JP3048702B2 - Polyamic acid copolymer, polyimide copolymer, polyimide film and methods for producing them - Google Patents
Polyamic acid copolymer, polyimide copolymer, polyimide film and methods for producing themInfo
- Publication number
- JP3048702B2 JP3048702B2 JP26279291A JP26279291A JP3048702B2 JP 3048702 B2 JP3048702 B2 JP 3048702B2 JP 26279291 A JP26279291 A JP 26279291A JP 26279291 A JP26279291 A JP 26279291A JP 3048702 B2 JP3048702 B2 JP 3048702B2
- Authority
- JP
- Japan
- Prior art keywords
- polyamic acid
- polyimide
- polyimide film
- acid copolymer
- stirred
- 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
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐熱性に優れ、高弾
性、低熱膨張性、適度な柔軟性を持つポリイミドフィル
ムを与えるポリアミック酸共重合体、それからなるポリ
イミド共重合体及びポリイミドフィルム並びにそれらの
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 polyamic acid copolymer which gives a polyimide film having excellent heat resistance, high elasticity, low thermal expansion and moderate flexibility, a polyimide copolymer comprising the same, a polyimide film and a polyimide film thereof. And a method for producing the same.
【０００２】[0002]
【従来の技術】従来、ポリイミド樹脂は優れた耐熱性と
ともに電気絶縁性にも優れ、電気機器を初めとして、広
く工業材料として用いられている。ポリイミド樹脂は、
このように他のポリマーに比べ種々の優れた特性を持つ
が、技術の進歩とともに、ポリイミド樹脂に求められる
要求特性も高度なものとなり、用途に応じて種々の性能
を合わせ持つことが望まれている。材料としての強度と
いう点から、高弾性であるということが望ましい。ま
た、適度な柔軟性を持つことも望まれる。温度変化に対
しても寸法変化が小さいことが好ましいので、低熱膨張
性であることが必要である。2. Description of the Related Art Hitherto, a polyimide resin has excellent electrical insulation as well as excellent heat resistance, and is widely used as an industrial material including electric equipment. Polyimide resin is
In this way, it has various superior properties compared to other polymers, but with the advancement of technology, the required properties required for polyimide resin also become advanced, and it is desired to have various performances depending on the application. I have. It is desirable that the material has high elasticity from the viewpoint of strength as a material. It is also desirable to have appropriate flexibility. Since it is preferable that the dimensional change is small with respect to the temperature change, it is necessary to have low thermal expansion.
【０００３】例えば、ピロメリット酸無水物とパラフェ
ニレンジアミンといった剛直鎖のみを用いれば、高弾性
と低熱膨張性を併せ持つポリイミドを合成することがで
きる。しかし、この構造では、非常に脆いフィルムしか
得ることはできない。かくして、高弾性、適度な柔軟性
及び低熱膨張性という物性を充分に満足するポリイミド
が求められている。For example, if only a rigid straight chain such as pyromellitic anhydride and paraphenylenediamine is used, a polyimide having both high elasticity and low thermal expansion can be synthesized. However, with this structure, only very brittle films can be obtained. Thus, there is a need for a polyimide that sufficiently satisfies the physical properties of high elasticity, moderate flexibility, and low thermal expansion.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、耐熱性に優
れ、高弾性、低熱膨張性、適度な柔軟性などの優れた特
性を有するポリイミドフィルムを与えるポリアミック酸
共重合体、それからなるポリイミド共重合体、及びポリ
イミドフィルム並びにそれらの製造方法を提供すること
を目的とする。SUMMARY OF THE INVENTION The present invention relates to a polyamic acid copolymer which gives a polyimide film having excellent properties such as excellent heat resistance, high elasticity, low thermal expansion and moderate flexibility, and a polyimide copolymer comprising the same. An object of the present invention is to provide a polymer, a polyimide film, and a method for producing the same.
