JP4633288B2 - Resin composition - Google Patents

Description

（式中、Ｒ₅およびＲ₆は、それぞれＨ、Ｃｌ、Ｂｒまたは炭素数１〜８のアルキル基であり、それらは同一であっても異なっていてもよく、ｓおよびｔはそれぞれ１〜４の整数であって、ｓが２〜４の場合はＲ₅は互いに異なるものであってもよいし、ｔが２〜４の場合は互いに異なるものであってもよい。そして、Ｚは、炭素数１〜８のアルキレン基、炭素数２〜８のアルキリデン基、炭素数５〜１５のシクロアルキレン基、炭素数５〜１５のシクロアルキリデン基またはＳＯ₂、ＳＯ、Ｓ、Ｏ、ＣＯを示す。）
（Ａ２）を構成する２価フェノールの具体例としては、例えば、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ならびにこれらのアルキル（炭素数１〜８）又はハロゲン（塩素、臭素など）置換体（例えば臭素化ビスフェノールＡ）等が挙げられる。
これらの２価フェノールはそれぞれ単独で用いてもよいし、２種以上を組み合わせて用いてもよい。また、上述の脂肪族ジオールを組み合わせて用いてもよい。
これらの２価フェノールの中では、特にビスフェノールＡが好ましい。
【００４４】
（Ａ３）としては、例えば、有機ジイソシアネートと、ポリエステルジオール［分子量５００〜５０００またはそれ以上のポリエステルジオール、このジオール中でビニルモノマー（たとえばアクリロニトリルおよび／またはスチレン）を重合させて得られるポリマーポリオール等］、鎖伸長剤（ジオールたとえば１，４−ブチレングリコールおよび／またはジアミンたとえばエチレンジアミン）および必要により反応停止剤（一価アルコール、一級もしくは二級モノアミン、またはモノ−もしくはジ−アルカノールアミン）を、ワンショット法またはプレポリマー法により、反応させて得られるポリウレタンが挙げられる。
有機ジイソシアネートとしては、炭素数（ＮＣＯ基中の炭素を除く、以下同様）６〜２０の芳香族ジイソシアネート、炭素数２〜１８の脂肪族ジイソシアネート、炭素数４〜１５の脂環式ジイソシアネート、炭素数８〜１５の芳香脂肪族ジイソシアネート、これらのジイソシアネートの変性体及びこれらの２種以上の混合物が使用できる。具体例としては国際公開ＷＯ００／４７６５２号明細書に記載されたものが挙げられる。
【００４５】
ポリエステルジオールには、ジオール（低分子ジオールおよび／または分子量１０００以下のポリオキシアルキレンジオール）とジカルボン酸もしくはそのエステル形成性誘導体、またはジカルボン酸無水物およびアルキレンオキサイドとを反応させて得られる縮合ポリエステルジオ―ル、上述のジオールを開始剤として上述のラクトンを開環重合させて得られるポリラクトンジオ―ル、低分子ジオールと低級アルコール（炭素数１〜４）の炭酸ジエステルとを反応させて得られるポリカーボネートジオールなどが含まれる。
低分子ジオールとしては上述のグリコールが挙げられる。
ポリオキシアルキレンジオールとしては上述のものが挙げられる。
ジカルボン酸とラクトンとしては、上記（Ａ１）の原料として挙げたものが使用できる。
これらのポリエステルジオールの具体例としては、ポリエチレンアジペ−トジオール、ポリヘキサメチレンアジペ−トジオール、ポリカプロラクトンジオ―ルまたはポリヘキサメチレンカーボネートジオールなどが挙げられる。
上記の中で好ましいものはアジペート系熱可塑性ポリウレタンである。
【００４６】
（Ａ４）にはエステル基含有ビニルモノマーの（共）重合体、およびエステル基含有ビニルモノマーと他のビニルモノマーとの共重合体が含まれる。エステル基含有ビニルモノマーとしては、カルボキシル基含有ビニル系モノマーのエステルおよび不飽和アルコールのエステルが挙げられる。
カルボキシル基含有ビニル系モノマーのエステルには、不飽和カルボン酸［モノカルボン酸；例えば、（メタ）アクリル酸、クロトン酸、オレイン酸、４−ビニル安息香酸、ケイ皮酸；ポリカルボン酸、例えば、（無水）マレイン酸、フマル酸、イタコン酸、シトラコン酸］と炭素数１〜５０のアルコール［アルカノール、シクロアルカノール、ベンジルアルコール、ジオール（前述のグリコール、ポリオキシアルキレンジオール）、３級アミノ基含有アルコール、例えばジアルキル（炭素数１〜４）アルカノール（炭素数２〜４）アミン、Ｎ−ヒドロキシアルキル（炭素数２〜４）モルホリン、エポキシ含有アルコール（グリシドール等）］とのエステルが含まれる。
具体的には、炭素数１〜５０のアルキル基を有するアルキル（メタ）アクリレート、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、ヘプタデシル（メタ）アクリレート、エイコシル（メタ）アクリレート等が挙げられる。
不飽和アルコールのエステルとしては、不飽和アルコール［ビニルアルコール、（メタ）アリルアルコール、イソプロペニルアルコール等］と炭素数２〜１８のカルボン酸［モノカルボン酸、安息香酸、前述のジカルボン酸等］のエステル、例えば、酢酸ビニル、ビニルブチレート、プロピオン酸ビニル、酪酸ビニル、ジアリルフタレート、ジアリルアジペート、イソプロペニルアセテート、ビニル（メタ）アクリレート、メチル４−ビニルベンゾエート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、ビニルメトキシアセテート、ビニルベンゾエート等が挙げられる。
他のビニルモノマーとしては、ビニル系炭化水素［芳香族ビニル系炭化水素（スチレン、α−メチルスチレン等）、脂肪族ビニル系炭化水素（エチレン、プロピレン、ブタジエン等）］、含窒素ビニル系モノマー［アミド基含有ビニル系モノマー｛（メタ）アクリルアミド等｝、ニトリル基含有ビニル系モノマー｛（メタ）アクリロニトリル等｝、ハロゲン元素含有ビニル系モノマー［塩化ビニル、クロロプレン等］が挙げられる。
（Ａ４）の具体例としては、ポリメチルメタクリレート、スチレン／メタクリル酸メチル／アクリロニトリル共重合体、メタクリル酸メチル／ブタジエン／スチレン共重合体（ＭＢＳ樹脂）、エチレン／グリシジルメタクリレート共重合体、エチレン／酢酸ビニル／グリシジルメタクリレート共重合体等が挙げられる。
【００４７】
該（Ａ）のＭｗは２０，０００〜５００，０００またはそれ以上が好ましく、さらに好ましくは２５，０００〜４５，０００またはそれ以上である。
【００４８】
さらに本発明において、エステル結合を有する熱可塑性樹脂（Ａ）には、他の熱可塑性樹脂を配合してもよい。かかる他の熱可塑性樹脂としてはスチレン（共）重合体、例えば、スチレン／アクリロニトリル共重合体（ＡＳ樹脂）、アクリロニトリル／ブタジエン／スチレン共重合体（ＡＢＳ樹脂）、スチレン／ブタジエン共重合体；オレフィン（炭素数２〜８）（共）重合体、例えば、ポリエチレン、ポリプロピレン、エチレン／プロピレン共重合体、エチレン／４−メチルペンテン共重合体、エチレン／ブテン−１共重合体、ポリアセタール［例えば、ホルムアルデヒドの単独重合物およびトリオキサンとアルキレンオキサイド（例えばエチレンオキサイド、プロピレンオキサイド等）の共重合物］およびこれらの無水マレイン酸変性物等があげられる。
【００４９】
上記（Ａ）の熱可塑性樹脂の合計重量に対する配合割合は、３０〜９７重量％が好ましく、４０〜９０重量％が特に好ましい。
上記（Ｂ）の熱可塑性樹脂の合計重量に対する配合割合は、３〜５０重量％が好ましく、５〜４０重量％が特に好ましい。
上記の「他の熱可塑性樹脂」の熱可塑性樹脂の合計重量に対する配合割合は、０〜６７重量％が好ましく、０〜５０重量％が特に好ましい。
本発明における「熱可塑性樹脂の合計重量」とは、（Ａ）、（Ｂ）および上記「他の熱可塑性樹脂」の合計重量のことである。
【００５０】
また本発明の酸性リン酸エステル（Ｃ）としては、一般的にプラスチックの添加剤として使用される酸性リン酸エステルであればいずれも使用することができる。例えば、リン酸類の活性水素を１〜３個またはそれ以上の個数置換したものが挙げられる。リン酸類としては、リン酸、メタリン酸、オルトリン酸、亜リン酸、ホスホン酸、ピロリン酸、ジホスヒン酸、ジリン酸、ジホスホン酸等が挙げられる。活性水素を置換する基としてはアルキル基、アリール基、アルケニル基、ヒドロキシアルキル基（いずれも炭素数１〜３０）等が挙げられる。
上記の例としては、リン酸のモノアルキルエステル、モノアリールエステル、ジアルキルエステル、ジアリールエステル、亜リン酸のモノアルキルエステル、ピロリン酸のトリアルキルエステル等が挙げられる。これらの中で、好ましいものは一般式（１）で示されるものである。
【化７】

