリイミドフィルムの開発が求められている。 Thus, the demand for polyimide films is further increased, and development of polyimide films having excellent quality is required.
一方、ポリイミドフィルムは、前駆体であるポリアミド酸の有機溶媒中溶液を、支持体上に流延又は塗布して固化させた後、更に加熱処理する方法によって製造される場合が多い。更に具体的には、ジアミンと二無水物単量体からポリイミドの前駆体溶液を重合し、熱的イミド化又は化学的イミド化させるが、熱的イミド化の場合は、ポリイミド前駆体であるポリアミド酸ワニスから溶媒を除去してポリアミド酸フィルムを形成した後、加熱することにより、ポリイミドフィルムに変換される。化学的イミド化の場合は、ポリアミド酸ワニスに化学イミド化剤を混合してゲルフィルムを得、これを更に硬化・乾燥させてポリイミドフィルムを得る。 On the other hand, a polyimide film is often produced by a method in which a solution of a precursor polyamic acid in an organic solvent is cast or coated on a support and solidified, followed by further heat treatment. More specifically, a polyimide precursor solution is polymerized from diamine and dianhydride monomer, and thermal imidization or chemical imidization is performed. In the case of thermal imidization, polyamide which is a polyimide precursor is used. After removing the solvent from the acid varnish to form a polyamic acid film, it is converted to a polyimide film by heating. In the case of chemical imidization, a gel film is obtained by mixing a chemical imidizing agent with a polyamic acid varnish, and this is further cured and dried to obtain a polyimide film.
このような一般の方法によって得られたポリイミドフィルムは、電気絶縁特性を満足させなければならず、その１つとして絶縁破壊電圧が一定の水準以上であることが要求されている。 The polyimide film obtained by such a general method must satisfy electrical insulation characteristics, and as one of them, the dielectric breakdown voltage is required to be a certain level or higher.
ところが、ポリイミドフィルムのように、溶液状の前駆体を流延又は塗布し、これを硬化させる過程を経てフィルムを製造する場合には、加熱時間、あるいは硬化及び／又は部分的に乾燥したポリアミド酸フィルム（ゲルフィルム）の製造時間、あるいはその温度の制御などが不適である場合、フィルムの内部に異物が存在するおそれがある。一例として、ポリイミド樹脂の前駆体であるポリアミド酸が溶媒に溶解しているポリアミド酸溶液を、支持体の一面に塗布した後、約２５０℃程度までの処理温度で加熱処理して硬化させながらイミド化を行うことにより、ポリイミド樹脂が生成されるが、ポリイミド樹脂前駆体の塗膜の表面から熱風などによって加熱されるために、塗膜の表面と内部との温度差が大きくなり、その塗膜の表面からまず硬化及びイミド化が進行するため、内部にある溶剤の除去が遅くなるおそれがある。これは異物として残留する。このような異物は絶縁不良を生じさせる。 However, in the case of producing a film through a process of casting or applying a solution precursor and curing the same, such as a polyimide film, the heating time or the cured and / or partially dried polyamic acid is used. When the production time of the film (gel film) or the control of the temperature is inappropriate, there is a possibility that foreign matters exist inside the film. For example, after applying a polyamic acid solution in which a polyamic acid, which is a precursor of a polyimide resin, is dissolved in a solvent to one surface of a support, the imide is cured while being heated and cured at a processing temperature up to about 250 ° C. The polyimide resin is generated by performing the process, but since the surface of the polyimide resin precursor is heated by hot air or the like, the temperature difference between the surface of the coating and the inside increases, and the coating First, curing and imidization proceed from the surface of the resin, and thus there is a possibility that the removal of the solvent inside is delayed. This remains as foreign matter. Such foreign matter causes insulation failure.
本発明の目的は、絶縁不良の少ないプリント基板を得ることに適したポリイミドフィルムを提供することにある。 An object of the present invention is to provide a polyimide film suitable for obtaining a printed circuit board with little insulation failure.
また、本発明の他の目的は、２５μｍの厚さを基準とした絶縁破壊電圧が５ｋＶ以上を示すポリイミドフィルムを提供することにある。 Another object of the present invention is to provide a polyimide film having a dielectric breakdown voltage of 5 kV or more based on a thickness of 25 μm.
また、本発明の別の目的は、２５μｍの厚さを基準とした絶縁破壊電圧が８ｋＶ以上を示すポリイミドフィルムを提供することにある。 Another object of the present invention is to provide a polyimide film having a dielectric breakdown voltage of 8 kV or more based on a thickness of 25 μm.
本発明の一実施形態では、ポリイミドフィルムロール上の、５１４ｍｍ又は１０２８ｍｍの幅と１５００ｍの長さを有する面積範囲を、光学欠陥検出器中を通過させて検出したとき、直径５０μｍ以上の長軸を有する欠陥が含まれる場合、波長分散型蛍光Ｘ線分析装置によってＣ強度を測定したとき、欠陥ではない部位とのＣ強度値の差が７０〜２５０である欠陥の数が前記面積範囲あたり５個以下である、ポリイミドフィルムの提供に関する。 In one embodiment of the present invention, when an area range having a width of 514 mm or 1028 mm and a length of 1500 m on a polyimide film roll is detected by passing through an optical defect detector, a major axis having a diameter of 50 μm or more is detected. In the case where the defects are included, when the C intensity is measured by the wavelength dispersive X-ray fluorescence spectrometer, the number of defects having a C intensity value difference of 70 to 250 from the non-defect portion is 5 per area range. It is related with provision of the polyimide film which is the following.
本発明の実施形態に係るポリイミドフィルムは、酸無水物とジアミンの反応によって合成されたポリイミド前駆体から形成されるか、或いは酸無水物とジアミンの反応によって合成されたポリイミド前駆体と有機溶媒を含むポリイミド前駆体溶液から形成される。この際、有機溶媒は１００〜２５０℃の沸点であってもよい。 The polyimide film according to the embodiment of the present invention is formed from a polyimide precursor synthesized by a reaction between an acid anhydride and a diamine, or a polyimide precursor synthesized by a reaction between an acid anhydride and a diamine and an organic solvent. Formed from a polyimide precursor solution. At this time, the organic solvent may have a boiling point of 100 to 250 ° C.