【０００５】[0005]
【課題を解決するための手段】上記の問題を解決するた
めに、本発明者らはポリイミドの分子構造について鋭意
検討の結果、特定の構造単位を有するポリイミドが高弾
性、低熱膨張性と適度の柔軟性を備えていることを見い
だし本発明を完成した。即ち、本発明の第１は、下記式Means for Solving the Problems In order to solve the above problems, the present inventors have made intensive studies on the molecular structure of polyimide, and as a result, it has been found that polyimide having a specific structural unit has high elasticity, low thermal expansion property and moderate The inventors have found that the present invention has flexibility and completed the present invention. That is, the first aspect of the present invention is as follows:
【０００６】[0006]
【化４】 Embedded image
【０００７】（ただし、Ｒ2 、Ｒ4 は直線性ジアミン残
基、Ｒ6 は屈曲性ジアミン残基、Ｒ3はピロメリット酸
二無水物残基又はピロメリット酸二無水物の残基を示
し、Ｒ1、Ｒ5 は(Where R 2 and R 4 are linear diamine residues, R 6 is a flexible diamine residue, and R 3 is a pyromellitic dianhydride residue or a pyromellitic dianhydride residue) , R 1 , R 5 are
【０００８】[0008]
【化５】 Embedded image
【０００９】の中から任意に選ばれたものの残基であ
り、ｎは３以上の整数を表す。）で表される構造単位を
有するポリアミック酸共重合体を、上記ポリアミック酸
共重合体を製造するための本発明の第２は、少なくとも
１種の直線性ジアミン２ｎ当量に、ピロメリット酸二無
水物又はピロメリット酸二無水物から選ばれる少なくと
も１種のテトラカルボン酸二無水物ｎ当量を加えて反応
させた後、[0009] It is a residue arbitrarily selected from the above, and n represents an integer of 3 or more. A second aspect of the present invention for producing the polyamic acid copolymer having the structural unit represented by the formula (1) is to add 2 n equivalents of at least one linear diamine to pyromellitic dianhydride. After reacting by adding n equivalents of at least one tetracarboxylic dianhydride selected from anhydride or pyromellitic dianhydride,
【００１０】[0010]
【化６】 Embedded image
【００１１】の中から選ばれる少なくとも１種のテトラ
カルボン酸二無水物（ｎ＋１）当量を加えて反応させ、
次いで、少なくとも１種の屈曲性ジアミン１当量加えて
反応させることを特徴とする上記ポリアミック酸共重合
体の製造方法を、At least one tetracarboxylic dianhydride (n + 1) equivalent selected from the above is added and reacted,
Subsequently, the method for producing the polyamic acid copolymer, wherein one equivalent of at least one flexible diamine is added and reacted,
【００１２】本発明の第３は、上記第１発明で得られる
ポリアミック酸共重合体を脱水閉環してなるポリイミド
共重合体を、A third aspect of the present invention is to provide a polyimide copolymer obtained by dehydrating and cyclizing the polyamic acid copolymer obtained in the first aspect,
【００１３】本発明の第４は、上記第２発明で得られる
ポリアミック酸共重合体を脱水閉環することを特徴とす
るポリイミド共重合体の製造方法を、A fourth aspect of the present invention relates to a method for producing a polyimide copolymer, comprising dehydrating and cyclizing the polyamic acid copolymer obtained in the second aspect of the present invention.
【００１４】本発明の第５は、上記第１発明で得られる
ポリアミック酸共重合体を脱水閉環してなる下記構造単
位を有するポリイミドフィルムを、A fifth aspect of the present invention is to provide a polyimide film having the following structural unit obtained by dehydrating and cyclizing the polyamic acid copolymer obtained in the first aspect of the present invention:
【００１５】本発明の第６は、上記第２発明で得られる
ポリアミック酸共重合体を支持体上に流延塗布して脱水
閉環することを特徴とするポリイミドフィルムの製造方
法を、それぞれ内容とするものである。A sixth aspect of the present invention relates to a method for producing a polyimide film, wherein the polyamic acid copolymer obtained in the second aspect is cast on a support and subjected to dehydration and ring closure. Is what you do.
【００１６】以下、本発明を詳細に説明する。本発明の
中で用い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
並ぶ構造を持つジアミン化合物をさす。例えば、Hereinafter, the present invention will be described in detail. The linear diamine used in the present invention does not include a bending group such as an ether group, a methylene group, a propargyl group, a hexafluoropropargyl group, and a carbonyl group in a main chain, and has a nitrogen atom of two amino groups. Diamine compounds having a structure in which the carbon atoms to which they are bonded are aligned. For example,
【００１７】[0017]
【化７】 Embedded image
【００１８】（ただし、ＸはＦ，Ｃｌ，Ｂｒ，ＣＨ3 ，
ＣＨ3 Ｏ又はＣＦ3 を示す。）等のジアミンを例示する
ことができる。(Where X is F, Cl, Br, CH 3 ,
Shows CH 3 O or CF 3 . And the like.
