JP4048252B2 - Heat-resistant resin additive and heat-resistant resin composition containing the additive - Google Patents

Description

【化８】

ここで、上記式中のｎ１は、４〜２００が好ましく、ｎ２は２〜２０が好ましく、ｎ３は１０〜２００が好ましい。
また、本発明の耐熱性樹脂組成物は、前記耐熱性樹脂用添加剤とフェノール樹脂、メラミン樹脂、脂肪族ポリイミド、芳香族ポリイミド、脂肪族ポリアミド、芳香族ポリアミド、ポリアミドイミド、ポリメチルペンテン、ポリフェニレンサルファイド、ポリエーテルサルホン、ポリエーテルエーテルケトン、ポリベンゾイミダゾール、ポリベンゾオキサゾール、ポリベンゾチアゾールよりなる群から選ばれる融点２００℃以上の耐熱性樹脂を含有することを特徴としており、耐熱性樹脂としては、芳香族ポリイミド、芳香族ポリアミド、ポリベンゾイミダゾールが好ましい。さらに、本発明の成型体は、前記耐熱性樹脂用添加剤とフェノール樹脂、メラミン樹脂、脂肪族ポリイミド、芳香族ポリイミド、脂肪族ポリアミド、芳香族ポリアミド、ポリアミドイミド、ポリメチルペンテン、ポリフェニレンサルファイド、ポリエーテルサルホン、ポリエーテルエーテルケトン、ポリベンゾイミダゾール、ポリベンゾオキサゾール、ポリベンゾチアゾールよりなる群から選ばれる融点２００℃以上の耐熱性樹脂からなることを特徴としており、耐熱性樹脂としては、芳香族ポリイミド、芳香族ポリアミド、ポリベンゾイミダゾールが好ましい。
【０００６】
【発明の実施の形態】
本発明の耐熱性樹脂用添加剤は、重量平均分子量が５,０００以上５０，０００以下の高分子化合物であり、分子内に下記式（Ｉ）で表される繰り返し単位及び下記式（II）で表される繰り返し単位を有している。ここで、重量平均分子量は、ゲルパーミュエーションクロマトグラフィー法による。
【化９】

【化１０】

【０００７】
上記式（II）において、Ｒ３は２価の有機基であるが、具体的には、次式（III−１〜１１）等を挙げることができる。
【化１１】

【０００８】
本発明の耐熱性樹脂用添加剤は、マレイミド又はマレイミド誘導体と、有機ポリシロキサン構造を有するケイ素含有マクロモノマーからなる単量体混合物を、従来公知の重合法により調製しても良く、マレイミド又はマレイミド誘導体と、分子内に官能基を有する単量体を含有する単量体混合物を、従来公知の重合法により重合して得られる共重合体を前駆体として、その前駆体の官能基と有機ポリシロキサン構造を有する化合物の反応性基を反応させて調製しても良い。
【０００９】
本発明の耐熱性樹脂用添加剤の調製に使用するマレイミド又はマレイミド誘導体としては、下記式（IV）で表される化合物を挙げることができる。
【化１２】

上記式（IV）において、Ｒ７は、水素、アルキル基、シクロアルキル基、ヒドロキシアルキル基、アルコキシアルキル基、アリール基のいずれかである。具体的には、マレイミド、エチルマレイミド、ブチルマレイミド、オクチルマレイミド、シクロヘキシルマレイミド、ヒドロキシエチルマレイミド、ヒドロキシブチルマレイミド、エトキシエチルマレイミド、ブトキシエチルマレイミド、シクロヘキシルマレイミド、フェニルマレイミド、メチルフェニルマレイミド、ヒドロキシフェニルマレイミド、カルボキシフェニルマレイミド、メトキシフェニルマレイミド、ベンジルマレイミドなどを挙げることができる。特に、有機シロキサン構造を有するケイ素含有マクロモノマーと共重合させる場合は、共重合性の良い、マレイミド、シクロヘキシルマレイミド、フェニルマレイミド、ベンジルマレイミドが好ましい。
【００１０】
本発明の耐熱樹脂用添加剤の調製に使用することのできる有機ポリシロキサン構造を有するケイ素含有マクロモノマーは、分子末端に重合性不飽和結合を有し、分子内に有機ポリシロキサン構造を有するマクロモノマーであり、ＧＰＣ法による重量平均分子量が１，０００〜２０，０００のものが好ましい。また、分子末端の重合性不飽和基は、前記マレイミド又はマレイミド誘導体との共重合性の良い（メタ）アクリロイル基が好ましい。有機ポリシロキサン構造を有するケイ素含有マクロモノマーの具体例としては、下記式（Ｖ−1,2,3）などを挙げることができ、例えば、片末端メタクリロイル基変性シリコーンとしてはサイラプレーンＦＭ−０７１１，ＦＭ−０７１２（チッソ（株）製）などが市販されている。
【化１３】