（ｎは１または２である。Ｒ₁は炭素数１〜３０の１価の炭化水素基を示し、ｎが２の場合同一であっても異なっていてもよい。）
一般式（１）において、Ｒ₁で表される炭素原子数１〜３０のアルキル基としては、メチル、エチル、ｎ−およびｉ−プロピル、ｎ−，ｉ−，ｓｅｃ−およびｔ−ブチル、アミル、第３アミル、ヘキシル、オクチル、イソオクチル、２−エチルヘキシル、第３オクチル、ノニル、第３ノニル、イソノニル、デシル、イソデシル、ドデシル、トリデシル、イソトリデシル、テトラデシル、ヘキサデシル、オクタデシル、エイコシル、トリアンコンチル等があげられる。ｎが２の場合、２個のＲ₁は同一でも異なっていても良い。
酸性リン酸エステルとして、さらに好ましいものは、上記Ｒ₁が炭素数８〜３０の酸性リン酸エステルであり、特に好ましいものは、リン酸のモノステアリルエステルおよびリン酸のジステアリルエステルである。
【００５１】
上記酸性リン酸エステルは、たとえば、対応するトリアルキルフォスフェートまたは対応するリン酸類のトリエステルもしくはテトラエステルを加水分解する方法、オキシ塩化リンと対応するアルカノールとを反応させた後加水分解する方法あるいは五酸化リンと対応するアルカノールとを反応させる方法等の周知の方法によって合成することができる。
【００５２】
また、本発明のアルカリ金属および／またはアルカリ土類金属の塩（Ｄ）としては、アルカリ金属（リチウム、ナトリウム、カリウムなど）および／またはアルカリ土類金属（マグネシウム、カルシウムなど）の有機酸（炭素数１〜１２のモノ−またはジカルボン酸たとえばギ酸，酢酸，プロピオン酸，シュウ酸，コハク酸など；炭素数１〜２０のスルホン酸たとえばメタンスルホン酸、ｐ−トルエンスルホン酸など；チオシアン酸等）の塩、および無機酸（ハロゲン化水素酸たとえば塩酸、臭化水素酸、過塩素酸、硫酸、リン酸等）の塩が含まれる。
具体例としては、酢酸リチウム、塩化マグネシウム、塩化カルシウム、臭化ナトリウム、臭化カリウム、臭化マグネシウム、過塩素酸カリウム、硫酸カリウム、燐酸カリウム、チオシアン酸カリウムなどを挙げることができる。これらのうち好ましいのはハライド（とくに塩化リチウム、塩化ナトリウム、塩化カリウム）および酢酸塩（とくに酢酸カリウム）である。
【００５３】
（Ｃ）および（Ｄ）は、（Ｃ）／（Ｄ）の重量比が１〜５０、かつ、（Ｃ）と（Ｄ）の合計重量が熱可塑性樹脂の合計重量に対して０．００１〜５重量％となるように含有される。（Ｃ）／（Ｄ）の重量比は１未満、あるいは５０を越えると帯電防止性および樹脂物性が低下する。（Ｃ）と（Ｄ）の合計重量が熱可塑性樹脂の合計重量に対して、０．００１重量％未満、あるいは５．０重量％を越えると帯電防止性および樹脂物性が低下する。
（Ｃ）／（Ｄ）の重量比は、２〜３０が特に好ましく、５〜２５がさらに好ましい。（Ｃ）と（Ｄ）の合計重量が熱可塑性樹脂の合計重量に対して０．００１〜３が特に好ましく、０．０１〜２がさらに好ましい。
【００５４】
また、本発明の樹脂組成物としては、必要により亜リン酸エステルを加えることができる。亜リン酸エステルとしては、一般式（２）、（３）、（４）および（５）で表される。
【化８】

（Ｒ₂、Ｒ₂’、Ｒ₂”は炭素数１〜２５の１価の炭化水素基であり、それぞれ同一であっても異なっていてもよい。）
【化９】

（ｍは２〜４の整数である。Ｒ₃は炭素数１〜４０の炭化水素基であり、ｍが２の場合２価、ｍが３の場合３価、ｍが４の場合４価である。Ｒ₃’およびＲ₃”は炭素数１〜２５の１価の炭化水素基であり、それぞれ同一であっても異なっていてもよい。）
【化１０】

（ｋは１または２である。Ｒ₄は炭素数１〜４０の炭化水素基であり、ｋが１の場合２価、ｋが２の場合４価である。Ｒ₄’は炭素数１〜２５の１価の炭化水素基であり、ｋが２の場合それぞれ同一であっても異なっていてもよい。）
【化１１】

