JP2004107626A - Carbon fiber reinforced thermoplastic resin composition, molding material and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a carbon fiber reinforced thermoplastic resin composition excellent in mechanical properties, electric conductivity and moldability, a molding material and a molded article molded using the molding material. <P>SOLUTION: The carbon fiber reinforced thermoplastic resin composition contains a component (A) and a component (B) as follows. The component (A), 25-99wt.%, is at least a thermoplastic resin selected from the group consisting of a polycarbonate, styrene resin, polyamide, polyester, polyphenylene sulfide, modified polyphenylene ether, polyetherimide, polyolefin and polyacetal resin. The component (B), 1-75wt.%, is a carbon fiber obtained by applying 0.1-5wt.% of a copolymer at least containing 55-99wt.% of a salt of a diamine having an oxyalkylene group and a dicarboxylic acid as a component (c1) and 1-45wt.% of an amino acid, a lactam and/or a salt of a diamine and a dicarboxylic acid as a component (c2) based on 100wt.% of the carbon fiber. <P>COPYRIGHT: (C)2004,JPO

Description

【００３８】
また、構造単位の３０モル％未満を、下記構造式で示される構造単位で構成することが可能である。
【００３９】
【化２】

【００４０】
これらＰＰＳ樹脂の溶融粘度は、溶融混練が可能であれば特に制限はないが、好ましくは１０〜５０，０００ポイズ（３００℃、剪断速度１，０００／秒）の範囲内であり、特に好ましくは１０〜５，０００ポイズである。
【００４１】
本発明で使用される変性ポリフェニレンエーテル樹脂は、下記構造式（Ｒ_１は炭
素数１〜３の低級アルキル基、Ｒ_２，Ｒ_３は水素原子または炭素数１〜３の低級アルキル基である）で示される構造単位を主鎖に含む重合体であり、ホモポリマー、コポリマーまたはグラフトポリマーのいずれを用いてもよい。
【００４２】
【化３】