式（Ｖ−１〜３）において、ｎ４、ｎ５及びｎ６は正の整数であるが、１０〜２００の整数であることが好ましい。
【００１１】
前記マレイミド又はマレイミド誘導体と前記有機シロキサン構造を有するケイ素含有マクロモノマーとの共重合は、従来公知の重合法により調製することができるが、不純物の少ない塊状重合法及び溶液重合法が好ましい。また、共重合可能なその他の単量体を共重合させても良い。その他の単量体は、マレイミド又はマレイミド誘導体１００重量部に対して２００重量部以下、好ましくは１００重量部以下、特に好ましくは１〜５０重量部である。共重合可能なその他の単量体として、（メタ）アクリル酸及びその塩、（メタ）アクリル酸メチル、（メタ）アクリル酸ブチルなどの（メタ）アクリル酸アルキル、（メタ）アクリル酸メトキシエチルなどの（メタ）アクリル酸アルコキシアルキル、（メタ）アクリル酸ヒドロキシエチルなどの（メタ）アクリル酸ヒドロキシアルキル、（メタ）アクリル酸シクロヘキシルなどの（メタ）アクリル酸シクロアルキル、（メタ）アクリル酸トリフロロエチルなどのハロゲン化（メタ）アクリル酸アルキル、（メタ）アクリル酸フェニルなどの（メタ）アクリル酸アリール、スチレン、メチルスチレン、メトキシスチレン、クロロスチレンなどの芳香族ビニル類、塩化ビニル、酢酸ビニル、（メタ）アクリルアミド、（メタ）アクリロニトリルなどを挙げることができる。
【００１２】
また、本発明の耐熱性樹脂用添加剤は、マレイミド又はマレイミド誘導体と、分子内に官能基を有する単量体を含有する単量体混合物を従来公知の重合法により重合して得られる共重合体を前駆体として、その前駆体の官能基と有機ポリシロキサン構造を有する化合物の反応性基を反応させて調製しても良い。この場合使用することのできる分子内に官能基を有する単量体としては、アクリル酸、メタクリル酸、クロトン酸、イタコン酸などのカルボキシル基含有単量体、2-ヒドロキシエチル（メタ）アクリレート、4-ヒドロキシブチル（メタ）アクリレートなどの水酸基含有単量体、N-メチロールアクリルアミドなどのアミド基含有単量体、グリシジル（メタ）アクリレートなどのエポキシ基含有単量体などを挙げることができる。
【００１３】
そして、上記前駆体と下記式（VI）で表される有機ポリシロキサン構造を有する化合物とを反応させることにより、本発明の耐熱性樹脂用添加剤が得られる。
【化１４】

