JP2006312699A - Soluble terminal-modified imide oligomer and varnish and cured product thereof - Google Patents

Soluble terminal-modified imide oligomer and varnish and cured product thereof Download PDF

Info

Publication number
JP2006312699A
JP2006312699A JP2005136729A JP2005136729A JP2006312699A JP 2006312699 A JP2006312699 A JP 2006312699A JP 2005136729 A JP2005136729 A JP 2005136729A JP 2005136729 A JP2005136729 A JP 2005136729A JP 2006312699 A JP2006312699 A JP 2006312699A
Authority
JP
Japan
Prior art keywords
terminal
imide oligomer
modified imide
cured product
room temperature
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.)
Granted
Application number
JP2005136729A
Other languages
Japanese (ja)
Other versions
JP4263182B2 (en
Inventor
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
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kawasaki Heavy Industries Ltd
Japan Aerospace Exploration Agency JAXA
Ube Corp
Original Assignee
Kawasaki Heavy Industries Ltd
Japan Aerospace Exploration Agency JAXA
Ube Industries Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kawasaki Heavy Industries Ltd, Japan Aerospace Exploration Agency JAXA, Ube Industries Ltd filed Critical Kawasaki Heavy Industries Ltd
Priority to JP2005136729A priority Critical patent/JP4263182B2/en
Publication of JP2006312699A publication Critical patent/JP2006312699A/en
Application granted granted Critical
Publication of JP4263182B2 publication Critical patent/JP4263182B2/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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 molding properties such as low melting viscosity, and having high heat resistance and high mechanical properties such as elasticity modulus, tensile strength and elongation, and to provide a cured product thereof. <P>SOLUTION: The soluble terminal-modified imide oligomer of the present invention is expressed by general formula (1) (wherein, R<SB>1</SB>, R<SB>2</SB>, and R<SB>3</SB>each represent an aromatic diamine residue; R<SB>1</SB>is an aromatic diamine residue expressed by general formula (2); m and n each satisfy the relation of m≥0 in the case of R<SB>3</SB>=R<SB>1</SB>, and m≥1, n≥0, and 1≤m+n≤20 and 0≤m/(m+n)≤1 in case of R<SB>3</SB>=R<SB>2</SB>; and sequence of a repeating unit may be either block-like or random-like). <P>COPYRIGHT: (C)2007,JPO&INPIT

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−（２−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ポリイミド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 having a terminal modified with 4- (2-phenylethynyl) phthalic anhydride is considered to have an excellent balance of moldability, heat resistance, and mechanical properties. For example, Patent Document 1, Patent Document 2, and Non-Patent Document It is introduced in Patent Document 1 and Non-Patent Document 2. The patent document 1 aims to provide a terminal-modified imide oligomer having excellent heat resistance and mechanical properties of the cured product and high practicality, and a cured product thereof. 2,3,3′4′-biphenyltetra Disclosed are a terminal-modified imide oligomer obtained by reacting a carboxylic dianhydride, an aromatic diamine compound and 4- (2-phenylethynyl) phthalic anhydride and having a logarithmic viscosity of 0.05 to 1, and a cured product thereof. Has been. As an effect of the invention, a novel terminal-modified imide oligomer having high practicality can be obtained, and a novel terminal-modified polyimide having excellent mechanical properties such as heat resistance, elastic modulus, tensile strength and elongation can be obtained. It is described that a cured product can be obtained.

しかし、そのこれらの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℃を意味する。）で２０重量％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 特表２００３−５２６７０４号公報 P. M. Hergenrother and 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, these terminal-modified imide oligomers are used in an organic solvent such as N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) at room temperature (in this specification, room temperature means 23 ° C. ± 2 ° C.). However, when this varnish is stored, it often gels after several days, and it is difficult to stably store a high concentration varnish for a long period of time. have. 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 Special table 2003-526704 gazette PM Hergenrother and 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）で表されるオリゴマーを提供する。

Figure 2006312699
ただし、上記式中、Ｒ１、Ｒ２、Ｒ３は芳香族ジアミン残基を表し、Ｒ１は下記一般式（２）で示される芳香族ジアミン残基である。ｍおよびｎは、Ｒ３＝Ｒ１の場合はｍ≧０、Ｒ３＝Ｒ２の場合はｍ≧１で、ｎ≧０、１≦ｍ＋ｎ≦２０および０≦ｍ／（ｍ＋ｎ）≦１の関係を満たし、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。
Figure 2006312699
 The present invention provides an oligomer represented by the general formula (1) as a novel terminal-modified imide oligomer.
Figure 2006312699
 However, in the above formulas, R 1, R 2, R 3 represents an aromatic diamine residue, R 1 is an aromatic diamine residue represented by the following general formula (2). m and n, in the case of R 3 = R 1 at m ≧ 0, R 3 = For R 2 m ≧ 1, n ≧ 0,1 ≦ m + n ≦ 20 and 0 ≦ m / (m + n ) ≦ 1 of Satisfying the relationship, the arrangement of repeating units may be either block-like or random.
Figure 2006312699

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を提供する。
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を提供する。 Moreover, this invention provides the varnish containing the terminal modified imide oligomer represented by Formula (1).
Moreover, this invention provides the hardened | cured material obtained by heat-curing the terminal modified imide oligomer or its varnish represented by Formula (1).

