JP3573543B2 - Thermosetting resin composition - Google Patents

Description

（式中、Ｘは、−ＣＨ_２ −，−Ｃ（ＣＨ_３ ）_２ −，−ＳＯ_２ −，−ＳＯ−または−Ｏ−を示す。）
【００１２】
上記一般式（１）で表されるビスマレイミドとしては、例えば、
Ｎ，Ｎ’−４，４’−（３，３’−ジメチルジフェニルメタン）ビスマレイミド、
Ｎ，Ｎ’−４，４’−（３，３’−ジエチルジフェニルメタン）ビスマレイミド、
Ｎ，Ｎ’−４，４’−ジフェニルメタンビスマレイミド、
Ｎ，Ｎ’−４，４’−２，２−ジフェニルプロパンビスマレイミド、
Ｎ，Ｎ’−４，４’−ジフェニルエーテルビスマレイミド、
Ｎ，Ｎ’−３，３’−ジフェニルスルホンビスマレイミド、
Ｎ，Ｎ’−４，４’−ジフェニルスルホンビスマレイミド、
Ｎ，Ｎ’−４，４’−ジフェニルスルホキシドビスマレイミド、
Ｎ，Ｎ’−４，４’−ジフェニルスルフィドビスマレイミド、
Ｎ，Ｎ’−４，４’−ベンゾフェノンビスマレイミド、
等を挙げることができる。
【００１３】
中でも、下記式（２）で表されるＮ，Ｎ’−４，４’−ジフェニルメタンビスマレイミド（ＢＤＭ）、Ｎ，Ｎ’−４，４’−ジフェニルエーテルビスマレイミド、Ｎ，Ｎ’−ｍ−トルイレンビスマレイミド、２，２−ビス［４−（４−マレイミドフェノキシ）フェニル］プロパン、Ｎ，Ｎ’−４，４’−ジフェニルスルホンビスマレイミド、Ｎ，Ｎ’−４，４’−ベンゾフェノンビスマレイミド等が硬化後の樹脂の耐熱性の点で好ましい。特に、Ｎ，Ｎ’−４，４’−ジフェニルメタンビスマレイミド、Ｎ，Ｎ’−４，４’−ジフェニルエーテルビスマレイミド、Ｎ，Ｎ’−ｍ−トルイレンビスマレイミド、２，２−ビス［４−（４−マレイミドフェノキシ）フェニル］プロパンが好ましい。具体的には、チバガイギー社製のマトリミド５２９２系の上述の式（２）で表されるＮ，Ｎ’−４，４’−ジフェニルメタンビスマレイミド等の市販品を使用することができる。
【００１４】
【化２】

【００１５】
上述の芳香族ビスマレイミド（Ａ）は、単独で使用してもよく、また、２種以上を併用してもよい。アルケニルフェノールとの相溶性がよく、熱硬化性樹脂組成物の溶融粘度を下げることができるなど樹脂の反応性と機械的特性の点から、融点が１７０℃以下のものを用いることが好ましい。
【００１６】
本発明に用いられるＣＨ_２ ＝ＣＨＣＨ_２ −のアリル基を有するアルケニルフェノール（Ｂ）は、下記一般式（３）で表される化合物である。
【００１７】
【化３】

（式中、Ｒ^１ またはＲ^２ は、それぞれ独立にアリル基を表し、Ｙは、ｎｉｌ（なし）、−Ｃ（ＣＨ_３ ）_２ −、−ＣＨ_２ −、−Ｃ（ＣＦ_３ ）_２ −を表し、ｎは１〜４の整数を表す。）
【００１８】
ここで、Ｒ^１ またはＲ^２ は、それぞれ独立にアリル基を表す。アリル基は、芳香環上の位置は特に限定されないが、１〜４個が環上で左右対象の位置に存在することが好ましい。この理由は、硬化後の樹脂のガラス転移温度が高くなるからである。
【００１９】
具体的には、下記式（４）で表される２，２’−ジアリルビスフェノールＡ（ＤＢＡ）、４，４’−ジヒドロキシ−３，３’−ジアリルジフェニル、ビス（４−ヒドロキシ−３−アリルフェニル）メタン、２，２−ビス（４−ヒドロキシ−３，５−ジアリルフェニル）プロパン、２，２−ジアリルビスフェノールＦ等が挙げられる。また、ポリフェノール類と、塩化アリルまたは臭化アリルとの反応生成物のアリル化率がフェノール性ＯＨ基に対して５０％以上１００％以下で、かつクライゼン転移したアリル基がフェノール性ＯＨ基に対して２０％以上のアルケニルフェノールも使用することができる。より具体的には、チバガイギー社製のマトリミド５２９２系の上述の式（４）で表される２，２’−ジアリルビスフェノールＡ等の市販品を使用することができる。
【００２０】
【化４】