【００１４】
前駆体は、マレイミド又はマレイミド誘導体、分子内に反応性基を有する単量体以外に、耐熱性樹脂との親和性、相溶性などを考慮して、共重合可能なその他の単量体を共重合させても良い。その他の単量体は、マレイミド又はマレイミド誘導体１００重量部に対して２００重量部以下、好ましくは１００重量部以下、特に好ましくは１〜５０重量部である。前駆体において、共重合可能なその他の単量体として、（メタ）アクリル酸メチル、（メタ）アクリル酸ブチルなどの（メタ）アクリル酸アルキル、（メタ）アクリル酸メトキシエチルなどの（メタ）アクリル酸アルコキシアルキル、（メタ）アクリル酸シクロヘキシルなどの（メタ）アクリル酸シクロアルキル、（メタ）アクリル酸トリフロロエチルなどのハロゲン化（メタ）アクリル酸アルキル、（メタ）アクリル酸フェニルなどの（メタ）アクリル酸アリール、スチレン、メチルスチレン、メトキシスチレン、クロロスチレンなどの芳香族ビニル類、塩化ビニル、酢酸ビニル、（メタ）アクリルアミド、（メタ）アクリロニトリルなどを挙げることができる。
【００１５】
本発明の耐熱性樹脂添加剤は、重量平均分子量が５，０００〜５０，０００の高分子化合物であるが、より好ましくは７，０００〜３５，０００である。そして、上式（Ｉ）におけるｎ１は４〜２００が好ましく、特に６〜１００が好ましい。さらに、上式（II）におけるｎ２は２〜２０が好ましい。この繰り返し単位が多くなると重量平均分子量が高くなり、重量平均分子量が上限値を超えると、耐熱性樹脂との相溶性が低下して、その効果が安定しなくなる。
【００１６】
本発明の耐熱性樹脂組成物は、前記耐熱性樹脂用添加剤と耐熱性樹脂を含有するが、耐熱性樹脂としては、融点２００℃以上であり、より好ましくは２５０℃以上、特に好ましくは３００℃以上の樹脂である。前記耐熱性樹脂としては、フェノール樹脂、メラミン樹脂、脂肪族ポリイミド、芳香族ポリイミド、脂肪族ポリアミド、芳香族ポリアミド、ポリアミドイミド、ポリメチルペンテン、ポリフェニレンサルファイド、ポリエーテルサルホン、ポリエーテルエーテルケトン、ポリベンゾイミダゾール、ポリベンゾオキサゾール、ポリベンゾチアゾールが挙げられるが、脂肪族及び芳香族ポリイミド、芳香族ポリアミド、ポリベンゾイミダゾールが好ましい。前記耐熱性樹脂用添加剤の配合量は、前記耐熱性樹脂１００重量部に対して、前記耐熱性樹脂用添加剤０．１〜１０重量部が好ましく、特に０．５〜５重量部が好ましい。また、耐熱性樹脂組成物の調製は、溶液ブレンド法、溶融ブレンド法または重合ブレンド法を適宜選択すれば良い。
【００１７】
本発明の成型体は、前記耐熱性樹脂用添加剤と前記耐熱性樹脂からなる成型体である。溶液ブレンド法により調製した耐熱性樹脂組成物を使用する場合は溶媒を揮散させることにより成型でき、溶融ブレンド法により調製した耐熱性樹脂組成物を使用する場合は溶融又は半溶融状態で押出成型、射出成型などの従来公知の成型法をにより成型できる。また、重合ブレンド法の場合は、前記耐熱性樹脂用添加剤を耐熱性樹脂の前駆体に混合して、重合することによって成型できる。たとえば、テレフタル酸クロライド、フェニレンジアミン及び前記耐熱性樹脂用添加剤を混合した後に、重合して成型しても良い。
【００１８】
特に、溶液ブレンド法により調製した耐熱性樹脂組成物を使用して、溶媒キャスト法により得られたフィルム等の成型体は、溶媒を用いない溶融ブレンド法や重合ブレンド法と比較すると、前記耐熱性樹脂用添加剤の添加量がより少ない量で同一の効果が得られるため、溶融ブレンド法や重合ブレンド法と比較すると耐熱性の低下をより抑えることができる。
【００１９】
本発明の耐熱性樹脂組成物および成型体は、電子写真式複写機の定着ローラーや搬送ベルト、面状発熱体の被覆材、各種モーターの被覆材、壁紙、化粧板、各種建材、フレキシブルプリント基板用保護フィルム、基板用各種絶縁用途等に使用することができる。また、本発明の耐熱性樹脂組成物および成型体には、その効果を損なわない範囲で、充填剤、色材、耐候性付与剤、紫外線吸収剤、酸化防止剤、撥水剤、防かび剤、可塑剤等を添加しても良い。
【００２０】
【実施例】
つぎに、本発明を実施例及び比較例を用いてさらに具体的に説明するが、本発明は以下の実施例によって限定されるものではない。
【００２１】
（実施例１）
攪拌装置、窒素ガス導入管、温度計および環流冷却管を備えたフラスコに、重量平均分子量（Ｍｗ）が１，０００のケイ素含有マクロモノマー（FM-0711；チッソ（株）製）６０重量部、N-フェニルマレイミド４０重量部及びメチルイソブチルケトン１００重量部を仕込み、フラスコ内に窒素ガスを導入しながら３０分攪拌して窒素置換を行った後、フラスコの内容物を９５℃に加熱した。
ついで、β−メルカプトプロピオン酸２重量部を攪拌下のフラスコ内に添加した。フラスコ内の内容物が９５℃に維持しながら、１時間毎に重合開始剤アゾビスイソブチロニトリル（和光純薬（株）製）０．３重量部を３回添加した。β−メルカプトプロピオン酸の添加から４．５時間後にメチルイソブチルケトン３００重量部をフラスコ内に加えた後、室温まで冷却して、ポリマー濃度２０％の共重合体溶液（Ａ−１）を得た。得られた共重合体のＭｗは、１３，０００であった。
【００２２】
（実施例２）
β−メルカプトプロピオン酸２重量部を１重量部に代えた以外は実施例１と同様にしてポリマー濃度２０％の共重合体溶液（Ａ−２）を得た。得られた共重合体のＭｗは、２１，０００であった。
【００２３】
（実施例３）
N-フェニルマレイミドをN-シクロヘキシルマレイミドに代えた以外は同様にしてポリマー濃度２０％の共重合体溶液（Ａ−３）を得た。得られた共重合体のＭｗは、１５，０００であった。
【００２４】
（実施例４）
ケイ素含有マクロモノマーをＭｗ５，０００のケイ素含有マクロモノマー（X-22-174DX：信越化学工業(株)製）に代えた以外は同様にしてポリマー濃度２０％の共重合体溶液（Ａ−４）を得た。得られた共重合体のＭｗは、２５，０００であった。
【００２５】
（実施例５）
攪拌装置、窒素ガス導入管、温度計および環流冷却管を備えたフラスコに、N-フェニルマレイミド４０重量部、メタクリル酸５重量部及びメチルイソブチルケトン１００重量部を仕込み、フラスコ内に窒素ガスを導入しながら３０分攪拌して窒素置換を行った後、フラスコの内容物を９５℃に加熱した。
ついで、β−メルカプトプロピオン酸１重量部を攪拌下のフラスコ内に添加した。フラスコ内の内容物が９５℃に維持しながら、１時間毎に重合開始剤としてアゾビスイソブチロニトリル（和光純薬（株）製）０．３重量部を３回添加した。β−メルカプトプロピオン酸の添加から４．５時間後にｐ−トルエンスルホン酸０．１重量部とＭｗが１０００の片末端水酸基変性シリコーン（FM-0411；チッソ（株）製）５５重量部を添加し、更に６時間撹拌した。その後メチルイソブチルケトン３００重量部をフラスコ内に加えた後、室温まで冷却して、ポリマー濃度２０％の共重合体溶液（Ａ−５）を得た。得られた共重合体のＭｗは、１４，０００であった。
【００２６】
（比較例１）
N-フェニルマレイミドをメチルメタクリレートに代えた以外は実施例１と同様にしてポリマー濃度２０％の共重合体溶液（Ｃ−１）を得た。得られた共重合体のＭｗは、１３，０００であった。
【００２７】
（比較例２）
β−メルカプトプロピオン酸２重量部を０．２重量部に代えた以外は実施例１と同様にしてポリマー濃度２０％の共重合体溶液（Ｃ−２）を得た。得られた共重合体のＭｗは、６０，０００であった。
【００２８】
（比較例３）
ケイ素含有マクロモノマーを使用せず、N-フェニルマレイミド１００重量部に代えた以外は実施例１と同様にしてポリマー濃度２０％の共重合体溶液（Ｃ−３）を得た。得られた共重合体のＭｗは、１３，０００であった。
【００２９】
（実施例６〜３２、比較例３〜２０）
表１に示す配合により、耐熱性樹脂組成物を調製し、下記方法により耐熱性樹脂フィルムを作成し、得られたフィルムの耐汚染性試験及び剥離力測定試験を行った。試験結果を表1に示す。尚、表１において、ＰＡは芳香族ポリアミド（テクノーラ（登録商標）：帝人(株)製）の１０％ジメチルアセトアミド溶液、ＰＢＩはポリベンゾイミダゾール（PBI MR Solution：クラリアントジャパン(株)製）の１０％ジメチルアセトアミド溶液、ＰＩはポリイミド（Ｋａｐｔｏｎ（登録商標）：東レデュポン(株)製）、Ｃ−４は重量平均分子量１，０００のケイ素含有マクロモノマー（FM-0711：チッソ(株)製）、Ｃ−５はシリコーンオイル（TSF4702：東芝シリコーン(株)製）であり、表中の組成物欄の数値は固形分の重量部を示している。
【表１】