（ｐは１〜４の整数である。Ｒ₇は炭素数１〜４０の炭化水素基であり、ｐが１〜４の場合各１〜４価である。Ｒ₇’、Ｒ₇”は炭素数１〜２５の１価の炭化水素基であり、ｐが２〜４の場合それぞれ同一であっても異なっていてもよい。）
【００５５】
上記一般式（２）で表される亜リン酸エステルの例としては、トリラウリルフォスファイト、トリイソオクチルフォスファイト、トリオレイルフォスファイト、トリフェニルフォスファイト、トリオクタデシルフォスファイト、トリイソデシルフォスファイト、トリノルマルブチルフォスファイト、トリス−２−エチルヘキシル−フォスファイト、トリステアリルフォスファイト、トリス−２，４−ジ第３ブチルフェニルフォスファイト、トリストリデシルフォスファイト、トリス−４−フェニルフェノール−フォスファイト、トリスノニルフェニルフォスファイト、フェニルジイソデシルフォスファイト、フェニルジオクチルフォスファイト、ジフェニルノニルフェニルフォスファイト、ジフェニルイソデシルフォスファイト、ジフェニルイソオクチルフォスファイト、ジフェニルデシルフォスファイト、ジフェニルトリデシルフォスファイトなどが挙げられる。
【００５６】
上記一般式（３）で表される亜リン酸エステルの例としては、テトラフェニルジプロピレングリコールジフォスファイト、テトララウリルビスフェノールＡ−ジフォスファイト、テトラトリデシルビスフェノールＡ−ジフォスファイト、テトラフェニルテトラトリデシルペンタエリスリトール−テトラフォスファイト等が挙げられる。
【００５７】
上記一般式（４）で表される亜リン酸エステルの例としては、ジイソデシルペンタエリスリトール−ジフォスファイト、ジラウリルペンタエリスリトール−ジフォスファイト、ジステアリルペンタエリスリトール−ジフォスファイト、ジノニルフェニルペンタエリスリトール−ジフォスファイト、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトール−ジフォスファイト等が挙げられる。
【００５８】
上記一般式（５）で表される亜リン酸エステルの例としては、テトラキス（２，４−ジターシャリーブチルフェノール）４，４’−ビフェニレンジフォスフォナイト（Ｐ−ＥＰＱ）等が挙げられる。
亜リン酸エステルとして好ましいものは、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトール−ジフォスファイトである。
亜リン酸エステルは、（Ｃ）の重量に基づいて、０〜１００重量％であることが好ましく、０〜８０重量％であることがさらに好ましい。
【００５９】
本発明の樹脂組成物は、公知の各種混合機を用いて前記（Ａ）〜（Ｄ）各成分を混練することによって得ることができる。混合機としては例えば押し出し機、ブラベンダー、ニーダーおよびバンバリーミキサーなどが挙げられる。
【００６０】
混練時の各成分の添加順序については特に限定はないが、例えば、▲１▼（Ａ）〜（Ｄ）をブレンドし混練する方法；▲２▼少量の（Ａ）と（Ｂ）〜（Ｄ）とをブレンド、混練した後、残りの（Ａ）を混練する方法；および▲３▼（Ｂ）〜（Ｄ）をブレンド、混練した後、（Ａ）を混練する方法が挙げられる。これらのうち▲２▼および▲３▼の方法はマスターバッチまたはマスターペレットと呼ばれる方法である。分散性が良く永久帯電防止性と機械的強度に優れる組成物が得られる点で、▲２▼の方法が本発明の樹脂組成物の製造法として特に好ましい。
上記樹脂組成物を製造する際、（Ｄ）を添加する方法については組成物中への効果的な分散のさせ易さから、ポリエーテルエステルアミド（Ｂ）中に予め分散させておくことが好ましい。また、（Ｂ）中へ（Ｄ）を分散させる場合、（Ｂ）の製造（重合）時に予め該（Ｄ）を添加し分散させておくのが特に好ましい。
【００６１】
さらに、本発明の樹脂組成物に非イオン性、アニオン性、カチオン性もしくは両性の界面活性剤を含有させ、帯電防止性を一層向上させてもよい。
非イオン性界面活性剤としては、高級アルコール（炭素数１０〜３０）ＥＯ付加物、脂肪酸ＥＯ付加物、高級アルキルアミン（炭素数１０〜３０）ＥＯ付加物、ポリプロピレングリコール（重合度３〜１７）ＥＯ付加物等のポリエチレングリコール型非イオン界面活性剤；ポリエチレンオキサイド（重合度４〜２０）、グリセリンの脂肪酸エステル、ペンタエリスリットの脂肪酸エステル、ソルビットおよびソルビタンの脂肪酸エステル、多価（３〜６価）アルコールのアルキルエーテル、アルカノールアミン類の脂肪族アミド等の多価（３〜６価）アルコール型非イオン界面活性剤などが挙げられる。
アニオン性界面活性剤としては、高級脂肪酸（炭素数１０〜３０）のアルカリ金属塩等のカルボン酸塩類；高級アルコール（炭素数１０〜３０）硫酸エステル塩、高級アルキルエーテル（炭素数１０〜３０）硫酸エステル塩等の硫酸エステル塩類、アルキル（炭素数８〜３０）ベンゼンスルホン酸塩、アルカン（炭素数８〜３０）スルホン酸塩、パラフィンスルホン酸塩等のスルホン酸塩類などが挙げられる。
カチオン性界面活性剤としては、アルキル（炭素数８〜３０）トリメチルアンモニウム塩等の第４級アンモニウム塩類などが挙げられる。
両性界面活性剤としては、高級アルキル（炭素数８〜３０）アミノプロピオン酸塩等のアミノ酸型両性界面活性剤、高級アルキル（炭素数８〜３０）ジメチルベタイン、高級アルキル（炭素数８〜３０）ジヒドロキシエチルベタイン等のベタイン型両性界面活性剤などが挙げられる。
これらは単独でも２種以上を併用してもよい。これらのうち好ましいものはアニオン性界面活性剤であり、特に好ましいものはアルキルベンゼンスルホン酸塩、アルカンスルホン酸塩、パラフィンスルホン酸塩等のスルホン酸塩類である。
上記界面活性剤の添加量は、特に制約はないが、樹脂組成物の合計重量に対して０．１〜５重量％が好ましい。添加する方法については限定はないが、ポリエーテルエステルアミド合成時に添加してもよいし、溶融混練時に添加してもよい。
【００６２】
また本発明の樹脂組成物には種々の用途に応じ、該組成物の特性を阻害しない範囲で他の樹脂用添加剤を任意に添加することができる。該添加剤としては、顔料、染料、充填剤（例えば、タルク、マイカ、炭酸カルシウム）、核剤（例えばソルビトール、安息香酸金属塩）、ガラス繊維、滑剤（例えば、ステアリン酸カルシウム、ステアリン酸ブチル、オレイン酸アミド、ポリオレフィンワックス、パラフィンワックス）、可塑剤（例えば、フタル酸エステル、リン酸エステル、トルエンスルホンアミド）、離型剤［例えば、（カルボキシル、ヒドロキシル）変性シリコーンオイル、パラフィンワックス、ポリオレフィンワックス］、酸化防止剤（例えば、ヒンダードフェノール）、難燃剤（例えば、ハロゲン系難燃剤、リン系難燃剤、アンチモン系難燃剤、金属水酸化物系難燃剤）、紫外線吸収剤（例えば、ヒンダードアミン、ベンゾトリアゾール）等が挙げられる。
【００６３】
上記添加剤の添加量は、特に制約はないが、充填剤および可塑剤の場合、樹脂組成物の合計重量に対して１〜８０重量％が好ましい。
一方、顔料、染料、核剤、滑剤、離型剤、酸化防止剤、紫外線吸収剤及び難燃剤の場合、樹脂組成物の合計重量に対して０．０１〜１０重量％が好ましい。
【００６４】
本発明の樹脂組成物は成形材料として有用であり、その成形方法としては射出成形、圧縮成形、カレンダ成形、スラッシュ成形、回転成形、押出成形、ブロー成形、フィルム成形（キャスト法、テンター法、インフレーション法等）等が挙げられ、目的に応じて任意の方法で成形できる。
【００６５】
本発明の樹脂組成物を用いて成形してなる成形品は、優れた機械的強度および永久帯電防止性を有すると共に、良好な塗装性ならびに印刷性を有する。
該成形品を塗装する方法としては、例えばエアスプレー塗装、エアレススプレー塗装、静電スプレー塗装、浸漬塗装、ローラー塗装、刷毛塗り等が挙げられるが、これらに限定されるものではない。
塗料としては、例えば、ポリエステルメラミン樹脂系塗料、エポキシメラミン樹脂系塗料、アクリルメラミン樹脂系塗料、アクリルウレタン樹脂系塗料等のプラスチックの塗装に一般に用いられる塗料が挙げられる。塗装膜厚（乾燥膜厚）は目的に応じて適宜選択することができるが通常１０〜５０μｍである。
また、該成形品に印刷する方法としては、一般的にプラスチックの印刷に用いられている印刷法であればいずれも用いることができ、例えばグラビア印刷、フレキソ印刷、スクリーン印刷、オフセット印刷等が挙げられる。印刷インキとしてはプラスチックの印刷に通常用いられるものが使用できる。
【００６６】
本発明の樹脂組成物は、家電・ＯＡ機器・ゲーム機器・事務機器用のハウジング製品、各種プラスチック容器、各種包材用フィルム、床材用シート、マット、自動車部品等の帯電防止性を必要とする各種成形材料として極めて有用である。
【００６７】
【実施例】
以下、実施例により本発明をさらに説明するが、本発明はこれに限定されるものではない。実施例中の「部」は重量部、「％」は重量％を示す。
なお実施例および比較例に記載した成形品の物性評価は、以下の方法によって実施した。
【００６８】
［ポリエーテルエステルアミドの製造］
製造例１
ステンレス製オートクレーブに、ε−カプロラクタム１０５部、アジピン酸１７．１部、「イルガノックス１０１０」（酸化防止剤、チバガイギー社製）０．３部および水７部を仕込み、窒素置換後、２２０℃で加圧密閉下４時間加熱撹拌し、両末端にカルボキシル基を有する酸価１００のポリアミドオリゴマーを１１７部得た。次に数平均分子量２，０００のビスフェノールＡのＥＯ付加物２２５部、酢酸ジルコニル０．５部を加え、２４５℃、１ｍｍＨｇ以下の減圧下の条件で５時間重合し、粘稠なポリマ−を得た。このポリマ−をベルト上にストランド状で取り出し、ペレタイズする事によってポリエーテルエステルアミド［Ｂ−１］を得た。このものの還元粘度は２．１０であった。
【００６９】
製造例２
ステンレス製オートクレーブに、ε−カプロラクタム８３．５部、テレフタル酸１６．５部、「イルガノックス１０１０」０．３部および水６部を仕込み、窒素置換後、２２０℃で加圧密閉下４時間加熱撹拌し、両末端にカルボキシル基を有する酸価１１２のポリアミドオリゴマー９６部を得た。次に数平均分子量２，０００のビスフェノールＡのＥＯ付加物１９２部および酢酸ジルコニル０．５部を加え、２４５℃、１ｍｍＨｇ以下の減圧下の条件で５時間重合し、粘稠なポリマーを得た。以下、製造例１と同様な操作を行い、ポリエーテルエステルアミド［Ｂ−２］を得た。このものの還元粘度は２．１０であった。
【００７０】
実施例１〜６、比較例１〜５
エステル結合を有する熱可塑性樹脂（Ａ）｛［Ａ−２］は（Ａ）と他の熱可塑性樹脂を含有する。｝として以下のものを使用した。
［Ａ−１］：シクロヘキサンジメタノール／エチレングリコール／テレフタル酸共重合物〔商品名 ＥＡＳＴＥＲ ＰＥＴＧ６７６３ イーストマンケミカルジャパン（株）製］
［Ａ−２］：ポリカーボネートおよびアクリロニトリル／スチレン／ブタジエン共重合物（ＡＢＳ樹脂）混合物（ポリカーボネート／ＡＢＳ樹脂重量比＝７０／３０）〔商品名 ユーピロン ＧＰ−１ 三菱瓦斯化学（株）製〕
［Ａ−３］：ポリブチレンテレフタレート〔商品名 バロックス ３１０ 日本ジーイープラスチックス（株）製〕
［Ａ−４］：ポリエステル系熱可塑性ポリウレタン〔商品名 パンデックス Ｔ−５１６５ 大日本インキ化学（株）製〕
［Ａ−５］：ポリメチルメタクリレート〔商品名 アクリペット ＶＨ 三菱レーヨン（株）製〕
酸性リン酸エステル（Ｃ）として以下のものを使用した。
［Ｃ−１］：モノステアリルリン酸およびジステアリルリン酸混合物〔商品名；アデカスタブ ＡＸ−７１ アデカアーガス（株）製 〕
［Ｃ−２］：モノラウリルリン酸〔日本化学（株）製または大八化学（株）製〕アルカリ金属および／またはアルカリ土類金属の塩として以下のものを使用した。
［Ｄ−１］：塩化リチウム（ポリエーテルエステルアミド製造時に添加）
［Ｄ−２］：酢酸カリウム（ポリエーテルエステルアミド製造時に添加）
［Ｄ−３］：塩化マグネシウム（ポリエーテルエステルアミド製造時に添加）
表１に示す処方（表中、数字は配合する部を示す。）に従って、上記（Ａ）〜（Ｃ）［（Ｄ）は（Ｂ）の製造時に添加］を、ヘンシェルミキサーで３分間ブレンドした後、ベント付き２軸押出機にて、以下のような各温度、１００ｒｐｍ、滞留時間５分の条件で溶融混練して、本発明の樹脂組成物および比較例の樹脂組成物を得た。