【００１９】一方、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
構造を持つジアミン化合物をさす。例えば、On the other hand, a flexible diamine is an ether group,
A methylene group, a propargyl group, a hexafluoropropargyl group, a diamine containing a bending group such as a carbonyl group in the main chain,
Alternatively, in the case where a bending group is not contained, a diamine compound having a structure in which a nitrogen atom of two amino groups and a carbon atom bonded thereto are not arranged in a straight line. For example,
【００２０】[0020]
【化８】 Embedded image
【００２１】（ただし、ＸはＨ，Ｆ，Ｃｌ，Ｂｒ，ＣＨ
3 −，ＣＨ3 Ｏ−，ＣＦ3 −を示す。）等のジアミンを
例示することができる。一般に、ポリイミドの分子構造
と弾性率は密接な関係にあり、例えばピロメリット酸と
パラフェニレンジアミンといった直線的で剛直な構造を
用いることにより高弾性と低熱膨張性を有するポリイミ
ドフィルムを得ることができるが、この様なフィルムは
同時に脆く柔軟性に欠ける。(Where X is H, F, Cl, Br, CH
3- , CH 3 O- and CF 3 -are shown. And the like. In general, the molecular structure and elastic modulus of polyimide are closely related, and a polyimide film having high elasticity and low thermal expansion can be obtained by using a linear and rigid structure such as pyromellitic acid and paraphenylenediamine. However, such films are also brittle and lack flexibility.
【００２２】本発明者らは、ポリイミドの分子構造につ
いて種々検討を行った結果、下記の構造単位を有するポ
リイミドが高弾性、低熱膨張性、低吸湿性と適度な柔軟
性を備えていることを見いだし、本発明はかかる知見に
基づくものである。The present inventors have conducted various studies on the molecular structure of polyimide and found that polyimide having the following structural unit has high elasticity, low thermal expansion, low moisture absorption and moderate flexibility. The present invention has been found based on such findings.
【００２３】[0023]
【化９】 Embedded image
【００２４】（ただし、Ｒ2 、Ｒ4 は直線性ジアミン残
基、Ｒ6 は屈曲性ジアミン残基、Ｒ3 はピロメリット酸
二無水物残基又はピロメリット酸二無水物誘導体の残基
を示し、Ｒ1 、Ｒ5 は(Where R 2 and R 4 are linear diamine residues, R 6 is a flexible diamine residue, and R 3 is a pyromellitic dianhydride residue or a pyromellitic dianhydride derivative residue) And R 1 and R 5 are
【００２５】[0025]
【化１０】 Embedded image
【００２６】の中から任意に選ばれたものの残基であ
り、構造単位中の繰り返し数ｎは３以上の整数を表
す。） このポリイミドの平均分子量は、１００００〜１０００
０００であることが望ましい。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、１０
０００００を越えるとポリイミド前駆体であるポリアミ
ック酸ワニスの粘度が高くなりすぎ取扱いが難しくなっ
て好ましくない。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 residue is a residue arbitrarily selected from among the above, and the repeating number n in the structural unit represents an integer of 3 or more. The average molecular weight of this polyimide is 10,000 to 1000
000 is desirable. Average molecular weight 10,000
If it is less than 10, the resulting film becomes brittle, while
If it exceeds 00000, the viscosity of the polyamic acid varnish, which is a polyimide precursor, becomes too high and handling becomes difficult, which is not preferable. It is also possible to compound various organic additives, inorganic fillers, or various reinforcing materials with the polyimide film.
【００２７】構造単位中の繰り返し数ｎは１０以下であ
ることが望ましく、それを越えると柔軟性の低い脆いフ
ィルムになる。またこのような構造を持つポリイミドフ
ィルムの熱膨張係数はいずれも１０-5以下の低熱膨張性
を示す。The number of repetitions n in the structural unit is desirably 10 or less, and if it exceeds this, a brittle film having low flexibility is obtained. In addition, the polyimide film having such a structure has a low thermal expansion coefficient of 10 -5 or less.
【００２８】本発明のポリイミド共重合体及びポリイミ
ドフィルムは上記の様に各構成単位が規則的に並んでい
ることが重要であり、ランダムな構造をとれば上記のよ
うな効果は得られない。このような規則性を実現するた
めには以下の様な合成法を用いる。このポリイミド共重
合体は、その前駆体であるポリアミック酸共重合体溶液
から得られるが、このポリアミック酸共重合体溶液は、
酸二無水物成分とジアミ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。It is important that the constituent units of the polyimide copolymer and the polyimide film of the present invention are regularly arranged as described above, and the above effects cannot be obtained if a random structure is adopted. To realize such regularity, the following synthesis method is used. This polyimide copolymer is obtained from the precursor polyamic acid copolymer solution, the polyamic acid copolymer solution,
It is obtained by polymerizing in an organic polar solvent using substantially equimolar amounts of the acid dianhydride component and the diamine component.
