JP2004250584A - Polyimide resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyimide resin composition that gives a cured product having high heat resistance, a low dielectric constant, a low dielectric loss tangent and good mechanical properties such as tensile strength and tensile elongation, when an epoxy resin is used as a curing agent. <P>SOLUTION: The polyimide resin composition contains a polyimide resin (X) having a carboxylic group and an aliphatic structure (1) with a number-average molecular weight of 100-1,000 at the terminal, preferably a polyimide resin having a carboxylic group, the aliphatic structure (1), a urethane bond, an imide ring, an isocyanurate ring and a cyclic polyaliphatic structure (3) and a polyimide resin (Y) having a carboxylic group and a linear polyaliphatic structure (2) with a number-average molecular weight of 300-6,000, preferably a polyimide resin having a carboxylic group, the linear polyaliphatic structure (2) with a number-average molecular weight of 300-6,000, a urethane bond, an imide ring, an isocyanurate ring and the cyclic polyaliphatic structure (3). <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

（ただし、式中のＲ_１は炭素数原子６〜１３の環式脂肪族構造を有する有機基、Ｒ_２は数平均分子量１００〜１，０００の脂肪族構造、Ｒ_３は数平均分子量３００〜６，０００の線状炭化水素構造を示す。）
【化４】

【００１６】
前記ポリイミド樹脂（Ｘ）とポリイミド樹脂（Ｙ）の重量比（Ｘ）／（Ｙ）は、特に限定されないが、通常５／９５〜９５／５であり、なかでも耐熱性、機械物性に優れ、コーティング適性の良好なポリイミド樹脂組成物が得られることから、１０／９０〜８０／２０が好ましく、１５／８５〜６０／４０が特に好ましい。なお、前記ポリイミド樹脂（Ｘ）の含有割合が大きい場合、コーティング適性が良好となるが耐熱性および機械物性が低下し、逆にポリイミド樹脂（Ｙ）の含有割合が大きい場合、耐熱性および機械物性に優れるがコーティング適性が低下する傾向があるため、使用する目的や用途に応じて、前記重量比（Ｘ）／（Ｙ）を適宜選択もしくは調整することが好ましい。
【００１７】
なお、本発明において、ポリイミド樹脂（Ｘ）、（Ｙ）の酸価、イソシアヌレート環の濃度、数平均分子量および重量平均分子量は、以下の方法で測定したものである。
（１）酸価：ＪＩＳ Ｋ−５６０１−２−１に準じて測定する。尚、試料の希釈溶剤としては、無水酸の酸価も測定できるようにアセトン／水（９／１体積比）の混合溶剤で酸価０のものを使用する。
（２）イソシアヌレート環の濃度：^１３Ｃ−ＮＭＲ分析〔溶媒：重水素化ジメチルスルホキシド（ＤＭＳＯ−ｄ_６）を行い、１４９ｐｐｍにあるイソシアヌレート環に起因する炭素原子のスペクトル強度から検量線を用いてポリイミド樹脂（Ｘ）１ｇ当たりのイソシアヌレート環の濃度（ｍｍｏｌ）を求める。なお、^１３Ｃ−ＮＭＲ分析により１６９ｐｐｍにあるイミド環に起因する炭素原子のスペクトル強度から同様にイミド環の濃度を求めることもできる。
（３）数平均分子量と重量平均分子量：ゲルパーミネーションクロマトグラフィー（ＧＰＣ）によりポリスチレン換算の数平均分子量と重量平均分子量を求める。
【００１８】
なお、ポリイミド樹脂（Ｘ）中における脂肪族構造（１）部分の含有率とポリイミド樹脂（Ｘ）中における線状多価脂肪族構造（２）部分の含有率は、ポリイミド樹脂（Ｘ）、（Ｙ）が後記する製造方法で製造したポリイミド樹脂である場合、合成原料中におけるアルコール化合物（ａ１）の使用重量割合またはポリオール化合物（ａ２）の使用重量割合からそれぞれ求めることができる。また、前記脂肪族構造（１）部分の数平均分子量はアルコール化合物（ａ１）の数平均分子量から求めることができ、線状多価脂肪族構造（２）部分の数平均分子量は前記ポリオール化合物（ａ２）の数平均分子量から求めることができる。
【００１９】
製造方法が不明のポリイミド樹脂（Ｘ）、（Ｙ）中における脂肪族構造（１）部分や線状多価脂肪族構造（２）部分の含有率と数平均分子量は、ポリイミド樹脂（Ｘ）、（Ｙ）を通常の加水分解法、例えば有機アミンの存在下で熱処理してウレタン結合を分解して脂肪族構造（１）部分と線状多価脂肪族構造（２）部分を前記ポリイミド樹脂（Ｘ）、（Ｙ）から切り離し、これらがイミド構造部分に比較して低極性であることを利用して、ジクロロメタン等の低極性有機溶剤で抽出し、抽出量の測定とＧＰＣ分析とを行うことで求めることができる。
【００２０】
本発明のポリイミド樹脂組成物に用いる前記ポリイミド樹脂（Ｘ）、（Ｙ）の製造方法は、特に限定されないが、ポリイミド樹脂（Ｘ）の製造方法としては、ポリイソシアネート化合物（ａ０）と、脂肪族構造（１）を有するアルコール化合物であって、脂肪族構造（１）部分の数平均分子量が１００〜１，０００のアルコール化合物（ａ１）を反応させて得られる末端にイソシアネート基を有するプレポリマー（Ａ１）と、３個以上のカルボキシル基を有するポリカルボン酸の酸無水物（Ｂ）を有機溶剤中で反応させる方法が好ましい。また、ポリイミド樹脂（Ｙ）の製造方法としては、ポリイソシアネート化合物（ａ０）と、線状多価脂肪族構造（２）を有するポリオール化合物であって、線状多価脂肪族構造（２）部分の数平均分子量が３００〜６，０００のポリオール化合物（ａ２）を反応させて得られる末端にイソシアネート基を有するプレポリマー（Ａ２）と、３個以上のカルボキシル基を有するポリカルボン酸の酸無水物（Ｂ）を有機溶剤中で反応させる方法が好ましい。
【００２１】
例えば、前記ポリイミド樹脂（Ｘ）、（Ｙ）の製造方法によりポリイミド樹脂（Ｘ２）を製造するには、炭素原子数が６〜１３の環式脂肪族構造を有するジイソシアネートから誘導されるイソシアヌレート環を有するポリイソシアネートと脂肪族構造を有するアルコール化合物であって、脂肪族構造部分の数平均分子量が１００〜１，０００のアルコール化合物（ａ１）反応させて得られる末端にイソシアネート基を有するプレポリマーと、トリカルボン酸の酸無水物を有機溶剤中で反応させればよいし、ポリイミド樹脂（Ｙ２）を製造するには、炭素原子数が６〜１３の環式脂肪族構造を有するジイソシアネートから誘導されるイソシアヌレート環を有するポリイソシアネートと線状多価脂肪族構造を有するポリオール化合物であって、線状多価脂肪族構造部分の数平均分子量が３００〜６，０００のポリオール化合物（ａ２）を反応させて得られる末端にイソシアネート基を有するプレポリマーと、トリカルボン酸の酸無水物を有機溶剤中で反応させればよい。
【００２２】
なお、前記末端にイソシアネート基を有するプレポリマーを得るには、有機溶剤中で、ポリイソシアネート化合物（ａ０）と、アルコール化合物（ａ１）またはポリオール化合物（ａ２）とを、前記アルコール化合物（ａ１）またはポリオール化合物（ａ２）中の水酸基に対してポリイソシアネート化合物（ａ０）中のイソシアネート基が過剰となる条件下で反応させる方法が好ましい。
【００２３】
前記ポリイソシアネート化合物（ａ０）と、アルコール化合物（ａ１）またはポリオール化合物（ａ２）の反応の際の反応温度は通常５０〜１５０℃、好ましくは６０〜１００℃であり、この反応で得られたプレポリマー（Ａ１）、（Ａ２）とポリカルボン酸の酸無水物（Ｂ）の反応の際の反応温度は通常８０〜２５０℃、好ましくは１００〜２００℃である。
【００２４】
この際に用いるアルコール化合物（ａ１）またはポリオール化合物（ａ２）中の水酸基に対するポリイソシアネート化合物（ａ０）中のイソシアネート基のモル比（ＮＣＯ／ＯＨ）は通常１．２〜２０、好ましくは１．５〜１０である。また、この際には各種のウレタン化触媒を使用することができる。
【００２５】
前記ポリイミド樹脂（Ｘ）、（Ｙ）の製造方法では、前記プレポリマー（Ａ）と前記ポリカルボン酸の酸無水物（Ｂ）とを有機溶剤中で反応させてポリイミド樹脂を得る際、これらプレポリマー（Ａ）とポリカルボン酸の酸無水物（Ｂ）との重量比を変えることによって、得られるポリイミド樹脂（Ｘ）、（Ｙ）の分子量および酸価を調整することができる。また、この際に触媒を使用しても良く、さらに酸化防止剤や重合禁止剤等を併用してもよい。
【００２６】
前記プレポリマー（Ａ）と前記ポリカルボン酸の酸無水物（Ｂ）の重量比（Ａ）／（Ｂ）は通常９０／１０〜５０／５０であるが、なかでも硬化物の耐熱性、機械物性に優れるポリイミド樹脂（Ｘ）、（Ｙ）が得られることから８０／２０〜６０／４０が好ましい。
【００２７】
前記ポリイソシアネート化合物（ａ０）は、分子内に２個以上のイソシアネート基を有する化合物であり、例えば、芳香族ポリイソシアネート、脂肪族ポリイソシアネート（環式脂肪族ポリイソシアネートを含む）；これらポリイソシアネートのヌレート体、ビュレット体、アダクト体、アロハネート体等が挙げられる。
【００２８】
前記芳香族ポリイソシアネート化合物としては、例えば、ｐ−フェニレンジイソシアネート、ｍ−フェニレンジイソシアネート、ｐ−キシレンジイソシアネート、ｍ−キシレンジイソシアネート、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、４，４′−ジフェニルメタンジイソシアネート、ポリメチレンポリフェニルポリイソシアネート（クルードＭＤＩ）、ポリメチレンポリフェニルイソシアネート、３，３′−ジメチルジフェニル−４，４′−ジイソシアネート、３，３′−ジエチルジフェニル−４，４′−ジイソシアネート、ｍ−キシレンジイソシアネート、ｐ−キシレンジイソシアネート、１，３−ビス（α，α−ジメチルイソシアナートメチル）ベンゼン、テトラメチルキシリレンジイソシアネート、ジフェニレンエーテル−４，４′−ジイソシアネート、ナフタレンジイソシアネート等が挙げられる。
【００２９】
前記脂肪族ポリイソシアネート化合物としては、例えば、ヘキサメチレンジイソシアネート、リジンジイソシアネート、トリメチルヘキサメチレンメチレンジイソシアネート、イソホロンジイソシアネート、４，４′−ジシクロヘキシルメタンジイソシアネート、水素添加キシレンジイソシアネート、ノルボヌレンジイソシアネート等が挙げられる。
【００３０】
前記ポリイソシアネート化合物（ａ０）としては、有機溶剤溶解性やエポキシ樹脂や有機溶剤との相溶性が良好で、硬化物の誘電率と誘電正接が低いポリイミド樹脂が得られることから、脂肪族ポリイソシアネートが好ましい。また、硬化物の耐熱性の良好なポリイミド樹脂が得られることからイソシアヌレート型ポリイソシアネートが好ましい。
【００３１】
更に、前記ポリイソシアネート化合物（ａ０）としては、有機溶剤溶解性やエポキシ樹脂や有機溶剤との相溶性が良好で、硬化物の誘電率と誘電正接が低く、耐熱性が良好なポリイミド樹脂が得られることから、脂肪族ポリイソシアネートから誘導されるイソシアヌレート環を有するポリイソシアネート化合物（ａ０１）がより好ましく、環式脂肪族ポリイソシアネートから誘導されるイソシアヌレート環を有するポリイソシアネート化合物が更に好ましい。前記環式脂肪族ポリイソシアネートから誘導されるイソシアヌレート環を有するポリイソシアネート化合物としては、イソシアヌレート環の１モルに対して環式脂肪族構造を２〜３モル倍有するものが挙げられるが、該環式脂肪族構造を２．５〜３モル倍有するものがより好ましい。
【００３２】
前記ポリイソシアネート化合物（ａ０１）としては、例えば、１種または２種以上の脂肪族ジイソシアネート化合物を、第４級アンモニウム塩等のイソシアヌレート化触媒の存在下あるいは非存在下において、イソシアヌレート化することにより得られるものであって、３量体、５量体、７量体等のイソシアヌレートの混合物からなるもの等が挙げられる。前記ポリイソシアネート化合物（ａ０１）の具体例としては、イソホロンジイソシアネートのイソシアヌレート型ポリイソシアネート、ヘキサメチレンジイソシアネートのイソシアヌレート型ポリイソシアネート、水素添加キシレンジイソシアネートのイソシアヌレート型ポリイソシアネート、ノルボルナンジイソシアネートのイソシアヌレート型ポリイソシアネート等が挙げられる。
【００３３】
前記ポリイソシアネート化合物（ａ０１）としては、有機溶剤溶解性や硬化物の耐熱性が良好なポリイミド樹脂が得られることから、ポリイソシアネート化合物（ａ０）１００重量部中に３量体のイソシアヌレートを３０重量部以上含有するものが好ましく、５０重量部以上含有するものが特に好ましい。
【００３４】
また、前記ポリイソシアネート化合物（ａ０１）としては、イソシアネート基の含有率が１０〜３０重量％であることも、有機溶剤溶解性や硬化物の耐熱性が良好なポリイミド樹脂が得られることからより好ましい。従って、前記ポリイソシアネート化合物（ａ０１）としては、環式脂肪族ポリイソシアネートから誘導されるイソシアヌレート環を有するポリイソシアネート化合物であって、イソシアネート基の含有率が１０〜３０重量％であるものが最も好ましい。
【００３５】
前記イソシアヌレート環を有するポリイソシアネートは、他のポリイソシアネートと併用しても良いが、イソシアヌレート型ポリイソシアネートを単独で使用するのが好ましい。
【００３６】
前記アルコール化合物（ａ１）は、脂肪族構造（１）を有するアルコール化合物であって、脂肪族構造（１）部分の数平均分子量が１００〜１，０００のアルコール化合物であり、なかでも、硬化物の機械物性と誘電特性のバランスが良好なポリイミド樹脂が得られることから、脂肪族構造（１）部分の数平均分子量が２００〜７００のアルコール化合物が好ましく、脂肪族構造（１）が線状脂肪族構造であって、線状脂肪族構造部分の数平均分子量が２００〜７００のアルコール化合物がより好ましい。脂肪族構造（１）部分の数平均分子量が１００未満のアルコール化合物では硬化物の誘電率と誘電正接が高くなるため好ましくなく、脂肪族構造部分の数平均分子量が１，０００を越えるアルコール化合物では硬化物の機械物性が不良となるため好ましくない。前記アルコール化合物（ａ１）としては、１級から３級のアルコール化合物が使用可能であるが反応性の面から１級または２級のアルコール化合物が好ましい。また、アルコール化合物（ａ１）は単独で用いても２種以上併用してもよい。
【００３７】
前記アルコール化合物（ａ１）が有する脂肪族構造は、直鎖状でも良いし分岐状でも良く、また、飽和でも不飽和でも良いが、加熱時の物性変化や安定性の面から飽和の脂肪族構造であることがより好ましい。
【００３８】
前記アルコール化合物（ａ１）としては、例えば、炭素原子数６〜７０の脂肪族アルコール、炭素原子数６〜７０のアルキル基を有するアルキルフェノール、アルキレンオキサイドで変性された炭素原子数６〜７０のアルキル基を有するアルキルフェノール等が挙げられ、なかでも炭素原子数６〜７０の脂肪族アルコールが好ましい。
【００３９】
前記炭素原子数６〜７０の脂肪族アルコールとしては、例えば、ラウリルアルコール、オレイルアルコール等の天然油脂を原料とする高級アルコール、石油化学製品を原料とする高級アルコール等があるが、いずれも使用することが可能である。その製法としては、還元法、ケン化法、オキソ法、液層酸価法等が挙げられるる。高級アルコールの原料は、単独で用いても２種以上併用してもかまわない。
【００４０】
このような脂肪族アルコールとしては、例えば、三菱化学（株）製のダイヤドールシリーズ（ダイヤドール７、９、１１、１３、１３５、９１１、１１５Ｈ、１１５Ｌ等）、ドバノールシリーズ（ドバノール２３、２５、４５等）；花王（株）製のカルコールシリーズ（カルコール２０９８，４０９８，６０９８，６８７０，６８５０，８０９８，８６８８，２００ＧＤ、２２０−８０等）；新日本理化（株）製のコノールシリーズ（コノール１０Ｍ、１０Ｗ、１０ＷＳ、１０Ｄ、１０９８、２０Ｆ、１２７５、２０Ｐ、１４６５、１４９５、３０ＣＫ、１６６８、１６９５、３０Ｔ、３０ＴＤ、３０Ｆ、３０ＳＳ、２２６５、２２８０、３０ＲＣ、３０ＯＣ、３０ＣＫ−Ｒ等）、アンジェコールシリーズ（アンジェコール５０Ａ、６０ＡＮ、７０ＡＮ、８０ＡＮ、８５ＡＮ、９０Ｎ、９０ＮＲ、９０ＮＨＲ等）、リカコールシリーズ（リカコール９０Ｂ、９０ＢＲ、９０ＢＲＨＲ等）、エヌジェコールシリーズ（エヌジェコール１６０Ｂ、１６０ＢＲ、２００Ａ、２００ＡＴ、２４０Ａ、Ｃ３２−３６等）；等が挙げられる。
【００４１】
前記ポリオール化合物（ａ２）は、線状多価脂肪族構造（２）を有するポリオール化合物であって、線状多価脂肪族構造（２）部分の数平均分子量が３００〜６，０００のポリオール化合物であり、なかでも、有機溶剤溶解性やエポキシ樹脂や有機溶剤との相溶性に優れ、硬化物の機械物性が良好で、硬化物の誘電率と誘電正接が低く、造膜性に優れるポリイミド樹脂が得られることから、線状多価脂肪族構造（２）部分の数平均分子量が７００〜４，５００のポリオール化合物が好ましく、線状多価脂肪族構造（２）部分の数平均分子量が８００〜４，２００のポリオール化合物がより好ましい。線状多価脂肪族構造（２）部分の数平均分子量が３００未満のポリオール化合物では、硬化物の誘電率と誘電正接が高くなるため好ましくなく、線状多価脂肪族構造（２）部分の数平均分子量が６，０００を越えるポリオール化合物では、有機溶剤溶解性やエポキシ樹脂や有機溶剤との相溶性と硬化物の機械物性が不良となるため好ましくない。
【００４２】
前記ポリオール化合物（ａ２）としては、例えば、線状多価脂肪族構造（２）の末端および／または側鎖に結合した水酸基を合計で１分子当たり平均２個以上有する化合物が挙げられる。前記線状多価脂肪族構造（２）は、直鎖状でも良いし分岐状でも良い。また、前記線状多価脂肪族構造（２）は、飽和でも良いし不飽和でも良いが、加熱時の物性変化や安定性の面から飽和の脂肪族構造がより好ましい。
【００４３】
