JP2006104440A

JP2006104440A - Soluble terminal-modified imide oligomer and varnish and cured product thereof

Info

Publication number: JP2006104440A
Application number: JP2005183950A
Authority: JP
Inventors: Yuichi Ishida; 雄一石田; Toshio Ogasawara; 俊夫小笠原; Rikio Yokota; 力男横田; Takeshi Goto; 健後藤; Takeshi Sasaki; 健佐々木; Hideo Ozawa; 秀生小澤
Original assignee: Kawasaki Heavy Industries Ltd; Japan Aerospace Exploration Agency JAXA; Ube Industries Ltd
Current assignee: Kawasaki Heavy Industries Ltd; Japan Aerospace Exploration Agency JAXA; Ube Corp
Priority date: 2004-09-08
Filing date: 2005-06-23
Publication date: 2006-04-20
Anticipated expiration: 2025-06-23
Also published as: JP4787552B2

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new terminal-modified imide oligomer and varnish excellent in solubility in an organic solvent, solution storage stability and forming properties such as low melting viscosity and having high heat resistance and high mechanical properties such as tensile strength and elongation and a cured product thereof. <P>SOLUTION: The soluble new terminal-modified imide oligomer is represented by general formula (1) [R is an aromatic diamine residue; m and n each satisfy the formulas m≥0, n≥0, 1≤m+n≤20 and 0≤m/(m+n)≤1 and sequence of recurring unit may be block-like or random-like]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、末端変性イミドオリゴマーおよびワニス並びにその硬化物に関し、特に、航空機や宇宙産業用機器をはじめとして易成形性かつ高耐熱性が求められる広い分野で使用可能な部材の材料に関するものである。 TECHNICAL FIELD The present invention relates to terminal-modified imide oligomers and varnishes and cured products thereof, and particularly relates to materials for members that can be used in a wide range of fields that require easy moldability and high heat resistance, including aircraft and space industry equipment. .

芳香族ポリイミドは高分子系で最高レベルの耐熱性を有し、機械特性、電気特性などにも優れていることから、広い分野で素材として用いられている。
一方、芳香族ポリイミドは一般に加工性に乏しく、特に溶融成形や繊維強化複合材料のマトリックス樹脂として用いることは不向きである。このため、末端を熱架橋基で変性したイミドオリゴマーが提案されている。なかでも、末端を４−フェニルエチニル無水フタル酸で変性したイミドオリゴマーが成形性、耐熱性、力学特性のバランスに優れているとされ、例えば、特許文献１、特許文献２および非特許文献１、非特許文献２において紹介されている。その特許文献１には硬化物の耐熱性および機械的特性が良好で、実用性の高い末端変性イミドオリゴマーおよびその硬化物を提供することを目的とし、２，３，３’
，４’−ビフェニルテトラカルボン酸二無水物と芳香族ジアミン化合物と４−（２−フェニルエチニル）無水フタル酸とを反応させて得られ、対数粘度が０．０５〜１である末端変性イミドオリゴマーおよびその硬化物が開示されている。そして、その発明の効果として、実用性の高い新規な末端変性イミドオリゴマーを得ることができること、また、耐熱性や弾性率、引張強度および伸び等の機械的特性が良好な新規な末端変性イミドオリゴマーの硬化物を得ることができると記載されている。 Aromatic polyimide is a polymer-based material that has the highest level of heat resistance and is excellent in mechanical properties and electrical properties, and is therefore used as a material in a wide range of fields.
On the other hand, aromatic polyimide is generally poor in processability, and is not particularly suitable for use as a matrix resin for melt molding or fiber reinforced composite materials. For this reason, an imide oligomer having a terminal modified with a thermal crosslinking group has been proposed. Among them, an imide oligomer whose terminal is modified with 4-phenylethynyl phthalic anhydride is considered to have excellent balance of moldability, heat resistance, and mechanical properties. For example, Patent Document 1, Patent Document 2, and Non-Patent Document 1, It is introduced in Non-Patent Document 2. The Patent Document 1 aims to provide a terminal-modified imide oligomer having a good heat resistance and mechanical properties of the cured product and high practicality, and a cured product thereof.
, 4′-biphenyltetracarboxylic dianhydride, an aromatic diamine compound and 4- (2-phenylethynyl) phthalic anhydride are reacted to form a terminal-modified imide oligomer having a logarithmic viscosity of 0.05 to 1 And cured products thereof. As an effect of the invention, a novel terminal-modified imide oligomer having high practicality can be obtained, and a novel terminal-modified imide oligomer having excellent mechanical properties such as heat resistance, elastic modulus, tensile strength, and elongation. It is described that a cured product can be obtained.

しかし、これらに紹介されている末端変性イミドオリゴマーは、Ｎ−メチル−２−ピロリドン（以下ＮＭＰと略称する。）などの有機溶媒に室温（本明細書で室温とは２３℃±２℃を想定する。）で２０ｗｔ％以下しか溶解せず、またこのワニスを保存しておくとしばしば数日後にゲル化する現象が見られ、高濃度のワニスを長期間安定に保存しておくことは難しいという問題を持っている。また、溶解性を上げるための手段の一つとして屈曲性の大きい構造を導入する方法が挙げられるが、この場合、一般的に硬化物の耐熱性が低くなる。
特開２０００−２１９７４１号公報「末端変性イミドオリゴマーおよびその硬化物」平成１２年８月８日公開特表２００３−５２６７０４号公報「圧入、トランスファー成形用高能力樹脂組成物とその製造法」平成１５年９月９日公表 P. M. Hergenrotherand J. G. Smith Jr., Polymer, 35, 4857 (1994) R. Yokota, S. Yamamoto, S. Yano, T. Sawaguchi, M. Hasegawa, H. Yamaguchi, H. Ozawa and R. Sato, High Perform. Polym., 13, S61 (2001) However, the terminal-modified imide oligomer introduced in them is assumed to be room temperature (in this specification, room temperature is 23 ° C. ± 2 ° C.) in an organic solvent such as N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP). And only 20 wt% or less is dissolved, and if this varnish is stored, a phenomenon of gelation is often observed after several days, and it is difficult to stably store a high concentration varnish for a long period of time. Have a problem. In addition, as one of the means for increasing the solubility, there is a method of introducing a structure having high flexibility, but in this case, the heat resistance of the cured product is generally lowered.
JP 2000-219741 A "Terminal-modified imide oligomer and cured product thereof" Released on August 8, 2000 JP 2003-526704 A "High-performance resin composition for press-fitting and transfer molding and its manufacturing method" Published on September 9, 2003 PM Hergenrotherand JG Smith Jr., Polymer, 35, 4857 (1994) R. Yokota, S. Yamamoto, S. Yano, T. Sawaguchi, M. Hasegawa, H. Yamaguchi, H. Ozawa and R. Sato, High Perform. Polym., 13, S61 (2001)

本発明は、有機溶媒に対する溶解性、溶液保存安定性および低溶融粘度等の成形性に優れ、硬化物の耐熱性および弾性率、引張強度および伸び等の機械的特性の高い新規な末端変性イミドオリゴマーおよびワニス並びにその硬化物を提供することを目的とする。 The present invention is a novel terminal-modified imide that is excellent in moldability such as solubility in organic solvents, solution storage stability and low melt viscosity, and has high mechanical properties such as heat resistance and elastic modulus, tensile strength and elongation of cured products. An object is to provide oligomers and varnishes and cured products thereof.

本発明は、新規な末端変性イミドオリゴマーとして一般式（１）で表されるものを提示する。

ただし、上記式中、Ｒは芳香族ジアミン残基を表す。ｍおよびｎは、それぞれｍ≧０、ｎ≧０、１≦ｍ＋ｎ≦２０および０≦ｍ／（ｍ＋ｎ）≦１の関係を満たすものであり、繰り返し単位の配列はブロック的、ランダム的のいずれであってもよい。 The present invention presents a novel terminal-modified imide oligomer represented by the general formula (1).

However, in said formula, R represents an aromatic diamine residue. m and n satisfy the relationship of m ≧ 0, n ≧ 0, 1 ≦ m + n ≦ 20 and 0 ≦ m / (m + n) ≦ 1, respectively, and the arrangement of repeating units is either block-like or random There may be.

又、本発明は、式（１）で表される末端変性イミドオリゴマーを含むワニスである。
又、本発明は、式（１）で表される末端変性イミドオリゴマーまたはそのワニスを加熱硬化して得られる硬化物である。 Moreover, this invention is a varnish containing the terminal modified imide oligomer represented by Formula (1).
Moreover, this invention is a hardened | cured material obtained by heat-curing the terminal modified imide oligomer represented by Formula (1), or its varnish.