【００２９】ここで該ポリアミック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は、例えば、ジメチ
ルスルホキシド、ジエチルスルホキシド等のスルホキシ
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等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
等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−ピロリドン等のピロリドン系溶
媒、フェノール、ｏ−、ｍ−、またはｐ−クレゾール、
キシレノール、ハロゲン化フェノール、カテコール等の
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−ブチロラクトン等を挙げることができ、これら
を単独または混合物として用いるのが望ましいが、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。The organic polar solvent used in the reaction for producing the polyamic acid copolymer includes, for example, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide N, N-
Acetamide solvents such as dimethylacetamide and N, N-diethylacetamide; pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone; phenol, o-, m- or p-cresol;
Xylenol, halogenated phenols, phenolic solvents such as catechol, or hexamethylphosphoramide, γ-butyrolactone, and the like can be mentioned, and it is preferable to use these alone or as a mixture, and further, xylene, toluene, etc. Partial use of aromatic hydrocarbons is also possible.
【００３０】具体的にポリアミック酸共重合体溶液の合
成法を例示する。 容器に、有機極性溶媒と少なくとも１種の直線性ジア
ミンを２ｎ当量とり、冷却攪拌する。 ピロメリット酸二無水物又はピロメリット酸二無水物
誘導体から選ばれる少なくとも１種のテトラカルボン酸
二無水物ｎ当量を上記混合液に加え、好ましくは２０分
以上冷却攪拌する。 下記から選ばれる少なくとも１種のテトラカルボン酸
二無水物（ｎ＋１）当量を加え、好ましくは２０分以上
冷却攪拌する。A method for synthesizing a polyamic acid copolymer solution will be specifically described. 2 n equivalents of an organic polar solvent and at least one linear diamine are placed in a container, and cooled and stirred. N Equivalent of at least one tetracarboxylic dianhydride selected from pyromellitic dianhydride or a pyromellitic dianhydride derivative is added to the above mixed solution, and the mixture is cooled and stirred preferably for 20 minutes or more. At least one tetracarboxylic dianhydride (n + 1) equivalent selected from the following is added, and the mixture is cooled and stirred preferably for 20 minutes or more.
【００３１】[0031]
【化１１】 Embedded image
【００３２】屈曲性ジアミン１種もしくは２種以上の
１当量を徐々に冷却攪拌しながら加え、該ポリアミック
酸共重合体溶液を得る。 また、このポリアミック酸共重合体は前記の有機極性溶
媒中に５〜４０重量％、好ましくは１０〜３０重量％溶
解されているのが取扱いの面からも望ましい。この芳香
族ポリアミック酸共重合体溶液から本発明のポリイミド
フィルムを得るためには熱的に脱水する熱的方法、脱水
剤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フィルムの伸びや引
張強度等の機械特性がすぐれたものになるので好まし
い。One or more equivalents of one or more flexible diamines are gradually added with cooling and stirring to obtain the polyamic acid copolymer solution. The polyamic acid copolymer is preferably dissolved in the organic polar solvent in an amount of 5 to 40% by weight, preferably 10 to 30% by weight, from the viewpoint of handling. In order to obtain the polyimide film of the present invention from the aromatic polyamic acid copolymer solution, any of a thermal method of thermally dehydrating and a chemical method using a dehydrating agent may be used. This is preferable because the resulting polyimide film has excellent mechanical properties such as elongation and tensile strength.
【００３３】以下にポリイミドフィルムの作製方法につ
いての例を説明する。上記ポリアミック酸重合体又はそ
の溶液に化学量論以上の脱水剤と触媒量の第３級アミン
を加えた溶液をトラム或いはエンドレスベルト上に流延
又は塗布して膜状とし、その膜を１５０℃以下の温度で
約５〜９０分間乾燥し、自己支持性のポリアミック酸の
膜を得る。ついで、これを支持体より引き剥がし端部を
固定する。その後約１００〜５００℃まで徐々に加熱す
ることによりイミド化し、冷却後ドラム又はエンドレス
ベルトより取り外し、本発明のポリイミドフィルムを得
る。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、無水安息香酸等の芳香族酸無水物などが
挙げられる。また触媒としては、例えばトリエチルアミ
ンなどの脂肪族第３級アミン類、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
リン等の複素環式第３級アミン類などが挙げられる。An example of a method for producing a polyimide film will be described below. A solution obtained by adding a dehydrating agent having a stoichiometric amount or more and a catalytic amount of a tertiary amine to the polyamic acid polymer or a solution thereof is cast or coated on a tram or an endless belt to form a film. It is dried at the following temperature for about 5 to 90 minutes to obtain a self-supporting polyamic acid film. Next, this is peeled off from the support and the end is fixed. Thereafter, it is imidized by gradually heating to about 100 to 500 ° C., and after cooling, is removed from a drum or an endless belt to obtain a polyimide film of the present invention. Examples of the dehydrating agent mentioned here include aliphatic acid anhydrides such as acetic anhydride, and aromatic acid anhydrides such as benzoic anhydride. Examples of the catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, picoline and isoquinoline.