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。   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.

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−（４−アミノフェノキシ）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、一般式中（１）中、ｍおよびｎは、Ｒ３＝Ｒ１の場合はｍ≧０、Ｒ３＝Ｒ２の場合はｍ≧１で、ｎ≧０、１≦ｍ＋ｎ≦２０および０≦ｍ／（ｍ＋ｎ）≦１の関係を満たし、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３０重量％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。さらに、硬化後のフィルムの引張破断伸びが８％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 includes 2,3,3 ′, 4′-biphenyltetracarboxylic acids and 9,9-bis (4- (4-aminophenoxy) phenyl) fluorene. The equivalent amount of each acid group and the equivalent amount of each amino group are roughly equivalent to 4- (2-phenylethynyl) phthalic anhydride (hereinafter sometimes abbreviated as PEPA). Preferably, it is an imide oligomer obtained by reacting in a solvent, and the terminal (preferably both ends) of the imide oligomer is acetylene based on 4- (2-phenylethynyl) phthalic anhydride. In addition, in the general formula (1), m and n are m ≧ 0 when R 3 = R 1 , R 3 = R In the case of m ≧ 1, satisfying the relationship n ≧ 0,1 ≦ m + n ≦ 20 and 0 ≦ m / (m + n ) ≦ 1, more preferably 0.25 ≦ m / (m + n ) ≦ 1, more preferably It is a terminally modified imide oligomer that is an integer satisfying the relationship of 0.5 ≦ m / (m + n) ≦ 1 and is a solid (powder) at room temperature (23 ° C.) having a relatively low molecular weight. Furthermore, a terminal-modified imide oligomer that can be dissolved in an organic solvent such as NMP at a solid content of 30% by weight 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. Furthermore, the terminal modified imide oligomer whose tensile fracture elongation of the film after hardening is 8% 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−（４−アミノフェノキシ）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、９，９−ビス（４−アミノフェニル）フルオレ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- (4-aminophenoxy) phenyl) 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-aminophen ) Methane, 4,4'-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] hexafluoropropyl Bread, 9,9-bis (4-aminophenyl) etc. can be mentioned fluorene, may 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 solvent include N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), N, N-diethylacetamide, N-methylcaprolactam, γ-butyrolactone (GBL), cyclohexanone, and the like. It is done. 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.