本発明により、有機溶媒に対する溶解性、溶液保存安定性および低溶融粘度等の成形性に優れ、硬化物の耐熱性および弾性率、引張強度および伸び等の機械的特性の高い新規な末端変性イミドオリゴマーおよびワニス並びにその硬化物を得ることができる。ワニスに用いる溶媒は、Ｎ−メチル−２−ピロリドンなどのアミド系溶媒に加え、窒素非含有であるγ−ブチロラクトンなどのエステル系溶媒、シクロヘキサノンなどのケトン系溶媒も使用できる。このイミドオリゴマーワニスはアミド酸オリゴマーワニスに比べ耐加水分解性に対して大きく優れることから、粘度低下等を起こさずに長期間安定に保存できる。 According to the present invention, a novel terminal-modified imide having excellent moldability such as solubility in organic solvents, solution storage stability and low melt viscosity, and high mechanical properties such as heat resistance and elastic modulus, tensile strength and elongation of the cured product Oligomers and varnishes and cured products thereof can be obtained. As a solvent used for the varnish, in addition to an amide solvent such as N-methyl-2-pyrrolidone, an ester solvent such as γ-butyrolactone and a ketone solvent such as cyclohexanone which are free of nitrogen can be used. Since this imide oligomer varnish is greatly superior in hydrolysis resistance compared to an amic acid oligomer varnish, it can be stored stably for a long period of time without causing a decrease in viscosity.

本発明の一般式（１）で表される末端変性イミドオリゴマーは、２，３，３’，４’−ビフェニルテトラカルボン酸類と９，９−ビス（４−アミノフェニル）フルオレンを含む芳香族ジアミン化合物と４−（２−フェニルエチニル）無水フタル酸（以下、ＰＥＰＡと略記することもある）とを、各酸基の当量の合計と各アミノ基の当量とが概略等量となるようにして、好適には溶媒中で反応させて得られるイミドオリゴマーであって、そのイミドオリゴマーの末端（好適には両末端）に４−（２−フェニルエチニル）無水フタル酸に基づくアセチレン性の付加重合可能な不飽和末端基およびイミドオリゴマーの主鎖にイミド結合を有し、しかも、好ましくは一般式（１）中のｍ、ｎが、ｍ≧０、ｎ≧０、１≦ｍ＋ｎ≦２０および０≦ｍ／（ｍ＋ｎ）≦１、より好ましくは０．２５≦ｍ／（ｍ＋ｎ）≦１、さらに好ましくは０．５≦ｍ／（ｍ＋ｎ）≦１の関係を満たす整数であって比較的低分子量である常温（２３℃）で固体（粉末状）の末端変性イミドオリゴマーである。さらに、ＮＭＰなどの有機溶媒に室温で固形分３０ｗｔ％以上溶解可能な末端変性イミドオリゴマーが好ましい。さらに、硬化後のガラス転移温度（Ｔｇ）が３００℃以上である末端変性イミドオリゴマーが好ましい。 The terminal-modified imide oligomer represented by the general formula (1) of the present invention is an aromatic diamine containing 2,3,3 ′, 4′-biphenyltetracarboxylic acid and 9,9-bis (4-aminophenyl) fluorene. The compound and 4- (2-phenylethynyl) phthalic anhydride (hereinafter sometimes abbreviated as PEPA) are so prepared that the total equivalent of each acid group and the equivalent of each amino group are approximately equivalent. An imide oligomer obtained by reacting in a solvent, preferably an acetylenic addition polymerization based on 4- (2-phenylethynyl) phthalic anhydride at the terminal (preferably both terminals) of the imide oligomer An unsaturated end group and an imide bond in the main chain of the imide oligomer, and preferably m and n in the general formula (1) are m ≧ 0, n ≧ 0, 1 ≦ m + n ≦ 20 and 0 ≦. m / (m n) ≦ 1, more preferably 0.25 ≦ m / (m + n) ≦ 1, more preferably an integer that satisfies the relationship of 0.5 ≦ m / (m + n) ≦ 1, and having a relatively low molecular weight ( It is a terminally modified imide oligomer that is solid (powder) at 23 ° C. Furthermore, a terminal-modified imide oligomer that can be dissolved in an organic solvent such as NMP at a solid content of 30 wt% or more at room temperature is preferable. Furthermore, the terminal modified imide oligomer whose glass transition temperature (Tg) after hardening is 300 degreeC or more is preferable.

前記の２，３，３’，４’−ビフェニルテトラカルボン酸類とは、２，３，３’，４’−ビフェニルテトラカルボン酸、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物（ａ−ＢＰＤＡ）、あるいは２，３，３’，４’−ビフェニルテトラカルボン酸のエステルまたは塩などの酸誘導体であり、特に、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物が最適である。 The 2,3,3 ′, 4′-biphenyltetracarboxylic acids are 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride Product (a-BPDA), or an acid derivative such as an ester or salt of 2,3,3 ′, 4′-biphenyltetracarboxylic acid, in particular, 2,3,3 ′, 4′-biphenyltetracarboxylic acid Anhydrides are optimal.

本発明においては、前記の２，３，３’，４’−ビフェニルテトラカルボン酸類の一部（好ましくは５０モル％以下、特に好ましくは２５モル％以下）が、他の芳香族テトラカルボン酸類、例えば３，３’，４，４’−ビフェニルテトラカルボン酸二無水物（ｓ−ＢＰＤＡ）、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物（ＢＴＤＡ）、ピロメリット酸二無水物（ＰＭＤＡ）、２，２−ビス（３，４−ジカルボキシフェニル）メタン二無水物、ビス（３，４−カルボキシフェニル）エーテル二無水物などで置換されていても良い。 In the present invention, a part of the 2,3,3 ′, 4′-biphenyltetracarboxylic acid (preferably 50 mol% or less, particularly preferably 25 mol% or less) is used as another aromatic tetracarboxylic acid, For example, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA), 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA), pyromellitic dianhydride (PMDA), 2,2-bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-carboxyphenyl) ether dianhydride and the like.

９，９−ビス（４−アミノフェニル）フルオレンとともに用いる前記の芳香族ジアミン化合物としては、１，４−ジアミノベンゼン、１，３−ジアミノベンゼン、１，２−ジアミノベンゼン、２，６−ジエチル−１，３−ジアミノベンゼン、４，６−ジエチル−２−メチル−１，３−ジアミノベンゼン、３，５−ジエチルトルエン−２，６−ジアミン、４，４’−ジアミノジフェニルエーテル（４，４’−ＯＤＡ）、３，４’−ジアミノジフェニルエーテル（３，４’−ＯＤＡ）、３，３’−ジアミノジフェニルエーテル、３，３’−ジアミノベンゾフェノン、４，４’−ジアミノベンゾフェノン、３，３’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルメタン、ビス（２，６−ジエチル−４−アミノフェニル）メタン、４，４’−メチレン−ビス（２，６−ジエチルアニリン）、ビス（２−エチル−６−メチル−４−アミノフェニル）メタン、４，４’−メチレン−ビス（２−エチル−６−メチルアニリン）、２，２−ビス（３−アミノフェニル）プロパン、２，２−ビス（４−アミノフェニル）プロパン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス（３−アミノフェノキシ）ベンゼン、１，４−ビス（４−アミノフェノキシ）ベンゼン、１，４−ビス（３−アミノフェノキシ）ベンゼン、ベンジジン、３，３’−ジメチルベンジジン、２，２−ビス（４−アミノフェノキシ）プロパン、２，２−ビス（３−アミノフェノキシ）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などを挙げることができ、それらを単独、あるいは２種以上を併用することができる。特に、芳香族ジアミン化合物として、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あるいは１，３−ビス（４−アミノフェノキシ）ベンゼンが好適である。 Examples of the aromatic diamine compound used together with 9,9-bis (4-aminophenyl) fluorene include 1,4-diaminobenzene, 1,3-diaminobenzene, 1,2-diaminobenzene, 2,6-diethyl- 1,3-diaminobenzene, 4,6-diethyl-2-methyl-1,3-diaminobenzene, 3,5-diethyltoluene-2,6-diamine, 4,4′-diaminodiphenyl ether (4,4′- ODA), 3,4'-diaminodiphenyl ether (3,4'-ODA), 3,3'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane 4,4′-diaminodiphenylmethane, bis (2,6-diethyl-4-aminophenyl) methane, '-Methylene-bis (2,6-diethylaniline), bis (2-ethyl-6-methyl-4-aminophenyl) methane, 4,4'-methylene-bis (2-ethyl-6-methylaniline), 2,2-bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) Benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, benzidine, 3,3′-dimethylbenzidine, 2,2-bis (4-aminophenoxy) propane 2,2-bis (3-aminophenoxy) propane, 2,2-bis [4 ′-(4 ″ -aminophenoxy) phenyl] hexafluoropropane, etc. Bets can be, can be used in combination thereof alone, or two or more. In particular, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, or 1,3-bis (4-aminophenoxy) benzene is preferable as the aromatic diamine compound.