【００３４】[0034]
【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、ＯＤＡは４，４′−ジアミノジフェニ
ルエーテル、ＢＡＰＢは４，４′−ビス（４−アミノフ
ェノキシ）ビフェニル、ｐ−ＰＤＡはパラフェニレンジ
アミン、ＴＰＥ−Ｑは１，４−ビス（４−アミノフェノ
キシ）ベンゼン、ＢＡＰＰは２，２−ビス〔４−（４−
アミノフェノキシ）フェニル〕プロパン、ＰＭＤＡはピ
ロメリット酸二無水物、ＢＴＤＡはベンゾフェノンテト
ラカルボン酸二無水物、ＢＰＤＡは３，３′，４，４′
−ビフェニル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, ODA is 4,4'-diaminodiphenyl ether, BAPB is 4,4'-bis (4-aminophenoxy) biphenyl, p-PDA is paraphenylenediamine, and TPE-Q is 1,4-bis (4- Aminophenoxy) benzene and BAPP are 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane, PMDA is pyromellitic dianhydride, BTDA is benzophenonetetracarboxylic dianhydride, BPDA is 3,3 ', 4,4'
-Biphenyltetracarboxylic dianhydride, DMF represents dimethylformamide.
【００３５】実施例１ ２リットルのセパラブルフラスコにＤＭＦとｐ−ＰＤＡ
を６当量とり、ジアミノ化合物が完全に溶解するまで室
温でよく混合しその後、氷で冷却しながら攪拌した。次
に、ＰＭＤＡ３当量を加え、４０分冷却攪拌した。そし
て、ＢＴＤＡ４当量を一気に加え、４０分冷却攪拌し
た。ＯＤＡ１当量をＤＭＦに溶かし、徐々に加え、この
あと１時間冷却攪拌し、ポリアミック酸のＤＭＦ溶液を
得た。なおＤＭＦの使用量は、ジアミノ化合物および芳
香族テトラカルボン酸化合物のモノマー仕込濃度が１８
重量％となるようにした。ポリアミック酸溶液をガラス
板上に流延塗布し、約１００℃に約３０分間乾燥後、ポ
リアミック酸塗膜をガラス板より剥し、その塗膜を支持
枠に固定し、その後約１００℃で約３０分間、約２００
℃で約６０分間、約３００℃で約６０分間加熱し、脱水
閉環乾燥し、約２５ミクロンのポリイミドフィルムを得
た。得られたポリイミドフィルムの物性を表１に示し
た。Example 1 DMF and p-PDA were placed in a 2-liter separable flask.
Was mixed at room temperature until the diamino compound was completely dissolved, and then stirred while cooling with ice. Next, 3 equivalents of PMDA were added, and the mixture was cooled and stirred for 40 minutes. Then, 4 equivalents of BTDA were added all at once, and the mixture was cooled and stirred for 40 minutes. One equivalent of ODA was dissolved in DMF, added gradually, and then cooled and stirred for 1 hour to obtain a DMF solution of polyamic acid. The amount of DMF used is such that the monomer charge concentration of the diamino compound and the aromatic tetracarboxylic acid compound is 18%.
% By weight. The polyamic acid solution was applied on a glass plate by casting and dried at about 100 ° C. for about 30 minutes. Then, the polyamic acid coating film was peeled off from the glass plate, and the coating film was fixed on a support frame. About 200 minutes
The resultant was heated at about 60 ° C. for about 60 minutes and at about 300 ° C. for about 60 minutes. Table 1 shows the physical properties of the obtained polyimide film.
【００３６】実施例２ ２リットルのセパラブルフラスコにＤＭＦとｐ−ＰＤＡ
を６当量とり、ジアミノ化合物が完全に溶解するまで室
温でよく混合しその後、氷で冷却しながら攪拌した。次
に、ＰＭＤＡ３当量を加え、４０分冷却攪拌した。そし
て、ＢＴＤＡ４当量を一気に加え、４０分冷却攪拌し
た。ＴＰＥ−Ｑ１当量をＤＭＦに溶かし、徐々に加え、
このあと１時間冷却攪拌し、ポリアミック酸のＤＭＦ溶
液を得た。実施例１と同様の方法で焼成し、ポリイミド
フィルムを得た。得られたポリイミドフィルムの物性を
表１に示した。Example 2 DMF and p-PDA were placed in a 2-liter separable flask.
