JP3048690B2 - Method for producing polyimide film - Google Patents
Method for producing polyimide filmInfo
- Publication number
- JP3048690B2 JP3048690B2 JP20338891A JP20338891A JP3048690B2 JP 3048690 B2 JP3048690 B2 JP 3048690B2 JP 20338891 A JP20338891 A JP 20338891A JP 20338891 A JP20338891 A JP 20338891A JP 3048690 B2 JP3048690 B2 JP 3048690B2
- Authority
- JP
- Japan
- Prior art keywords
- tetracarboxylic dianhydride
- diamine
- equivalents
- polyimide film
- linear
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、適度な柔軟性と高い弾
性率を有するため優れた寸法安定性を持つポリイミドフ
ィルムの製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyimide film having a suitable flexibility and a high elastic modulus and excellent dimensional stability.
【０００２】[0002]
【従来の技術】ポリイミドは、一般に、耐熱性、電気絶
縁性、耐薬品性及び耐放射線性に優れており、フレキシ
ブルプリント基板の絶縁層等の用途に広く利用されてい
る。最近、製造工程中のテンションによって生じる歪を
小さく抑え非常に微細な加工を可能にするという目的の
ために、従来よりも機械強度の高いポリイミドフィル
ム、特に弾性率の高いポリイミドフィルムが求められて
いる。そこで弾性率を上げるための試みとして、例えば
パラフェニレンジアミンのような直線性芳香族ジアミン
と芳香族テトラカルボン酸二無水物の共重合体からポリ
イミドフィルムの製造を試みたが、このポリイミドフィ
ルムは高弾性率を示すが柔軟性に欠けるという欠点があ
った。そのため、直線性芳香族ジアミンと共に屈曲性芳
香族ジアミンを用いて芳香族テトラカルボン酸二無水物
と共重合を行い、柔軟なポリイミドフィルムを製造する
ことを試みたが、このポリイミドフィルムは柔軟性は示
すが弾性率は低くなるという欠点を持つ。2. Description of the Related Art Polyimide is generally excellent in heat resistance, electrical insulation, chemical resistance, and radiation resistance, and is widely used as an insulating layer of a flexible printed circuit board. Recently, for the purpose of minimizing distortion caused by tension during the manufacturing process and enabling extremely fine processing, a polyimide film having higher mechanical strength than the conventional one, particularly a polyimide film having a high elastic modulus, is required. . Therefore, as an attempt to increase the elastic modulus, for example, an attempt was made to produce a polyimide film from a copolymer of a linear aromatic diamine such as paraphenylenediamine and an aromatic tetracarboxylic dianhydride. Although it has an elastic modulus, it has the disadvantage of lacking flexibility. Therefore, it was attempted to produce a flexible polyimide film by copolymerizing with aromatic tetracarboxylic dianhydride using a flexible aromatic diamine together with a linear aromatic diamine, but this polyimide film has flexibility. As shown, it has the drawback that the elastic modulus is low.
【０００３】以上のことにより、適度な柔軟性と高い弾
性率を併せ持ったポリイミドフィルムの出現が望まれて
いた。In view of the above, the appearance of a polyimide film having both moderate flexibility and a high elastic modulus has been desired.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、適度な柔軟
性を有しながら高い弾性率を持つポリイミドフィルムを
提供することを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyimide film having a moderate elasticity and a high elastic modulus.
【０００５】[0005]
【課題を解決するための手段】即ち、本発明は、有機溶
媒中で直線性ジアミン２当量に対しテトラカルボン酸二
無水物を２当量より多く３当量以下である量を添加して
反応させ、続いて屈曲性ジアミンとテトラカルボン酸二
無水物をジアミン類とテトラカルボン酸二無水物類の添
加総量が実質的に等モルとなるように添加し反応させて
得られるポリアミド酸を熱的又は化学的方法によりイミ
ド化し、下記一般式で表される反復単位を有し、その反
復単位中の繰り返し単位の繰り返し数ｎが２以上である
ポリイミドフィルムを得ることを特徴とするポリイミド
フィルムの製造方法を内容とするものである。That is, the present invention provides a reaction in which an amount of more than 2 equivalents and 3 equivalents or less of tetracarboxylic dianhydride is added to 2 equivalents of a linear diamine in an organic solvent, and the reaction is carried out. Subsequently, a polyamic acid obtained by adding and reacting a flexible diamine and a tetracarboxylic dianhydride such that the total amount of the diamines and the tetracarboxylic dianhydrides is substantially equimolar is reacted thermally or chemically. A method for producing a polyimide film having a repeating unit represented by the following general formula, wherein a number n of repeating units in the repeating unit is 2 or more. Content.