【００３０】
・耐熱性樹脂フィルムの調製
耐熱性樹脂組成物を、５０μｍＰＥＴフィルム（ＰＥＴ−５０１１、リンテック（株）製）にドクターブレードで塗布し、熱風乾燥機に入れて１３０℃で３０分加熱乾燥して、厚み４０μｍの耐熱性樹脂フィルムを得た。
・耐汚染性試験
耐熱性樹脂フィルムに、マジックインキ（登録商標）で１センチメートル四方の正方形状にマークし、滲みを目視で観察する。さらにこれを脱脂綿で拭き取り表面の汚染状態を目視で観察する。同一箇所へのマーク及び拭き取りを１０回繰り返し、滲みと汚染状態を観察する。滲みについては、滲みがあるものを「×」、僅かに滲みがあるものを「△」、滲みがないものを「○」とし、汚染状態については、油性インキのマークが消えたものを「○」、跡が残ったものを「×」とした。尚、評価しなかった項目については「−」で表記した。
・剥離力試験
ＪＩＳ Ｚ ０２３７の８．粘着力に準拠する方法による。セロハン粘着テープ（ニチバン（株）製、１８ｍｍ幅）を、温度２５℃、相対湿度６５％雰囲気下、試験フィルムに２ｋｇローラーで圧着する。圧着後、２５℃、６５％雰囲気に静置し、１５分経過後と２４時間経過後に、速度３００ｍｍ／ｍｉｎでセロハン粘着テープを９０度方向に引きはがし、そのときの粘着力を測定する。
【００３１】
【発明の効果】
本発明の耐熱性樹脂用添加剤は、主鎖にマレイミド又はマレイミド誘導体に由来する繰り返し単位を有し、側鎖に有機ポリシロキサン構造を有するために、耐熱性樹脂と相溶性が良く、少量添加により耐熱性樹脂の耐汚染性や剥離性を大幅に向上するものである。
また、本発明の耐熱性樹脂組成物は、前記耐熱性樹脂用添加剤を含有しており、フィルムなどにしたときに表面の耐汚染性や剥離性に優れており、広く使用できるものである。さらに、本発明の成型体は、前記耐熱樹脂用添加剤と耐熱性樹脂からなり、耐熱性樹脂が有する耐熱性を維持しながら、耐汚染性、剥離性及び離型性に優れたものである。[0001]
[Technical field to which the invention belongs]
The present invention relates to an additive for a heat-resistant resin widely used in insulating materials for covering heating elements and motors used in household electrical equipment, information equipment, medical equipment, and the like, and the additive And a molded body using the heat resistant resin composition.
[0002]
[Prior art]
Conventionally, a silicon resin, a fluororesin, an epoxy resin, a phenol resin, a polycarbonate resin, or the like has been used as a material for covering or contacting a heating element, a motor, or the like. For example, in electrophotographic copying machines and thermal transfer printing devices, due to the demand for high-speed printing, coating materials such as fixing rollers and thermal heads are required to have higher heat resistance and excellent releasability. It has become.
For an electrophotographic copying machine, Japanese Patent Application Laid-Open No. 61-219049 discloses an electrophotographic photosensitive member having a surface layer made of a silicone type comb polymer and a polycarbonate type resin. In this case, the heat resistance of the polycarbonate-type resin is not sufficient for printing at higher speed. JP-A-11-156971 discloses a seamless tubular film mainly composed of a thermosetting polyimide resin in which fluorine resin particles are dispersed and ubiquitous. In this film, in order to obtain the required releasability, the fluororesin particle concentration increases and the strength of the film decreases. That is, with this film, it is difficult to achieve both releasability and material strength. Further, JP-A-2000-215969 discloses a sheet heating element in which a heat-resistant insulating resin sheet is laminated and insulation-coated, and examples of the heat-resistant insulating resin sheet include polyimide, polyetherimide, aromatic polyamide, and the like. Are listed. This resin-coated planar heating element is not sufficient in the stain resistance and releasability of the resin surface.
Thus, there is no resin material that satisfies all of heat resistance, material strength, surface contamination resistance, and releasability.
[0003]
[Problems to be solved by the invention]
The present invention provides an additive for a heat-resistant resin that significantly improves surface contamination resistance and mold release property in a heat-resistant resin such as an aromatic polyamide without causing a substantial decrease in heat resistance or material strength. It is another object of the present invention to provide a heat resistant resin composition containing the additive for the heat resistant resin.
[0004]
[Means for Solving the Problems]
As a result of intensive research to solve the above problems, the present inventor has found that a compound having a repeating unit derived from maleimide or a maleimide derivative in the molecule and having an organic polysiloxane structure in the molecular side chain is heat resistant. It has been found that the above-mentioned problems can be solved by blending with a resin, and the present invention has been completed.
[0005]
That is, the additive for heat-resistant resin of the present invention is a polymer compound having a weight average molecular weight of 5,000 or more and 50,000 or less, and the repeating unit represented by the following formula (I) and the following formula ( It has a repeating unit represented by II).
[Chemical 7]