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−（４−アミノフェノキシ）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、全成分の酸無水基（または隣接するジカルボン酸基）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 (especially this acid dianhydride) and 9,9-bis (4- (4-amino). An aromatic diamine compound containing phenoxy) phenyl) fluorene, and 4- (2-phenylethynyl) phthalic anhydride, the total amount of acid anhydride groups (or adjacent dicarboxylic acid groups) of all components and the total amount of amino groups Using each component in an approximately equal amount, each component is polymerized in the above-mentioned solvent at a reaction temperature of about 100 ° C. or lower, particularly 80 ° C. or lower to produce an “oligomer having an amide-acid bond”. Then, whether the amidic acid oligomer (also referred to as an amic acid oligomer) is added by a method of adding an imidizing agent at a low temperature of about 0 to 140 ° C. or by a method of heating to a high temperature of 140 to 275 ° C. Te, by dehydration and cyclization, it is possible to obtain a terminal to 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−（４−アミノフェノキシ）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の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- (4-aminophenoxy) phenyl) 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. (2-Phenylethynyl) phthalic anhydride is added and dissolved uniformly, and then reacted with stirring at a reaction temperature of about 5 to 60 ° C. for about 1 to 180 minutes to produce the terminal-modified amic acid oligomer. The liquid is stirred at 140 to 275 ° C. for 5 minutes to 24 hours to imidize the amic acid oligomer to form a terminal-modified imide oligomer. If necessary, the reaction liquid is cooled to around room temperature. That method can be mentioned. 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 1 to 1000 kg / cm 2 at 10 to 280 ° C. for about 1 second to 100 minutes. The preform 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いくつかの実施例を示すが、これによって本発明を限定するものではない。また、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−６３００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８０−９０μｍのフィルムとした。 The following examples are given to illustrate the invention, but are not intended to limit the invention. 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-6300 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 80-90 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−（４−アミノフェノキシ）フェニル）フルオレン１．３３２ｇ（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１２．５ｍＬ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時間重合反応させアミド酸オリゴマーを生成した。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時間反応させ末端変性し、続けて１７５℃で５時間攪拌しイミド結合させた。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、Ｒ２及びＲ３がジフェニルエーテル基で表され、平均としてｍ＝１．２５、ｎ＝２．７５のランダム共重合体である。冷却後、反応液を２００ｍＬのイオン交換水に投入し、析出した粉末を濾別した。８０ｍＬ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：５．６６８ｇ（９７％）。
1Ｈ−ＮＭＲ（３００ＭＨｚ，ＤＭＳＯ−ｄ6）：δ８．２３、８．１２、８．０１、８．００、７．９１、７．６２、７．４７、７．２１、７．１０、６．９６
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。硬化前の最低溶融粘度は５００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８９μｍ）は、Ｔｇが３３２℃（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２．６４ＧＰａ、破断強度が１１２ＭＰａ、破断伸びが１１．６％であった。 Example 1
To a three-necked 100 mL flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, was added 1.332 g (2.5 mmol) of 9,9-bis (4- (4-aminophenoxy) phenyl) fluorene, 4,4 ′. -1.502 g (7.5 mmol) of diaminodiphenyl ether and 12.5 mL of N-methyl-2-pyrrolidone were added, and after dissolution, 2.354 g (8 mmol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride ) And a polymerization reaction at room temperature for 2 hours under a nitrogen stream to produce an amic acid oligomer. To this reaction solution, 0.993 g (4 mmol) of 4- (2-phenylethynyl) phthalic anhydride was added and reacted at room temperature for 18 hours under a nitrogen stream, followed by terminal modification, followed by stirring at 175 ° C. for 5 hours for imide bonding. It was. The obtained terminal-modified imide oligomer is a random copolymer in which R 2 and R 3 are represented by a diphenyl ether group in the general formula (1), and m = 1.25 and n = 2.75 on average. After cooling, the reaction solution was poured into 200 mL of ion exchange water, and the precipitated powder was separated by filtration. The powder obtained by washing with 80 mL of methanol for 30 minutes and filtering was dried under reduced pressure at 60 ° C. for 1 day to obtain a product.
Yield: 5.668 g (97%).
1 H-NMR (300 MHz, DMSO-d 6 ): δ 8.23, 8.12, 8.01, 8.00, 7.91, 7.62, 7.47, 7.21, 7.10, 6 .96
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 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. The minimum melt viscosity before curing was 500 poise (340 ° C.). A film-like cured product (thickness 89 μm) obtained by heating this terminal-modified imide oligomer at 370 ° C. for 1 hour using a hot press has a Tg of 332 ° C. (DSC) and a 5% weight loss temperature by TGA is It was 560 ° C. Further, the mechanical properties of the cured product in the form of a film were as follows: the elastic modulus was 2.64 GPa, the breaking strength was 112 MPa, and the breaking elongation was 11.6%.

（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−（４−アミノフェノキシ）フェニル）フルオレン１．７７５ｇ（３．３３ｍｍｏｌ）、４，４’−ジアミノジフェニルエーテル１．３３５ｇ（６．６７ｍｍｏｌ）とＮ−メチル−２−ピロリドン１３．０ｍＬ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時間重合反応させアミド酸オリゴマーを生成した。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時間反応させ末端変性し、続けて１７５℃で５時間攪拌しイミド結合させた。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、Ｒ２及びＲ３がジフェニルエーテル基で表され、平均としてｍ＝１．６７、ｎ＝２．３３のランダム共重合体である。冷却後、反応液を２００ｍＬのイオン交換水に投入し、析出した粉末を濾別した。８０ｍＬ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：５．９６３ｇ（９８％）。
1Ｈ−ＮＭＲ（３００ＭＨｚ，ＤＭＳＯ−ｄ6）：δ８．２２、８．１２、８．０８、８．０２、８．００、７．６２、７．４６、７．４１、７．２１、７．１０、６．９６
ＩＲ（ＫＢｒ，ｃｍ-1）：３４４８、２２１２、１７７７、１７２０、１６１５、１５００、１３７７、１２９４、１２３９、１１７０、１１１５、１０８９、１０１４、９４３、８７８、８２５、７４０、６８９
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。硬化前の最低溶融粘度は６７０ポイズ（３４６℃）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３２９℃（ＤＳＣ）、ＴＧＡによる５％重量減少温度は５５７℃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２．６４ＧＰａ、破断強度が１１１ＭＰａ、破断伸びが１０．７％であった。 (Example 2)
In a three-necked 100 mL flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 1.775 g (3.33 mmol) of 9,9-bis (4- (4-aminophenoxy) phenyl) fluorene, 4,4 ′ -1.335 g (6.67 mmol) of diaminodiphenyl ether and 13.0 mL of N-methyl-2-pyrrolidone were added, and after dissolution, 2.354 g (8 mmol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride ) And a polymerization reaction at room temperature for 2 hours under a nitrogen stream to produce an amic acid oligomer. To this reaction solution, 0.993 g (4 mmol) of 4- (2-phenylethynyl) phthalic anhydride was added and reacted at room temperature for 18 hours under a nitrogen stream, followed by terminal modification, followed by stirring at 175 ° C. for 5 hours for imide bonding. It was. The obtained terminal-modified imide oligomer is a random copolymer in which R 2 and R 3 are represented by a diphenyl ether group in the general formula (1), and m = 1.67 and n = 2.33 on average. After cooling, the reaction solution was poured into 200 mL of ion exchange water, and the precipitated powder was separated by filtration. The powder obtained by washing with 80 mL of methanol for 30 minutes and filtering was dried under reduced pressure at 60 ° C. for 1 day to obtain a product.
Yield: 5.963 g (98%).
1 H-NMR (300 MHz, DMSO-d 6 ): δ 8.22, 8.12, 8.08, 8.02, 8.00, 7.62, 7.46, 7.41, 7.21, 7 .10, 6.96
IR (KBr, cm −1 ): 3448, 2212, 1777, 1720, 1615, 1500, 1377, 1294, 1239, 1170, 1115, 1089, 1014, 943, 878, 825, 740, 689
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. The minimum melt viscosity before curing was 670 poise (346 ° C.). A 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 329 ° C. (DSC) and a 5% weight loss temperature by TGA is It was 557 ° C. Further, the mechanical properties of the cured product in the form of a film were as follows: the elastic modulus was 2.64 GPa, the breaking strength was 111 MPa, and the breaking elongation was 10.7%.

