JP3836215B2 - Antistatic resin composition - Google Patents

Description

【００２０】
〔式中、R¹は側鎖に炭素数１以上のアルキル基を少なくとも１本有する炭素数８以上の分岐型飽和脂肪族アルキル基を示す。R²、R³、R⁴は、水素原子もしくは炭素数１〜２のアルキル基を表し、これらは全てが同一であっても異なっていてもよい。〕
【００２１】
【化１３】

【００２２】
〔式中、R⁵、R⁶はそれぞれ、炭素数８以上の飽和脂肪族アルキル基を表し、R⁵、R⁶のうち少なくとも１個は、側鎖に炭素数１以上のアルキル基を少なくとも１本有する分岐脂肪族アルキル基を示す。R⁷、R⁸は水素原子もしくは炭素数１〜２のアルキル基を表し、これらは全てが同一であっても異なっていてもよい。〕
【００２３】
【化１４】

【００２４】
〔式中、R⁹、R¹⁰ 、R¹¹ はそれぞれ、炭素数８以上の飽和脂肪族アルキル基を表し、R⁹、R¹⁰ 、R¹¹ のうち少なくとも１個は、側鎖に炭素数１以上のアルキル基を少なくとも１本有する分岐脂肪族アルキル基を示す。R¹² は水素原子もしくは炭素数１〜２のアルキル基を表す。〕
【００２５】
【化１５】

【００２６】
〔式中、R¹³ 、R¹⁴ は、同一又は異なり、それぞれ、置換基を有していてもよい炭素数12以上のアルキル基を示す。〕
【００２７】
【化１６】

【００２８】
〔式中、R¹⁵ 、R¹⁶ は、同一又は異なり、それぞれ、置換基を有していてもよい炭素数１２以上のアルキル基を示し、R¹⁷ は、水素原子、置換基を有していてもよい炭素数２乃至７のアルキル基又はアリール基を示し、R¹⁸ は、水素原子、置換基を有していてもよい炭素数１乃至７のアルキル基又はアリール基を示す。〕
【００２９】
【化１７】

【００３０】
〔式中、R¹⁹ 、R²⁰ 、R²¹ は、同一又は異なり、それぞれ、置換基を有していてもよい炭素数８以上のアルキル基を示し、R²² は、水素原子、置換基を有していてもよい炭素数１以上のアルキル基又はアリール基を示す。〕
【００３１】
【化１８】

【００３２】
〔式中、R²³は置換基を有していてもよい炭素数８以上のアルキル基を示し、R²⁴は置換基を有していてもよい炭素数１乃至１１のアルキル基を示し、R²⁵、R²⁶は、同一又は異なり、それぞれ、置換基を有していてもよい炭素数１乃至７のアルキル基を示す。X は、対イオンを表す。〕
【００３３】
【化１９】

【００３４】
〔式中、R²⁷ 、R²⁸ 、R²⁹ 、R³⁰ はそれぞれ、炭素数６〜12の飽和脂肪族アルキル基を表す。〕
また、本発明の（ｂ）第４アンモニウムイオンとしては、オキシアルキレンユニットを含む基を少なくとも１個有する第４アンモニウムイオンもまた好適である。かかる第４アンモニウムイオンとしては、下記一般式（１）〜（３）で表される第４アンモニウムイオンが挙げられる。
【００３５】
【化２０】

【００３６】
〔式中、R³¹ は、炭素数２乃至４のオキシアルキレンユニットからなるモノ又はポリオキシアルキレン基を示し、R³²、R³³は、同一又は異なり、それぞれ、置換基を有していてもよい炭素数１乃至３０のアルキル基及び炭素数２乃至４のオキシアルキレンユニットからなるモノ又はポリオキシアルキレン基の群から選ばれる置換基を示す。オキシアルキレンユニットの付加モル数は、１乃至５０である。R³⁴ は、水素原子、置換基を有していてもよい炭素数１乃至８のアルキル基又はアリール基を示す。〕
【００３７】
【化２１】

【００３８】
〔式中、R³⁵ は、置換基を有していてもよい炭素数１以上のアルキルユニット及び炭素数２乃至４のオキシアルキレンユニットからなるアルキルモノもしくはポリオキシアルキレン基、水素原子もしくは置換基を有していてもよい炭素数１以上のアルキルユニット及び炭素数２乃至４のオキシアルキレンユニットからなるアルキルフェニルモノもしくはポリオキシアルキレン基、又は、置換基を有していてもよい炭素数２以上のアシルユニット及び炭素数２乃至４のオキシアルキレンユニットからなるアシルモノもしくはポリオキシアルキレン基を示し、R³⁶ 、R³⁷ は、同一又は異なり、それぞれ、置換基を有していてもよい炭素数１乃至３０のアルキル基、炭素数２乃至４のオキシアルキレンユニットからなるモノ又はポリオキシアルキレン基、置換基を有していてもよい炭素数１以上のアルキルユニット及び炭素数２乃至４のオキシアルキレンユニットからなるアルキルモノ又はポリオキシアルキレン基、水素原子又は置換基を有していてもよい炭素数１以上のアルキルユニット及び炭素数２乃至４のオキシアルキレンユニットからなるアルキルフェニルモノ又はポリオキシアルキレン基、並びに、置換基を有していてもよい炭素数２以上のアシルユニット及び炭素数２乃至４のオキシアルキレンユニットからなるアシルモノ又はポリオキシアルキレン基の群から選ばれる置換基を示す。オキシアルキレンユニットの付加モル数は、１乃至５０である。R³⁸ は、水素原子、置換基を有していてもよい炭素数１乃至８のアルキル基又はアリール基を示す。〕
【００３９】
【化２２】