[Chemical 8]

Here, n1 in the above formula is preferably 4 to 200, n2 is preferably 2 to 20, and n3 is preferably 10 to 200.
Further, the heat-resistant resin composition of the present invention comprises the additive for heat-resistant resin and phenol resin, melamine resin, aliphatic polyimide, aromatic polyimide, aliphatic polyamide, aromatic polyamide, polyamideimide, polymethylpentene, polyphenylene. It is characterized by containing a heat-resistant resin having a melting point of 200 ° C. or higher selected from the group consisting of sulfide, polyethersulfone, polyetheretherketone, polybenzimidazole, polybenzoxazole, and polybenzothiazole. Is preferably aromatic polyimide, aromatic polyamide, or polybenzimidazole. Furthermore, the molded article of the present invention comprises the additive for heat-resistant resin and phenol resin, melamine resin, aliphatic polyimide, aromatic polyimide, aliphatic polyamide, aromatic polyamide, polyamideimide, polymethylpentene, polyphenylene sulfide, poly It is characterized by comprising a heat-resistant resin having a melting point of 200 ° C. or more selected from the group consisting of ether sulfone, polyether ether ketone, polybenzimidazole, polybenzoxazole, and polybenzothiazole. Polyimide, aromatic polyamide and polybenzimidazole are preferred.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The additive for heat-resistant resin of the present invention is a polymer compound having a weight average molecular weight of 5,000 or more and 50,000 or less, a repeating unit represented by the following formula (I) in the molecule and the following formula (II) It has the repeating unit represented by these. Here, the weight average molecular weight is determined by gel permeation chromatography.
[Chemical 9]

[Chemical Formula 10]

[0007]
In the above formula (II), R3 is a divalent organic group, and specific examples thereof include the following formulas (III-1 to 11).
Embedded image

[0008]
The additive for a heat resistant resin of the present invention may be prepared by preparing a monomer mixture comprising maleimide or a maleimide derivative and a silicon-containing macromonomer having an organic polysiloxane structure by a conventionally known polymerization method. A copolymer obtained by polymerizing a monomer mixture containing a derivative and a monomer having a functional group in the molecule by a conventionally known polymerization method is used as a precursor. You may prepare by making the reactive group of the compound which has a siloxane structure react.
[0009]
As the maleimide or maleimide derivative used for the preparation of the additive for heat-resistant resin of the present invention, a compound represented by the following formula (IV) can be exemplified.
Embedded image

In the above formula (IV), R7 is any one of hydrogen, an alkyl group, a cycloalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, and an aryl group. Specifically, maleimide, ethylmaleimide, butylmaleimide, octylmaleimide, cyclohexylmaleimide, hydroxyethylmaleimide, hydroxybutylmaleimide, ethoxyethylmaleimide, cyclohexylmaleimide, phenylmaleimide, methylphenylmaleimide, hydroxyphenylmaleimide, carboxy Examples thereof include phenylmaleimide, methoxyphenylmaleimide, and benzylmaleimide. In particular, when copolymerizing with a silicon-containing macromonomer having an organosiloxane structure, maleimide, cyclohexylmaleimide, phenylmaleimide, and benzylmaleimide having good copolymerizability are preferable.
[0010]
The silicon-containing macromonomer having an organic polysiloxane structure that can be used for the preparation of the additive for heat-resistant resins of the present invention has a polymerizable unsaturated bond at the molecular end and has an organic polysiloxane structure in the molecule. A monomer having a weight average molecular weight of 1,000 to 20,000 by the GPC method is preferred. The polymerizable unsaturated group at the molecular end is preferably a (meth) acryloyl group having good copolymerizability with the maleimide or maleimide derivative. Specific examples of the silicon-containing macromonomer having an organic polysiloxane structure include the following formula (V-1,2,3). For example, silaplane FM-0711 is used as one-end methacryloyl group-modified silicone. FM-0712 (manufactured by Chisso Corporation) is commercially available.
Embedded image