（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−（４−アミノフェノキシ）フェニル）フルオレン２．６６３ｇ（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時間重合反応させアミド酸オリゴマーを生成した。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時間反応させ末端変性し、続けて１７５℃で５時間攪拌しイミド結合させた。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、Ｒ２及びＲ３がジフェニルエーテル基で表され、平均としてｍ＝２．５、ｎ＝１．５のランダム共重合体である。冷却後、反応液を２００ｍＬのイオン交換水に投入し、析出した粉末を濾別した。８０ｍＬ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：６．５３１ｇ（９８％）。
1Ｈ−ＮＭＲ（３００ＭＨｚ，ＤＭＳＯ−ｄ6）：δ８．２３、８．１１、８．０９、８．０１、７．９１、７．４６、７．４１、７．３４、７．２１、７．１０、６．９６
ＩＲ（ＫＢｒ，ｃｍ-1）：３４４６、２２１２、１７７７、１７２０、１６１５、１４９９、１３７６、１２９３、１２３９、１１７０、１１１５、１０８９、１０１４、９４３、８７８、８２５、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。硬化前の最低溶融粘度は１２００ポイズ（３３９℃）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８９μｍ）は、Ｔｇが３２５℃（ＤＳＣ）、ＴＧＡによる５％重量減少温度は５５７℃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２．４７ＧＰａ、破断強度が１０５ＭＰａ、破断伸びが１０．６％であった。 (Example 3)
To a three-necked 100 mL flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 2.663 g (5 mmol) of 9,9-bis (4- (4-aminophenoxy) phenyl) fluorene, 4,4′-diamino was added. Add 1.001 g (5 mmol) of diphenyl ether and 14.2 mL of N-methyl-2-pyrrolidone, and after dissolution, add 2.354 g (8 mmol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride. Then, polymerization reaction was carried out at room temperature for 2 hours under a nitrogen stream to produce an amic acid oligomer. To this reaction solution, 0.993 g (4 mmol) of 4- (2-phenylethynyl) phthalic anhydride was added and reacted at room temperature for 18 hours under a nitrogen stream, followed by terminal modification, followed by stirring at 175 ° C. for 5 hours for imide bonding. It was. The obtained terminal-modified imide oligomer is a random copolymer in which R 2 and R 3 are represented by diphenyl ether groups in the general formula (1), and m = 2.5 and n = 1.5 on average. After cooling, the reaction solution was poured into 200 mL of ion exchange water, and the precipitated powder was separated by filtration. The powder obtained by washing with 80 mL of methanol for 30 minutes and filtering was dried under reduced pressure at 60 ° C. for 1 day to obtain a product.
Yield: 6.531 g (98%).
1 H-NMR (300 MHz, DMSO-d 6 ): δ 8.23, 8.11, 8.09, 8.01, 7.91, 7.46, 7.41, 7.34, 7.21, 7 .10, 6.96
IR (KBr, cm −1 ): 3446, 2212, 1777, 1720, 1615, 1499, 1376, 1293, 1239, 1170, 1115, 1089, 1014, 943, 878, 825, 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. The minimum melt viscosity before curing was 1200 poise (339 ° C.). The film-like cured product (thickness 89 μm) obtained by heating this terminal-modified imide oligomer at 370 ° C. for 1 hour using a hot press has a Tg of 325 ° C. (DSC) and a 5% weight loss temperature by TGA is It was 557 ° C. Further, the mechanical properties of the cured product in the form of a film were as follows: the elastic modulus was 2.47 GPa, the breaking strength was 105 MPa, and the breaking elongation was 10.6%.