【００４０】
〔式中、R³⁹、R⁴⁰、R⁴¹ は、同一又は異なり、それぞれ、置換基を有していてもよい炭素数１乃至３０のアルキル基、炭素数２乃至４のオキシアルキレンユニットからなるモノ又はポリオキシアルキレン基、置換基を有していてもよい炭素数１以上のアルキルユニット及び炭素数２乃至４のオキシアルキレンユニットからなるアルキルモノ又はポリオキシアルキレン基、水素原子又は置換基を有していてもよい炭素数１以上のアルキルユニット及び炭素数２乃至４のオキシアルキレンユニットからなるアルキルフェニルモノ又はポリオキシアルキレン基、並びに、置換基を有していてもよい炭素数２以上のアシルユニット及び炭素数２乃至４のオキシアルキレンユニットからなるアシルモノ又はポリオキシアルキレン基の群から選ばれる置換基を示し、R⁴² は、水素原子、置換基を有していてもよい炭素数１乃至８のアルキル基又はアリール基を示す。オキシアルキレンユニットの付加モル数は、１乃至５０である。
【００４１】
また、Y 、Z 、Wの内、少なくとも１つは、-CH₂O-、-CH₂COO-、-CH₂CH₂COO-、-CH₂OCO-、-CH₂CH₂OCO-、-(CH₂)_mNHCO-、-(CH₂)_mNHCO-CH₂O-の群から選ばれる連結基を示し、残りはアンモニウム基の窒素原子と直接結合する単結合を表す。m は、１乃至４の整数を表す。〕
これらの第４アンモニウムイオンのうち、一般式（Ｉ）で表される第４アンモニウムイオン、一般式（IV）で表される第４アンモニウムイオン、一般式(VIII)で表される第４アンモニウムイオンが特に好ましい。
【００４２】
また、本発明の樹脂組成物に用いられる第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩の平均面間隔は、20〜50Åが好ましく、さらに好ましくは20〜40Åである。平均面間隔が、20Åより小さいと、樹脂、特に熱可塑性樹脂との相溶性が悪くなり、分散不良となり十分な帯電防止効果を発現しない。また、平均面間隔が、50Åを超えると、樹脂との相溶性は向上するが、第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩自身の体積固有抵抗が高くなり、その結果、熱可塑性樹脂中に配合しても充分な帯電防止効果を発現しなくなる。こで、「面間隔」とは、結晶学的には、Ｘ線回折で反射を与えるような層状の繰り返し単位距離を示すもので、層状珪酸塩のように実質的に厚みを持つものでは、１層分の厚さをも含む。つまり、本発明における面間隔は、図２における層状の繰り返し単位２の距離Ｌ₂ をいう。
【００４３】
また、本発明に用いられる第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩（有機変性粘土）の体積固有抵抗率は、10¹³Ω・ｃｍ以下、好ましくは10¹¹Ω・ｃｍ以下、さらに好ましくは10⁹ Ω・ｃｍ以下である。有機変性層状珪酸塩の体積固有抵抗が低いほど、樹脂に練り込んだ際に樹脂の体積固有抵抗を下げることができ、使用量が少量で済む。また有機変性層状珪酸塩の体積固有抵抗が10¹³Ω・ｃｍを超えると、30重量部使用しても良好な帯電防止性が得られない。
【００４４】
本発明の有機変性粘土は、上記のような湿式法他に、予め第４アンモニウムイオンにより処理された有機変性粘土と、アニオン性化合物とをヘンシェルミキサーなどで混合する乾式法により得ることもできる。
【００４５】
上記により得られた第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩、すなわち有機変性粘土は、通常行われる成型加工方法により樹脂と混練することができる。例えば、熱可塑性樹脂と所定量の第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩、また必要に応じて他の酸化防止剤などの樹脂添加剤と共に予めスーパーミキサーやタンブラーなどでブレンドし二軸押出機やニーダー、ミキシングロール等により加熱混練することにより混練が可能である。混練した樹脂組成物は粉砕機やペレタイザーによりペレット化し、その後目的に応じて射出成型機や押出成型機を用いて型物やフィルム、チューブ等に成型加工することができる。
【００４６】
また、予め高濃度に第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩を練り込んだ樹脂ペレット（マスターバッチ）を調製して、成型時に所定の濃度に希釈して使用する方法も何等問題なく利用することができる。
【００４７】
尚、第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩を樹脂とを溶融混練する際、予めトルエンなどの有機溶剤で第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩を膨潤させたものを用いると、より効率よく樹脂中に分散させることが出来る。
【００４８】