前記ポリオール化合物（ａ２）としては、ポリオレフィン構造やポリジエン構造を有するポリオール化合物であって、ポリオレフィン構造やポリジエン構造を有するポリオールの数平均分子量が３００〜６，０００のポリオール化合物およびその水素添加物が挙げられる。前記オレフィンとしては、例えば、エチレン、プロピレン、ブテン、イソブチレン、ペンテン、メチルペンテン等が挙げられ、前記ジエンとしては、例えば、ペンタジエン、ヘキサジエン、ペンタジエン、イソプレン、ブタジエン、プロパジエン、ジメチルブタジエン等が挙げられる。
【００４４】
前記ポリオール化合物（ａ２）の具体例としては、ポリエチレン系ポリオール、ポリプロピレン系ポリオール、ポリブタジエンポリオール、水素添加ポリブタジエンポリオール、ポリイソプレンポリオール、水素添加ポリイソプレンポリオール等であって、線状炭化水素構造部分の数平均分子量３００〜６，０００のポリオール化合物が挙げられる。これらは、単独で用いても、２種以上併用しても良い。
【００４５】
前記ポリオール化合物（ａ２）の水酸基の数は、平均２〜３個であることが、ゲル化しにくく、分子成長が良好で、硬化物の機械物性に優れるポリイミド樹脂が得られることから好ましい。更に水酸基の数は、平均２〜２．５個のものが特に好ましい。
【００４６】
前記ポリオール化合物（ａ２）の市販品としては、例えば、日本曹達（株）製のＮＩＳＳＯ ＰＢ（Ｇシリーズ）、出光石油化学（株）製のＰｏｌｙ−ｂｄ等の両末端に水酸基を有する液状ポリブタジエン；日本曹達（株）製のＮＩＳＳＯ ＰＢ（ＧＩシリーズ）、三菱化学（株）製のポリテールＨ、ポリテールＨＡ等の両末端に水酸基を有する水素添加ポリブタジエン；出光石油化学（株）製のＰｏｌｙ−ｉＰ等の両末端に水酸基を有する液状Ｃ５系重合体；出光石油化学（株）製のエポール、クラレ（株）製のＴＨ−１、ＴＨ−２、ＴＨ−３等の両末端に水酸基を有する水素添加ポリイソプレンなどが挙げられる。
【００４７】
さらに、前記ポリオール化合物（ａ２）としては、前記したような線状多価脂肪族構造（２）を有するポリオール化合物に各種多塩基酸やポリイソシアネートを反応させて得られるエステル変性ポリオール化合物やウレタン変性ポリオール化合物も使用可能である。
【００４８】
前記ポリオール化合物（ａ２）としては、ポリブタジエンポリオールおよび／または水素添加ポリブタジエンポリオールが好ましく、なかでも、水素添加ポリブタジエンポリオールがより好ましい。
【００４９】
なお、前記ポリイミド樹脂（Ｙ）の製造方法において、ポリオール化合物（ａ２）は、本発明の効果を損ねない程度にその他の水酸基含有化合物と併用しても良い。このときその他の水酸基含有化合物は、全水酸基含有化合物中の５０重量％以下で使用することが望ましい。
【００５０】
前記その他の水酸基含有化合物としては、飽和のポリオールでも、不飽和のポリオールでも、アルコールでも良いが、ポリオールが好ましく、例えば、低分子のポリオールとして、エチレングリコール、１，３−プロピレングリコール、１，２−プロピレングリコール、ネオペンチルグリコール、１，３−ブタンジオール、１，４−ブタンジオール、１，６−ヘキサンジオール、１，９−ノナンジオール、１，１０−デカンジオール、２，２，４−トリメチル−１，３−ペンタンジオール、３−メチル−１，５−ペンタンジオール、シクロヘキサンジメチロール、１，４−シクロヘキサンジオール、トリシクロデカンジメチロール、水添ビスフェノールＡ、トリメチロールエタン、トリメチロールプロパン、ジトリメチロールエタン、ジトリメチロールプロパン、グリセリン、ジグリセロール、３−メチルペンタン−１，３，５−トリオール、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、２，２，６，６−テトラメチロールシクロヘキサノール−１、マンニット、ソルビトール、イノシトール、グルコース、ジエチレングリコール、ジプロピレングリコール、ジクロロネオペンチルグリコール、ジブロモネオペンチルグリコール、ヒドロキシピバリン酸ネオペンチルグリコールエステル、スピログリコール、エチレンオキサイド付加ビスフェノールＡ、プロピレンオキサイド付加ビスフェノ−ルＡ、ジメチロールプロピオン酸、ジメチロールブタン酸等の２官能ジオール；トリス２ヒドロキシエチルイソシアヌレート等が挙げられる。
【００５１】
また、オリゴマーや高分子量のポリオールとして、エチレンオキサイド、プロピレンオキサイド、テトラヒドロフラン、ブチレンオキサイド等の環状エーテル化合物から重合されるポリエチレンポリオール；ポリプロピレンポリオール、ポリテトラメチレンポリオール、ポリブチレンポリオール、等のポリエーテルポリオールやこれら環状エーテルの共重合体であるポリエーテルポリオール；上述の低分子ポリオールと多塩基酸から合成されるポリエステルポリオール、；ポリカーボネートポリオール、ウレタンポリオール、ポリジメチルシロキサンポリオール等のシリコンポリオール；アクリルポリオール；エポキシポリオール等のオリゴマーが挙げられる。
【００５２】
本発明で用いる３個以上のカルボキシル基を有するポリカルボン酸の酸無水物（Ｂ）としては、例えば、トリカルボン酸の酸無水物、テトラカルボン酸の酸無水物等が挙げられる。
【００５３】
トリカルボン酸の酸無水物としては、例えば、無水トリメリット酸、ナフタレン−１，２，４−トリカルボン酸無水物等が挙げられる。
【００５４】
テトラカルボン酸の酸無水物としては、例えば、ピロメリット酸二無水物、ベンゾフェノン−３，４，３′，４′−テトラカルボン酸二無水物、ジフェニルエーテル−３，４，３′，４′−テトラカルボン酸二無水物、ベンゼン−１，２，３，４−テトラカルボン酸二無水物、ビフェニル−３，４，３′，４′−テトラカルボン酸二無水物、ビフェニル−２，３，２′，３′−テトラカルボン酸二無水物、ナフタレン−２，３，６，７−テトラカルボン酸二無水物、ナフタレン−１，２，４，５−テトラカルボン酸二無水物、ナフタレン−１，８，４，５−テトラカルボン酸二無水物、デカヒドロナフタレン−１，８，４，５−テトラカルボン酸二無水物、４，８−ジメチル−１，２，３，５，６，７−ヘキサヒドロナフタレン−１，２，５，６−テトラカルボン酸二無水物、
【００５５】
２，６−ジクロロナフタレン−１，８，４，５−テトラカルボン酸二無水物、２，７−ジクロロナフタレン−１，８，４，５−テトラカルボン酸二無水物、２，３，６，７−テトラクロロナフタレン−１，８，４，５−テトラカルボン酸二無水物、フェナントレン−１，２，９，１０−テトラカルボン酸二無水物、ベリレン−３，４，９，１０−テトラカルボン酸二無水物、ビス（２，３−ジカルボキシフェニル）メタン二無水物、ビス（３，４−ジカルボキシフェニル）メタン二無水物、１，１−ビス（２，３−ジカルボキシフェニル）エタン二無水物、１，１−ビス（３，４−ジカルボキシフェニル）エタン二無水物、２，２−ビス（２，３−ジカルボキシフェニル）プロパン二無水物、２，３−ビス（３，４−ジカルボキシフェニル）プロパン二無水物、ビス（３，４−ジカルボキシフェニル）スルホン二無水物、ビス（３，４−ジカルボキシフェニル）エーテル二無水物等の分子内に芳香族有機基を有するテトラカルボン酸の無水物が挙げられる。これらの１種又は２種以上を用いることが可能である。また、トリカルボン酸の無水物とテトラカルボン酸の無水物を混合して使用してもよい。
【００５６】
前記ポリイミド樹脂（Ｘ）、（Ｙ）の製造方法で用いる有機溶剤としては、系中にあらかじめ存在させてから化反応を行っても、途中で導入してもよく、その使用するタイミングや量には制限は特にないが、前記プレポリマー（Ａ）と前記ポリカルボン酸の酸無水物（Ｂ）の反応の開始時には存在させておくことが好ましい。また、この反応に際して適切な反応速度を維持するために系中の有機溶剤の割合は、反応系の８０重量％以下が好ましく、１０〜７０重量％がより好ましい。かかる有機溶剤としては、原料成分としてイソシアネート基を含有する化合物を使用するため、水酸基やアミノ基等の活性プロトンを有しない非プロトン性極性溶剤が好ましい。
【００５７】
前記非プロトン性極性溶剤としては、例えば、エーテル系溶剤、エステル系溶剤、ケトン系溶剤等が挙げられる。なかでもエーテル系溶剤は、弱い極性を持ち、前記末端にイソシアネート基を有するプレポリマー（Ａ）と３個以上のカルボキシル基を有するポリカルボン酸の無水物（Ｂ）とのイミド化反応において優れた反応場を提供する。
【００５８】
かかるエーテル系溶剤としては、例えば、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジブチルエーテル等のエチレングリコールジアルキルエーテル類；ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、トリエチレングリコールジメチルエーテル、トリエチレングリコールジエチルエーテル、トリエチレングリコールジブチルエーテル等のポリエチレングリコールジアルキルエーテル類；
【００５９】
エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート等のエチレングリコールモノアルキルエーテルアセテート類；ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、トリエチレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノエチルエーテルアセテート、トリエチレングリコールモノブチルエーテルアセテート、等のポリエチレングリコールモノアルキルエーテルアセテート類；
【００６０】
プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、プロピレングリコールジブチルエーテル等のプロピレングリコールジアルキルエーテル類；ジプロピレングリコールジメチルエーテル、ジプロピレングリコールジエチルエーテル、ジプロピレングリコールジブチルエーテル、トリプロピレングリコールジメチルエーテル、トリプロピレングリコールジエチルエーテル、トリプロピレングリコールジブチルエーテル等のポリプロピレングリコールジアルキルエーテル類；プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート等のプロピレングリコールモノアルキルエーテルアセテート類；
【００６１】
ジプロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノエチルエーテルアセテート、ジプロピレングリコールモノブチルエーテルアセテート、トリプロピレングリコールモノメチルエーテルアセテート、トリプロピレングリコールモノエチルエーテルアセテート、トリプロピレングリコールモノブチルエーテルアセテート等のポリプロピレングリコールモノアルキルエーテルアセテート類；低分子のエチレン−プロピレン共重合体等の共重合ポリエーテルグリコールのジアルキルエーテル類；共重合ポリエーテルグリコールのモノアセテートモノアルキルエーテル類；共重合ポリエーテルグリコールのアルキルエステル類；共重合ポリエーテルグリコールのモノアルキルエステルモノアルキルエーテル類等が挙げられる。
【００６２】
エステル系溶剤としては、例えば、酢酸エチル、酢酸ブチル等が挙げられる。ケトン系溶剤としては、アセトン、メチルエチルケトン、シクロヘキサノン等が挙げられる。また、これらにジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、ジメチルスルフォキシド、スルホラン、γ−ブチロラクトンなどの極性溶媒を併用することもできる。
【００６３】
本発明のポリイミド樹脂組成物は、前記ポリイミド樹脂（Ｘ）とポリイミド樹脂（Ｙ）を含有するものであるが、熱硬化性のポリイミド樹脂組成物とするには、さらにエポキシ樹脂（Ｚ）を含有させることが必要であり、更に必要によりフェノール性水酸基を２個以上有する化合物（Ｆ）を含有させてもよい。
【００６４】
前記エポキシ樹脂（Ｚ）としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等のビスフェノール型エポキシ樹脂；フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノール型ノボラック等のノボラック型エポキシ樹脂；ジシクロペンタジエンと各種フェノール類と反応させて得られる各種ジシクロペンタジエン変性フェノール樹脂のエポキシ化物；２，２′，６，６′−テトラメチルビフェノールのエポキシ化物等のビフェニル型エポキシ樹脂；ナフタレン骨格を有するエポキシ樹脂；フルオレン骨格を有するエポキシ樹脂等の芳香族系エポキシ樹脂やこれら芳香族系エポキシ樹脂の水素添加物；ネオペンチルグリコールジグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル等の脂肪族エポキシ樹脂；３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレート、ビス−（３，４−エポキヒシクロヘキシル）アジペート等の脂環式エポキシ樹脂；トリグリシジルイソシアヌレート等のごときヘテロ環含有エポキシ樹脂等が挙げられる。これらのなかでも、耐熱性に優れる熱硬化性ポリイミド樹脂組成物が得られることから、芳香族系エポキシ樹脂が好ましい。
【００６５】
ポリイミド樹脂（Ｘ）および（Ｙ）の合計とエポキシ樹脂（Ｚ）の配合比率としては、ポリイミド樹脂（Ｘ）および（Ｙ）の合計とエポキシ樹脂（Ｚ）の重量比（ＸＹ）／（Ｚ）が１〜１０となる範囲であることが好ましく、１〜５となる範囲であることがより好ましい。また、ポリイミド樹脂（Ｘ）および（Ｙ）中の合計のカルボキシル基（ｘｙ）とエポキシ樹脂（Ｚ）中のエポキシ基（ｚ）のモル比（ｘｙ）／（ｚ）としては、０．７〜１．３であることが好ましい。
【００６６】
ポリイミド樹脂（Ｘ）および（Ｙ）とエポキシ樹脂（Ｚ）を含有してなる熱硬化性のポリイミド樹脂組成物は、硬化時の架橋密度等の制御のためフェノール性水酸基を２個以上有する化合物（Ｆ）をさらに含有させることが好ましい。ポリイミド樹脂（Ｘ）および（Ｙ）とエポキシ樹脂（Ｚ）での架橋密度をフェノール性水酸基を２個以上有する化合物（Ｆ）を併用することで高めることが可能であり、これによりガラス転移点以上の温度における線膨張係数等を低下させることが可能である。前記架橋密度を高め、線膨張係数等を低下させるため、前記熱硬化性のポリイミド樹脂組成物中のポリイミド樹脂（Ｘ）および（Ｙ）とエポキシ樹脂（Ｚ）とフェノール性水酸基を２個以上有する化合物（Ｆ）の配合比率は、これらの合計１００重量部対して、ポリイミド樹脂（Ｘ）および（Ｙ）の合計が４０〜８５重量部、エポキシ樹脂（Ｚ）が１０〜４０重量部、フェノール性水酸基を２個以上有する化合物（Ｆ）が５〜２０重量部であることが好ましい。また、ポリイミド樹脂（Ｘ）および（Ｙ）中の合計のカルボキシル基（ｘｙ）とフェノール性水酸基を２個以上有する化合物（Ｆ）中の水酸基（ｆ）の合計とエポキシ樹脂（Ｚ）中のエポキシ基（ｚ）のモル比（ｘｙ＋ｆ）／（ｚ）としては、０．７〜１．３であることが好ましい。
【００６７】
前記フェノール性水酸基を２個以上有する化合物（Ｆ）としては、例えば、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ等のビスフェノール系化合物；フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールノボラック樹脂、フェノールサリチルアルデヒドノボラック樹脂、テルペンジフェノールノボラック樹脂等のノボラック系樹脂；ビフェノール、ビフェノールノボラック、テトラメチルビフェノール、これらの誘導体等のビフェノール系化合物；フェノールフルオレン、クレゾールフルオレン等のフルオレン系化合物等が挙げられる。これらのなかでも、耐熱性に優れる熱硬化性ポリイミド樹脂組成物が得られることから、フェノール性水酸基を３個以上有する化合物が好ましい。
【００６８】
ポリイミド樹脂（Ｘ）および（Ｙ）とエポキシ樹脂（Ｚ）を含有し、必要によりフェノール性水酸基を２個以上有する化合物（Ｆ）を含有する熱硬化性のポリイミド樹脂組成物は、前記以外の硬化剤や硬化促進剤を併用することができ、例えば、メラミン、ジシアンジアミド、グアナミンやその誘導体、アミン類、水酸基を１個有するフェノール類、有機フォスフィン類、ホスホニュウム塩類、４級アンモニュウム塩類、多塩基酸無水物、光カチオン触媒、シアネート化合物、イソシアネート化合物、ブロックイソシアネート化合物等が挙げられる。
【００６９】
また、前記した熱硬化性のポリイミド樹脂組成物は、種々の充填材、有機顔料、無機顔料、体質顔料、防錆剤等を添加することができる。これらは単独でも２種以上を併用してもよい。
【００７０】
前記充填材としては、例えば、硫酸バリウム、チタン酸バリウム、酸化けい素酸粉、微粒状酸化けい素、シリカ、タルク、クレー、炭酸マグネシウム、炭酸カルシウム、酸化アルミニウム、水酸化アルムニウム、雲母等が挙げられる。
【００７１】
前記有機顔料としては、アゾ顔料；フタロシアニン・ブルー、フタロシアニン・グリーン等の銅フタロシアニン系顔料、キナクリドン系顔料等が挙げられる。
【００７２】
前記無機顔料としては、例えば、黄鉛、ジンククロメート、モリブデート・オレンジの如きクロム酸塩；紺青の如きフェロシアン化物、酸化チタン、亜鉛華、ベンガラ、酸化鉄；炭化クロムグリーンの如き金属酸化物、カドミウムイエロー、カドミウムレッド；硫化水銀の如き金属硫化物、セレン化物；硫酸鉛の如き硫酸塩；群青の如き珪酸塩；炭酸塩、コバルト・バイオレッド；マンガン紫の如き燐酸塩；アルミニウム粉、亜鉛末、真鍮粉、マグネシウム粉、鉄粉、銅粉、ニッケル粉の如き金属粉；カーボンブラック等が挙げられる。
【００７３】
また、その他の着色、防錆、体質顔料のいずれも使用することができる。これらは単独でも２種以上を併用してもよい。
【００７４】
前記した熱硬化性のポリイミド樹脂組成物は、通常、キャスト法、含浸、塗装等目的の方法で塗工施行される。硬化温度は８０〜３００℃で、硬化時間は２０分間〜５時間である。
【００７５】
【実施例】
次に、本発明を実施例、比較例によりさらに具体的に説明する。以下において、部および％は特に断りのない限り、すべて重量基準であるものとする。
【００７６】
合成例１
攪拌装置、温度計、コンデンサーを付けた２０リットルのフラスコに、ジエチレングリコールモノエチルエーテルアセテート（以下、ＥＤＧＡと略記する。）４９０６ｇと、イソホロンジイソシアネートから誘導されるイソシアヌレート環を有するポリイソシアネート（以下ＩＰＤＩ−Ｎと略記する。イソシアネート基含有率１８．２％、イソシアヌレート環含有トリイソシアネート含有率８５％）２７６０ｇ（イソシアネート基として１２モル）と、エヌジェコール２００Ａ〔新日本理化（株）製分岐型脂肪族アルコール、水酸基価１８４ｍｇＫＯＨ／ｇ、数平均分子量３０５〕６１０ｇ（水酸基として２モル）を仕込み、攪拌を行いながら発熱に注意して８０℃に昇温した後、３時間反応を行った。次いで、無水トリメリット酸（以下、ＴＭＡと略記する。）１５３６ｇ（８モル）を仕込み、１６０℃まで昇温した後、４時間反応させた。反応は発泡とともに進行し、系内は薄茶色のクリアな液体となり、カルボキシル基と脂肪族構造（１）を末端に有するポリイミド樹脂の溶液を得た。