（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−（４−アミノフェノキシ）フェニル）フルオレン０５．３２６ｇ（１０ｍｍｏｌ）とＮ−メチル−２−ピロリドン１７．６ｍＬ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時間重合反応させアミド酸オリゴマーを生成した。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時間反応させ末端変性し、続けて１７５℃で５時間攪拌しイミド結合させた。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、Ｒ３がフルオリニリデンジフェニルエーテル基で表され、平均としてｍ＝４、ｎ＝０である。冷却後、反応液を２００ｍＬのイオン交換水に投入し、析出した粉末を濾別した。８０ｍＬ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：８．１９６ｇ（９９％）。
1Ｈ−ＮＭＲ（３００ＭＨｚ，ＤＭＳＯ−ｄ6）：δ８．１９、８．１１、８．０７、７．９９、７．６１、７．４４、７．４１、７．１４、７．１０、６．９５
ＩＲ（ＫＢｒ，ｃｍ-1）：３４４７、２２１２、１７７７、１７２０、１６１４、１４９９、１３７６、１２９４、１２３９、１１６９、１１１４、１０８９、１０１４、９４３、８７６、８２４、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。硬化前の最低溶融粘度は１６７０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フィルム状の硬化物（厚さ８６μｍ）は、Ｔｇが３１７℃（ＤＳＣ）、ＴＧＡによる５％重量減少温度は５５１℃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１０７ＭＰａ、破断伸びが９．５％であった。 Example 4
In a three-necked 100 mL flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 05.326 g (10 mmol) of 9,9-bis (4- (4-aminophenoxy) phenyl) fluorene and N-methyl-2- 17.6 mL of pyrrolidone was added and dissolved, and then 2,354 g (8 mmol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride was added, followed by polymerization reaction at room temperature for 2 hours in a nitrogen stream. An oligomer was produced. To this reaction solution, 0.993 g (4 mmol) of 4- (2-phenylethynyl) phthalic anhydride was added and reacted at room temperature for 18 hours under a nitrogen stream, followed by terminal modification, followed by stirring at 175 ° C. for 5 hours for imide bonding. It was. The obtained terminal-modified imide oligomer is represented by the general formula (1), in which R 3 is represented by a fluorenylidene diphenyl ether group, and m = 4 and n = 0 on average. After cooling, the reaction solution was poured into 200 mL of ion exchange water, and the precipitated powder was separated by filtration. The powder obtained by washing with 80 mL of methanol for 30 minutes and filtering was dried under reduced pressure at 60 ° C. for 1 day to obtain a product.
Yield: 8.196 g (99%).
1 H-NMR (300 MHz, DMSO-d 6 ): δ 8.19, 8.11, 8.07, 7.99, 7.61, 7.44, 7.41, 7.14, 7.10, 6 .95
IR (KBr, cm −1 ): 3447, 2212, 1777, 1720, 1614, 1499, 1376, 1294, 1239, 1169, 1114, 1089, 1014, 943, 876, 824, 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. The minimum melt viscosity before curing was 1670 poise (347 ° 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 317 ° C. (DSC) and a 5% weight loss temperature by TGA is It was 551 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 107 MPa, and a breaking elongation of 9.5%.

（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２時間重合反応させアミド酸オリゴマーを生成した。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時間反応させ末端変性し、続けて１７５℃で５時間攪拌しイミド結合させた。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 polymerized for 2 hours at room temperature under a nitrogen stream to produce an amic acid oligomer. To this reaction solution, 0.993 g (4 mmol) of 4- (2-phenylethynyl) phthalic anhydride was added and reacted at room temperature for 18 hours under a nitrogen stream, followed by terminal modification, followed by stirring at 175 ° C. for 5 hours for imide bonding. It was. 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２時間重合反応させアミド酸オリゴマーを生成した。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時間反応させ末端変性し、続けて１７５℃で５時間攪拌しイミド結合させた。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. Polymerization reaction was performed for 2 hours to produce an amic acid oligomer. To this reaction solution, 0.993 g (4 mmol) of 4- (2-phenylethynyl) phthalic anhydride was added and reacted at room temperature for 18 hours under a nitrogen stream, followed by terminal modification, followed by stirring at 175 ° C. for 5 hours for imide bonding. It was. 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.