【００４３】
具体的には、ポリ（２，６−ジメチル−１，４−フェニレン）エーテル、ポリ（２，６−ジエチル−１，４−フェニレン）エーテル、ポリ（２，６−ジプロピル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−エチル−１，４−フェニレン）エーテルなどが挙げられ、中でもポリ（２，６−ジメチル−１，４−フェニレン）エーテル、２，６−ジメチルフェノール、２，３，６−トリメチルフェノール共重合体およびこれらにスチレンをグラフトしたグラフト重合体が好ましい。
【００４４】
ポリフェニレンエーテル樹脂の変性方法については、特に限定されるものではなく、ポリフェニレンエーテル樹脂と不飽和脂肪族カルボン酸もしくは、その酸無水物を溶融混練する通常公知の方法で行うことができる。
【００４５】
本発明で使用されるポリアセタール樹脂は、オキシメチレン単位を主たる繰り返し単位とするポリマーであり、オキシメチレン単位のみからなるいわゆるポリアセタールホモポリマーであっても、主としてオキシメチレン単位からなり、主鎖中に２〜８個の隣接する炭素原子を有するオキシアルキレン単位を１５重量％以下含有するいわゆるポリアセタールコポリマーのいずれであってもよく、これらは１種または２種以上で用いることができる。
【００４６】
ポリアセタール樹脂の製造方法は特に制限はなく、例えば、高純度のホルムアルデヒドを有機アミン、有機あるいは無機の錫化合物、金属水酸化物のような塩基性重合触媒を含有する有機溶媒中に導入して重合し、重合体を濾別した後、無水酢酸中、酢酸ナトリウムの存在下で加熱してポリマー末端をアセチル化して製造する公知の方法が例示できる。
【００４７】
本発明に使用されるポリエーテルイミド樹脂は、２．２．３．３．−テトラカルボキシジフェニレンエーテル二無水物と一般式Ｈ２ＮＲＮＨ２（Ｒは６個から２０個の炭素原子を有する芳香族炭化水素およびハロゲン化誘導体）で表されるジアミンを有機溶媒の存在下で水を除去しながら合成する方法や、芳香族ビス・エーテル濡素異物と有機ジアミンとの水と有機溶剤の界面条件下での反応による合成により得られるものである。
【００４８】
本発明に使用されるポリオレフィン系樹脂は、特に制限はないが、アイソタクテックホモポリプロピレン、プロピレンとエチレン、１・ブテンなどのプロピレン以外のα・オレフィンとからなるランダムポリプロピレン、ブロックポリプロピレン、シンジオタクチックポリプロピレンなどの結晶性ポリプロピレン系樹脂、高密度ポリエチレン（ＨＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、低密度ポリエチレン（ＬＤＰＥ）、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）、超高分子量ポリエチレンなどの結晶性ポリエチレン系樹脂や、ポリブテン・１やポリ・４・メチルペンテン・１などの炭素数が３を越えるα・オレフィンを主成分とする結晶性重合体など、あるいはこれらの混合物を挙げることができる。これら結晶性ポリオレフィン　系樹脂の中でも経済性、成形性の観点から、結晶性ポリプロピレン系樹脂が最も好ましく用いられる。
【００４９】
前記ポリオレフィン系樹脂を不飽和カルボン酸もしくはその誘導体、不飽和エポキシ化合物、不飽和イミド化合物などの変性剤をグラフト化した、変性・結晶性ポリオレフィン　系樹脂も好ましく用いられる。結晶性ポリオレフィン　系樹脂の変性方法としては、溶融混練法、溶液法、スラリー法を挙げることができ、いずれの方法によっても好ましく行うことができる。溶融混練法の場合には、変性に用いる前記変性剤（不飽和カルボン酸化合物またはその誘導体、不飽和エポキシ化合物、不飽和イミド化合物）と、ラジカル重合用触媒を併存させて、押出機を用いて、１５０から３５０℃の温度に加熱して溶融混練すればよい。一方、溶液法、スラリー法の場合には、キシレンなどの有機溶剤に結晶性ポリオレフィン系樹脂、変性剤、およびラジカル重合触媒とを溶解、あるいはスラリー状態とし、８０から３５０℃の温度で撹拌しながら変性すればよい。配合する変性剤の量は、結晶性ポリオレフィン系樹脂１００重量部に対して、０．０１から１０重量％が好ましい。
【００５０】
前記変性剤である不飽和カルボン酸化合物としては、アクリル酸、α−エチルアクリル酸、メタクリル酸、マレイン酸、フマール酸、ハロゲン化マレイン酸、シトラコン酸、テトラヒドロフタル酸、メチルテトラヒドロフタル酸、ハロゲン化シトラコン酸、クロトン酸、ハロゲン化クロトン酸、イタコン酸、ハロゲン化イタコン酸、シス・４・シクロヘキセン・１，２・ジカルボン酸、エンド・ビシクロ・（２、２，１）・５・ヘプテン・２，３・ジカルボン酸、メチル・エンド・シス・ビシクロ・（２，２，１）・５・ヘプテン・２，３・ジカルボン酸、エンド・ビシクロ・（２，２，１）・１，２，２，２，７，７・ヘキサクロロ・２・ヘプテン・５，６・ジカルボン酸など、あるいはこれらの混合物を挙げることができる。
【００５１】
不飽和カルボン酸化合物の誘導体は、前記不飽和カルボン酸化合物の酸ハライド、無水、エステル、アミド、イミド、金属塩などを挙げることができ、例えば塩化マレニル、マレイミド、無水マレイン酸、無水シトラコン酸、マレイン酸モノメチル、マレイン酸ジメチル、グリシジルマレエートなど、あるいはこれらの混合物を挙げることができる。この中で、好ましいものとしては、無水マレイン酸、無水ナジック酸を挙げることができる。
【００５２】
不飽和エポキシ化合物としては、グリシジルアクリレート、グリシジルメタクリレート、イタコン酸モノグリシジルエステル、イタコン酸ジグリシジルエステル、ブテントリカルボン酸モノグリシジルエステル、ブテントリカルボン酸ジグリシジルエステル、ブテントリカルボン酸トリグリシジルエステル、ｐ・スチレンカルボン酸グリシジルエステル、アリルグリシジルエーテル、２・メチルアリルグリシジルエーテル、スチレン・ｐ・グリシジルエーテル、ｐ・グリシジルスチレン、３，４・エポキシ・１・ブテン、３，４・エポキシ・３・メチル・１・ブテン、３，４・エポキシ・１・ペンテン、３，４・エポキシ・３・メチル・１・ペンテン、５，６・エポキシ・１・ヘキセンおよびビニルシクロヘキセンモノオキシドなど、あるいはこれらの混合物を挙げることができる。
【００５３】
不飽和イミド化合物としては、例えばマレイミド、Ｎ・メチルマレイミド、Ｎ・エチルマレイミド、Ｎ・プロピルマレイミド、Ｎ・ブチルマレイミド、Ｎ・オクチルマレイミド、Ｎ・フェニルマレイミド、Ｎ・（ｏ・メチルフェニル）マレイミド、Ｎ・（ｍ・メチルフェニル）マレイミド、Ｎ・（ｐ・メチルフェニル）マレイミド、Ｎ・（メトキシフェニル）マレイミド、Ｎ・（クロルフェニル）マレイミド、Ｎ・（カルボキシフェニル）マレイミド、Ｎ・ベンジルマレイミド、Ｎ・ナフチルマレイミド、Ｎ・シクロヘキシルマレイミド、イタコンイミド、Ｎ・メチルイタコンイミド、Ｎ・フェニルイタコンイミドなどを挙げることができる。中でもＮ・シクロヘキシルマレイミド、Ｎ・ベンジルマレイミド、Ｎ・フェニルマレイミド、Ｎ・（カルボキシフェニル）マレイミドが好ましく用いられる。これらの不飽和カルボン酸もしくはその誘導体、不飽和エポキシ化合物、あるいは不飽和イミド化合物は１種類であっても、２種類以上を組み合わせて用いてもかまわない。
【００５４】
ラジカル重合用触媒としては、例えばベンゾイルペルオキシド、ジクロルベンゾイルペルオキシド、ジクミルペルオキシド、ジ・ｔｅｒｔ・ブチルペルオキシド、２，５・ジメチル・２，５・ジ（ペルオキシベンゾエート）ヘキシン・３、１，４・ビス（ｔｅｒｔ・ブチルペルオキシイソプロピル）ベンゼン、ラウロイルペルオキシド、ｔｅｒｔ・ブチルペルアセテート、２，５・ジメチル・２，５・ジ（ｔｅｒｔ・ブチルペルオキシ）ヘキシン・３、２，５・ジメチル・２，５・ジ（ｔｅｒｔ・ブチルペルオキシ）ヘキサン、ｔｅｒｔ・ブチルペルベンゾエート、ｔｅｒｔ・ブチルペルフェニルアセテート、ｔｅｒｔ・ブチルペルイソブチレート、ｔｅｒｔ・ブチルペル・ｓｅｃ・オクトエート、ｔｅｒｔ・ブチルペルピバレート、クミルペルピバレート、ｔｅｒｔ・ブチルペルジエチルアセテート、アゾビスイソブチロニトリル、ジメチルアゾイソブチレートなど、あるいはこれらの混合物を挙げることができる。中でも、好ましいものとしてはジクミルペルオキシド、ジ・ｔｅｒｔ・ブチルペルオキシド、２，５・ジメチル・２，５・ジ（ｔｅｒｔ・ブチルペルオキシ）ヘキシン・３、２，５・ジメチル・２，５・ジ（ｔｅｒｔ・ブチルペルオキシ）ヘキサン、１，４・ビス（ｔｅｒｔ・ブチルペルオキシイソプロピル）ベンゼンなどのジアルキルペルオキシドを挙げることができる。
【００５５】
前記方法により得られる変性・結晶性ポリオレフィン系樹脂は特に制限はないが、ＭＦＲ（ポリプロピレン系の場合２３０℃、ポリエチレン系の場合１９０℃）が０．０１〜１０００ｇ／１０分程度であり、好ましくは０．１〜１００ｇ／１０分のものが成形性の観点から好ましい。
【００５６】
上記成分（Ａ）の熱可塑性樹脂は、例えば寸法安定性、意匠性、経済性、生産性、成形品の外観品位を優先する場合にはポリカーボネート樹脂やスチレン系樹脂、ポリオレフィン系樹脂などが好ましく選択され、機械特性、耐熱性、耐薬品性、流動性を優先する場合にはポリアミド樹脂、ポリエステル樹脂、ポリフェニレンスルフィド樹脂や変性ポリフェニレンエーテル樹脂、ポリアセタール樹脂、ポリエーテルイミド樹脂が好ましく選択されるが、これに限定されるものでなく、適宜単独または２種以上を使用することができる。さらには、熱可塑性樹脂を予め溶融混練し、ポリマーアロイとして使用してもよい。
【００５７】
本発明における成分（Ｂ）の炭素繊維とは、炭素の含有率が８５〜１００重量％の範囲内にあり、少なくとも部分的にはグラファイト構造を有する繊維状材料を意味する。かかる繊維状材料の具体例としては、ポリアクリロニトリル系炭素繊維、レーヨン系炭素繊維、リグニン系炭素繊維、ピッチ系炭素繊維、気相成長炭素繊維、カーボンナノチューブなどが挙げられる。中でも、成形体の良好な機械特性および導電性を満足し、かつ安価なコストを実現できる点でポリアクリロニトリル系炭素繊維が好適に用いられる。なかでも、引張強度が３ＧＰａ以上であり、引張弾性率が３５０ＧＰａ以下のものが機械特性、取扱性、経済性のバランスの観点から好ましく用いられる。ここで「炭素繊維の引張強度」および「炭素繊維の引張弾性率」とは、ＪＩＳ　Ｒ　７６０１に基づいた樹脂含浸ストランド法で測定した強度および弾性率である。
【００５８】
また、得られる炭素繊維強化熱可塑性樹脂組成物の導電性を高める観点で、炭素繊維の電気抵抗が４０Ω・ｇ／ｍ^２未満であることが好ましく、３８Ω・ｇ／ｍ^２未満であることがより好ましく、３７Ω・ｇ／ｍ^２未満であることがさらに好ましい。「炭素繊維の電気抵抗」とは、１ｍ長の炭素繊維の両端に測定端子を接続する２線式測定法で測定した長さ当たりの電気抵抗値に、炭素繊維の同長さ当たりの重量を乗じたものを意味し、この際、通常の製造法において得られる繊維束の形態で測定しても良く、この場合も同様に得られた長さ当たりの電気抵抗値に繊維束の同長さ当たりの重量を乗じて求める。
【００５９】
同様に好ましい炭素繊維としては、広角Ｘ線回折法により測定された結晶サイズ（Ｌｃ）が、１〜６ｎｍ、より好ましくは１．３〜４．５ｎｍ、特に好ましくは１．６〜３．６ｎｍの範囲内である。Ｌｃが１ｎｍ以上であることは、炭素繊維の炭化もしくは黒鉛化が十分であり、炭素繊維自体の導電性および弾性率が良好になる。また、このような炭素繊維を用いた樹脂組成物、およびそれからつくられる成形品は導電性の向上が期待できるだけでなく、機械特性、中でも剛性の向上が期待できる。一方、Ｌｃが６ｎｍ以内であるということは、炭素繊維の過剰な炭化もしくは黒鉛化を抑えることになり、炭素繊維自体の導電性が優れ、かつ、炭素繊維の折損を防ぐことが期待できる。そのため、樹脂組成物中の繊維長さは長くなり、優れた電気的特性が得られるだけでなく機械特性の中でとくに高い機械強度が期待できる。ここで、広角Ｘ線回折法によるＬｃの測定は、日本学術振興会第１１７委員会、炭素、３６、ｐ２５（１９６３）に記載された方法に基づいて測定できる。
【００６０】
さらには、炭素繊維のＸ線光電子分光法により測定される炭素繊維表面の酸素（Ｏ）と炭素（Ｃ）の原子数の比である表面酸素濃度（Ｏ／Ｃ）が、好ましくは０．０３〜０．０８の範囲内、より好ましくは０．０４〜０．０７の範囲内である。表面酸素濃度（Ｏ／Ｃ）が、０．０３〜０．０８の範囲内であれば、得られる炭素繊維強化熱可塑性樹脂組成物の機械特性を大きく損なうことなく、本発明の目的である導電性を効率的にに向上させることが可能である。
【００６１】
炭素繊維の形状としては特に制限はなく、連続繊維であるロービング、所定の長さにカットしたチョップド糸、粉砕したミルド糸が使用できるが、熱可塑性樹脂と炭素繊維を混合（コンパウンド）する工程での利便性、取扱性の観点から、一般にチョップド糸が好ましく用いられる。このチョップド糸における繊維長さは特に限定されるものでは無いが、サイジング剤により集束性を十分に発揮しカットされたあとの形状を十分に維持し得る点、コンパウンド、および成形の際に、容易に繊維を樹脂中に分散し、あるいは、強い剪断力を受けた場合にもある程度の繊維長を維持し、結果として成形品の導電性、および機械的特性を十分に満足し得る点で１〜２６ｍｍの範囲内が好ましく、２〜１５ｍｍの範囲内がより好ましい。
【００６２】
また、炭素繊維は、炭素繊維強化熱可塑性樹脂組成物の生産性、炭素繊維の取扱性の観点から、好ましくは１．５万〜１０万本の範囲内、より好ましくは４万〜８万の範囲内で束ねられたものである。
【００６３】
本発明の炭素繊維強化熱可塑性樹脂組成物は、第１，第２発明とも、成分（Ａ）の熱可塑性樹脂が２５〜９９重量％、好ましくは３５〜９７重量％、より好ましくは５０〜９５重量％の範囲内と、成分（Ｂ）の炭素繊維が、１〜７５重量％、好ましくは３〜６５重量％、より好ましくは５〜５０重量％の範囲内から構成されるものである。成分（Ｂ）が１重量％未満では導電性が不十分である場合があり、７５重量％を越えると成形性が劣る場合がある。
【００６４】
ここで第１発明の炭素繊維強化熱可塑性樹脂組成物の特徴は、導電性、成形性を向上させる目的で、成分（Ｂ）の炭素繊維に、サイジング剤として、少なくとも成分（ｃ１）のオキシアルキレン基を有するジアミンとジカルボン酸の塩５５〜９９重量％と、成分（ｃ２）のアミノ酸、ラクタムおよび／またはジアミンとジカルボン酸の塩１〜４５重量％とからなる共重合体（ｃ）を付着せしめた炭素繊維を用いるものである。
【００６５】
上記共重合体（ｃ）の付着量は、炭素繊維１００重量％に対し０．１〜５重量％の範囲内であり、好ましくは１〜４重量％の範囲内である。付着量が０．１重量％未満では導電性向上効果が不十分となる場合があり、５重量％を越えると炭素繊維の繊維束が硬くなり、熱可塑性樹脂と混練する前の段階で生産性、経済性を損なう場合がある。
【００６６】
また、共重合体（ｃ）を付着させる方法については特に制限はなく、例えば共重合体を溶液にし、炭素繊維を浸漬あるいは、炭素繊維に溶液を滴下、散布した後、溶媒を乾燥、除去する方法などが例示できる。
【００６７】
なお、炭素繊維は共重合体（ｃ）以外にも、本発明の目的を損なわない範囲で、エポキシ樹脂、ウレタン樹脂、アクリル樹脂や種々の熱可塑性樹脂など通常公知のサイジング剤を１種または２種以上併用してもよい。例えば、共重合体（ｃ）を付着させた後、通常公知のサイジング剤をさらに付着させる方法や、予め通常公知のサイジング剤を付着させた後、共重合体（ｃ）を付着させる方法、さらに共重合体（ｃ）と通常公知のサイジング剤を同時に付着させる方法などが例示できる。
【００６８】
また、第２発明の炭素繊維強化熱可塑性樹脂組成物は、導電性、成形性を向上させる目的で、成分（Ｃ）の共重合体として、成分（ｃ１）のオキシアルキレン基を有するジアミンとジカルボン酸の塩５５〜９９重量％と、成分（ｃ２）のアミノ酸、ラクタムおよび／またはジアミンとジカルボン酸の塩１〜４５重量％からなる共重合体を添加するものである。共重合体の添加量としては、炭素繊維強化熱可塑性樹脂組成物１００重量％中に、成分（Ｃ）を０．０１〜１０重量％、より好ましくは０．１〜８重量％、さらに好ましくは０．２〜５重量％の範囲内である。成分（Ｃ）が０．０１重量％未満では導電性向上効果が不十分となる場合があり、１０重量％を越えると得られる成形品の機械特性を損なう場合がある。