また、本発明の実施形態に係るポリイミドフィルムは、酸無水物とジアミンの反応によって合成されたポリイミド前駆体と溶媒を含むポリイミド前駆体溶液を、支持体上に塗布した後、５０〜２００℃で１分〜１時間乾燥させる工程を経て得てもよい。この際、乾燥により溶媒残留量が５０％以下となるように実施して得てもよく、前記乾燥の後に更に５０〜５００℃で１分〜１時間加熱硬化させてイミド化する工程を経て得てもよい。 Moreover, the polyimide film which concerns on embodiment of this invention is 50-200 degreeC after apply | coating the polyimide precursor solution containing the polyimide precursor and solvent which were synthesize | combined by reaction of an acid anhydride and diamine on a support body. You may obtain through the process of drying for 1 minute-1 hour. At this time, the solvent may be obtained by drying so that the residual solvent amount is 50% or less, and after the drying, the solvent is further cured by heating and imidizing at 50 to 500 ° C. for 1 minute to 1 hour. May be.
本発明の実施形態に係るポリイミドフィルムは、絶縁不良を考慮して、絶縁破壊電圧が５ｋＶ以上であってもよく、絶縁破壊電圧が８ｋＶ以上であってもよい。 The polyimide film according to the embodiment of the present invention may have a dielectric breakdown voltage of 5 kV or higher or a dielectric breakdown voltage of 8 kV or higher in consideration of insulation failure.
本発明では、所定の大きさの欠陥として認識される部位が若干検出されても、波長分散型蛍光Ｘ線分析装置によってＣ強度を検出したとき、欠陥ではない部位に対して７０〜２５０のＣ強度差を示す欠陥の数が一定の面積範囲に対して５個以下であるポリイミドフィルムであれば、絶縁破壊電圧が高くて絶縁不良を起こすおそれが少ないため、可撓性プリント基板、ＴＡＢ用キャリアテープのベースフィルム、磁気記録用テープのベースフィルムなどの絶縁材料として利用できる。 In the present invention, even if a portion recognized as a defect of a predetermined size is detected a little, when C intensity is detected by a wavelength dispersive X-ray fluorescence spectrometer, 70 to 250 C is detected for a portion that is not a defect. A polyimide film having a number of defects showing a difference in strength of 5 or less with respect to a certain area range has a high dielectric breakdown voltage and is less likely to cause insulation failure. It can be used as an insulating material such as a tape base film and a magnetic recording tape base film.
以下、本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail.
本発明の一実施形態では、ポリイミドフィルムは、５１４ｍｍ又は１０２８ｍｍの幅と１５００ｍの長さを有するフィルムロールの面積範囲を、光学欠陥検出器を通過させて検出し、直径５０μｍ以上の長軸を有する欠陥が含まれる場合において、波長分散型蛍光Ｘ線分析装置によってＣ強度を測定したとき、欠陥ではない部位に対するＣ強度値との差が７５〜２５０である欠陥の数が、前記面積範囲あたり５個以下であることを特徴とする。 In one embodiment of the present invention, the polyimide film detects the area range of a film roll having a width of 514 mm or 1028 mm and a length of 1500 m by passing through an optical defect detector and has a major axis of 50 μm or more in diameter. In the case where a defect is included, when the C intensity is measured by a wavelength dispersive X-ray fluorescence spectrometer, the number of defects having a difference of 75 to 250 with respect to the C intensity value for a non-defect portion is 5 per area range. It is characterized by having no more than one.
ここで、光学欠陥検出器は、フィルムの形状を２次元イメージ化し、予め設定された大きさ以上の欠陥を分析して検出する機器であって、特に本発明における有意な欠陥とは、長軸を基準とした直径が５０μｍ以上の欠陥である。５０μｍより小さい直径の欠陥は、フィルムの物性に影響を与えない程度の、無視しても構わない程度の大きさである。 Here, the optical defect detector is a device that converts a film shape into a two-dimensional image and analyzes and detects a defect having a size larger than a preset size. In particular, a significant defect in the present invention is a long axis. Is a defect having a diameter of 50 μm or more. A defect having a diameter smaller than 50 μm is a size that does not affect the physical properties of the film and can be ignored.
また、本発明のポリイミドフィルムは、このように光学欠陥分析器によって検出された欠陥を、波長分散型蛍光Ｘ線分析装置でＣ強度を測定したとき、欠陥ではない部位のＣ強度値との差が７０〜２５０である欠陥の数が、前記面積範囲に対して５個以下であるが、この際、波長分散型蛍光Ｘ線分析装置で検出されるＣ強度とは、検出する測定試料における炭素の含量のことを指す。前記面積範囲を光学欠陥分析器で検出された際に検出された欠陥を、波長分散型蛍光Ｘ線分析装置によってＣ強度測定したとき、欠陥ではない部位におけるＣ強度値との差が７０〜２５０である欠陥の数が前記面積範囲に対して５個以下のとき、フィルムの絶縁破壊電圧を高めることができる。 In addition, the polyimide film of the present invention has a difference from the C intensity value of the portion that is not a defect when the C intensity of the defect detected by the optical defect analyzer is measured by a wavelength dispersive X-ray fluorescence analyzer. The number of defects having a thickness of 70 to 250 is 5 or less with respect to the area range. At this time, the C intensity detected by the wavelength dispersive X-ray fluorescence analyzer is the carbon in the measurement sample to be detected. Refers to the content of. When the C intensity of a defect detected when the area range is detected by an optical defect analyzer is measured by a wavelength dispersive X-ray fluorescence analyzer, the difference from the C intensity value at a site that is not a defect is 70 to 250. When the number of defects is 5 or less with respect to the area range, the dielectric breakdown voltage of the film can be increased.
このような様相を示すとき、絶縁破壊電圧は、フィルムの厚さが２５μｍのときに５ｋＶ以上、好ましくは８ｋＶ以上である。 When such an aspect is exhibited, the dielectric breakdown voltage is 5 kV or more, preferably 8 kV or more when the thickness of the film is 25 μm.
ポリイミドフィルムは、主鎖中に酸イミド結合を持つ高分子物質としてのポリイミド樹脂からなり、例えばピロメリット酸無水物、テトラカルボン酸無水物などの酸無水物と、例えばｐ−フェニレンジアミンなどのジアミンの重合反応によって合成されたポリイミド前駆体を、その後に再加熱などによる反応によって開環状態から閉環化させることにより生成する。 The polyimide film is composed of a polyimide resin as a polymer substance having an acid imide bond in the main chain, such as an acid anhydride such as pyromellitic acid anhydride or tetracarboxylic acid anhydride, and a diamine such as p-phenylenediamine. The polyimide precursor synthesized by the polymerization reaction is then closed by ring closure from a ring-opened state by a reaction such as reheating.