【００２１】
上述のアルケニルフェノール（Ｂ）は、単独で使用してもよく、２種以上を併用してもよい。２，２’−ジアリルビスフェノールＡ、２，２−ビス（４−ヒドロキシ−３，５−ジアリルフェニル）プロパン、２，２’−ジアリルビスフェノールＦ等が硬化後の樹脂のガラス転移温度が高いため好ましく、特に、上述の式（４）の２，２’−ジアリルビスフェノールＡ、２，２’−ジアリルビスフェノールＦが相溶性や硬化物の耐熱温度が高いために好ましい。
【００２２】
本発明に使用するアルケニルフェノール（Ｂ）の配合量は、ビスマレイミド（Ａ）１００重量部に対して５８〜１００重量部である。アルケニルフェノール（Ｂ）の配合量をこの範囲としたのは、５８重量部未満では、混練性が低下し、１００重量部を越えると機械的強度が低下するためである。
５８〜９３重量部であることが好ましく、特に、５８〜８６重量部であることが好ましい。
【００２３】
本発明に用いるポリエーテルケトン（Ｃ）は、エーテル部分が、ジフェニルエーテルであって、フタロイル部分のカルボニル基がオルト位、メタ位およびパラ位の少なくとも１種である共重合体であって、下記式（５）で表される構造式を示す。
【００２４】
【化５】

【００２５】
ｘ／ｙ（モル比）＝１００／０〜１０／９０、特に１００／０〜２０／８０である。ｘ／ｙのモル比が、１００／０の場合は、ポリエーテルケトンのフタロイル部分がオルト位のみからなることを意味する。
具体的には、オルトフタロイルジフェニルエーテル重縮合体（ＰＰＤＥ）、オルトフタロイルジフェニルエーテルとメタフタロイルジフェニルエーテルとの共重縮合体（ＰＰＩＤＥ）、オルトフタロイルジフェニルエーテルとパラフタロイルジフェニルエーテルとの共重縮合体、オルトフタロイルジフェニルエーテルとメタフタロイルジフェニルエーテルとパラフタロイルジフェニルエーテルとの三元共重縮合体等が挙げられる。
中でも、オルトフタロイルジフェニルエーテルとメタフタロイルジフェニルエーテルの共重縮合体であるのが、硬化物の機械的強度、ガラス転移温度の低下なしで強靱性化するという点で好ましい。
【００２６】
フタロイル部分が、オルト位とメタ位とを含む共重縮合体である場合のモル比は、オルト位：メタ位が、９０：１０〜１０：９０特に、７０：３０〜３０：７０であるのが、硬化物の耐熱性の維持、作業性の向上の点で好ましい。
さらに、フタロイル部分が、オルト位とメタ位とパラ位とを含む三元共重縮合体である場合、オルト位：メタ位：パラ位のモル比は、８０：１０：１０〜２０：４０：４０であるのが、硬化物の耐熱性の向上の点で好ましい。
【００２７】
ポリエーテルケトン（Ｃ）は、ｉ）フタロイル部分が、オルト位である重縮合体（ＰＰＤＥ）のみである場合、ｏ−フタロイルジクロライドとジフェニルエーテルをほぼ等モル、或いは過剰モルの割合で加え、例えば、塩化アルミニウム、メチレンジクロライドの存在下で、窒素雰囲気中−６０℃で１時間攪拌してエーテル化し、温度を徐々に高めて−２０℃の温度で６時間程、さらに室温で１日撹拌することで製造する。メタンスルホン酸／五酸化二リン系触媒（上田らMacromolecules, 20, 2675(1987)）を用いて、ＰＰＤＥをカップリングさせて高分子量のＰＰＤＥにすることもできる。
【００２８】
ｉｉ）フタロイル部分がオルト位とメタ位である共重縮合体の場合は、ジフェニルエーテルに、ｏ−フタルロイルジクロライドとｍ−フタルロイルジクロライドを加え、オルト位の重縮合体のみの場合と同様に反応させて製造する。
【００２９】
iii)フタロイル部分がオルト位とパラ位である共重縮合体の場合は、ＰＰＤＥの場合と同様に製造される。
触媒を用いる場合は、フリーデル−クラフツ（Friedel-Crafts）系触媒やメタンスルホン酸／五酸化二リン系触媒等を用いて反応させて得ることができる。
【００３０】
ポリエーテルケトン（Ｃ）は少量の低分子量部を含んでいる。数平均分子量（Ｍｎ）は、この低分子量部の存在に敏感であり、分子量（Ｍｗ）としては、Ｍ_ＧＰＣ （標準ポリスチレンを使用するゲルパーミエーションクロマトグラフィーのピーク値）を用いるのが好ましい。ポリエーテルケトン（Ｃ）の平均分子量（Ｍ_ＧＰＣ ）は、３，０００ 〜１００，０００ 特に、５，０００ 〜５０，０００であるのが、靱性と耐熱性のバランスの点で好ましい。
【００３１】
本発明に用いるポリエーテルケトン（Ｃ）の配合量は、芳香族ビスマレイミド（Ａ）１００重量部に対して、５〜１００重量部、特に１０〜６０重量部であるのが好ましい。５重量部未満では、靱性の向上が見られず、１００重量部超では、耐熱性が低下する。
【００３２】
本発明の熱硬化性樹脂組成物は、硬化触媒を用いなくてもよいが、さらに硬化触媒を加えてもよい。
硬化触媒には特に限定はないが、ジクミルペルオキシド、２，５−ジメチル−２，５−ジ（ｔ−ブチルペルオキシ）ヘキシン−３、ジ−ｔ−ブチルペルオキシド等が例示される。
中でも特に、２，５−ジメチル−２，５−ジ（ｔ−ブチルペルオキシ）ヘキシン−３等は好適に例示される。
硬化触媒の使用量は、芳香族ビスマレイミド（Ａ）１００重量部に対して、０．１〜５重量部、特に０．５〜１重量部であるのが、貯蔵安定性と硬化速度のバランスの点で好ましい。
【００３３】
また、本発明の熱硬化性樹脂組成物においては、希望する物性、粘性的な性質等を付与するために、必要に応じて充填材、可塑剤、溶剤等を混合してもよい。
【００３４】
このような本発明の熱硬化性樹脂組成物の製造および硬化方法は、通常のビスマレイミド樹脂と同様でよい。
例えば、所定量のビスマレイミドとアルケニルビスフェノールとポリエーテルケトンと、さらに必要により硬化触媒等の添加物を加えて撹拌・混合し、本発明の熱硬化性樹脂組成物を得る。
得られた組成物は、特別な溶媒を用いなくてもアルケニルフェノールの液相に混練され、均質である。
その後、例えば所定形状のモールドに充填し、ビスマレイミド樹脂（化合物）の種類等に応じて必要に応じて、例えば、１８０〜２５０℃程度に加熱して、硬化物を得る。
得られた硬化物は、ミクロ相分離構造を形成し、耐熱性や機械的特性を損なうことなく、靱性に優れている。
【００３５】
本発明の熱硬化性樹脂組成物は、その優れた耐熱性、強靱性を生かして、電気・電子材料、航空および宇宙材料（あるいは複合材料）、各種接着剤、注型材料、各種成型材料等の各種の用途に好適に使用可能である。
【００３６】
【実施例】
以下、本発明の具体的実施例を挙げ、本発明をより具体的に説明する。
（実施例１〜１１、および比較例１）
１．ポリエーテルケトン（ＰＰＤＥ１〜７）の合成
１：１〜１：１．２のモル比でジフェニルエーテルとフタロイルクロライドとを仕込み、触媒としてＦｒｉｅｄｅｌ−Ｃｒａｆｔｓ系触媒（塩化アルミニウム）を加え、下記表１に示すポリエーテルケトン（ＰＰＤＥ１〜４）を合成した。
また、メタンスルホン酸／五酸化二リン系触媒によるＰＰＤＥのカップリング反応で高分子量のＰＰＤＥ５〜７を合成した。
重合温度および時間、収率［％］、平均分子量Ｍ_ＧＰＣ および数平均分子量Ｍｎ（いずれもＧＰＣで測定）、Ｍｗ／Ｍｎ、ガラス転移温度Ｔｇ（［℃］ ＤＳＣで測定）を表１に示す。
【００３７】
２．ポリエーテルケトン（ＰＰＩＤＥ１および２）の合成
１：０．４９：０．４９〜１：０．５１：０．５１のモル比でジフェニルエーテルとｏ−フタロイルクロライドとｍ−フタロイルクロライドとを仕込み、触媒としてFriedel-Crafts系触媒（塩化アルミニウム）を加え、下記表１に示すフタロイル部分の全量中のメタ位のモル％を、５０モル％（オルト位：メタ位＝１：１）としたポリエーテルケトン（ＰＰＩＤＥ１および２）の合成を行った。
【００３８】
【表１】