本発明においては、末端変性（エンドキャップ）用の不飽和酸二無水物として４−（２−フェニルエチニル）無水フタル酸を使用する。前記の４−（２−フェニルエチニル）無水フタル酸は、酸類の合計量に対して５−２００モル％、特に５−１５０モル％の範囲内の割合で使用することが好ましい。 In the present invention, 4- (2-phenylethynyl) phthalic anhydride is used as the unsaturated acid dianhydride for terminal modification (end cap). The 4- (2-phenylethynyl) phthalic anhydride is preferably used in a proportion within the range of 5-200 mol%, particularly 5-150 mol%, based on the total amount of acids.

前記の有機溶媒としては、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、Ｎ，Ｎ−ジエチルアセトアミド、Ｎ−メチルカプロラクタム、γ−ブチロラクトン（ＧＢＬ）、シクロヘキサノンなどが挙げられる。これらの溶媒は単独で用いてもよく、２種以上を併用してもよい。これらの溶媒の選択に関しては可溶性ポリイミドについての公知技術を適用することができる。 Examples of the organic solvent include N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), N, N-diethylacetamide, N-methylcaprolactam, γ-butyrolactone (GBL), cyclohexanone, and the like. Can be mentioned. These solvents may be used alone or in combination of two or more. With respect to the selection of these solvents, known techniques for soluble polyimides can be applied.

これらイミドオリゴマーワニスは加水分解の恐れがないため、アミド酸オリゴマーワニスに比べ粘度低下等を起こさずに長期間安定に保存できる。長期間保存する際の溶媒は、ゲル化を防ぐためにより良溶媒であるＮ−メチル−２−ピロリドンなどのアミド系溶媒を用いることが望ましい。 Since these imide oligomer varnishes have no fear of hydrolysis, they can be stably stored for a long period of time without causing a decrease in viscosity or the like as compared with an amic acid oligomer varnish. As a solvent for long-term storage, it is desirable to use an amide solvent such as N-methyl-2-pyrrolidone, which is a good solvent, in order to prevent gelation.

以下、製造法の例について説明する。
本発明の末端変性イミドオリゴマーは、例えば、前記の２，３，３’，４’−ビフェニルテトラカルボン酸類（特に、この酸二無水物）と、９，９−ビス（４−アミノフェニル）フルオレンを含む芳香族ジアミン化合物と、４−（２−フェニルエチニル）無水フタル酸とが、全成分の酸無水物基（または隣接するジカルボン酸基）の当量の全量とアミノ基の全量とがほぼ等量になるように使用して、各成分を、前述の溶媒中で、約１００℃以下、特に８０℃以下の反応温度で重合させて、「アミド−酸結合を有するオリゴマー」を生成し、次いで、そのアミド酸オリゴマー（アミック酸オリゴマーともいう）を、約０〜１４０℃の低温でイミド化剤を添加する方法によるか、あるいは１４０〜２７５℃の高温に加熱する方法によるかして、脱水・環化させて、末端に４−（２−フェニルエチニル）無水フタル酸残基を有するイミドオリゴマーを得ることができる。 Hereinafter, an example of the manufacturing method will be described.
The terminal-modified imide oligomer of the present invention includes, for example, the aforementioned 2,3,3 ′, 4′-biphenyltetracarboxylic acid (particularly, this acid dianhydride) and 9,9-bis (4-aminophenyl) fluorene. And 4- (2-phenylethynyl) phthalic anhydride are substantially equal in the total amount of acid anhydride groups (or adjacent dicarboxylic acid groups) and the total amount of amino groups. In amounts, each component is polymerized in the aforementioned solvent at a reaction temperature of about 100 ° C. or less, particularly 80 ° C. or less to produce an “oligomer having an amide-acid bond”; The amidic acid oligomer (also referred to as an amic acid oligomer) is dehydrated by a method of adding an imidizing agent at a low temperature of about 0 to 140 ° C or a method of heating to a high temperature of 140 to 275 ° C. Is cyclized, it is possible to obtain the ends 4- (2-phenylethynyl) imide oligomer having a phthalic anhydride residue.

本発明の末端変性イミドオリゴマーの特に好ましい製法としては、例えば９，９−ビス（４−アミノフェニル）フルオレンを含む芳香族ジアミン化合物を前述の溶媒中に均一に溶解後、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物を溶液中に加えて均一に溶解後約５〜６０℃の反応温度で１〜１８０分程度攪拌し、この反応溶液に、４−（２−フェニルエチニル）無水フタル酸を加えて均一に溶解後約５〜６０℃の反応温度で１〜１８０分程度攪拌しながら反応させて前記の末端変性アミド酸オリゴマーを生成した後、その反応液を１４０〜２７５℃で５分〜２４時間攪拌して前記のアミド酸オリゴマーをイミド化反応させて末端変性イミドオリゴマーを生成させ、必要ならば、反応液を室温付近まで冷却する方法を挙げることができる。前記の反応において、全反応工程あるいは一部の反応工程を窒素ガス、アルゴンガスなどの不活性ガスの雰囲気あるいは真空中で行うことが好適である。 As a particularly preferable production method of the terminal-modified imide oligomer of the present invention, for example, an aromatic diamine compound containing 9,9-bis (4-aminophenyl) fluorene is uniformly dissolved in the aforementioned solvent, and then 2, 3, 3 ′. , 4′-biphenyltetracarboxylic dianhydride is added to the solution and uniformly dissolved, and then stirred at a reaction temperature of about 5 to 60 ° C. for about 1 to 180 minutes. To this reaction solution, 4- (2-phenylethynyl) ) After the phthalic anhydride is added and dissolved uniformly, the reaction is carried out at a reaction temperature of about 5 to 60 ° C. with stirring for about 1 to 180 minutes to produce the terminal-modified amic acid oligomer. Examples include a method in which the amidic acid oligomer is imidized by stirring at a temperature of 5 minutes to 24 hours to form a terminal-modified imide oligomer, and if necessary, the reaction solution is cooled to around room temperature. Can. In the above reaction, it is preferable that all or some of the reaction steps are performed in an atmosphere of an inert gas such as nitrogen gas or argon gas or in a vacuum.

前述のようにして生成した末端変性イミドオリゴマーは、必要があれば反応液を水中等に注ぎ込んで、粉末状の生成物として単離して、粉末状として、あるいは必要なときにその粉末生成物を溶媒に溶解して使用してもよく、また、反応液を、そのままか、あるいは適宜濃縮または希釈するかして、末端変性イミドオリゴマーの溶液組成物（ワニス）として使用してもよい。なお、本発明の末端変性オリゴマーは、分子量の異なるものを混合したものでもよい。また、本発明の末端変性イミドオリゴマーは、他の可溶性ポリイミドと混合してもよい。 The terminal-modified imide oligomer produced as described above can be isolated by pouring the reaction solution into water or the like, if necessary, and isolated as a powdery product, or as a powdery product or when necessary. You may use it, melt | dissolving in a solvent, and you may use it as a solution composition (varnish) of a terminal-modified imide oligomer by making a reaction liquid as it is, or concentrating or diluting suitably. The terminal-modified oligomer of the present invention may be a mixture of different molecular weights. Moreover, you may mix the terminal modified imide oligomer of this invention with another soluble polyimide.

本発明の末端変性イミドオリゴマーの硬化物は、例えば、前記の末端変性イミドオリゴマーのワニスを支持体に塗布し、２８０〜５００℃で５〜２００分間加熱硬化してフィルムとすることができる。また、末端変性イミドオリゴマーの粉体を金型などの型内に充填し、１０〜２８０℃で１〜１０００ｋｇ／ｃｍ２で１秒〜１００分程度の圧縮成形によって予備成形体を形成し、この予備成形体を２８０〜５００℃で１０分〜４０時間程度加熱して、硬化物を得ることができる。 The cured product of the terminal-modified imide oligomer of the present invention can be obtained, for example, by coating the above-mentioned terminal-modified imide oligomer varnish on a support and heating and curing at 280 to 500 ° C. for 5 to 200 minutes. Further, the terminal-modified imide oligomer powder is filled in a mold such as a mold, and a preform is formed by compression molding at 10 to 280 ° C. at 1 to 1000 kg / cm 2 for about 1 second to 100 minutes. The molded body can be heated at 280 to 500 ° C. for about 10 minutes to 40 hours to obtain a cured product.