（比較例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−ジアミノフェニル）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。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、７．９８、７．９６、７．６１、７．５６、７．４７、７．４４、７．３８、７．３７、７．３５、７．３３、７．３０
ＩＲ（ＫＢｒ，ｃｍ-1）：３４４８、２２１２、１７７８、１７２２、１６１６、１５０４、１３７３、１２４０、１１６９、１１１７、１０９０、１０２０、９４３、８７９、８２１、７３８、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。また硬化前の状態は粉状形態であって、加熱しても粘性はみられなかった。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フィルム状にはならずに粉末を押し固めた状態であり、この硬化物のＴｇは３７６℃（ＤＳＣ）、ＴＧＡによる５％重量減少温度は５６６℃であった。 (Comparative Example 3)
To a three-necked 100 mL flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 3,484 g (10 mmol) of 9,9-bis (4-diaminophenyl) 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. 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, 7.98, 7.96, 7.61, 7.56, 7.47, 7.44, 7.38, 7 .37, 7.35, 7.33, 7.30
IR (KBr, cm −1 ): 3448, 2212, 1778, 1722, 1616, 1504, 1373, 1240, 1169, 1117, 1090, 1020, 943, 879, 821, 738, 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. Moreover, the state before hardening was a powdery form, and even if it heated, viscosity was not seen. The cured product obtained by heating this terminal-modified imide oligomer at 370 ° C. for 1 hour using a hot press is a state in which the powder is pressed without being formed into a film, and the Tg of this cured product is 376 ° C. ( DSC), 5% weight loss temperature by TGA was 566 ° C.

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、フィルム化も容易であり、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であり、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利用可能な材料である。   The present invention is excellent in moldability such as solubility in organic solvents, solution storage stability and low melt viscosity, can be easily formed into a film, and has mechanical properties such as heat resistance and elastic modulus, tensile strength and elongation of the cured product. These are highly terminally modified imide oligomers and varnishes, and cured products thereof, which can be used in a wide range of fields that require easy moldability and high heat resistance, including aircraft and space industry equipment.

Claims (7)

一般式（１）で表される末端変性イミドオリゴマー。
Figure 2006312699
 （式中、Ｒ１、Ｒ２、Ｒ３は芳香族ジアミン残基を表し、Ｒ１は下記一般式（２）で示される芳香族ジアミン残基である。ｍおよびｎは、Ｒ３＝Ｒ１の場合はｍ≧０、Ｒ３＝Ｒ２の場合はｍ≧１で、ｎ≧０、１≦ｍ＋ｎ≦２０および０≦ｍ／（ｍ＋ｎ）≦１の関係を満たし、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。）
Figure 2006312699
 A terminal-modified imide oligomer represented by the general formula (1).
Figure 2006312699
 (In the formula, R 1 , R 2 and R 3 represent an aromatic diamine residue, and R 1 is an aromatic diamine residue represented by the following general formula (2). M and n are R 3 = R. In the case of 1 , m ≧ 0, in the case of R 3 = R 2 m ≧ 1, satisfying the relationship of n ≧ 0, 1 ≦ m + n ≦ 20 and 0 ≦ m / (m + n) ≦ 1, and the arrangement of repeating units is (It may be either block or random.)
Figure 2006312699
 Ｎ−メチル−２−ピロリドンに対し室温で固形分濃度３０重量％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 N-methyl-2-pyrrolidone at a solid content concentration of 30% by weight 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. フィルム形状での引張破断伸びが８％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 elongation at break in a film shape is 8% or more.
JP2005136729A 2005-05-09 2005-05-09 Soluble end-modified imide oligomer and varnish and cured product thereof Expired - Fee Related JP4263182B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2005136729A JP4263182B2 (en) 2005-05-09 2005-05-09 Soluble end-modified imide oligomer and varnish and cured product thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2005136729A JP4263182B2 (en) 2005-05-09 2005-05-09 Soluble end-modified imide oligomer and varnish and cured product thereof

Publications (2)

Publication Number Publication Date
JP2006312699A true JP2006312699A (en) 2006-11-16
JP4263182B2 JP4263182B2 (en) 2009-05-13

Family

ID=37534317

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2005136729A Expired - Fee Related JP4263182B2 (en) 2005-05-09 2005-05-09 Soluble end-modified imide oligomer and varnish and cured product thereof

Country Status (1)

Country Link
JP (1) JP4263182B2 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010027020A1 (en) 2008-09-03 2010-03-11 株式会社カネカ Soluble terminally modified imide oligomer using 2-phenyl-4,4'-diaminodiphenyl ether, varnish, cured product thereof, imide prepreg thereof, and fiber-reinforced laminate having excellent heat resistance
JP2011057824A (en) * 2009-09-09 2011-03-24 Daiwa Can Co Ltd Imide oligomer blend composition
JP2011132168A (en) * 2009-12-24 2011-07-07 Mitsubishi Electric Corp Thermosetting addition-reactive polyimide compound, thermosetting addition-reactive polyimide composition, and semiconductor devices using them
WO2012128165A1 (en) 2011-03-18 2012-09-27 株式会社カネカ Resin-transfer-moldable terminal-modified imide oligomer using 2-phenyl-4,4'-diaminodiphenyl ether and having excellent moldability, mixture thereof, varnish containing same, and cured resin thereof and fiber-reinforced cured resin thereof made by resin transfer molding and having excellent heat resistance
JP2013241553A (en) * 2012-05-22 2013-12-05 Hideo Nishino Thermosetting polyimide comprising cardo type diamine
WO2014181670A1 (en) 2013-05-10 2014-11-13 株式会社カネカ Polyimide resin composition comprising terminal-modified imide oligomer prepared using 2-phenyl-4,4'-diaminodiphenyl ether and aromatic thermoplastic polyimide prepared using oxydiphthalic acid, varnish, polyimide resin composition molded article having excellent heat resistance and mechanical properties, prepreg, and fiber-reinforced composite material containing said prepreg
US10047246B2 (en) 2014-05-12 2018-08-14 Kaneka Corporation Varnish including 2-phenyl-4,4′-diaminodiphenyl ether, imide resin composition having excellent moldability, cured resin molded article having excellent breaking elongation, prepreg thereof, imide prepreg thereof, and fiber-reinforced material thereof having high heat resistance and excellent mechanical strength
JPWO2017195393A1 (en) * 2016-05-09 2019-02-28 株式会社カネカ Terminal-modified imide oligomer, varnish, cured product thereof, film, and imide prepreg and fiber-reinforced composite material using the same