【００３９】
３．熱硬化性樹脂組成物の作製および硬化
２，２’−ジアリルビスフェノールＡ８５重量部に、１で得られた各ＰＰＤＥ１〜７、または２．で得られた各ＰＰＩＤＥを改質剤とし表２に示す量加え、１３０℃に加熱し、混合、攪拌してＰＰＤＥまたはＰＰＩＤＥを溶解した後、４，４’−ビスマレイミドジフェニルメタン１００重量部を加えて混合、攪拌して、本発明の熱硬化性樹脂組成物を作製した。
【００４０】
作製した熱硬化性樹脂組成物を、あらかじめ１６０℃に加熱しておいた型（予め離型剤を薄く塗布）に注型し、下記の条件によって硬化を行った。
熱硬化性樹脂組成物は、１６０℃で３時間加熱した後、１８０℃に昇温して１時間、さらに２００℃に昇温して２時間、次いで２５０℃に昇温して６時間加熱して硬化を行った。さらに、室温までゆっくり冷却し、２５０℃から５０℃まで５時間を要した。
【００４１】
得られた硬化物について、破壊靱性値Ｋ_ＩＣ（３点曲げ試験片で測定）、曲げ強度（ＪＩＳ Ｋ６９１１に準拠）、曲げ弾性率（ＪＩＳ Ｋ６９１１に準拠）、およびガラス転移温度Ｔｇ（℃ ＤＳＣで測定）を測定し、また、目視によって性状を観察した。
結果を下記表２に示す。なお、表２において、ＰＰＤＥを添加せず、ビスマレイミド化合物１００重量部、ジアリルビスフェノール８５重量部のみからなる組成物の例を「対照」 （比較例１）とし、また表２中のｎは試験サンプルの数である。
【００４２】
また、図１にＰＰＤＥを１０ｗｔ％添加した場合（図１中○で表示）、およびイソフタロイルを５０モル％含有するＰＰＩＤＥを１０ｗｔ％添加した場合（図１中□で表示）の、ポリエーテルケトンの分子量と、硬化物の破壊靱性値Ｋ_ＩＣ、曲げ弾性率、曲げ強さ、ガラス転移温度との関係を示す。図１中●は未改質の硬化物の値である。
そして、図２にＰＰＤＥの分子量が８，３００ （ＰＰＤＥ２ 図２中○で表示）およびＰＰＩＤＥの分子量が２１，８００（ＰＰＩＤＥ１ 図２中□で表示）のポリエーテルケトン添加量と、硬化物の破壊靱性値Ｋ_ＩＣ、曲げ弾性率、曲げ強さ、ガラス転移温度との関係をそれぞれ示す。図２中●は未改質硬化物の値である。
【００４３】
【表２】