【００６９】
なお、上述したように、第１発明における共重合体（ｃ）と第２発明における成分（Ｃ）の共重合体は、いずれも少なくとも成分（ｃ１）のオキシアルキレン基を有するジアミンとジカルボン酸の塩５５〜９９重量％、好ましくは６０〜９０重量％と、成分（ｃ２）のアミノ酸、ラクタムおよびまたはジアミンとジカルボン酸の塩１〜４５重量％、好ましくは１０〜３０重量％からなる共重合体であるが、成分（ｃ１）の割合が５５重量％未満でも、９９重量％を越えても、本発明の導電性向上効果が不十分となる場合や機械特性が低下する場合がある。
【００７０】
ここで、成分（ｃ１）のオキシアルキレン基を有するジアミンとジカルボン酸の塩とは、オキシアルキレン基を有するジアミン化合物とジカルボン酸化合物とを実質的に当モルで反応させた塩のことである。なお、ここでいう「実質的に当モル」とは、オキシアルキレン基を有するジアミン化合物とジカルボン酸化合物との比率が１±０．１の範囲であることを意味し、この範囲内であれば、重合速度や到達重合度の観点から、本発明の効果を発現するに十分である。
【００７１】
また、成分（ｃ１）を構成するオキシアルキレン基を有するジアミン化合物としては、ポリオキシエチレン骨格、ポリオキシプロピレン骨格を有するポリアルキレングリコールの両末端をジアミンに変性したものが好ましく用いられ、なかでもビスアミノプロピルポリエチレングリコールが特に好ましい。また、前記オキシアルキレン基を有するジアミン化合物の分子量は得られる成形品の導電性の観点から、数平均分子量が２０００以下のものが好ましく、さらに好ましくは１０００以下のものが好ましく用いられる。
【００７２】
さらに、前記ジカルボン酸としては、アジピン酸、スペリン酸、アゼライン酸、セバシン酸、ドデカン二酸、テレフタル酸、イソフタル酸、２−クロロテレフタル酸、２−メチルテレフタル酸、５−メチルイソフタル酸、５−ナトリウムスルホイソフタル酸、２，６−ナフタレンジカルボン酸、ヘキサヒドロテレフタル酸、ヘキサヒドロイソフタル酸などの脂肪族、脂環族、芳香族のジカルボン酸が挙げられ、中でもアジピン酸、アゼライン酸、セバシン酸が塩の到達重合度の点から好ましく用いられ、とりわけアジピン酸がより好ましく用いられる。また、これらのジカルボン酸は１種または２種以上を併用してもよい。
【００７３】
ここで、成分（ｃ２）アミノ酸、ラクタムあるいはジアミンとジカルボン酸を主たる成分とする重合体は、ポリアミドを形成しうるものである。その具体例としては、６−アミノカプロン酸、１１−アミノウンデカン酸、１２−アミノドデカン酸、ｐ−アミノメチル安息香酸などのアミノ酸、ε−カプロラクタム、ω−ラウロラクタムなどのラクタム、テトラメチレンジアミン、ヘキサメチレンジアミン、２−メチルペンタメチレンジアミン、ノナメチレンジアミン、ウンデカメチレンジアミン、ドデカメチレンジアミン、２，２，４−トリメチルヘキサメチレンジアミン、２，４，４−トリメチルヘキサメチレンジアミン、５−メチルノナメチレンジアミン、メタキシリレンジアミン、パラキシリレンジアミン、１，３−ビス（アミノメチル）シクロヘキサン、１，４−ビス（アミノメチル）シクロヘキサン、１−アミノ−３−アミノメチル−３，５，５−トリメチルシクロヘキサン、ビス（４−アミノシクロヘキシル）メタン、ビス（３−メチル−４−アミノシクロヘキシル）メタン、２，２−ビス（４−アミノシクロヘキシル）プロパン、ビス（アミノプロピル）ピペラジン、アミノエチルピペラジンなどの脂肪族、脂環族、芳香族のジアミン、およびアジピン酸、スペリン酸、アゼライン酸、セバシン酸、ドデカン二酸、テレフタル酸、イソフタル酸、２−クロロテレフタル酸、２−メチルテレフタル酸、５−メチルイソフタル酸、５−ナトリウムスルホイソフタル酸、２，６−ナフタレンジカルボン酸、ヘキサヒドロテレフタル酸、ヘキサヒドロイソフタル酸などの脂肪族、脂環族、芳香族のジカルボン酸が挙げられ、かつこれらの原料から誘導されるホモポリマーまたはコポリマーを用いることができる。中でも、導電性の観点からラクタム環が開環重合して得られるものが好ましく、ε−カプロラクタムを用いることが特に好ましい。
【００７４】
第１発明における共重合体（ｃ）および第２発明における成分（Ｃ）の共重合体の相対粘度（９８％硫酸法）ηｒについては特に制限はないが、成形性と生産性の観点から１．５〜４．５の範囲内が好ましく、１．８〜３．５の範囲内がより好ましい。相対粘度ηｒの測定方法は次の方法が用いられる。すなわち、成分（Ｂ）約１ｇを９８％硫酸に溶解し１００ｃｃ溶液とし、２５℃下でオストワルド粘度計を使用して測定する。
【００７５】
第１，第２発明の炭素繊維強化熱可塑性樹脂組成物は、導電性を一層高める目的で、さらに成分（Ｄ）として、導電性付与剤を添加することが好ましい。ここで、好ましい添加量としては、炭素繊維強化熱可塑性樹脂組成物１００重量％中に、成分（Ｄ）を０．０１〜１０重量％の範囲内であり、さらに好ましくは０．１〜８重量％の範囲内である。
【００７６】
本発明で使用する導電性付与剤としては、例えばカーボンブラック、アモルファスカーボン粉末、天然黒鉛粉末、人造黒鉛粉末、膨張黒鉛粉末、ピッチマイクロビーズ、気相成長炭素繊維、カーボンナノチューブなどが例として挙げられるが、その中でも導電性向上の観点からカーボンブラック、気相成長炭素繊維またはカーボンナノチューブが好ましい。
【００７７】
かかるカーボンブラックとしては、例えばファーネスブラック、アセチレンブラック、サーマルブラック、チャンネルブラックなどが挙げられ、これらの単独または２種類以上ブレンドしたカーボンブラックでもよい。中でも、価格、導電性付与効果などの総合的な面から、ファーネスブラックが好ましい。
【００７８】
また、カーボンナノチューブとしては、例えば、単層ナノチューブ、多層ナノチューブなどを使用することができ、これらを２種以上併用したものでも良い。また、カーボンナノチューブの添加効果を高めるために、カーボンナノチューブの表面を官能基で修飾したり、プラズマ処理を施すなどしてもよい。特に好ましいカーボンナノチューブとしては、導電性の観点からは単層ナノチューブ、二層ナノチューブであり、供給性、経済性の観点からは多層ナノチューブである。
【００７９】
また、第１、第２発明とも炭素繊維強化熱可塑性樹脂組成物には、難燃性を付与する目的で、さらに成分（Ｅ）として、難燃剤を添加することが好ましい。ここで、好ましい添加量としては、機械特性とのバランスの観点から炭素繊維強化熱可塑性樹脂組成物１００重量％中に成分（Ｅ）を０．１〜２０重量％の範囲内であり、さらに好ましくは１〜１０重量％の範囲内である。
【００８０】
いずれの発明も使用される難燃剤には特に制限はなく、ハロゲン系、燐系、無機系などの公知な難燃剤を使用できる。具体的には、テトラブロモビスフェノールＡ（ＴＢＢＡ）及びその誘導体、デカブロモジフェニルエーテル、ブロモビスフェノールＳ、テトラブロモ無水フタル酸、ポリジブロモフェニレンオキサイド、ヘキサブロモシクロドデカン、、エチレンビステトラブロモフタルイミド、エチレンビスジブロモノルボランジカルモキシルイミド、ペンタブロモジフェニルオキサイド、テトラデカブロモジフェノキシベンゼン、ヘキサブロモベンゼン、臭素化エポキシ系難燃剤、臭素化ポリカーボネート系難燃剤、臭素化ポリフェニレンオキサイド系難燃剤、臭素化スチレン系難燃剤などのハロゲン系難燃剤、赤燐、アルキルホスフェート、アリルホスフェート、アルキルアリルフォスフェート、芳香族縮合燐酸エステル、塩化ホスフォニトリル誘導体、ホスフォノアミド系難燃剤、ビニルホスフォネート、アリルホスフォネート、ポリ燐酸アンモニウム、ポリ燐酸アミド、メラミンホスフェートなどの燐系難燃剤、水酸化マグネシウム、水酸化アルミニウム、水酸化バリウム、水酸化亜鉛、水酸化アルミニウム、水酸化ジルコニウム、三酸化アンチモン、四酸化アンチモン、五酸化アンチモン、酸化錫、水酸化錫、酸化ジルコニウム、酸化モリブデン、モリブデン酸アンモニウム、硼酸亜鉛、硼酸バリウム、アルミン酸カルシウム、クレーなどの無機系難燃剤、さらにはメラミン、メラミンシアヌレートなどの含窒素系、シリコーン系重合体、ポリテトラフルオロエチレン（ＰＴＦＥ）などの難燃助剤を挙げることができるが、機械特性とのバランス、環境への負荷および難燃性の観点から燐系難燃剤、とりわけ燐酸エステル、赤燐が好ましい。
【００８１】
さらに、本発明の炭素繊維強化熱可塑性樹脂組成物には、要求される特性に応じ、本発明の目的を損なわない範囲で無機充填材、添加剤、他の熱可塑性樹脂を添加しても良い。
【００８２】
無機充填材としては特に制限はなく、公知なものを使用することができる。具体例としては、ガラス繊維、ガラス粉末、ガラスビーズ、アラミド繊維、アルミナ繊維、アラミド繊維、炭化珪素繊維、セラミック繊維、アスベスト繊維、石膏繊維、金属繊維、層状珪酸塩（モンモリロナイト、バイデライト、ノントロナイト、サポナイト、ヘクトライト、ソーコナイト、バーミキュライトなどのスメクタイト系粘土鉱物、ハロイサイト、カネマイト、ケニヤイト、燐酸ジルコニウム、燐酸チタニウムなどの各種粘土鉱物、Ｌｉ型フッ素テニオライト、Ｎａ型フッ素テニオライト、Ｎａ型四珪素フッ素雲母、Ｌｉ型四珪素フッ素雲母等の膨潤性合成雲母）、焼成クレイ、タルク、シリカ、酸化マグネシウム、酸化チタン、珪酸カルシウム、金属ウィスカー、ワラステナイト、ゼオライト、セリナイト、カオリン、ベントナイト、アルミナシリコート、マイカ、酸化チタン、チタン酸カリウム、炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛、ハイドロタルサイト、酸化鉄、フェライト、金属粉、水酸化鉄、窒化硼素などが挙げられる。これらは単独または２種以上を併用してもよい。なお、形状にも制限はなく、パウダー状、フレーク状、繊維状、ウィスカーバルーン状などの公知な形状で使用できる。
【００８３】
無機充填材の中でも、層状珪酸塩に属するものは、その層間を有機オニウムイオン化処理したものを使用しても良い。有機オニウムイオンとしては、特に制限はないがアンモニウムイオンやホスホニウムイオン、スルホニウムイオンなどが挙げられる。有機オニウム化処理は、元来層間に存在する交換性陽イオンを有機オニウムイオンで交換することを示し、その方法については特に制限はなく従来の方法で行うことができる。例えば、水、メタノール、エタノールなどの極性溶媒中でのイオン交換反応による方法や、層状珪酸塩に液状あるいは溶融させたアンモニウム塩を直接反応させる方法などが挙げられる。
【００８４】
添加剤としては、結晶核剤、紫外線吸収剤、酸化防止剤、制振剤、抗菌剤、防虫剤、防臭剤、着色防止剤、熱安定剤、離型剤、帯電防止剤、可塑剤、滑剤、着色剤、顔料、染料、発泡剤、制泡剤、カップリング剤などが使用できる。
【００８５】
他の熱可塑性樹脂としては、液晶ポリエステル、ポリアリーレート、ポリメチルメタクリレート樹脂（ＰＭＭＡ）などのアクリル樹脂、塩化ビニル、ポリイミド（ＰＩ）、ポリアミドイミド（ＰＡＩ）、ポリエーテルイミド（ＰＥＩ）、ポリスルホン、ポリエーテルスルホン、ポリケトン、ポリエーテルケトン、ポリエーテルエーテルケトン（ＰＥＥＫ）ポリエチレン、ポリプロピレン等のポリオレフィン、変性ポリオレフィン、フェノール樹脂、フェノキシ樹脂などの熱可塑性樹脂、さらにはエチレン／プロピレン共重合体、エチレン／１−ブテン共重合体、エチレン／プロピレン／ジエン共重合体、エチレン／一酸化炭素／ジエン共重合体、エチレン／（メタ）アクリル酸エチル共重合体、エチレン／（メタ）アクリル酸グリシジル、エチレン／酢酸ビニル／（メタ）アクリル酸グリシジル共重合体、ポリエーテルエステルエラストマー、ポリエーテルエーテルエラストマー、ポリエーテルエステルアミドエラストマー、ポリエステルアミドエラストマー、ポリエステルエステルエラストマーなどの各種エラストマー類などが挙げられ、これらの１種または２種以上を併用しても良い。
【００８６】
本発明の炭素繊維強化熱可塑性樹脂組成物はその導電性の観点から、ＡＳＴＭＤ２５７−９９に基づく表面抵抗率（単位はＬｏｇΩ／ｃｍ^２）で１２以下であることが好ましい。より好ましい範囲としては、得られる成形品が、帯電防止性、制電性を目的として使用される場合には５〜１０の範囲内、電磁波シールド性を目的として使用される場合には５以下であり、とりわけメッキを必要としない高いレベルの電磁波シールド性を目的として使用される場合には３以下である。
【００８７】
本発明の炭素繊維強化熱可塑性樹脂組成物の好ましい形態の１つであるペレットは、通常公知の方法で製造することができる。すなわち、各成分の全量及び必要に応じて他の添加剤を一括して溶融混練する方法、成分の一部を溶融混練しその途中から残りの成分を添加する方法、成分の一部を予め溶融混練してペレットとし残りの成分と再度溶融混練する方法、及び特定成分同士を別途溶融混練してペレットをブレンドする方法などが挙げられる。
【００８８】
ここで、溶融混練する方法には特に制限はなく、単軸押出機、二軸押出機やニーダーなどの溶融状態下での機械的剪断を行うことができる装置であれば良い。好ましい方法としては、機械的剪断がかかるシリンダー温度（ただし原料供給部は除く）を熱可塑性樹脂の融点またはガラス転移温度より少なくとも１０℃以上高くし、スクリュウとしては炭素繊維を分散させるための混練部を設け、ダイス径を大きくすることなどが挙げられる。さらに、溶融混練時に発生する水分や、低分子量の揮発成分を除去する目的でベント口を設ける方法、溶融混練の途中から成分を添加できるようにホッパー口を複数個設ける方法も好んで用いられる。
【００８９】
本発明の成形材料は、上述した炭素繊維強化熱可塑性樹脂組成物からなるものである。成形材料の形態としては、ペレット、フレークなどを使用することができるが、好ましくは一般的な射出成形に使用されるペレットである。
【００９０】
また、本発明の成形材料は、他の成形材料と混合してもよい。他の成形材料としては、例えば他の熱可塑性樹脂、添加剤、またはこれらを予め混練したマスターバッチ、さらには本発明の炭素繊維強化熱可塑性樹脂の成形品を粉砕してなる再生材などが例示できる。かかる成形材料は、例えば射出成形、ブロー成形、押出成形、プレス成形、圧縮成形、インサート成形などの公知な成形方法によって成形される。中でも、生産性の観点からは射出成形が好ましい。
【００９１】
また、本発明の成形材料の好ましい、もう１つの形態としては、プレス成形やスタンピング圧縮成形に使用される板状、シート状成形材料である。
【００９２】
かかる板状、シート状成形材料の製造方法としては、あらかじめ強化繊維と熱可塑性樹脂とを混合する抄造することによりマット化し、得られたマットをダブルベルトプレスや平板プレスを用いて加熱加圧含浸する方法、強化繊維マットに溶融させた熱可塑性樹脂を押出機を用いてＴダイから板状、シート状に出して加熱含浸する方法、強化繊維マットと熱可塑性樹脂シートをサンドイッチして加熱含浸する方法などが例示できる。形態としてはスタンパブルシート、発泡シート、プリプレグ等があげられる。
【００９３】
また、本発明のシート状成形材料は、例えば、プレス成形、オートクレーブ成形、スタンピング圧縮成形等の公知の成形方法で成形出来るが、生産性等の観点からプレス成形法が好ましい。
【００９４】