本発明に用いられる樹脂としては、熱可塑性樹脂が好適であり、ポリオレフィン系樹脂、ポリスチレン系樹脂、ニトリル基含有樹脂、ポリ（メタ）アクリル酸系樹脂、ポリエステル系樹脂、ポリアミド系樹脂およびこれら熱可塑性樹脂のブレンド系樹脂が挙げられる。この内、ポリオレフィン系樹脂でもポリプロピレン系樹脂は、ポリプロピレンの単独重合体の他に、プロピレンと他のα−オレフィン、例えばエチレン、ブテン−1,4 −メチルペンテン−１、ヘキセン−１等とのランダム共重合体又はブロック共重合体を用いることができる。これらの中でもプロピレン単独重合体又は全構成単量体成分の70重量％以上がプロピレンであるプロピレン共重合体が好ましく、成型性等からメルトフローは 0.1〜100 ｇ／10分のものが特に好ましい。また、使用するポリプロピレン系樹脂中の触媒残渣についても、重合時に使用されるその種類や重合後の残留濃度等に関係なく、本発明の第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩を配合して帯電防止剤として使用することができる。
【００４９】
本発明の樹脂組成物は、樹脂100 重量部中に、（ａ）アニオン性化合物と（ｂ）第４アンモニウムイオンにより有機変性された膨潤性層状珪酸塩２乃至30重量部が、
（１）１次凝集体及び／又は凝集体の短径が500 nm以下の２次凝集体の形で、かつ、
（２）平均最近接粒子間距離が500 nm以下、
の状態で分散していることを特徴とし、永久帯電防止性に優れた樹脂組成物である。
【００５０】
第４アンモニウムイオンで変性された有機層状珪酸塩を樹脂組成物に配合することは公知であるが、上記のように（１）１次凝集体及び／又は凝集体の短径が500 nm以下の２次凝集体の形で、かつ、（２）平均最近接粒子間距離が500 nm以下の状態で有機変性層状珪酸塩を樹脂中に微分散させることは知られていない。本発明では、第４アンモニウムイオンで変性する際にアニオン性化合物を併用することにより、上記（１）、（２）のような微分散を実現すると共に、汎用の混合機によってもかかる均一な微分散が容易に得られることを見出したものである。なお、かかる分散状態は後述の実施例の方法により確認できる。
【００５１】
本発明の組成物中の有機変性粘土の配合量は、帯電防止効果を目的とする使用では、樹脂 100重量部に対して１〜30重量部、好ましくは１〜15重量部、さらに好ましくは１〜10重量部である。第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩の配合量が、 1.0重量部未満では、帯電防止効果が不十分であり、30重量部より多いと帯電防止効果の発現が飽和して、それ以上に添加量を増やす効果がなくなるばかりでなく、樹脂物性の低下を招く等の弊害が発生し好ましくない。
【００５２】
一方、成型機でバージンの樹脂と混合して希釈使用されることを目的とするマスターバッチなどのように、樹脂に有機変性粘土を高濃度に練り込む場合は、樹脂 100重量部に対して、30重量部以上添加することは何等問題は無い。
【００５３】
本発明においては、公知の界面活性剤型帯電防止剤を本発明の効果を阻害しない範囲で併用し、帯電防止効果をさらに向上させることができる。併用される帯電防止剤としては、グリセリン脂肪酸エステル、アルキルアミンのエチレンオキサイド付加物、脂肪酸ジエタノールアミド、ソルビタン脂肪酸エステルのエチレンオキサイド付加物、アルカンスルホン酸ナトリウム等が挙げられ、帯電防止剤のイオン性に関係なく使用することが出来る。また、添加量も通常使用される添加量で良く、その添加量は熱可塑性樹脂 100重量部に対して 0.1〜５重量部である。
【００５４】
本発明の樹脂組成物には、上記界面活性剤型の帯電防止剤以外に、酸化防止剤、紫外線吸収剤、滑剤、難燃剤、着色剤、分散剤、離型剤、ガラス繊維、タルク、炭酸カルシウム等、公知の樹脂添加剤や補強剤、充填剤等を必要に応じて添加することができる。
【００５５】
ここで使用される樹脂添加剤のうち、一部の酸化防止剤や紫外線吸収剤に使用されるフェノール系の化合物は、有機変性粘土との相互作用により着色することがある。そのため、極力これらの添加剤は使用を控えることが好ましいが、酸化防止剤などについては、リン系やイオウ系の酸化防止剤に代替することや、あるいはリン系やイオウ系酸化防止剤とフェノール系酸化防止剤とを併用するなどの方法により着色を抑えることができる。
【００５６】
【実施例】
以下に実施例及び比較例により本発明をさらに詳しく説明するが、本発明はこれらの実施例等によりなんら限定されるものではない。なお、「部」は特に示さない限り「重量部」を意味するものとする。
【００５７】
実施例１