この際、ポリイミド前駆体は溶媒に可溶である。溶媒に溶解することによりポリアミド酸溶液からなる状態で支持体上に塗布され、乾燥によってその溶媒がある程度除去されることにより、支持体上に接着する。 At this time, the polyimide precursor is soluble in the solvent. By dissolving in a solvent, it is coated on the support in the state of the polyamic acid solution, and the solvent is removed to some extent by drying, thereby adhering to the support.
使用可能な溶媒としては、例えば、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミドなどのホルムアミド系溶媒；Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミドなどのアセトアミド系溶媒；Ｎ−メチル−２−ピロリドン、Ｎ−ビニル−２−ピロリドンなどのピロリドン系溶媒；フェノール、ｏ−、ｍ−又はｐ−クレゾール、キシレノール、ハロゲン化フェノール、カテコールなどのフェノール系溶媒；テトラヒドロフラン、ジオキサン、ジオキソランなどのエーテル系溶媒；メタノール、エタノール、ブタノールなどのアルコール系溶媒；ブチルセロソルブなどのセロソルブ系溶媒；ヘキサメチルリン酸アミド；γ−ブチロラクトンなどを挙げることができる。 Usable solvents include, for example, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide; acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide; N-methyl Pyrrolidone solvents such as -2-pyrrolidone and N-vinyl-2-pyrrolidone; phenol solvents such as phenol, o-, m- or p-cresol, xylenol, halogenated phenol, catechol; tetrahydrofuran, dioxane, dioxolane, etc. Examples include ether solvents; alcohol solvents such as methanol, ethanol, and butanol; cellosolv solvents such as butyl cellosolve; hexamethylphosphoric acid amide; and γ-butyrolactone.
通常、イミド化のための加熱処理温度が約２５０℃であることを考慮し、好ましくは沸点１００〜２５０℃の溶媒を使用し、具体的には１５０〜１７０℃の溶媒を使用する。 Usually, considering that the heat treatment temperature for imidization is about 250 ° C., a solvent having a boiling point of 100 to 250 ° C. is preferably used, and specifically, a solvent having a temperature of 150 to 170 ° C. is used.
本発明におけるポリイミド前駆体を得るために使用される酸無水物は、特に限定されないが、例えば２，２’−ヘキサフルオロプロピリデンジフタル酸２無水物、２，２−ビス（４−ヒドロキシフェニル）プロパンジベンゾエート−３，３’，４，４’−テトラカルボン酸２無水物、ブタンテトラカルボン酸２無水物、１，２，３，４−シクロブタンテトラカルボン酸２無水物、１，３−ジメチル−１，２，３，４−シクロブタンテトラカルボン酸２無水物、１，２，３，４−シクロペンタンテトラカルボン酸２無水物、２，３，５−トリカルボキシシクロペンチル酢酸２無水物、３，５，６−トリカルボキシノルボルナン−２−酢酸２無水物、２，３，４，５−テトラヒドロフランテトラカルボン酸２無水物、５−（２，５−ジオキソテトラヒドロフラニル）−３−メチル−３−シクロヘキセン−１，２−ジカルボン酸２無水物、ビシクロ［２，２，２］−オクト−７−エン−２，３，５，６−テトラカルボン酸２無水物などの脂肪族又は脂環式テトラカルボン酸２無水物；ピロメリット酸２無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸２無水物、３，３’，４，４’−ビフェニルスルホンテトラカルボン酸２無水物、１，４，５，８−ナフタレンテトラカルボン酸２無水物、２，３，６，７−ナフタレンテトラカルボン酸２無水物、３，３’，４，４’−ビフェニルエーテルテトラカルボン酸２無水物、３，３’，４，４’−ジメチルジフェニルシランテトラカルボン酸２無水物、３，３’，４，４’−テトラフェニルシランテトラカルボン酸２無水物、１，２，３，４−フランテトラカルボン酸２無水物、４，４’−ビス（３，４−ジカルボキシフェノキシ）ジフェニルスルフィド２無水物、４，４’−ビス（３，４−ジカルボキシフェノキシ）ジフェニルスルホン２無水物、４，４’−ビス（３，４−ジカルボキシフェノキシ）ジフェニルプロパン２無水物、３，３’，４，４’−ペルフルオロイソプロピリデンジフタル酸２無水物、３，３’，４，４’−ビフェニルテトラカルボン酸２無水物、ビス（フタル酸）フェニルホスフィンオキシド２無水物、ｐ−フェニレン−ビス（トリフェニルフタル酸）２無水物、ｍ−フェニレン−ビス（トリフェニルフタル酸）２無水物、ビス（トリフェニルフタル酸）−４，４’−ジフェニルエーテル２無水物、ビス（トリフェニルフタル酸）−４，４’−ジフェニルメタン２無水物などの芳香族テトラカルボン酸２無水物；１，３，３ａ，４，５，９ｂ−（ヘキサヒドロ−２，５−ジオキソ−３−フラニル）−ナフト［１，２−ｃ］フラン−１，３−ジオン、１，３，３ａ，４，５，９ｂ−ヘキサヒドロ−５−メチル−５−（テトラヒドロ−２，５−ジオキソ−３−フラニル）−ナフト［１，２−ｃ］フラン−１，３−ジオン、１，３，３ａ、４，５，９ｂ−ヘキサヒドロ−８−メチル−５−（テトラヒドロ−２，５−ジオキソ−３−フラニル）−ナフト［１，２−ｃ］フラン−１，３−ジオンなどを挙げることができ、これらの１種のみを使用してもよく、２種以上を混合して使用してもよい。 Although the acid anhydride used in order to obtain the polyimide precursor in this invention is not specifically limited, For example, 2,2'-hexafluoropropylidenediphthalic dianhydride, 2,2-bis (4-hydroxyphenyl) ) Propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3- Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3 , 5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxoteto Hydrofuranyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Aliphatic or alicyclic tetracarboxylic dianhydrides such as pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′- Biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4 ′ -Biphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1 2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) Diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenyl) Phthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'- Aromatic tetracarboxylic dianhydrides such as diphenylmethane dianhydride; 1,3,3a, 4,5,9b- (hexahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan -1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan -1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan -1,3-dione etc. can be mentioned, Only 1 type of these may be used and 2 or more types may be mixed and used.