本発明の成形材料を成形してなる成形品は、優れた機械特性、導電性を活かし種々の用途に展開できる。例えば、各種ギヤー、各種ケース、センサー、ＬＥＤランプ、コネクター、ソケット、抵抗器、リレーケース、スイッチ、コイルボビン、コンデンサー、パソコン、光ピックアップ、発振子、各種端子板、変成器、プラグ、プリント配線板、チューナー、スピーカー、マイクロフォン、ヘッドフォン、小型モーター、磁気ヘッドベース、パワーモジュール、筐体、半導体、液晶ディスプレー部品、ＦＤＤキャリッジ、ＦＤＤシャーシ、ＨＤＤ部品、モーターブラッシュホルダー、パラボラアンテナ、コンピューター関連部品などに代表される電気・電子部品、ＶＴＲ部品、テレビ部品、アイロン、ヘアードライヤー、炊飯器部品、電子レンジ部品、音響部品、オーディオ・レーザーディスク・コンパクトディスクなどの音声機器部品、照明部品、冷蔵庫部品、エアコン部品、タイプライター部品、ワードプロセッサー部品などに代表される家庭・事務電気製品部品、パチンコ、スロットマシン、ゲーム機などに代表される遊技・娯楽製品部品、オフィスコンピューター関連部品、電話機関連部品、ファクシミリ関連部品、複写機関連部品、洗浄用治具、オイルレス軸受、船尾軸受、水中軸受などの各種軸受、モーター部品、ライター、タイプライターなどに代表される機械関連部品、顕微鏡、双眼鏡、カメラ、時計などに代表される光学機器、精密機械関連部品、オルタネーターターミナル、オルタネーターコネクター、ＩＣレギュレーター、ライトディヤー用ポテンショメーターベース、排気ガスバルブなどの各種バルブ、燃料関係・排気系・吸気系各種パイプ、エアーインテークノズルスノーケル、インテークマニホールド、燃料ポンプ、エンジン冷却水ジョイント、キャブレターメインボディー、キャブレタースペーサー、排気ガスセンサー、冷却水センサー、油温センサー、ブレーキパットウェアーセンサー、スロットルポジションセンサー、クランクシャフトポジションセンサー、エアーフローメーター、ブレーキバット磨耗センサー、エアコン用サーモスタットベース、暖房温風フローコントロールバルブ、ラジエーターモーター用ブラッシュホルダー、ウォーターポンプインペラー、タービンべイン、ワイパーモーター関係部品、デュストリビュター、スタータースィッチ、スターターリレー、トランスミッション用ワイヤーハーネス、ウィンドウオッシャーノズル、エアコンパネルスィッチ基板、燃料関係電磁気弁用コイル、ヒューズ用コネクター、ホーンターミナル、電装部品絶縁板、ステップモーターローター、ランプソケット、ランプリフレクター、ランプハウジング、ブレーキピストン、ソレノイドボビン、エンジンオイルフィルター、点火装置ケース、遊戯用器具、トイレタリー用品、玩具用品、化学プラント、航空部品、ヘッドランプドア、ラジエータグリル、カウルベントグリル、アウトサイドグリップ、サイドバイザ、サイドモールディング、リヤパネルガーニッシュ、ルーフカバー、エアスクープ、スポイラ等の自動車外装品、インストルメントパネル、インストルメントクラスタパネル、インストルメントパネルパッド、インストルメントアッパガーニッシュ、グローブボックス、グローブボックスドア、ベンチレータグリル、デフロスタグリル、デミスタグリル、アッシュトレイ、フロントパッケージトレイ、オーディオパネル、スイッチパネル、スピーカグリル、コンソールボックス、オーバヘッドコンソール、サンバイザ、ステアリングコラムカバー、アームレスト、フットレスト、アシストグリップ、ドアプルハンドル、スカッフプレート、トリム、ヘッドライニング、サンシェード、コートフック、ラック、グリップレール、ガードバー、パーティションボード、リヤパッケージトレイ、スペアタイヤカバー等の自動車内装品、そのほかの自動車部材、自動車艤装品などの各種用途に有用であるが、上記の中でも特にパソコン、ディスプレー、携帯電話、携帯情報端末などの電気、電子機器、ＯＡ機器の用途で、帯電防止性、制電性を活かした部品、部材、カバーなどに、また優れた電磁波シールド性を活かして筐体など、また、成形性、制電性強度等を活かして、自動車部品、自動車外装品、自動車内装品、自動車艤装品などにも好適に用いることができる。
【００９５】
【実施例】
以下、実施例により本発明をさらに詳細に説明するが、下記実施例は本発明を制限するものではなく、前、後記の主旨を逸脱しない範囲で変更実施することは、全て本発明の技術的範囲に包含される。
【００９６】
まず、本発明の実施例および比較例に用いた成分は以下の通りである。
（参考例１）
ε−カプロラクタム３０重量％と、数平均分子量８００のポリエチレングリコールから得られるビスアミノプロピルポリエチレングリコールとアジピン酸のモル比１の塩７０重量％の割合で容量１リットルの重合缶に仕込み、内部を窒素置換後、２５０℃で１ＭＰａの加圧下、撹拌しながらで２時間重合し反応を完結させた。重合終了後、加熱を停止し、重合缶下部から吐出したポリマーをシート状にし、５ｍｍ角程度にカットした。得られた共重合体の相対粘度は２．５であった。
（参考例２）
前記と同様の方法で、ε−カプロラクタム５重量％と、数平均分子量８００のポリエチレングリコールから得られるビスアミノプロピルポリエチレングリコールとアジピン酸のモル比１の塩９５重量％からなる共重合体を重合した。相対粘度は２．５であった。
成分（Ａ）熱可塑性樹脂樹脂
Ａ−１：ポリアミド６６樹脂
東レ（株）製　アミラン　ＣＭ３００１
Ａ−２：ポリカーボネート樹脂
ＧＥプラスチックス社製　レキサン１４１Ｒ
Ａ−３：ＡＢＳ樹脂
東レ（株）製　トヨラック　Ｔ−１００Ａ
Ａ−４：ポリエーテルイミド樹脂
ＧＥプラスチックス社製　ウルテム１０００
Ａ−５：ポリプロピレン樹脂
三井住友ポリオレフィン（株）製　三井住友ポリプロ　Ｊ８３０ＨＶ
Ａ−６：ポリブチレンテレフタレート樹脂
東レ（株）製　トレコン　１４０１Ｘ０６
Ａ−７：ポリフェニレンスルフィド樹脂
東レ（株）製　トレリナ　Ａ５０４
Ａ−８：変性ポリフェニレン系樹脂
日本ＧＥプラスチックス社製　ノリル　Ｎ３００
Ａ−９：ポリアセタール樹脂
東レ（株）製　アミラス　Ｓ７６１
成分（Ｂ）炭素繊維
Ｂ−１：ＰＡＮ系炭素繊維チョップド糸
ポリアクリロニトリルを主成分とする共重合体から紡糸、焼成処理を行い、総フィラメント数４８、０００本の炭素繊維連続トウを得た。
なお、この連続トウの特性は次の通りであった。
【００９７】
単位長さ当たり質量　　　３．３ｇ／ｍ
比重　　　　　　　　　　１．８
引張強度　　　　　　　　３．０ＧＰａ
引張弾性率　　　　　２２５．０ＧＰａ
電気抵抗　　　　　　　３６．０Ω・ｇ／ｍ^２
Ｏ／Ｃ　　　　　　　　　０．０４
炭素繊維連続トウに、参考例１で調整した共重合体を濃度６重量％の水溶液に調製し、含浸法により付着せしめた後、カートリッジカッターを用いて、炭素繊維を６ｍｍ長にカットし、さらにその後、熱風乾燥機で１９０℃で５分間乾燥してチョップド糸を得た。このとき得られたチョップド糸に付着している共重合体の付着量は４重量％であった。
【００９８】
なお、共重合体およびサイジング剤の付着量の測定は次の手法により行った。共重合体を付着した炭素繊維を約５ｇを採取し、耐熱ガラス製の容器に投入する。次に、この容器を１２０℃で３時間乾燥し、吸湿しないように注意しながら室温まで冷却後、秤量した炭素繊維の重量をＷ_１（ｇ）とする。次いで、容器ごと、窒素雰囲気中、４５０℃で１５分間加熱後、吸湿しないように注意しながら室温まで冷却し、秤量した炭素繊維の重量をＷ_２（ｇ）とする。
【００９９】
以上の処理を経て、共重合体およびサイジング剤の付着量を、次式により求める。
【０１００】
付着量＝１００×（Ｗ_１−Ｗ_２）／Ｗ_２（単位：重量％）
Ｂ−２：ＰＡＮ系炭素繊維チョップド糸
前記炭素繊維連続トウに、サイジング剤としてエポキシ樹脂（商品名Ｅｐ８２８（油化シェル製）および商品名Ｅｐ１００１（油化シェル製）の等量混合品）を炭素繊維連続トウに予め付着させた後に、ウレタン樹脂（１、６−ヘキサメチレンカーボネートジオールとヘキサメチレンジイソシアネートとを重合した自己乳化型ポリウレタン樹脂）を付着せしめた後、チョップド糸とした。サイジング剤の付着量は４重量％であった。
【０１０１】
Ｂ−３：ＰＡＮ系炭素繊維チョップド糸
ＳＧＬカーボン社製　ＳＩＧＲＡＦＩＬ　Ｃ２５−ＰＵＴ
成分（Ｃ）共重合体
Ｃ−１：参考例１で調整した共重合体
Ｃ−２：参考例２で調整した共重合体
成分（Ｄ）導電性付与剤
ファーネスブラック
平均粒径５０μｍ、ＤＢＰ吸収量１３０ｃｍ^３／１００ｇ
成分（Ｅ）難燃剤
燐化学工業（株）製　赤燐
平均粒径３０μｍ、伝導率２００μＳ／ｃｍ
成分（Ｆ）その他の成分
ポリアミド６ホモポリマー
東レ（株）製　アミラン　ＣＭ１０１０
（実施例１〜５、比較例１〜６）
日本製鋼所（株）ＴＥＸ−３０α型２軸押出機（スクリュー直径３０ｍｍ、Ｌ／Ｄ＝３２）を使用し、成分（Ａ）、成分（Ｃ）、成分（Ｄ）および成分（Ｅ）をメインホッパーより供給し、次いでその下流のサイドホッパーから炭素繊維（Ｂ）を供給し、バレル温度２８０℃、回転数１５０ｒｐｍにて十分混練し、さらに下流の真空ベントより脱気を行う。供給は重量フィーダーにより表１、２に示す重量割合となるよう調整する。溶融樹脂をダイス口（φ５ｍｍ）より吐出し、得られたストランドを冷却後、カッターにて切断してペレット状の成形材料とした。
【０１０２】
得られたペレットを熱風乾燥で９０℃×３ｈｒ、さらに真空乾燥で８０℃×６ｈｒの乾燥を行い、水分率０．１％以下になるよう十分乾燥させた後、日本製鋼所（株）製Ｊ３５０ＥＩＩＩ型射出成形機を用いて、シリンダー温度：３００℃、金型温度：７０℃にて特性評価用試験片を成形した。
【０１０３】
得られた試験片は２３℃、５０％ＲＨに調整された恒温恒湿室に２４時間放置後に特性評価試験に供した。また、得られたペレット状の成形材料は真空下で８０℃、１２時間の乾燥を行い、かつデシケーター中で室温、３時間保管した乾燥状態として成形性評価に供した。
【０１０４】
上記実施例と比較例の重量割合と評価結果は後述の表１、２のとおりである。
【０１０５】
（実施例６〜８、比較例７〜１０）
２軸押出機のバレル温度を３００℃、成形における射出成形機のバレル温度を３２０℃とし、前記と同様の方法で成形材料および成形品を製造し、評価に供した。重量割合および評価結果は後述の表３の通りである。
（実施例９〜１０、比較例１１〜１２）
２軸押出機のバレル温度を２５０℃、成形における射出成形機のバレル温度を２６０℃とし、前記と同様の方法で成形材料および成形品を製造し、評価に供した。重量割合と評価結果は後述の表４の通りである。
【０１０６】
（実施例１１、比較例１３）
２軸押出機のバレル温度を３８０℃、成形における射出成形機のバレル温度を３８０℃とし、前記と同様の方法で成形材料および成形品を製造し、評価に供した。重量割合と評価結果は後述の表５の通りである。
【０１０７】
（実施例１２、比較例１４）
２軸押出機のバレル温度を２３０℃、成形における射出成形機のバレル温度を２４０℃とし、前記と同様の方法で成形材料および成形品を製造し、評価に供した。重量割合と評価結果は後述の表５の通りである。
【０１０８】
（実施例１３、比較例１５）
２軸押出機のバレル温度を２５０℃、成形における射出成形機のバレル温度を２６０℃とし、前記と同様の方法で成形材料および成形品を製造し、評価に供した。重量割合と評価結果は後述の表５の通りである。
【０１０９】
（実施例１４、比較例１６）
２軸押出機のバレル温度を３２０℃、成形における射出成形機のバレル温度を３３０℃とし、前記と同様の方法で成形材料および成形品を製造し、評価に供した。重量割合と評価結果は後述の表５の通りである。　（実施例１５、比較例１７）
２軸押出機のバレル温度を２７０℃、成形における射出成形機のバレル温度を２８０℃とし、前記と同様の方法で成形材料および成形品を製造し、評価に供した。重量割合と評価結果は後述の表５の通りである。
【０１１０】
（実施例１６、比較例１８）
２軸押出機のバレル温度を２１０℃、成形における射出成形機のバレル温度を２２０℃とし、前記と同様の方法で成形材料および成形品を製造し、評価に供した。重量割合と評価結果は後述の表５の通りである。
【０１１１】
（実施例１７、比較例１９）
日本製鋼所（株）ＴＥＸ−３０α型２軸押出機（スクリュー直径３０ｍｍ、Ｌ／Ｄ＝３２）を使用し、成分（Ａ）、成分（Ｃ）をメインホッパーより供給し、次いでその下流のサイドホッパーから炭素繊維（Ｂ）を供給し、バレル温度２３０℃、回転数１５０ｒｐｍにて十分混練し、さらに下流の真空ベントより脱気を行う。供給は重量フィーダーにより表６に示す重量割合となるよう調整する。溶融樹脂をダイス口（縦５ｍｍ、横幅１００ｍｍ）より吐出し、得られたシートを冷却後、カッターにて３００ｍｍに切断して長さ３００ｍｍ、幅１００ｍｍ、厚み５ｍｍシート状の成形材料とした。
【０１１２】
得られたシートを熱風乾燥で９０℃×３ｈｒ、さらに真空乾燥で８０℃×６ｈｒの乾燥を行い、水分率０．１％以下になるよう十分乾燥させた後、熱プレス機を用いて、上部熱版温度：２３０℃、下部熱版温度：２３０℃、成形圧力１．０ＭＰａ、成形時間１０ｍｉｎにて特性評価用成形品を作成した。これを（株）三栄鉄工所製、型式Ｄ−５１型ダイヤモンドカッターを用い、長さ８０ｍｍ、幅１０ｍｍ、厚み４．０ｍｍの曲げ試験片を作成した。
【０１１３】
得られた試験片は２３℃、５０％ＲＨに調整された恒温恒湿室に２４時間放置後に特性評価試験に供した。評価結果は表６にまとめて示す。
【０１１４】
次に、成形材料および成形品の特性評価方法について以下に示す。
（１）成形品の導電性（表面抵抗率）
試験片は、長さ８０ｍｍ×幅８０ｍｍ×厚さ３ｍｍの板状成形品に、導電性ペースト（藤倉化成（株）製ドータイト）を図１のように塗布し、ＡＢ間、ＡＣ間、ＢＤ間、ＣＤ間の抵抗を測定し、その４種の測定値の平均値をもって表面抵抗率（単位はＬｏｇΩ／ｃｍ^２）として求めた。測定には、アドバンテスト社製デジタルマルチメーターＲ６５８１を用いた。表面抵抗率の値の小さい方が導電性に優れる。
【０１１５】
（２）繊維強化樹脂組成物の成形性
ＡＳＴＭ　１２３８−９５に従い、成形材料の流動性（ＭＦＲ）を求めた。測定は、東洋精機製作所製メルトインデクサーを用い、実施例１〜５、比較例１〜６については測定温度２８０℃、荷重１０００ｇ、滞留６分で行った。また、実施例６〜８、比較例７〜１０については測定温度３００℃、荷重１０００ｇ、滞留６分で行った。さらに、実施例９〜１０、比較例１１〜１２については測定温度２５０℃、荷重２１６０ｇ、滞留６分で行った。実施例１１、比較例１３については測定温度３６０℃、荷重１０００ｇ、滞留６分で行った。実施例１２、１７、比較例１４，１９については測定温度２３０℃、荷重１０００ｇ、滞留６分で行った。実施例１３、比較例１５については測定温度２５０℃、荷重１０００ｇ、滞留６分で行った。実施例１４、比較例１６については測定温度３３０℃、荷重１０００ｇ、滞留６分で行った。実施例１５，比較例１７については測定温度２８０℃、荷重１０００ｇ、滞留６分で行った。実施例１６，比較例１８については測定温度１９０℃、荷重１０００ｇ、滞留６分で行った。ＭＦＲの値の大きい方が成形性に優れることを意味する。
【０１１６】
（３）成形品の力学特性
ＡＳＴＭ　Ｄ７９０規格に従い、曲げ試験を行った。用いた試験片の厚みは６．４ｍｍで、試験片の水分率０．１％以下、雰囲気温度２３℃、湿度５０重量％において曲げ弾性率（ＧＰａ）、曲げ強度（ＭＰａ）を求めた。
【０１１７】
また、実施例１７，比較例１９については、ＪＩＳ　Ｋ７０１７（繊維強化プラスチック　曲げ特性の求め方）規格に従い、曲げ試験を行った。用いた試験片の厚みは４．０ｍｍで、試験片の水分率０．１％以下、雰囲気温度２３℃、湿度５０重量％において曲げ弾性率（ＧＰａ）、曲げ強度（ＭＰａ）を求めた。
【０１１８】
（４）Ｉｚｏｄ衝撃強度
ＡＳＴＭ　Ｄ２５６規格に従い、モールドノッチ付きアイゾット衝撃試験を行った。用いた試験片の厚みは３．２ｍｍで、試験片の水分率０．１％以下、雰囲気温度２３℃、湿度５０重量％においてＩｚｏｄ衝撃強度（Ｊ／ｍ）を求めた。
【０１１９】
（５）難燃性
ＵＬ−９４規格に基づいた難燃性試験にて評価した。難燃性レベルはＶ−０＞Ｖ−１＞Ｖ−２＞ＨＢの順に低下する。用いた試験片の厚みは１．６ｍｍである。
【０１２０】
最後に、以上に述べた各実施と各比較例において、上記評価項目の導電性、力学的特性、成形性、経済性を導電性、成形性、力学的特性、経済性の順に重み付けて評価し、また、これら特性のバランスなども考慮して総合判断することにし、その判断結果を、○○○：特に優れる、○○：より優れる、○：優れる、△：劣る、×：特に劣るとした。
【０１２１】
各実施例と比較例において得られた各特性と総合評価を次の表１〜６に纏めて記載した。
【０１２２】
【表１】