【００７１】
【表１】

【００７２】
性能試験
本発明の樹脂組成物および比較例の樹脂組成物について、射出成形機を用いて試験片を作成し、外観、表面固有抵抗値、ＩＺＯＤ衝撃強度および引張降伏点強度を評価した。射出成形機のシリンダー温度は以下のような各温度、金型温度５０℃で試験片を作成した。その結果を表２に示した。外観、表面固有抵抗値、ＩＺＯＤ衝撃強度および引張降伏点強度の評価は下記の方法により行った。

（２）表面固有抵抗値：（ａ）水洗前；成形後の試験片を、２３℃、湿度５０％ＲＨ雰囲気下に４８時間放置した後、ＡＳＴＭ Ｄ２５７−７８（Ｒｅａｐｐｒｏｖｅｄ １９８３）に準拠し測定した。
（ｂ）水洗後；成形後、試験片を洗剤（ママレモン；ライオン(株)製）水溶液で洗浄処理し、次いでイオン交換水で充分洗ったのち、表面の水分を乾燥除去してから２３℃、湿度５０％ＲＨ雰囲気下に２４時間放置した後、ＡＳＴＭ Ｄ２５７−７８（Ｒｅａｐｐｒｏｖｅｄ １９８３）に準拠し測定した。
（３）ＩＺＯＤ衝撃強度：ＪＩＳ Ｋ７１１０−１９８４に準拠（ノッチ付、 ３．２ｍｍ厚）。
（４）引張降伏点強度：ＪＩＳ Ｋ７１１３−１９８１に準拠。
【００７３】
【表２】