【００４４】
表２および図１に示される結果より明らかなように、ポリエーテルケトンの分子量に対する硬化物の特性は、分子量の増大と共に破壊靱性値Ｋ_ＩＣが増加し、曲げ弾性率は、分子量の増加とともにやや低下する傾向が見られたものの、曲げ強度、ガラス転移点ともに優れた機械特性を示している。
【００４５】
また、表２および図２に示される結果より明らかなように、ポリエーテルケトンの添加量に対する硬化物の特性は、ポリエーテルケトンの添加量の増加と共に破壊靱性値Ｋ_ＩＣは増加する。曲げ弾性率はやや低下する傾向が見られたものの、曲げ強度、ガラス転移点とともに優れた機械特性を示している。特にＰＰＩＤＥは曲げ強度、曲げ弾性率の低下を抑えて、破壊靱性値Ｋ_ＩＣを著しく増加させている。また、添加量が増加するにつれて硬化物は不透明になった。なお、各硬化物のＴｇ測定時のＤＳＣ曲線において不明確な吸熱ピークは、観測されなかった。
【００４６】
図３に、改質剤としてＰＰＤＥを１０重量％添加したビスマレイミド樹脂から得られた組成物の温度と動的（貯蔵）粘度、損失正接Ｔａｎδの関係を示すグラフを示した。
図４に、改質剤としてＰＰＩＤＥを１０重量％または１５重量％添加したビスマレイミド樹脂から得られた組成物の温度と動的（貯蔵）粘度、損失正接Ｔａｎδの関係を示すグラフを示した。図３、４いずれもポリエーテルケトンに基づくα’−緩和ピークが出現し、硬化物中に相分離構造が存在することを示している。
さらに、硬化物の断面のモルホロジーを、走査型電子顕微鏡（ＳＥＭ）を用いて観察した。結果を図５〜図７に示す。
図５〜図６から、本発明のＰＰＤＥ改質硬化物のモルホロジーは、ビスマレイミドマトリックス中に分散したＰＰＤＥ粒子を持つ海島構造であり、ＰＰＤＥの分子量増加と共に粒径は大きくなっている。図７からＰＰＩＤＥ改質硬化物のモルホロジーは共連続相構造であり、ポリエーテルケトンによる改質では共連続相構造による強靱な硬化物が得られていることがわかる。
以上の結果より、本発明の効果は明らかである。
【００４７】
【発明の効果】
以上詳細に説明したように、本発明によれば、耐熱性や機械的強度等の本来ビスマレイミド樹脂が有する優れた特性を損なうことなく、しかも高い強靱性を有する熱硬化性樹脂組成物およびその硬化物を得ることができる。本発明は、これらの効果の内少なくとも１つを有するものである。
【図面の簡単な説明】
【図１】ＰＰＤＥ、ＰＰＩＤＥの分子量と得られた熱硬化性樹脂組成物の硬化物の破壊靱性値Ｋ_ＩＣ、曲げ弾性率、曲げ強度およびＴｇとの関係を示すグラフである。
【図２】ＰＰＤＥ、ＰＰＩＤＥの添加量と得られた熱硬化性樹脂組成物の硬化物の破壊靱性値Ｋ_ＩＣ、曲げ弾性率、曲げ強度およびＴｇとの関係を示すグラフである。
【図３】改質剤としてＰＰＤＥを１０重量％添加したビスマレイミド樹脂から得られた組成物の温度と貯蔵粘度、Ｔａｎδの関係を示すグラフである。
【図４】改質剤としてＰＰＩＤＥ（Ｍｗ２１，８００、ＩＰ５０モル％）を１０重量％または１５重量％添加したビスマレイミド樹脂から得られた組成物の温度と貯蔵粘度、Ｔａｎδの関係を示すグラフである。
【図５】実施例５の硬化物の走査型電子顕微鏡による断面を示す図面代用写真である。
【図６】実施例７の硬化物の走査型電子顕微鏡による断面を示す図面代用写真である。
【図７】実施例１１の硬化物の走査型電子顕微鏡による断面を示す図面代用写真である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a bismaleimide resin having excellent toughness. Further, the present invention relates to a cured product containing the thermosetting resin composition.
[0002]
[Prior art]
Conventionally used organic synthetic polymer adhesives include adhesives containing epoxy resins, acrylic resins, fluororesins, phenolic resins, polyester resins, silicone resins, bismaleimide resins, and the like. Among them, epoxy resins and bismaleimide resins are listed as resins having excellent heat resistance and mechanical strength, but have a problem that they are brittle.
[0003]
Therefore, attempts have been made to add a modifier to these resins to achieve toughness. For example, as a method of modifying an epoxy resin, for example, a study by Tomoi et al. (Eur. Polym. J.) shows that by adding polyester to the epoxy resin, the toughness can be increased without impairing the heat resistance and flexural modulus of the epoxy resin. 31, 275 (1995)). It has been reported in a study by Iijima et al. (J. Appl. Polym. Sci., 43, 1685 (1991)) that it is effective to add polyphthaloyl diphenyl ether (PPDE) as a modifier for epoxy resin. I have.
[0004]
On the other hand, bismaleimide (BMI) resin and its cured product have higher heat resistance than epoxy resin, and are excellent resins having the same workability as epoxy resin. However, the application range of bismaleimide resin is high performance. With the spread of advanced technology fields such as composite materials and electronic materials, higher performance bismaleimide resins, especially bismaleimide resins that maintain heat resistance and mechanical properties and have excellent toughness, are required, and various improvements are required. It has been subjected.
As a method for modifying such a bismaleimide resin, a method has been reported in which a polyether of diphenyl ketone and bisphenol, a polyether sulfone (PES), a polyester of alkyl phthalate, and a thermoplastic polyimide are added as modifiers. .
It is also known that a composition of a bismaleimide resin and an alkenylphenol is a composition excellent in workability.
However, there is no known modifier capable of obtaining high toughness without impairing the inherent properties of bismaleimide resin having high heat resistance and mechanical strength.
Furthermore, in applications that require higher performance, such as advanced technologies such as aviation materials and electric and electronic materials, few bismaleimide resins with satisfactory properties are still obtained, and cured products with excellent performance are obtained. There is a further need for bismaleimide resin compositions that can be used.
[0005]
On the other hand, Japanese Patent Application Laid-Open No. 2-165945 discloses a prepreg of a bismaleimide resin matrix which is physically enhanced by using a thermoplastic fiber made of polyetherketone as a base material. No polymer blends of ketones (PEK) have been reported.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a thermosetting resin composition capable of obtaining a cured product having high toughness without impairing the excellent properties of a cured product of a bismaleimide resin, such as heat resistance and mechanical strength, and the like. It is to provide a cured product. The present invention achieves at least one of the above objects.
[0007]
[Means for Solving the Problems]