第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩の調製は、次の手順で行った。アニオン性化合物として平均炭素数14のアルキルスルホン酸ナトリウム（ＳＡＳ）10ｇを溶解させた70℃の水10リットルに膨潤性層状珪酸塩（クニミネ工業（株）製、商品名：クニピア−Ｆ） 100ｇを加え分散・溶解させる。これに、４級アンモニウム塩として有効分68％のコータミン 280ＧＰ（花王（株）製）110 ｇを水／エタノール＝１／１溶液 300mlに溶解して前記膨潤性層状珪酸塩の懸濁液に攪拌しながら添加し、１時間、70℃で攪拌した。生成物を固液分離、洗浄して未反応の膨潤性層状珪酸塩、アンモニウム塩、副生塩類を除去した後、乾燥、粉砕して第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩を得た。得られた第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩を後述の方法でポリプロピレン系樹脂に練り込みテストピースを作成して性能評価を行った。なお、本例においては、コータミン 280ＧＰは膨潤性層状珪酸塩のカチオン交換容量の1.3 等量の添加量である。
【００５８】
実施例２
アニオン性化合物としてピロリン酸ナトリウムを用いる以外は実施例１と同様の方法で第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩を調製し、後述の方法でポリプロピレン系樹脂に練り込みテストピースを作成して性能評価を行った。
【００５９】
実施例３
アニオン性化合物としてペレックスＯＴＰ（花王（株）製、ジアルキルスルホコハク酸ナトリウム）を用いる以外は実施例１と同様の方法で第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩を調製し、後述の方法でポリプロピレン系樹脂に練り込みテストピースを作成して性能評価を行った。
【００６０】
実施例４
第４アンモニウム塩としてコータミンＤ８６（花王（株）製、塩化ジオクタデシルジメチルアンモニウム）を用いる以外は実施例１と同様の方法で第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩を調製し、後述の方法でポリプロピレン系樹脂に練り込みテストピースを作成して性能評価を行った。
【００６１】
実施例５
第４アンモニウム塩としてコータミンＤ８６（花王（株）製、塩化ジオクタデシルジメチルアンモニウム）を、アニオン性化合物としてＣ₁₂モノアルキルフォスフェート（ＭＡＰ）を用いる以外は実施例１と同様の方法で第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩を調製し、後述の方法でポリプロピレン系樹脂に練り込みテストピースを作成して性能評価を行った。
【００６２】
実施例６
熱可塑性樹脂としてポリスチレンを用いる以外は、実施例１と同様の方法で第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩を調製し、後述の方法でポリスチレン樹脂に練り込みテストピースを作成して性能評価を行った。
【００６３】
実施例７
熱可塑性樹脂としてＡＢＳ樹脂を用いる以外は、実施例１と同様の方法で第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩を調製し、後述の方法でＡＢＳ樹脂に練り込みテストピースを作成して性能評価を行った。
【００６４】
実施例８
第４アンモニウム塩としてテトラデシルアンモニウムブロマイド（ＴＤＡＢ）（東京化成工業（株）製）を用いる以外は実施例１と同様の方法で第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩を調製し、後述の方法でポリプロピレン系樹脂に練り込みテストピースを作成して性能評価を行った。
【００６５】
実施例９
アニオン性化合物としてピロリン酸ナトリウムを用いる以外は実施例８と同様の方法で第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩を調製し、後述の方法でポリプロピレン系樹脂に練り込みテストピースを作成して性能評価を行った。
【００６６】
実施例10
第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩の調製は、次の手順で行った。70℃の水10リットルに膨潤性層状珪酸塩（クニミネ工業（株）製、商品名：クニピア−Ｆ） 100ｇを加え分散させる。これに、４級アンモニウム塩として有効分68％のコータミン 280ＧＰ（花王（株）製）110 ｇを水／エタノール＝１／１溶液 300mlに溶解して前記膨潤性層状珪酸塩の懸濁液に攪拌しながら添加し、１時間、70℃で攪拌した。生成物を固液分離、洗浄して未反応の膨潤性層状珪酸塩、アンモニウム塩、副生塩類を除去した後、乾燥、粉砕して第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩を得た。次いで第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩100 重量部に対して、アニオン性化合物として実施例１のＳＡＳ10重量部を、ヘンシェルミキサーで乾式混合を行い、アニオン性化合物による変性を行った。得られた第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩を後述の方法でポリプロピレン系樹脂に練り込みテストピースを作成して性能評価を行った。