Was mixed at room temperature until the diamino compound was completely dissolved, and then stirred while cooling with ice. Next, 3 equivalents of PMDA were added, and the mixture was cooled and stirred for 40 minutes. Then, 4 equivalents of BTDA were added all at once, and the mixture was cooled and stirred for 40 minutes. Dissolve 1 equivalent of TPE-Q in DMF and slowly add
Thereafter, the mixture was cooled and stirred for 1 hour to obtain a polyamic acid DMF solution. It was fired in the same manner as in Example 1 to obtain a polyimide film. Table 1 shows the physical properties of the obtained polyimide film.
【００３７】実施例３ ２リットルのセパラブルフラスコにＤＭＦとｐ−ＰＤＡ
を６当量とり、ジアミノ化合物が完全に溶解するまで室
温でよく混合しその後、氷で冷却しながら攪拌した。次
に、ＰＭＤＡ３当量を加え、４０分冷却攪拌した。そし
て、ＢＴＤＡ４当量を一気に加え、４０分冷却攪拌し
た。ＢＡＰＢ１当量をＤＭＦに溶かし、徐々に加え、こ
のあと１時間冷却攪拌し、ポリアミック酸のＤＭＦ溶液
を得た。実施例１と同様の方法で焼成し、ポリイミドフ
ィルムを得た。得られたポリイミドフィルムの物性を表
１に示した。Example 3 DMF and p-PDA were placed in a 2-liter separable flask.
Was mixed at room temperature until the diamino compound was completely dissolved, and then stirred while cooling with ice. Next, 3 equivalents of PMDA were added, and the mixture was cooled and stirred for 40 minutes. Then, 4 equivalents of BTDA were added all at once, and the mixture was cooled and stirred for 40 minutes. One equivalent of BAPB was dissolved in DMF, added gradually, and then cooled and stirred for 1 hour to obtain a polyamic acid DMF solution. It was fired in the same manner as in Example 1 to obtain a polyimide film. Table 1 shows the physical properties of the obtained polyimide film.
【００３８】実施例４ ２リットルのセパラブルフラスコにＤＭＦとｐ−ＰＤＡ
を６当量とり、ジアミノ化合物が完全に溶解するまで室
温でよく混合しその後、氷で冷却しながら攪拌した。次
に、ＰＭＤＡ３当量を加え、４０分冷却攪拌した。そし
て、ＢＴＤＡ４当量を一気に加え、４０分冷却攪拌し
た。ＢＡＰＰ１当量をＤＭＦに溶かし、徐々に加え、こ
のあと１時間冷却攪拌し、ポリアミック酸のＤＭＦ溶液
を得た。実施例１と同様の方法で焼成し、ポリイミドフ
ィルムを得た。得られたポリイミドフィルムの物性を表
１に示した。Example 4 DMF and p-PDA were placed in a 2-liter separable flask.
Was mixed at room temperature until the diamino compound was completely dissolved, and then stirred while cooling with ice. Next, 3 equivalents of PMDA were added, and the mixture was cooled and stirred for 40 minutes. Then, 4 equivalents of BTDA were added all at once, and the mixture was cooled and stirred for 40 minutes. One equivalent of BAPP was dissolved in DMF, added gradually, and then cooled and stirred for 1 hour to obtain a DMF solution of polyamic acid. It was fired in the same manner as in Example 1 to obtain a polyimide film. Table 1 shows the physical properties of the obtained polyimide film.
【００３９】実施例５ ２リットルのセパラブルフラスコにＤＭＦとｐ−ＰＤＡ
を８当量とり、ジアミノ化合物が完全に溶解するまで室
温でよく混合しその後、氷で冷却しながら攪拌した。次
に、ＰＭＤＡ４当量を加え、４０分冷却攪拌した。そし
て、ＢＴＤＡ５当量を一気に加え、４０分冷却攪拌し
た。ＯＤＡ１当量をＤＭＦに溶かし、徐々に加え、この
あと１時間冷却攪拌し、ポリアミック酸のＤＭＦ溶液を
得た。実施例１と同様の方法で焼成し、ポリイミドフィ
ルムを得た。得られたポリイミドフィルムの物性を表１
に示した。Example 5 DMF and p-PDA were placed in a 2-liter separable flask.
Was added at room temperature until the diamino compound was completely dissolved, and then stirred while cooling with ice. Next, 4 equivalents of PMDA were added, and the mixture was cooled and stirred for 40 minutes. Then, 5 equivalents of BTDA were added all at once, and the mixture was cooled and stirred for 40 minutes. One equivalent of ODA was dissolved in DMF, added gradually, and then cooled and stirred for 1 hour to obtain a DMF solution of polyamic acid. It was fired in the same manner as in Example 1 to obtain a polyimide film. Table 1 shows the physical properties of the obtained polyimide film.
It was shown to.