The present inventors have made intensive efforts to solve the above-mentioned problems of the prior art. As a result, a polymer blend of bismaleimide and a polyether ketone represented by the following formula (5) can be used without adding a solvent. The present inventors have found that a thermosetting resin composition having toughness can be obtained while maintaining heat resistance and mechanical properties without setting the curing temperature to a high temperature of 300 ° C. or higher, and reached the present invention.
[0008]
That is, the present invention provides (A) 100 parts by weight of an aromatic bismaleimide, (B) 58 to 100 parts by weight of an alkenylphenol, and (C) 5 to 100 parts by weight of a polyether ketone represented by the following formula (5). to provide a thermosetting resin composition containing a.
And it is preferable that the polyether ketone is a polycondensate having a phthaloyl moiety at the ortho position and the meta position.
A cured product obtained by heat-curing the above-mentioned thermosetting resin composition is provided.
[0009]
Hereinafter, the thermosetting resin composition of the present invention will be described in detail.
The thermosetting resin composition of the present invention is obtained by toughening a bismaleimide resin using polyetherketone as a modifier.
[0010]
The aromatic bismaleimide (A) used in the thermosetting resin composition of the present invention can be obtained by a known method of reacting a corresponding aromatic diamine with maleic anhydride.
As the aromatic bismaleimide (A),
N, N'-m-phenylenebismaleimide,
N, N'-p-phenylenebismaleimide,
N, N'-m-toluylenebismaleimide,
N, N'-4,4'-biphenylenebismaleimide;
N, N′-4,4 ′-(3,3′-dimethylbiphenylene) bismaleimide,
Examples thereof include 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane and bismaleimide represented by the following general formula (1).
[0011]
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(In the formula, _{X, -CH 2 -, - C (} CH 3) 2 -, - SO 2 -, - SO- or -O- shown.)
[0012]
As the bismaleimide represented by the general formula (1), for example,
N, N'-4,4 '-(3,3'-dimethyldiphenylmethane) bismaleimide,
N, N'-4,4 '-(3,3'-diethyldiphenylmethane) bismaleimide,
N, N'-4,4'-diphenylmethane bismaleimide;
N, N'-4,4'-2,2-diphenylpropanebismaleimide;
N, N'-4,4'-diphenylether bismaleimide,
N, N'-3,3'-diphenylsulfonebismaleimide;
N, N'-4,4'-diphenylsulfonebismaleimide;
N, N'-4,4'-diphenylsulfoxide bismaleimide;
N, N'-4,4'-diphenyl sulfide bismaleimide;
N, N'-4,4'-benzophenone bismaleimide;
And the like.
[0013]
Among them, N, N'-4,4'-diphenylmethanebismaleimide (BDM), N, N'-4,4'-diphenylether bismaleimide, N, N'-m-toluene represented by the following formula (2) Irene bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, N, N'-4,4'-diphenylsulfonebismaleimide, N, N'-4,4'-benzophenone bismaleimide Are preferred from the viewpoint of heat resistance of the cured resin. Particularly, N, N'-4,4'-diphenylmethanebismaleimide, N, N'-4,4'-diphenyletherbismaleimide, N, N'-m-toluylenebismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane is preferred. Specifically, commercially available products such as N, N'-4,4'-diphenylmethanebismaleimide represented by the above formula (2) of Matrimid 5292 series manufactured by Ciba Geigy can be used.
[0014]
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[0015]
The above-mentioned aromatic bismaleimide (A) may be used alone or in combination of two or more. It is preferable to use one having a melting point of 170 ° C. or less from the viewpoint of the reactivity and mechanical properties of the resin, such as good compatibility with alkenylphenol and reduction of the melt viscosity of the thermosetting resin composition.
[0016]
The alkenyl phenol (B) having an allyl group of CH ₂ ＣＨCHCH ₂ — used in the present invention is a compound represented by the following general formula (3).
[0017]
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(Wherein, R ^{1 and} R ² each independently represent an allyl group, and Y represents nil (none), —C (CH ₃ ) ₂ —, —CH ₂ —, —C (CF ₃ ) ₂ — And n represents an integer of 1 to 4.)
[0018]
Here, R ^{1 and} R ² each independently represent an allyl group. The position of the allyl group on the aromatic ring is not particularly limited, but it is preferable that 1 to 4 allyl groups are present at symmetric positions on the ring. The reason for this is that the glass transition temperature of the cured resin increases.
[0019]
Specifically, 2,2′-diallylbisphenol A (DBA), 4,4′-dihydroxy-3,3′-diallyldiphenyl, bis (4-hydroxy-3-allyl) represented by the following formula (4) Phenyl) methane, 2,2-bis (4-hydroxy-3,5-diallylphenyl) propane, 2,2-diallylbisphenol F and the like. The allylation ratio of the reaction product of polyphenols and allyl chloride or allyl bromide is 50% or more and 100% or less with respect to the phenolic OH group, and the Claisen-transferred allyl group is compared with the phenolic OH group. Up to 20% alkenylphenol can also be used. More specifically, a commercially available product such as 2,2'-diallylbisphenol A represented by the above formula (4) of Matrimid 5292 series manufactured by Ciba Geigy can be used.
[0020]
Embedded image