【００６７】
比較例１
アニオン性化合物を用いない他は、実施例１と同様の方法で第４アンモニウムイオンを導入した膨潤性層状珪酸塩を調製し、後述の方法でポリプロピレン樹脂に練り込みテストピースを作成して性能評価を行った。
【００６８】
比較例２
アニオン性化合物を用いない他は、実施例４と同様の方法で第４アンモニウムイオンを導入した膨潤性層状珪酸塩を調製し、後述の方法でポリプロピレン樹脂に練り込みテストピースを作成して性能評価を行った。
【００６９】
比較例３
アニオン性化合物を用いない他は、実施例９と同様の方法で第４アンモニウムイオンを導入した膨潤性層状珪酸塩を調製し、後述の方法でポリプロピレン樹脂に練り込みテストピースを作成して性能評価を行った。
【００７０】
比較例４
比較例１において、ポリプロピレン樹脂に変性膨潤性層状珪酸塩を練り込む際に、ＳＡＳを0.5 重量部添加してテストピースを作成して性能評価を行った。
【００７１】
比較例５
第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩を用いずに、ポリプロピレン系樹脂でテストピースを作成して性能評価を行った。
【００７２】
比較例６
第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩を用いずに、ポリスチレン樹脂でテストピースを作成して性能評価を行った。
【００７３】
比較例７
第４アンモニウムイオンとアニオンを導入した膨潤性層状珪酸塩を用いずに、ＡＢＳ樹脂でテストピースを作成して性能評価を行った。
【００７４】
＜性能評価＞
上記実施例１〜10で得られた有機変性膨潤性層状珪酸塩を用いて、下記の方法で樹脂と混練し、性能評価を行った。
膨潤性層状珪酸塩と熱可塑性樹脂との混練は、次のように行った。熱可塑性樹脂として、ポリプロピレン系樹脂（プロピレン−エチレンランダム共重合体：グランドポリマー（株）製、Ｆ３５７Ｈ）、ポリスチレン樹脂（旭化成（株）製、スタイラック６６６）及びＡＢＳ樹脂（旭化成（株）製、スタイラック１８２）を用い、各々の熱可塑性樹脂 100部に対して、表１〜２の組合せで、有機変性した膨潤性層状珪酸塩５部を配合し、スーパーミキサーで混合後、二軸押出機（東洋精機（株）製、ラボプラストミルＭＥ型）で混練しペレット化した。このペレットを用いて50×100 ×１mmのテストピースを成型し、成型直後の帯電防止効果を測定した。また、比較例１〜４で得られた有機変性膨潤性層状珪酸塩を用いて同様にテストピースを調製して帯電防止効果を測定した。更に、比較例５〜７は樹脂のみでテストピースを調製して帯電防止効果を測定した。
【００７５】
帯電防止効果の評価は、25℃、50％ＲＨに調節された恒温、恒湿室にて、表面及び体積固有抵抗、帯電圧半減期の測定、ダートチャンバーテストにより行った。
表面固有抵抗および体積固有抵抗の測定は、高抵抗測定器（ＡＤＶＡＮＴＥＳＴ社製、Ｒ8340Ａ）を用いて測定した。
帯電圧半減期の測定は、宍戸静電気（株）製スタチックオネストメーターを用いて印加電圧10kVにて帯電圧の半減期を測定した。
ダートチャンバー（ＤＣ）テストは、ＡＳＴＭに準拠した自社製ダートチャンバー試験器にてトルエンを燃焼させ、すすの付着試験を行った。この時の評価基準は下記の通りである。
○：すす付着なし
△：部分的にすす付着あり
×：全体的にすす付着あり
分散性の評価は、透過型電子顕微鏡（ＴＥＭ）を用い、任意の20μｍ×20μｍの範囲のＴＥＭ像10点より、その中に存在する 500nm以上の凝集体粒子の数をカウントし、その数により分散性の比較を行った（分散性評価Ａ）。この時の評価基準は下記の通りである。
○： 500nm以上の粒子認められず
△： 500nm以上の粒子が１〜10個
×： 500nm以上の粒子が10個以上
また、分散性評価ＡのＴＥＭ像において、１次凝集体又は最短径が500nm 以下の２次凝集体粒子のみをピック・アップし、それらの有機変性層状珪酸塩粒子相がＴＥＭ画面上で占める面積の総和と、樹脂マトリックス相がＴＥＭ画面上で占める面積の総和と、両相の密度（ｇ／cm³ ）とから、平均最近接粒子間距離が500 nm以下の分散度を満足する有機変性層状珪酸塩粒子が樹脂100 重量部に対して２乃至30重量部の範疇にあるか否かを判じた（分散性評価Ｂ）。この時の評価基準は下記の通りである。
○：70％以上のＴＥＭ像について満足する
△：50％以上70％未満のＴＥＭ像について満足する
×：50％未満のＴＥＭ像について満足する
更に、実施例１〜10及び比較例１〜３で得られた有機変性膨潤性層状珪酸塩の面間隔を、理学電機（株）製：RU-200、CuK α−40kV Ｘ線回折装置を用いて測定した。これらの評価結果を表１〜２に示す。
【００７６】
【表１】