In formula (V-1 to 3), n4, n5 and n6 are positive integers, but are preferably integers of 10 to 200.
[0011]
The copolymerization of the maleimide or maleimide derivative and the silicon-containing macromonomer having the organosiloxane structure can be prepared by a conventionally known polymerization method, but a bulk polymerization method and a solution polymerization method with few impurities are preferable. Also, other copolymerizable monomers may be copolymerized. The other monomer is 200 parts by weight or less, preferably 100 parts by weight or less, particularly preferably 1 to 50 parts by weight with respect to 100 parts by weight of maleimide or maleimide derivative. Other monomers that can be copolymerized include (meth) acrylic acid and its salts, methyl (meth) acrylate, alkyl (meth) acrylates such as butyl (meth) acrylate, methoxyethyl (meth) acrylate, etc. (Meth) acrylic acid alkoxyalkyl, (meth) acrylic acid hydroxyalkyl (meth) acrylic acid, methacrylic acid cyclohexyl (meth) acrylic acid cycloalkyl, (meth) acrylic acid trifluoroethyl Halogenated alkyl (meth) acrylates, aryl (meth) acrylates such as phenyl (meth) acrylate, aromatic vinyls such as styrene, methylstyrene, methoxystyrene, chlorostyrene, vinyl chloride, vinyl acetate, ( Such as (meth) acrylamide, (meth) acrylonitrile It can be mentioned.
[0012]
The additive for a heat-resistant resin of the present invention is a copolymer obtained by polymerizing a monomer mixture containing maleimide or a maleimide derivative and a monomer having a functional group in the molecule by a conventionally known polymerization method. It may be prepared by using a coalescence as a precursor and reacting a functional group of the precursor with a reactive group of a compound having an organic polysiloxane structure. Examples of monomers having functional groups in the molecule that can be used in this case include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, and itaconic acid, 2-hydroxyethyl (meth) acrylate, 4 Examples thereof include hydroxyl group-containing monomers such as -hydroxybutyl (meth) acrylate, amide group-containing monomers such as N-methylolacrylamide, and epoxy group-containing monomers such as glycidyl (meth) acrylate.
[0013]
And the additive for heat resistant resins of this invention is obtained by making the said precursor and the compound which has an organic polysiloxane structure represented by following formula (VI) react.
Embedded image