[0021]
The above-mentioned alkenylphenol (B) may be used alone or in combination of two or more. 2,2'-diallylbisphenol A, 2,2-bis (4-hydroxy-3,5-diallylphenyl) propane, 2,2'-diallylbisphenol F, and the like are preferable because the glass transition temperature of the cured resin is high. In particular, 2,2′-diallylbisphenol A and 2,2′-diallylbisphenol F of the above formula (4) are preferred because of their high compatibility and high heat resistance of the cured product.
[0022]
The blending amount of the alkenylphenol (B) used in the present invention is 58 to 100 parts by weight based on 100 parts by weight of the bismaleimide (A). The reason why the blending amount of the alkenylphenol (B) is within this range is that if the amount is less than 58 parts by weight, the kneadability decreases, and if it exceeds 100 parts by weight, the mechanical strength decreases.
It is preferably from 58 to 93 parts by weight, and particularly preferably from 58 to 86 parts by weight.
[0023]
The polyether ketone (C) used in the present invention is a copolymer in which the ether moiety is diphenyl ether, and the carbonyl group of the phthaloyl moiety is at least one of the ortho, meta and para positions. The structural formula represented by (5) is shown.
[0024]
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[0025]
x / y (molar ratio) = 100/0 to 10/90, particularly 100/0 to 20/80. When the molar ratio x / y is 100/0, it means that the phthaloyl portion of the polyether ketone consists only of the ortho position.
Specifically, ortho-phthaloyl diphenyl ether polycondensate (PPDE), co-polycondensate of ortho-phthaloyl diphenyl ether and metaphthaloyl diphenyl ether (PPIDE), and co-polycondensate of ortho-phthaloyl diphenyl ether and para-phthaloyl diphenyl ether And ternary copolycondensates of orthophthaloyl diphenyl ether, metaphthaloyl diphenyl ether, and paraphthaloyl diphenyl ether.
Among them, a copolycondensate of ortho-phthaloyl diphenyl ether and meta-phthaloyl diphenyl ether is preferable in that the toughness is improved without lowering the mechanical strength and glass transition temperature of the cured product.
[0026]
When the phthaloyl moiety is a copolycondensate containing an ortho position and a meta position, the molar ratio of the ortho position to the meta position is from 90:10 to 10:90, particularly from 70:30 to 30:70. Is preferred in terms of maintaining the heat resistance of the cured product and improving workability.
Furthermore, when the phthaloyl moiety is a ternary polycondensate containing an ortho position, a meta position and a para position, the molar ratio of the ortho position: meta position: para position is 80:10:10 to 20:40: A value of 40 is preferred from the viewpoint of improving the heat resistance of the cured product.
[0027]
The polyether ketone (C) is obtained by adding i- phthaloyl dichloride and diphenyl ether in substantially equimolar or excess mole ratio when i) the phthaloyl moiety is only the polycondensate (PPDE) at the ortho position. , Aluminum chloride and methylene dichloride, in a nitrogen atmosphere, stirred at -60 ° C for 1 hour to etherify, gradually increased the temperature, stirred at -20 ° C for about 6 hours, and further stirred at room temperature for 1 day. To be manufactured. Using a methanesulfonic acid / diphosphorus pentoxide catalyst (Ueda et al., Macromolecules, 20, 2675 (1987)), PPDE can also be coupled to high molecular weight PPDE.
[0028]
ii) In the case of a copolycondensate in which the phthaloyl moiety is in the ortho position and the meta position, o- phthaloyl dichloride and m-phthalloyl dichloride are added to diphenyl ether, and the reaction is carried out in the same manner as in the case of only the ortho position polycondensate. Let it be manufactured.
[0029]
iii) In the case of a copolycondensate where the phthaloyl moiety is at the ortho and para positions, it is produced in the same manner as in the case of PPDE.
When a catalyst is used, it can be obtained by reacting with a Friedel-Crafts catalyst or a methanesulfonic acid / diphosphorus pentoxide catalyst.
[0030]
Polyetherketone (C) contains a small amount of low molecular weight parts. The number average molecular weight (Mn) is sensitive to the presence of this low molecular weight part, and it is preferable to use _MGPC (peak value of gel permeation chromatography using standard polystyrene) as the molecular weight (Mw). Average molecular weight of the polyether ketone _{(C) (M GPC)} is 3,000 to 100,000 particularly, and even 5,000 to 50,000 is preferable in terms of balance between toughness and heat resistance.
[0031]
The amount of the polyetherketone (C) used in the present invention is preferably 5 to 100 parts by weight, particularly preferably 10 to 60 parts by weight, based on 100 parts by weight of the aromatic bismaleimide (A). If the amount is less than 5 parts by weight, no improvement in toughness is observed, and if it exceeds 100 parts by weight, heat resistance decreases.
[0032]
The thermosetting resin composition of the present invention does not need to use a curing catalyst, but may further include a curing catalyst.
The curing catalyst is not particularly limited, and examples thereof include dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, di-t-butyl peroxide and the like.
Of these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 and the like are particularly preferred.
The amount of the curing catalyst used is 0.1 to 5 parts by weight, particularly 0.5 to 1 part by weight, per 100 parts by weight of the aromatic bismaleimide (A). It is preferred in terms of.
[0033]
Further, in the thermosetting resin composition of the present invention, a filler, a plasticizer, a solvent, and the like may be mixed as necessary in order to impart desired physical properties, viscous properties, and the like.
[0034]
The method for producing and curing such a thermosetting resin composition of the present invention may be the same as that of a normal bismaleimide resin.
For example, a predetermined amount of bismaleimide, alkenyl bisphenol, polyether ketone, and, if necessary, additives such as a curing catalyst are added and stirred and mixed to obtain a thermosetting resin composition of the present invention.
The obtained composition is kneaded with a liquid phase of alkenylphenol without using a special solvent and is homogeneous.
Then, for example, it is filled in a mold having a predetermined shape, and if necessary, depending on the type of bismaleimide resin (compound), is heated to, for example, about 180 to 250 ° C. to obtain a cured product.
The obtained cured product forms a microphase-separated structure, and has excellent toughness without impairing heat resistance and mechanical properties.
[0035]
The thermosetting resin composition of the present invention makes use of its excellent heat resistance and toughness to make use of electric / electronic materials, aviation and space materials (or composite materials), various adhesives, casting materials, various molding materials, and the like. Can be suitably used for various applications.
[0036]
【Example】
Hereinafter, the present invention will be described more specifically with reference to specific examples of the present invention.
(Examples 1 to 11 and Comparative Example 1)
1. Synthesis of polyetherketone (PPDE1-7) Diphenyl ether and phthaloyl chloride were charged at a molar ratio of 1: 1 to 1: 1.2, and a Friedel-Crafts catalyst (aluminum chloride) was added as a catalyst. The indicated polyetherketone (PPDE1-4) was synthesized.
Further, high-molecular-weight PPDEs 5 to 7 were synthesized by a coupling reaction of PPDE with a methanesulfonic acid / diphosphorus pentoxide catalyst.
Table 1 shows the polymerization temperature and time, yield [%], average molecular weight _MGPC and number average molecular weight Mn (all measured by GPC), Mw / Mn, and glass transition temperature Tg ([° C] measured by DSC).
[0037]
2. Synthesis of polyether ketone (PPIDE 1 and 2) Diphenyl ether, o-phthaloyl chloride and m-phthaloyl chloride were charged at a molar ratio of 1: 0.49: 0.49 to 1: 0.51: 0.51; A polyether having a Friedel-Crafts catalyst (aluminum chloride) added thereto as a catalyst and having a molar percentage of meta position of 50 mol% (ortho position: meta position = 1: 1) in the total amount of the phthaloyl portion shown in Table 1 below Ketones (PPIDE 1 and 2) were synthesized.
[0038]
[Table 1]