【００７７】
得られたポリイミド樹脂溶液をＫＢｒ板に塗装し、溶剤を揮発させた試料の赤外線吸収スペクトルを測定した結果、イソシアネート基の特性吸収である２２７０ｃｍ^−１が完全に消滅し、７２５ｃｍ^−１と１７８０ｃｍ^−１と１７２０ｃｍ^−１にイミド環の吸収、１６９０ｃｍ^−１と１４６０ｃｍ^−１にイソシアヌレート環の特性吸収、１５５０ｃｍ^−１にウレタン結合の特性吸収が確認された。また、ポリイミド樹脂の酸価は固形分換算で９１ｍｇＫＯＨ／ｇ、イソシアヌレート環の濃度は０．９０ｍｍｏｌ／ｇ（樹脂固形分換算）、数平均分子量（以下、Ｍｎと略記する。）は２，３００、重量平均分子量（以下、Ｍｗと略記する。）は４，４００であった。以下、このポリイミド樹脂溶液を（Ｘ−１）と略記する。
【００７８】
合成例２
攪拌装置、温度計、コンデンサーを付けた２０リットルのフラスコに、ＥＤＧＡ ４８５６ｇと、ＩＰＤＩ−Ｎ ２０７０ｇ（イソシアネート基として９モル）と、１，６−ヘキサンジイソシアネートから誘導されるイソシアヌレート環を有するポリイソシアネート（以下ＨＤＩ−Ｎと略記する。イソシアネート基含有率２２．９％、イソシアヌレート環含有トリイソシアネート含有率６３．３％）５５０ｇ（イソシアネート基として３モル）を仕込み、混合した後、エヌジェコール２４０Ａ〔新日本理化（株）製分岐型脂肪族アルコール、水酸基価１６０、平均分子量３５０〕７００ｇ（水酸基として２モル）を仕込み、攪拌を行いながら発熱に注意して８０℃に昇温した。この温度で３時間反応を行った後、ＴＭＡ １５３６ｇ（８モル）を仕込み、１６０℃まで昇温した後、４時間反応させた。反応は発泡とともに進行し、系内は薄茶色のクリアな液体となり、カルボキシル基と脂肪族構造（１）を末端に有するポリイミド樹脂の溶液を得た。
【００７９】
得られたポリイミド樹脂溶液を用いて実施例１と同様に赤外線吸収スペクトルを測定した結果、イソシアネート基の特性吸収である２２７０ｃｍ^−１が完全に消滅し、７２５ｃｍ^−１と１７８０ｃｍ^−１と１７２０ｃｍ^−１にイミド環の吸収、１６９０ｃｍ^−１と１４６０ｃｍ^−１にイソシアヌレート環の特性吸収、１５５０ｃｍ^−１にウレタン結合の特性吸収が確認された。また、ポリイミド樹脂の酸価は固形分換算で８８、イソシアヌレート環の濃度は０．９０ｍｍｏｌ／ｇ（樹脂固形分換算）、Ｍｎは２，４００、Ｍｗは４，６００であった。以下、このポリイミド樹脂溶液を（Ｘ−２）と略記する。
【００８０】
合成例３
攪拌装置、温度計、コンデンサーを付けた２０リットルのフラスコに、ＥＤＧＡ ５０２２ｇと、ＩＰＤＩ−Ｎ １３８０ｇ（イソシアネート基として６モル）と、ノルボヌレンジイソシアネートから誘導されるイソシアヌレート環を有するポリイソシアネート（以下ＮＢＤＩ−Ｎと略記する。イソシアネート基含有率１８．７５％、イソシアヌレート環含有トリイソシアネート含有率６５．５％）１３４４ｇ（イソシアネート基として６モル）を仕込み、８０℃で加熱溶解させた後、エヌジェコール２００Ａ ６１０ｇ（水酸基として２モル）を仕込み、攪拌を行いながら８０℃で５時間反応させ、次いでＴＭＡ １５３６ｇ（８モル）を仕込で１７０℃まで昇温した後、４時間反応させた。反応は発泡とともに進行し、系内は薄茶色のクリアな液体となり、カルボキシル基と脂肪族構造（１）を末端に有するポリイミド樹脂の溶液を得た。
【００８１】
得られたポリイミド樹脂溶液を用いて実施例１と同様に赤外線吸収スペクトルを測定した結果、イソシアネート基の特性吸収である２２７０ｃｍ^−１が完全に消滅し、７２５ｃｍ^−１と１７８０ｃｍ^−１と１７２０ｃｍ^−１にイミド環の吸収、１６９０ｃｍ^−１と１４６０ｃｍ^−１にイソシアヌレート環の特性吸収、１５５０ｃｍ^−１にウレタン結合の特性吸収が確認された。また、ポリイミド樹脂の酸価は固形分換算で８６、イソシアヌレート環の濃度は０．９０ｍｍｏｌ／ｇ（樹脂固形分換算）、Ｍｎは２，２００、Ｍｗは４，７００であった。以下、このポリイミド樹脂溶液を（Ｘ−３）と略記する。
【００８２】
合成例４
攪拌装置、温度計、コンデンサーを付けた２０リットルのフラスコに、ＥＤＧＡ ４５６５．８ｇと、ＩＰＤＩ−Ｎ ２０７０ｇ（イソシアネート基として９モル）と、４，４′−ジシクロヘキシルメタンジイソシアネート２６２ｇ（イソシアネート基として２モル）と、エヌジェコールＣ３２−３６〔新日本理化（株）製分岐型脂肪族アルコール、水酸基価１００、数平均分子量５６１〕８９０ｇ（水酸基として１．５９モル）を仕込み、攪拌を行いながら発熱に注意して８０℃に昇温した。この温度で３時間反応を行った後、ＴＭＡ １３４４ｇ（７モル）を仕込み、１８０℃まで昇温して３時間反応させた。反応は発泡とともに進行し、系内は薄茶色のクリアな液体となり、カルボキシル基と脂肪族構造（１）を末端に有するポリイミド樹脂の溶液を得た。
ポリイミド樹脂の溶液を得た。
【００８３】
得られたポリイミド樹脂溶液を用いて実施例１と同様に赤外線吸収スペクトルを測定した結果、イソシアネート基の特性吸収である２２７０ｃｍ^−１が完全に消滅し、７２５ｃｍ^−１と１７８０ｃｍ^−１と１７２０ｃｍ^−１にイミド環の吸収、１６９０ｃｍ^−１と１４６０ｃｍ^−１にイソシアヌレート環の特性吸収、１５５０ｃｍ^−１にウレタン結合の特性吸収が確認された。また、ポリイミド樹脂の酸価は固形分換算で８６、イソシアヌレート環の濃度は０．７２ｍｍｏｌ／ｇ（樹脂固形分換算）、Ｍｎは２，６４０、Ｍｗは４，０００であった。以下、このポリイミド樹脂溶液を（Ｘ−４）と略記する。
【００８４】
合成例５
攪拌装置、温度計、コンデンサーを付けた２０リットルのフラスコに、ＥＤＧＡ ４９５１ｇと、ＩＰＤＩ−Ｎ ２７６０ｇ（イソシアネート基として１２モル）と、ポリテールＨＡ〔三菱化学（株）製の両末端に水酸基を有する水素添加液状ポリブタジエン、数平均分子量２，１００、水酸基価５１．２ｍｇＫＯＨ／ｇ〕２１９１ｇ（水酸基として２モル）を仕込み、攪拌を行いながら発熱に注意して８０℃に昇温した後、３時間反応を行った。次いで、さらにＥＤＧＡ １５３６ｇとＴＭＡ １５３６ｇ（８モル）を仕込み、１６０℃まで昇温した後、４時間反応させた。反応は発泡とともに進行した。系内は薄茶色のクリアな液体となり、カルボキシル基と線状多価脂肪族構造（２）を有するポリイミド樹脂の溶液を得た。
【００８５】
得られたポリイミド樹脂溶液を用いて実施例１と同様に赤外線吸収スペクトルを測定した結果、イソシアネート基の特性吸収である２２７０ｃｍ^−１が完全に消滅し、７２５ｃｍ^−１と１７８０ｃｍ^−１と１７２０ｃｍ^−１にイミド環の吸収、１６９０ｃｍ^−１と１４６０ｃｍ^−１にイソシアヌレート環の特性吸収、１５５０ｃｍ^−１にウレタン結合の特性吸収が確認された。また、ポリイミド樹脂の酸価は固形分換算で７９、イソシアヌレート環の濃度は０．６６ｍｍｏｌ／ｇ（樹脂固形分換算）、Ｍｎは５，９００、Ｍｗは４，０００であった。以下、このポリイミド樹脂溶液を（Ｙ−１）と略記する。
【００８６】
合成例６
攪拌装置、温度計、コンデンサーを付けた２０リットルのフラスコに、ＥＤＧＡ ４３００ｇと、ＩＰＤＩ−Ｎ ２０７０ｇ（イソシアネート基として９モル）と、ＨＤＩ−Ｎ ５５０ｇ（イソシアネート基として３モル）を仕込み、混合して均一とした後、ポリテールＨＡ ２１９１ｇ（水酸基として２モル）を加えて攪拌を行いながら発熱に注意して８０℃に昇温した後、３時間反応を行った。次いで、ＴＭＡ １５３６ｇ（８モル）を仕込み、１６０℃まで昇温した後、４時間反応させた。この際の反応は、発泡とともに進行し、粘度が高くなり、系内が攪拌しにくくなったときに、さらにＥＤＧＡ２０００ｇを加えて行った。系内は薄茶色のクリアな液体となり、カルボキシル基と線状多価脂肪族構造（２）を有するポリイミド樹脂の溶液を得た。
【００８７】
得られたポリイミド樹脂溶液を用いて実施例１と同様に赤外線吸収スペクトルを測定した結果、イソシアネート基の特性吸収である２２７０ｃｍ^−１が完全に消滅し、７２５ｃｍ^−１と１７８０ｃｍ^−１と１７２０ｃｍ^−１にイミド環の吸収、１６９０ｃｍ^−１と１４６０ｃｍ^−１にイソシアヌレート環の特性吸収、１５５０ｃｍ^−１にウレタン結合の特性吸収が確認された。さらに、また、ポリイミド樹脂の酸価は固形分換算で８５、イソシアヌレート環の濃度は０．６８ｍｍｏｌ／ｇ、Ｍｎは５，５００、Ｍｗは２２，０００であった。以下、このポリイミド樹脂溶液を（Ｙ−２）と略記する。
【００８８】
合成例７
攪拌装置、温度計、コンデンサーを付けた２０リットルのフラスコに、ＥＤＧＡ ５３１０ｇと、ＩＰＤＩ−Ｎ １３８０ｇ（イソシアネート基として６モル）と、ＮＢＤＩ−Ｎ １３４４ｇ（イソシアネート基として６モル）を仕込み、８０℃で加熱溶解させ、ポリテールＨＡ ２１９１ｇ（水酸基２モル）をさらに仕込み、攪拌を行いながら８０℃にて５時間反応を行った後、ＴＭＡ １５３６ｇ（８モル）を仕込み、１７０℃まで昇温した後、４時間反応させた。反応は発泡とともに進行した。系内は薄茶色のクリアな液体となり、カルボキシル基と線状多価脂肪族構造（２）を有するポリイミド樹脂の溶液を得た。
【００８９】
得られたポリイミド樹脂溶液を用いて実施例１と同様に赤外線吸収スペクトルを測定した結果、イソシアネート基の特性吸収である２２７０ｃｍ^−１が完全に消滅し、７２５ｃｍ^−１と１７８０ｃｍ^−１と１７２０ｃｍ^−１にイミド環の吸収、１６９０ｃｍ^−１と１４６０ｃｍ^−１にイソシアヌレート環の特性吸収、１５５０ｃｍ^−１にウレタン結合の特性吸収が確認された。また、ポリイミド樹脂の酸価は固形分換算で７５、イソシアヌレート環の濃度は０．７２ｍｍｏｌ／ｇ、Ｍｎは４，４００、Ｍｗは２１．０００であった。以下、このポリイミド樹脂溶液を（Ｙ−３）と略記する。
【００９０】
合成例８
攪拌装置、温度計、コンデンサーを付けた２０リットルのフラスコに、ＥＤＧＡ ５６３６ｇと、ＩＰＤＩ−Ｎ ２７６０ｇ（イソシアネート基として１２モル）と、ＮＩＳＳＯ−ＰＢ Ｇ−３０００〔日本曹達（株）製の両末端に水酸基を有する液状ポリブタジエン、数平均分子量２，８００、水酸基価３９〕２８７６ｇ（水酸基として２モル）を仕込み、攪拌を行いながら発熱に注意して８０℃に昇温した後、３時間反応を行った。次いで、さらにＥＤＧＡ １５３７ｇとＴＭＡ １５３６ｇ（８モル）を仕込み、１６０℃まで昇温した後、４時間反応させた。反応は発泡とともに進行した。系内は薄茶色のクリアな液体となり、カルボキシル基と線状多価脂肪族構造（２）を有するポリイミド樹脂の溶液を得た。
【００９１】
得られたポリイミド樹脂溶液を用いて実施例１と同様に赤外線吸収スペクトルを測定した結果、イソシアネート基の特性吸収である２２７０ｃｍ^−１が完全に消滅し、７２５ｃｍ^−１と１７８０ｃｍ^−１と１７２０ｃｍ^−１にイミド環の吸収、１６９０ｃｍ^−１と１４６０ｃｍ^−１にイソシアヌレート環の特性吸収、１５５０ｃｍ^−１にウレタン結合の特性吸収が確認された。また、ポリイミド樹脂の酸価は固形分換算で７０、イソシアヌレート環の濃度は０．５９ｍｍｏｌ／ｇ、Ｍｎは５，４００、Ｍｗは３２，０００であった。以下、このポリイミド樹脂溶液を（Ｙ−４）と略記する。
【００９２】
合成例９
攪拌装置、温度計、コンデンサーを付けた２０リットルのフラスコに、ＥＤＧＡ ５７１２ｇと、ＩＰＤＩ−Ｎ ２７６０ｇ（イソシアネート基として１２モル）と、ＮＩＳＳＯ−ＰＢ ＧＩ−３０００〔日本曹達（株）製の両末端に水酸基を有する水素添加液状ポリブタジエン、数平均分子量４，０００、水酸基価２８〕２９５２ｇ（水酸基として１．４７モル）を仕込み、攪拌を行いながら発熱に注意して８０℃に昇温した後、３時間反応を行った。次いで、さらにＥＤＧＡ １７２８ｇとＴＭＡ １７２８ｇ（９モル）を仕込み、１６０℃まで昇温した後、４時間反応させた。反応は発泡とともに進行した。系内は薄茶色のクリアな液体となり、カルボキシル基と線状多価脂肪族構造（２）を有するポリイミド樹脂の溶液を得た。
【００９３】
得られたポリイミド樹脂溶液を用いて実施例１と同様に赤外線吸収スペクトルを測定した結果、イソシアネート基の特性吸収である２２７０ｃｍ^−１が完全に消滅し、７２５ｃｍ^−１と１７８０ｃｍ^−１と１７２０ｃｍ^−１にイミド環の吸収、１６９０ｃｍ^−１と１４６０ｃｍ^−１にイソシアヌレート環の特性吸収、１５５０ｃｍ^−１にウレタン結合の特性吸収が確認された。また、ポリイミド樹脂の酸価は固形分換算で７４、イソシアヌレート環の濃度は０．５７ｍｍｏｌ／ｇ、Ｍｎは３，６００、Ｍｗは２４，０００であった。以下、このポリイミド樹脂溶液を（Ｙ−５）と略記する。
【００９４】
合成例１０
攪拌装置、温度計、コンデンサーを付けた２０リットルのフラスコに、ＥＤＧＡ ５２８４ｇと、ＩＰＤＩ−Ｎ ２７６０ｇ（イソシアネート基として１２モル）と、４，４′−ジシクロヘキシルメタンジイソシアネート〔水素添加ジフェニルメタンジイソシアネート（水素添加ＭＤＩ）〕５２４ｇ（イソシアネート基として４モル）と、ＴＨ−２１〔クラレ（株）製の両末端に水酸基を有する水素添加ポリイソプレン、数平均分子量２，６００、水酸基価５６．１〕２０００ｇ（水酸基として２モル）を仕込み、攪拌を行いながら発熱に注意して８０℃に昇温した後、３時間反応を行った。次いで、さらにＥＤＧＡ １５３６ｇとＴＭＡ １５３６ｇ（８モル）を仕込み、１６０℃まで昇温した後、４時間反応させた。反応は発泡とともに進行した。系内は薄茶色のクリアな液体となり、カルボキシル基と線状多価脂肪族構造（２）を有するポリイミド樹脂の溶液を得た。
【００９５】
得られたポリイミド樹脂溶液を用いて実施例１と同様に赤外線吸収スペクトルを測定した結果、イソシアネート基の特性吸収である２２７０ｃｍ^−１が完全に消滅し、７２５ｃｍ^−１と１７８０ｃｍ^−１と１７２０ｃｍ^−１にイミド環の吸収、１６９０ｃｍ^−１と１４６０ｃｍ^−１にイソシアヌレート環の特性吸収、１５５０ｃｍ^−１にウレタン結合の特性吸収が確認された。また、ポリイミド樹脂の酸価は固形分換算で７２、イソシアヌレート環の濃度は０．６４ｍｍｏｌ／ｇ、Ｍｎは５，１００、Ｍｗは２３，０００であった。以下、このポリイミド樹脂溶液を（Ｙ−６）と略記する。
【００９６】
合成例１１
攪拌装置、温度計、コンデンサーを付けた２０リットルのフラスコに、ＥＤＧＡ ５４５１ｇと、ＩＰＤＩ−Ｎ ２７６０ｇ（イソシアネート基として１２モル）と、ジフェニルメタンジイソシアネート５００ｇ（イソシアネート基として２モル）と、ポリテールＨＡ ２１９１ｇ（水酸基として２モル）を仕込み、攪拌を行いながら発熱に注意して８０℃に昇温した後、３時間反応を行った。次いで、さらにＥＤＧＡ １５３６ｇとＴＭＡ １３４４ｇ（７モル）と無水ピロメリット酸２１８ｇ（１モル）を仕込み、１６０℃まで昇温した後、４時間反応させた。反応は発泡とともに進行した。系内は薄茶色のクリアな液体となり、カルボキシル基と線状多価脂肪族構造（２）を有するポリイミド樹脂の溶液を得た。
【００９７】
得られたポリイミド樹脂溶液を用いて実施例１と同様に赤外線吸収スペクトルを測定した結果、イソシアネート基の特性吸収である２２７０ｃｍ^−１が完全に消滅し、７２５ｃｍ^−１と１７８０ｃｍ^−１と１７２０ｃｍ^−１にイミド基の特性吸収、１６９０ｃｍ^−１と１４６０ｃｍ^−１にイソシアヌレート環の特性吸収、１５５０ｃｍ^−１にウレタン結合の特性吸収が確認された。また、ポリイミド樹脂の酸価は固形分換算で７３、イソシアヌレート環の濃度は０．６３ｍｍｏｌ／ｇ、Ｍｎは５，６００、Ｍｗは３２，０００であった。以下、このポリイミド樹脂溶液を（Ｙ−７）と略記する。
【００９８】
合成例１２
攪拌装置、温度計、コンデンサーを付けた２０リットルのフラスコに、ＥＤＧＡ ５０２０ｇと、イソホロンジイソシアネート２２２０ｇ（イソシアネート基含有率３７．８％）と、ポリテールＨＡ ２１９１ｇ（水酸基として２モル）を仕込み、攪拌を行いながら発熱に注意して８０℃に昇温した後、３時間反応を行った。次いで、さらにＴＭＡ ９６０ｇ（５モル）を仕込み、１６０℃まで昇温した後、４時間反応させた。反応は発泡とともに進行した。系内は薄茶色のクリアな液体となり、カルボキシル基と線状多価脂肪族構造（２）を有するポリイミド樹脂の溶液を得た。
【００９９】
得られたポリイミド樹脂溶液を用いて実施例１と同様に赤外線吸収スペクトルを測定した結果、イソシアネート基の特性吸収である２２７０ｃｍ^−１が完全に消滅し、７２５ｃｍ^−１と１７８０ｃｍ^−１と１７２０ｃｍ^−１にイミド環の吸収、１５５０ｃｍ^−１にウレタン結合の特性吸収が確認された。また、ポリイミド樹脂の酸価は固形分換算で５３、イソシアヌレート環の濃度は０ｍｍｏｌ／ｇ、Ｍｎは４，１００、Ｍｗは１２，５００であった。以下、このポリイミド樹脂溶液を（Ｙ−８）と略記する。
【０１００】
比較合成例１
攪拌装置、温度計、コンデンサーを付けた１０リットルのフラスコに、ジメチルホルムアミド１４９６ｇと、イソホロンジイソシアネート８８８ｇ（イソシアネート基として８モル）と、ＴＭＡ ９６０ｇ（５モル）を仕込み、１６０℃まで昇温して反応させた後、４時間反応させた。反応は発泡とともに進行した。系内は薄茶色のクリア液体となり、カルボキシル基を有するポリイミド樹脂の溶液を得た。
【０１０１】
得られたポリイミド樹脂溶液を用いて実施例１と同様に赤外線吸収スペクトルを測定した結果、イソシアネート基の特性吸収である２２７０ｃｍ^−１が完全に消滅し、７２５ｃｍ^−１と１７８０ｃｍ^−１と１７２０ｃｍ^−１にイミド基の吸収が確認された。また、ポリイミド樹脂の酸価は固形分換算で９４、Ｍｎは７７０、Ｍｗは２，５００であった。以下、このポリイミド樹脂溶液を（Ｘ′−１）と略記する。
【０１０２】
比較合成例２
攪拌装置、温度計、コンデンサーを付けた１０リットルのフラスコに、ＥＤＧＡ １４９６ｇと、ＩＰＤＩ−Ｎ ２７６０ｇ（イソシアネート基として１２モル）と、ＴＭＡ １７２８ｇ（水酸基として９モル）を仕込み、１５０℃まで昇温した後、８時間反応させた。反応は発泡とともに進行した。系内は薄茶色のクリアな液体となり、カルボキシル基を有するポリイミド樹脂の溶液を得た。
【０１０３】
得られたポリイミド樹脂溶液を用いて実施例１と同様に赤外線吸収スペクトルを測定した結果、イソシアネート基の特性吸収である２２７０ｃｍ^−１が完全に消滅し、７２５ｃｍ^−１と１７８０ｃｍ^−１と１７２０ｃｍ^−１にイミド環の吸収、１６９０ｃｍ^−１と１４６０ｃｍ^−１にイソシアヌレート環の特性吸収、１５５０ｃｍ^−１にウレタン結合の特性吸収が確認された。また、ポリイミド樹脂の酸価は固形分換算で９５、イソシアヌレート環の濃度は０．６４ｍｍｏｌ／ｇ、Ｍｎは４，１００、Ｍｗは１２，０００であった。以下、このポリイミド樹脂溶液を（Ｘ′−２）と略記する。
【０１０４】
実施例１〜１３および比較例１〜２
第１表〜第２表に示す配合により本発明の熱硬化性ポリイミド樹脂組成物Ｎｏ．１〜１３と、比較対照用熱硬化性ポリイミド樹脂組成物Ｎｏ．１′〜２′を調製した。尚、これらの樹脂組成物は、いずれも硬化触媒としてトリフェニルフォスフィン１部を添加した。尚、第１表〜第２表中の数値は、樹脂固形分の配合重量を表す。
【０１０５】
【表１】