【００４０】実施例６ ２リットルのセパラブルフラスコにＤＭＦとｐ−ＰＤＡ
を８当量とり、ジアミノ化合物が完全に溶解するまで室
温でよく混合しその後、氷で冷却しながら攪拌した。次
に、ＰＭＤＡ４当量を加え、４０分冷却攪拌した。そし
て、ＢＰＤＡ５当量を一気に加え、４０分冷却攪拌し
た。ＴＰＥ−Ｑ１当量をＤＭＦに溶かし、徐々に加え、
このあと１時間冷却攪拌し、ポリアミック酸のＤＭＦ溶
液を得た。実施例１と同様の方法で焼成し、ポリイミド
フィルムを得た。得られたポリイミドフィルムの物性を
表１に示した。Example 6 DMF and p-PDA were placed in a 2-liter separable flask.
Was added at room temperature until the diamino compound was completely dissolved, and then stirred while cooling with ice. Next, 4 equivalents of PMDA were added, and the mixture was cooled and stirred for 40 minutes. Then, 5 equivalents of BPDA were added at once, and the mixture was cooled and stirred for 40 minutes. Dissolve 1 equivalent of TPE-Q in DMF and slowly add
Thereafter, the mixture was cooled and stirred for 1 hour to obtain a polyamic acid DMF solution. It was fired in the same manner as in Example 1 to obtain a polyimide film. Table 1 shows the physical properties of the obtained polyimide film.
【００４１】実施例７ ２リットルのセパラブルフラスコにＤＭＦとｐ−ＰＤＡ
を６当量とり、ジアミノ化合物が完全に溶解するまで室
温でよく混合しその後、氷で冷却しながら攪拌した。次
に、ＰＭＤＡ３当量を加え、４０分冷却攪拌した。そし
て、ＢＰＤＡ４当量を一気に加え、４０分冷却攪拌し
た。ＯＤＡ１当量をＤＭＦに溶かし、徐々に加え、この
あと１時間冷却攪拌し、ポリアミック酸のＤＭＦ溶液を
得た。実施例１と同様の方法で焼成し、ポリイミドフィ
ルムを得た。得られたポリイミドフィルムの物性を表１
に示した。Example 7 DMF and p-PDA were placed in a 2-liter separable flask.
Was mixed at room temperature until the diamino compound was completely dissolved, and then stirred while cooling with ice. Next, 3 equivalents of PMDA were added, and the mixture was cooled and stirred for 40 minutes. Then, 4 equivalents of BPDA were added all at once, and the mixture was cooled and stirred for 40 minutes. One equivalent of ODA was dissolved in DMF, added gradually, and then cooled and stirred for 1 hour to obtain a DMF solution of polyamic acid. It was fired in the same manner as in Example 1 to obtain a polyimide film. Table 1 shows the physical properties of the obtained polyimide film.
It was shown to.
【００４２】比較例１ 実施例１と同様の方法により、ＰＭＤＡとＯＤＡを等モ
ルずつ用いて、ポリイミドフィルムを得た。得られたポ
リイミドフィルムの物性を表１に示した。Comparative Example 1 In the same manner as in Example 1, a polyimide film was obtained by using PMDA and ODA in equimolar amounts. Table 1 shows the physical properties of the obtained polyimide film.
【００４３】比較例２ ２リットルのセパラブルフラスコにＤＭＦ、ｐ−ＰＤＡ
を６当量と、ＯＤＡ１当量をとり、ジアミノ化合物が完
全に溶解するまで室温でよく混合しその後、氷で冷却し
ながら攪拌した。次に、ＢＴＤＡ４当量とＰＭＤＡ３当
量を徐々に加え、このあと１時間冷却攪拌し、ポリアミ
ック酸のＤＭＦ溶液を得た。実施例１と同様の方法で焼
成し、ポリイミドフィルムを得た。得られたポリイミド
フィルムの物性を表１に示した。Comparative Example 2 DMF and p-PDA were placed in a 2-liter separable flask.
6 equivalents and 1 equivalent of ODA were mixed well at room temperature until the diamino compound was completely dissolved, and then stirred while cooling with ice. Next, 4 equivalents of BTDA and 3 equivalents of PMDA were gradually added, followed by cooling and stirring for 1 hour to obtain a DMF solution of polyamic acid. It was fired in the same manner as in Example 1 to obtain a polyimide film. Table 1 shows the physical properties of the obtained polyimide film.