以下に本発明を説明するために実施例を示すが、これによって本発明を限定するものではない。
各特性の測定条件は、次のとおりとした。
試験方法
（１）核磁気共鳴スペクトル分析（¹Ｈ−ＮＭＲ）：日本電子製ＪＮＭ−ＡＬ３００型を用いて共鳴周波数３００ＭＨｚで測定した。測定溶媒は、重水素化溶媒である重水素化ジメチルスルホキシドＤＭＳＯ−ｄ₆を用いた。
（２）赤外分光分析（ＩＲ）：日本分光製ＦＴ／ＩＲ６１０型を用いて、ＫＢｒ錠剤法により測定した。
（３）熱重量分析：セイコーインスツルメンツ製ＴＧＡ−６２００型熱重量分析装置（ＴＧＡ）を用い、アルゴン気流下、１０℃／ｍｉｎ．の昇温速度により測定した。
（４）ガラス転移温度：セイコーインスツルメンツ製ＤＳＣ−６２００型示差走査熱量計（ＤＳＣ）を用い、アルゴン気流下、１０℃／ｍｉｎ．の昇温速度により測定した。
（５）レオロジー測定：ＴＡインスツルメンツ製ＡＲ２０００型レオメーターを用い、２５ｍｍパラレルプレートで４℃／ｍｉｎ．の昇温速度により測定した。
（６）引張試験：オリエンテック社製ＴＥＮＳＩＬＯＮ／ＵＴＭ−II−２０を用い、室温にて、引張速度５ｍｍ／ｍｉｎで行った。試験片形状は、長さ２０ｍｍ、幅３ｍｍ、厚さ８０−１１５μｍのフィルムとした。 Examples are given below to illustrate the present invention, but the present invention is not limited thereby.
The measurement conditions for each characteristic were as follows.
Test Method (1) Nuclear Magnetic Resonance Spectrum Analysis ( ¹ H-NMR): Measured at a resonance frequency of 300 MHz using a JNM-AL300 type manufactured by JEOL. As a measurement solvent, deuterated dimethyl sulfoxide DMSO-d ₆ which is a deuterated solvent was used.
(2) Infrared spectroscopic analysis (IR): Measured by KBr tablet method using FT / IR610 type manufactured by JASCO Corporation.
(3) Thermogravimetric analysis: A TGA-6200 type thermogravimetric analyzer (TGA) manufactured by Seiko Instruments Inc. was used at 10 ° C./min. It measured with the temperature increase rate of.
(4) Glass transition temperature: DSC-6200 type differential scanning calorimeter (DSC) manufactured by Seiko Instruments Inc. was used at 10 ° C./min. It measured with the temperature increase rate of.
(5) Rheology measurement: AR2000 type rheometer manufactured by TA Instruments, 4 ° C / min. With a 25 mm parallel plate. It measured with the temperature increase rate of.
(6) Tensile test: TENSILON / UTM-II-20 manufactured by Orientec Co., Ltd. was used at room temperature at a tensile speed of 5 mm / min. The specimen shape was a film having a length of 20 mm, a width of 3 mm, and a thickness of 80 to 115 μm.

（実施例１）
温度計、攪拌子、窒素導入管を備えた３つ口の１００ｍＬフラスコに、９，９−ビス（４−アミノフェニル）フルオレン０．３４８４ｇ（１ｍｍｏｌ）、４，４’−ジアミノジフェニルエーテル１．８０２ｇ（９ｍｍｏｌ）とＮ−メチル−２−ピロリドン１２．８ｍＬを加え、溶解後、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物２．３５４ｇ（８ｍｍｏｌ）を入れ、窒素気流下、室温で２時間攪拌した。この反応溶液に４−（２−フェニルエチニル）無水フタル酸０．９９３ｇ（４ｍｍｏｌ）を入れ、窒素気流下、室温で１８時間、続けて１７５℃で５時間攪拌した。冷却後、反応液を１５０ｍＬのイオン交換水に投入し、析出した粉末を濾別した。６０ｍＬのメタノールで３０分洗浄し、濾別して得られた粉末を６０℃で１日間減圧乾燥し、生成物を得た。収量：４．９９８ｇ（９７％）。
¹Ｈ−ＮＭＲ（３００ＭＨｚ，ＤＭＳＯ−ｄ₆）：δ８．２１、８．１２、８．０２、８．００、７．９２、７．６３、７．４７、７．２５、７．２２、７．２０
ＩＲ（ＫＢｒ，ｃｍ^-1）：３４４６、２２１２、１７７８、１７２０、１６１６、１５０２、１４２７、１３７７、１２９８、１２４１、１１６９、１１１５、１０９０、１０１６、９４３、８７９、８２７、７４１、６９０
上記で得られた末端変性イミドオリゴマーの未硬化物は、ＮＭＰ溶媒に室温で３５％以上可溶、ＧＢＬ溶媒に３０％以上可溶であったが、室温保管では数日後にゲル化が見られた。硬化前の最低溶融粘度は１０００ポイズ（３３６℃）であった。この末端変性イミドオリゴマーをホットプレスを用いて３７０℃で１時間加熱して得られたフィルム状の硬化物（厚さ８８μｍ）は、Ｔｇが３４３℃（ＤＳＣ）、ＴＧＡによる５％重量減少温度は５５３℃であった。また、このフィルム形状の硬化物の引張試験による力学的性質は、弾性率が２．５６ＧＰａ、破断強度が１０９ＭＰａ、破断伸びが７．６％であった。 Example 1
To a three-necked 100 mL flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 0.3484 g (1 mmol) of 9,9-bis (4-aminophenyl) fluorene, 1.802 g of 4,4′-diaminodiphenyl ether ( 9 mmol) and 12.8 mL of N-methyl-2-pyrrolidone were added and dissolved, and then 2,354 g (8 mmol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride was added, and the mixture was heated at room temperature under a nitrogen stream. For 2 hours. To this reaction solution was added 0.993 g (4 mmol) of 4- (2-phenylethynyl) phthalic anhydride, and the mixture was stirred at room temperature for 18 hours and then at 175 ° C. for 5 hours under a nitrogen stream. After cooling, the reaction solution was poured into 150 mL of ion exchange water, and the precipitated powder was separated by filtration. The powder obtained by washing with 60 mL of methanol for 30 minutes and filtered off was dried under reduced pressure at 60 ° C. for 1 day to obtain a product. Yield: 4.998 g (97%).
¹ H-NMR (300 MHz, DMSO-d ₆ ): δ 8.21, 8.12, 8.02, 8.00, 7.92, 7.63, 7.47, 7.25, 7.22, 7 .20
IR (KBr, cm ⁻¹ ): 3446, 2212, 1778, 1720, 1616, 1502, 1427, 1377, 1298, 1241, 1169, 1115, 1090, 1016, 943, 879, 827, 741, 690
The uncured product of the terminal-modified imide oligomer obtained above was soluble in NMP solvent at 35% or more at room temperature and soluble in GBL solvent at 30% or more, but gelation was observed after several days when stored at room temperature. It was. The minimum melt viscosity before curing was 1000 poise (336 ° C.). A film-like cured product (thickness 88 μm) obtained by heating this terminal-modified imide oligomer at 370 ° C. for 1 hour using a hot press has a Tg of 343 ° C. (DSC) and a 5% weight loss temperature by TGA is It was 553 ° C. The mechanical properties of this film-shaped cured product by a tensile test were an elastic modulus of 2.56 GPa, a breaking strength of 109 MPa, and a breaking elongation of 7.6%.