【００７４】
表２から明らかなように本発明の樹脂組成物は、比較例に比較し永久帯電防止性に優れ、かつ機械的特性に優れている。すなわち、従来達し得なかった優れた永久帯電防止性と機械的特性とを併せ有する樹脂組成物である。
【００７５】
【発明の効果】
本発明のポリオレフィン系樹脂組成物は、従来の技術では達し得なかった優れた永久帯電防止性を有し、かつ機械的特性および成形性にも優れる。
上記効果を奏することから本発明の樹脂組成物は、家電・ＯＡ機器用のハウジング製品、各種プラスチック容器、自動車部品等の帯電防止性を必要とする各種成形材料として極めて有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin composition. More specifically, the present invention relates to a thermoplastic resin composition useful as a molding material for various plastic molded articles.
[0002]
[Prior art]
Conventionally, as a method for imparting permanent antistatic property to a thermoplastic resin having an ester bond, a method of adding a polyether ester amide has been known. However, in this method, due to the interaction between the polyether ester amide and the thermoplastic resin having an ester bond, the low molecular weight of the thermoplastic resin and the polyether ester amide is lowered, the resin strength is lowered, and molding failure is caused. There was a problem.
To solve this problem, a method has been proposed in which a phosphite compound and / or a phenol compound is added to and added to a polycarbonate resin, but a sufficient effect has not been obtained. (Japanese Patent Laid-Open No. 5-43787)
[0003]
[Problems to be solved by the invention]
It is an object of the present invention to provide a thermoplastic resin composition having an ester bond having permanent antistatic properties and excellent mechanical strength.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have found that in a resin composition comprising a thermoplastic resin (A) having an ester bond and a polyether ester amide (B), an acidic phosphate ester (C ), And an alkali metal and / or alkaline earth metal salt (D) having a weight ratio of (C) / (D) of 1 to 30 And a resin composition characterized in that the total weight of (C) and (D) is 0.001 to 5% by weight based on the total weight of the thermoplastic resin, and a molded product thereof The present invention has also found that the molded article has permanent antistatic properties and excellent mechanical strength, and has reached the present invention.
[0005]
Examples of the polyether ester amide (B) include those that are at least one selected from the group consisting of the following i) to iv).
i) From at least one component selected from the group consisting of polyamide-forming monomers and polyamides, at least one component selected from the group consisting of polyester-forming monomers and polyesters, and optionally from the group consisting of diols and diamines Polyether ester amide obtained by reacting at least one selected component;
ii) a polyether ester amide obtained by reacting a diol with at least one component selected from the group consisting of polyamide-forming monomers and carboxyl group-containing polyamides;
iii) a polyether ester amide obtained by reacting a component comprising a carboxyl group-containing polyester with a diamine; and
iv) A polyether ester amide obtained by reacting a diol and a diamine with a component selected from the group consisting of a dicarboxylic acid, an ester-forming derivative thereof, a lactone and a hydroxycarboxylic acid.
[0006]
As the polyester-forming monomer, at least one selected from the group consisting of the following (1) to (3) can be used.
(1) Carbonic acid or dicarboxylic acid and / or its ester-forming derivative and diol
(2) Lactone
(3) Hydroxycarboxylic acid
[0007]
As the dicarboxylic acid, for example, dicarboxylic acids having 2 to 48 carbon atoms can be used, and examples thereof include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids.
[0008]
Aliphatic dicarboxylic acids include saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, methyl succinic acid, dimethyl malonic acid, β-methyl glutaric acid, ethyl succinic acid, isopropyl malonic acid, adipic acid, Pimelic acid, suberic acid, azelaic acid, sebacic acid, decanediic acid, undecanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, hexadecanediic acid, octadecanediic acid and icosandiic acid, etc., and unsaturated aliphatic dicarboxylic acids such as, for example, Maleic acid, fumaric acid, citraconic acid, mesaconic acid and the like can be mentioned.
[0009]
Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, tetrabromophthalic acid, methyl isophthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipic acid, Examples include β-phenyladipic acid, biphenyl-2,2′-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 5-sulfoisophthalate, and potassium 5-sulfoisophthalate.
[0010]
Examples of the alicyclic dicarboxylic acid include 1,3-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarboxylic acid. Examples include acid, 1,4-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid, and dicyclohexyl-4,4-dicarboxylic acid.
In addition, dimer acid [a dimer of fatty acid (having 8 to 24 carbon atoms, such as oleic acid, linoleic acid, linolenic acid)] can also be used.
[0011]
Ester-forming derivatives include esters of dicarboxylic acids, acid anhydrides and acid halides. Examples thereof include carbonic acid and dialkyl (carbon number 1 to 4) ester (dimethyl ester, diethyl ester, dibutyl ester) and diphenyl ester of the above dicarboxylic acid, and acid anhydrides (phthalic anhydride, etc.).
[0012]
As the diol, glycol and / or polyoxyalkylene diol and dihydric phenol can be used.
[0013]
As glycol, C2-C20 aliphatic glycol, C5-C12 alicyclic glycol, C8-C26 araliphatic glycol, etc. can be used.
[0014]
Aliphatic glycols include alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-hexanediol, 1 , 4-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,10-decanediol, 1,18-octadecanediol, and 1 , 20-eicosanediol; and di (thio) alkylene glycols such as diethylene glycol and thiodiethylene glycol.
[0015]
Examples of alicyclic glycols include cycloalkylene glycols such as 1-hydroxymethyl-1-cyclobutanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1-methyl-3, 4-cyclohexanediol, 2-hydroxymethylcyclohexanol, 4-hydroxymethylcyclohexanol, 1,4-cyclohexanedimethanol, and bicycloalkylene glycols such as 1,1′-dihydroxy-1,1′-dicyclohexylmethane Can be mentioned.
[0016]
Examples of the araliphatic glycol include 1,4-dihydroxymethylbenzene, 2-phenyl 1,3-propanediol, 2-phenyl 1,4-butanediol, 2-benzyl 1,3-propanediol, and triphenylethylene. Examples include glycol, tetraphenylethylene glycol, and benzopinacol.
[0017]
As the dihydric phenol, phenol having 6 to 30 carbon atoms can be used. Specifically, monocyclic dihydric phenols such as catechol, resorcinol, hydroquinone; condensed ring dihydric phenols such as dihydroxynaphthalene; bisphenols such as bisphenol A, bisphenol F, bisphenol S, dihydroxy diphenyl ether, dihydroxy diphenyl thioether; And binaphthol; and alkyl (1 to 10 carbon atoms) or halogen (chlorine, bromine, etc.) substitutes thereof (for example, brominated bisphenol A).
[0018]
The polyoxyalkylene diol includes a compound having two active hydrogen atoms, such as a compound having a structure in which an alkylene oxide (hereinafter referred to as AO) is added to a glycol, amine, dicarboxylic acid, dihydric phenol or the like (AO addition mole). Number; usually 2 to 100 moles) and mixtures of two or more thereof.
AO includes 2 to 30 (preferably 2 to 4) carbon atoms such as ethylene oxide (EO), propylene oxide (PO), 1,2-, 2,3- and 1,3-butylene oxide, tetrahydrofuran. (THF), styrene oxide, α-olefin oxide having 5 to 30 carbon atoms, epichlorohydrin and the like.
AO may be used alone or in combination of two or more. In the latter case, block addition (chip type, balance type, active secondary type, etc.), random addition, or a mixed system thereof may be used.
[0019]
As the glycol, dihydric phenol and dicarboxylic acid to which AO is added, those exemplified above can be used.
[0020]
Examples of the amine include aliphatic or aromatic primary monoamines having 1 to 20 carbon atoms, aliphatic secondary diamines having 4 to 18 carbon atoms, heterocyclic primary (or secondary di) amines having 4 to 13 carbon atoms, An alicyclic secondary polyamine having 6 to 14 carbon atoms and an aromatic secondary diamine having 8 to 14 carbon atoms can be used.
[0021]
Aliphatic or aromatic primary monoamines include alkyl or alkenyl amines such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, s-butylamine, isobutylamine, n-amylamine, isoamylamine, n -Hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-octadecylamine, n-icosylamine and oleylamine; arylamines such as aniline and toluidine; N, N'-dialkyl (1 to 4 carbon atoms) ) Aminoalkyl (2 to 10 carbon atoms) amine such as dimethylaminoethylamine.
[0022]
Examples of the aliphatic secondary diamine include N, N′-dialkyl (C1 to C4) alkylene (C2 to C10) diamine, such as N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N , N'-dibutylethylenediamine, N, N'-dimethylpropylenediamine, N, N'-diethylpropylenediamine, N, N'-dibutylpropylenediamine, N, N'-dimethyltetramethylenediamine, N, N'- Diethyltetramethylenediamine, N, N′-dibutyltetramethylenediamine, N, N′-dimethylhexamethylenediamine, N, N′-diethylhexamethylenediamine, N, N′-dibutylhexamethylenediamine, N, N′- Dimethyl decamethylene diamine, N, N'-diethyl decamethylene diamine and N, N'-dibutylde Camethylenediamine etc. are mentioned.
[0023]
Examples of the heterocyclic primary (or secondary di) amine include piperazine, 1-aminopiperidine, 1-aminohomopiperidine, 2-aminothiazole, 2-aminobenzothiazole, 3-aminotriazine, and 3-amino. Examples include -9-methylcarbazole, 9-aminofluorene, and alkyls (having 1 to 10 carbon atoms) or halogen-substituted products thereof.
[0024]
Examples of the alicyclic secondary diamine include N, N′-dimethyl-1,2-cyclobutanediamine, N, N′-diethyl-1,2-cyclobutanediamine, N, N′-dibutyl-1,2- Cyclobutanediamine, N, N'-dimethyl-1,4-cyclohexanediamine, N, N'-diethyl-1,4-cyclohexanediamine, N, N'-dibutyl-1,4-cyclohexanediamine, N, N'- Dimethyl-1,3-cyclohexanediamine, N, N′-diethyl-1,3-cyclohexanediamine, N, N′-dibutyl-1,3-cyclohexanediamine and their alkyl (C 1-10) or halogen substitution Examples include the body.
[0025]
Examples of the aromatic secondary diamine include N, N′-dimethyl-phenylenediamine, N, N′-dimethyl-xylylenediamine, N, N′-dimethyl-diphenylmethanediamine, and N, N′-dimethyl-diphenyldiamine. -Terdiamine, N, N'-dimethyl-benzidine, N, N'-dimethyl-1,4-naphthalenediamine and the like.
[0026]
As the lactone, a lactone having 4 to 20 carbon atoms can be used. For example, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-pimerolactone, γ-caprolactone, γ-decanolactone, enanthate. Examples include lactone, laurolactone, undecanolactone, and eicosanolactone.
[0027]
As the hydroxycarboxylic acid, a hydroxycarboxylic acid having 2 to 20 carbon atoms can be used. For example, hydroxyacetic acid, lactic acid, ω-hydroxycaproic acid, ω-hydroxyenanthic acid, ω-hydroxycaprylic acid, ω-hydroxypergonic acid , Ω-hydroxycapric acid, 11-hydroxyundecanoic acid, 12-hydroxydodecanoic acid and 20-hydroxyeicosanoic acid.
[0028]
Polyester is prepared by using the above polyester-forming monomer and a known polyester forming method [a method of reacting a diol with a dicarboxylic acid or an ester-forming derivative thereof or a dicarboxylic acid anhydride and AO, a lactone or a hydroxycarboxylic acid using a diol or a dicarboxylic acid as an initiator. It can be produced by a method of reacting an acid or a method combining these. For example, the method described in Japanese Patent Publication No. 58-19696 can be mentioned.
The polyester includes a carboxyl group-containing polyester and a hydroxyl group-containing polyester.
[0029]
As the polyamide-forming monomer, at least one selected from the group consisting of the following (1) to (3) can be used.
(1) Aminocarboxylic acid
(2) Lactam
(3) Nylon salt obtained from diamine and dicarboxylic acid
[0030]
As the aminocarboxylic acid, an aminocarboxylic acid having 2 to 20 carbon atoms can be used. Examples include capric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and 20-aminoeicosanoic acid.
[0031]
As the lactam, a lactam having 4 to 20 carbon atoms can be used. Examples include undecanolactam, eicosanolactam and 5-phenyl-2-piperidone.
[0032]
As the diamine, a diamine having 2 to 20 carbon atoms can be used, and aliphatic, alicyclic, and aromatic diamines are included. Examples include ethylene diamine, tetramethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, decamethylene diamine, eicosane diamine, xylylene diamine, and cyclohexyl diamine.
[0033]
As the dicarboxylic acid, those described above can be used.
Nylon salts obtained from diamine and dicarboxylic acid include: ethylenediamine and adipic acid nylon salt, tetramethylenediamine and adipic acid nylon salt, hexamethylenediamine and adipic acid nylon salt, xylylenediamine and adipic acid nylon salt, Nylon salt of decamethylenediamine and adipic acid, nylon salt of hexamethylenediamine and decanedioic acid, nylon salt of xylylenediamine and decanedioic acid, nylon salt of hexamethylenediamine and dodecanedioic acid and hexamethylenediamine and 1,4-cyclohexanedicarboxylic acid The nylon salt of an acid is mentioned.
[0034]
Examples of the polyamide include those obtained by ring-opening polymerization or dehydration polycondensation of a polyamide-forming monomer by a known method. Polyamide includes carboxyl group-containing polyamide and amino group-containing polyamide.
Specific examples of polyamides include nylon 6,6, nylon 6,9, nylon 6,12, nylon 6, nylon 11, nylon 12, nylon 4,6, a copolymer of nylon 6 and nylon 6,6, nylon 6 And a copolymer of nylon 6 and nylon 6, a copolymer of nylon 6 and nylon 6, 6 and nylon 12, or a copolymer of diamine and / or dicarboxylic acid.
[0035]
A carboxyl group-containing polyamide is obtained by adding a dicarboxylic acid as a molecular weight modifier to a polyamide-forming monomer and subjecting it to ring-opening polymerization or polycondensation, and obtained by depolymerizing a polyamide with a dicarboxylic acid as a molecular weight modifier. Things can be used.
[0036]
The carboxyl group-containing polyamide can be easily produced by a known method. In the former case, for example, the method described in JP-B-4-72855, and in the latter case, for example, JP-B-7-91526. Can be produced by the method described in the above.
[0037]
Among the above polyether ester amides (B), preferred are the polyether ester amides belonging to the group ii) above, wherein the carboxyl group-containing polyamide has a number average molecular weight (hereinafter referred to as Mn) of 200 to 5,000. A polyether ester amide derived from (b1) and an AO adduct (b2) and / or polyoxyalkylene glycol (b3) of a dihydric phenol having an Mn of 300 to 5,000, particularly preferred is ( It is a polyether ester amide derived from b1) and an EO adduct of a dihydric phenol having an Mn of 300 to 5,000.
The number average molecular weight (Mn) and the weight average molecular weight (Mw) described above and below are values obtained by gel permeation chromatography (GPC) using polystyrene as a standard.
[0038]
The polyether ester amide (B) can be easily produced from the above components i to iv by a known polyesterification reaction, polyamidation reaction, or amide-ester exchange reaction.
The temperature of these reactions is usually 200 to 280 ° C. In general, the polyesterification and amide-ester exchange reaction are carried out in the presence of an inert gas or under reduced pressure. Polyamidation is performed under normal pressure to pressurized conditions in the presence of an inert gas. Specifically, it can be produced by a method described in JP-B-4-72855.
[0039]
Moreover, a well-known esterification catalyst is normally used for said polyamidation reaction. Examples of the catalyst include antimony-based catalysts such as antimony trioxide; tin-based catalysts such as monobutyltin oxide; titanium-based catalysts such as tetrabutyl titanate; tetraalkyl zirconates (for example, tetrabutyl zirconate), zirconium organic acid salts Zirconium-based catalysts such as (for example, zirconyl acetate); metal acetate-based catalysts such as zinc acetate; and combinations of two or more of these. Of these, preferred are a zirconium-based catalyst and a metal acetate-based catalyst, and particularly preferred is zirconyl acetate. The usage-amount of a catalyst is 0.1 to 5 weight% normally with respect to the total weight of a reaction material.
[0040]
Reduced viscosity (η) of (B) _SP / C, C = 0.5 wt% m-cresol solution, 25 ° C .; the same applies hereinafter) is not particularly limited, but is preferably 0.5 or more from the viewpoint of heat resistance and 4.0 from the viewpoint of moldability. The following is preferred. More preferably, it is 0.6-3.0.
[0041]
Examples of the thermoplastic resin (A) having an ester bond in the present invention include a thermoplastic polyester resin (A1), a polycarbonate resin (A2), a polyester-based thermoplastic polyurethane resin (A3), and an ester group-containing vinyl monomer (co-polymer). ) Polymer (A4) and the like.
[0042]
(A1) includes condensed polyesters and polylactones. Examples of the condensed polyester include a condensate of the above-mentioned dicarboxylic acid or an ester-forming derivative component thereof and the above-mentioned diol component (of which the polyoxyalkylenediol has a degree of polymerization of 1 to 10), the above-mentioned hydroxycarboxylic acid These condensates can be mentioned. Examples of the polylactone include a ring-opening polymer of the above lactone using the above diol or dicarboxylic acid as an initiator.
Furthermore, these (A1) include branched components such as trivalent or tetravalent carboxylic acids such as tricarballylic acid, trimesic acid, trimellitic acid, pyromellitic acid and / or glycerin, trimethylolpropane, pentaerythritol, etc. The polyhydric (trivalent or tetravalent) alcohol may be copolymerized in a small amount, for example, 1 mol% or less, more preferably 0.5 mol% within a range not inhibiting the thermoplasticity.
Specifically, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, poly (cyclohexane-1,4-dimethylene) terephthalate, cyclohexanedimethanol / ethylene glycol / terephthalic acid copolymer, polyneopentylene terephthalate Examples include polybutylene adipate, polyethylene adipate, and poly-ε-caprolactone.
Of these, preferred are polybutylene terephthalate and cyclohexanedimethanol / ethylene glycol / terephthalic acid copolymer.
[0043]
(A2) includes a polymer having a structural unit represented by the general formula (6), and examples thereof include those having a structure derived from dihydric phenol and phosgene or a derivative thereof.
[Chemical 6]