【０１２３】
【表２】

【０１２４】
【表３】

【０１２５】
【表４】

【０１２６】
【表５】

【０１２７】
【表６】

【０１２８】
すなわち、表１の実施例及び比較例より以下のことが明らかである。
【０１２９】
実施例１の第１発明からなる組成物は、比較例１に対し導電性と成形性に優れている。また、実施例２の第２発明からなる組成物も同様に、高い機械特性および難燃性を満足し、比較例２に対し導電性と成形性に優れている。これらの実施例は電磁波シールド性レベルの導電性、高い機械特性および難燃性を満足することから、電気・電子機器の筐体などの用途に有用である。
【０１３０】
表２の実施例及び比較例より以下のことが明らかである。
【０１３１】
実施例３，４の第１発明からなる組成物は、比較例３，４に対しそれぞれ導電性と成形性に優れていることから、より少ない炭素繊維の量で目的とする導電性が得られることから、成形性、経済性、導電性の最高到達点の観点からも有利である。また、炭素繊維の添加量を本発明の範囲以上に高めた比較例５では、コンパウンドが不可能であった。また、実施例５の第２発明からなる組成物も同様に、比較例６に対し導電性と成形性に優れている。
【０１３２】
表３の実施例及び比較例より以下のことが明らかである。
【０１３３】
実施例６の第１発明からなる組成物は、比較例７に対し導電性と成形性に優れており、上記実施例と同様の効果が再現された。また、実施例７〜８の第２発明からなる組成物も同様に、比較例８に対し導電性と成形性に優れている。特に、実施例８では、共重合体（Ｃ）の組成割合をより好ましい範囲とすることで、より優れた導電性、成形性の向上効果が得られた。また、共重合体の添加量を本発明の範囲以上に増量した比較例９では、樹脂組成物が発泡するなど、良好な生産性と特性が得られなかった。さらに、比較例１０のように共重合体のかわりに、ポリアミド６ホモポリマーを添加しても導電性、力学特性とも大きな向上効果は認められない。
【０１３４】
表４の実施例及び比較例より以下のことが明らかである。
【０１３５】
実施例９の第１発明からなる組成物は、比較例１１に対し導電性と成形性に優れており、さらには、実施例１０の本第２発明からなる組成物も同様に、比較例１１に対し導電性と成形性に優れていることから、導電性を必要とする用途に有用である。
【０１３６】
表５の実施例及び比較例より以下のことが明らかである。
【０１３７】
実施例１１の組成物は、比較例１３に対し、また、実施例１２の組成物は比較例１４に対し、また、実施例１３の組成物は、比較例１５に対し、また、実施例１４の組成物は比較例１６に対し、また、実施例１５の組成物は比較例１７に対し、また、実施例１６の組成物は比較例１８に対し導電性と成形性に優れており、導電性を必要とする用途に有用である。
【０１３８】
表６の実施例及び比較例より以下のことが明らかである。
【０１３９】
実施例１７の組成物は、比較例１９に対し導電性と成形性に優れており導電性を必要とする用途に有用である。
【０１４０】
【発明の効果】
本発明の炭素繊維強化熱可塑性樹脂組成物、成形材料および成形品は、高い機械特性だけでなく、導電性、成形性に優れたものであり、特に電気・電子機器、ＯＡ機器、家電機器、自動車用途の各種部品または筐体等の一般産業分野に極めて好適である。
【図面の簡単な説明】
【図１】本発明の樹脂組成物からなる成形物の表面抵抗率を測定するための試験片の平面図である。
【符号の説明】
１：導電性ペースト塗布範囲Ａ
２：導電性ペースト塗布範囲Ｂ
３：導電性ペースト塗布範囲Ｃ
４：導電性ペースト塗布範囲Ｄ[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an improvement of a thermoplastic resin composition reinforced with carbon fibers, and further relates to a molding material comprising the thermoplastic resin composition and a molded article obtained by molding the molding material. More specifically, the present invention relates to a thermoplastic resin composition having not only high mechanical properties but also excellent conductivity and moldability.
[0002]
[Prior art]
Since the carbon fiber reinforced thermoplastic resin composition is excellent in strength, rigidity, dimensional stability, conductivity, etc., it can be used for parts and housings of electric / electronic devices such as personal computers, OA devices, AV devices, mobile phones, and the like. It is used in a wide range of fields such as optical equipment, precision machinery, automobiles, aircraft, entertainment and toys, and home and office electrical products, and the demand is increasing year by year.
[0003]
2. Description of the Related Art In recent years, with the development of the field of electric and electronic devices such as computers and portable information terminals, components, housings, internal members, and the like have been required to have higher electromagnetic wave shielding properties and antistatic properties than ever before. In order to enhance the electromagnetic wave shielding property and the antistatic property, it is necessary to sufficiently increase the conductivity of the molded article.
[0004]
In the above-mentioned applications, a thermoplastic resin is used from the viewpoint of designability, lightness, moldability and productivity, and particularly, a polycarbonate resin and a styrene-based resin are polyamide resin, polyester resin, Polyphenylene sulfide resin, polyolefin resin, modified polyphenylene ether resin, polyacetal resin and polyetherimide resin are suitably used in terms of excellent mechanical properties, chemical resistance, heat resistance and the like.
[0005]
However, since the thermoplastic resin represented by the above does not conduct electricity by nature, it is necessary to add a large amount of carbon fiber in order to increase the conductivity of a molded product. Here, increasing the amount of carbon fiber not only impairs lightness and economy, but also often leads to an increase in viscosity during the process, making melt-kneading and molding difficult, and often deteriorating surface appearance characteristics. Therefore, there is a need for a technique for increasing conductivity without increasing the amount of carbon fibers and at the same time improving moldability.
[0006]
Therefore, as means for improving conductivity without increasing the amount of carbon fiber, use of carbon fiber having polyvinylpyrrolidone attached thereto in Patent Document 1 and use of Elbamide (trade name, manufactured by DuPont) in Patent Documents 2 and 3 are described. There is disclosed a carbon fiber reinforced resin composition having excellent conductivity composed of carbon fiber to which a representative terpolymer polyamide is attached as a sizing agent and a thermoplastic resin such as a polycarbonate resin. Patent Document 4 discloses a resin composition comprising an antistatic agent represented by a polyamide block copolymer, a polycarbonate resin, and carbon fibers.
[0007]
However, the effect of improving these conductivity is not sufficient, and it is necessary to add a larger amount of carbon fiber to achieve the desired conductivity, and the economy, lightness, moldability, and surface appearance of the molded product are reduced. In some cases, the intrinsic properties of the resin composition such as quality are impaired.
[0008]
Furthermore, for example, as described in Non-Patent Document 1, such a terpolymer is not water-soluble and is soluble only in an organic solvent such as chloroform. The method of attachment involves using a large amount of an organic solvent such as chloroform as a solvent in the coating step, and it is extremely difficult to implement industrially from the viewpoint of productivity, economic efficiency, and environmental load. .
[0009]
[Patent Document 1] JP-A-57-56586
[0010]
[Patent Document 2] US Pat. No. 6,231,788
[0011]
[Patent Document 3] US Pat. No. 6,248,262
[0012]
[Patent Document 4] JP-A-2001-72850
[0013]
[Non-patent document 1] Catalog issued by DuPont Japan (model: S1018-7-892C @ TY)
[0014]
[Problems to be solved by the invention]
In view of the background of the prior art, the present invention has a high mechanical property, a thermoplastic resin composition reinforced with carbon fibers excellent in conductivity and moldability, a molding material comprising the thermoplastic resin composition, And a molded article obtained by molding the molding material.
[0015]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to achieve the above object. As a result, the present inventors have found that compounding a carbon fiber with a specific component attached thereto (first invention) or mixing a specific component simultaneously with the carbon fiber (first example) 2) can solve the problem of the present invention.
[0016]
That is, the first invention of the present invention is a carbon fiber reinforced thermoplastic resin composition comprising at least the following components (A) and (B).
[0017]
Component (A): at least one thermoplastic resin selected from the group consisting of polycarbonate resin, styrene resin, polyamide resin, polyester resin, polyphenylene sulfide resin, modified polyphenylene ether resin, polyetherimide resin, polyolefin resin and polyacetal resin. 25-99% by weight
Component (B): at least 55 to 99% by weight of a salt of a diamine and a dicarboxylic acid having an oxyalkylene group as the component (c1), and amino acids, lactams and / or salts 1 to 45 of a diamine and a dicarboxylic acid as the component (c2). 1 to 75% by weight of carbon fiber in which a copolymer containing 0.1% to 5% by weight is attached to 100% by weight of carbon fiber
A second invention of the present invention is a carbon fiber-reinforced thermoplastic resin composition comprising at least the following components (A) to (C).
[0018]
Component (A): at least one thermoplastic resin selected from the group consisting of polycarbonate resin, styrene resin, polyamide resin, polyester resin, polyphenylene sulfide resin, modified polyphenylene ether resin, polyetherimide resin, polyolefin resin and polyacetal resin. 25-99% by weight
Component (B): 1 to 75% by weight of carbon fiber
Component (C): at least 55 to 99% by weight of a salt of a diamine and a dicarboxylic acid having an oxyalkylene group as the component (c1); and {1 to 45% of a salt of an amino acid, lactam and / or a diamine and a dicarboxylic acid as the component (c2)]. % By weight of the copolymer is 0.01 to 10% by weight based on 100% by weight of the carbon fiber reinforced thermoplastic resin composition.
Further, another invention of the present invention is a molding material and a molded article comprising the above-mentioned carbon fiber reinforced thermoplastic resin composition.
[0019]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described specifically.
[0020]
As the thermoplastic resin of the component (A) in the present invention, polycarbonate resin, styrene resin, polyamide resin, polyester resin, polyphenylene sulfide resin (PPS resin), modified polyphenylene ether resin (modified PPE resin), polyacetal resin (POM resin) ) It is at least one selected from polyolefin resins such as polyetherimide resin (PEI resin), polypropylene resin (PP resin), and polyethylene resin (PE resin).
[0021]
As the polycarbonate resin, an aromatic polycarbonate, an aliphatic polycarbonate, an alicyclic polycarbonate, and an aromatic-aliphatic polycarbonate can be used. Among them, an aromatic polycarbonate is preferably used.
[0022]
The aromatic polycarbonate resin is a polymer or a copolymer obtained by reacting an aromatic hydroxy compound or a small amount thereof with a carbonate precursor. The method for producing the aromatic polycarbonate resin is not particularly limited, and it can be produced by a generally known phosgene method or a transesterification method.
[0023]
Examples of the aromatic hydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis (4-hydroxyphenyl) methane, and 1,1-bis (4-hydroxyphenyl) Ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) ) Propane, 2,2-bis (hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, hydroquinone, resorcinol, 4,6-dimethyl-2,4, 6-tri (4-hydroxyphenyl) heptene, 2,4,6-dimethyl-2,4,6-tri 4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene, 1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyaryl) oxindole, 5-chloro-3,3-bis (4-hydroxyaryl) oxindole, 5,7-dichloro-3,3- Bis (4-hydroxyaryl) oxindole, 5-bromo-3,3-bis (4-hydroxyaryl) oxindole and the like may be mentioned, and these may be used alone or in combination of two or more. Among them, bis (4-hydroxyphenyl) alkane is preferably used, and bisphenol A is particularly preferred. Further, for the purpose of imparting flame retardancy, a compound in which at least one tetraalkylphosphonium sulfonate is bonded to the aromatic dihydroxy compound and / or a phenolic hydroxyl group-containing polymer or oligomer having a siloxane structure is used. Good
As the carbonate precursor, carbonyl halide, carbonate ester or haloformate is used, and specific examples include phosgene and diphenyl carbonate.
[0024]
The molecular weight of the polycarbonate resin is preferably 14,000 to 30,000, more preferably 15,000 to 28,000, and more preferably 16,000 to 26,000 in terms of viscosity average molecular weight from the viewpoint of moldability and mechanical properties of the obtained molded article. 000 is particularly preferred. Here, the viscosity average molecular weight is a value obtained by using a solution obtained by sufficiently dissolving 0.7 g of a carbonate resin in 100 ml of methylene chloride and converting from a solution viscosity measured at a temperature of 25 ° C.
[0025]
The styrene resin used in the present invention is a polymer containing an aromatic vinyl monomer as a main component. Specific examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene, o-ethylstyrene, o-chlorostyrene and o, p-methylstyrene. Examples thereof include dichlorostyrene, and styrene and α-methylstyrene are particularly preferably used, and these may be used alone or in combination of two or more.
[0026]
Further, for the purpose of imparting properties such as chemical resistance and heat resistance to the styrene resin, another vinyl monomer copolymerizable with the aromatic vinyl monomer may be copolymerized. Specific examples of these other copolymerizable vinyl monomers include acrylonitrile, methacrylonitrile, ethacrylonitrile, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, ( N-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, chloromethyl (meth) acrylate, glycidyl (meth) acrylate, Examples include maleic anhydride, itaconic anhydride, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide, and acrylonitrile is particularly preferably used.
[0027]
The molecular weight of the styrene resin is preferably in the range of 50,000 to 300,000 in terms of styrene in terms of weight average molecular weight, from the viewpoint of moldability and mechanical properties of the obtained molded article,
80,000 to 200,000 is particularly preferred. The weight average molecular weight mentioned here can be measured by a generally known technique using gel permeation chromatography.
[0028]
Further, for the purpose of improving the impact resistance of the styrene-based resin, a rubber-modified styrene-based resin in which rubbery polymer particles are dispersed in a styrene-based resin may be used. Here, as the rubbery polymer used, polybutadiene rubber, styrene-butadiene copolymer, hydrogenated styrene-butadiene rubber, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer and isoprene rubber are used. Among them, polybutadiene and styrene-butadiene copolymer are preferable. However, since these rubbery polymers and styrene-based resins are inherently incompatible, impact resistance can be further improved by grafting a component compatible with the matrix to the rubbery polymer. The composition of the graft component, the amount of the graft, and the like are not particularly limited, but are preferably adjusted so as not to impair the dispersibility of the rubbery polymer.
[0029]
Specific examples of the styrene resin include polystyrene, high impact polystyrene, styrene / acrylonitrile copolymer resin (AS resin), modified AS resin, acrylonitrile / acrylic rubber / styrene copolymer resin (AAS resin), and acrylonitrile / Examples include an ethylene propylene rubber / styrene copolymer resin (AES resin) and an ABS resin. Among them, an AS resin and an ABS resin are preferably used. The method for producing the styrene resin is not particularly limited, and the styrene resin can be produced by a conventionally known method. A method for grafting an aromatic vinyl monomer and another monomer copolymerizable therewith to the rubbery polymer can also be produced by a conventionally known method.
[0030]
The polyamide resin used in the present invention is a polymer containing amino acids, lactams or diamines and dicarboxylic acids as main components. Specific examples thereof include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, p-aminomethylbenzoic acid, lactams such as ε-caprolactam, ω-laurolactam, tetramethylenediamine, hexamethylene Methylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylene Diamine, meta-xylylenediamine, para-xylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethyl Cyclohexane, Aliphatics such as bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine and aminoethylpiperazine; Alicyclic, aromatic diamines and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, Aliphatic, alicyclic and aromatic dicarboxylic acids such as 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid and hexahydroisophthalic acid, and derived from these raw materials Homopolymers or copolymers can be used.
[0031]
Among them, specific examples of useful polyamide resins include polycaproamide, polyhexamethylene adipamide, polytetramethylene adipamide, polyhexamethylene sebacamide, polyhexamethylene dodecamide, polyundecaneamide, polydodecanamide, Polycaproamide / polyhexamethylene terephthalamide copolymer, polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer, polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer, polyhexamethylene adipamide / polyhexamethylene isophthalate Amide / polycaproamide copolymer, polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer, polyhexamethylene terephthalamide / polydodecane Copolymer, polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer, polyxylylene adipamide, polyhexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide copolymer and mixtures thereof Is mentioned.
[0032]
Although the molecular weight of these polyamide resins is not particularly limited, a preferable standard is a relative viscosity of 1.5 to 5.0 measured at 25 ° C. in a 1% concentrated sulfuric acid solution. Is in the range of 2.0 to 4.0.
[0033]
The polyester resin used in the present invention comprises at least one acid component substantially selected from terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, etc., and ethylene glycol, propylene glycol, butylene glycol, and hexylene. Glycol or polyethylene glycol, which is obtained by polycondensation with at least one diol component selected from polyalkylene glycols such as polytetramethylene glycol, and specifically, polybutylene terephthalate, polypropylene terephthalate, polyethylene terephthalate, In addition to polyhexylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycyclohexane-1,4-dimethylol terephthalate, etc., polyethylene isophthalate / Isophthalate, etc. copolyesters such as polybutylene isophthalate / isophthalate and the like.
[0034]
Furthermore, these polyesters further include other third components such as adipic acid, sebacic acid, dodecandionic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, dimer acid, phthalic acid, 4,4′-diphenylcarboxylic acid, Copolymerize sulfoisophthalic acid, hexahydroterephthalic acid, cyclohexanedicarboxylic acid, ethylene oxide adduct of bisphenol A, cyclohexanedimethanol, cyclohexanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, etc. be able to.
[0035]
Although the molecular weight of these polyester resins is not particularly limited, as a preferable standard, the relative viscosity measured at 25 ° C. in a 0.5% orthochlorophenol solution is in the range of 1.0 to 2.0. A preferable standard is in the range of 1.2 to 1.8.
[0036]
The polyphenylene sulfide resin used in the present invention is a polymer containing at least 70 mol%, more preferably at least 90 mol% of a structural unit represented by the following structural formula.
[0037]
Embedded image

[0038]
Further, less than 30 mol% of the structural unit can be constituted by the structural unit represented by the following structural formula.
[0039]
Embedded image

[0040]
The melt viscosity of these PPS resins is not particularly limited as long as melt kneading is possible, but is preferably in the range of 10 to 50,000 poise (300 ° C., shear rate 1,000 / sec), and particularly preferably. 10 to 5,000 poise.
[0041]
The modified polyphenylene ether resin used in the present invention has the following structural formula (R₁Is charcoal
A lower alkyl group having a prime number of 1 to 3, R₂, R₃Is a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms) in the main chain, and any of a homopolymer, a copolymer or a graft polymer may be used.
[0042]
Embedded image