本発明におけるポリイミド前駆体を得るために使用されるジアミンは、特に限定されないが、例えばｐ−フェニレンジアミン、ｍ−フェニレンジアミン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノフェニルエタン、４，４’−ジアミノフェニルエーテル、４，４’−ジアミノフェニルスルフィド、４，４’−ジアミノフェニルスルホン、１，５−ジアミノナフタレン、３，３−ジメチル−４，４’−ジアミノビフェニル、５−アミノ−１−（４’−アミノフェニル）−１，３，３−トリメチルインダン、６−アミノ−１−（４’−アミノフェニル）−１，３，３−トリメチルインダン、４，４’−ジアミノベンズアニリド、３，５−ジアミノ−３’−トリフルオロメチルベンズアニリド、３，５−ジアミノ−４’−トリフルオロメチルベンズアニリド、３，４’−ジアミノジフェニルエーテル、２，７−ジアミノフルオレン、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン、４，４’−メチレン−ビス（２−クロロアニリン）、２，２’，５，５’−テトラクロロ−４，４’−ジアミノビフェニル、２，２’−ジクロロ−４，４’−ジアミノ−５，５’−ジメトキシビフェニル、３，３’−ジメトキシ−４，４’−ジアミノビフェニル、４，４’−ジアミノ−２，２’−ビス（トリフルオロメチル）ビフェニル、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］ヘキサフルオロプロパン、１，４−ビス（４−アミノフェノキシ）ベンゼン、４，４’−ビス（４−アミノフェノキシ）−ビフェニル、１，３’−ビス（４−アミノフェノキシ）ベンゼン、９，９−ビス（４−アミノフェニル）フルオレン、４，４’−（ｐ−フェニレンイソプロピリデン）ビスアニリン、４，４’−（ｍ−フェニレンイソプロピリデン）ビスアニリン、２，２’−ビス［４−（４−アミノ−２−トリフルオロメチルフェノキシ）フェニル］ヘキサフルオロプロパン、４，４’−ビス［４−（４−アミノ−２−トリフルオロメチル）フェノキシ］−オクタフルオロビフェニルなどの芳香族ジアミン；ジアミノテトラフェニルチオフェンなどの芳香環に結合した２つのアミノ基と当該アミノ基の窒素原子以外のヘテロ原子を有する芳香族ジアミン；１，１−メタキシリレンジアミン、１，３−プロパンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、４，４−ジアミノヘプタメチレンジアミン、１，４−ジアミノシクロヘキサン、イソホロンジアミン、テトラヒドロジシクロペンタジエニレンジアミン、ヘキサヒドロ−４，７−メタノインダニレンジメチレンジアミン、トリシクロ［６，２，１，０，２，７］−ウンデシレンジメチルジアミン、４，４’−メチレンビス（シクロヘキシルアミン）などの脂肪族ジアミン及び脂環式ジアミン；などを挙げることができる。これらのジアミンは１種のみを使用してもよく、２種以上を組み合わせて使用してもよい。 The diamine used for obtaining the polyimide precursor in the present invention is not particularly limited. For example, p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminophenylethane, 4 , 4′-diaminophenyl ether, 4,4′-diaminophenyl sulfide, 4,4′-diaminophenyl sulfone, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4′-diaminobiphenyl, 5-amino -1- (4′-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 4,4′-diaminobenz Anilide, 3,5-diamino-3'-trifluoromethylbenzanilide, 3,5-diamino-4'-trifluoro Romethylbenzanilide, 3,4'-diaminodiphenyl ether, 2,7-diaminofluorene, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-methylene-bis (2-chloroaniline), 2,2 ′, 5,5′-tetrachloro-4,4′-diaminobiphenyl, 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy- 4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenyl) Noxy) -biphenyl, 1,3′-bis (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′ -(M-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-bis [4- (4-amino Aromatic diamines such as 2-trifluoromethyl) phenoxy] -octafluorobiphenyl; aromatic diamines having two amino groups bonded to an aromatic ring such as diaminotetraphenylthiophene and heteroatoms other than nitrogen atoms of the amino group 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, Pentamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoin danylylene And aliphatic diamines such as methylene diamine, tricyclo [6,2,1,0,2,7] -undecylene diamine, 4,4′-methylene bis (cyclohexylamine), and alicyclic diamines. These diamines may be used alone or in combination of two or more.
その他に、本発明のポリイミドフィルムには、摺動性、熱伝導性、導電性、耐コロナ性などのフィルムの様々な特性を改善させる目的で充填剤を添加してもよい。 In addition, a filler may be added to the polyimide film of the present invention for the purpose of improving various properties of the film such as slidability, thermal conductivity, conductivity, and corona resistance.
充填剤としては、特に限定されないが、好ましくは例えばシリカ、酸化チタン、アルミナ、窒化ケイ素、窒化ホウ素、リン酸水素カルシウム、リン酸カルシウム、雲母などを挙げることができる。 Examples of the filler include, but are not limited to, silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica, and the like.
前記ポリアミド酸の重合では、酸成分とジアミン成分とを反応させる手法を適宜調製し、複数種の重合方法を使用することができる。具体的には、例えば以下の１）〜５）に示したような重合方法を使用するのが好ましい。
１）芳香族ジアミンを有機溶媒中に溶解し、この芳香族ジアミンと実質的に同モルの芳香族テトラカルボン酸二無水物とを反応させて重合する方法；
２）芳香族テトラカルボン酸二無水物とこれに対して過少モル量の芳香族ジアミン化合物とを有機溶媒中で反応させ、両末端に酸無水物基を有する予備重合体を得、しかる後に、全体工程で芳香族テトラカルボン酸二無水物と芳香族ジアミン化合物が実質的に同モルとなるように芳香族ジアミン化合物を用いて重合させる方法；
３）芳香族テトラカルボン酸二無水物とこれに対して過剰モル量の芳香族ジアミン化合物とを有機溶媒中で反応させ、両末端にアミノ基を持つ予備重合体を得、しかる後に、ここに芳香族ジアミン化合物を更に添加した後、全体工程で芳香族テトラカルボン酸二無水物と芳香族ジアミン化合物が実質的に同モルとなるように芳香族テトラカルボン酸二無水物を用いて重合する方法；
４）芳香族テトラカルボン酸二無水物を有機溶媒中に溶解及び／又は分散させた後、実質的に同モルとなるように芳香族ジアミン化合物を用いて重合させる方法；
５）実質的に同モルの芳香族テトラカルボン酸二無水物と芳香族ジアミンとの混合物を有機溶媒中で反応させて重合する方法。
In the polymerization of the polyamic acid, a technique for reacting an acid component and a diamine component can be appropriately prepared, and a plurality of polymerization methods can be used. Specifically, it is preferable to use a polymerization method as shown in the following 1) to 5), for example.