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8846552B2 (en) 2008-09-03 2014-09-30 Kaneka Corporation Soluble terminally modified imide oligomer using 2-phenyl-4, 4′-diaminodiphenyl ether, varnish, cured product thereof, imide prepreg thereof, and fiber-reinforced laminate having excellent heat resistance
WO2010027020A1 (en) 2008-09-03 2010-03-11 株式会社カネカ Soluble terminally modified imide oligomer using 2-phenyl-4,4'-diaminodiphenyl ether, varnish, cured product thereof, imide prepreg thereof, and fiber-reinforced laminate having excellent heat resistance
JP2011057824A (en) * 2009-09-09 2011-03-24 Daiwa Can Co Ltd Imide oligomer blend composition
JP2011132168A (en) * 2009-12-24 2011-07-07 Mitsubishi Electric Corp Thermosetting addition-reactive polyimide compound, thermosetting addition-reactive polyimide composition, and semiconductor devices using them
WO2012128165A1 (en) 2011-03-18 2012-09-27 株式会社カネカ Resin-transfer-moldable terminal-modified imide oligomer using 2-phenyl-4,4'-diaminodiphenyl ether and having excellent moldability, mixture thereof, varnish containing same, and cured resin thereof and fiber-reinforced cured resin thereof made by resin transfer molding and having excellent heat resistance
EP2687508A1 (en) * 2011-03-18 2014-01-22 Kaneka Corporation Resin-transfer-moldable terminal-modified imide oligomer using 2-phenyl-4,4'-diaminodiphenyl ether and having excellent moldability, mixture thereof, varnish containing same, and cured resin thereof and fiber-reinforced cured resin thereof made by resin transfer molding and having excellent heat resistance
EP2687508A4 (en) * 2011-03-18 2014-11-12 Kaneka Corp Resin-transfer-moldable terminal-modified imide oligomer using 2-phenyl-4,4'-diaminodiphenyl ether and having excellent moldability, mixture thereof, varnish containing same, and cured resin thereof and fiber-reinforced cured resin thereof made by resin transfer molding and having excellent heat resistance
US9051430B2 (en) 2011-03-18 2015-06-09 Kaneka Corporation Resin-transfer-moldable terminal-modified imide oligomer using 2-phenyl-4,4′diaminodiphenyl ether and having excellent moldability, mixture thereof, varnish containing same, and cured resin thereof and fiber-reinforced cured resin thereof made by resin transfer molding and having excellent heat resistance
JP2013241553A (en) * 2012-05-22 2013-12-05 Hideo Nishino Thermosetting polyimide comprising cardo type diamine
WO2014181670A1 (en) 2013-05-10 2014-11-13 株式会社カネカ Polyimide resin composition comprising terminal-modified imide oligomer prepared using 2-phenyl-4,4'-diaminodiphenyl ether and aromatic thermoplastic polyimide prepared using oxydiphthalic acid, varnish, polyimide resin composition molded article having excellent heat resistance and mechanical properties, prepreg, and fiber-reinforced composite material containing said prepreg
US10017666B2 (en) 2013-05-10 2018-07-10 Kaneka Corporation Polyimide resin composition and varnish produced from terminal-modified imide oligomer prepared using 2-phenyl-4,4′-diaminodiphenyl ether and thermoplastic aromatic polyimide prepared using oxydiphthalic acid, polyimide resin composition molded article and prepreg having excellent heat resistance and mechanical characteristic, and fiber-reinforced composite material thereof
US10815390B2 (en) 2013-05-10 2020-10-27 Kaneka Corporation Polyimide resin composition and varnish produced from terminal-modified imide oligomer prepared using 2-phenyl-4,4′-diaminodiphenyl ether and thermoplastic aromatic polyimide prepared using oxydiphthalic acid, polyimide resin composition molded article and prepreg having excellent heat resistance and mechanical characteristic, and fiber-reinforced composite material thereof
US10047246B2 (en) 2014-05-12 2018-08-14 Kaneka Corporation Varnish including 2-phenyl-4,4′-diaminodiphenyl ether, imide resin composition having excellent moldability, cured resin molded article having excellent breaking elongation, prepreg thereof, imide prepreg thereof, and fiber-reinforced material thereof having high heat resistance and excellent mechanical strength
JPWO2017195393A1 (en) * 2016-05-09 2019-02-28 株式会社カネカ Terminal-modified imide oligomer, varnish, cured product thereof, film, and imide prepreg and fiber-reinforced composite material using the same
US10526450B2 (en) 2016-05-09 2020-01-07 Kaneka Corporation Terminally modified imide oligomer, varnish, cured products thereof, film, and imide prepreg and fiber-reinforced composite material using these