[0043]
Specifically, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ) Ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether and the like, among which poly (2,6-dimethyl-1,4-phenylene) ether, 2,6-dimethylphenol, , 3,6-trimethylphenol copolymers and graft polymers obtained by grafting styrene onto them are preferred.
[0044]
The method for modifying the polyphenylene ether resin is not particularly limited, and it can be performed by a generally known method of melt-kneading the polyphenylene ether resin and the unsaturated aliphatic carboxylic acid or an acid anhydride thereof.
[0045]
The polyacetal resin used in the present invention is a polymer having an oxymethylene unit as a main repeating unit. Even a so-called polyacetal homopolymer composed of only an oxymethylene unit is mainly composed of an oxymethylene unit and has a main chain of 2%. Any so-called polyacetal copolymer containing 15% by weight or less of oxyalkylene units having from 8 to 8 adjacent carbon atoms may be used, and one or more of these may be used.
[0046]
The method for producing the polyacetal resin is not particularly limited.For example, high-purity formaldehyde is introduced into an organic solvent containing a basic polymerization catalyst such as an organic amine, an organic or inorganic tin compound, or a metal hydroxide, and is polymerized. Then, after the polymer is filtered off, a known method can be exemplified in which the polymer is heated in acetic anhydride in the presence of sodium acetate to acetylate the polymer terminal.
[0047]
The polyetherimide resin used in the present invention is 2.2.3.3. -Removal of water in the presence of an organic solvent from a tetracarboxydiphenylene ether dianhydride and a diamine represented by the general formula H2NRNH2 (R is an aromatic hydrocarbon having 6 to 20 carbon atoms and a halogenated derivative) And a synthesis by a reaction between an aromatic bis ether ether foreign substance and an organic diamine under an interface condition between water and an organic solvent.
[0048]
Polyolefin-based resin used in the present invention is not particularly limited, isotactic homopolypropylene, random polypropylene composed of propylene and α-olefin other than propylene such as ethylene and 1-butene, block polypropylene, syndiotactic Crystalline polypropylene resins such as polypropylene, crystalline polyethylene resins such as high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ultra-high-molecular-weight polyethylene Examples thereof include resins, crystalline polymers mainly composed of α-olefin having more than 3 carbon atoms such as polybutene-1 and poly-4-methylpentene-1 and the like, and mixtures thereof. Among these crystalline polyolefin -based resins, a crystalline polypropylene-based resin is most preferably used from the viewpoint of economy and moldability.
[0049]
A modified / crystalline polyolefin resin obtained by grafting a modifier such as an unsaturated carboxylic acid or a derivative thereof, an unsaturated epoxy compound, or an unsaturated imide compound to the polyolefin resin is also preferably used. Examples of the method for modifying the crystalline polyolefin -based resin include a melt-kneading method, a solution method, and a slurry method, which can be preferably performed by any of the methods. In the case of the melt-kneading method, the modifying agent (unsaturated carboxylic acid compound or its derivative, unsaturated epoxy compound, unsaturated imide compound) used for the modification and a radical polymerization catalyst are used together, and an extruder is used. , 150-350 ° C. and melting and kneading. On the other hand, in the case of a solution method or a slurry method, a crystalline polyolefin-based resin, a modifying agent, and a radical polymerization catalyst are dissolved in an organic solvent such as xylene, or a slurry state is formed, and the mixture is stirred at a temperature of 80 to 350 ° C. It may be modified. The amount of the modifier to be blended is preferably 0.01 to 10% by weight based on 100 parts by weight of the crystalline polyolefin resin.
[0050]
Examples of the unsaturated carboxylic acid compound as the modifier include acrylic acid, α-ethylacrylic acid, methacrylic acid, maleic acid, fumaric acid, halogenated maleic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, halogenated Citraconic acid, crotonic acid, halogenated crotonic acid, itaconic acid, halogenated itaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-bicyclo- (2,2,1) -5-heptene-2, 3, dicarboxylic acid, methyl-endo-cis-bicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic acid, endo-bicyclo- (2,2,1) -1,2,2,2 Examples thereof include 2,7,7-hexachloro-2-heptene-5,6-dicarboxylic acid and the like, and mixtures thereof.
[0051]
Derivatives of unsaturated carboxylic acid compounds include acid halides, anhydrides, esters, amides, imides, metal salts and the like of the unsaturated carboxylic acid compounds, such as maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, Monomethyl maleate, dimethyl maleate, glycidyl maleate and the like, or a mixture thereof can be mentioned. Among them, preferred are maleic anhydride and nadic anhydride.
[0052]
Examples of the unsaturated epoxy compound include glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, diglycidyl itaconate, monoglycidyl butenetricarboxylate, diglycidyl butenetricarboxylate, triglycidyl butenetricarboxylate, p-styrenecarboxylate Acid glycidyl ester, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene / p / glycidyl ether, p / glycidyl styrene, 3,4 / epoxy / 1 / butene, 3,4 / epoxy / 3 / methyl / 1 / butene , 3,4 epoxy 1 pentene, 3,4 epoxy 3 methyl 1 pentene, 5,6 epoxy 1 hexene and vinylcyclohexene monoxide, etc. It can be mixtures thereof.
[0053]
Examples of unsaturated imide compounds include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-octylmaleimide, N-phenylmaleimide, N- (o-methylphenyl) maleimide, N. (m.methylphenyl) maleimide, N. (p.methylphenyl) maleimide, N. (methoxyphenyl) maleimide, N. (chlorophenyl) maleimide, N. (carboxyphenyl) maleimide, N.benzylmaleimide, N -Naphthylmaleimide, N-cyclohexylmaleimide, itaconimide, N-methylitaconimide, N-phenylitaconimide and the like. Among them, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, and N- (carboxyphenyl) maleimide are preferably used. These unsaturated carboxylic acids or derivatives thereof, unsaturated epoxy compounds or unsaturated imide compounds may be used alone or in combination of two or more.
[0054]
Examples of the radical polymerization catalyst include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3,1,4. Bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperacetate, 2,5, dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5. Di (tert-butylperoxy) hexane, tert-butylperbenzoate, tert-butylperphenylacetate, tert-butylperisobutyrate, tert-butylpersec-octoate, tert-butylperpivalate, cumyl Rupibareto, tert · butyl peroxide diethyl acetate, azobisisobutyronitrile, dimethyl azoisobutyrate, etc., or can be mixtures thereof. Among them, preferred are dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di ( Examples thereof include dialkyl peroxides such as tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene.
[0055]
The modified / crystalline polyolefin-based resin obtained by the above method is not particularly limited, but has an MFR (230 ° C. for a polypropylene-based resin, 190 ° C. for a polyethylene-based resin) of about 0.01 to 1000 g / 10 min, preferably Those having a concentration of 0.1 to 100 g / 10 minutes are preferable from the viewpoint of moldability.
[0056]
As the thermoplastic resin of the component (A), for example, when priority is given to dimensional stability, design, economy, productivity, and appearance quality of a molded product, a polycarbonate resin, a styrene resin, a polyolefin resin, or the like is preferably selected. When the mechanical properties, heat resistance, chemical resistance, and fluidity are prioritized, polyamide resins, polyester resins, polyphenylene sulfide resins and modified polyphenylene ether resins, polyacetal resins, and polyetherimide resins are preferably selected. However, the present invention is not limited to these, and one or two or more of them can be used as appropriate. Further, a thermoplastic resin may be melt-kneaded in advance and used as a polymer alloy.
[0057]
The carbon fiber of the component (B) in the present invention means a fibrous material having a carbon content in the range of 85 to 100% by weight and having a graphite structure at least partially. Specific examples of such a fibrous material include polyacrylonitrile-based carbon fiber, rayon-based carbon fiber, lignin-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, and carbon nanotube. Among them, polyacrylonitrile-based carbon fibers are preferably used because they satisfy the good mechanical properties and conductivity of the molded product and can realize low cost. Among them, those having a tensile strength of 3 GPa or more and a tensile modulus of 350 GPa or less are preferably used from the viewpoint of balance between mechanical properties, handleability, and economy. Here, the "tensile strength of carbon fiber" and "tensile elastic modulus of carbon fiber" are the strength and elastic modulus measured by a resin-impregnated strand method based on JIS R # 7601.
[0058]
From the viewpoint of increasing the conductivity of the obtained carbon fiber reinforced thermoplastic resin composition, the electric resistance of the carbon fiber is 40 Ω · g / m.²Less than 38 Ω · g / m²Is more preferably less than 37 Ω · g / m²More preferably, it is less than. "Electric resistance of carbon fiber" refers to the electric resistance per length measured by a two-wire measuring method in which measuring terminals are connected to both ends of a 1-m long carbon fiber, and the weight per carbon fiber of the same length. In this case, it may be measured in the form of a fiber bundle obtained by a normal manufacturing method, and in this case, similarly, the obtained electrical resistance value per length is equal to the length of the fiber bundle. Multiply by the weight per unit.
[0059]
Similarly, preferred carbon fibers have a crystal size (Lc) of 1 to 6 nm, more preferably 1.3 to 4.5 nm, particularly preferably 1.6 to 3.6 nm, as measured by wide-angle X-ray diffraction. Within range. When Lc is 1 nm or more, carbonization or graphitization of the carbon fiber is sufficient, and the conductivity and elastic modulus of the carbon fiber itself become good. The resin composition using such carbon fibers and the molded article made therefrom can be expected not only to improve conductivity, but also to improve mechanical properties, especially rigidity. On the other hand, when Lc is within 6 nm, excessive carbonization or graphitization of the carbon fiber is suppressed, and the conductivity of the carbon fiber itself is excellent, and breakage of the carbon fiber can be expected. Therefore, the fiber length in the resin composition becomes longer, and not only excellent electrical properties can be obtained, but also particularly high mechanical strength can be expected among the mechanical properties. Here, the measurement of Lc by the wide-angle X-ray diffraction method can be measured based on the method described in 117th Committee of the Japan Society for the Promotion of Science, Carbon, 36, p25 (1963).
[0060]
Further, the surface oxygen concentration (O / C), which is the ratio of the number of atoms of oxygen (O) and carbon (C) on the surface of the carbon fiber measured by X-ray photoelectron spectroscopy of the carbon fiber, is preferably 0.03. It is in the range of 0.08, more preferably in the range of 0.04 to 0.07. When the surface oxygen concentration (O / C) is in the range of 0.03 to 0.08, the conductive property which is the object of the present invention can be obtained without significantly impairing the mechanical properties of the obtained carbon fiber reinforced thermoplastic resin composition. Efficiency can be efficiently improved.
[0061]
There is no particular limitation on the shape of the carbon fiber, and roving that is a continuous fiber, chopped yarn cut to a predetermined length, and milled yarn can be used. In the step of mixing (compounding) the thermoplastic resin and the carbon fiber, In general, chopped yarn is preferably used from the viewpoints of convenience and handleability. The fiber length of the chopped yarn is not particularly limited, but the sizing agent exerts sufficient convergence and can maintain the shape after being cut, a compound, and easily formed. The fibers are dispersed in the resin, or maintain a certain fiber length even when subjected to strong shearing force, and as a result, the conductivity of the molded article, and the point that the mechanical properties can be sufficiently satisfied, It is preferably within a range of 26 mm, more preferably within a range of 2 to 15 mm.
[0062]
Further, from the viewpoint of the productivity of the carbon fiber-reinforced thermoplastic resin composition and the handleability of the carbon fiber, the carbon fiber is preferably in the range of 15,000 to 100,000, more preferably 40,000 to 80,000. It is bundled within the range.
[0063]
In the carbon fiber reinforced thermoplastic resin composition of the present invention, the thermoplastic resin of the component (A) is 25 to 99% by weight, preferably 35 to 97% by weight, more preferably 50 to 95% in both the first and second inventions. %, And the carbon fiber of the component (B) is comprised in the range of 1 to 75% by weight, preferably 3 to 65% by weight, more preferably 5 to 50% by weight. If the component (B) is less than 1% by weight, the conductivity may be insufficient, and if it exceeds 75% by weight, the moldability may be poor.
[0064]
Here, the feature of the carbon fiber-reinforced thermoplastic resin composition of the first invention is that at least the oxyalkylene of the component (c1) is added to the carbon fiber of the component (B) as a sizing agent for the purpose of improving conductivity and moldability. A copolymer (c) consisting of 55 to 99% by weight of a salt of a diamine having a group and a dicarboxylic acid and 1 to 45% by weight of a salt of an amino acid, a lactam and / or a diamine and a dicarboxylic acid as the component (c2) is adhered. In this case, carbon fibers are used.
[0065]
The adhesion amount of the copolymer (c) is in the range of 0.1 to 5% by weight, preferably in the range of 1 to 4% by weight, based on 100% by weight of the carbon fiber. If the amount is less than 0.1% by weight, the effect of improving conductivity may be insufficient. If the amount is more than 5% by weight, the fiber bundle of carbon fibers becomes hard, and the productivity is increased before kneading with the thermoplastic resin. In some cases, the economy may be impaired.
[0066]
The method for adhering the copolymer (c) is not particularly limited. For example, after the copolymer is made into a solution and the carbon fiber is immersed or the solution is dropped and sprayed on the carbon fiber, the solvent is dried and removed. A method can be exemplified.
[0067]
As the carbon fiber, one or two or more types of commonly known sizing agents such as epoxy resin, urethane resin, acrylic resin and various thermoplastic resins may be used in addition to the copolymer (c) as long as the object of the present invention is not impaired. More than one species may be used in combination. For example, after the copolymer (c) is adhered, a method of further adhering a generally known sizing agent, or a method of adhering a commonly known sizing agent in advance and then adhering the copolymer (c), A method of simultaneously adhering the copolymer (c) and a generally known sizing agent can be exemplified.
[0068]
Further, the carbon fiber-reinforced thermoplastic resin composition of the second invention is used as a copolymer of the component (C) as a copolymer of the component (c1) with a diamine having an oxyalkylene group and a dicarboxylic acid for the purpose of improving conductivity and moldability. A copolymer comprising 55 to 99% by weight of an acid salt and 1 to 45% by weight of a salt of an amino acid, a lactam and / or a diamine and a dicarboxylic acid as the component (c2) is added. The amount of the copolymer is 0.01 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.1 to 8% by weight, based on 100% by weight of the carbon fiber-reinforced thermoplastic resin composition. It is in the range of 0.2 to 5% by weight. If the component (C) is less than 0.01% by weight, the effect of improving the conductivity may be insufficient, and if it exceeds 10% by weight, the mechanical properties of the obtained molded article may be impaired.
[0069]
As described above, the copolymer (c) in the first invention and the copolymer of the component (C) in the second invention are each composed of at least a diamine and a dicarboxylic acid having an oxyalkylene group of the component (c1). A copolymer comprising 55 to 99% by weight, preferably 60 to 90% by weight of a salt and 1 to 45% by weight, preferably 10 to 30% by weight of a salt of an amino acid, a lactam and / or a diamine and a dicarboxylic acid as the component (c2). However, if the proportion of the component (c1) is less than 55% by weight or more than 99% by weight, the effect of improving the conductivity of the present invention may be insufficient or the mechanical properties may be reduced.
[0070]
Here, the salt of a diamine having an oxyalkylene group and a dicarboxylic acid of the component (c1) is a salt obtained by reacting a diamine compound having an oxyalkylene group with a dicarboxylic acid compound in substantially equimolar amounts. Here, “substantially equimolar” means that the ratio of the diamine compound having an oxyalkylene group to the dicarboxylic acid compound is in the range of 1 ± 0.1, and if the ratio is within this range. In view of the polymerization rate and the ultimate degree of polymerization, it is sufficient to exhibit the effects of the present invention.
[0071]
As the diamine compound having an oxyalkylene group constituting the component (c1), a polyalkylene glycol having a polyoxyethylene skeleton or a polyoxypropylene skeleton in which both terminals are modified with a diamine is preferably used. Aminopropyl polyethylene glycol is particularly preferred. In addition, the molecular weight of the diamine compound having an oxyalkylene group is preferably 2,000 or less, more preferably 1,000 or less, from the viewpoint of conductivity of the obtained molded article.
[0072]
Further, as the dicarboxylic acid, adipic acid, spearic acid, azelaic acid, sebacic acid, dodecandioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-methylisophthalic acid, Aliphatic, alicyclic, and aromatic dicarboxylic acids such as sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid include adipic acid, azelaic acid, and sebacic acid. It is preferably used in terms of the degree of polymerization of the salt, and more preferably adipic acid. These dicarboxylic acids may be used alone or in combination of two or more.
[0073]
Here, component (c2), a polymer containing amino acids, lactams or diamines and dicarboxylic acids as main components, can form a polyamide. Specific examples thereof include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, p-aminomethylbenzoic acid, lactams such as ε-caprolactam, ω-laurolactam, tetramethylenediamine, hexamethylene Methylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylene Diamine, meta-xylylenediamine, para-xylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethyl Cyclohexane, Aliphatics such as bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine and aminoethylpiperazine; Alicyclic, aromatic diamines and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, Aliphatic, alicyclic and aromatic dicarboxylic acids such as 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid and hexahydroisophthalic acid, and derived from these raw materials Homopolymers or copolymers can be used. Among them, those obtained by ring-opening polymerization of a lactam ring are preferable from the viewpoint of conductivity, and it is particularly preferable to use ε-caprolactam.
[0074]
The relative viscosity (98% sulfuric acid method) ηr of the copolymer (c) in the first invention and the copolymer of the component (C) in the second invention is not particularly limited, but from the viewpoint of moldability and productivity, 1 It is preferably in the range of 0.5 to 4.5, more preferably in the range of 1.8 to 3.5. The following method is used for measuring the relative viscosity ηr. That is, about 1 g of the component (B) is dissolved in 98% sulfuric acid to prepare a 100 cc solution, and the solution is measured at 25 ° C. using an Ostwald viscometer.
[0075]
The carbon fiber reinforced thermoplastic resin compositions of the first and second inventions are preferably further added with a conductivity-imparting agent as component (D) for the purpose of further increasing conductivity. Here, as a preferable addition amount, the component (D) is in the range of 0.01 to 10% by weight, more preferably 0.1 to 8% by weight in 100% by weight of the carbon fiber reinforced thermoplastic resin composition. %.
[0076]
Examples of the conductivity imparting agent used in the present invention include, for example, carbon black, amorphous carbon powder, natural graphite powder, artificial graphite powder, expanded graphite powder, pitch micro beads, vapor-grown carbon fiber, carbon nanotube, and the like. However, among them, carbon black, vapor grown carbon fiber or carbon nanotube is preferable from the viewpoint of improving conductivity.
[0077]
Such carbon black includes, for example, furnace black, acetylene black, thermal black, channel black, and the like, and may be a single carbon black or a blend of two or more thereof. Above all, furnace black is preferred from the comprehensive aspects such as the price and the effect of imparting conductivity.
[0078]
As the carbon nanotube, for example, a single-walled nanotube, a multi-walled nanotube, or the like can be used, and a combination of two or more of these may be used. Further, in order to enhance the effect of adding the carbon nanotube, the surface of the carbon nanotube may be modified with a functional group, or a plasma treatment may be performed. Particularly preferred carbon nanotubes are single-walled nanotubes and double-walled nanotubes from the viewpoint of conductivity, and multi-walled nanotubes from the viewpoint of supply and economy.
[0079]
In both the first and second inventions, it is preferable to add a flame retardant as component (E) to the carbon fiber reinforced thermoplastic resin composition for the purpose of imparting flame retardancy. Here, as a preferable addition amount, the component (E) is in the range of 0.1 to 20% by weight in 100% by weight of the carbon fiber reinforced thermoplastic resin composition from the viewpoint of balance with mechanical properties, and more preferably. Is in the range of 1 to 10% by weight.
[0080]
There is no particular limitation on the flame retardant used in any of the inventions, and known flame retardants such as halogen-based, phosphorus-based, and inorganic-based flame retardants can be used. Specifically, tetrabromobisphenol A (TBBA) and its derivatives, decabromodiphenyl ether, bromobisphenol S, tetrabromophthalic anhydride, polydibromophenylene oxide, hexabromocyclododecane, ethylenebistetrabromophthalimide, ethylenebisdibromono Luborane dicarmoxylimide, pentabromodiphenyl oxide, tetradecabromodiphenoxybenzene, hexabromobenzene, brominated epoxy flame retardant, brominated polycarbonate flame retardant, brominated polyphenylene oxide flame retardant, brominated styrene flame retardant Halogen-based flame retardants such as red phosphorus, alkyl phosphate, allyl phosphate, alkyl allyl phosphate, aromatic condensed phosphate, phosphonitrile chloride derivative Phosphonamide flame retardants, vinyl phosphonates, allyl phosphonates, phosphorus flame retardants such as ammonium polyphosphate, polyphosphoramide, melamine phosphate, magnesium hydroxide, aluminum hydroxide, barium hydroxide, zinc hydroxide, Aluminum hydroxide, zirconium hydroxide, antimony trioxide, antimony tetroxide, antimony pentoxide, tin oxide, tin hydroxide, zirconium oxide, molybdenum oxide, ammonium molybdate, zinc borate, barium borate, calcium aluminate, clay, etc. Inorganic flame retardants, nitrogen-containing flame retardants such as melamine and melamine cyanurate, silicone polymers, and flame retardant aids such as polytetrafluoroethylene (PTFE) can be mentioned. Load and flame retardancy System flame retardant, especially phosphates, red phosphorus are preferred.
[0081]
Furthermore, the carbon fiber-reinforced thermoplastic resin composition of the present invention may be added with an inorganic filler, an additive, and other thermoplastic resins within a range that does not impair the purpose of the present invention, depending on the required properties. .
[0082]
The inorganic filler is not particularly limited, and any known inorganic filler can be used. Specific examples include glass fiber, glass powder, glass beads, aramid fiber, alumina fiber, aramid fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, metal fiber, layered silicate (montmorillonite, beidellite, nontronite) , Saponite, hectorite, sauconite, smectite clay minerals such as vermiculite, halloysite, kanemite, keniyaite, zirconium phosphate, titanium phosphate and other clay minerals, Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluoromica, Swellable synthetic mica such as Li-type silicon tetrafluoride mica), calcined clay, talc, silica, magnesium oxide, titanium oxide, calcium silicate, metal whiskers, wollastenite, zeolite, cellinite, kaolin, bentona DOO, potassium alumina silicate coating, mica, titanium oxide, titanate, calcium carbonate, magnesium carbonate, zinc carbonate, hydrotalcite, iron oxide, ferrite, metal powder, iron hydroxide, etc. boron nitride and the like. These may be used alone or in combination of two or more. The shape is not limited, and it can be used in a known shape such as a powder shape, a flake shape, a fiber shape, and a whisker balloon shape.