(Wherein R _Five And R ₆ Are each H, Cl, Br or an alkyl group having 1 to 8 carbon atoms, which may be the same or different, s and t are each an integer of 1 to 4, and s is 2 In case of ~ 4, R _Five May be different from each other, or may be different from each other when t is 2 to 4. Z is an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, or SO. ₂ , SO, S, O, CO are shown. )
Specific examples of the dihydric phenol constituting (A2) include, for example, bisphenol A, bisphenol F, bisphenol S, and alkyl (1 to 8 carbon atoms) or halogen (chlorine, bromine, etc.) substituted products (for example, bromine). Bisphenol A) and the like.
These dihydric phenols may be used alone or in combination of two or more. Moreover, you may use combining the above-mentioned aliphatic diol.
Among these dihydric phenols, bisphenol A is particularly preferable.
[0044]
Examples of (A3) include organic diisocyanates and polyester diols (polyester diols having a molecular weight of 500 to 5000 or more, polymer polyols obtained by polymerizing vinyl monomers (for example, acrylonitrile and / or styrene) in the diols, etc.) One-shot, chain extenders (diols such as 1,4-butylene glycol and / or diamines such as ethylenediamine) and optionally quenchers (monohydric alcohols, primary or secondary monoamines, or mono- or di-alkanolamines) The polyurethane obtained by making it react by a method or a prepolymer method is mentioned.
As organic diisocyanate, C6-C20 aromatic diisocyanate, C2-C18 aliphatic diisocyanate, C4-C15 alicyclic diisocyanate, carbon number (excluding carbon in NCO group, the same applies hereinafter) 8-15 araliphatic diisocyanates, modified products of these diisocyanates and mixtures of two or more of these can be used. Specific examples include those described in International Publication No. WO 00/47652.
[0045]
The polyester diol may be a condensed polyester diol obtained by reacting a diol (low molecular diol and / or polyoxyalkylene diol having a molecular weight of 1000 or less) with a dicarboxylic acid or an ester-forming derivative thereof, or a dicarboxylic acid anhydride and an alkylene oxide. A polylactone diol obtained by ring-opening polymerization of the above lactone using the above diol as an initiator, obtained by reacting a low molecular diol with a carbonic acid diester of a lower alcohol (1 to 4 carbon atoms). Polycarbonate diol and the like are included.
Examples of the low molecular diol include the above-described glycols.
Examples of the polyoxyalkylene diol include those described above.
As the dicarboxylic acid and lactone, those mentioned above as the raw material of (A1) can be used.
Specific examples of these polyester diols include polyethylene adipate diol, polyhexamethylene adipate diol, polycaprolactone diol or polyhexamethylene carbonate diol.
Of these, preferred are adipate thermoplastic polyurethanes.
[0046]
(A4) includes (co) polymers of ester group-containing vinyl monomers, and copolymers of ester group-containing vinyl monomers and other vinyl monomers. Examples of the ester group-containing vinyl monomer include esters of carboxyl group-containing vinyl monomers and esters of unsaturated alcohols.
Esters of carboxyl group-containing vinyl monomers include unsaturated carboxylic acids [monocarboxylic acids; eg (meth) acrylic acid, crotonic acid, oleic acid, 4-vinylbenzoic acid, cinnamic acid; polycarboxylic acids such as (Anhydrous) maleic acid, fumaric acid, itaconic acid, citraconic acid] and alcohols having 1 to 50 carbon atoms [alkanol, cycloalkanol, benzyl alcohol, diol (the aforementioned glycol, polyoxyalkylene diol), tertiary amino group-containing alcohol For example, esters with dialkyl (C1-4) alkanol (C2-4) amine, N-hydroxyalkyl (C2-4) morpholine, epoxy-containing alcohol (glycidol, etc.)].
Specifically, an alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl. (Meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate and the like.
Examples of unsaturated alcohol esters include unsaturated alcohols [vinyl alcohol, (meth) allyl alcohol, isopropenyl alcohol, etc.] and carboxylic acids having 2 to 18 carbon atoms [monocarboxylic acid, benzoic acid, the aforementioned dicarboxylic acid, etc.]. Esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl (meth) acrylate, methyl 4-vinylbenzoate, cyclohexyl (meth) acrylate, benzyl (meth) Examples include acrylate, phenyl (meth) acrylate, vinyl methoxyacetate, vinyl benzoate and the like.
Other vinyl monomers include vinyl hydrocarbons [aromatic vinyl hydrocarbons (styrene, α-methylstyrene, etc.), aliphatic vinyl hydrocarbons (ethylene, propylene, butadiene, etc.)], nitrogen-containing vinyl monomers [ Examples thereof include amide group-containing vinyl monomers {(meth) acrylamide and the like}, nitrile group-containing vinyl monomers {(meth) acrylonitrile and the like}, and halogen element-containing vinyl monomers [vinyl chloride, chloroprene and the like].
Specific examples of (A4) include polymethyl methacrylate, styrene / methyl methacrylate / acrylonitrile copolymer, methyl methacrylate / butadiene / styrene copolymer (MBS resin), ethylene / glycidyl methacrylate copolymer, ethylene / acetic acid. Examples include vinyl / glycidyl methacrylate copolymer.
[0047]
The Mw of (A) is preferably 20,000 to 500,000 or more, more preferably 25,000 to 45,000 or more.
[0048]
Furthermore, in this invention, you may mix | blend another thermoplastic resin with the thermoplastic resin (A) which has an ester bond. Such other thermoplastic resins include styrene (co) polymers such as styrene / acrylonitrile copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), styrene / butadiene copolymer; olefin ( (Co) polymers such as polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / 4-methylpentene copolymer, ethylene / butene-1 copolymer, polyacetal [for example, formaldehyde Homopolymers, copolymers of trioxane and alkylene oxides (for example, ethylene oxide, propylene oxide, etc.), and maleic anhydride-modified products thereof.
[0049]
The blending ratio with respect to the total weight of the thermoplastic resin (A) is preferably 30 to 97% by weight, particularly preferably 40 to 90% by weight.
The blending ratio with respect to the total weight of the thermoplastic resin (B) is preferably 3 to 50% by weight, particularly preferably 5 to 40% by weight.
The blending ratio of the “other thermoplastic resin” with respect to the total weight of the thermoplastic resin is preferably 0 to 67% by weight, particularly preferably 0 to 50% by weight.
The “total weight of the thermoplastic resin” in the present invention is the total weight of (A), (B) and the above “other thermoplastic resin”.
[0050]
As the acidic phosphate ester (C) of the present invention, any acidic phosphate ester generally used as an additive for plastics can be used. For example, one obtained by substituting 1 to 3 or more active hydrogens of phosphoric acids. Examples of phosphoric acids include phosphoric acid, metaphosphoric acid, orthophosphoric acid, phosphorous acid, phosphonic acid, pyrophosphoric acid, diphosphinic acid, diphosphoric acid, and diphosphonic acid. Examples of the group that substitutes active hydrogen include an alkyl group, an aryl group, an alkenyl group, and a hydroxyalkyl group (all having 1 to 30 carbon atoms).
Examples of the above include monoalkyl esters, monoaryl esters, dialkyl esters, diaryl esters of phosphoric acid, monoalkyl esters of phosphorous acid, trialkyl esters of pyrophosphoric acid, and the like. Of these, preferred are those represented by the general formula (1).
[Chemical 7]