[0039]
3. 1. Preparation and curing of thermosetting resin composition To 85 parts by weight of 2,2′-diallylbisphenol A, each of PPDEs 1 to 7 obtained in 1 or 2. Each PPIDE obtained in the above was used as a modifier and added in the amount shown in Table 2, heated to 130 ° C., mixed and stirred to dissolve PPDE or PPIDE, and then 100 parts by weight of 4,4′-bismaleimidediphenylmethane was added. The mixture was mixed and stirred to prepare a thermosetting resin composition of the present invention.
[0040]
The prepared thermosetting resin composition was cast in a mold (a thin coating of a release agent was previously applied) heated to 160 ° C. and cured under the following conditions.
The thermosetting resin composition is heated at 160 ° C. for 3 hours, then heated to 180 ° C. for 1 hour, further heated to 200 ° C. for 2 hours, and then heated to 250 ° C. and heated for 6 hours. Cured. Furthermore, it cooled slowly to room temperature, and required 5 hours from 250 degreeC to 50 degreeC.
[0041]
For the obtained cured product, the fracture toughness value K _IC (measured with a three-point bending test piece), the bending strength (according to JIS K6911), the flexural modulus (according to JIS K6911), and the glass transition temperature Tg (° C Measurement), and the properties were visually observed.
The results are shown in Table 2 below. In Table 2, an example of a composition consisting of 100 parts by weight of a bismaleimide compound and only 85 parts by weight of diallyl bisphenol without adding PPDE was taken as a “control” (Comparative Example 1). Number of samples.
[0042]
In addition, in FIG. 1, 10 wt% of PPDE was added (indicated by 中 in FIG. 1), and when 10 wt% of PPIDE containing 50 mol% of isophthaloyl was added (indicated by □ in FIG. 1), The relationship between the molecular weight and the fracture toughness value K _IC of the cured product, flexural modulus, flexural strength, and glass transition temperature is shown. In FIG. 1, ● represents the value of an unmodified cured product.
FIG. 2 shows the addition amount of polyether ketone having a molecular weight of PPDE of 8,300 (indicated by ○ in FIG. 2) and a molecular weight of PPIDE of 21,800 (indicated by □ in FIG. 2), and the destruction of the cured product. The relationships among toughness value K _IC , flexural modulus, flexural strength and glass transition temperature are shown. 2 in FIG. 2 indicates the value of the unmodified cured product.
[0043]
[Table 2]