【０００６】[0006]
【化２】 Embedded image
【０００７】（Ｒ1 、Ｒ5 はテトラカルボン酸二無水物
残基、Ｒ3 はＲ1 と一致するテトラカルボン酸二無水物
残基、Ｒ2 は直線性ジアミン残基、Ｒ4 は屈曲性ジアミ
ン残基を表し、Ｒ6 はＲ4 と一致するジアミン残基を表
し、Ｒ1 とＲ5 は同一であっても異なっていてもよく、
また、ｍは自然数を表す。）(R 1 and R 5 are tetracarboxylic dianhydride residues, R 3 is a tetracarboxylic dianhydride residue corresponding to R 1 , R 2 is a linear diamine residue, and R 4 is flexible Represents a diamine residue, R 6 represents a diamine residue corresponding to R 4 , R 1 and R 5 may be the same or different,
M represents a natural number. )
【０００８】本発明者らは適度な柔軟性と高弾性率を有
するポリイミドフィルムを得るべく種々の屈曲性ジアミ
ンと直線性ジアミンとテトラカルボン酸二無水物の共重
合ポリイミドフィルムを検討した結果、屈曲性ジアミン
と直線性ジアミンの組成比が同一であっても、直線性ジ
アミンとテトラカルボン酸二無水物からなる繰り返し単
位を２回以上連続させた構造を有するポリイミドフィル
ムと、直線性ジアミンとテトラカルボン酸二無水物から
なる繰り返し単位が２回以上連続しない構造を持つポリ
イミドフィルムでは異なった物性を示すことを見い出し
た。即ち、直線性ジアミンとテトラカルボン酸二無水物
からなる繰り返し単位を２回以上連続させた構造を有す
るポリイミドフィルムは、直線性ジアミンとテトラカル
ボン酸二無水物からなる繰り返し単位が２回以上連続し
ない構造を持つポリイミドフィルムと比較して、吸水率
等の化学的特性に悪影響を及ぼすことなく高い弾性率を
示すことを見い出し、本発明に到達した。The present inventors have studied various copolymerized polyimide films of flexible diamine, linear diamine and tetracarboxylic dianhydride in order to obtain a polyimide film having appropriate flexibility and high elastic modulus. Even if the composition ratio of the linear diamine and the linear diamine is the same, a polyimide film having a structure in which the repeating unit composed of the linear diamine and the tetracarboxylic dianhydride is continued twice or more, the linear diamine and the tetracarboxylic acid It has been found that a polyimide film having a structure in which a repeating unit composed of an acid dianhydride is not continuous twice or more exhibits different physical properties. That is, a polyimide film having a structure in which a repeating unit composed of a linear diamine and a tetracarboxylic dianhydride is continuous twice or more, a repeating unit composed of a linear diamine and a tetracarboxylic dianhydride is not continuous twice or more. Compared with a polyimide film having a structure, it has been found that the film exhibits a high elastic modulus without adversely affecting chemical properties such as water absorption, and has reached the present invention.
【０００９】一般式中の繰り返し数ｎは、２以上１０以
下の範囲にあることが好ましく、また、このポリイミド
の平均分子量は１００００〜１００００００であること
が望ましい。繰り返し数ｎ、ｍが２未満では本発明の効
果が充分でなく、また１０を越えると柔軟性に欠けるフ
ィルムとなる。平均分子量が１００００未満では、でき
あがったフィルムが脆くなり、一方、１００００００を
越えるとポリイミド前駆体であるポリアミド酸ワニスの
粘度が高くなりすぎ取扱いが難しくなる。また、このポ
リイミドフィルムに各種の有機添加剤、或いは無機のフ
ィラー類、或いは各種の強化材を複合することも可能で
ある。The number of repetitions n in the general formula is preferably in the range of 2 or more and 10 or less, and the average molecular weight of this polyimide is desirably 10,000 to 1,000,000. If the number of repetitions n and m is less than 2, the effect of the present invention is not sufficient, and if it exceeds 10, the film lacks flexibility. If the average molecular weight is less than 10,000, the resulting film becomes brittle. On the other hand, if it exceeds 1,000,000, the viscosity of the polyamic acid varnish, which is a polyimide precursor, becomes too high and handling becomes difficult. It is also possible to compound various organic additives, inorganic fillers, or various reinforcing materials with the polyimide film.