（実施例２）
温度計、攪拌子、窒素導入管を備えた３つ口の１００ｍＬフラスコに、９，９−ビス（４−アミノフェニル）フルオレン０．８７１ｇ（２．５ｍｍｏｌ）、４，４’−ジアミノジフェニルエーテル１．５０２ｇ（７．５ｍｍｏｌ）とＮ−メチル−２−ピロリドン１３．３ｍＬを加え、溶解後、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物２．３５４ｇ（８ｍｍｏｌ）を入れ、窒素気流下、室温で２時間攪拌した。この反応溶液に４−（２−フェニルエチニル）無水フタル酸０．９９３ｇ（４ｍｍｏｌ）を入れ、窒素気流下、室温で２０時間、続けて１７５℃で５時間攪拌した。得られた末端変性イミドオリゴマーは、前記一般式（１）において、Ｒがジフェニルエーテル基で表され、平均としてｍ＝１．５、ｎ＝３．７５である。冷却後、反応液を１５０ｍＬのイオン交換水に投入し、析出した粉末を濾別した。６０ｍＬのメタノールで３０分洗浄し、濾別して得られた粉末を６０℃で１日間減圧乾燥し、生成物を得た。収量：５．６２８ｇ（９８％）。
¹Ｈ−ＮＭＲ（３００ＭＨｚ，ＤＭＳＯ−ｄ₆）：δ８．２４、８．１３、８．０３、８．０１、７．９９、７．６３、７．４８、７．３７、７．２９、７．２３
ＩＲ（ＫＢｒ，ｃｍ^-1）：３４４６、２２１２、１７７６、１７１８、１６１６、１５００、１３７６、１２４０、１１６９、１１１６、１０８９、９５０、８８１、８２３、７４０、６９０
上記で得られた末端変性イミドオリゴマーの未硬化物は、ＮＭＰ溶媒に室温で４０％以上可溶であり、室温保管では１〜２ヶ月後にゲル化が見られたものの、冷凍保管では２ヵ月後もゲル化はみられなかった。ＧＢＬ溶媒に室温で４０％以上可溶であり、室温保管では数日間はゲル化が見られなかったものの、１〜２週間後にゲル化が見られた。硬化前の最低溶融粘度は３３８０ポイズ（３４８℃）であった。この末端変性イミドオリゴマーをホットプレスを用いて３７０℃で１時間加熱して得られたフィルム状の硬化物は、Ｔｇが３５３℃（ＤＳＣ）、ＴＧＡによる５％重量減少温度は５５３℃であった。また、このフィルム形状の硬化物（厚さ９４μｍ）の引張試験による力学的性質は、弾性率が２．８７ＧＰａ、破断強度が１２２ＭＰａ、破断伸びが７．７％であった。 (Example 2)
In a three-necked 100 mL flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 0.871 g (2.5 mmol) of 9,9-bis (4-aminophenyl) fluorene, 4,4′-diaminodiphenyl ether; Add 502 g (7.5 mmol) and 13.3 mL of N-methyl-2-pyrrolidone, dissolve, and then add 2.354 g (8 mmol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride to nitrogen. The mixture was stirred at room temperature for 2 hours under an air stream. To this reaction solution was added 0.993 g (4 mmol) of 4- (2-phenylethynyl) phthalic anhydride, and the mixture was stirred at room temperature for 20 hours and then at 175 ° C. for 5 hours under a nitrogen stream. In the obtained terminal-modified imide oligomer, in the general formula (1), R is represented by a diphenyl ether group, and m = 1.5 and n = 3.75 on average. After cooling, the reaction solution was poured into 150 mL of ion exchange water, and the precipitated powder was separated by filtration. The powder obtained by washing with 60 mL of methanol for 30 minutes and filtered off was dried under reduced pressure at 60 ° C. for 1 day to obtain a product. Yield: 5.628 g (98%).
¹ H-NMR (300 MHz, DMSO-d ₆ ): δ 8.24, 8.13, 8.03, 8.01, 7.99, 7.63, 7.48, 7.37, 7.29, 7 .23
IR (KBr, cm ⁻¹ ): 3446, 2212, 1776, 1718, 1616, 1500, 1376, 1240, 1169, 1116, 1089, 950, 881, 823, 740, 690
The uncured product of the terminal-modified imide oligomer obtained above is soluble in NMP solvent by 40% or more at room temperature, and gelation was observed after 1 to 2 months when stored at room temperature, but after 2 months when stored frozen. No gelation was observed. Although it was soluble in GBL solvent by 40% or more at room temperature and gelation was not observed for several days when stored at room temperature, gelation was observed after 1 to 2 weeks. The minimum melt viscosity before curing was 3380 poise (348 ° C.). The film-like cured product obtained by heating this terminal-modified imide oligomer at 370 ° C. for 1 hour using a hot press had a Tg of 353 ° C. (DSC) and a 5% weight loss temperature by TGA of 553 ° C. . The mechanical properties of this cured film (thickness: 94 μm) as determined by a tensile test were an elastic modulus of 2.87 GPa, a breaking strength of 122 MPa, and a breaking elongation of 7.7%.

（実施例３）
温度計、攪拌子、窒素導入管を備えた３つ口の１００ｍＬフラスコに、９，９−ビス（４−アミノフェニル）フルオレン１．７４２ｇ（５ｍｍｏｌ）、４，４’−ジアミノジフェニルエーテル１．００１ｇ（５ｍｍｏｌ）とＮ−メチル−２−ピロリドン１４．２ｍＬを加え、溶解後、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物２．３５４ｇ（８ｍｍｏｌ）を入れ、窒素気流下、室温で２時間攪拌した。この反応溶液に４−（２−フェニルエチニル）無水フタル酸０．９９３ｇ（４ｍｍｏｌ）を入れ、窒素気流下、室温で２０時間、続けて１７５℃で５時間攪拌した。得られた末端変性イミドオリゴマーは、前記一般式（１）において、Ｒがジフェニルエーテル基で表され、平均としてｍ＝１．５、ｎ＝２．５である。冷却後、反応液を１５０ｍＬのイオン交換水に投入し、析出した粉末を濾別した。６０ｍＬのメタノールで３０分洗浄し、濾別して得られた粉末を６０℃で１日間減圧乾燥し、生成物を得た。収量：５．５８１ｇ（９７％）。
¹Ｈ−ＮＭＲ（３００ＭＨｚ，ＤＭＳＯ−ｄ₆）：δ８．２３、８．１１、８．０２、８．００、７．６４、７．５９、７．４９、７．４８、７．３８、７．３７、７．３４、７．３１、７．２７、７．２４
ＩＲ（ＫＢｒ，ｃｍ^-1）：３４４６、２２１２、１７７６、１７１８、１６１６、１５００、１３７６、１２４０、１１６９、１１１６、１０８９、９５０、８８１、８２３、７４０、６９０
上記で得られた末端変性イミドオリゴマーの未硬化物は、ＮＭＰ溶媒に室温で４０％以上可溶であり、室温保管、冷凍保管ともに２ヵ月後もゲル化はみられなかった。ＧＢＬ溶媒に室温で４０％以上可溶であり、室温保管では２週間はゲル化が見られなかったものの、１〜２ヶ月後にゲル化が見られた。硬化前の最低溶融粘度は１８１００ポイズ（３４９℃）であった。この末端変性イミドオリゴマーをホットプレスを用いて３７０℃で１時間加熱して得られたフィルム状の硬化物（厚さ１１２μｍ）は、Ｔｇが３６２℃（ＤＳＣ）、ＴＧＡによる５％重量減少温度は５６１℃であった。また、このフィルム形状の硬化物の引張試験による力学的性質は、弾性率が２．６５ＧＰａ、破断強度が１１２ＭＰａ、破断伸びが６．９％であった。 (Example 3)
To a three-necked 100 mL flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 1.742 g (5 mmol) of 9,9-bis (4-aminophenyl) fluorene, 1.001 g of 4,4′-diaminodiphenyl ether ( 5 mmol) and 14.2 mL of N-methyl-2-pyrrolidone were added and dissolved, and 2,354 g (8 mmol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride was added, and the mixture was allowed to flow at room temperature under a nitrogen stream For 2 hours. To this reaction solution was added 0.993 g (4 mmol) of 4- (2-phenylethynyl) phthalic anhydride, and the mixture was stirred at room temperature for 20 hours and then at 175 ° C. for 5 hours under a nitrogen stream. In the terminal-modified imide oligomer obtained, in the general formula (1), R is represented by a diphenyl ether group, and m = 1.5 and n = 2.5 on average. After cooling, the reaction solution was poured into 150 mL of ion exchange water, and the precipitated powder was separated by filtration. The powder obtained by washing with 60 mL of methanol for 30 minutes and filtered off was dried under reduced pressure at 60 ° C. for 1 day to obtain a product. Yield: 5.581 g (97%).
¹ H-NMR (300 MHz, DMSO-d ₆ ): δ 8.23, 8.11, 8.02, 8.00, 7.64, 7.59, 7.49, 7.48, 7.38, 7 .37, 7.34, 7.31, 7.27, 7.24
IR (KBr, cm ⁻¹ ): 3446, 2212, 1776, 1718, 1616, 1500, 1376, 1240, 1169, 1116, 1089, 950, 881, 823, 740, 690
The uncured product of the terminal-modified imide oligomer obtained above was soluble in NMP solvent by 40% or more at room temperature, and gelation was not observed after 2 months in both room temperature storage and frozen storage. It was soluble in GBL solvent by 40% or more at room temperature, and gelation was observed after 1 to 2 months although gelation was not observed for 2 weeks when stored at room temperature. The minimum melt viscosity before curing was 18100 poise (349 ° C.). A film-like cured product (thickness 112 μm) obtained by heating this terminal-modified imide oligomer with a hot press at 370 ° C. for 1 hour has a Tg of 362 ° C. (DSC) and a 5% weight loss temperature by TGA is It was 561 degreeC. The mechanical properties of this film-shaped cured product by a tensile test were an elastic modulus of 2.65 GPa, a breaking strength of 112 MPa, and a breaking elongation of 6.9%.