[0044]
As is clear from the results shown in Table 2 and FIG. 1, the properties of the cured product with respect to the molecular weight of the polyether ketone show that the fracture toughness value K _IC increases with an increase in the molecular weight, and the flexural modulus increases slightly with an increase in the molecular weight. Although there was a tendency to decrease, both the bending strength and the glass transition point show excellent mechanical properties.
[0045]
Further, as is clear from the results shown in Table 2 and FIG. 2, the characteristics of the cured product with respect to the added amount of polyether ketone show that the fracture toughness value K _IC increases with the added amount of polyether ketone. Although the flexural modulus tends to decrease slightly, it shows excellent mechanical properties as well as flexural strength and glass transition point. In particular, PPIDE suppresses a decrease in flexural strength and flexural modulus, and significantly increases the fracture toughness value K _IC . The cured product became opaque as the added amount increased. In addition, an unclear endothermic peak was not observed in the DSC curve at the time of Tg measurement of each cured product.
[0046]
FIG. 3 is a graph showing the relationship among the temperature, the dynamic (storage) viscosity, and the loss tangent Tanδ of the composition obtained from the bismaleimide resin to which 10% by weight of PPDE was added as a modifier.
FIG. 4 is a graph showing the relationship between the temperature, the dynamic (storage) viscosity, and the loss tangent Tanδ of the composition obtained from the bismaleimide resin to which 10% by weight or 15% by weight of PPIDE was added as a modifier. In all of FIGS. 3 and 4, an α′-relaxation peak based on polyetherketone appeared, indicating that a phase-separated structure was present in the cured product.
Furthermore, the morphology of the cross section of the cured product was observed using a scanning electron microscope (SEM). The results are shown in FIGS.
5 to 6, the morphology of the PPDE-modified cured product of the present invention is a sea-island structure having PPDE particles dispersed in a bismaleimide matrix, and the particle size increases as the molecular weight of PPDE increases. From FIG. 7, it can be seen that the morphology of the PPIDE-modified cured product is a co-continuous phase structure, and that a modified cured product of polyetherketone provides a tough cured product due to the bi-continuous phase structure.
From the above results, the effect of the present invention is clear.
[0047]
【The invention's effect】
As described in detail above, according to the present invention, a thermosetting resin composition having high toughness without impairing the excellent properties inherently possessed by bismaleimide resin such as heat resistance and mechanical strength, and its high toughness A cured product can be obtained. The present invention has at least one of these effects.
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between the molecular weight of PPDE and PPIDE and the fracture toughness value K _IC , flexural modulus, flexural strength and Tg of a cured product of the obtained thermosetting resin composition.
FIG. 2 is a graph showing the relationship between the amounts of PPDE and PPIDE added and the fracture toughness value K _IC , flexural modulus, flexural strength and Tg of a cured product of the obtained thermosetting resin composition.
FIG. 3 is a graph showing the relationship between the temperature, storage viscosity, and Tan δ of a composition obtained from a bismaleimide resin to which 10% by weight of PPDE was added as a modifier.
FIG. 4 is a graph showing the relationship between the temperature, storage viscosity, and Tan δ of a composition obtained from a bismaleimide resin to which 10% or 15% by weight of PPIDE (Mw 21,800, IP 50 mol%) is added as a modifier. is there.
FIG. 5 is a drawing substitute photograph showing a cross section of the cured product of Example 5 by a scanning electron microscope.
FIG. 6 is a drawing substitute photograph showing a cross section of the cured product of Example 7 by a scanning electron microscope.
FIG. 7 is a drawing substitute photograph showing a cross section of the cured product of Example 11 taken with a scanning electron microscope.

Claims (3)

(A) 100 parts by weight of an aromatic bismaleimide,
(B) 58 to 100 parts by weight of alkenyl phenol, and
(C) A thermosetting resin composition comprising 5 to 100 parts by weight of a polyether ketone represented by the following formula .

(Where x / y (molar ratio) = 100/0 to 10/90) The thermosetting resin composition according to claim 1, wherein the polyether ketone is a polycondensate having a phthaloyl portion at an ortho position and a meta position. A cured product obtained by heating and curing the thermosetting resin composition according to claim 1 .

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