【００１０】次に、本発明のポリイミドフィルムの製造
方法について説明する。このポリイミド共重合体は、そ
の前駆体であるポリアミド酸共重合体溶液から得られ
る。このポリアミド酸共重合体溶液は、テトラカルボン
酸二無水物成分とジアン成分を実質等モル使用し有機極
性溶媒中で重合して得られるが、直線性ジアミンとテト
ラカルボン酸二無水物からなる繰り返し単位が複数回連
続する構造を持つポリアミド酸共重合体溶液を得るため
には、テトラカルボン酸二無水物及びジアミンの添加順
序と添加量を制御して反応させる必要がある。具体的に
は直線性ジアミン２当量に対しテトラカルボン酸二無水
物を２当量より多く３当量以下である量を反応させる
か、またはテトラカルボン酸二無水物２当量に対し直線
性ジアミンを２当量より多く３当量以下である量を反応
させて直線性ジアミンとテトラカルボン酸二無水物から
なる繰り返し単位が複数回連続している酸無水物末端又
はアミン末端を有するプレポリマーを得て、続いて屈曲
性ジアミンとテトラカルボン酸二無水物をジアミン類と
テトラカルボン酸二無水物類の添加総量が実質的に等モ
ルとなるように添加し反応させて得ることができる。更
に、直線性ジアミンとテトラカルボン酸二無水物からな
る繰り返し単位の連続する回数が一定になるように制御
すると、より優れた物性を付与することができるため、
製造方法としてはこの方法を用いるのが好ましい。以下
に、このポリアミド酸共重合体溶液の製造手順を例示す
る。Next, a method for producing the polyimide film of the present invention will be described. This polyimide copolymer is obtained from a polyamic acid copolymer solution as its precursor. This polyamic acid copolymer solution is obtained by polymerizing in an organic polar solvent using substantially equimolar amounts of a tetracarboxylic dianhydride component and a dian component, and is obtained by repeating a linear diamine and a tetracarboxylic dianhydride. In order to obtain a polyamic acid copolymer solution having a structure in which units are continuous a plurality of times, it is necessary to control the order and amount of addition of the tetracarboxylic dianhydride and the diamine to carry out the reaction. Specifically, the amount of the tetracarboxylic dianhydride to be reacted is more than 2 equivalents and not more than 3 equivalents to 2 equivalents of the linear diamine, or 2 equivalents of the linear diamine is added to 2 equivalents of the tetracarboxylic dianhydride. More than 3 equivalents or less are reacted to obtain an anhydride- or amine-terminated prepolymer in which a repeating unit composed of a linear diamine and a tetracarboxylic dianhydride is repeated a plurality of times, and subsequently, It can be obtained by adding and reacting a flexible diamine and a tetracarboxylic dianhydride such that the total amount of the diamines and the tetracarboxylic dianhydride becomes substantially equimolar. Furthermore, when the number of continuous repeating units composed of linear diamine and tetracarboxylic dianhydride is controlled to be constant, more excellent physical properties can be provided,
It is preferable to use this method as a manufacturing method. Hereinafter, the procedure for producing the polyamic acid copolymer solution will be exemplified.
【００１１】（１）直線性ジアミン化合物（ｂ）Ａ当量
（Ａは２以上の自然数）にテトラカルボン酸二無水物
（ａ）をＡ当量より多く（Ａ＋１）当量以下添加し有機
極性溶媒中にて反応させ、両末端に酸無水物基を有する
プレポリマーを得て、続いてここに屈曲性ジアミン化合
物（ｄ）を、全ジアミン（（ｂ）＋（ｄ））がテトラカ
ルボン酸二無水物（ａ）と実質的に等量になるように添
加する共重合方法。この方法により直線性ジアミン残基
１分子とテトラカルボン酸二無水物残基１分子から成る
繰り返し単位が複数回連続したユニットが屈曲性ジアミ
ン残基と先と同一のテトラカルボン酸二無水物残基から
成る繰り返し単位によってつながれたポリアミド酸共重
合体を得る。(1) A linear diamine compound (b) A equivalent (A is a natural number of 2 or more) of tetracarboxylic dianhydride (a) is added to A equivalent (A is a natural number of 2 or more). To obtain a prepolymer having acid anhydride groups at both ends. Subsequently, a flexible diamine compound (d) is added thereto, and all diamines ((b) + (d)) are tetracarboxylic dianhydrides. A copolymerization method in which (a) is added in a substantially equivalent amount. According to this method, a repeating unit consisting of one molecule of a linear diamine residue and one molecule of a tetracarboxylic dianhydride residue is repeated a plurality of times to form a unit of the same tetracarboxylic dianhydride residue as the flexible diamine residue. To obtain a polyamic acid copolymer linked by a repeating unit consisting of
【００１２】（２）直線性ジアミン化合物（ｂ）Ａ当量
（Ａは２以上の自然数）に対してテトラカルボン酸二無
水物（ａ）を（Ａ＋１）当量用い有機極性溶媒中で反応
させ、両末端に酸無水物基を有するプレポリマーを得
て、続いてここに、屈曲性ジアミン成分（ｄ）を追加添
加後、全ジアミン成分（（ｂ）＋（ｄ））と実質的に等
モルになるように、不足分のテトラカルボン酸二無水物
（ｃ）を添加反応させる共重合方法。この方法により直
線性ジアミン残基１分子とテトラカルボン酸二無水物残
基１分子から成る繰り返し単位が複数回連続したユニッ
トが、屈曲性ジアミン残基とテトラカルボン酸二無水物
残基から成る繰り返し単位によってつながれたポリアミ
ド酸共重合体を得る。(2) Linear diamine compound (b) A equivalent (A is a natural number of 2 or more) of tetracarboxylic dianhydride (a) is used for (A + 1) equivalent of A equivalent (A is a natural number of 2 or more) to react in an organic polar solvent. A prepolymer having an acid anhydride group at a terminal is obtained, and then, after a flexible diamine component (d) is additionally added thereto, it is substantially equimolar to all diamine components ((b) + (d)). A copolymerization method in which a shortage of tetracarboxylic dianhydride (c) is added and reacted. According to this method, a repeating unit composed of one molecule of a linear diamine residue and one molecule of a tetracarboxylic dianhydride residue is repeated a plurality of times to form a repeating unit composed of a flexible diamine residue and a tetracarboxylic dianhydride residue. A polyamic acid copolymer linked by units is obtained.