[0083]
Among the inorganic fillers, those belonging to the layered silicate may be those in which the interlayer is treated with organic onium ionization. The organic onium ion is not particularly limited, and examples thereof include an ammonium ion, a phosphonium ion, and a sulfonium ion. The organic onium conversion treatment indicates that exchangeable cations originally existing between layers are exchanged with organic onium ions, and the method is not particularly limited, and can be performed by a conventional method. For example, a method by an ion exchange reaction in a polar solvent such as water, methanol and ethanol, a method of directly reacting a liquid or molten ammonium salt with a layered silicate, and the like can be mentioned.
[0084]
Additives include crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, coloring inhibitors, heat stabilizers, release agents, antistatic agents, plasticizers, lubricants , A coloring agent, a pigment, a dye, a foaming agent, an antifoaming agent, a coupling agent, and the like.
[0085]
Other thermoplastic resins include liquid crystal polyester, polyarylate, acrylic resin such as polymethyl methacrylate resin (PMMA), vinyl chloride, polyimide (PI), polyamideimide (PAI), polyetherimide (PEI), polysulfone, Polyethers such as polyethersulfone, polyketone, polyetherketone, polyetheretherketone (PEEK) polyethylene and polypropylene, modified polyolefins, thermoplastic resins such as phenolic resins and phenoxy resins, and ethylene / propylene copolymers, ethylene / 1 -Butene copolymer, ethylene / propylene / diene copolymer, ethylene / carbon monoxide / diene copolymer, ethylene / ethyl (meth) acrylate copolymer, ethylene / (meth) acrylate glycidyl, Various elastomers such as ren / vinyl acetate / glycidyl (meth) acrylate copolymer, polyetherester elastomer, polyetherether elastomer, polyetheresteramide elastomer, polyesteramide elastomer, polyesterester elastomer, and the like. One type or two or more types may be used in combination.
[0086]
The carbon fiber reinforced thermoplastic resin composition of the present invention has a surface resistivity based on ASTM D257-99 (unit is LogΩ / cm) from the viewpoint of conductivity.²) Is preferably 12 or less. A more preferable range is 5 to 10 when the obtained molded article is used for the purpose of antistatic property and antistatic property, and 5 or less when it is used for the purpose of shielding electromagnetic wave. Yes, especially when used for a high level of electromagnetic wave shielding properties that do not require plating.
[0087]
The pellet, which is one of the preferred forms of the carbon fiber reinforced thermoplastic resin composition of the present invention, can be produced by a generally known method. That is, a method in which the entire amount of each component and, if necessary, other additives are melt-kneaded at once, a method in which some components are melt-kneaded and the remaining components are added in the middle, and a portion of the components are melted in advance. Examples of the method include a method of kneading and forming pellets and melt-kneading with the remaining components again, and a method of separately melt-kneading specific components and blending the pellets.
[0088]
Here, the method of melt-kneading is not particularly limited, and any device capable of performing mechanical shearing in a molten state, such as a single-screw extruder, a twin-screw extruder, or a kneader, may be used. As a preferred method, the temperature of the cylinder to which mechanical shearing is applied (excluding the raw material supply section) is set to be at least 10 ° C. higher than the melting point or glass transition temperature of the thermoplastic resin, and the screw is a kneading section for dispersing carbon fibers. And increasing the die diameter. Further, a method of providing a vent port for the purpose of removing water and low molecular weight volatile components generated during melt kneading, and a method of providing a plurality of hopper ports so that components can be added during melt kneading are also preferably used.
[0089]
The molding material of the present invention comprises the above-mentioned carbon fiber reinforced thermoplastic resin composition. As the form of the molding material, pellets, flakes and the like can be used, and preferably, pellets used for general injection molding.
[0090]
The molding material of the present invention may be mixed with other molding materials. Examples of other molding materials include, for example, other thermoplastic resins, additives, a masterbatch in which these are kneaded in advance, and a recycled material obtained by grinding a molded article of the carbon fiber-reinforced thermoplastic resin of the present invention. it can. Such a molding material is molded by a known molding method such as injection molding, blow molding, extrusion molding, press molding, compression molding, and insert molding. In particular, injection molding is preferable from the viewpoint of productivity.
[0091]
Another preferable embodiment of the molding material of the present invention is a plate-like or sheet-like molding material used for press molding or stamping compression molding.
[0092]
As a method for producing such a sheet-like or sheet-like molding material, matting is performed by mixing papers in advance by mixing a reinforcing fiber and a thermoplastic resin, and the obtained mat is impregnated with heat and pressure using a double belt press or a flat plate press. A method in which a thermoplastic resin melted in a reinforcing fiber mat is extruded into a plate shape or a sheet shape from a T-die using an extruder and heated and impregnated, and the reinforcing fiber mat and the thermoplastic resin sheet are sandwiched and heated and impregnated. A method can be exemplified. Examples of the form include a stampable sheet, a foam sheet, a prepreg, and the like.
[0093]
Further, the sheet-shaped molding material of the present invention can be molded by a known molding method such as press molding, autoclave molding, stamping compression molding, etc., but the press molding method is preferred from the viewpoint of productivity and the like.
[0094]
A molded article obtained by molding the molding material of the present invention can be developed for various uses by utilizing its excellent mechanical properties and conductivity. For example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, personal computers, optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, Tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystal display parts, FDD carriages, FDD chassis, HDD parts, motor brush holders, parabolic antennas, computer related parts, etc. Electrical / electronic parts, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts , Refrigerator parts, air conditioner parts, typewriter parts, home and office electrical product parts represented by word processor parts, etc., game / entertainment product parts represented by pachinko machines, slot machines, game machines, etc., office computer related parts, telephone related Parts, facsimile-related parts, copier-related parts, cleaning jigs, various bearings such as oilless bearings, stern bearings, underwater bearings, motor-related parts, mechanical parts such as lighters, typewriters, microscopes, binoculars, Optical devices such as cameras and watches, precision machinery-related parts, alternator terminals, alternator connectors, IC regulators, potentiometer bases for light deer, various valves such as exhaust gas valves, and various pipes related to fuel, exhaust, and intake systems. Air intake Nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter , Brake butt wear sensor, Thermostat base for air conditioner, Heated hot air flow control valve, Brush holder for radiator motor, Water pump impeller, Turbine vane, Wiper motor related parts, Distributor, Starter switch, Starter relay, Transmission wire Harness, window washer nozzle, air conditioner panel switch board, fuel related Electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, play equipment, toiletry supplies , Toy supplies, chemical plants, aviation parts, headlamp doors, radiator grills, cowl vent grilles, outside grips, side visors, side moldings, rear panel garnishes, roof covers, air scoops, spoilers and other automotive exterior parts, instrument panels, instruments Instrument cluster panel, instrument panel pad, instrument upper garnish, glove box, glove box door, ventilator grip , Defroster grill, demister grill, ash tray, front package tray, audio panel, switch panel, speaker grill, console box, overhead console, sun visor, steering column cover, armrest, footrest, assist grip, door pull handle, scuff plate, trim, It is useful for various uses such as headlinings, sunshades, coat hooks, racks, grip rails, guard bars, partition boards, rear package trays, spare tire covers, and other automotive interior components, other automotive components, and automotive fittings. Among them, parts and parts that make use of antistatic properties and antistatic properties for electric, electronic equipment and OA equipment such as personal computers, displays, mobile phones, personal digital assistants, etc. Suitable for, cover, etc., and housing etc. making use of excellent electromagnetic wave shielding properties, and also for car parts, car exterior parts, car interior parts, car outfitting parts, etc. by making use of moldability, antistatic strength etc. Can be used.
[0095]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following Examples do not limit the present invention, and all modifications and alterations that do not depart from the gist of the preceding and following descriptions are technical aspects of the present invention. Included in the scope.
[0096]
First, components used in Examples and Comparative Examples of the present invention are as follows.
(Reference Example 1)
30% by weight of ε-caprolactam and 70% by weight of a salt of bisaminopropyl polyethylene glycol obtained from polyethylene glycol having a number average molecular weight of 800 and adipic acid at a molar ratio of 1 were charged into a 1-liter polymerization vessel at a rate of 70% by weight. After the substitution, polymerization was carried out at 250 ° C. under a pressure of 1 MPa with stirring for 2 hours to complete the reaction. After the completion of the polymerization, the heating was stopped, and the polymer discharged from the lower portion of the polymerization can was formed into a sheet and cut into about 5 mm square. The relative viscosity of the obtained copolymer was 2.5.
(Reference Example 2)
In the same manner as described above, a copolymer composed of 5% by weight of ε-caprolactam and 95% by weight of a salt of bisaminopropyl polyethylene glycol obtained from polyethylene glycol having a number average molecular weight of 800 and adipic acid at a molar ratio of 1 was polymerized. . The relative viscosity was 2.5.
Component (A) thermoplastic resin
A-1: Polyamide 66 resin
Amilan CM3001 manufactured by Toray Industries, Inc.
A-2: Polycarbonate resin
GE Plastics' Lexan 141R
A-3: ABS resin
Toyolac T-100A manufactured by Toray Industries, Inc.
A-4: Polyetherimide resin
Ultem 1000 manufactured by GE Plastics
A-5: Polypropylene resin
Sumitomo Mitsui Polyolefin Co., Ltd. Sumitomo Mitsui Polypro J830HV
A-6: Polybutylene terephthalate resin
Toray Corporation 1401X06
A-7: Polyphenylene sulfide resin
Torelina A504 manufactured by Toray Industries, Inc.
A-8: Modified polyphenylene resin
Noril N300 manufactured by GE Plastics Japan
A-9: Polyacetal resin
Amylas S761 manufactured by Toray Industries, Inc.
Component (B) carbon fiber
B-1: PAN-based carbon fiber chopped yarn
Spinning and baking were performed from a copolymer containing polyacrylonitrile as a main component to obtain a continuous tow having 48,000 carbon fibers in total.
The characteristics of the continuous tow were as follows.
[0097]
Mass per unit length 3.3 g / m
Specific gravity 1.8
Tensile strength 3.0 GPa
Tensile modulus 225.0 GPa
Electric resistance 36.0Ω · g / m²
O / C 0.04
After preparing the copolymer prepared in Reference Example 1 in an aqueous solution having a concentration of 6% by weight on a continuous tow of carbon fibers and attaching it by an impregnation method, the carbon fibers were cut into 6 mm lengths using a cartridge cutter. Then, it was dried at 190 ° C. for 5 minutes with a hot air drier to obtain a chopped yarn. At this time, the amount of the copolymer adhering to the obtained chopped yarn was 4% by weight.
[0098]
In addition, the measurement of the adhesion amount of the copolymer and the sizing agent was performed by the following method. About 5 g of the carbon fiber to which the copolymer is attached is sampled and put into a heat-resistant glass container. Next, the container was dried at 120 ° C. for 3 hours, and cooled to room temperature while taking care not to absorb moisture.₁(G). Next, the whole container was heated at 450 ° C. for 15 minutes in a nitrogen atmosphere, cooled to room temperature while taking care not to absorb moisture, and the weight of the weighed carbon fiber was reduced to W.₂(G).
[0099]
After the above processing, the adhesion amount of the copolymer and the sizing agent is determined by the following equation.
[0100]
Adhesion amount = 100 × (W₁-W₂) / W₂(Unit: wt%)
B-2: PAN-based carbon fiber chopped yarn
After the epoxy resin (equivalent mixture of Ep828 (trade name, manufactured by Yuka Shell) and Ep1001 (trade name, manufactured by Yuka Shell)) as a sizing agent was previously attached to the carbon fiber continuous tow, After attaching a urethane resin (a self-emulsifying polyurethane resin obtained by polymerizing 1,6-hexamethylene carbonate diol and hexamethylene diisocyanate), a chopped yarn was obtained. The amount of the sizing agent attached was 4% by weight.
[0101]
B-3: PAN-based carbon fiber chopped yarn
SIGRAFIL C25-PUT manufactured by SGL Carbon
Component (C) copolymer
C-1: copolymer prepared in Reference Example 1
C-2: copolymer prepared in Reference Example 2
Component (D) Conductivity imparting agent
Furnace black
Average particle size 50μm, DBP absorption 130cm³/ 100g
Component (E) Flame retardant
Red phosphorus manufactured by Rin Chemical Co., Ltd.
Average particle size 30 μm, conductivity 200 μS / cm
Component (F) Other components
Polyamide 6 homopolymer
Amilan CM1010 manufactured by Toray Industries, Inc.
(Examples 1 to 5, Comparative Examples 1 to 6)
Using a TEX-30α type twin screw extruder (Screw diameter 30 mm, L / D = 32) manufactured by Japan Steel Works, Ltd., the components (A), (C), (D) and (E) are mainly used. The carbon fiber (B) is supplied from the hopper, and then the carbon fiber (B) is supplied from the downstream side hopper, sufficiently kneaded at a barrel temperature of 280 ° C. and a rotation number of 150 rpm, and further deaerated from a vacuum vent downstream. The supply is adjusted by a weight feeder so that the weight ratio is as shown in Tables 1 and 2. The molten resin was discharged from a die opening (φ5 mm), and the obtained strand was cooled and cut with a cutter to obtain a pellet-shaped molding material.
[0102]
The obtained pellets were dried at 90 ° C. × 3 hr by hot air drying and further at 80 ° C. × 6 hr by vacuum drying, and sufficiently dried so as to have a moisture content of 0.1% or less, and then J350EIII manufactured by Japan Steel Works, Ltd. Using a mold injection molding machine, a test piece for characteristic evaluation was molded at a cylinder temperature of 300 ° C and a mold temperature of 70 ° C.
[0103]
The obtained test piece was subjected to a characteristic evaluation test after being left for 24 hours in a thermo-hygrostat adjusted to 23 ° C. and 50% RH. The obtained pellet-shaped molding material was dried under vacuum at 80 ° C. for 12 hours, and stored in a desiccator at room temperature for 3 hours to be subjected to moldability evaluation.
[0104]
The weight ratios and evaluation results of the above Examples and Comparative Examples are as shown in Tables 1 and 2 described below.
[0105]
(Examples 6 to 8, Comparative Examples 7 to 10)
The barrel temperature of the twin-screw extruder was set at 300 ° C., and the barrel temperature of the injection molding machine at the time of molding was set at 320 ° C. A molding material and a molded product were produced in the same manner as described above, and were subjected to evaluation. The weight ratio and evaluation results are as shown in Table 3 below.
(Examples 9 to 10, Comparative Examples 11 to 12)
The barrel temperature of the twin-screw extruder was set to 250 ° C., and the barrel temperature of the injection molding machine in the molding was set to 260 ° C. A molding material and a molded product were produced in the same manner as described above, and were subjected to evaluation. The weight ratio and the evaluation results are as shown in Table 4 below.
[0106]
(Example 11, Comparative Example 13)
The barrel temperature of the twin-screw extruder was set to 380 ° C., and the barrel temperature of the injection molding machine in molding was set to 380 ° C. A molding material and a molded article were produced in the same manner as described above, and were subjected to evaluation. The weight ratio and evaluation results are as shown in Table 5 below.
[0107]
(Example 12, Comparative Example 14)
The barrel temperature of the twin-screw extruder was 230 ° C., and the barrel temperature of the injection molding machine during molding was 240 ° C. A molding material and a molded product were produced in the same manner as described above, and were subjected to evaluation. The weight ratio and evaluation results are as shown in Table 5 below.
[0108]
(Example 13, Comparative example 15)
The barrel temperature of the twin-screw extruder was set to 250 ° C., and the barrel temperature of the injection molding machine in the molding was set to 260 ° C. A molding material and a molded product were produced in the same manner as described above, and were subjected to evaluation. The weight ratio and evaluation results are as shown in Table 5 below.
[0109]
(Example 14, Comparative Example 16)
The barrel temperature of the twin-screw extruder was set to 320 ° C., and the barrel temperature of the injection molding machine in the molding was set to 330 ° C. A molding material and a molded product were produced in the same manner as described above, and were subjected to evaluation. The weight ratio and evaluation results are as shown in Table 5 below. (Example 15, Comparative Example 17)
The barrel temperature of the twin-screw extruder was set at 270 ° C., and the barrel temperature of the injection molding machine during molding was set at 280 ° C., and molding materials and molded articles were produced in the same manner as described above, and were used for evaluation. The weight ratio and evaluation results are as shown in Table 5 below.
[0110]
(Example 16, Comparative Example 18)
The barrel temperature of the twin-screw extruder was set at 210 ° C., and the barrel temperature of the injection molding machine during molding was set at 220 ° C. A molding material and a molded product were produced in the same manner as described above, and were subjected to evaluation. The weight ratio and evaluation results are as shown in Table 5 below.
[0111]
(Example 17, Comparative Example 19)
Using a TEX-30α type twin screw extruder (screw diameter 30 mm, L / D = 32) of Nippon Steel Works Co., Ltd., supply the components (A) and (C) from the main hopper, and then feed the downstream side The carbon fiber (B) is supplied from the hopper, kneaded sufficiently at a barrel temperature of 230 ° C. and a rotation speed of 150 rpm, and further deaerated from a downstream vacuum vent. The supply is adjusted by a weight feeder so that the weight ratio is as shown in Table 6. The molten resin was discharged from a die opening (length 5 mm, width 100 mm), and after cooling the obtained sheet, it was cut into 300 mm with a cutter to obtain a sheet-shaped molding material having a length of 300 mm, a width of 100 mm and a thickness of 5 mm.
[0112]
The obtained sheet is dried at 90 ° C. × 3 hr by hot air drying and further at 80 ° C. × 6 hr by vacuum drying, and sufficiently dried so as to have a moisture content of 0.1% or less. A hot plate temperature: 230 ° C., a lower hot plate temperature: 230 ° C., a molding pressure of 1.0 MPa, and a molding time of 10 min were used to produce molded products for characteristic evaluation. A bending test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4.0 mm was prepared using a model D-51 diamond cutter manufactured by Sanei Ironworks Co., Ltd.
[0113]
The obtained test piece was subjected to a characteristic evaluation test after being left for 24 hours in a thermo-hygrostat adjusted to 23 ° C. and 50% RH. The evaluation results are summarized in Table 6.
[0114]
Next, a method for evaluating characteristics of a molding material and a molded product will be described below.
(1) Conductivity (surface resistivity) of molded products
A test piece was prepared by applying a conductive paste (Dotite manufactured by Fujikura Kasei Co., Ltd.) to a plate-like molded product having a length of 80 mm × a width of 80 mm × a thickness of 3 mm as shown in FIG. , CD, and the surface resistivity (in units of LogΩ / cm) is determined as the average of the four measured values.²). A digital multimeter R6581 manufactured by Advantest was used for the measurement. The smaller the value of the surface resistivity, the better the conductivity.
[0115]
(2) Moldability of fiber reinforced resin composition
The flowability (MFR) of the molding material was determined according to ASTM # 1238-95. The measurement was carried out using a melt indexer manufactured by Toyo Seiki Seisaku-sho, at a measurement temperature of 280 ° C, a load of 1000 g and a residence time of 6 minutes for Examples 1 to 5 and Comparative Examples 1 to 6. In Examples 6 to 8 and Comparative Examples 7 to 10, the measurement was performed at a measurement temperature of 300 ° C., a load of 1000 g, and a residence time of 6 minutes. Further, Examples 9 to 10 and Comparative Examples 11 to 12 were performed at a measurement temperature of 250 ° C., a load of 2160 g, and a residence time of 6 minutes. Example 11 and Comparative Example 13 were performed at a measurement temperature of 360 ° C., a load of 1000 g, and a residence time of 6 minutes. Examples 12 and 17 and Comparative Examples 14 and 19 were performed at a measurement temperature of 230 ° C, a load of 1000 g, and a residence time of 6 minutes. For Example 13 and Comparative Example 15, the measurement was performed at a measurement temperature of 250 ° C., a load of 1000 g, and a residence time of 6 minutes. For Example 14 and Comparative Example 16, the measurement was performed at a measurement temperature of 330 ° C., a load of 1000 g, and a residence time of 6 minutes. For Example 15 and Comparative Example 17, the measurement was performed at a measurement temperature of 280 ° C., a load of 1000 g, and a residence time of 6 minutes. Example 16 and Comparative Example 18 were performed at a measurement temperature of 190 ° C., a load of 1000 g, and a residence time of 6 minutes. A higher MFR value means better moldability.
[0116]
(3) Mechanical properties of molded products
A bending test was performed according to ASTM D790 standard. The thickness of the test piece used was 6.4 mm, and the flexural modulus (GPa) and bending strength (MPa) were determined at a moisture content of 0.1% or less, an atmosphere temperature of 23 ° C., and a humidity of 50% by weight.
[0117]
Further, for Example 17 and Comparative Example 19, a bending test was performed in accordance with JIS K7017 (Fiber Reinforced Plastics: Determination of bending characteristics) standard. The thickness of the test piece used was 4.0 mm, and the flexural modulus (GPa) and flexural strength (MPa) were determined at a moisture content of 0.1% or less, an atmosphere temperature of 23 ° C., and a humidity of 50% by weight.
[0118]
(4) Izod impact strength
An Izod impact test with a mold notch was performed according to ASTM D256 standard. The thickness of the test piece used was 3.2 mm, and the Izod impact strength (J / m) was determined at a moisture content of 0.1% or less, an atmosphere temperature of 23 ° C., and a humidity of 50% by weight.
[0119]
(5) Flame retardancy
It was evaluated in a flame retardancy test based on UL-94 standard. The flame retardancy level decreases in the order of V-0> V-1> V-2> HB. The thickness of the test piece used is 1.6 mm.
[0120]
Finally, in each of the above-described embodiments and comparative examples, the conductivity, mechanical properties, moldability, and economy of the above evaluation items were weighted and evaluated in the order of conductivity, moldability, mechanical properties, and economy. In addition, comprehensive judgment is made in consideration of the balance of these characteristics and the like, and the judgment results are as follows: ○: particularly excellent, ○: more excellent, ：: excellent, Δ: inferior, ×: particularly inferior. .
[0121]
The properties and overall evaluation obtained in each example and comparative example are summarized and described in the following Tables 1 to 6.
[0122]
[Table 1]