【００７７】
【表２】

【００７８】
【発明の効果】
本発明によれば、従来の有機変性粘土に比べて、樹脂への分散性が著しく向上し、少ない混練力で樹脂への分散が容易になる。その結果、少ない添加量で帯電防止効果と高い透明性を付与できる制電性樹脂組成物を得ることができる。さらには、混練した後の樹脂着色を抑えることができる。
【図面の簡単な説明】
【図１】本発明における平均最近接粒子間を説明するモデル図である。
【図２】本発明における面間隔を説明するモデル図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin composition containing a specific organically modified layered silicate.
[0002]
[Prior art and problems to be solved by the invention]
In general, swellable layered silicates (clay minerals) form primary agglomerates in which flat plates of 100 μm × 100 μm × 1 μm (thickness) are laminated in layers, and are negatively coupled with positively charged clay mineral plates. An aggregated structure (secondary aggregate) called a card house structure is formed in which the charged end faces are combined. However, this secondary agglomerate made of hydrophilic clay mineral can also be easily dissociated into the primary agglomerate in water and dispersed in water.
[0003]
In addition, sodium ions existing as counter ions between clay mineral layers can be converted into lipophilic swellable layered silicates (organic modified clays) by ion exchange with cationic organic substances such as quaternary ammonium ions. . Organically modified clay is generally used as an organic solvent-based thickener for preventing dripping of paint. In this case, since the organic solvent used as the dispersion medium of the organic solvent-based paint is relatively high in polarity, it imparts a thickening effect that can be easily dispersed without any special treatment. Can do. However, a nonpolar solvent such as liquid paraffin cannot disaggregate the aggregated structure, so it does not disperse at all and does not function as a thickener.
[0004]
On the other hand, attempts have been made in recent years to improve mechanical properties and thermal properties by kneading organically modified clay as a conventional thickener rather than by kneading it with a thermoplastic resin. For example, as disclosed in JP-A-62-74957, etc., it is disclosed that the thermal and mechanical properties are remarkably improved by finely dispersing an organically modified clay in a polyamide resin. This system was surface-treated with a so-called polymer in which the polyamide of the matrix resin was highly polar and the polyamide was grown by ion exchange with sodium quaternized 12-aminododecanoic acid between the clay layers. Since it is an organically modified clay, it has a high affinity with the base resin and can impart a high degree of dispersibility.
[0005]
However, organically modified clay treated with such quaternized 12-aminododecanoic acid and organically modified with quaternary ammonium salts such as dioctadecyldimethylammonium chloride usually used as a thickener for paints. Even if the modified clay is to be dispersed in another thermoplastic resin, it is generally difficult to disperse the aggregate and finely disperse it, and the aggregate due to poor dispersion can be observed with the naked eye in the thermoplastic resin. In particular, thermoplastic resins such as polyolefins and styrene-based resins have no functional groups like polyamide and have low polarity, so that they are poorly compatible with organically modified clay and are more difficult to disperse.
[0006]
The same applies to solvent systems, and organically modified clay, which can be dispersed relatively easily in polar solvents such as toluene and impart a thickening effect, is hardly dispersed in nonpolar solvents such as liquid paraffin. If simply mixed, it is difficult to solve the secondary aggregate and lead to a monodispersed state, and it is not possible to impart a thickening effect.
[0007]
Also, at the molding site, a master batch in which a surfactant type antistatic agent, a pigment and the like are kneaded in a resin at a high concentration is generally used after being diluted with a natural resin. Even when preparing and using a high-concentration masterbatch of organically modified clay in the same manner, if it is diluted with a molding machine with poor kneading performance, it can be sufficiently finely dispersed if the dispersibility of the organically modified clay is poor. As a result, the physical property improving function cannot be exhibited, and the original performance of the resin may be deteriorated.
[0008]
Thus, in order to finely disperse the organically modified clay in a non-polar thermoplastic resin or solvent that is difficult to finely disperse, and to impart a physical property improvement or thickening effect, the quaternary used for the modification of the organically modified clay. In addition to optimizing the ammonium salt, it is necessary to use a mixer or kneader having higher dispersibility, and it is practically difficult to improve the function with a general-purpose processing machine.
[0009]
[Means for Solving the Problems]
As a result of intensive studies on the surface treatment for improving the dispersibility of the organically modified clay in the resin, the present inventors used an anionic compound in combination with the organic modification of the swellable layered silicate with quaternary ammonium ions. As a result, it has been found that dispersibility can be remarkably improved even for nonpolar resins. When the organically modified clay prepared in this way is melt-mixed with a resin, it can be uniformly and finely dispersed with a slight kneading force compared to conventional organically modified clay. The inventors have found that an effect can be imparted and have completed the present invention.
[0010]
That is, according to the present invention, 2 to 30 parts by weight of a swellable layered silicate organically modified with (a) an anionic compound and (b) quaternary ammonium ion in 100 parts by weight of a resin,
(1) Primary aggregates and / or secondary aggregates having a minor axis of 500 nm or less, and
(2) The average distance between nearest neighbor particles is 500 nm or less,