【０１０６】
【表２】

【０１０７】
第１表〜第２表の脚注
・Ｎ６８０ ：大日本インキ化学工業（株）製クレゾールノボラックエポキシ樹脂 ＥＰＩＣＬＯＮ Ｎ−６８０（軟化点８０℃、エポキシ当量２１３ｇ／ｅｑ）
・ＨＰ７２００ ：大日本インキ化学工業（株）製ジシクロペンタジエン変性エポキシ樹脂 ＥＰＩＣＬＯＮ ＨＰ−７２００（軟化点６１℃、エポキシ当量２５７ｇ／ｅｑ）
・ＥＸＡ４７００：大日本インキ化学工業（株）製多官能ナフタレンノボラック型エポキシ樹脂 ＥＰＩＣＬＯＮ ＥＸＡ−４７００（エポキシ当量１６２ｇ／ｅｑ）
・ＴＤ２０９０ ：大日本インキ化学工業（株）フェノールノボラック樹脂 フェノライト ＴＤ−２０９０（軟化点１２０℃、水酸基当量１０５ｇ／ｅｑ）
【０１０８】
試験例１〜１３および比較試験例１〜２
前記本発明の熱硬化性ポリイミド樹脂組成物Ｎｏ．１〜１３と比較対照用熱硬化性ポリイミド樹脂組成物Ｎｏ．１′〜２′を用いて、下記に示す方法で、相溶性試験、塗膜造膜性試験、ガラス転移点（Ｔｇ）測定、引っ張り試験、プレッシャークッカー耐性試験（ＰＣＴ）、ハンダ耐熱性試験および導電特性測定を行った。結果を第３表〜第４表に示す。
【０１０９】
（１）相溶性試験
第１表〜第２表に示す配合により熱硬化性ポリイミド樹脂組成物Ｎｏ．１〜１３と、比較対照用熱硬化性ポリイミド樹脂組成物Ｎｏ．１′〜２′を調製した際の相溶状態と、さらに得られた樹脂組成物をガラス板に塗装し、１２０℃で乾燥した後の塗膜の状態を、下記の評価基準で評価した。
評価基準
◎：攪拌により容易に均一となり、塗膜面にも異物等が見られない。
○：攪拌により均一となり、塗膜面にも異物等が見られない。
△：攪拌により均一になりにくく、塗膜面にもやや異物等が見られる。
×：均一に溶解せず、塗膜面は、はじき、異物、不溶解物が確認できる。
【０１１０】
（２）塗膜造膜性試験
熱硬化性ポリイミド樹脂組成物を乾燥後の膜厚が３０μｍになるようにブリキ板にアプリケーターにて塗布後、１１０℃で３０分間乾燥させて得た試験片を、室温にて２４時間放置し、塗膜外観を以下の評価基準で評価した。
評価基準
○：塗膜にクラック等の異常は見られない。
△：塗膜に若干クラックが見られる。
×：塗膜全面にクラックが発生した。
【０１１１】
（３）ガラス転移点（Ｔｇ）測定
＜試験用試験片の作製＞
熱硬化性ポリイミド樹脂組成物を硬化後の膜厚が５０μｍになるようにブリキ基板上に塗装し、１２０℃で２０分間乾燥した後、１５０℃と１７０℃でそれぞれ１時間硬化させて、２種の硬化塗膜を作成し、室温まで冷却した後、硬化塗膜を塗装板から切り出し、Ｔｇ測定用試料とした。
＜Ｔｇ測定方法＞
前記Ｔｇ測定用試料を用い、下記の条件で動的粘弾性を測定し、得られたスペクトルのＴａｎδの最大の温度をＴｇとした。
測定機器：レオメトッリク社製ＲＳＡ−ＩＩ
治具：引っ張り
チャック間：２０ｍｍ
測定温度：２５〜３００℃
測定周波数：１Ｈｚ
昇温速度：３℃／ｍｉｎ
【０１１２】
（４）引っ張り試験
＜試験用試験片の作製＞
熱硬化性ポリイミド樹脂組成物を硬化後の膜厚が５０μｍになるように、ブリキ基板上に塗装した。次いでこの塗装板を１２０℃で２０分間乾燥した後、１５０℃と１７０℃で１時間硬化させた２水準の硬化塗膜を作成した。室温まで冷却した後、硬化膜を所定の大きさに切り出し、基板から単離して測定用試料とした。
＜引っ張り試験測定方法＞
前記Ｔｇ測定用試料と同様にして１７０℃で１時間硬化させた測定サンプルを５枚作成し、下記の条件で引っ張り試験を行い、破断強度と破断伸度を求めた。
測定機器：東洋ボールドウィン社製テンシロン
サンプル形状：１０ｍｍ×７０ｍｍ
チャック間：２０ｍｍ
引っ張り速度：１０ｍｍ／ｍｉｎ
測定雰囲気：２２℃、４５％ＲＨ
【０１１３】
（５）プレッシャークッカー耐性試験（ＰＣＴ）
熱硬化性ポリイミド樹脂組成物を、銅回路パ夕一ン形成したガラスエポキシ系プリント基板上に硬化後の膜厚が５０μｍになるように塗装を行った。次いでこの塗装板を１２０℃で２０分間乾燥した後、１７０℃で１時間硬化させてテストピースを作成し、プレッシャークッカー試験機（株式会社平山製作所製ＰＣ−３０４ＲＩＩＩ）で１２１℃、１００％ＲＨ（飽和蒸気圧下）で５０時間処理した後、室温状態にもどし、外観の変化を目視にて下記評価基準で評価した。また、前記テストピース上の塗膜に１ｍｍ間隔で碁盤目状のクロスカットを入れ、その上にセロハンテープを貼り付けてピーリング試験を行い、塗膜の剥離数を数えて、下記基準で塗膜の付着性を評価した。
▲１▼外観評価基準
◎：試験前後で変化、異常が見られない。
○：試験後、塗膜面積の５％未満の範囲でブリスター、白化、溶解等の塗膜異常が確認できる。
△：試験後、塗膜面積の５％以上３０％未満の範囲でブリスター、白化、溶解等の塗膜異常が確認できる。
×：試験後、塗膜面積の３０％以上の範囲でブリスター、白化、溶解等の塗膜異常が確認できる。
▲２▼付着性評価基準
◎：碁盤目状塗膜の剥離なし。
○：碁盤目状塗膜１００個に対して剥離した塗膜数が２０個未満。
△：碁盤目状塗膜１００個に対して剥離した塗膜数が２０個以上７０個未満。
×：碁盤目状塗膜１００個に対して剥離した塗膜数が７０個以上。
【０１１４】
（６）ハンダ耐熱性試験
前記プレッシャークッカー耐性試験と同様に作成し、２５×２５ｍｍの大きさに切断したテストピースを、塗膜面を下にして２６０℃の半田浴に１０秒間浮かせるのを１サイクルとして、３サイクル行い、塗膜の膨れ等の欠陥と密着性を下記の評価基準で評価した。
評価基準
◎：試験前後で全く変化が見られない。
○：試験後、塗膜面積の５％未満の範囲で欠陥や剥離等が見られる。
△：試験後、塗膜面積の５％以上３０％未満の範囲で欠陥や剥離等が見られる。
×：試験後、塗膜面積の３０％以上の範囲で欠陥や剥離等が見られる。
【０１１５】
（７）誘電特性測定
熱硬化性ポリイミド樹脂組成物を硬化後の膜厚が２００μｍになるようにブリキ基板上に塗装し、１２０℃で２０分間乾燥した後、１５０℃で１時間硬化させ冷却した後、剥離した硬化塗膜を切り出した測定用試料を、アジレントテクノロジー社製４２９１Ｂを用いて、周波数は１ＧＨｚの条件で誘電率（ε）と誘電損失（Ｔａｎδ）を測定した。
【０１１６】
【表３】