【００１３】（３）直線性ジアミン化合物（ｂ）Ａ当量
（Ａは２以上の自然数）に対してテトラカルボン酸二無
水物（ａ）を（Ａ＋１）当量用い、有機極性溶媒中で反
応させ両末端に酸無水物基を有するプレポリマーを得
て、続いてここに、屈曲性ジアミン成分（ｄ）２当量を
加え両末端にアミン基を有するプレポリマーを得る。続
いてテトラカルボン酸二無水物（ｃ）２当量を加え両末
端に酸無水物を有するプレポリマーを得る。このように
両末端に酸無水物基又はアミノ基を有するプレポリマー
を得るように屈曲性ジアミンまたはテトラカルボン酸二
無水物を順次添加していく。その後、両末端に酸無水物
基を有するプレポリマーに対しては屈曲性ジアミン
（ｄ）を、両末端にアミノ基を有するプレポリマーに対
してはテトラカルボン酸二無水物（ｃ）を各々１当量添
加する共重合方法。この方法により、上記（２）よりも
更に繰り返しパターンが制御されたポリアミド酸共重合
体を得る。繰り返しパターンの制御されたポリアミド酸
共重合体を得るには、勿論これ以外の方法を用いてもよ
く、更には異種のポリアミド酸溶液の混合により得るこ
とも可能である。上記の中でも（３）の方法を用いると
特性の面で優れたものが得られるので好ましい。尚、上
記（２）、（３）中のテトラカルボン酸二無水物（ａ）
および（ｃ）は同一であっても異なっていてもよい。(3) Linear diamine compound (b) Using (A + 1) equivalent of tetracarboxylic dianhydride (a) with respect to A equivalent (A is a natural number of 2 or more) and reacting in an organic polar solvent, A prepolymer having an acid anhydride group at a terminal is obtained, and then 2 equivalents of a flexible diamine component (d) are added thereto to obtain a prepolymer having an amine group at both ends. Subsequently, 2 equivalents of tetracarboxylic dianhydride (c) are added to obtain a prepolymer having acid anhydrides at both ends. As described above, a flexible diamine or tetracarboxylic dianhydride is sequentially added so as to obtain a prepolymer having an acid anhydride group or an amino group at both terminals. Thereafter, a flexible diamine (d) is added to the prepolymer having acid anhydride groups at both ends, and a tetracarboxylic dianhydride (c) is added to the prepolymer having amino groups at both ends. A copolymerization method in which equivalent amounts are added. By this method, a polyamic acid copolymer in which the repetition pattern is further controlled than in the above (2) is obtained. In order to obtain a polyamic acid copolymer having a controlled repetition pattern, it is a matter of course that other methods may be used, and it is also possible to obtain a polyamic acid copolymer by mixing different types of polyamic acid solutions. Among them, the method (3) is preferable because excellent properties can be obtained. Incidentally, the tetracarboxylic dianhydride (a) in the above (2) and (3)
And (c) may be the same or different.
【００１４】上記のポリアミド酸を得るために用いるテ
トラカルボン酸二無水物（ａ）、（ｃ）としては種々の
ものを用いることができるが、高弾性率を発現させるた
めには平面性を保存した構造が好ましく、特にピロメリ
ット酸二無水物、ビフェニルテトラカルボン酸二無水
物、ベンゾフェノンテトラカルボン酸二無水物を用いる
のが好ましい。Various tetracarboxylic dianhydrides (a) and (c) used for obtaining the above-mentioned polyamic acid can be used, but in order to exhibit a high elastic modulus, the flatness is preserved. In particular, it is preferable to use pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, and benzophenonetetracarboxylic dianhydride.
【００１５】上述の（ｂ）で示される直線性ジアミンと
はエーテル基、メチレン基、プロパギル基、ヘキサフル
オロプロパギル基、カルボニル基等の屈曲基を主鎖中に
含まず、２個のアミノ基の窒素原子とそれらが結合して
いる炭素原子が一直線に並ぶジアミンのことをいい、こ
の例としてｐ−フェニレンジアミン、３，３′−ジヒド
ロキシ−４，４′−ジアミノビフェニル、３，３′−ジ
メチル−４，４′−ジアミノビフェニル、３，３′−ジ
メトキシ−４，４′−ジアミノビフェニル、３，３′−
ジクロロ−４，４′−ジアミノビフェニル、３，３′−
ジフルオロ−４，４′−ジアミノビフェニル等を挙げる
ことができ、これらは単独又は２種以上組み合わせて用
いられる。また、（ｄ）で表される屈曲性ジアミンとは
エーテル基、メチレン基、プロパギル基、ヘキサフルオ
ロプロパギル基、カルボニル基等の屈曲基を主鎖中に含
むジアミン、または、屈曲基を含まない場合は、２個の
アミノ基の窒素原子とそれらと結合する炭素原子が一直
線に並ばないジアミンのことをいい、前者の例として
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〕ヘキサフロオロプロパン、４，４′−
ビス（４−アミノフェノキシ）ビフェニル、ビス〔４−
（４−アミノフェノキシ）フェニル〕スルフォン、ビス
〔４−（３−アミノフェノキシ）フェニル〕スルフォ
ン、４，４′−ジアミノジフェニルエーテル、３，４′
−ジアミノジフェニルエーテル、ビス〔４−（４−アミ
ノフェノキシ）フェニル〕エーテル、１，４−ビス（４
−アミノフェノキシ）ベンゼン、１，３−ビス（４−ア
ミノフェノキシ）ベンゼン、２，２−ビス（４−アミノ
フェニル）プロパン、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′−ジアミノベン
ゾフェノン等を挙げることができ、また、後者の例とし
ては、ｍ−フェニレンジアミン、ｏ−フェニレンジアミ
ン等を挙げることができ、これらは単独又は２種以上組
み合わせて用いられる。The linear diamine represented by the above (b) means that two amino groups which do not contain a bending group such as an ether group, a methylene group, a propargyl group, a hexafluoropropargyl group, a carbonyl group in the main chain. Is a diamine in which the nitrogen atom and the carbon atom to which they are bonded are aligned, and examples thereof include p-phenylenediamine, 3,3'-dihydroxy-4,4'-diaminobiphenyl, and 3,3'- Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-