（実施例４）
温度計、攪拌子、窒素導入管を備えた３つ口の１００ｍＬフラスコに、９，９−ビス（４−アミノフェニル）フルオレン３．４８４ｇ（１０ｍｍｏｌ）とＮ−メチル−２−ピロリドン１４．２ｍＬを加え、溶解後、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物２．３５４ｇ（８ｍｍｏｌ）を入れ、窒素気流下、室温で２時間攪拌した。この反応溶液に４−（２−フェニルエチニル）無水フタル酸０．９９３ｇ（４ｍｍｏｌ）を入れ、窒素気流下、室温で１８時間、続けて１７５℃で５時間攪拌した。得られた末端変性イミドオリゴマーは、前記一般式（１）において、ｍ＝４、ｎ＝０である。冷却後、反応液を１５０ｍＬのイオン交換水に投入し、析出した粉末を濾別した。６０ｍＬのメタノールで３０分洗浄し、濾別して得られた粉末を６０℃で１日間減圧乾燥し、生成物を得た。収量：６．４１９ｇ（９９％）。
¹Ｈ−ＮＭＲ（３００ＭＨｚ，ＤＭＳＯ−ｄ₆）：δ８．１９、８．０６、８．００、７．９８、７．６２、７．５７、７．４６、７．３８、７．３５、７．３３、７．３０
ＩＲ（ＫＢｒ，ｃｍ^-1）：３４４７、２２１２、１７７７、１７２０、１６１５、１５００、１３７６、１２９３、１２３９、１１７０、１１１５、１０８９、１０１４、９４３、８７９、８２５、７３９、６９０
上記で得られた末端変性イミドオリゴマーの未硬化物は、ＮＭＰ溶媒に室温で４０％以上可溶であり、室温保管、冷凍保管ともに２ヵ月後もゲル化はみられなかった。ＧＢＬ溶媒に室温で４０％以上可溶であり、室温保管では２週間はゲル化が見られなかったものの、１〜２ヶ月後にゲル化が見られた。この末端変性イミドオリゴマーをホットプレスを用いて３７０℃で１時間加熱して得られた硬化物はフィルム状にはならずに粉末を押し固めた状態であり、Ｔｇが３７６℃（ＤＳＣ）、ＴＧＡによる５％重量減少温度は５６６℃であった。 Example 4
To a three-necked 100 mL flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 3.484 g (10 mmol) of 9,9-bis (4-aminophenyl) fluorene and 14.2 mL of N-methyl-2-pyrrolidone were added. In addition, after dissolution, 2.354 g (8 mmol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride was added and stirred at room temperature for 2 hours under a nitrogen stream. To this reaction solution was added 0.993 g (4 mmol) of 4- (2-phenylethynyl) phthalic anhydride, and the mixture was stirred at room temperature for 18 hours and then at 175 ° C. for 5 hours under a nitrogen stream. The obtained terminal-modified imide oligomer has m = 4 and n = 0 in the general formula (1). After cooling, the reaction solution was poured into 150 mL of ion exchange water, and the precipitated powder was separated by filtration. The powder obtained by washing with 60 mL of methanol for 30 minutes and filtered off was dried under reduced pressure at 60 ° C. for 1 day to obtain a product. Yield: 6.419 g (99%).
¹ H-NMR (300 MHz, DMSO-d ₆ ): δ 8.19, 8.06, 8.00, 7.98, 7.62, 7.57, 7.46, 7.38, 7.35, 7 .33, 7.30
IR (KBr, cm ⁻¹ ): 3447, 2212, 1777, 1720, 1615, 1500, 1376, 1293, 1239, 1170, 1115, 1089, 1014, 943, 879, 825, 739, 690
The uncured product of the terminal-modified imide oligomer obtained above was soluble in NMP solvent by 40% or more at room temperature, and gelation was not observed after 2 months in both room temperature storage and frozen storage. It was soluble in GBL solvent by 40% or more at room temperature, and gelation was observed after 1 to 2 months although gelation was not observed for 2 weeks when stored at room temperature. The cured product obtained by heating this terminal-modified imide oligomer with a hot press at 370 ° C. for 1 hour is a state in which the powder is pressed and not formed into a film, and Tg is 376 ° C. (DSC), TGA The 5% weight loss temperature was 566 ° C.

（実施例５）
温度計、攪拌子、窒素導入管を備えた３つ口の１００ｍＬフラスコに、９，９−ビス（４−アミノフェニル）フルオレン０．６９７ｇ（２ｍｍｏｌ）、１，３−ビス（４−アミノフェノキシ）ベンゼン０．５８５ｇ（２ｍｍｏｌ）、４，４’−ジアミノジフェニルエーテル１．２０１ｇ（６ｍｍｏｌ）とＮ−メチル−２−ピロリドン１０．８ｍＬを加え、溶解後、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物２．３５４ｇ（８ｍｍｏｌ）を入れ、窒素気流下、室温で４時間攪拌した。この反応溶液に４−（２−フェニルエチニル）無水フタル酸０．９９３ｇ（４ｍｍｏｌ）を入れ、窒素気流下、室温で１７時間、続けて１７５℃で５時間攪拌した。得られた末端変性イミドオリゴマーは、前記一般式（１）において、Ｒがジフェニルエーテル基及び１，４−ジフェノキシベンゼン基（モル比３：１）で表され、平均としてｍ＝０、ｎ＝４である。冷却後、反応液を１５０ｍＬのイオン交換水に投入し、析出した粉末を濾別した。６０ｍＬのメタノールで３０分洗浄し、濾別して得られた粉末を６０℃で１日間減圧乾燥し、生成物を得た。収量：５．３７７ｇ（９８％）。
¹Ｈ−ＮＭＲ（３００ＭＨｚ，ＤＭＳＯ−ｄ₆）：δ８．２５、８．１４、８．０２、７．６４、７．４９、７．３９、７．３０、７．２３、６．８６、６．７８
ＩＲ（ＫＢｒ，ｃｍ^-1）：３４４６、２２１２、１７７８、１７２２、１６１６、１５０２、１４２７、１３７７、１２９２、１２３８、１１６９、１１１７、１０９０、１０１６、９６８、９４３、８７９、８２７、７９０、７４０、６９０
上記で得られた末端変性イミドオリゴマーの未硬化物は、ＮＭＰ溶媒に室温で４０％以上可溶であり、室温保管、冷凍保管ともに２ヵ月後もゲル化はみられなかった。ＧＢＬ溶媒に室温で４０％以上可溶であり、室温保管では数日間はゲル化が見られなかったものの、１〜２週間後にゲル化が見られた。硬化前の最低溶融粘度は１３７０ポイズ（３４０℃）であった。この末端変性イミドオリゴマーをホットプレスを用いて３７０℃で１時間加熱して得られたフィルム状の硬化物（厚さ８０μｍ）は、Ｔｇが３３０℃（ＤＳＣ）、ＴＧＡによる５％重量減少温度は５５０℃であった。また、このフィルム形状の硬化物の引張試験による力学的性質は、弾性率が２．８０ＧＰａ、破断強度が１１８ＭＰａ、破断伸びが８．０％であった。 (Example 5)
In a three-necked 100 mL flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 0.697 g (2 mmol) of 9,9-bis (4-aminophenyl) fluorene, 1,3-bis (4-aminophenoxy) 0.585 g (2 mmol) of benzene, 1.201 g (6 mmol) of 4,4′-diaminodiphenyl ether and 10.8 mL of N-methyl-2-pyrrolidone were added and dissolved, and then 2,3,3 ′, 4′-biphenyltetra 2.354 g (8 mmol) of carboxylic dianhydride was added and stirred at room temperature for 4 hours under a nitrogen stream. To this reaction solution was added 0.993 g (4 mmol) of 4- (2-phenylethynyl) phthalic anhydride, and the mixture was stirred at room temperature for 17 hours and then at 175 ° C. for 5 hours under a nitrogen stream. The obtained terminal-modified imide oligomer is represented by the general formula (1) in which R is represented by a diphenyl ether group and a 1,4-diphenoxybenzene group (molar ratio 3: 1), and m = 0 and n = 4 on average. It is. After cooling, the reaction solution was poured into 150 mL of ion exchange water, and the precipitated powder was separated by filtration. The powder obtained by washing with 60 mL of methanol for 30 minutes and filtered off was dried under reduced pressure at 60 ° C. for 1 day to obtain a product. Yield: 5.377 g (98%).
¹ H-NMR (300 MHz, DMSO-d ₆ ): δ 8.25, 8.14, 8.02, 7.64, 7.49, 7.39, 7.30, 7.23, 6.86, ₆ .78
IR (KBr, cm ⁻¹ ): 3446, 2212, 1778, 1722, 1616, 1502, 1427, 1377, 1292, 1238, 1169, 1117, 1090, 1016, 968, 943, 879, 827, 790, 740, 690
The uncured product of the terminal-modified imide oligomer obtained above was soluble in NMP solvent by 40% or more at room temperature, and gelation was not observed after 2 months in both room temperature storage and frozen storage. Although it was soluble in GBL solvent by 40% or more at room temperature and gelation was not observed for several days when stored at room temperature, gelation was observed after 1 to 2 weeks. The minimum melt viscosity before curing was 1370 poise (340 ° C.). The film-like cured product (thickness 80 μm) obtained by heating this terminal-modified imide oligomer at 370 ° C. for 1 hour using a hot press has a Tg of 330 ° C. (DSC) and a 5% weight loss temperature by TGA is It was 550 ° C. In addition, the mechanical properties of the cured product in the form of a film were as follows: the elastic modulus was 2.80 GPa, the breaking strength was 118 MPa, and the breaking elongation was 8.0%.