【０１１７】
【表４】

【０１１８】
【表５】

【０１１９】
第３表〜第５表の結果から明らかなように、実施例の熱硬化性ポリイミド樹脂組成物からなる硬化塗膜は、非常に高いＴｇを示しており、高温においても耐熱性を発揮できうる材料と言える。さらに、こうした高Ｔｇを有しながら、誘電率と誘電正接が低く誘電特性が良好で、機械物性的にも伸度が大きいという特徴を有している。また、ＰＣＴ耐性や半田耐熱試験においても非常に高い耐性を有している。
【０１２０】
一方、比較試験例１の熱硬化性ポリイミド樹脂組成物からなる硬化塗膜は、実施例の硬化塗膜に比較して低いＴｇであり、破断伸度、ＰＣＴ耐性、半田耐熱性、誘電率、誘電正接においても悪い結果であった。また、比較試験例２の熱硬化性ポリイミド樹脂組成物からなる硬化塗膜は、非常に高いＴｇを示しているが、実施例の硬化塗膜に比較してＰＣＴ耐性（付着性）、誘電率、誘電正接において悪い結果であった。
【０１２１】
【発明の効果】
本発明の熱硬化性ポリイミド樹脂組成物は、耐熱性に優れ、誘電率と誘電正接が低く、しかも、引張強度、引張伸度等の機械物性の良好な硬化物が得られる。また、本発明の製造方法によれば、本発明の硬化性ポリイミド樹脂組成物に用いるポリイミド樹脂が容易に製造できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a polyimide resin composition useful in the field of various heat-resistant coating materials and electric insulating materials, for example, interlayer insulating materials for printed wiring boards, build-up materials, insulating materials for semiconductors, heat-resistant adhesives, and the like. .
[0002]
[Prior art]
In recent years, there has been a demand for improvement in heat resistance and electrical properties of resins in various fields mainly in the electric and electronic industries. Under these circumstances, in response to the above demand, as a heat-resistant resin composition, a polyisocyanate containing an isocyanurate ring, an aromatic isocyanate, and a polycarboxylic acid containing a lactam and an acid anhydride are synthesized in a cresol-based solvent. A polyimide amide resin composition containing a polyamide imide resin and an epoxy resin is known (for example, see Patent Document 1).
[0003]
In addition, a strong odor such as the cresol is not a highly toxic solvent, but a general-purpose solvent, for example, a ketone-based solvent, an ester-based solvent, a polyimide resin that can be dissolved in an aprotic polar organic solvent such as an ether-based solvent, for example, a molecule. A method for producing a polyimide resin obtained by reacting an aliphatic isocyanate compound having at least two isocyanate groups and / or an alicyclic isocyanate compound with a tricarboxylic anhydride and / or a tetracarboxylic anhydride, and A polyimide resin composition containing the polyimide resin and the epoxy resin is known (for example, see Patent Document 2).
[0004]
However, a cured product obtained by curing the polyimide resin composition containing the polyimide resin and the epoxy resin described in Patent Document 1 and Patent Document 2 is excellent in heat resistance, but has a high dielectric constant and a high dielectric loss tangent, In addition, there is a problem that it is hard and brittle because of poor mechanical properties such as tensile strength and tensile elongation.
[0005]
In order to solve the above-mentioned problems, the present applicant has a thermosetting polyimide resin composition containing a polyimide resin having a carboxyl group and a linear hydrocarbon structure having a number average molecular weight of 300 to 6,000, and an epoxy resin, and a polyimide resin. Thermosetting polyimide resin composition containing a method for producing a resin (JP-A-2002-368036), a polyimide resin having a carboxyl group and an aliphatic structure having a number average molecular weight of 100 to 1,000 at an end, and an epoxy resin And a method for producing a polyimide resin (JP-A-2002-376846).
[0006]
[Patent Document 1]
JP-A-55-137161 (pages 2-5)
[Patent Document 2]
JP 2001-316469 A (page 3-9)
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a cured product having excellent heat resistance, a low dielectric constant and a low dielectric loss tangent, and excellent mechanical properties such as tensile strength and tensile elongation when an epoxy resin is used as a curing agent. An object of the present invention is to provide a polyimide resin composition.
[0008]
[Means for Solving the Problems]
The present inventor has made intensive studies in view of the above problems, and as a result, obtained a polyimide resin (X) having a carboxyl group and an aliphatic structure (1) having a number average molecular weight of 100 to 1,000 at the terminal, a carboxyl group and A polyimide resin composition containing a polyimide resin (Y) having a linear polyvalent aliphatic structure (2) having a number average molecular weight of 300 to 6,000 is combined with an epoxy resin (Z) to form a thermosetting polyimide resin composition. It was found that when used as a coating material, the coating suitability was good, the heat resistance was excellent, the mechanical properties were excellent, and a good cured product having a low dielectric constant and a low dielectric loss tangent was obtained, and the present invention was completed. .
[0009]
That is, the present invention relates to a polyimide resin (X) having a carboxyl group and an aliphatic structure (1) having a number average molecular weight of 100 to 1,000 at the terminal thereof, and a linear polymer having a carboxyl group and a number average molecular weight of 300 to 6,000. It is intended to provide a polyimide resin composition containing a polyimide resin (Y) having a valent aliphatic structure (2).
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The polyimide resin (X) used in the present invention may be a polyimide resin having a carboxyl group and an aliphatic structure (1) having a number average molecular weight of 100 to 1,000 at the terminal, and the polyimide resin (Y) may have a carboxyl group and a number average molecular weight of 100 to 1,000. Any polyimide resin having a linear polyvalent aliphatic structure (2) having a molecular weight of 300 to 6,000 may be used. However, in the present invention, the carboxyl group may be an acid anhydride group thereof. In the present invention, the aliphatic structure (1) may be any of a cyclic aliphatic structure, a linear aliphatic structure, and a structure having both a cyclic aliphatic structure and a linear aliphatic structure. And an acyclic aliphatic structure. Examples of the acyclic aliphatic structure include a linear or branched aliphatic structure. Among them, a branched aliphatic structure is preferable because the polyimide resin is less likely to crystallize and handling is easy. The linear polyvalent aliphatic structure (2) may be linear or branched, and may be saturated or unsaturated. However, the saturated aliphatic structure (2) may be saturated or unsaturated in view of changes in physical properties and stability during heating. Is more preferred.
[0011]
Among the polyimide resins (X), a general-purpose solvent such as a ketone solvent, an ester solvent, and an aprotic polar organic solvent such as an ether solvent have excellent solubility, heat resistance, and mechanical properties. A polyimide resin (X1) having an aliphatic structure (1) having a number average molecular weight of 100 to 1,000, a urethane bond, an imide ring, an isocyanurate ring, and a cyclic polyvalent aliphatic structure (3) is preferable. It is particularly preferred that the aliphatic structure (1) is a linear aliphatic structure having a number average molecular weight of 200 to 700. Among the polyimide resins (X), the linear polyvalent aliphatic structure having a carboxyl group and a number average molecular weight of 300 to 6,000 (2) because of its excellent solubility in general-purpose solvents, heat resistance, and mechanical properties. Resin (Y1) having a carboxylic acid, a urethane bond, an imide ring, an isocyanurate ring, and a cyclic polyvalent aliphatic structure (3) is preferable, and a polyimide resin having a good balance between mechanical properties and dielectric properties of a cured product is obtained. For this reason, it is particularly preferable that the linear polyvalent aliphatic structure (2) is a linear polyvalent aliphatic structure having a number average molecular weight of 700 to 4,500.
[0012]
The content of the aliphatic structure (1) portion in the polyimide resin (X) and the content of the linear polyvalent aliphatic structure (2) portion in the polyimide resin (Y) are the same or different. However, from the viewpoint of obtaining a cured product having good coating suitability, excellent heat resistance and excellent mechanical properties, and a low dielectric constant and a low dielectric loss tangent, each has a preferred content of 10 to 50% by weight. 20-40% by weight is particularly preferred.
[0013]
Examples of the polyimide resin (X1) include a structural unit represented by the following general formula (I) and a terminal structure represented by the following general formula (II), and the following general formulas (IV) and (V) And a polyimide resin (X2) having at least one of the terminal structures represented by (VI). Among them, an acid value (in terms of solid content) of 20 to 250 and an aliphatic structure (1) portion When the number average molecular weight is 200 to 700, the content of the aliphatic structure (1) portion is 20 to 40% by weight, the concentration of the isocyanurate ring is 0.3 to 1.2 mmol / g, and the number average molecular weight is 1, Polyimide resins having a weight average molecular weight of 2,000 to 30,000 and a weight average molecular weight of 2,000 to 100,000 are particularly preferred. Further, the polyimide resin (X) most preferably has an acid value of 20 to 150 in terms of solids, a number average molecular weight of 1,000 to 10,000, and a weight average molecular weight of 2,000 to 2,000. Most preferably, it is 50,000.
[0014]
The polyimide resin (Y1) has, for example, a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (III), and has the following general formula (IV), ( V) and a polyimide resin (Y2) having at least one of the terminal structures represented by (VI). Among them, an acid value (in terms of resin solid content) of 20 to 250, and a linear polyvalent fat The group (2) has a number average molecular weight of 700 to 4,500, the linear polyvalent aliphatic structure (2) has a total content of 20 to 40% by weight, and the isocyanurate ring has a concentration of 0.1 to 4% by weight. A polyimide resin having a number average molecular weight of 3 to 1.2 mmol / g, a number average molecular weight of 2,000 to 30,000, and a weight average molecular weight of 3,000 to 100,000 is particularly preferable. Furthermore, the polyimide resin (Y) most preferably has an acid value of 20 to 150 in terms of solids, a number average molecular weight of 2,000 to 10,000, and a weight average molecular weight of 3,000 to Most preferably, it is 50,000.
[0015]
Embedded image

(However, R in the formula ₁ Is an organic group having a cycloaliphatic structure having 6 to 13 carbon atoms, R ₂ Is an aliphatic structure having a number average molecular weight of 100 to 1,000, R ₃ Represents a linear hydrocarbon structure having a number average molecular weight of 300 to 6,000. )
Embedded image