[0014]
In addition to maleimide or a maleimide derivative or a monomer having a reactive group in the molecule, the precursor may be copolymerized with other copolymerizable monomers in consideration of the affinity and compatibility with the heat-resistant resin. It may be polymerized. The other monomer is 200 parts by weight or less, preferably 100 parts by weight or less, particularly preferably 1 to 50 parts by weight with respect to 100 parts by weight of maleimide or maleimide derivative. Other monomers that can be copolymerized in the precursor include methyl (meth) acrylate, alkyl (meth) acrylates such as butyl (meth) acrylate, and (meth) acrylic such as methoxyethyl (meth) acrylate. Alkoxyalkyl acid, (meth) acrylic acid cycloalkyl such as cyclohexyl (meth) acrylate, halogenated (meth) acrylic acid such as trifluoroethyl (meth) acrylate, (meth) acrylic acid such as phenyl (meth) acrylate Aromatic vinyls such as aryl acrylate, styrene, methylstyrene, methoxystyrene, chlorostyrene, vinyl chloride, vinyl acetate, (meth) acrylamide, (meth) acrylonitrile, and the like can be given.
[0015]
The heat-resistant resin additive of the present invention is a polymer compound having a weight average molecular weight of 5,000 to 50,000, more preferably 7,000 to 35,000. And, n1 in the above formula (I) is preferably 4 to 200, particularly preferably 6 to 100. Further, n2 in the above formula (II) is preferably 2-20. When the number of repeating units increases, the weight average molecular weight increases, and when the weight average molecular weight exceeds the upper limit, the compatibility with the heat resistant resin decreases, and the effect becomes unstable.
[0016]
The heat-resistant resin composition of the present invention contains the heat-resistant resin additive and a heat-resistant resin. The heat-resistant resin has a melting point of 200 ° C. or higher , more preferably 250 ° C. or higher, and particularly preferably 300. Resin having a temperature of ℃ or higher. It is a the heat-resistant resins, phenolic resins, melamine resins, aliphatic polyimides, aromatic polyimides, aliphatic polyamide, aromatic polyamide, polyamide-imide, polymethyl pentene, polyphenylene sulfide, polyether sulfone, polyether ether ketones, polybenzimidazole, polybenzoxazole, poly benzothiadiazolyl zone le including but aliphatic and aromatic polyimides, aromatic polyamides, polybenzimidazoles are preferred. The amount of the heat-resistant resin additive is preferably 0.1 to 10 parts by weight, particularly preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the heat-resistant resin. . Moreover, what is necessary is just to select the solution blend method, the melt blend method, or the polymerization blend method suitably for preparation of a heat resistant resin composition.
[0017]
The molded body of the present invention is a molded body composed of the heat-resistant resin additive and the heat-resistant resin. When using a heat resistant resin composition prepared by a solution blend method, it can be molded by volatilizing the solvent, and when using a heat resistant resin composition prepared by a melt blend method, it is extruded in a molten or semi-molten state, It can be molded by a conventionally known molding method such as injection molding. Moreover, in the case of the polymerization blend method, it can shape | mold by mixing the said additive for heat resistant resins with the precursor of a heat resistant resin, and superposing | polymerizing. For example, terephthalic acid chloride, phenylenediamine, and the additive for heat-resistant resin may be mixed and then polymerized and molded.
[0018]
In particular, using a heat-resistant resin composition prepared by a solution blend method, a molded body such as a film obtained by a solvent cast method is more resistant to the heat resistance than a melt blend method or a polymerization blend method that does not use a solvent. Since the same effect can be obtained with a smaller amount of the additive for resin, a decrease in heat resistance can be further suppressed as compared with the melt blending method or the polymerization blending method.
[0019]
The heat-resistant resin composition and molded product of the present invention are a fixing roller and a conveyor belt of an electrophotographic copying machine, a coating material for a planar heating element, a coating material for various motors, wallpaper, a decorative board, various building materials, and a flexible printed circuit board. It can be used for protective films for substrates, various insulating applications for substrates and the like. In addition, the heat resistant resin composition and molded article of the present invention have a filler, a coloring material, a weather resistance imparting agent, an ultraviolet absorber, an antioxidant, a water repellent, and a fungicide as long as the effect is not impaired. A plasticizer or the like may be added.
[0020]
【Example】
Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples.
[0021]
Example 1
In a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 60 parts by weight of a silicon-containing macromonomer (FM-0711; manufactured by Chisso Corporation) having a weight average molecular weight (Mw) of 1,000, After charging 40 parts by weight of N-phenylmaleimide and 100 parts by weight of methyl isobutyl ketone, the mixture was stirred for 30 minutes while introducing nitrogen gas into the flask and replaced with nitrogen, and then the contents of the flask were heated to 95 ° C.
Subsequently, 2 parts by weight of β-mercaptopropionic acid was added to the stirred flask. While maintaining the content in the flask at 95 ° C., 0.3 part by weight of a polymerization initiator azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) was added three times every hour. After 4.5 hours from the addition of β-mercaptopropionic acid, 300 parts by weight of methyl isobutyl ketone was added to the flask, and then cooled to room temperature to obtain a copolymer solution (A-1) having a polymer concentration of 20%. . Mw of the obtained copolymer was 13,000.
[0022]
(Example 2)
A copolymer solution (A-2) having a polymer concentration of 20% was obtained in the same manner as in Example 1 except that 2 parts by weight of β-mercaptopropionic acid was changed to 1 part by weight. Mw of the obtained copolymer was 21,000.
[0023]
(Example 3)
A copolymer solution (A-3) having a polymer concentration of 20% was obtained in the same manner except that N-phenylmaleimide was replaced with N-cyclohexylmaleimide. Mw of the obtained copolymer was 15,000.
[0024]
Example 4
A copolymer solution (A-4) having a polymer concentration of 20% was used except that the silicon-containing macromonomer was replaced with a silicon-containing macromonomer having an Mw of 5,000 (X-22-174DX: manufactured by Shin-Etsu Chemical Co., Ltd.). Got. Mw of the obtained copolymer was 25,000.
[0025]
(Example 5)
A flask equipped with a stirrer, nitrogen gas inlet tube, thermometer and reflux condenser is charged with 40 parts by weight of N-phenylmaleimide, 5 parts by weight of methacrylic acid and 100 parts by weight of methyl isobutyl ketone, and nitrogen gas is introduced into the flask. The mixture was stirred for 30 minutes while purging with nitrogen, and then the contents of the flask were heated to 95 ° C.
Subsequently, 1 part by weight of β-mercaptopropionic acid was added to the stirred flask. While maintaining the content in the flask at 95 ° C., 0.3 part by weight of azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was added three times every hour. 4.5 hours after the addition of β-mercaptopropionic acid, 0.1 part by weight of p-toluenesulfonic acid and 55 parts by weight of one-end hydroxyl-modified silicone (FM-0411; manufactured by Chisso Corporation) with Mw of 1000 were added. The mixture was further stirred for 6 hours. Thereafter, 300 parts by weight of methyl isobutyl ketone was added into the flask and then cooled to room temperature to obtain a copolymer solution (A-5) having a polymer concentration of 20%. Mw of the obtained copolymer was 14,000.
[0026]
(Comparative Example 1)
A copolymer solution (C-1) having a polymer concentration of 20% was obtained in the same manner as in Example 1 except that N-phenylmaleimide was replaced with methyl methacrylate. Mw of the obtained copolymer was 13,000.
[0027]
(Comparative Example 2)
A copolymer solution (C-2) having a polymer concentration of 20% was obtained in the same manner as in Example 1 except that 2 parts by weight of β-mercaptopropionic acid was changed to 0.2 parts by weight. Mw of the obtained copolymer was 60,000.
[0028]
(Comparative Example 3)
A copolymer solution (C-3) having a polymer concentration of 20% was obtained in the same manner as in Example 1 except that the silicon-containing macromonomer was not used and that 100 parts by weight of N-phenylmaleimide was used. Mw of the obtained copolymer was 13,000.
[0029]
(Examples 6 to 32, Comparative Examples 3 to 20)
A heat resistant resin composition was prepared according to the formulation shown in Table 1, a heat resistant resin film was prepared by the following method, and a stain resistance test and a peel force measurement test were performed on the obtained film. The test results are shown in Table 1. In Table 1, PA is a 10% dimethylacetamide solution of aromatic polyamide (Technola (registered trademark): manufactured by Teijin Ltd.), and PBI is 10 of polybenzimidazole (PBI MR Solution: manufactured by Clariant Japan). % Dimethylacetamide solution, PI is polyimide (Kapton (registered trademark): manufactured by Toray DuPont), C-4 is a silicon-containing macromonomer (FM-0711: manufactured by Chisso) having a weight average molecular weight of 1,000, C-5 is a silicone oil (TSF4702: manufactured by Toshiba Silicone Co., Ltd.), and the numerical value in the composition column in the table indicates the weight part of the solid content.
[Table 1]