1) A method in which an aromatic diamine is dissolved in an organic solvent, and the aromatic diamine is reacted with substantially the same mole of an aromatic tetracarboxylic dianhydride to polymerize it;
2) Aromatic tetracarboxylic dianhydride and a small molar amount of aromatic diamine compound are reacted with each other in an organic solvent to obtain a prepolymer having acid anhydride groups at both ends. A method of polymerizing with an aromatic diamine compound so that the aromatic tetracarboxylic dianhydride and the aromatic diamine compound have substantially the same mole in the whole process;
3) An aromatic tetracarboxylic dianhydride and an excess molar amount of an aromatic diamine compound are reacted in an organic solvent to obtain a prepolymer having amino groups at both ends. A method in which an aromatic tetracarboxylic dianhydride is further added and then polymerized using the aromatic tetracarboxylic dianhydride so that the aromatic tetracarboxylic dianhydride and the aromatic diamine compound have substantially the same mole in the entire process. ;
4) A method in which an aromatic tetracarboxylic dianhydride is dissolved and / or dispersed in an organic solvent and then polymerized using an aromatic diamine compound so as to have substantially the same mole;
5) A method in which a mixture of substantially the same moles of aromatic tetracarboxylic dianhydride and aromatic diamine is reacted in an organic solvent for polymerization.
ポリイミド前駆体及び溶媒を含むポリイミド前駆体溶液を支持体上に塗布した後、乾燥過程を経て溶媒を除去し、この際、残留溶媒量が５０％以下となるように乾燥を行うことが、ポリイミドフィルム内への異物の残留を防止するために好ましい。 After applying a polyimide precursor solution containing a polyimide precursor and a solvent onto a support, the solvent is removed through a drying process, and at this time, drying is performed so that the residual solvent amount is 50% or less. This is preferable in order to prevent foreign matter from remaining in the film.
また、乾燥工程は、５０〜２００℃で１分〜１時間実施する。 Moreover, a drying process is implemented at 50-200 degreeC for 1 minute-1 hour.
このような乾燥温度範囲のとき、ポリイミド前駆体溶液中の溶媒の揮発が効率よく行われる。 In such a drying temperature range, the solvent in the polyimide precursor solution is efficiently volatilized.
支持体上に塗布、乾燥されたポリイミド前駆体は、加熱などによる反応によって開環状態から閉環化されることによりポリイミド樹脂が生成されるが、５０〜５００℃で１分〜１時間加熱硬化させることによりイミド化することができる。 The polyimide precursor coated and dried on the support is cyclized from the ring-opened state by a reaction such as heating to produce a polyimide resin, but is heated and cured at 50 to 500 ° C. for 1 minute to 1 hour. Can be imidized.
以下、本発明を実施例に基づいて詳細に説明する。本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described in detail based on examples. The present invention is not limited to these examples.
［実施例１］
沸点１５０〜１６０℃のＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）２０３．７２９ｇに４，４’−ジアミノジフェニルメタン（ＭＤＡ）１１．８９６２ｇとｐ−フェニレンジアミ（ＭＤＡ）４．３２５６ｇを溶解し、この溶液を０℃に維持した。４，４’−オキジフタル酸二無水物（ＯＤＰＡ）１５．５１１ｇを徐々に添加し、１時間撹拌してＯＤＰＡを完全に溶解させた。この溶液に３，３’，４，４'−ベンゾフェノンテトラカルボン酸二無水物（ＢＴＤＡ）６．４４４６ｇを徐々に添加して１時間撹拌することにより完全に溶解させた後、ピロメリット酸二無水物（ＰＭＤＡ）６．５４３６ｇを更に添加して１時間撹拌し、２３℃における溶液粘度２５００ポアズ、固形分濃度１８．０重量％のポリアミド酸溶液を得た。
[Example 1]
This solution was prepared by dissolving 11.8962 g of 4,4′-diaminodiphenylmethane (MDA) and 4.3256 g of p-phenylenediam (MDA) in 203.729 g of N, N-dimethylformamide (DMF) having a boiling point of 150 to 160 ° C. Was maintained at 0 ° C. 15.511 g of 4,4′-oxydiphthalic dianhydride (ODPA) was gradually added and stirred for 1 hour to completely dissolve ODPA. After gradually adding 6.4446 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) to this solution and stirring for 1 hour, pyromellitic dianhydride was dissolved. 6.5436 g of a product (PMDA) was further added and stirred for 1 hour to obtain a polyamic acid solution having a solution viscosity of 2500 poise at 23 ° C. and a solid content concentration of 18.0% by weight.
得られた溶液に溶液重量対比０．０１〜１０重量比の範囲で一定量の充填剤を分散させた後、撹拌しながら真空ポンプを用いて１時間脱泡し、更に０℃に冷却させた。このポリアミド酸溶液１００ｇに酢酸無水物１１．４ｇ、イソキノリン４．８ｇ及びＤＭＦ３３．８ｇからなる硬化剤を混合してステンレス鋼材質の硬板に流延、塗布した。得られたポリアミド酸溶液の塗布されたアルミニウム箔を１００℃で３００秒間加熱してゲルフィルムを得た後（残留溶媒量５０％）、アルミニウム箔から剥離してフィルムの一部の縁部をフレームに固定させた。 After a certain amount of filler was dispersed in the obtained solution in a range of 0.01 to 10 weight ratio with respect to the weight of the solution, it was degassed for 1 hour using a vacuum pump while stirring, and further cooled to 0 ° C. . A curing agent composed of 11.4 g of acetic anhydride, 4.8 g of isoquinoline, and 33.8 g of DMF was mixed with 100 g of this polyamic acid solution, and the mixture was cast and applied to a stainless steel hard plate. The obtained aluminum foil coated with the polyamic acid solution was heated at 100 ° C. for 300 seconds to obtain a gel film (residual solvent amount: 50%), and then peeled off from the aluminum foil to frame a part of the edge of the film. Fixed to.