Dichloro-4,4'-diaminobiphenyl, 3,3'-
Difluoro-4,4'-diaminobiphenyl and the like can be mentioned, and these are used alone or in combination of two or more. The flexible diamine represented by (d) is a diamine containing a bending group such as an ether group, a methylene group, a propargyl group, a hexafluoropropargyl group, or a carbonyl group in a main chain, or does not include a bending group. The term "diamine" refers to a diamine in which the nitrogen atom of two amino groups and the carbon atom bonded thereto are not aligned, and 2,2-bis [4- (4-aminophenoxy) phenyl] propane is an example of the former. 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 4,4'-
Bis (4-aminophenoxy) biphenyl, bis [4-
(4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4'-diaminodiphenyl ether, 3,4 '
-Diaminodiphenyl ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis (4
-Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-Diaminobenzophenone and the like, and examples of the latter include m-phenylenediamine, o-phenylenediamine and the like, which may be used alone or in combination of two or more.
【００１６】また、該ポリアミド酸共重合体の生成反応
に使用される有機極性溶媒として、ジメチルスルホキシ
ド、ジエチルスルホキシドなどのスルホキシド系溶媒、
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、あるいはヘキサメチルホスホルアミド、γ−
ブチロラクトンなどを挙げることができ、これらを単独
又は混合物として用いるのが望ましく、更にはキシレ
ン、トルエンのような芳香族炭化水素の一部使用も可能
である。また、このポリアミド酸共重合体は各々前記の
有機極性溶媒中に５〜４０重量％、好ましくは１０〜３
０重量％溶解されているのが取扱いの面からも望まし
い。As the organic polar solvent used in the reaction for producing the polyamic acid copolymer, a sulfoxide-based solvent such as dimethyl sulfoxide and diethyl sulfoxide;
Formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide; acetamido solvents such as N, N-dimethylacetamide and N, N-diethylacetamide; N-methyl-2-pyrrolidone;
Pyrrolidone-based solvents such as vinyl-2-pyrrolidone, phenol-based solvents such as phenol, o-, m- or p-cresol, xylenol, halogenated phenol, catechol, or hexamethylphosphoramide, γ-
Butyrolactone and the like can be mentioned, and it is desirable to use these alone or as a mixture, and it is also possible to partially use aromatic hydrocarbons such as xylene and toluene. Each of the polyamic acid copolymers is 5 to 40% by weight, preferably 10 to 3% by weight in the above-mentioned organic polar solvent.
0% by weight is desirable from the viewpoint of handling.
【００１７】次いで、このポリアミド酸溶液からポリイ
ミドフィルムを製造する方法については、従来公知の方
法を用いることができる。即ち、熱的に脱水する熱的方
法、脱水剤と触媒を用いる化学的方法のいずれを用いて
もよいが、化学的方法によると生成するポリイミド重合
体の機械特性が優れたものになるので好ましい。なお、
ここで言う脱水剤としては、例えば無水酢酸等の脂肪族
酸無水物、フタル酸無水物等の芳香族酸無水物などが挙
げられ、これらは単独又は２種以上組み合わせて用いら
れる。また触媒として、例えばトリエチルアミンなどの
脂肪族第３級アミン類、Ｎ，Ｎ−ジメチルアニリン等の
芳香族第３級アミン類、ピリジン、ピコリン、イソキノ
リン、キノリン等の複素環式第３級アミン類などが挙げ
られ、これらは単独又は２種以上組み合わせて用いられ
る。このようにして、適度な柔軟性と高い弾性率を併せ
持つポリイミドフィルムを得ることができる。Next, as a method for producing a polyimide film from the polyamic acid solution, a conventionally known method can be used. That is, any of a thermal method of thermally dehydrating and a chemical method using a dehydrating agent and a catalyst may be used, but the chemical method is preferable because the mechanical properties of the polyimide polymer produced are excellent. . In addition,
Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as phthalic anhydride. These may be used alone or in combination of two or more. Examples of the catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as N, N-dimethylaniline, and heterocyclic tertiary amines such as pyridine, picoline, isoquinoline and quinoline. And these may be used alone or in combination of two or more. In this way, a polyimide film having both appropriate flexibility and high elastic modulus can be obtained.