[0016]
The weight ratio (X) / (Y) of the polyimide resin (X) and the polyimide resin (Y) is not particularly limited, but is usually 5/95 to 95/5, and is excellent in heat resistance and mechanical properties. From the viewpoint of obtaining a polyimide resin composition having good coating suitability, 10/90 to 80/20 is preferable, and 15/85 to 60/40 is particularly preferable. When the content of the polyimide resin (X) is large, the coating suitability is good, but the heat resistance and mechanical properties are reduced. Conversely, when the content of the polyimide resin (Y) is large, the heat resistance and mechanical properties are poor. However, it is preferable to appropriately select or adjust the weight ratio (X) / (Y) according to the purpose or application of use, since the coating ratio tends to decrease.
[0017]
In the present invention, the acid value, the concentration of the isocyanurate ring, the number average molecular weight and the weight average molecular weight of the polyimide resins (X) and (Y) are measured by the following methods.
(1) Acid value: Measured according to JIS K-5601-2-1. As a diluting solvent for the sample, a mixed solvent of acetone / water (9/1 volume ratio) having an acid value of 0 is used so that the acid value of the acid anhydride can be measured.
(2) Concentration of isocyanurate ring: ^Thirteen C-NMR analysis [solvent: deuterated dimethyl sulfoxide (DMSO-d ₆ ) Is carried out, and the concentration (mmol) of the isocyanurate ring per 1 g of the polyimide resin (X) is determined from the spectral intensity of the carbon atom due to the isocyanurate ring at 149 ppm using a calibration curve. In addition, ^Thirteen The concentration of the imide ring can be similarly determined from the spectral intensity of the carbon atom at 169 ppm due to the imide ring by C-NMR analysis.
(3) Number average molecular weight and weight average molecular weight: The number average molecular weight and weight average molecular weight in terms of polystyrene are determined by gel permeation chromatography (GPC).
[0018]
The content of the aliphatic structure (1) portion in the polyimide resin (X) and the content of the linear polyvalent aliphatic structure (2) portion in the polyimide resin (X) were determined by the polyimide resin (X), ( When Y) is a polyimide resin produced by a production method described later, it can be determined from the used weight ratio of the alcohol compound (a1) or the used weight ratio of the polyol compound (a2) in the synthesis raw materials. The number average molecular weight of the aliphatic structure (1) can be determined from the number average molecular weight of the alcohol compound (a1), and the number average molecular weight of the linear polyvalent aliphatic structure (2) can be calculated from the polyol compound (a). It can be determined from the number average molecular weight of a2).
[0019]
The content and number average molecular weight of the aliphatic structure (1) portion and the linear polyvalent aliphatic structure (2) portion in the polyimide resins (X) and (Y) whose production method is unknown are as follows. (Y) is subjected to a usual hydrolysis method, for example, heat treatment in the presence of an organic amine to decompose a urethane bond to form an aliphatic structure (1) portion and a linear polyvalent aliphatic structure (2) portion with the polyimide resin ( X) and (Y), which are extracted with a low-polarity organic solvent such as dichloromethane by utilizing the fact that they are less polar than the imide structure portion, and the amount of extraction is measured and GPC analysis is performed. Can be obtained by
[0020]
The method for producing the polyimide resins (X) and (Y) used in the polyimide resin composition of the present invention is not particularly limited. Examples of the method for producing the polyimide resin (X) include a polyisocyanate compound (a0) and an aliphatic resin. A prepolymer having an isocyanate group at an end obtained by reacting an alcohol compound having the structure (1), wherein the alcohol compound (a1) having a number average molecular weight of 100 to 1,000 in the aliphatic structure (1) is reacted. A method of reacting A1) with an acid anhydride (B) of a polycarboxylic acid having three or more carboxyl groups in an organic solvent is preferred. The method for producing the polyimide resin (Y) includes a polyisocyanate compound (a0) and a polyol compound having a linear polyvalent aliphatic structure (2), wherein the linear polyvalent aliphatic structure (2) (A2) having a terminal isocyanate group obtained by reacting a polyol compound (a2) having a number average molecular weight of 300 to 6,000, and an acid anhydride of a polycarboxylic acid having three or more carboxyl groups A method of reacting (B) in an organic solvent is preferred.
[0021]
For example, to produce the polyimide resin (X2) by the method for producing the polyimide resins (X) and (Y), an isocyanurate ring derived from a diisocyanate having a cyclic aliphatic structure having 6 to 13 carbon atoms is used. And a prepolymer having an isocyanate group at the terminal obtained by reacting an alcohol compound having an aliphatic structure with an alcohol compound having an aliphatic structure, wherein the alcohol compound has a number average molecular weight of 100 to 1,000 (a1). , An acid anhydride of tricarboxylic acid may be reacted in an organic solvent, and a polyimide resin (Y2) is produced from a diisocyanate having a cyclic aliphatic structure having 6 to 13 carbon atoms. A polyisocyanate having an isocyanurate ring and a polyol compound having a linear polyvalent aliphatic structure, Reaction of a prepolymer having an isocyanate group at a terminal obtained by reacting a polyol compound (a2) having a polyvalent aliphatic structural portion with a number average molecular weight of 300 to 6,000 with an acid anhydride of tricarboxylic acid in an organic solvent You can do it.
[0022]
In order to obtain a prepolymer having an isocyanate group at the terminal, a polyisocyanate compound (a0) and an alcohol compound (a1) or a polyol compound (a2) are mixed with an alcohol compound (a1) or an organic compound in an organic solvent. A method is preferred in which the reaction is carried out under such conditions that the isocyanate groups in the polyisocyanate compound (a0) become excessive with respect to the hydroxyl groups in the polyol compound (a2).
[0023]
The reaction temperature in the reaction between the polyisocyanate compound (a0) and the alcohol compound (a1) or the polyol compound (a2) is usually 50 to 150 ° C., preferably 60 to 100 ° C. The reaction temperature in the reaction between the polymers (A1) and (A2) and the acid anhydride of the polycarboxylic acid (B) is usually 80 to 250 ° C, preferably 100 to 200 ° C.
[0024]
At this time, the molar ratio (NCO / OH) of the isocyanate group in the polyisocyanate compound (a0) to the hydroxyl group in the alcohol compound (a1) or the polyol compound (a2) is usually 1.2 to 20, preferably 1.5. 10 to 10. In this case, various urethanization catalysts can be used.
[0025]
In the method for producing the polyimide resins (X) and (Y), the prepolymer (A) and the acid anhydride (B) of the polycarboxylic acid are reacted in an organic solvent to obtain a polyimide resin. By changing the weight ratio between the polymer (A) and the acid anhydride of the polycarboxylic acid (B), the molecular weight and the acid value of the obtained polyimide resins (X) and (Y) can be adjusted. At this time, a catalyst may be used, and an antioxidant and a polymerization inhibitor may be used in combination.
[0026]
The weight ratio (A) / (B) of the prepolymer (A) and the acid anhydride (B) of the polycarboxylic acid is usually 90/10 to 50/50. 80/20 to 60/40 is preferable because polyimide resins (X) and (Y) having excellent physical properties can be obtained.
[0027]
The polyisocyanate compound (a0) is a compound having two or more isocyanate groups in the molecule, for example, aromatic polyisocyanate, aliphatic polyisocyanate (including cycloaliphatic polyisocyanate); Nurate body, burette body, adduct body, allohanate body and the like can be mentioned.
[0028]
Examples of the aromatic polyisocyanate compound include p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 4,4. '-Diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate (crude MDI), polymethylene polyphenyl isocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4'- Diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, 1,3-bis (α, α-dimethyl isocyanatomethyl) benzene, tetramethyl xylylene diisocyanate, Diphenylene ether-4,4'-diisocyanate, naphthalene diisocyanate and the like can be mentioned.
[0029]
Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene methylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbonulene diisocyanate, and the like.
[0030]
As the polyisocyanate compound (a0), an aliphatic polyisocyanate is preferable because a polyimide resin having good solubility in an organic solvent and compatibility with an epoxy resin or an organic solvent and having a low dielectric constant and a low dielectric loss tangent of a cured product is obtained. Is preferred. Further, an isocyanurate-type polyisocyanate is preferable because a polyimide resin having good heat resistance of the cured product can be obtained.
[0031]
Furthermore, as the polyisocyanate compound (a0), a polyimide resin having good solubility in an organic solvent and compatibility with an epoxy resin or an organic solvent, a low dielectric constant and a low dielectric loss tangent of a cured product, and excellent heat resistance can be obtained. Therefore, a polyisocyanate compound (a01) having an isocyanurate ring derived from an aliphatic polyisocyanate is more preferable, and a polyisocyanate compound having an isocyanurate ring derived from a cycloaliphatic polyisocyanate is more preferable. Examples of the polyisocyanate compound having an isocyanurate ring derived from the cycloaliphatic polyisocyanate include those having a cyclic aliphatic structure in an amount of 2 to 3 moles per 1 mole of the isocyanurate ring. Those having a cyclic aliphatic structure by 2.5 to 3 times by mole are more preferable.
[0032]
As the polyisocyanate compound (a01), for example, one or two or more aliphatic diisocyanate compounds are isocyanurated in the presence or absence of an isocyanuration catalyst such as a quaternary ammonium salt. And a mixture of isocyanurates such as trimer, pentamer, and heptamer. Specific examples of the polyisocyanate compound (a01) include isocyanurate-type polyisocyanate of isophorone diisocyanate, isocyanurate-type polyisocyanate of hexamethylene diisocyanate, isocyanurate-type polyisocyanate of hydrogenated xylene diisocyanate, and isocyanurate-type polyisocyanate of norbornane diisocyanate. And isocyanates.
[0033]
As the polyisocyanate compound (a01), a polyimide resin having good solubility in an organic solvent and heat resistance of a cured product can be obtained. Therefore, 30 parts of trimer isocyanurate is added to 100 parts by weight of the polyisocyanate compound (a0). Those containing at least 50 parts by weight are preferred, and those containing at least 50 parts by weight are particularly preferred.
[0034]
Further, as the polyisocyanate compound (a01), a content of an isocyanate group of 10 to 30% by weight is more preferable because a polyimide resin having good solubility in an organic solvent and heat resistance of a cured product is obtained. . Therefore, the polyisocyanate compound (a01) is most preferably a polyisocyanate compound having an isocyanurate ring derived from a cycloaliphatic polyisocyanate and having an isocyanate group content of 10 to 30% by weight. preferable.
[0035]
The polyisocyanate having an isocyanurate ring may be used in combination with another polyisocyanate, but it is preferable to use an isocyanurate type polyisocyanate alone.
[0036]
The alcohol compound (a1) is an alcohol compound having an aliphatic structure (1), and has a number average molecular weight of 100 to 1,000 in the aliphatic structure (1) portion. An alcohol compound having a number average molecular weight of 200 to 700 in the aliphatic structure (1) portion is preferable since a polyimide resin having a good balance between mechanical properties and dielectric properties of the aliphatic structure (1) is obtained. Alcohol compounds having a group structure and a number average molecular weight of a linear aliphatic structure portion of 200 to 700 are more preferable. Alcohol compounds having a number average molecular weight of the aliphatic structure (1) portion of less than 100 are not preferred because the dielectric constant and dielectric loss tangent of the cured product are increased. It is not preferable because the mechanical properties of the cured product become poor. As the alcohol compound (a1), primary to tertiary alcohol compounds can be used, but primary or secondary alcohol compounds are preferable from the viewpoint of reactivity. The alcohol compound (a1) may be used alone or in combination of two or more.
[0037]
The aliphatic structure of the alcohol compound (a1) may be linear or branched, and may be saturated or unsaturated. However, from the viewpoint of changes in physical properties and stability upon heating, the saturated aliphatic structure may be used. Is more preferable.
[0038]
Examples of the alcohol compound (a1) include an aliphatic alcohol having 6 to 70 carbon atoms, an alkylphenol having an alkyl group having 6 to 70 carbon atoms, and an alkyl group having 6 to 70 carbon atoms modified with an alkylene oxide. And an aliphatic alcohol having 6 to 70 carbon atoms is preferable.
[0039]
Examples of the aliphatic alcohol having 6 to 70 carbon atoms include higher alcohols derived from natural fats and oils such as lauryl alcohol and oleyl alcohol, higher alcohols derived from petrochemical products, and the like. It is possible. Examples of the production method include a reduction method, a saponification method, an oxo method, and a liquid layer acid value method. Raw materials for higher alcohols may be used alone or in combination of two or more.
[0040]
Such aliphatic alcohols include, for example, Diadol series (Diadol 7, 9, 11, 13, 135, 911, 115H, 115L, etc.) and Dovanol series (Dovanol 23, 25) manufactured by Mitsubishi Chemical Corporation. , 45 etc.); Calcol series manufactured by Kao Corporation (Calcol 2098, 4098, 6098, 6870, 6850, 8098, 8688, 200GD, 220-80, etc.); Connol series manufactured by Shin Nippon Rika Co., Ltd. Conor 10M, 10W, 10WS, 10D, 1098, 20F, 1275, 20P, 1465, 1495, 30CK, 1668, 1695, 30T, 30TD, 30F, 30SS, 2265, 2280, 30RC, 30OC, 30CK-R, etc.), Angers Call series (Angecol 50A, 60AN 70AN, 80AN, 85AN, 90N, 90NR, 90NHR, etc., Liccacol series (Licacol 90B, 90BR, 90BRHR, etc.), and Negecole series (Negekol 160B, 160BR, 200A, 200AT, 240A, C32-36, etc.); Is mentioned.
[0041]
The polyol compound (a2) is a polyol compound having a linear polyvalent aliphatic structure (2), and the number average molecular weight of the linear polyvalent aliphatic structure (2) portion is 300 to 6,000. Among them, polyimide resin with excellent solubility in organic solvents, compatibility with epoxy resins and organic solvents, good mechanical properties of cured products, low dielectric constant and dielectric loss tangent of cured products, and excellent film forming properties Is preferable, the number average molecular weight of the linear polyvalent aliphatic structure (2) portion is preferably from 700 to 4,500, and the number average molecular weight of the linear polyvalent aliphatic structure (2) portion is 800. ~ 4,200 polyol compounds are more preferred. A polyol compound having a linear polyvalent aliphatic structure (2) portion having a number average molecular weight of less than 300 is not preferred because the dielectric constant and the dielectric loss tangent of the cured product are increased. A polyol compound having a number average molecular weight exceeding 6,000 is not preferred because the solubility in an organic solvent, the compatibility with an epoxy resin or an organic solvent, and the mechanical properties of a cured product are poor.
[0042]
Examples of the polyol compound (a2) include a compound having an average of two or more hydroxyl groups bonded to the terminal and / or side chain of the linear polyvalent aliphatic structure (2) per molecule in total. The linear polyvalent aliphatic structure (2) may be linear or branched. The linear polyvalent aliphatic structure (2) may be saturated or unsaturated, but a saturated aliphatic structure is more preferable from the viewpoint of change in physical properties and stability during heating.
[0043]
Examples of the polyol compound (a2) include a polyol compound having a polyolefin structure or a polydiene structure, and a polyol compound having a polyolefin structure or a polydiene structure having a number average molecular weight of 300 to 6,000 and a hydrogenated product thereof. Can be Examples of the olefin include ethylene, propylene, butene, isobutylene, pentene, and methylpentene. Examples of the diene include pentadiene, hexadiene, pentadiene, isoprene, butadiene, propadiene, and dimethylbutadiene.
[0044]
Specific examples of the polyol compound (a2) include polyethylene polyols, polypropylene polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polyisoprene polyols, hydrogenated polyisoprene polyols, and the like. Polyol compounds having an average molecular weight of 300 to 6,000 are exemplified. These may be used alone or in combination of two or more.
[0045]
The number of hydroxyl groups in the polyol compound (a2) is preferably 2 to 3 on average, since it is difficult to gel, the molecular growth is good, and a polyimide resin having excellent mechanical properties of a cured product can be obtained. Further, the number of hydroxyl groups is particularly preferably 2 to 2.5 on average.
[0046]
Commercially available products of the polyol compound (a2) include, for example, liquid polybutadiene having hydroxyl groups at both ends such as NISSO PB (G series) manufactured by Nippon Soda Co., Ltd. and Poly-bd manufactured by Idemitsu Petrochemical Co .; Hydrogenated polybutadiene having hydroxyl groups at both ends, such as NISSO PB (GI series) manufactured by Nippon Soda Co., Ltd., and Polytail H and Polytail HA manufactured by Mitsubishi Chemical Corporation; Poly-iP manufactured by Idemitsu Petrochemical Co., Ltd. Liquid C5 polymer having hydroxyl groups at both ends of the above; hydrogenated having hydroxyl groups at both ends such as Epol manufactured by Idemitsu Petrochemical Co., Ltd., TH-1, TH-2 and TH-3 manufactured by Kuraray Co., Ltd. And polyisoprene.
[0047]
Further, as the polyol compound (a2), an ester-modified polyol compound or a urethane-modified polyol compound obtained by reacting a polyol compound having a linear polyvalent aliphatic structure (2) with various polybasic acids or polyisocyanates as described above. Polyol compounds can also be used.
[0048]
As the polyol compound (a2), polybutadiene polyol and / or hydrogenated polybutadiene polyol are preferable, and among them, hydrogenated polybutadiene polyol is more preferable.
[0049]
In the method for producing the polyimide resin (Y), the polyol compound (a2) may be used in combination with another hydroxyl group-containing compound to such an extent that the effects of the present invention are not impaired. At this time, the other hydroxyl group-containing compounds are desirably used in an amount of 50% by weight or less of the total hydroxyl group-containing compounds.
[0050]
As the other hydroxyl group-containing compound, a saturated polyol, an unsaturated polyol, or an alcohol may be used, but a polyol is preferable. For example, as a low molecular polyol, ethylene glycol, 1,3-propylene glycol, 1,2 -Propylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 2,2,4-trimethyl -1,3-pentanediol, 3-methyl-1,5-pentanediol, cyclohexane dimethylol, 1,4-cyclohexanediol, tricyclodecane dimethylol, hydrogenated bisphenol A, trimethylolethane, trimethylolpropane, ditriol Methylolethane, ditri Tyrolpropane, glycerin, diglycerol, 3-methylpentane-1,3,5-triol, pentaerythritol, dipentaerythritol, tripentaerythritol, 2,2,6,6-tetramethylolcyclohexanol-1, mannitol, Sorbitol, inositol, glucose, diethylene glycol, dipropylene glycol, dichloroneopentyl glycol, dibromoneopentyl glycol, neopentyl glycol hydroxypivalate, spiro glycol, ethylene oxide-added bisphenol A, propylene oxide-added bisphenol A, dimethylolpropion Bifunctional diols such as acid and dimethylolbutanoic acid; and tris-2-hydroxyethyl isocyanurate.
[0051]
Further, as oligomers or high molecular weight polyols, polyethylene oxides polymerized from cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran and butylene oxide; polyether polyols such as polypropylene polyol, polytetramethylene polyol, polybutylene polyol, and the like; Polyether polyols which are copolymers of these cyclic ethers; polyester polyols synthesized from the aforementioned low molecular weight polyols and polybasic acids; silicone polyols such as polycarbonate polyols, urethane polyols and polydimethylsiloxane polyols; acrylic polyols; epoxy polyols And the like.
[0052]
Examples of the acid anhydride (B) of a polycarboxylic acid having three or more carboxyl groups used in the present invention include an acid anhydride of a tricarboxylic acid and an acid anhydride of a tetracarboxylic acid.
[0053]
Examples of the tricarboxylic acid anhydride include trimellitic anhydride, naphthalene-1,2,4-tricarboxylic anhydride, and the like.
[0054]
Examples of tetracarboxylic acid anhydrides include pyromellitic dianhydride, benzophenone-3,4,3 ', 4'-tetracarboxylic dianhydride and diphenyl ether-3,4,3', 4'- Tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,4,3 ', 4'-tetracarboxylic dianhydride, biphenyl-2,3,2 ', 3'-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1, 8,4,5-tetracarboxylic dianhydride, decahydronaphthalene-1,8,4,5-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7- Hexahydronaphthalene-1,2,5 6-tetracarboxylic dianhydride,
[0055]
2,6-dichloronaphthalene-1,8,4,5-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,8,4,5-tetracarboxylic dianhydride, 2,3,6 7-tetrachloronaphthalene-1,8,4,5-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, berylen-3,4,9,10-tetracarboxylic acid Acid dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane Dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,3-bis (3 4-dicarboxyphenyl) Anhydrous tetracarboxylic acid having an aromatic organic group in the molecule such as lopan dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride Things. One or two or more of these can be used. Further, a mixture of an anhydride of a tricarboxylic acid and an anhydride of a tetracarboxylic acid may be used.
[0056]
As the organic solvent used in the method for producing the polyimide resins (X) and (Y), the chemical reaction may be carried out after being previously present in the system, or may be introduced in the middle, depending on the timing and amount used. Is not particularly limited, but is preferably present at the beginning of the reaction between the prepolymer (A) and the acid anhydride (B) of the polycarboxylic acid. In order to maintain an appropriate reaction rate during this reaction, the proportion of the organic solvent in the system is preferably 80% by weight or less, more preferably 10 to 70% by weight of the reaction system. As such an organic solvent, an aprotic polar solvent having no active proton such as a hydroxyl group or an amino group is preferable because a compound containing an isocyanate group is used as a raw material component.
[0057]
Examples of the aprotic polar solvent include ether solvents, ester solvents, and ketone solvents. Among them, ether solvents have weak polarity and are excellent in the imidization reaction between the prepolymer (A) having an isocyanate group at the terminal and the anhydride (B) of a polycarboxylic acid having three or more carboxyl groups. Provides a reaction field.
[0058]
Examples of such ether solvents include ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl. Ethers, polyethylene glycol dialkyl ethers such as triethylene glycol dibutyl ether;
[0059]
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate; diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate Polyethylene glycol monoalkyl ether acetates such as triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate;
[0060]
Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether and propylene glycol dibutyl ether; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol Propylene glycol dialkyl ethers such as propylene glycol dibutyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate;
[0061]
Polypropylene glycol monoalkyl ether such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, and tripropylene glycol monobutyl ether acetate Acetates; dialkyl ethers of copolymerized polyether glycols such as low-molecular ethylene-propylene copolymers; monoacetate monoalkyl ethers of copolymerized polyether glycols; alkyl esters of copolymerized polyether glycols; Monoalkyl esters of ether glycols It is.
[0062]
Examples of the ester solvent include ethyl acetate, butyl acetate and the like. Examples of ketone solvents include acetone, methyl ethyl ketone, cyclohexanone, and the like. In addition, a polar solvent such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, and γ-butyrolactone can be used in combination.
[0063]
The polyimide resin composition of the present invention contains the polyimide resin (X) and the polyimide resin (Y). However, to obtain a thermosetting polyimide resin composition, the polyimide resin composition further contains the epoxy resin (Z). The compound (F) having two or more phenolic hydroxyl groups may be further contained as necessary.
[0064]
Examples of the epoxy resin (Z) include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin; phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol type novolak Novolak-type epoxy resins; epoxides of various dicyclopentadiene-modified phenol resins obtained by reacting dicyclopentadiene with various phenols; biphenyls such as epoxides of 2,2 ', 6,6'-tetramethylbiphenol Type epoxy resin; epoxy resin having a naphthalene skeleton; aromatic epoxy resins such as epoxy resin having a fluorene skeleton, and hydrogenated products of these aromatic epoxy resins; neopentyl glycol diglycide Aliphatic epoxy resins such as ethylene ether and 1,6-hexanediol diglycidyl ether; fats such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis- (3,4-epoxycyclohexyl) adipate Cyclic epoxy resins; heterocyclic-containing epoxy resins such as triglycidyl isocyanurate; Among these, aromatic epoxy resins are preferred because a thermosetting polyimide resin composition having excellent heat resistance can be obtained.