[0030]
-Preparation of heat-resistant resin film The heat-resistant resin composition was applied to a 50 µm PET film (PET-5011, manufactured by Lintec Corporation) with a doctor blade, placed in a hot air dryer and heated and dried at 130 ° C for 30 minutes, A heat-resistant resin film having a thickness of 40 μm was obtained.
-Contamination resistance test A heat-resistant resin film is marked with a square square of 1 cm with Magic Ink (registered trademark), and bleeding is visually observed. Further, this is wiped off with absorbent cotton and the surface contamination state is visually observed. Repeat the mark and wipe to the same location 10 times and observe bleeding and contamination. As for bleeding, “×” indicates that there is bleeding, “△” indicates that there is slight bleeding, and “○” indicates that there is no bleeding, and “O” indicates that the oil-based ink mark has disappeared for the contamination state. ”, And“ × ”indicates that the mark remained. Items that were not evaluated were indicated by “−”.
・ Peeling force test JIS Z 0237 no. According to the method based on adhesive strength. A cellophane adhesive tape (manufactured by Nichiban Co., Ltd., 18 mm width) is pressure-bonded to the test film with a 2 kg roller in an atmosphere at a temperature of 25 ° C. and a relative humidity of 65%. After crimping, the sample is left in an atmosphere of 25 ° C. and 65%, and after 15 minutes and 24 hours, the cellophane adhesive tape is peeled off at 90 ° direction at a speed of 300 mm / min, and the adhesive strength at that time is measured.
[0031]
【The invention's effect】
The additive for heat-resistant resin of the present invention has a repeating unit derived from maleimide or a maleimide derivative in the main chain and has an organic polysiloxane structure in the side chain, so it is compatible with the heat-resistant resin and is added in a small amount. This greatly improves the stain resistance and peelability of the heat resistant resin.
Further, the heat-resistant resin composition of the present invention contains the heat-resistant resin additive, has excellent surface contamination resistance and peelability when formed into a film, and can be widely used. . Furthermore, the molded article of the present invention is composed of the heat-resistant resin additive and a heat-resistant resin, and is excellent in stain resistance, peelability and releasability while maintaining the heat resistance of the heat-resistant resin. .

Claims (14)

It is a polymer compound having a weight average molecular weight of 5,000 or more and 50,000 or less, and has a repeating unit represented by the following formula (I) and a repeating unit represented by the following formula (II) in the molecule. Phenol resin, melamine resin, aliphatic polyimide, aromatic polyimide, aliphatic polyamide, aromatic polyamide, polyamideimide, polymethylpentene, polyphenylene sulfide, polyethersulfone, polyetheretherketone, polybenzimidazole, poly An additive for a heat resistant resin having a melting point of 200 ° C. or higher selected from the group consisting of benzoxazole and polybenzothiazole .

  The additive for a heat resistant resin according to claim 1, wherein n1 in the formula (I) is an integer of 4 or more and 200 or less.   The additive for heat-resistant resin according to claim 1, wherein n2 in the formula (II) is an integer of 2 or more and 20 or less.   The additive for heat-resistant resin according to claim 1, wherein n3 in the formula (II-1) is an integer of 10 or more and 200 or less. A weight-average molecular weight of 50,000 or less of the polymer compound 5,000, both that having a repeating unit represented by the repeating units and formula represented by the following formula in the molecule (I) (II) Polymer, phenol resin, melamine resin, aliphatic polyimide, aromatic polyimide, aliphatic polyamide, aromatic polyamide, polyamideimide, polymethylpentene, polyphenylene sulfide, polyethersulfone, polyetheretherketone, polybenzimidazole, A heat resistant resin composition comprising a heat resistant resin having a melting point of 200 ° C. or higher selected from the group consisting of polybenzoxazole and polybenzothiazole .

  6. The heat resistant resin composition according to claim 5, wherein n1 in the formula (I) is an integer of 4 or more and 200 or less.   6. The heat resistant resin composition according to claim 5, wherein n2 in the formula (II) is an integer of 2 or more and 20 or less. 6. The heat resistant resin composition according to claim 5, wherein n3 in the formula (II-1) is an integer of 10 or more and 200 or less.   6. The heat resistant resin composition according to claim 5, wherein the heat resistant resin is a resin selected from the group consisting of aromatic polyimide, aromatic polyamide, and polybenzimidazole. Copolymer having a weight average molecular weight of 5,000 or more and 50,000 or less and having a repeating unit represented by the following formula (I) and a repeating unit represented by the following formula (II) in the molecule Combined with phenolic resin, melamine resin, aliphatic polyimide, aromatic polyimide, aliphatic polyamide, aromatic polyamide, polyamideimide, polymethylpentene , polyphenylene sulfide, polyethersulfone, polyetheretherketone, polybenzimidazole, polybenzo A molded article comprising a heat-resistant resin having a melting point of 200 ° C or higher selected from the group consisting of oxazole and polybenzothiazole .

  The molded object according to claim 10, wherein n1 in the formula (I) is an integer of 4 or more and 200 or less.   The molded object according to claim 10, wherein n2 in the formula (II) is an integer of 2 or more and 20 or less.   The molded article according to claim 10, wherein n3 in the formula (II-1) is an integer of 10 or more and 200 or less.   The molded product according to claim 10, wherein the heat-resistant resin is a resin selected from the group consisting of aromatic polyimide, aromatic polyamide, and polybenzimidazole.