The antistatic resin composition is characterized in that it is dispersed in the above state. Here, the “particles” refer to individual maximum units of continuous organically modified clay phases that exist independently in the resin. In the phase forming the secondary aggregate, the secondary aggregate is not the primary aggregate unit. Further, the “distance” between the particles is not the distance L between the centers of gravity of the particles 1 in FIG. 1 but the distance L between the outer edges of the particles 1. ₁ Shall be pointed to.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the clay mineral used in the present invention include smectite, vermiculite, mica, and kaolinite. These clay minerals have cations that can exchange ions between layers, and sodium is preferred as the cation species. In addition, cationic species other than sodium contained in naturally occurring clay minerals can also be suitably used by ion exchange with sodium by kneading with an ion exchange resin or sodium hydroxide.
[0012]
The exchangeable cation amount (cation exchange capacity: CEC) of these clay minerals is preferably 50 meq / 100 g or more, more preferably 70 meq / 100 g or more. When a clay mineral with a CEC of less than 50 meq / 100 g is used, the amount of exchange with quaternary ammonium ions is reduced and it is not sufficiently organically modified, the affinity with the resin is lowered, the dispersibility is lowered, and antistatic The effect cannot be obtained. Preferable examples of such a swellable layered compound include many smectite clay minerals. Among these, montmorillonite, hectorite, mica, and the like are preferable. Further, as the swellable layered silicate used, artificially synthesized minerals such as hectorite and mica can be suitably used in addition to naturally occurring minerals.
[0013]
The organically modified clay used in the present invention can be produced according to a known method, but differs in that an anionic compound is used in combination. In a usual modification method, an aqueous solution of a quaternary ammonium salt or a water / alcohol mixed solution, an alcohol solution is added to a swellable layered silicate dissolved in water. The present invention is a step of performing this organic modification, It is characterized by adding an anionic compound (a).
[0014]
As a specific production method, a swellable layered silicate is dispersed in water in which an anionic compound is previously dissolved, and a predetermined amount of a quaternary ammonium salt is reacted with stirring while heating as necessary. Can be manufactured. Moreover, it can also manufacture by adding an anionic compound to the organic modified clay aqueous dispersion before the filtration and dehydration process of the organic modified clay manufactured by the well-known method. The organically modified clay surface-treated with an anionic compound can be removed by drying after removing salts and unreacted products by-produced by ordinary separation and washing steps. Moreover, when it is not necessary to consider the influence of by-product salts and unreacted substances, the washing and drying steps can be omitted and the resin can be used as it is.
[0015]
Examples of the anionic compound (a) used in the present invention include alkyl sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, naphthalene sulfonate formaldehyde condensate Na salt, dialkyl sulfosuccinate ester salt, and condensed phosphate. , Alkyl sulfoacetates, alkyl phosphate esters, N-acyl amino acid salts, alkyl ether carboxylates, α-olefin sulfonates, N-acyl methyl taurines, higher alcohol sulfates, alkyl ether sulfates, higher alcohols Examples thereof include compounds selected from the group consisting of ethoxy sulfate, polyoxyethylene alkylphenyl ether sulfate, monoglycerate and alkyl ether phosphate ester salt. Further, carboxylic acids such as benzenecarboxylic acid or a salt thereof, alkylcarboxylic acid or a salt thereof, hydroxyalkylcarboxylic acid or a salt thereof, unsaturated alkylcarboxylic acid or a salt thereof, phenols, naphthols, thioacids, amino acids ( For example, 6-aminohexanoic acid, 12-aminododecanoic acid, N-phenylglycine, 3-aminocrotonic acid, etc.), polymeric acids (eg, low molecular weight acrylic acid polymer or copolymer, styrene-anhydride) A maleic acid copolymer etc.) can also be used as the anionic compound (a) of the present invention. Of these, the anionic compound (a) of the present invention is particularly preferably an alkyl sulfonate and a condensed phosphate (such as pyrophosphate, tripolyphosphate, polyphosphate).
[0016]
The amount of the anionic compound (a) used when preparing the organically modified clay of the present invention is 1 to 30 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of the clay mineral used. Preferably it is 3-10 weight part. If the amount of the anionic compound used is less than 1 part by weight, it is insufficient to neutralize the cationic charge of the clay mineral, and is insufficient to inhibit the formation of the aggregate structure. Addition exceeding 30 parts by weight exceeds the amount necessary for neutralization of the cation charge, and the addition effect is not recognized, and solid-liquid separation of the organically modified clay is difficult during the process of preparing the organically modified clay. Such as the need to wash away excess anions.
[0017]
The quaternary ammonium salt (b) used for the preparation of the organically modified clay is used in an amount corresponding to 1.0 to 2.0 equivalents, preferably 1.1 to 1.6 equivalents, of the cation exchange capacity of the swellable layered silicate. Even when the amount of the component (b) is less than 1.0 equivalent, it is possible to disperse with a kneading machine having a high dispersibility such as a roll kneader. As a result, the antistatic effect is inferior and the appearance and transparency are deteriorated due to poor dispersion. Further, the effect is saturated even if the amount of the component (b) is increased.
[0018]
The (b) quaternary ammonium ion used in the present invention is preferably a quaternary ammonium ion having at least one alkyl group having 8 or more carbon atoms. Examples of the quaternary ammonium ion include the following general formulas (I) to (I): And quaternary ammonium ions represented by VIII).
[0019]
Embedded image