[0065]
The mixing ratio of the sum of the polyimide resins (X) and (Y) and the epoxy resin (Z) is as follows: the weight ratio of the sum of the polyimide resins (X) and (Y) and the epoxy resin (Z) (XY) / (Z) Is preferably in the range of 1 to 10, more preferably 1 to 5. The molar ratio (xy) / (z) of the total carboxyl group (xy) in the polyimide resins (X) and (Y) to the epoxy group (z) in the epoxy resin (Z) is 0.7 to 0.7. It is preferably 1.3.
[0066]
The thermosetting polyimide resin composition containing the polyimide resins (X) and (Y) and the epoxy resin (Z) is a compound having two or more phenolic hydroxyl groups for controlling the crosslinking density and the like at the time of curing. It is preferable to further include F). The crosslink density between the polyimide resins (X) and (Y) and the epoxy resin (Z) can be increased by using the compound (F) having two or more phenolic hydroxyl groups in combination, thereby increasing the glass transition point or higher. It is possible to reduce the coefficient of linear expansion at the temperature of. In order to increase the crosslink density and decrease the linear expansion coefficient and the like, the thermosetting polyimide resin composition has two or more polyimide resins (X) and (Y), an epoxy resin (Z), and two or more phenolic hydroxyl groups. The compounding ratio of the compound (F) is such that the total amount of the polyimide resins (X) and (Y) is 40 to 85 parts by weight, the epoxy resin (Z) is 10 to 40 parts by weight, The compound (F) having two or more hydroxyl groups is preferably 5 to 20 parts by weight. Further, the total of the carboxyl groups (xy) in the polyimide resins (X) and (Y) and the total of the hydroxyl groups (f) in the compound (F) having two or more phenolic hydroxyl groups and the epoxy in the epoxy resin (Z) The molar ratio (xy + f) / (z) of the group (z) is preferably from 0.7 to 1.3.
[0067]
Examples of the compound having two or more phenolic hydroxyl groups (F) include bisphenol compounds such as bisphenol A, bisphenol F, and bisphenol S; phenol novolak resins, cresol novolak resins, bisphenol novolak resins, phenol salicylaldehyde novolak resins, Novolak resins such as terpene diphenol novolak resin; biphenol compounds such as biphenol, biphenol novolak, tetramethylbiphenol and derivatives thereof; fluorene compounds such as phenolfluorene and cresolfluorene. Among these, a compound having three or more phenolic hydroxyl groups is preferable since a thermosetting polyimide resin composition having excellent heat resistance can be obtained.
[0068]
A thermosetting polyimide resin composition containing the polyimide resins (X) and (Y) and the epoxy resin (Z) and, if necessary, the compound (F) having two or more phenolic hydroxyl groups, is obtained by curing other than the above. Agents and curing accelerators can be used in combination, for example, melamine, dicyandiamide, guanamine and its derivatives, amines, phenols having one hydroxyl group, organic phosphines, phosphonium salts, quaternary ammonium salts, polybasic acid anhydrides Products, photocationic catalysts, cyanate compounds, isocyanate compounds, blocked isocyanate compounds and the like.
[0069]
The above-mentioned thermosetting polyimide resin composition may contain various fillers, organic pigments, inorganic pigments, extender pigments, rust preventives and the like. These may be used alone or in combination of two or more.
[0070]
Examples of the filler include barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica and the like. Can be
[0071]
Examples of the organic pigment include azo pigments; copper phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; and quinacridone pigments.
[0072]
Examples of the inorganic pigments include: chromates such as graphite, zinc chromate and molybdate orange; ferrocyanides such as dark blue; titanium oxide, zinc white, red iron oxide; iron oxide; metal oxides such as chromium carbide green; Cadmium yellow, cadmium red; metal sulfides such as mercury sulfide, selenide; sulfates such as lead sulfate; silicates such as ultramarine blue; carbonates, cobalt bio red; phosphates such as manganese purple; aluminum powder; zinc powder Metal powder such as brass powder, magnesium powder, iron powder, copper powder and nickel powder; and carbon black.
[0073]
In addition, any of other coloring, rust prevention, and extender pigments can be used. These may be used alone or in combination of two or more.
[0074]
The above-mentioned thermosetting polyimide resin composition is usually applied by a casting method, impregnation, coating, or another method. The curing temperature is from 80 to 300 ° C, and the curing time is from 20 minutes to 5 hours.
[0075]
【Example】
Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following, all parts and percentages are by weight unless otherwise specified.
[0076]
Synthesis Example 1
In a 20-liter flask equipped with a stirrer, a thermometer and a condenser, 4906 g of diethylene glycol monoethyl ether acetate (hereinafter abbreviated as EDGA) and a polyisocyanate having an isocyanurate ring derived from isophorone diisocyanate (hereinafter referred to as IPDI- Abbreviated as N. 2,760 g (12 mol as isocyanate group) of isocyanate group content 18.2%, isocyanurate ring-containing triisocyanate content, and ENGECOL 200A [Branched aliphatic alcohol manufactured by Nippon Rika Co., Ltd.] 610 g (2 mol as a hydroxyl group) of 184 mg KOH / g and a hydroxyl value of 184 mg KOH / g, and the mixture was heated to 80 ° C. with stirring while paying attention to heat generation and reacted for 3 hours. Next, 1536 g (8 mol) of trimellitic anhydride (hereinafter abbreviated as TMA) was charged, heated to 160 ° C., and reacted for 4 hours. The reaction proceeded with foaming, and the system became a light brown clear liquid, and a solution of a polyimide resin having a carboxyl group and an aliphatic structure (1) at the terminal was obtained.
[0077]
The resulting polyimide resin solution was applied to a KBr plate, and the infrared absorption spectrum of a sample obtained by evaporating the solvent was measured. As a result, the characteristic absorption of the isocyanate group was 2270 cm. ^-1 Disappeared completely, 725cm ^-1 And 1780cm ^-1 And 1720cm ^-1 Absorption of imide ring, 1690cm ^-1 And 1460cm ^-1 Characteristic absorption of isocyanurate ring, 1550cm ^-1 In addition, characteristic absorption of urethane bond was confirmed. The acid value of the polyimide resin is 91 mgKOH / g in terms of solids, the concentration of isocyanurate rings is 0.90 mmol / g (resin solids), and the number average molecular weight (hereinafter abbreviated as Mn) is 2,300. And the weight average molecular weight (hereinafter abbreviated as Mw) was 4,400. Hereinafter, this polyimide resin solution is abbreviated as (X-1).
[0078]
Synthesis Example 2
In a 20-liter flask equipped with a stirrer, a thermometer and a condenser, 4856 g of EDGA, 2070 g of IPDI-N (9 mol as isocyanate group) and polyisocyanate having an isocyanurate ring derived from 1,6-hexanediisocyanate (Hereinafter abbreviated as HDI-N; isocyanate group content 22.9%, isocyanurate ring-containing triisocyanate content 63.3%), 550 g (3 mol as isocyanate group) were charged and mixed, and then NJECOL 240A [New A branched aliphatic alcohol manufactured by Nippon Rika Co., Ltd., having a hydroxyl value of 160 and an average molecular weight of 350] 700 g (2 mol as a hydroxyl group) was charged, and the temperature was raised to 80 ° C. while being careful of heat generation while stirring. After performing the reaction at this temperature for 3 hours, 1536 g (8 mol) of TMA was charged, the temperature was raised to 160 ° C., and the reaction was performed for 4 hours. The reaction proceeded with foaming, and the system became a light brown clear liquid, and a solution of a polyimide resin having a carboxyl group and an aliphatic structure (1) at the terminal was obtained.
[0079]
Using the obtained polyimide resin solution, the infrared absorption spectrum was measured in the same manner as in Example 1. As a result, the characteristic absorption of the isocyanate group was 2,270 cm. ^-1 Disappeared completely, 725cm ^-1 And 1780cm ^-1 And 1720cm ^-1 Absorption of imide ring, 1690cm ^-1 And 1460cm ^-1 Characteristic absorption of isocyanurate ring, 1550cm ^-1 In addition, characteristic absorption of urethane bond was confirmed. The acid value of the polyimide resin was 88 in terms of solids, the concentration of isocyanurate rings was 0.90 mmol / g (in terms of resin solids), Mn was 2,400, and Mw was 4,600. Hereinafter, this polyimide resin solution is abbreviated as (X-2).
[0080]
Synthesis Example 3
In a 20-liter flask equipped with a stirrer, a thermometer, and a condenser, 5022 g of EDGA, 1380 g of IPDI-N (6 moles as isocyanate groups), and a polyisocyanate having an isocyanurate ring derived from norbonulylene diisocyanate (hereinafter, referred to as a polyisocyanate). 1344 g (6 mol of isocyanate group content) of isocyanate group content 18.75%, isocyanurate ring-containing triisocyanate content was charged, and heated and dissolved at 80 ° C., followed by engecol. 610 g (2 moles as hydroxyl groups) of 200A was charged and reacted at 80 ° C. for 5 hours while stirring, and then 1536 g (8 moles) of TMA was charged to 170 ° C. and reacted for 4 hours. The reaction proceeded with foaming, and the system became a light brown clear liquid, and a solution of a polyimide resin having a carboxyl group and an aliphatic structure (1) at the terminal was obtained.
[0081]
Using the obtained polyimide resin solution, the infrared absorption spectrum was measured in the same manner as in Example 1. As a result, the characteristic absorption of the isocyanate group was 2,270 cm. ^-1 Disappeared completely, 725cm ^-1 And 1780cm ^-1 And 1720cm ^-1 Absorption of imide ring, 1690cm ^-1 And 1460cm ^-1 Characteristic absorption of isocyanurate ring, 1550cm ^-1 In addition, characteristic absorption of urethane bond was confirmed. The acid value of the polyimide resin was 86 in terms of solids, the concentration of isocyanurate rings was 0.90 mmol / g (resin solids), Mn was 2,200, and Mw was 4,700. Hereinafter, this polyimide resin solution is abbreviated as (X-3).
[0082]
Synthesis Example 4
In a 20-liter flask equipped with a stirrer, a thermometer and a condenser, 4565.8 g of EDGA, 2070 g of IPDI-N (9 mol as isocyanate group), 262 g of 4,4'-dicyclohexylmethane diisocyanate (2 mol as isocyanate group) ) And 890 g (1.59 mol as a hydroxyl group) of NJecoll C32-36 [branched aliphatic alcohol manufactured by Shin Nippon Rika Co., Ltd., hydroxyl value 100, number average molecular weight 561], and pay attention to heat generation while stirring. To 80 ° C. After performing the reaction at this temperature for 3 hours, 1344 g (7 mol) of TMA was charged, the temperature was raised to 180 ° C., and the reaction was performed for 3 hours. The reaction proceeded with foaming, and the system became a light brown clear liquid, and a solution of a polyimide resin having a carboxyl group and an aliphatic structure (1) at the terminal was obtained.
A solution of a polyimide resin was obtained.
[0083]
Using the obtained polyimide resin solution, the infrared absorption spectrum was measured in the same manner as in Example 1. As a result, the characteristic absorption of the isocyanate group was 2,270 cm. ^-1 Disappeared completely, 725cm ^-1 And 1780cm ^-1 And 1720cm ^-1 Absorption of imide ring, 1690cm ^-1 And 1460cm ^-1 Characteristic absorption of isocyanurate ring, 1550cm ^-1 In addition, characteristic absorption of urethane bond was confirmed. The acid value of the polyimide resin was 86 in terms of solids, the concentration of isocyanurate rings was 0.72 mmol / g (resin solids), Mn was 2,640, and Mw was 4,000. Hereinafter, this polyimide resin solution is abbreviated as (X-4).
[0084]
Synthesis Example 5
In a 20-liter flask equipped with a stirrer, a thermometer, and a condenser, 4951 g of EDGA, 2760 g of IPDI-N (12 mol as an isocyanate group), and polytail HA [produced by Mitsubishi Chemical Co., Ltd. Addition liquid polybutadiene, number average molecular weight 2,100, hydroxyl value 51.2 mg KOH / g] 2191 g (2 mol as a hydroxyl group) was added, and the mixture was heated to 80 ° C. while paying attention to heat generation while stirring, and then reacted for 3 hours. went. Next, 1536 g of EDGA and 1536 g (8 mol) of TMA were further charged, and heated to 160 ° C., followed by a reaction for 4 hours. The reaction proceeded with foaming. The inside of the system became a light brown clear liquid, and a solution of a polyimide resin having a carboxyl group and a linear polyvalent aliphatic structure (2) was obtained.
[0085]
Using the obtained polyimide resin solution, the infrared absorption spectrum was measured in the same manner as in Example 1. As a result, the characteristic absorption of the isocyanate group was 2,270 cm. ^-1 Disappeared completely, 725cm ^-1 And 1780cm ^-1 And 1720cm ^-1 Absorption of imide ring, 1690cm ^-1 And 1460cm ^-1 Characteristic absorption of isocyanurate ring, 1550cm ^-1 In addition, characteristic absorption of urethane bond was confirmed. The acid value of the polyimide resin was 79 in terms of solids, the concentration of isocyanurate rings was 0.66 mmol / g (in terms of resin solids), Mn was 5,900, and Mw was 4,000. Hereinafter, this polyimide resin solution is abbreviated as (Y-1).
[0086]
Synthesis Example 6
In a 20-liter flask equipped with a stirrer, a thermometer, and a condenser, 4300 g of EDGA, 2070 g of IPDI-N (9 mol as an isocyanate group), and 550 g of HDI-N (3 mol as an isocyanate group) were charged and mixed. After homogenization, 2191 g of polytail HA (2 mol as a hydroxyl group) was added, and the mixture was heated to 80 ° C. while paying attention to heat while stirring and reacted for 3 hours. Next, 1536 g (8 mol) of TMA was charged, the temperature was raised to 160 ° C., and the mixture was reacted for 4 hours. The reaction at this time proceeded with foaming, and when the viscosity increased and the system became difficult to stir, 2000 g of EDGA was further added. The inside of the system became a light brown clear liquid, and a solution of a polyimide resin having a carboxyl group and a linear polyvalent aliphatic structure (2) was obtained.
[0087]
Using the obtained polyimide resin solution, the infrared absorption spectrum was measured in the same manner as in Example 1. As a result, the characteristic absorption of the isocyanate group was 2,270 cm. ^-1 Disappeared completely, 725cm ^-1 And 1780cm ^-1 And 1720cm ^-1 Absorption of imide ring, 1690cm ^-1 And 1460cm ^-1 Characteristic absorption of isocyanurate ring, 1550cm ^-1 In addition, characteristic absorption of urethane bond was confirmed. Further, the acid value of the polyimide resin was 85 in terms of solid content, the concentration of the isocyanurate ring was 0.68 mmol / g, Mn was 5,500, and Mw was 22,000. Hereinafter, this polyimide resin solution is abbreviated as (Y-2).
[0088]
Synthesis Example 7
In a 20-liter flask equipped with a stirrer, a thermometer, and a condenser, 5310 g of EDGA, 1380 g of IPDI-N (6 mol as an isocyanate group), and 1344 g of NBDI-N (6 mol as an isocyanate group) were charged. After heating and dissolving, 2191 g (2 mol of hydroxyl groups) of polytail HA were further charged and reacted at 80 ° C. for 5 hours while stirring, then 1536 g (8 mol) of TMA was charged, and the temperature was raised to 170 ° C. Allowed to react for hours. The reaction proceeded with foaming. The inside of the system became a light brown clear liquid, and a solution of a polyimide resin having a carboxyl group and a linear polyvalent aliphatic structure (2) was obtained.
[0089]
Using the obtained polyimide resin solution, the infrared absorption spectrum was measured in the same manner as in Example 1. As a result, the characteristic absorption of the isocyanate group was 2,270 cm. ^-1 Disappeared completely, 725cm ^-1 And 1780cm ^-1 And 1720cm ^-1 Absorption of imide ring, 1690cm ^-1 And 1460cm ^-1 Characteristic absorption of isocyanurate ring, 1550cm ^-1 In addition, characteristic absorption of urethane bond was confirmed. The acid value of the polyimide resin was 75 in terms of solid content, the concentration of the isocyanurate ring was 0.72 mmol / g, Mn was 4,400, and Mw was 21.000. Hereinafter, this polyimide resin solution is abbreviated as (Y-3).
[0090]
Synthesis Example 8
In a 20-liter flask equipped with a stirrer, a thermometer, and a condenser, 5636 g of EDGA, 2760 g of IPDI-N (12 mol as an isocyanate group), and NISSO-PBG-3000 [both ends of Nippon Soda Co., Ltd. A liquid polybutadiene having a hydroxyl group, a number average molecular weight of 2,800, and a hydroxyl value of 39] 2876 g (2 mol as a hydroxyl group) were charged, and the mixture was heated to 80 ° C. with stirring while paying attention to heat generation, and reacted for 3 hours. . Next, 1537 g of EDGA and 1536 g (8 mol) of TMA were further charged, and the mixture was heated to 160 ° C. and reacted for 4 hours. The reaction proceeded with foaming. The inside of the system became a light brown clear liquid, and a solution of a polyimide resin having a carboxyl group and a linear polyvalent aliphatic structure (2) was obtained.
[0091]
Using the obtained polyimide resin solution, the infrared absorption spectrum was measured in the same manner as in Example 1. As a result, the characteristic absorption of the isocyanate group was 2,270 cm. ^-1 Disappeared completely, 725cm ^-1 And 1780cm ^-1 And 1720cm ^-1 Absorption of imide ring, 1690cm ^-1 And 1460cm ^-1 Characteristic absorption of isocyanurate ring, 1550cm ^-1 In addition, characteristic absorption of urethane bond was confirmed. The acid value of the polyimide resin was 70 in terms of solid content, the concentration of the isocyanurate ring was 0.59 mmol / g, Mn was 5,400, and Mw was 32,000. Hereinafter, this polyimide resin solution is abbreviated as (Y-4).
[0092]
Synthesis Example 9
In a 20-liter flask equipped with a stirrer, a thermometer and a condenser, 5712 g of EDGA, 2760 g of IPDI-N (12 mol as isocyanate group), and NISSO-PBGI-3000 [both ends of Nippon Soda Co., Ltd. Hydrogenated liquid polybutadiene having a hydroxyl group, number average molecular weight 4,000, hydroxyl value 28] 2952 g (1.47 mol as a hydroxyl group) were charged, and the mixture was heated to 80 ° C. while paying attention to heat while stirring, and then 3 hours. The reaction was performed. Next, 1728 g of EDGA and 1728 g (9 mol) of TMA were further charged and heated to 160 ° C., followed by a reaction for 4 hours. The reaction proceeded with foaming. The inside of the system became a light brown clear liquid, and a solution of a polyimide resin having a carboxyl group and a linear polyvalent aliphatic structure (2) was obtained.
[0093]
Using the obtained polyimide resin solution, the infrared absorption spectrum was measured in the same manner as in Example 1. As a result, the characteristic absorption of the isocyanate group was 2,270 cm. ^-1 Disappeared completely, 725cm ^-1 And 1780cm ^-1 And 1720cm ^-1 Absorption of imide ring, 1690cm ^-1 And 1460cm ^-1 Characteristic absorption of isocyanurate ring, 1550cm ^-1 In addition, characteristic absorption of urethane bond was confirmed. The acid value of the polyimide resin was 74 in terms of solid content, the concentration of the isocyanurate ring was 0.57 mmol / g, Mn was 3,600, and Mw was 24,000. Hereinafter, this polyimide resin solution is abbreviated as (Y-5).
[0094]
Synthesis Example 10
In a 20-liter flask equipped with a stirrer, a thermometer and a condenser, 5284 g of EDGA, 2760 g of IPDI-N (12 mol as isocyanate groups), 4,4'-dicyclohexylmethane diisocyanate [hydrogenated diphenylmethane diisocyanate (hydrogenated MDI )] 524 g (4 mol as an isocyanate group) and TH-21 [a hydrogenated polyisoprene having a hydroxyl group at both terminals manufactured by Kuraray Co., Ltd., number average molecular weight 2,600, hydroxyl value 56.1] 2000 g (as a hydroxyl group) 2 mol), and the mixture was heated to 80 ° C. while paying attention to heat generation while stirring, and then reacted for 3 hours. Next, 1536 g of EDGA and 1536 g (8 mol) of TMA were further charged, and heated to 160 ° C., followed by a reaction for 4 hours. The reaction proceeded with foaming. The inside of the system became a light brown clear liquid, and a solution of a polyimide resin having a carboxyl group and a linear polyvalent aliphatic structure (2) was obtained.
[0095]
Using the obtained polyimide resin solution, the infrared absorption spectrum was measured in the same manner as in Example 1. As a result, the characteristic absorption of the isocyanate group was 2,270 cm. ^-1 Disappeared completely, 725cm ^-1 And 1780cm ^-1 And 1720cm ^-1 Absorption of imide ring, 1690cm ^-1 And 1460cm ^-1 Characteristic absorption of isocyanurate ring, 1550cm ^-1 In addition, characteristic absorption of urethane bond was confirmed. The acid value of the polyimide resin was 72 in terms of solid content, the concentration of the isocyanurate ring was 0.64 mmol / g, Mn was 5,100, and Mw was 23,000. Hereinafter, this polyimide resin solution is abbreviated as (Y-6).
[0096]
Synthesis Example 11
In a 20-liter flask equipped with a stirrer, a thermometer and a condenser, 5451 g of EDGA, 2760 g of IPDI-N (12 mol of isocyanate groups), 500 g of diphenylmethane diisocyanate (2 mol of isocyanate groups), and 2191 g of polytail HA (hydroxyl group) The mixture was heated to 80 ° C. while paying attention to heat generation while stirring, and then reacted for 3 hours. Next, 1536 g (1 mol) of EDGA, 1344 g (7 mol) of TMA, and 218 g (1 mol) of pyromellitic anhydride were further charged, heated to 160 ° C., and reacted for 4 hours. The reaction proceeded with foaming. The inside of the system became a light brown clear liquid, and a solution of a polyimide resin having a carboxyl group and a linear polyvalent aliphatic structure (2) was obtained.
[0097]
Using the obtained polyimide resin solution, the infrared absorption spectrum was measured in the same manner as in Example 1. As a result, the characteristic absorption of the isocyanate group was 2,270 cm. ^-1 Disappeared completely, 725cm ^-1 And 1780cm ^-1 And 1720cm ^-1 Characteristic absorption of imide group, 1690cm ^-1 And 1460cm ^-1 Characteristic absorption of isocyanurate ring, 1550cm ^-1 In addition, characteristic absorption of urethane bond was confirmed. The acid value of the polyimide resin was 73 in terms of solid content, the concentration of the isocyanurate ring was 0.63 mmol / g, Mn was 5,600, and Mw was 32,000. Hereinafter, this polyimide resin solution is abbreviated as (Y-7).
[0098]
Synthesis Example 12
A 20-liter flask equipped with a stirrer, a thermometer and a condenser was charged with 5020 g of EDGA, 2220 g of isophorone diisocyanate (37.8% of isocyanate group content), and 2191 g of polytail HA (2 mol as hydroxyl group), followed by stirring. After raising the temperature to 80 ° C. while paying attention to heat generation, the reaction was performed for 3 hours. Next, 960 g (5 mol) of TMA was further charged, and the temperature was raised to 160 ° C., followed by a reaction for 4 hours. The reaction proceeded with foaming. The inside of the system became a light brown clear liquid, and a solution of a polyimide resin having a carboxyl group and a linear polyvalent aliphatic structure (2) was obtained.
[0099]
Using the obtained polyimide resin solution, the infrared absorption spectrum was measured in the same manner as in Example 1. As a result, the characteristic absorption of the isocyanate group was 2,270 cm. ^-1 Disappeared completely, 725cm ^-1 And 1780cm ^-1 And 1720cm ^-1 Absorption of imide ring, 1550cm ^-1 In addition, characteristic absorption of urethane bond was confirmed. The acid value of the polyimide resin was 53 in terms of solid content, the concentration of the isocyanurate ring was 0 mmol / g, Mn was 4,100, and Mw was 12,500. Hereinafter, this polyimide resin solution is abbreviated as (Y-8).
[0100]
Comparative Synthesis Example 1
In a 10-liter flask equipped with a stirrer, a thermometer, and a condenser, 1496 g of dimethylformamide, 888 g of isophorone diisocyanate (8 mol as an isocyanate group), and 960 g (5 mol) of TMA were charged, and the temperature was raised to 160 ° C. for reaction. After the reaction, the reaction was performed for 4 hours. The reaction proceeded with foaming. The inside of the system became a light brown clear liquid, and a solution of a polyimide resin having a carboxyl group was obtained.
[0101]
Using the obtained polyimide resin solution, the infrared absorption spectrum was measured in the same manner as in Example 1. As a result, the characteristic absorption of the isocyanate group was 2,270 cm. ^-1 Disappeared completely, 725cm ^-1 And 1780cm ^-1 And 1720cm ^-1 The absorption of an imide group was confirmed. The acid value of the polyimide resin was 94 in terms of solid content, Mn was 770, and Mw was 2,500. Hereinafter, this polyimide resin solution is abbreviated as (X'-1).
[0102]
Comparative Synthesis Example 2
In a 10-liter flask equipped with a stirrer, a thermometer, and a condenser, 1496 g of EDGA, 2760 g of IPDI-N (12 mol of isocyanate groups), and 1728 g of TMA (9 mol of hydroxyl groups) were charged, and the temperature was raised to 150 ° C. Thereafter, the reaction was carried out for 8 hours. The reaction proceeded with foaming. The inside of the system became a light brown clear liquid, and a solution of a polyimide resin having a carboxyl group was obtained.
[0103]
Using the obtained polyimide resin solution, the infrared absorption spectrum was measured in the same manner as in Example 1. As a result, the characteristic absorption of the isocyanate group was 2,270 cm. ^-1 Disappeared completely, 725cm ^-1 And 1780cm ^-1 And 1720cm ^-1 Absorption of imide ring, 1690cm ^-1 And 1460cm ^-1 Characteristic absorption of isocyanurate ring, 1550cm ^-1 In addition, characteristic absorption of urethane bond was confirmed. The acid value of the polyimide resin was 95 in terms of solid content, the concentration of the isocyanurate ring was 0.64 mmol / g, Mn was 4,100, and Mw was 12,000. Hereinafter, this polyimide resin solution is abbreviated as (X′-2).
[0104]
Examples 1 to 13 and Comparative Examples 1 and 2
According to the formulations shown in Tables 1 and 2, the thermosetting polyimide resin composition No. 1 of the present invention was used. Nos. 1 to 13 and thermosetting polyimide resin composition Nos. 1 'to 2' were prepared. In each of these resin compositions, 1 part of triphenylphosphine was added as a curing catalyst. The numerical values in Tables 1 and 2 represent the weight of the resin solid content.
[0105]
[Table 1]