（実施例６）
温度計、攪拌子、窒素導入管を備えた３つ口の１００ｍＬフラスコに、９，９−ビス（４−アミノフェニル）フルオレン１．７４２ｇ（５ｍｍｏｌ）、４，４’−ジアミノジフェニルエーテル１．００１ｇ（５ｍｍｏｌ）とγ−ブチロラクトン１２．７ｍＬを加え、６０℃に加熱して溶解させた。室温まで冷却後、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物２．３５４ｇ（８ｍｍｏｌ）を入れ、窒素気流下、室温で５時間攪拌した。この反応溶液に４−（２−フェニルエチニル）無水フタル酸０．９９３ｇ（４ｍｍｏｌ）を入れ、窒素気流下、室温で１８時間、続けて１７５℃で５時間攪拌した。得られた末端変性イミドオリゴマーは、前記一般式（１）において、Ｒがジフェニルエーテル基で表され、平均としてｍ＝１．５、ｎ＝２．５である。冷却後、反応液を１５０ｍＬのイオン交換水に投入し、析出した粉末を濾別した。６０ｍＬのメタノールで３０分洗浄し、濾別して得られた粉末を６０℃で１日間減圧乾燥し、生成物を得た。収量：５．６２１ｇ（９８％）。
¹Ｈ−ＮＭＲ（３００ＭＨｚ，ＤＭＳＯ−ｄ₆）：δ８．２３、８．１２、８．０２、８．００、７．６３、７．５９、７．４８、７．３７、７．３４、７．３１、７．２７、７．２４
ＩＲ（ＫＢｒ，ｃｍ^-1）：３４４６、２２１２、１７７６、１７１８、１６１６、１５００、１３７６、１２４０、１１６９、１１１７、１０９０、９５０、８８１、８２３、７４０、６９０
上記で得られた末端変性イミドオリゴマーの未硬化物は、ＮＭＰ溶媒に室温で４０％以上可溶であり、室温保管、冷凍保管ともに２ヵ月後もゲル化はみられなかった。ＧＢＬ溶媒に室温で４０％以上可溶であり、室温保管では２週間はゲル化が見られなかったものの、１〜２ヶ月後にゲル化が見られた。硬化前の最低溶融粘度は１７２００ポイズ（３４７℃）であった。この末端変性イミドオリゴマーをホットプレスを用いて３７０℃で１時間加熱して得られた硬化物（厚さ１０８μｍ）は、Ｔｇが３６０℃（ＤＳＣ）、ＴＧＡによる５％重量減少温度は５６０℃であった。また、このフィルム形状の硬化物の引張試験による力学的性質は、弾性率が２．８０ＧＰａ、破断強度が１１７ＭＰａ、破断伸びが６．６％であった。 (Example 6)
To a three-necked 100 mL flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 1.742 g (5 mmol) of 9,9-bis (4-aminophenyl) fluorene, 1.001 g of 4,4′-diaminodiphenyl ether ( 5 mmol) and 12.7 mL of γ-butyrolactone were added and dissolved by heating to 60 ° C. After cooling to room temperature, 2,354 g (8 mmol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride was added and stirred at room temperature for 5 hours under a nitrogen stream. To this reaction solution was added 0.993 g (4 mmol) of 4- (2-phenylethynyl) phthalic anhydride, and the mixture was stirred at room temperature for 18 hours and then at 175 ° C. for 5 hours under a nitrogen stream. In the terminal-modified imide oligomer obtained, in the general formula (1), R is represented by a diphenyl ether group, and m = 1.5 and n = 2.5 on average. After cooling, the reaction solution was poured into 150 mL of ion exchange water, and the precipitated powder was separated by filtration. The powder obtained by washing with 60 mL of methanol for 30 minutes and filtered off was dried under reduced pressure at 60 ° C. for 1 day to obtain a product. Yield: 5.621 g (98%).
¹ H-NMR (300 MHz, DMSO-d ₆ ): δ 8.23, 8.12, 8.02, 8.00, 7.63, 7.59, 7.48, 7.37, 7.34, 7 .31, 7.27, 7.24
IR (KBr, cm ⁻¹ ): 3446, 2212, 1776, 1718, 1616, 1500, 1376, 1240, 1169, 1117, 1090, 950, 881, 823, 740, 690
The uncured product of the terminal-modified imide oligomer obtained above was soluble in NMP solvent by 40% or more at room temperature, and gelation was not observed after 2 months in both room temperature storage and frozen storage. It was soluble in GBL solvent by 40% or more at room temperature, and gelation was observed after 1 to 2 months although gelation was not observed for 2 weeks when stored at room temperature. The minimum melt viscosity before curing was 17200 poise (347 ° C.). A cured product (thickness 108 μm) obtained by heating this terminal-modified imide oligomer at 370 ° C. for 1 hour using a hot press has a Tg of 360 ° C. (DSC) and a 5% weight loss temperature by TGA of 560 ° C. there were. The mechanical properties of this film-shaped cured product by a tensile test were an elastic modulus of 2.80 GPa, a breaking strength of 117 MPa, and a breaking elongation of 6.6%.