固定されたフィルムを１５０℃、２５０℃、３５０℃、４５０℃で３０秒〜２４０秒間加熱した後、更に遠赤外線オーブンで３０秒〜１８０秒間加熱処理し、厚さ２５μｍ、幅５１４ｍｍ、長さ１５００ｍのポリイミドフィルムを得た。 The fixed film was heated at 150 ° C., 250 ° C., 350 ° C., and 450 ° C. for 30 seconds to 240 seconds, and further heat-treated in a far infrared oven for 30 seconds to 180 seconds. The thickness was 25 μm, the width was 514 mm, and the length was 1500 m. The polyimide film was obtained.
［実施例２］
ＤＭＦ１９８．５２８８ｇにＭＤＡ９．９１３５ｇとＰＤＡ５．４０７ｇを溶解し、この溶液を０℃に維持した。ＯＤＰＡ２１．７１５４ｇを徐々に添加し、１時間撹拌してＯＤＰＡを完全に溶解させた。この溶液にＰＭＤＡ６．５４３６ｇを更に添加して１時間撹拌し、２３℃における溶液粘度３１００ポアズ、固形分濃度１８．０重量％のポリアミド酸溶液を得た。
[Example 2]
MDA9.935g and PDA 5.407g were melt | dissolved in DMF18.5288g, and this solution was maintained at 0 degreeC. ODPA 21.7154 g was gradually added and stirred for 1 hour to completely dissolve ODPA. To this solution, 6.5436 g of PMDA was further added and stirred for 1 hour to obtain a polyamic acid solution having a solution viscosity of 3100 poise at 23 ° C. and a solid content concentration of 18.0% by weight.
このポリアミド酸溶液を使用した以外は実施例１と同様にしてポリイミドフィルムを製造した。 A polyimide film was produced in the same manner as in Example 1 except that this polyamic acid solution was used.
［実施例３］
ＤＭＦ１９９．２９８５ｇにＭＤＡ１０．９ｇとＰＤＡ４．８６６３ｇを溶解し、この溶液を０℃に維持した。ＯＤＰＡ１５．５１１ｇを徐々に添加し、１時間撹拌してＯＤＰＡを完全に溶解させた。この溶液にＢＴＤＡ４．８３３４５ｇを徐々に添加して１時間撹拌することにより完全に溶解させた後、ＰＭＤＡ７．６３７７ｇを更に添加して１時間撹拌し、２３℃における溶液粘度２７００ポアズ、固形分濃度１８．０重量％のポリアミド酸溶液を得た。
[Example 3]
10.9 g of MDA and 4.8663 g of PDA were dissolved in 199.2985 g of DMF, and this solution was maintained at 0 ° C. 15.511 g of ODPA was gradually added and stirred for 1 hour to completely dissolve ODPA. After gradually adding BTDA 4.83345g to this solution and stirring for 1 hour, PMDA 7.6377g was further added and stirred for 1 hour, and the solution viscosity at 23 ° C was 2700 poise, solid content concentration 18 A 0.0% by weight polyamic acid solution was obtained.
このポリアミド酸溶液を使用した以外は実施例１と同様にしてポリイミドフィルムを製造した。 A polyimide film was produced in the same manner as in Example 1 except that this polyamic acid solution was used.
［実施例４］
ＤＭＦ１９９．６２３１ｇにＭＤＡ９．９１３５ｇとＰＤＡ５．４０７ｇを溶解し、この溶液を０℃に維持した。ＯＤＰＡ１５．５１１ｇを徐々に添加し、１時間撹拌してＯＤＰＡを完全に溶解させた。この溶液にＢＴＤＡ６．４４４６ｇを徐々に添加して１時間撹拌することにより完全に溶解させた後、ＰＭＤＡ６．５４３６ｇを更に添加して１時間撹拌し、２３℃における溶液粘度２６００ポアズ、固形分濃度１８．０重量％のポリアミド酸溶液を得た。
[Example 4]
MDA9.9135g and PDA 5.407g were melt | dissolved in DMF199.231g, and this solution was maintained at 0 degreeC. 15.511 g of ODPA was gradually added and stirred for 1 hour to completely dissolve ODPA. After 6.4446 g of BTDA was gradually added to this solution and completely dissolved by stirring for 1 hour, 6.5436 g of PMDA was further added and stirred for 1 hour, and the solution viscosity at 23 ° C. was 2600 poise and the solid concentration was 18 A 0.0% by weight polyamic acid solution was obtained.
このポリアミド酸溶液を使用した以外は実施例１と同様にしてポリイミドフィルムを製造した。 A polyimide film was produced in the same manner as in Example 1 except that this polyamic acid solution was used.
［実施例５］
ＤＭＦ２０４．８２３２ｇにＭＤＡ１１．８９６２ｇとＰＤＡ４．３２５６ｇを溶解し、この溶液を０℃に維持した。ＯＤＰＡ９．３０６６ｇを徐々に添加し、１時間撹拌することによりＯＤＰＡを完全に溶解させた。この溶液にＢＴＤＡ１２．８８９２ｇを徐々に添加して１時間撹拌することにより完全に溶解させた後、ＰＭＤＡ６．５４３６ｇを更に添加して１時間撹拌し、２３℃における溶液粘度２４００ポアズ、固形分濃度１８．０重量％のポリアミド酸溶液を得た。
[Example 5]
MDA 11.8962g and PDA 4.3256g were melt | dissolved in DMF204.8232g, and this solution was maintained at 0 degreeC. ODPA 9.3066 g was gradually added and stirred for 1 hour to completely dissolve ODPA. After gradually adding 12.8992 g of BTDA to this solution and stirring it for 1 hour, PMDA 6.5436 g was further added and stirred for 1 hour, and the solution viscosity at 23 ° C. was 2400 poise and the solid content concentration was 18 A 0.0% by weight polyamic acid solution was obtained.
このポリアミド酸溶液を使用した以外は実施例１と同様にしてポリイミドフィルムを製造した。 A polyimide film was produced in the same manner as in Example 1 except that this polyamic acid solution was used.