[0106]
[Table 2]

[0107]
Footnotes for Tables 1 and 2
N680: Cresol novolak epoxy resin EPICLON N-680 (softening point 80 ° C, epoxy equivalent 213 g / eq) manufactured by Dainippon Ink and Chemicals, Inc.
・ HP7200: Dicyclopentadiene-modified epoxy resin EPICLON HP-7200 (softening point 61 ° C., epoxy equivalent 257 g / eq) manufactured by Dainippon Ink and Chemicals, Inc.
・ EXA4700: Multifunctional naphthalene novolak type epoxy resin EPICLON EXA-4700 (Epoxy equivalent: 162 g / eq) manufactured by Dainippon Ink and Chemicals, Inc.
-TD2090: Phenol novolac resin, Dainippon Ink and Chemicals, Inc. Phenolite TD-2090 (softening point 120 ° C, hydroxyl equivalent 105g / eq)
[0108]
Test Examples 1 to 13 and Comparative Test Examples 1 to 2
The thermosetting polyimide resin composition No. Comparative thermosetting polyimide resin composition Nos. 1 to 13 Using 1 ′ to 2 ′, a compatibility test, a coating film forming test, a glass transition point (Tg) measurement, a tensile test, a pressure cooker resistance test (PCT), a solder heat resistance test, Conductivity properties were measured. The results are shown in Tables 3 and 4.
[0109]
(1) Compatibility test
According to the formulations shown in Tables 1 and 2, the thermosetting polyimide resin composition No. Nos. 1 to 13 and thermosetting polyimide resin composition Nos. The compatible state at the time of preparing 1 ′ to 2 ′ and the state of the coating film after further coating the obtained resin composition on a glass plate and drying at 120 ° C. were evaluated according to the following evaluation criteria.
Evaluation criteria
◎: Uniformity was easily obtained by stirring, and no foreign matter or the like was observed on the coating film surface.
：: Uniform by stirring, no foreign matter or the like is seen on the coating film surface.
Δ: Difficult to be uniform by stirring, and some foreign matter and the like are seen on the coating film surface.
×: Not uniformly dissolved, repelling, foreign matter and insoluble matter can be confirmed on the coating film surface.
[0110]
(2) Film forming property test
After applying the thermosetting polyimide resin composition to a tin plate with an applicator so that the film thickness after drying becomes 30 μm, a test piece obtained by drying at 110 ° C. for 30 minutes is left at room temperature for 24 hours, The coating film appearance was evaluated according to the following evaluation criteria.
Evaluation criteria
：: No abnormalities such as cracks are observed in the coating film.
Δ: Some cracks are observed in the coating film.
X: Cracks occurred on the entire coating film.
[0111]
(3) Glass transition point (Tg) measurement
<Preparation of test specimen>
The thermosetting polyimide resin composition is coated on a tin plate so that the film thickness after curing becomes 50 μm, dried at 120 ° C. for 20 minutes, and then cured at 150 ° C. and 170 ° C. for 1 hour, respectively. After cooling to room temperature, the cured coating film was cut out from the coated plate to obtain a Tg measurement sample.
<Tg measurement method>
Using the Tg measurement sample, dynamic viscoelasticity was measured under the following conditions, and the maximum temperature of Tan δ in the obtained spectrum was defined as Tg.
Measuring instrument: RSA-II manufactured by Rheometrics
Jig: Pull
Between chucks: 20 mm
Measurement temperature: 25 to 300 ° C
Measurement frequency: 1 Hz
Heating rate: 3 ° C / min
[0112]
(4) Tensile test
<Preparation of test specimen>
The thermosetting polyimide resin composition was applied on a tin substrate so that the film thickness after curing became 50 μm. Next, the coated plate was dried at 120 ° C. for 20 minutes, and then cured at 150 ° C. and 170 ° C. for 1 hour to prepare two levels of cured coating films. After cooling to room temperature, the cured film was cut into a predetermined size, isolated from the substrate, and used as a sample for measurement.
<Tensile test measurement method>
Five measurement samples cured at 170 ° C. for 1 hour were prepared in the same manner as the Tg measurement sample, and a tensile test was performed under the following conditions to determine a breaking strength and a breaking elongation.
Measuring equipment: Tensilon manufactured by Toyo Baldwin
Sample shape: 10mm x 70mm
Between chucks: 20 mm
Pulling speed: 10mm / min
Measurement atmosphere: 22 ° C, 45% RH
[0113]
(5) Pressure cooker resistance test (PCT)
The thermosetting polyimide resin composition was applied on a glass epoxy printed circuit board on which a copper circuit pattern was formed so that the cured film thickness became 50 μm. Then, the coated plate was dried at 120 ° C. for 20 minutes, and then cured at 170 ° C. for 1 hour to prepare a test piece. (Under a saturated vapor pressure) for 50 hours, and then returned to room temperature, and the change in appearance was visually evaluated according to the following evaluation criteria. In addition, a cross-cut in a grid pattern was cut into the coating on the test piece at 1 mm intervals, a cellophane tape was stuck on it, and a peeling test was performed. Was evaluated for adhesion.
(1) Appearance evaluation criteria
：: No change or abnormality was observed before and after the test.
：: After the test, abnormalities of the coating film such as blister, whitening and dissolution can be confirmed in a range of less than 5% of the coating film area.
Δ: After the test, abnormality of the coating such as blister, whitening, dissolution, etc. can be confirmed in the range of 5% or more and less than 30% of the coating area.
C: After the test, abnormalities of the coating film such as blister, whitening, and dissolution can be confirmed in a range of 30% or more of the coating film area.
(2) Adhesion evaluation criteria
◎: No peeling of the grid-like coating film.
：: The number of peeled coating films is less than 20 for 100 grid-like coating films.
C: The number of peeled coating films was 100 or more and less than 70 for 100 grid-like coating films.
×: The number of peeled coating films is 100 or more for 100 grid-like coating films.
[0114]
(6) Solder heat resistance test
The test piece prepared in the same manner as the pressure cooker resistance test and cut into a size of 25 × 25 mm was floated in a solder bath at 260 ° C. for 10 seconds with the coating surface facing down for one cycle, and three cycles were performed. Defects such as swelling of the coating film and adhesion were evaluated according to the following evaluation criteria.
Evaluation criteria
A: No change is observed before and after the test.
：: Defects, peeling, etc. are observed in a range of less than 5% of the coating film area after the test.
Δ: After the test, defects and peeling are observed in the range of 5% or more and less than 30% of the coating film area.
×: Defects, peeling, and the like are observed in a range of 30% or more of the coating film area after the test.
[0115]
(7) Dielectric property measurement
The thermosetting polyimide resin composition is coated on a tin substrate so that the film thickness after curing becomes 200 μm, dried at 120 ° C. for 20 minutes, cured at 150 ° C. for 1 hour, cooled, and then peeled off. The dielectric sample (ε) and the dielectric loss (Tan δ) of the measurement sample from which the film was cut out were measured using Agilent Technologies 4291B at a frequency of 1 GHz.
[0116]
[Table 3]

[0117]
[Table 4]

[0118]
[Table 5]

[0119]
As is clear from the results of Tables 3 to 5, the cured coating film made of the thermosetting polyimide resin composition of the example shows a very high Tg, and can exhibit heat resistance even at a high temperature. It can be called a material. Furthermore, while having such a high Tg, the dielectric constant and the dielectric loss tangent are low, the dielectric properties are good, and the elongation is high in mechanical properties. Also, it has very high resistance in PCT resistance and solder heat resistance test.
[0120]
On the other hand, the cured coating film made of the thermosetting polyimide resin composition of Comparative Test Example 1 has a lower Tg than the cured coating film of the example, and has an elongation at break, PCT resistance, solder heat resistance, dielectric constant, Poor results were also obtained for the dielectric loss tangent. In addition, the cured coating film made of the thermosetting polyimide resin composition of Comparative Test Example 2 showed a very high Tg, but had a PCT resistance (adhesion) and a dielectric constant as compared with the cured coating film of the example. The result was poor in the dielectric loss tangent.
[0121]
【The invention's effect】
ADVANTAGE OF THE INVENTION The thermosetting polyimide resin composition of this invention is excellent in heat resistance, a dielectric constant and a dielectric loss tangent are low, and also the hardened | cured material with favorable mechanical properties, such as tensile strength and tensile elongation, is obtained. Further, according to the production method of the present invention, the polyimide resin used for the curable polyimide resin composition of the present invention can be easily produced.

Claims (11)

A polyimide resin (X) having a carboxyl group and an aliphatic structure (1) having a number average molecular weight of 100 to 1,000 at the terminal, and a linear polyvalent aliphatic structure having a carboxyl group and a number average molecular weight of 300 to 6,000 (2) A polyimide resin composition characterized by containing a polyimide resin (Y) having the following formula: A polyimide resin (X) having a carboxyl group, an aliphatic structure (1) having a number average molecular weight of 100 to 1,000, a urethane bond, an imide ring, an isocyanurate ring, and a cyclic polyvalent aliphatic structure (3) A polyimide resin (Y) having a carboxyl group, a linear polyvalent aliphatic structure (2) having a number average molecular weight of 300 to 6,000, a urethane bond, an imide ring, an isocyanurate ring, and a cyclic polyvalent aliphatic. The polyimide resin composition according to claim 1, which is a polyimide resin having the structure (3). The polyimide resin (X) has a structural unit represented by the following general formula (I) and a terminal structure represented by the following general formula (II), and has the following general formulas (IV), (V) and (VI) Wherein the polyimide resin (Y) comprises a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (III): The polyimide resin composition according to claim 2, which is a polyimide resin having at least one of terminal structures represented by the following general formulas (IV), (V) and (VI).

(However, in the formula, R ₁ is an organic group having a cyclic aliphatic structure having 6 to 13 carbon atoms, R ₂ is an aliphatic structure having a number average molecular weight of 100 to 1,000, and R ₃ is a number average molecular weight of 300 to 1,000.) It shows a linear polyvalent aliphatic structure of 6,000.)

The polyimide resin (X) has an acid value of 20 to 250, a number average molecular weight of the aliphatic structure (1) portion of 200 to 700, a content of the aliphatic structure (1) portion of 20 to 40% by weight, A polyimide resin having an isocyanurate ring concentration of 0.3 to 1.2 mmol / g, a number average molecular weight of 1,000 to 30,000, and a weight average molecular weight of 2,000 to 100,000; The resin (Y) has an acid value of 20 to 250, a linear polyvalent aliphatic structure (2) having a number average molecular weight of 700 to 4,500, and a total of the linear polyvalent aliphatic structure (2). Is 20 to 40% by weight, the concentration of the isocyanurate ring is 0.3 to 1.2 mmol / g, the number average molecular weight is 2,000 to 30,000, and the weight average molecular weight is 3,000. ~ 100,000 polyimide resin Polyimide resin composition according to claim 3. The polyimide resin composition according to claim 4, wherein the weight ratio (X) / (Y) of the polyimide resin (X) to the polyimide resin (Y) is 15/85 to 60/40. The polyimide resin (X) is a polyisocyanate compound (a0) and an alcohol compound having an aliphatic structure (1), wherein the number-average molecular weight of the aliphatic structure (1) portion is 100 to 1,000. a1) a polyimide obtained by reacting a prepolymer (A1) having an isocyanate group at the terminal obtained by the reaction with an acid anhydride of a polycarboxylic acid having three or more carboxyl groups (B) in an organic solvent. A polyimide resin (Y), which is a polyol compound having a polyisocyanate compound (a0) and a linear polyvalent aliphatic structure (2), wherein the number average of the linear polyvalent aliphatic structure (2) is A prepolymer (A2) having a terminal isocyanate group obtained by reacting a polyol compound (a2) having a molecular weight of 300 to 6,000 with three or more Acid anhydride of a polycarboxylic acid having a carboxyl group (B) a polyimide resin composition according to claim 1, wherein the polyimide resin obtained by reacting in an organic solvent. The polyimide resin (X) uses a polyisocyanate having an isocyanurate ring derived from a cycloaliphatic diisocyanate as the polyisocyanate compound (a0), and the alcohol compound (a1) has a number average molecular weight of an aliphatic structure (1) portion. To 200 parts by weight of a polyisocyanate compound (a0), an alcohol compound (a1) and an acid anhydride of a polycarboxylic acid having three or more carboxyl groups (B) (B). Is a polyimide resin obtained using a total of 20 to 40 parts by weight of the alcohol compound (a1), wherein the polyimide resin (Y) is an isocyanurate derived from a cycloaliphatic diisocyanate as the polyisocyanate compound (a0). Polyol isocyanate with ring As the product (a2), a polyol compound having a linear polyvalent aliphatic structure (2) having a number average molecular weight of 700 to 4,500 and having an average of 2 to 3 hydroxyl groups, and a polyisocyanate compound (a0) and a polyol For a total of 100 parts by weight of the compound (a2) and the acid anhydride of the polycarboxylic acid having three or more carboxyl groups (B), the polyol compound (a2) was obtained using a total of 20 to 40 parts by weight. The polyimide resin composition according to claim 6, which is a polyimide resin. The polyimide resin composition according to any one of claims 1 to 7, further comprising an epoxy resin (Z). The acid value of the mixture of the polyimide resin (X) and the polyimide resin (Y) is 20 to 250, and the total (XY) of the polyimide resin (X) and the polyimide resin (Y) and the weight of the epoxy resin (Z) The polyimide resin composition according to claim 8, wherein the ratio (XY) / (Z) is 1 to 10. The polyimide resin composition according to claim 8, further comprising a compound (F) having two or more phenolic hydroxyl groups. The polyimide resin (X) and the polyimide resin (Y) are based on a total of 100 parts by weight of the polyimide resin (X), the polyimide resin (Y), the epoxy resin (Z), and the compound (F) having two or more phenolic hydroxyl groups. The polyimide resin composition according to claim 10, wherein the total is 40 to 85 parts by weight, the epoxy resin (Z) is 10 to 40 parts by weight, and the compound (F) having two or more phenolic hydroxyl groups is 5 to 20 parts by weight. object.