[0123]
[Table 2]

[0124]
[Table 3]

[0125]
[Table 4]

[0126]
[Table 5]

[0127]
[Table 6]

[0128]
That is, the following is clear from the examples and comparative examples in Table 1.
[0129]
The composition according to the first invention of Example 1 is superior to Comparative Example 1 in conductivity and moldability. Similarly, the composition according to the second invention of Example 2 satisfies high mechanical properties and flame retardancy, and is superior to Comparative Example 2 in conductivity and moldability. Since these embodiments satisfy the conductivity of electromagnetic wave shielding level, high mechanical properties and flame retardancy, they are useful for applications such as housings of electric / electronic devices.
[0130]
The following is clear from the examples and comparative examples in Table 2.
[0131]
The compositions according to the first inventions of Examples 3 and 4 are superior to Comparative Examples 3 and 4, respectively, in conductivity and moldability, so that the desired conductivity can be obtained with a smaller amount of carbon fiber. Therefore, it is advantageous from the viewpoint of moldability, economy, and the highest point of conductivity. In Comparative Example 5 in which the amount of carbon fiber added was higher than the range of the present invention, compounding was not possible. Similarly, the composition according to the second invention of Example 5 is superior to Comparative Example 6 in conductivity and moldability.
[0132]
The following is clear from the examples and comparative examples in Table 3.
[0133]
The composition according to the first invention of Example 6 was superior to Comparative Example 7 in conductivity and moldability, and the same effect as in the above Example was reproduced. Similarly, the compositions according to the second inventions of Examples 7 and 8 are superior to Comparative Example 8 in conductivity and moldability. In particular, in Example 8, by setting the composition ratio of the copolymer (C) in a more preferable range, more excellent effects of improving conductivity and moldability were obtained. In Comparative Example 9 in which the amount of the copolymer was increased beyond the range of the present invention, good productivity and characteristics such as foaming of the resin composition could not be obtained. Furthermore, even if a polyamide 6 homopolymer is added instead of the copolymer as in Comparative Example 10, no significant improvement in the electrical conductivity and mechanical properties is observed.
[0134]
The following is clear from the examples and comparative examples in Table 4.
[0135]
The composition according to the first invention of Example 9 is superior in conductivity and moldability to Comparative Example 11, and the composition according to the second invention of Example 10 is also similar to Comparative Example 11. Because of its excellent conductivity and moldability, it is useful for applications requiring conductivity.
[0136]
The following is clear from the examples and comparative examples in Table 5.
[0137]
The composition of Example 11 is for Comparative Example 13, the composition of Example 12 is for Comparative Example 14, and the composition of Example 13 is for Comparative Example 15. The composition of Comparative Example 16 was superior to Comparative Example 16, the composition of Example 15 was superior to Comparative Example 17, and the composition of Example 16 was superior to Comparative Example 18 in conductivity and moldability. Useful for applications that require performance.
[0138]
The following is clear from the examples and comparative examples in Table 6.
[0139]
The composition of Example 17 is superior to Comparative Example 19 in conductivity and moldability, and is useful for applications requiring conductivity.
[0140]
【The invention's effect】
The carbon fiber-reinforced thermoplastic resin composition, molding material and molded article of the present invention have excellent mechanical properties, as well as excellent conductivity and moldability, and are particularly suitable for electric / electronic devices, OA devices, home appliances, It is very suitable for general industrial fields such as various parts or housings for automobile use.
[Brief description of the drawings]
FIG. 1 is a plan view of a test piece for measuring the surface resistivity of a molded product made of the resin composition of the present invention.
[Explanation of symbols]
1: conductive paste application area A
2: conductive paste application range B
3: Conductive paste application range C
4: Conductive paste application range D

Claims (17)

A carbon fiber reinforced thermoplastic resin composition comprising at least the following components (A) and (B).
Component (A): at least one thermoplastic resin selected from the group consisting of polycarbonate resin, styrene resin, polyamide resin, polyester resin, polyphenylene sulfide resin, modified polyphenylene ether resin, polyetherimide resin, polyolefin resin, and polyacetal resin. 25-99% by weight
Component (B): at least 55 to 99% by weight of a salt of an oxyalkylene group-containing diamine and a dicarboxylic acid as component (c1), and amino acids, lactams and / or salts of a diamine and a dicarboxylic acid as components (c2) 1 to 45. 1 to 75% by weight of carbon fibers in which a copolymer containing 0.1% to 5% by weight is attached to 100% by weight of carbon fibers A carbon fiber-reinforced thermoplastic resin composition comprising at least the following components (A) to (C).
Component (A): at least one thermoplastic resin selected from the group consisting of polycarbonate resin, styrene resin, polyamide resin, polyester resin, polyphenylene sulfide resin, modified polyphenylene ether resin, polyetherimide resin, polyolefin resin, and polyacetal resin. 25-99% by weight
Component (B): 1 to 75% by weight of carbon fiber
Component (C): at least 55 to 99% by weight of a salt of a diamine and a dicarboxylic acid having an oxyalkylene group as the component (c1), and amino acids, lactams and / or salts 1 to 45 of a diamine and a dicarboxylic acid as the component (c2). % By weight of the copolymer is 0.01 to 10% by weight based on 100% by weight of the carbon fiber reinforced thermoplastic resin composition. The carbon fiber reinforced thermoplastic resin composition according to claim 1 or 2, wherein the carbon fiber of the component (B) has an electric resistance value of less than 40 Ω · g / m ² . The surface oxygen concentration (O / C) which is the ratio of the number of atoms of oxygen (O) and carbon (C) on the surface of the carbon fiber measured by X-ray photoelectron spectroscopy of the carbon fiber of the component (B) is 0.03. The carbon fiber reinforced thermoplastic resin composition according to any one of claims 1 to 3, wherein The carbon fiber-reinforced thermoplastic resin composition according to any one of claims 1 to 4, wherein the oxyalkylene group of the component (c1) has a polyoxyethylene skeleton. The carbon fiber reinforced thermoplastic resin composition according to any one of claims 1 to 5, wherein the number average molecular weight of the diamine of the component (c1) is 2,000 or less. The carbon fiber reinforced thermoplastic resin composition according to any one of claims 1 to 6, wherein the dicarboxylic acid of the component (c1) is at least one selected from adipic acid, azelaic acid, and sebacic acid. The carbon fiber-reinforced thermoplastic resin composition according to any one of claims 1 to 7, wherein the component (c2) is ε-caprolactam. The carbon fiber-reinforced thermoplastic resin composition according to any one of claims 1 to 8, further comprising 0.01 to 10% by weight of a conductivity-imparting agent as component (D). The carbon fiber reinforced thermoplastic resin composition according to any one of claims 1 to 9, further comprising 0.1 to 20% by weight of a flame retardant as the component (E). The carbon fiber-reinforced thermoplastic resin composition according to any one of claims 1 to 10, wherein a surface resistivity (unit: LogΩ / cm2) based on ASTM D257-99 is 12 or less. A molding material comprising the carbon fiber-reinforced thermoplastic resin composition according to claim 1. A molding material obtained by mixing the molding material according to claim 12 with another molding material. The molding material according to claim 12, which is in the form of a sheet. A molded article comprising the carbon fiber-reinforced thermoplastic resin composition according to any one of claims 1 to 11. The molded article according to claim 15, wherein the use is a part or a housing of an electric / electronic device. The molded article according to claim 15, wherein the use is for an automobile member or an automobile fitting.

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