［実施例６］
ＤＭＦ２２２．１０２７ｇにＭＤＡ１２．８８７５５ｇとＰＤＡ３．７８４９ｇを溶解し、この溶液を０℃に維持した。ＯＤＰＡ６．２０４４ｇを徐々に添加し、１時間撹拌してＯＤＰＡを完全に溶解させた。この溶液にＢＴＤＡ１９．３３３８ｇを徐々に添加して１時間撹拌することにより完全に溶解させた後、ＰＭＤＡ６．５４３６ｇを更に添加して１時間撹拌し、２３℃における溶液粘度２２００ポアズ、固形分濃度１８．０重量％のポリアミド酸溶液を得た。
[Example 6]
MDA 12.88755g and PDA 3.7849g were melt | dissolved in DMF222.1027g, and this solution was maintained at 0 degreeC. 6.2044 g of ODPA was gradually added and stirred for 1 hour to completely dissolve ODPA. After gradually adding 19.3338 g of BTDA to this solution and stirring it completely for 1 hour, PMDA 6.5436 g was further added and stirred for 1 hour, and the solution viscosity at 23 ° C. was 2200 poise and the solid content concentration was 18 A 0.0% by weight polyamic acid solution was obtained.
このポリアミド酸溶液を使用した以外は実施例１と同様にしてポリイミドフィルムを製造した。 A polyimide film was produced in the same manner as in Example 1 except that this polyamic acid solution was used.
［実施例７］
ＤＭＦ１９８．１６５３ｇにＭＤＡ９．９１３５ｇとＰＤＡ５．４０７ｇを溶解し、この溶液を０℃に維持した。ＯＤＰＡ９．３０６６ｇを徐々に添加し、１時間撹拌してＯＤＰＡを完全に溶解させた。この溶液にＢＴＤＡ６．４４４６ｇを徐々に添加して１時間撹拌することにより完全に溶解させた後、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）５．８８４４ｇを徐々に添加して１時間撹拌することによりＢＰＤＡを完全に溶解させた後、ＰＭＤＡ６．５４３６ｇを更に添加して１時間撹拌し、２３℃における溶液粘度２３００ポアズ、固形分濃度１８．０重量％のポリアミド酸溶液を得た。
[Example 7]
MDA9.9135g and PDA 5.407g were melt | dissolved in DMF198.653g, and this solution was maintained at 0 degreeC. 9.3066 g of ODPA was gradually added and stirred for 1 hour to completely dissolve ODPA. BT446 (6.4446 g) was gradually added to this solution and completely dissolved by stirring for 1 hour, and then 5.8844 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) was gradually added. BPDA was completely dissolved by stirring for 1 hour, and then PMDA 6.5436 g was further added and stirred for 1 hour. Polyamide having a solution viscosity at 23 ° C. of 2300 poise and a solid content concentration of 18.0% by weight. An acid solution was obtained.
このポリアミド酸溶液を使用した以外は実施例１と同様にしてポリイミドフィルムを製造した。 A polyimide film was produced in the same manner as in Example 1 except that this polyamic acid solution was used.
［実施例８］
得られたポリアミド酸溶液の塗布されたアルミニウム箔を１３０℃で１００秒間加熱してゲルフィルムを得た後（残留溶媒量４０％）、アルミニウム箔から剥離してフィルムの一部の縁部をフレームに固定させたことを除き、実施例１と同様の方法によってポリアイミドフィルムを製造した。
[Example 8]
The obtained aluminum foil coated with the polyamic acid solution was heated at 130 ° C. for 100 seconds to obtain a gel film (residual solvent amount 40%), and then peeled off from the aluminum foil to frame a part of the edge of the film. A polyimide film was produced in the same manner as in Example 1 except that the film was fixed to 1.
固定されたフィルムを１５０℃、２５０℃、３５０℃、４５０℃で３０秒〜２４０秒間加熱した後、更に遠赤外線オーブンで３０秒〜１８０秒間加熱処理して厚さ２５μｍ、幅５１４ｍｍ、長さ１５００ｍのポリイミドフィルムを得た。 The fixed film was heated at 150 ° C., 250 ° C., 350 ° C., 450 ° C. for 30 seconds to 240 seconds, and further heat-treated in a far infrared oven for 30 seconds to 180 seconds to have a thickness of 25 μm, a width of 514 mm, and a length of 1500 m. The polyimide film was obtained.
［実施例９］
溶媒として沸点１６０〜１７０℃のＤＭＡｃを使用したことを除き、実施例１と同様の方法によってポリイミドフィルムを製造した。
[Example 9]
A polyimide film was produced in the same manner as in Example 1 except that DMAc having a boiling point of 160 to 170 ° C. was used as the solvent.
［実施例１０〜実施例１８］
最終フィルムロールの規格が厚さ２５μｍ、幅１０２８ｍｍ、長さ１５００ｍとなるように製造したことを除き、実施例１〜９と同様の方法によってそれぞれのフィルムを製造した。
[Examples 10 to 18]
Each film was produced by the same method as in Examples 1 to 9, except that the final film roll was produced such that the thickness was 25 μm, the width was 1028 mm, and the length was 1500 m.
実施例１〜１８から得られたポリイミドフィルムに対して光学欠陥検出器（ＩＭＡＧＥ２０００．ＤＡ，朝日測器社）をライン速度１．５〜２８ｍ／分の条件で通過させ、長軸を基準とした直径５０μｍ以上の欠陥を検出し、欠陥として指示された座標に該当する欠陥の数をカウントした。この際、光学欠陥検出器は、フィルムの形状を２次元イメージ化し、長軸の粒径が５０μｍ以上の異物を検出するようにセットされたものであり、測定子又は測定環境が変わる点に対する誤差範囲が±１０％程度のものである。 An optical defect detector (IMAGE2000.DA, Asahi Sokki Co., Ltd.) was passed through the polyimide films obtained from Examples 1 to 18 at a line speed of 1.5 to 28 m / min, and the major axis was used as a reference. Defects having a diameter of 50 μm or more were detected, and the number of defects corresponding to coordinates designated as defects was counted. At this time, the optical defect detector is set to detect a foreign object having a two-dimensional image of the shape of the film and having a major axis particle size of 50 μm or more. The range is about ± 10%.