【００１８】[0018]
【実施例】以下、実施例により本発明を具体的に説明す
るが、本発明はこれら実施例のみに限定されるものでは
ない。実施例中、ｐ−ＰＤＡはパラフェニレンジアミ
ン、ＯＤＡは４，４′−ジアミノジフェニルエーテル、
ＰＭＤＡはピロメリット酸二無水物、ＢＴＤＡは３，
３′，４，４′−ベンゾフェノンテトラカルボン酸二無
水物、ＤＭＦはジメチルホルムアミドを表す。EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, p-PDA is paraphenylenediamine, ODA is 4,4'-diaminodiphenyl ether,
PMDA is pyromellitic dianhydride, BTDA is 3,
3 ', 4,4'-benzophenonetetracarboxylic dianhydride, DMF represents dimethylformamide.
【００１９】比較例１ ２リットルのセパラブルフラスコに脱水精製したＤＭＦ
８１５ｇを入れ、ここに、ＯＤＡ４９．７５ｇ（０．２
４８モル）を投入し均一になるまで攪拌した。次にここ
にＰＭＤＡ１０８．３８ｇ（０．４９６モル）を添加
し、２時間反応させた。この間反応系を０℃の氷水で冷
却した。続いて、ここにｐ−ＰＤＡ２６．８７ｇ（０．
２４８モル）を添加し、更に４時間反応させて、固形分
１８．５重量％のポリアミド酸溶液を得た。このポリア
ミド酸溶液に脱水剤として無水酢酸、触媒としてピリジ
ンを添加した後、ガラス板上に流延塗布し、約１００℃
にて約９０秒乾燥した後、ポリアミド酸塗膜をガラス板
より剥し、その塗膜を支持枠に固定した。その後約１１
０℃で約９０秒、約２００℃で約６０秒、約３００℃で
約６０秒、続いて約４００℃で約６０秒加熱し、脱水閉
環、乾燥した後、上記支持枠より取り外し、約２５μｍ
のポリイミドフィルムを得た。このフィルムの初期弾性
率は６３０kg／mm2 、抗張力は２０kg／mm2 であり、伸
びは３５％、吸水率は４．２％であった。Comparative Example 1 DMF dehydrated and purified in a 2-liter separable flask
815 g, and ODA 49.75 g (0.2
(48 moles) and stirred until uniform. Next, 108.38 g (0.496 mol) of PMDA was added thereto and reacted for 2 hours. During this time, the reaction system was cooled with ice water at 0 ° C. Subsequently, 26.87 g of p-PDA (0.
(248 mol) was added thereto, and the mixture was further reacted for 4 hours to obtain a polyamic acid solution having a solid content of 18.5% by weight. After adding acetic anhydride as a dehydrating agent and pyridine as a catalyst to this polyamic acid solution, the solution is cast and applied on a glass plate, and is heated to about 100 ° C.
After drying for about 90 seconds, the polyamide acid coating film was peeled off from the glass plate, and the coating film was fixed to a support frame. Then about 11
After heating at 0 ° C. for about 90 seconds, about 200 ° C. for about 60 seconds, about 300 ° C. for about 60 seconds, followed by heating at about 400 ° C. for about 60 seconds, dehydration ring closure and drying, and then removing from the support frame, about 25 μm
Was obtained. The initial elastic modulus of this film was 630 kg / mm 2 , the tensile strength was 20 kg / mm 2 , the elongation was 35%, and the water absorption was 4.2%.
【００２０】実施例１ 比較例１と同様の手順でＤＭＦ８１５ｇにｐ−ＰＤＡ２
６．８７ｇ（０．２４８モル）、ＰＭＤＡ６７．７４
（０．３１０モル）、ＯＤＡ４９．７５ｇ（０．２４８
モル）、再びＰＭＤＡ４０．６５ｇ（０．１８６モル）
を順に加えて重合し、固形分濃度１８．５重量％のポリ
アミド酸溶液を得た。以下、比較例１と同様の操作によ
り約２５μｍの厚みを有するポリイミドフィルムを得
た。このフィルムの初期弾性率は７００kg／mm2 、抗張
力は２２kg／mm2 であり、伸びは２５％、吸水率は４．
０％であった。Example 1 In the same procedure as in Comparative Example 1, p-PDA2 was added to 815 g of DMF.
6.87 g (0.248 mol), PMDA 67.74
(0.310 mol), 49.75 g of ODA (0.248
Mol), again 40.65 g (0.186 mol) of PMDA
Were added in order and polymerized to obtain a polyamic acid solution having a solid concentration of 18.5% by weight. Hereinafter, a polyimide film having a thickness of about 25 μm was obtained by the same operation as in Comparative Example 1. The initial elastic modulus of this film is 700 kg / mm 2 , the tensile strength is 22 kg / mm 2 , the elongation is 25%, and the water absorption is 4.
It was 0%.
【００２１】実施例２ 比較例１と同様の手順でＤＭＦ８１５ｇにｐ−ＰＤＡ２
６．８７ｇ（０．２４８モル）、ＰＭＤＡ６７．７４ｇ
（０．３１０モル）、ＯＤＡ２４．８８ｇ（０．１２４
モル）、ＰＭＤＡ２７．１０ｇ（０．１２４モル）、Ｏ
ＤＡ２４．８８ｇ（０．１２４モル）、ＰＭＤＡ１３．
５５ｇ（０．０６２モル）を順に加えて重合し、固形分
濃度１８．５重量％のポリアミド酸溶液を得た。以下、
比較例１と同様の操作により約２５μｍの厚みを有する
ポリイミドフィルムを得た。このフィルムの初期弾性率
は７０８kg／mm2 、抗張力は２４kg／mm2 であり、伸び
は３０％、吸水率は４．０％であった。Example 2 In the same procedure as in Comparative Example 1, p-PDA2 was added to 815 g of DMF.