Also Published As

Publication number Publication date
JP4263182B2 (en) 2009-05-13

Similar Documents

Publication Publication Date Title
JP5522479B2 (en) Soluble terminal-modified imide oligomer using 2-phenyl-4,4&#39;-diaminodiphenyl ether, varnish, cured product thereof, imide prepreg thereof, and fiber-reinforced laminate having excellent heat resistance
JP4787552B2 (en) Soluble end-modified imide oligomer and varnish and cured product thereof
TWI475046B (en) Imide oligomer and polymide resin formed by heat-hardening such imide oligomer
US10047246B2 (en) Varnish including 2-phenyl-4,4′-diaminodiphenyl ether, imide resin composition having excellent moldability, cured resin molded article having excellent breaking elongation, prepreg thereof, imide prepreg thereof, and fiber-reinforced material thereof having high heat resistance and excellent mechanical strength
JP4263182B2 (en) Soluble end-modified imide oligomer and varnish and cured product thereof
JP4214531B2 (en) Soluble end-modified imide oligomer and varnish and cured product thereof
US20140148548A1 (en) Fluorine-Containing Polymerizable Monomer And Polymer Compound Using Same
JP4968540B2 (en) Soluble end-modified imide oligomer and varnish and cured product thereof
JP5050269B2 (en) Terminal-modified imide oligomer and varnish and cured product thereof having high elastic modulus
US10526450B2 (en) Terminally modified imide oligomer, varnish, cured products thereof, film, and imide prepreg and fiber-reinforced composite material using these
TW201641497A (en) New tetracarboxylic dianhydride, and polyimide and polyimide copolymer that are obtained from the new tetracarboxylic dianhydride
JP6202554B2 (en) Polyimide resin composition made of terminal-modified imide oligomer using 2-phenyl-4,4&#39;-diaminodiphenyl ether and aromatic thermoplastic polyimide using oxydiphthalic acid, and varnish, and heat resistance and mechanical properties Excellent molded article of polyimide resin composition, prepreg, and fiber reinforced composite material thereof
JP6332528B2 (en) Polyimide resin composition made of terminal-modified imide oligomer using 2-phenyl-4,4&#39;-diaminodiphenyl ether and aromatic thermoplastic polyimide using oxydiphthalic acid, and varnish, and heat resistance and mechanical properties Excellent molded article of polyimide resin composition, prepreg, and fiber reinforced composite material thereof
EP2687508B1 (en) Resin-transfer-moldable terminal-modified imide oligomer using 2-phenyl-4,4&#39;-diaminodiphenyl ether and having excellent moldability, mixture thereof, varnish containing same, and cured resin thereof and fiber-reinforced cured resin thereof made by resin transfer molding and having excellent heat resistance
JP4042861B2 (en) Imido prepreg and laminate
KR101288724B1 (en) Polyamic acid and polyimide coating layer
JP2011184492A (en) Soluble terminally modified imide oligomer and varnish, and cured product thereof
JP2008001791A (en) Soluble terminal-modified amic acid silyl ester oligomer, varnish and their cured product

Legal Events

Date Code Title Description
A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20071210

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20080108

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20080307

A02 Decision of refusal

Free format text: JAPANESE INTERMEDIATE CODE: A02

Effective date: 20080702

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20080829

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20080912

A911 Transfer of reconsideration by examiner before appeal (zenchi)

Free format text: JAPANESE INTERMEDIATE CODE: A911

Effective date: 20081022

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20081119

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20081209

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20090114

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20090210

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20120220

Year of fee payment: 3

R150 Certificate of patent or registration of utility model

Free format text: JAPANESE INTERMEDIATE CODE: R150

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20130220

Year of fee payment: 4

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20130220

Year of fee payment: 4

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20140220

Year of fee payment: 5

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

S111 Request for change of ownership or part of ownership

Free format text: JAPANESE INTERMEDIATE CODE: R313117

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

S533 Written request for registration of change of name

Free format text: JAPANESE INTERMEDIATE CODE: R313533

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

LAPS Cancellation because of no payment of annual fees