光学欠陥検出器によって欠陥が検出されると、欠陥として指示された座標に該当する位置の欠陥部分を含んで試片化し、この試片に対して欠陥部分をスポットして波長分散型蛍光Ｘ線分析装置を用いてＣ強度を検出し、当該ロールで試片化された正常部位の試片部分のＣ強度を検出した。その後、正常試片のＣ強度に対してその差が７０〜２５０のＣ強度を示す欠陥の数をカウントした。
この際、波長分散型蛍光Ｘ線分析装置としては、島津社のＥＰＭＡ１６００を使用し、加速電圧１５ｋＶ、ビームサイズ１０μｍの条件下で検出した。
その結果は表１の通りである。
When a defect is detected by the optical defect detector, a specimen including a defective portion at a position corresponding to the coordinates designated as the defect is formed into a specimen, and the wavelength-dispersed fluorescent X-ray is spotted by spotting the defective portion with respect to the specimen. C intensity | strength was detected using the analyzer, and C intensity | strength of the test piece part of the normal site | part made into the test piece with the said roll was detected. Thereafter, the number of defects having a C intensity of 70 to 250 with respect to the C intensity of the normal specimen was counted.
At this time, EPMA 1600 manufactured by Shimadzu Corporation was used as a wavelength dispersive X-ray fluorescence spectrometer, and detection was performed under conditions of an acceleration voltage of 15 kV and a beam size of 10 μm.
The results are shown in Table 1.
一方、表１のような結果が絶縁破壊電圧に及ぼす影響を確認するために、実施例１〜１８の試料の絶縁破壊電圧を測定した。 On the other hand, in order to confirm the influence of the results shown in Table 1 on the breakdown voltage, the breakdown voltages of the samples of Examples 1 to 18 were measured.
絶縁破壊電圧の測定方法は次の通りである。 The measuring method of the dielectric breakdown voltage is as follows.
絶縁破壊電圧測定器（モデル名ＤＰＡ７５、ＢＡＵＲ社製）を用いて、２３℃、５０％ＲＨの下にＡＳＴＭ Ｄ１４９基準に基づいて０Ｖ〜５００Ｖ／Ｓの速度で昇圧して絶縁破壊される電圧を測定した。 Using a dielectric breakdown voltage measuring instrument (model name DPA75, manufactured by BAUR), the voltage at which the dielectric breakdown is boosted at 23 V and 50% RH at a rate of 0 V to 500 V / S based on the ASTM D149 standard. It was measured.
表２の結果より、直径５０μｍ以上の長軸を有する欠陥が光学欠陥検出器によって検出されても、波長分散型蛍光Ｘ線分析装置でＣ強度を検出したとき、欠陥ではない部位に対して７０〜２５０の差を示す欠陥の数が５個以下の場合はいずれも、絶縁破壊電圧が８ｋＶ以上であって、絶縁性に優れるうえ、特にこのような特性を持つ欠陥の数が少ないほど絶縁破壊電圧が大きくなることが分かる。これは、波長分散型蛍光Ｘ線分析装置で検出されるＣ強度の値が均一な場合に絶縁材として有用であることを示す結果と言える。 From the results in Table 2, even when a defect having a major axis with a diameter of 50 μm or more is detected by the optical defect detector, when the C intensity is detected by the wavelength dispersive X-ray fluorescence analyzer, it is 70 for a portion that is not a defect. In any case where the number of defects showing a difference of ˜250 is 5 or less, the dielectric breakdown voltage is 8 kV or more and the insulation is excellent. In particular, the smaller the number of defects having such characteristics, the smaller the dielectric breakdown. It can be seen that the voltage increases. This can be said to be a result showing that it is useful as an insulating material when the value of the C intensity detected by the wavelength dispersive X-ray fluorescence analyzer is uniform.
Claims (8)
波長分散型蛍光Ｘ線分析装置によってＣ強度を測定したとき、欠陥ではない部位とのＣ強度値の差が７０〜２５０である欠陥の数が前記面積範囲あたり５個以下である、ポリイミドフィルム。 When the area range having a width of 514 mm or 1028 mm and a length of 1500 m on the polyimide film roll is detected by passing through an optical defect detector, and a defect having a major axis of 50 μm or more in diameter is included,
A polyimide film in which the number of defects having a C intensity value difference of 70 to 250 with respect to a portion that is not a defect is 5 or less per area area when the C intensity is measured by a wavelength dispersive X-ray fluorescence analyzer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102014570B (en) * | 2009-09-08 | 2012-08-22 | 上海长丰智能卡有限公司 | PCB (printed circuit board) carried tape for phone card with non-contact function |
| JP2020113597A (en) * | 2019-01-09 | 2020-07-27 | 日立化成株式会社 | Circuit board, manufacturing method thereof, and semiconductor device |
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| JPH01167341A (en) * | 1987-12-23 | 1989-07-03 | Nitto Denko Corp | Easily slippery polyimide film |
| JPH08253583A (en) * | 1995-03-14 | 1996-10-01 | Furukawa Electric Co Ltd:The | Polyimide resin molding |
| JP2001023148A (en) * | 1999-07-05 | 2001-01-26 | Toray Ind Inc | High modulus of elasticity film for magnetic medium, and magnetic recording tape |
| JP2006028216A (en) * | 2004-07-12 | 2006-02-02 | Kaneka Corp | Polyimide film and manufacturing method of the polyimide film |
| JP2006137884A (en) * | 2004-11-15 | 2006-06-01 | Toyobo Co Ltd | Method for manufacturing polyimide film |
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2007
- 2007-08-31 KR KR1020070088642A patent/KR20090022937A/en not_active Application Discontinuation
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- 2008-08-26 JP JP2008216536A patent/JP2009057556A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01167341A (en) * | 1987-12-23 | 1989-07-03 | Nitto Denko Corp | Easily slippery polyimide film |
| JPH08253583A (en) * | 1995-03-14 | 1996-10-01 | Furukawa Electric Co Ltd:The | Polyimide resin molding |
| JP2001023148A (en) * | 1999-07-05 | 2001-01-26 | Toray Ind Inc | High modulus of elasticity film for magnetic medium, and magnetic recording tape |
| JP2006028216A (en) * | 2004-07-12 | 2006-02-02 | Kaneka Corp | Polyimide film and manufacturing method of the polyimide film |
| JP2006137884A (en) * | 2004-11-15 | 2006-06-01 | Toyobo Co Ltd | Method for manufacturing polyimide film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102014570B (en) * | 2009-09-08 | 2012-08-22 | 上海长丰智能卡有限公司 | PCB (printed circuit board) carried tape for phone card with non-contact function |
| JP2020113597A (en) * | 2019-01-09 | 2020-07-27 | 日立化成株式会社 | Circuit board, manufacturing method thereof, and semiconductor device |
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