6.87 g (0.248 mol), PMDA 67.74 g
(0.310 mol), ODA 24.88 g (0.124
Mol), PMDA 27.10 g (0.124 mol), O
DA24.88 g (0.124 mol), PMDA13.
55 g (0.062 mol) were added in order and polymerized to obtain a polyamic acid solution having a solid content of 18.5% by weight. Less than,
By the same operation as in Comparative Example 1, a polyimide film having a thickness of about 25 μm was obtained. The initial elastic modulus of this film was 708 kg / mm 2 , the tensile strength was 24 kg / mm 2 , the elongation was 30%, and the water absorption was 4.0%.
【００２２】実施例３ 比較例１と同様の手順でＤＭＦ８１５ｇにｐ−ＰＤＡ２
６．８７ｇ（０．２４８モル）、ＰＭＤＡ８１．２９ｇ
（０．３７２モル）、ＯＤＡ４９．７５ｇ（０．２４８
モル）、再びＰＭＤＡ２７．０９ｇ（０．１２４モル）
を順に加えて重合し、固形分濃度１８．５重量％のポリ
アミド酸溶液を得た。以下、比較例１と同様の操作によ
り約２５μｍの厚みを有するポリイミドフィルムを得
た。このフィルムの初期弾性率は７１０kg／mm2 、抗張
力は２５kg／mm2 であり、伸びは３５％、吸水率は４．
１％であった。Example 3 In the same procedure as in Comparative Example 1, p-PDA2 was added to 815 g of DMF.
6.87 g (0.248 mol), PMDA 81.29 g
(0.372 mol), 49.75 g of ODA (0.248
Mol), again 27.09 g (0.124 mol) of PMDA
Were added in order and polymerized to obtain a polyamic acid solution having a solid concentration of 18.5% by weight. Hereinafter, a polyimide film having a thickness of about 25 μm was obtained by the same operation as in Comparative Example 1. The initial elastic modulus of this film is 710 kg / mm 2 , the tensile strength is 25 kg / mm 2 , the elongation is 35%, and the water absorption is 4.
1%.
【００２３】実施例４ 比較例１と同様の手順でＤＭＦ８１５ｇにｐ−ＰＤＡ２
５．１１ｇ（０．２３２モル）、ＰＭＤＡ７５．９８ｇ
（０．３４８モル）、ＯＤＡ４６．５０ｇ（０．２３２
モル）、ＢＴＤＡ３７．４１ｇ（０．１１６モル）を順
に加えて重合し、固形分濃度１８．５重量％のポリアミ
ド酸溶液を得た。以下、比較例１と同様の操作により約
２５μｍの厚みを有するポリイミドフィルムを得た。こ
のフィルムの初期弾性率は７９０kg／mm2 、抗張力は３
２kg／mm2 であり、伸びは３０％、吸水率は３．５％で
あった。以上の結果を表１に示す。Example 4 p-PDA2 was added to 815 g of DMF in the same procedure as in Comparative Example 1.
5.11 g (0.232 mol), PMDA 75.98 g
(0.348 mol), 46.50 g of ODA (0.232
Mol) and 37.41 g (0.116 mol) of BTDA were added in that order to carry out polymerization to obtain a polyamic acid solution having a solid concentration of 18.5% by weight. Hereinafter, a polyimide film having a thickness of about 25 μm was obtained by the same operation as in Comparative Example 1. This film has an initial modulus of elasticity of 790 kg / mm 2 and a tensile strength of 3
It was 2 kg / mm 2 , the elongation was 30%, and the water absorption was 3.5%. Table 1 shows the above results.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【発明の効果】本発明によれば、組成比を変えることな
く、従って吸水率等の化学的特性を高いレベルに維持し
ながら、適度な柔軟性と高い弾性率を併せもつポリイミ
ドフィルムを得ることができる。According to the present invention, it is possible to obtain a polyimide film having both moderate flexibility and a high elastic modulus without changing the composition ratio and thus maintaining a high level of chemical properties such as water absorption. Can be.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭64−16832（ＪＰ，Ａ) 特開 平１−282218（ＪＰ，Ａ) 特開 平５−59173（ＪＰ，Ａ) 特開 平５−51453（ＪＰ，Ａ) 特開 平４−335028（ＪＰ，Ａ) 特開 平４−320422（ＪＰ，Ａ) 特開 昭63−314242（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08G 73/00 - 73/26 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A 64-16832 (JP, A) JP-A 1-282218 (JP, A) JP-A 5-59173 (JP, A) JP-A 5- 51453 (JP, A) JP-A-4-335028 (JP, A) JP-A-4-320422 (JP, A) JP-A-63-314242 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08G 73/00-73/26 CA (STN) REGISTRY (STN)
Claims (3)
しテトラカルボン酸二無水物を２当量より多く３当量以
下である量を添加して反応させ、続いて屈曲性ジアミン
とテトラカルボン酸二無水物をジアミン類とテトラカル
ボン酸二無水物類の添加総量が実質的に等モルとなるよ
うに添加し反応させて得られるポリアミド酸を熱的又は
化学的方法によりイミド化し、下記一般式で表される反
復単位を有し、その反復単位中の繰り返し単位の繰り返
し数ｎが２以上であるポリイミドフィルムを得ることを
特徴とするポリイミドフィルムの製造方法。 【化１】 （Ｒ1 、Ｒ5 はテトラカルボン酸二無水物残基、Ｒ3 は
Ｒ1 と一致するテトラカルボン酸二無水物残基、Ｒ2 は
直線性ジアミン残基、Ｒ4 は屈曲性ジアミン残基、Ｒ6
はＲ4 と一致するジアミン残基を表し、Ｒ1 とＲ5 は同
一であっても異なっていてもよく、また、ｍは自然数を