(N is 1 or 2. R ₁ Represents a monovalent hydrocarbon group having 1 to 30 carbon atoms, and when n is 2, they may be the same or different. )
In the general formula (1), R ₁ Examples of the alkyl group having 1 to 30 carbon atoms represented by: methyl, ethyl, n- and i-propyl, n-, i-, sec- and t-butyl, amyl, tertiary amyl, hexyl, octyl, Examples include isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, tertiary nonyl, isononyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, triancontyl and the like. When n is 2, two R ₁ May be the same or different.
More preferred as the acidic phosphate ester is R ₁ Is an acidic phosphate having 8 to 30 carbon atoms, and particularly preferable are monostearyl ester of phosphoric acid and distearyl ester of phosphoric acid.
[0051]
The acidic phosphate ester is, for example, a method of hydrolyzing a corresponding trialkyl phosphate or a corresponding triester or tetraester of phosphoric acid, a method of hydrolyzing after reacting phosphorus oxychloride with a corresponding alkanol, or It can be synthesized by a known method such as a method of reacting phosphorus pentoxide with the corresponding alkanol.
[0052]
In addition, the alkali metal and / or alkaline earth metal salt (D) of the present invention includes an organic acid (carbon) of an alkali metal (lithium, sodium, potassium, etc.) and / or an alkaline earth metal (magnesium, calcium, etc.). 1 to 12 mono- or dicarboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid and succinic acid; sulfonic acids having 1 to 20 carbon atoms such as methanesulfonic acid and p-toluenesulfonic acid; And salts of inorganic acids (hydrohalic acids such as hydrochloric acid, hydrobromic acid, perchloric acid, sulfuric acid, phosphoric acid, etc.).
Specific examples include lithium acetate, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, magnesium bromide, potassium perchlorate, potassium sulfate, potassium phosphate, and potassium thiocyanate. Of these, halides (especially lithium chloride, sodium chloride, potassium chloride) and acetates (especially potassium acetate) are preferred.
[0053]
(C) and (D) have a weight ratio of (C) / (D) of 1 to 50, and the total weight of (C) and (D) is 0.001 to the total weight of the thermoplastic resin. It is contained so as to be 5% by weight. When the weight ratio of (C) / (D) is less than 1 or exceeds 50, the antistatic property and the physical properties of the resin are deteriorated. When the total weight of (C) and (D) is less than 0.001% by weight or more than 5.0% by weight with respect to the total weight of the thermoplastic resin, antistatic properties and resin physical properties are deteriorated.
The weight ratio of (C) / (D) is particularly preferably 2 to 30, and more preferably 5 to 25. The total weight of (C) and (D) is particularly preferably 0.001 to 3, and more preferably 0.01 to 2, based on the total weight of the thermoplastic resin.
[0054]
Moreover, as a resin composition of this invention, a phosphite can be added if necessary. The phosphite ester is represented by the general formulas (2), (3), (4) and (5).
[Chemical 8]

(R ₂ , R ₂ ', R ₂ "" Is a monovalent hydrocarbon group having 1 to 25 carbon atoms, which may be the same or different. "
[Chemical 9]

(M is an integer of 2 to 4. R _Three Is a hydrocarbon group having 1 to 40 carbon atoms, and is bivalent when m is 2, trivalent when m is 3, and tetravalent when m is 4. R _Three 'And R _Three "" Is a monovalent hydrocarbon group having 1 to 25 carbon atoms, which may be the same or different. "
Embedded image

(K is 1 or 2. R _Four Is a hydrocarbon group having 1 to 40 carbon atoms, and is bivalent when k is 1 and tetravalent when k is 2. R _Four 'Is a monovalent hydrocarbon group having 1 to 25 carbon atoms, and when k is 2, they may be the same or different. )
Embedded image