【００４４】[0044]
【表１】 １）理学電機製 ＴＭＡ８１４０により測定した１００
〜２００℃の熱膨張係数[Table 1] 1) 100 measured by TMA8140 manufactured by Rigaku Denki
Thermal expansion coefficient up to 200 ° C
【００４５】[0045]
【発明の効果】以上のように、酸二無水物及びジアミン
の配列を制御することにより、高弾性、低熱膨張性、適
度な柔軟性を持つポリイミドフィルムを得ることができ
る。As described above, by controlling the arrangement of the acid dianhydride and the diamine, a polyimide film having high elasticity, low thermal expansion and moderate flexibility can be obtained.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭59−108029（ＪＰ，Ａ) 特開 昭60−210894（ＪＰ，Ａ) 特開 昭63−166287（ＪＰ，Ａ) 特開 昭63−254131（ＪＰ，Ａ) 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-59-108029 (JP, A) JP-A-60-210894 (JP, A) JP-A-63-166287 (JP, A) 254131 (JP, A) 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 (6)
曲性ジアミン残基、Ｒ3はピロメリット酸二無水物残基
又はピロメリット酸二無水物の残基を示し、Ｒ1、Ｒ5
は 【化２】 の中から任意に選ばれたものの残基であり、ｎは３以上
の整数を表す。）で表される構造単位を有するポリアミ
ック酸共重合体。[Claim 1] The following formula: (However, R 2 and R 4 each represent a linear diamine residue, R 6 represents a flexible diamine residue, R 3 represents a pyromellitic dianhydride residue or a pyromellitic dianhydride residue, and R 1 , R 5
Is And n is an integer of 3 or more. A) a polyamic acid copolymer having a structural unit represented by the formula:
量に、ピロメリット酸二無水物又はピロメリット酸二無
水物から選ばれる少なくとも１種のテトラカルボン酸二
無水物ｎ当量を加えて反応させた後、 【化３】 の中から選ばれる少なくとも１種のテトラカルボン酸二
無水物（ｎ＋１）当量を加えて反応させ、次いで、少な
くとも１種の屈曲性ジアミン１当量加えて反応させるこ
とを特徴とする請求項１記載のポリアミック酸共重合体
の製造方法。2. A reaction is performed by adding 2 equivalents of at least one linear diamine to n equivalents of at least one tetracarboxylic dianhydride selected from pyromellitic dianhydride or pyromellitic dianhydride. Later, The reaction according to claim 1, wherein at least one kind of tetracarboxylic dianhydride (n + 1) selected from the group consisting of (n + 1) is added and reacted, and then at least one kind of flexible diamine is added and reacted. A method for producing a polyamic acid copolymer.
を脱水閉環してなるポリイミド共重合体。3. A polyimide copolymer obtained by dehydrating and ring-closing the polyamic acid copolymer according to claim 1.
るポリアミック酸共重合体を脱水閉環することを特徴と
するポリイミド共重合体の製造方法。4. A method for producing a polyimide copolymer, comprising subjecting the polyamic acid copolymer obtained in the production method according to claim 2 to dehydration ring closure.
を脱水閉環してなるポリイミドフィルム。5. A polyimide film obtained by dehydrating and ring-closing the polyamic acid copolymer according to claim 1.
るポリアミック酸共重合体を支持体上に流延塗布して脱
水閉環することを特徴とするポリイミドフィルムの製造
方法。6. A method for producing a polyimide film, comprising casting the polyamic acid copolymer obtained in the production method according to claim 2 on a support and dehydrating and ring-closing the polyimide film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26279291A JP3048702B2 (en) | 1991-09-13 | 1991-09-13 | Polyamic acid copolymer, polyimide copolymer, polyimide film and methods for producing them |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26279291A JP3048702B2 (en) | 1991-09-13 | 1991-09-13 | Polyamic acid copolymer, polyimide copolymer, polyimide film and methods for producing them |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0570590A JPH0570590A (en) | 1993-03-23 |
| JP3048702B2 true JP3048702B2 (en) | 2000-06-05 |
Family
ID=17380671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26279291A Expired - Lifetime JP3048702B2 (en) | 1991-09-13 | 1991-09-13 | Polyamic acid copolymer, polyimide copolymer, polyimide film and methods for producing them |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3048702B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11152331A (en) * | 1997-11-20 | 1999-06-08 | Kanegafuchi Chem Ind Co Ltd | Production of polyamic acid and polyimide film |
| KR20100017883A (en) * | 2004-09-24 | 2010-02-16 | 가부시키가이샤 가네카 | Process for production of polyimide film having high adhesiveness |
| US20080097073A1 (en) * | 2005-01-18 | 2008-04-24 | Kaneka Corporation | Novel Polyimide Film With Improved Adhesiveness |
| EP2782417A4 (en) | 2011-11-14 | 2015-08-05 | Konica Minolta Inc | Organic electroluminescence element and planar light-emitting body |
-
1991
- 1991-09-13 JP JP26279291A patent/JP3048702B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0570590A (en) | 1993-03-23 |
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