表す。）In an organic solvent, tetracarboxylic dianhydride is added and reacted in an organic solvent in an amount of more than 2 equivalents and 3 equivalents or less based on 2 equivalents of a linear diamine. The polyamic acid obtained by adding and reacting the anhydride so that the total amount of the diamines and the tetracarboxylic dianhydrides becomes substantially equimolar is imidized by a thermal or chemical method, and represented by the following general formula: A method for producing a polyimide film, comprising: obtaining a polyimide film having a repeating unit represented by the formula, wherein the number n of repeating units in the repeating unit is 2 or more. Embedded image (R 1 and R 5 are tetracarboxylic dianhydride residues, R 3 is a tetracarboxylic dianhydride residue corresponding to R 1 , R 2 is a linear diamine residue, and R 4 is a flexible diamine residue , R 6
Represents a diamine residue corresponding to R 4 , R 1 and R 5 may be the same or different, and m represents a natural number. )
ン酸二無水物を（Ａ＋１）当量、屈曲性ジアミンを（Ｂ
＋１）当量、テトラカルボン酸二無水物をＢ当量用いる
請求項１記載のポリイミドフィルムの製造方法（Ａは２
以上の自然数、Ｂは自然数を表す。）。2. A equivalent of a linear diamine, (A + 1) equivalent of a tetracarboxylic dianhydride, and (B) of a flexible diamine.
2. The method for producing a polyimide film according to claim 1, wherein +1) equivalents and B equivalents of tetracarboxylic dianhydride are used.
The above natural numbers, B, represent natural numbers. ).
ン酸二無水物を３当量、屈曲性ジアミンを２当量、テト
ラカルボン酸二無水物を１当量用いる請求項２記載のポ
リイミドフィルムの製造方法。3. The process for producing a polyimide film according to claim 2, wherein 2 equivalents of a linear diamine, 3 equivalents of a tetracarboxylic dianhydride, 2 equivalents of a flexible diamine and 1 equivalent of a tetracarboxylic dianhydride are used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20338891A JP3048690B2 (en) | 1991-07-18 | 1991-07-18 | Method for producing polyimide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20338891A JP3048690B2 (en) | 1991-07-18 | 1991-07-18 | Method for producing polyimide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0525273A JPH0525273A (en) | 1993-02-02 |
| JP3048690B2 true JP3048690B2 (en) | 2000-06-05 |
Family
ID=16473219
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|---|---|---|---|
| JP20338891A Expired - Lifetime JP3048690B2 (en) | 1991-07-18 | 1991-07-18 | Method for producing polyimide film |
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| Country | Link |
|---|---|
| JP (1) | JP3048690B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0551453A (en) * | 1991-08-22 | 1993-03-02 | Kanegafuchi Chem Ind Co Ltd | Polyamic acid copolymer, polyimide copolymer consisting of the same copolymer and polyimide film and production thereof |
| JP2831867B2 (en) * | 1991-08-28 | 1998-12-02 | 鐘淵化学工業株式会社 | Polyamic acid copolymer, polyimide copolymer comprising the same, polyimide film, and methods for producing them |
| US5859171A (en) * | 1997-05-21 | 1999-01-12 | Dupont Toray | Polyimide copolymer, polyimide copolymer resin molded products and their preparation |
| US6277495B1 (en) * | 1997-07-18 | 2001-08-21 | E. I. Du Pont De Nemours And Company | Polyimide film, a method for its manufacture and a polyimide film containing metal laminated plate |
| WO2000069948A1 (en) * | 1999-05-18 | 2000-11-23 | The Government Of The United States As Represented By The Administrator Of The National Aeronautics And Space Administration | Composition of and method for making high performance resins for infusion and transfer molding processes |
| JP2002138152A (en) * | 2000-08-24 | 2002-05-14 | Du Pont Toray Co Ltd | Polyimide film, method of producing the same and metal circuit board having the same as substrate |
| WO2008010409A1 (en) * | 2006-07-18 | 2008-01-24 | Kaneka Corporation | Polyimide film |
| TWI628068B (en) | 2009-08-21 | 2018-07-01 | 東麗 杜邦股份有限公司 | Polyimide film |
| US8445099B2 (en) * | 2009-11-30 | 2013-05-21 | E. I. Du Pont De Nemours And Company | Polyimide film |
-
1991
- 1991-07-18 JP JP20338891A patent/JP3048690B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0525273A (en) | 1993-02-02 |
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