（比較例１）
温度計、攪拌子、窒素導入管を備えた３つ口の１００ｍＬフラスコに、４，４’−ジアミノジフェニルエーテル２．００２ｇ（１０ｍｍｏｌ）とＮ−メチル−２−ピロリドン１２ｍＬを加え、溶解後、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物２．３５４ｇ（８ｍｍｏｌ）を加えて窒素気流下、室温で１時間攪拌した。その後、４−（２−フェニルエチニル）無水フタル酸０．９９３ｇ（４ｍｍｏｌ）を入れ、窒素気流下、室温で２時間攪拌した。オイルバス温１８０℃で４時間攪拌した。冷却後、反応液を１２０ｍＬのイオン交換水に投入し、析出した粉末を濾別した。６０ｍＬのメタノールで３０分洗浄し、濾別して得られた粉末を６０℃で１日間減圧乾燥し、生成物を得た。収量：４．８３４ｇ（９７％）。
¹Ｈ−ＮＭＲ（３００ＭＨｚ，ＤＭＳＯ−ｄ₆）：δ８．２５、８．１４、８．０２、７．９３、７．６３、７．４８、７．２２
ＩＲ（ＫＢｒ，ｃｍ^-1）：３４４８、２２１２、１７７８、１７２２、１６１６、１５０２、１４２５、１３７７、１２９０、１２４０、１１６９、１１１５、１０８８、１０１６、９４３、８７９、８２７、７９３、７４９、６９０
上記で得られた末端変性イミドオリゴマーの未硬化物は、ＮＭＰ溶媒に室温で２０％程度可溶であるが、室温保管では１日後にゲル化が見られた。硬化前の最低溶融粘度は８６０ポイズ（３４４℃）であった。この末端変性イミドオリゴマーをホットプレスを用いて３７０℃で１時間加熱して得られたフィルム状の硬化物（厚さ８６μｍ）は、Ｔｇが３３７℃（ＤＳＣ）、ＴＧＡによる５％重量減少温度は５７４℃であった。また、このフィルム形状の硬化物の引張試験による力学的性質は、弾性率が２．５５ＧＰａ、破断強度が１１８ＭＰａ、破断伸びが１５．５％であった。 (Comparative Example 1)
To a three-necked 100 mL flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 2.002 g (10 mmol) of 4,4′-diaminodiphenyl ether and 12 mL of N-methyl-2-pyrrolidone were added. 2,354 g (8 mmol) of 3,3 ′, 4′-biphenyltetracarboxylic dianhydride was added and stirred at room temperature for 1 hour under a nitrogen stream. Thereafter, 0.993 g (4 mmol) of 4- (2-phenylethynyl) phthalic anhydride was added and stirred at room temperature for 2 hours under a nitrogen stream. The mixture was stirred at an oil bath temperature of 180 ° C. for 4 hours. After cooling, the reaction solution was poured into 120 mL of ion exchange water, and the precipitated powder was separated by filtration. The powder obtained by washing with 60 mL of methanol for 30 minutes and filtered off was dried under reduced pressure at 60 ° C. for 1 day to obtain a product. Yield: 4.834 g (97%).
¹ H-NMR (300 MHz, DMSO-d ₆ ): δ 8.25, 8.14, 8.02, 7.93, 7.63, 7.48, 7.22
IR (KBr, cm ⁻¹ ): 3448, 2212, 1778, 1722, 1616, 1502, 1425, 1377, 1290, 1240, 1169, 1115, 1088, 1016, 943, 879, 827, 793, 749, 690
The uncured product of the terminal-modified imide oligomer obtained above was soluble in NMP solvent by about 20% at room temperature, but gelation was observed after 1 day when stored at room temperature. The minimum melt viscosity before curing was 860 poise (344 ° C.). A film-like cured product (thickness 86 μm) obtained by heating this terminal-modified imide oligomer at 370 ° C. for 1 hour using a hot press has a Tg of 337 ° C. (DSC) and a 5% weight loss temperature by TGA is It was 574 ° C. In addition, the mechanical properties of the cured product in the form of a film were as follows: the elastic modulus was 2.55 GPa, the breaking strength was 118 MPa, and the breaking elongation was 15.5%.

（比較例２）
温度計、攪拌子、窒素導入管を備えた３つ口の１００ｍＬフラスコに、４，４’−ジアミノジフェニルエーテル０．４００ｇ（２ｍｍｏｌ）、１，４−ビス（４−アミノフェノキシ）ベンゼン２．３３９ｇ（８ｍｍｏｌ）、とＮ−メチル−２−ピロリドン１２ｍＬを加え、溶解後、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物２．３５４ｇ（８ｍｍｏｌ）を加えて窒素気流下、室温で１時間攪拌した。その後、４−（２−フェニルエチニル）無水フタル酸０．９９３ｇ（４ｍｍｏｌ）を入れ、窒素気流下、室温で２時間攪拌した。オイルバス温１８０℃で４時間攪拌した。冷却後、反応液を１２０ｍＬのイオン交換水に投入し、析出した粉末を濾別した。６０ｍＬのメタノールで３０分洗浄し、濾別して得られた粉末を６０℃で１日間減圧乾燥し、生成物を得た。収量：５．５６０ｇ（９７％）。
¹Ｈ−ＮＭＲ（３００ＭＨｚ，ＤＭＳＯ−ｄ₆）：δ８．２４、８．１３、８．０４、８．０１、８．００、７．９２、７．６３、７．６２、７．５０、７．４９、７．４７、７．２２、７．２１
ＩＲ（ＫＢｒ，ｃｍ^-1）：３４４７、２２１２、１７７６、１７１８、１６１５、１５００、１３７５、１２３８、１１６６、１１１４、１０８５、１０１３、９４２、８７８、８２３、７３８、６８８
上記で得られた末端変性イミドオリゴマーの未硬化物は、ＮＭＰ溶媒に室温で２０％、５０℃で４０％以上可溶であった。この末端変性イミドオリゴマーをホットプレスを用いて３７０℃で１時間加熱して得られた硬化物は、Ｔｇが２９０℃（ＤＳＣ）、ＴＧＡによる５％重量減少温度は５３７℃であった。 (Comparative Example 2)
In a three-necked 100 mL flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 0.400 g (2 mmol) of 4,4′-diaminodiphenyl ether and 2.339 g of 1,4-bis (4-aminophenoxy) benzene ( 8 mmol), and 12 mL of N-methyl-2-pyrrolidone, and after dissolution, 2.354 g (8 mmol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride was added and at room temperature under a nitrogen stream. Stir for 1 hour. Thereafter, 0.993 g (4 mmol) of 4- (2-phenylethynyl) phthalic anhydride was added and stirred at room temperature for 2 hours under a nitrogen stream. The mixture was stirred at an oil bath temperature of 180 ° C. for 4 hours. After cooling, the reaction solution was poured into 120 mL of ion exchange water, and the precipitated powder was separated by filtration. The powder obtained by washing with 60 mL of methanol for 30 minutes and filtered off was dried under reduced pressure at 60 ° C. for 1 day to obtain a product. Yield: 5.560 g (97%).
¹ H-NMR (300 MHz, DMSO-d ₆ ): δ 8.24, 8.13, 8.04, 8.01, 8.00, 7.92, 7.63, 7.62, 7.50, 7 .49, 7.47, 7.22, 7.21
IR (KBr, cm ⁻¹ ): 3447, 2212, 1776, 1718, 1615, 1500, 1375, 1238, 1166, 1114, 1085, 1013, 942, 878, 823, 738, 688
The uncured product of the terminal-modified imide oligomer obtained above was soluble in NMP solvent by 20% at room temperature and 40% or more at 50 ° C. The cured product obtained by heating this terminal-modified imide oligomer at 370 ° C. for 1 hour using a hot press had a Tg of 290 ° C. (DSC) and a 5% weight loss temperature by TGA of 537 ° C.

Claims

一般式（１）で表される末端変性イミドオリゴマー。

（式中、Ｒは芳香族ジアミン残基を表す。ｍおよびｎは、それぞれｍ≧０、ｎ≧０、１≦ｍ＋ｎ≦２０および０≦ｍ／（ｍ＋ｎ）≦１の関係を満たすものであり、繰り返し単位の配列はブロック的、ランダム的のいずれであってもよい。） A terminal-modified imide oligomer represented by the general formula (1).

(In the formula, R represents an aromatic diamine residue. M and n satisfy the relationship of m ≧ 0, n ≧ 0, 1 ≦ m + n ≦ 20 and 0 ≦ m / (m + n) ≦ 1, respectively. The arrangement of repeating units may be either block or random.)

有機アミド溶媒に対し室温で固形分濃度３０ｗｔ％以上溶解可能な請求項１に記載の末端変性イミドオリゴマー。 The terminal-modified imide oligomer according to claim 1, which can be dissolved in an organic amide solvent at a solid content concentration of 30 wt% or more at room temperature.

請求項１または２に記載の末端変性イミドオリゴマーを有機溶媒に溶解してなるワニス。 A varnish obtained by dissolving the terminal-modified imide oligomer according to claim 1 or 2 in an organic solvent.

請求項１または２に記載の末端変性イミドオリゴマーを加熱硬化して得られる硬化物。 A cured product obtained by heat-curing the terminal-modified imide oligomer according to claim 1 or 2.

請求項３に記載のワニスを加熱硬化して得られる硬化物。 Hardened | cured material obtained by heat-curing the varnish of Claim 3.

ガラス転移温度（Ｔｇ）が３００℃以上である請求項４または５に記載の硬化物。
The cured product according to claim 4 or 5, wherein the glass transition temperature (Tg) is 300 ° C or higher.