(P is an integer of 1 to 4. R ₇ Is a hydrocarbon group having 1 to 40 carbon atoms, and each p is 1 to 4 valences when p is 1 to 4. R ₇ ', R ₇ "" Is a monovalent hydrocarbon group having 1 to 25 carbon atoms, and may be the same or different when p is 2 to 4. "
[0055]
Examples of the phosphite represented by the general formula (2) include trilauryl phosphite, triisooctyl phosphite, trioleyl phosphite, triphenyl phosphite, trioctadecyl phosphite, triisodecyl phosphite. , Trinormal butyl phosphite, tris-2-ethylhexyl phosphite, tristearyl phosphite, tris-2,4-ditertiary butylphenyl phosphite, tristridecyl phosphite, tris-4-phenylphenol phosphite , Trisnonyl phenyl phosphite, phenyl diisodecyl phosphite, phenyl dioctyl phosphite, diphenyl nonyl phenyl phosphite, diphenyl isodecyl phosphite, diphenyl Seo octyl phosphite, diphenyl decyl phosphite, and the like diphenyl tridecyl phosphite.
[0056]
Examples of the phosphite represented by the general formula (3) include tetraphenyl dipropylene glycol diphosphite, tetralauryl bisphenol A-diphosphite, tetratridecyl bisphenol A-diphosphite, tetraphenyl tetra Examples include tridecylpentaerythritol-tetraphosphite.
[0057]
Examples of the phosphite represented by the general formula (4) include diisodecylpentaerythritol-diphosphite, dilaurylpentaerythritol-diphosphite, distearylpentaerythritol-diphosphite, dinonylphenylpentaerythritol. -Diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite and the like.
[0058]
Examples of the phosphite represented by the general formula (5) include tetrakis (2,4-ditertiary butylphenol) 4,4′-biphenylene diphosphonite (P-EPQ).
Preferred as the phosphite is bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite.
The phosphite is preferably 0 to 100% by weight, more preferably 0 to 80% by weight, based on the weight of (C).
[0059]
The resin composition of the present invention can be obtained by kneading the components (A) to (D) using various known mixers. Examples of the mixer include an extruder, a brabender, a kneader, and a Banbury mixer.
[0060]
The order of addition of each component during kneading is not particularly limited. For example, (1) A method of blending (A) to (D) and kneading; (2) A small amount of (A) and (B) to (D ) Are blended and kneaded, and then the remaining (A) is kneaded; and (3) (B) to (D) are blended and kneaded, and then (A) is kneaded. Of these, methods (2) and (3) are called master batches or master pellets. The method (2) is particularly preferred as a method for producing the resin composition of the present invention in that a composition having good dispersibility and excellent permanent antistatic properties and mechanical strength can be obtained.
When the resin composition is produced, it is preferable that the method of adding (D) is previously dispersed in the polyether ester amide (B) from the viewpoint of effective dispersion in the composition. . When (D) is dispersed in (B), it is particularly preferable to add (D) and disperse it in advance during the production (polymerization) of (B).
[0061]
Furthermore, the resin composition of the present invention may contain a nonionic, anionic, cationic or amphoteric surfactant to further improve the antistatic property.
Nonionic surfactants include higher alcohol (10-30 carbon atoms) EO adduct, fatty acid EO adduct, higher alkylamine (10-30 carbon atoms) EO adduct, polypropylene glycol (degree of polymerization 3-17). Polyethylene glycol type nonionic surfactants such as EO adducts; polyethylene oxide (degree of polymerization 4 to 20), fatty acid ester of glycerin, fatty acid ester of pentaerythritol, fatty acid ester of sorbit and sorbitan, polyvalent (3 to 6 valences) And polyhydric (3-6 valent) alcohol type nonionic surfactants such as alcohol alkyl ethers and alkanolamine aliphatic amides.
Examples of anionic surfactants include carboxylates such as alkali metal salts of higher fatty acids (10 to 30 carbon atoms); higher alcohol (10 to 30 carbon atoms) sulfate esters, higher alkyl ethers (10 to 30 carbon atoms). Examples thereof include sulfate esters such as sulfate ester salts, and sulfonates such as alkyl (carbon number 8 to 30) benzene sulfonate, alkane (carbon number 8 to 30) sulfonate, and paraffin sulfonate.
Examples of the cationic surfactant include quaternary ammonium salts such as alkyl (carbon number 8 to 30) trimethylammonium salts.
As the amphoteric surfactant, amino acid-type amphoteric surfactants such as higher alkyl (carbon number 8 to 30) aminopropionate, higher alkyl (carbon number 8 to 30) dimethylbetaine, higher alkyl (carbon number 8 to 30) Examples include betaine-type amphoteric surfactants such as dihydroxyethyl betaine.
These may be used alone or in combination of two or more. Among these, preferred are anionic surfactants, and particularly preferred are sulfonates such as alkylbenzene sulfonate, alkane sulfonate, and paraffin sulfonate.
Although there is no restriction | limiting in particular in the addition amount of the said surfactant, 0.1 to 5 weight% is preferable with respect to the total weight of a resin composition. Although there is no limitation about the method to add, you may add at the time of the synthesis | combination of polyetheresteramide, and you may add at the time of melt-kneading.
[0062]
Moreover, according to various uses, the resin composition of this invention can add the additive for other resins arbitrarily in the range which does not inhibit the characteristic of this composition. Examples of the additives include pigments, dyes, fillers (eg, talc, mica, calcium carbonate), nucleating agents (eg, sorbitol, metal benzoate), glass fibers, lubricants (eg, calcium stearate, butyl stearate, olein) Acid amide, polyolefin wax, paraffin wax), plasticizer (eg, phthalate ester, phosphate ester, toluenesulfonamide), mold release agent [eg (carboxyl, hydroxyl) modified silicone oil, paraffin wax, polyolefin wax], Antioxidants (for example, hindered phenols), flame retardants (for example, halogen flame retardants, phosphorus flame retardants, antimony flame retardants, metal hydroxide flame retardants), ultraviolet absorbers (for example, hindered amines, benzotriazoles) ) And the like.
[0063]
The addition amount of the additive is not particularly limited, but in the case of a filler and a plasticizer, it is preferably 1 to 80% by weight with respect to the total weight of the resin composition.
On the other hand, in the case of pigments, dyes, nucleating agents, lubricants, mold release agents, antioxidants, ultraviolet absorbers and flame retardants, 0.01 to 10% by weight is preferable with respect to the total weight of the resin composition.
[0064]
The resin composition of the present invention is useful as a molding material. The molding methods include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method). And the like, and can be molded by any method depending on the purpose.
[0065]
A molded product formed by using the resin composition of the present invention has excellent mechanical strength and permanent antistatic properties, and also has good paintability and printability.
Examples of the method for coating the molded product include, but are not limited to, air spray coating, airless spray coating, electrostatic spray coating, immersion coating, roller coating, and brush coating.
Examples of the paint include paints generally used for plastic coating such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, and acrylic urethane resin paint. The coating film thickness (dry film thickness) can be appropriately selected according to the purpose, but is usually 10 to 50 μm.
In addition, as a method for printing on the molded product, any printing method generally used for plastic printing can be used, and examples thereof include gravure printing, flexographic printing, screen printing, and offset printing. It is done. As the printing ink, those usually used for printing plastics can be used.
[0066]
The resin composition of the present invention requires antistatic properties for housing products for home appliances / OA equipment / game equipment / office equipment, various plastic containers, films for various packaging materials, sheets for flooring materials, mats, automobile parts, etc. It is extremely useful as various molding materials.
[0067]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In the examples, “parts” represents parts by weight, and “%” represents% by weight.
The physical properties of the molded articles described in the examples and comparative examples were evaluated by the following methods.
[0068]
[Production of polyetheresteramide]
Production Example 1
A stainless steel autoclave was charged with 105 parts of ε-caprolactam, 17.1 parts of adipic acid, 0.3 part of “Irganox 1010” (an antioxidant, manufactured by Ciba Geigy), and 7 parts of water. The mixture was heated and stirred under pressure sealing for 4 hours to obtain 117 parts of a polyamide oligomer having an acid value of 100 having carboxyl groups at both ends. Next, 225 parts of an EO adduct of bisphenol A having a number average molecular weight of 2,000 and 0.5 part of zirconyl acetate were added and polymerized for 5 hours under conditions of 245 ° C. and 1 mmHg or less to obtain a viscous polymer. It was. The polymer was taken out as a strand on the belt and pelletized to obtain polyetheresteramide [B-1]. The reduced viscosity of this product was 2.10.
[0069]
Production Example 2
A stainless steel autoclave was charged with 83.5 parts of ε-caprolactam, 16.5 parts of terephthalic acid, 0.3 part of “Irganox 1010” and 6 parts of water, and after nitrogen substitution, heated at 220 ° C. under pressure and hermetic sealing for 4 hours. The mixture was stirred to obtain 96 parts of a polyamide oligomer having an acid value of 112 having carboxyl groups at both ends. Next, 192 parts of an EO adduct of bisphenol A having a number average molecular weight of 2,000 and 0.5 part of zirconyl acetate were added and polymerized for 5 hours under conditions of 245 ° C. and 1 mmHg or less under reduced pressure to obtain a viscous polymer. . Thereafter, the same operation as in Production Example 1 was performed to obtain polyether ester amide [B-2]. The reduced viscosity of this product was 2.10.
[0070]
Examples 1-6, Comparative Examples 1-5
Thermoplastic resin having an ester bond (A) {[A-2] contains (A) and another thermoplastic resin. } Was used as follows.
[A-1]: Cyclohexanedimethanol / ethylene glycol / terephthalic acid copolymer [trade name EASTER PETG6763 manufactured by Eastman Chemical Japan Co., Ltd.]
[A-2]: polycarbonate and acrylonitrile / styrene / butadiene copolymer (ABS resin) mixture (polycarbonate / ABS resin weight ratio = 70/30) [trade name Iupilon GP-1 manufactured by Mitsubishi Gas Chemical Co., Ltd.]
[A-3]: Polybutylene terephthalate [trade name Baroques 310 made by Nippon GE Plastics Co., Ltd.]
[A-4]: Polyester-based thermoplastic polyurethane [trade name: Pandex T-5165 manufactured by Dainippon Ink & Chemicals, Inc.]
[A-5]: Polymethyl methacrylate [Brand name Acripet VH manufactured by Mitsubishi Rayon Co., Ltd.]
The following were used as acidic phosphoric acid ester (C).
[C-1]: Monostearyl phosphate and distearyl phosphate mixture [trade name; ADK STAB AX-71 manufactured by Adeka Argus Co., Ltd.]
[C-2]: Monolauryl phosphate [manufactured by Nippon Chemical Co., Ltd. or Daihachi Chemical Co., Ltd.] The following salts were used as alkali metal and / or alkaline earth metal salts.
[D-1]: Lithium chloride (added during the production of polyetheresteramide)
[D-2]: Potassium acetate (added during the production of polyetheresteramide)
[D-3]: Magnesium chloride (added during the production of polyetheresteramide)
According to the formulation shown in Table 1 (the numbers in the table indicate the parts to be blended), the above (A) to (C) [(D) is added during the production of (B)] were blended for 3 minutes with a Henschel mixer. Thereafter, the resin composition of the present invention and the resin composition of the comparative example were obtained by melt-kneading with a vented twin-screw extruder under the following conditions of temperature, 100 rpm, and residence time of 5 minutes.

[0071]
[Table 1]

[0072]
performance test
About the resin composition of this invention and the resin composition of the comparative example, the test piece was created using the injection molding machine, and the external appearance, the surface specific resistance value, the IZOD impact strength, and the tensile yield point strength were evaluated. Test cylinders were prepared at the cylinder temperatures of the injection molding machine as shown below and at a mold temperature of 50 ° C. The results are shown in Table 2. Appearance, surface resistivity, IZOD impact strength, and tensile yield strength were evaluated by the following methods.

(2) Surface specific resistance value: (a) Before washing with water; after molding, the test piece was allowed to stand in an atmosphere of 23 ° C. and humidity 50% RH for 48 hours and then measured according to ASTM D257-78 (Reapproved 1983). .
(B) After washing; after molding, the test piece was washed with an aqueous solution of a detergent (Mama Lemon; manufactured by Lion Corporation), and then thoroughly washed with ion-exchanged water. After being allowed to stand in a 50% RH atmosphere for 24 hours, the measurement was performed according to ASTM D257-78 (Reapproved 1983).
(3) IZOD impact strength: Conforms to JIS K7110-1984 (with notch, 3.2 mm thickness).
(4) Tensile yield point strength: Conforms to JIS K7113-1981.
[0073]
[Table 2]

[0074]
As is apparent from Table 2, the resin composition of the present invention is excellent in permanent antistatic property and excellent in mechanical properties as compared with the comparative example. That is, it is a resin composition having both excellent permanent antistatic properties and mechanical properties that could not be achieved conventionally.
[0075]
【The invention's effect】
The polyolefin resin composition of the present invention has excellent permanent antistatic properties that could not be achieved by conventional techniques, and also has excellent mechanical properties and moldability.
Because of the above effects, the resin composition of the present invention is extremely useful as various molding materials that require antistatic properties, such as housing products for home appliances and OA equipment, various plastic containers, and automobile parts.

Claims (7)

In a resin composition comprising a thermoplastic resin having an ester bond (A) and a polyether ester amide (B), an acidic phosphate ester (C) and an alkali metal and / or alkaline earth metal salt (D) However, the weight ratio of (C) / (D) is 1 to 30 and the total weight of (C) and (D) is 0.001 to 5% by weight with respect to the total weight of the thermoplastic resin. A resin composition characterized by being contained. The resin composition according to claim 1, wherein (C) is represented by the following general formula (1).

(N is 1 or 2. R ₁ represents a monovalent hydrocarbon group having 1 to 30 carbon atoms, and when n is 2, they may be the same or different.)   (B) is a polyether ester amide derived from a carboxyl group-containing polyamide (b1) having a number average molecular weight of 200 to 5,000 and an alkylene oxide adduct (b2) of a dihydric phenol having a number average molecular weight of 300 to 5,000. The resin composition according to claim 1 or 2.   The resin composition according to any one of claims 1 to 3, wherein (B) is a polyether ester amide produced using a zirconium organic acid salt as a catalyst. (A) is a thermoplastic polyester resin (A1), the thermoplastic polyurethane resin (A2), according to claim 1-4 or a polycarbonate resin (A3) or the ester group-containing vinyl monomers (co) polymer (A4) The resin composition as described. The molded object formed by shape | molding the resin composition in any one of Claims 1-5 . A molded article obtained by coating or printing the molded body according to claim 6 .