[0020]
(In the formula, R ¹ Represents a branched saturated aliphatic alkyl group having 8 or more carbon atoms having at least one alkyl group having 1 or more carbon atoms in the side chain. R ² , R ^Three , R ^Four Represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and these may be all the same or different. ]
[0021]
Embedded image

[0022]
(In the formula, R ^Five , R ⁶ Each represents a saturated aliphatic alkyl group having 8 or more carbon atoms, R ^Five , R ⁶ At least one of them represents a branched aliphatic alkyl group having at least one alkyl group having 1 or more carbon atoms in the side chain. R ⁷ , R ⁸ Represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and these may be all the same or different. ]
[0023]
Embedded image

[0024]
(In the formula, R ⁹ , R ^Ten , R ¹¹ Each represents a saturated aliphatic alkyl group having 8 or more carbon atoms, R ⁹ , R ^Ten , R ¹¹ At least one of them represents a branched aliphatic alkyl group having at least one alkyl group having 1 or more carbon atoms in the side chain. R ¹² Represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. ]
[0025]
Embedded image

[0026]
(In the formula, R ¹³ , R ¹⁴ Are the same or different and each represents an alkyl group having 12 or more carbon atoms which may have a substituent. ]
[0027]
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[0028]
(In the formula, R ¹⁵ , R ¹⁶ Are the same or different and each represents an optionally substituted alkyl group having 12 or more carbon atoms, R ¹⁷ Represents a hydrogen atom, an optionally substituted alkyl group having 2 to 7 carbon atoms or an aryl group, and R ¹⁸ Represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms or an aryl group which may have a substituent. ]
[0029]
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[0030]
(In the formula, R ¹⁹ , R ²⁰ , R ^{twenty one} Are the same or different and each represents an optionally substituted alkyl group having 8 or more carbon atoms, R ^{twenty two} Represents a hydrogen atom, an alkyl group having 1 or more carbon atoms which may have a substituent, or an aryl group. ]
[0031]
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[0032]
(In the formula, R ^{twenty three} Represents an optionally substituted alkyl group having 8 or more carbon atoms, and R ^{twenty four} Represents an optionally substituted alkyl group having 1 to 11 carbon atoms, R ^{twenty five} , R ²⁶ Are the same or different and each represents an alkyl group having 1 to 7 carbon atoms which may have a substituent. X represents a counter ion. ]
[0033]
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[0034]
(In the formula, R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ Each represents a saturated aliphatic alkyl group having 6 to 12 carbon atoms. ]
In addition, as the (b) quaternary ammonium ion of the present invention, a quaternary ammonium ion having at least one group containing an oxyalkylene unit is also suitable. Examples of the quaternary ammonium ion include quaternary ammonium ions represented by the following general formulas (1) to (3).
[0035]
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[0036]
(In the formula, R ³¹ Represents a mono- or polyoxyalkylene group composed of an oxyalkylene unit having 2 to 4 carbon atoms, and R ³² , R ³³ Are the same or different and each is a substituent selected from the group of mono- or polyoxyalkylene groups consisting of an alkyl group having 1 to 30 carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms, which may have a substituent. Indicates. The added mole number of the oxyalkylene unit is 1 to 50. R ³⁴ Represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group which may have a substituent. ]
[0037]
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[0038]
(In the formula, R ³⁵ May have an alkyl mono- or polyoxyalkylene group consisting of an alkyl unit having 1 or more carbon atoms which may have a substituent and an oxyalkylene unit having 2 to 4 carbon atoms, a hydrogen atom or a substituent. An alkylphenyl mono- or polyoxyalkylene group composed of an alkyl unit having 1 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms, or an acyl unit having 2 or more carbon atoms which may have a substituent and 2 carbon atoms Represents an acyl mono- or polyoxyalkylene group consisting of 4 to 4 oxyalkylene units, R ³⁶ , R ³⁷ Are the same or different and each have an optionally substituted alkyl group having 1 to 30 carbon atoms, a mono- or polyoxyalkylene group composed of oxyalkylene units having 2 to 4 carbon atoms, and a substituent. An alkyl mono- or polyoxyalkylene group composed of an alkyl unit having 1 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms, a hydrogen atom or an alkyl unit having 1 or more carbon atoms which may have a substituent, and It consists of an alkylphenyl mono or polyoxyalkylene group composed of an oxyalkylene unit having 2 to 4 carbon atoms, an acyl unit having 2 or more carbon atoms which may have a substituent, and an oxyalkylene unit having 2 to 4 carbon atoms. A substituent selected from the group of acyl mono or polyoxyalkylene groups is shown. The added mole number of the oxyalkylene unit is 1 to 50. R ³⁸ Represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group which may have a substituent. ]
[0039]
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[0040]
(In the formula, R ³⁹ , R ⁴⁰ , R ⁴¹ Are the same or different and each have an optionally substituted alkyl group having 1 to 30 carbon atoms, a mono- or polyoxyalkylene group composed of oxyalkylene units having 2 to 4 carbon atoms, and a substituent. An alkyl mono- or polyoxyalkylene group composed of an alkyl unit having 1 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms, a hydrogen atom or an alkyl unit having 1 or more carbon atoms which may have a substituent, and It consists of an alkylphenyl mono or polyoxyalkylene group composed of an oxyalkylene unit having 2 to 4 carbon atoms, an acyl unit having 2 or more carbon atoms which may have a substituent, and an oxyalkylene unit having 2 to 4 carbon atoms. R represents a substituent selected from the group of acyl mono or polyoxyalkylene groups, R ⁴² Represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group which may have a substituent. The added mole number of the oxyalkylene unit is 1 to 50.
[0041]
In addition, at least one of Y 1, Z 2 and W is —CH ₂ O-, -CH ₂ COO-, -CH ₂ CH ₂ COO-, -CH ₂ OCO-, -CH ₂ CH ₂ OCO-、-(CH ₂ ) _m NHCO-,-(CH ₂ ) _m NHCO-CH ₂ 1 represents a linking group selected from the group of O—, and the remainder represents a single bond directly bonded to the nitrogen atom of the ammonium group. m represents an integer of 1 to 4. ]
Among these quaternary ammonium ions, quaternary ammonium ions represented by general formula (I), quaternary ammonium ions represented by general formula (IV), and quaternary ammonium ions represented by general formula (VIII) Is particularly preferred.
[0042]
In addition, the average interplanar spacing of the swellable layered silicate into which quaternary ammonium ions and anions are used for the resin composition of the present invention is preferably 20 to 50 mm, and more preferably 20 to 40 mm. If the average surface separation is less than 20 mm, the compatibility with the resin, particularly the thermoplastic resin, is deteriorated, resulting in poor dispersion and insufficient antistatic effect. In addition, when the average interplanar spacing exceeds 50 mm, the compatibility with the resin is improved, but the volume specific resistance of the swellable layered silicate itself into which quaternary ammonium ions and anions have been introduced increases, resulting in thermoplasticity. Even when blended in the resin, sufficient antistatic effect is not exhibited. Here, “surface spacing” is a crystallographically a layered repeating unit distance that gives reflection by X-ray diffraction, and has a thickness substantially like a layered silicate, The thickness for one layer is also included. That is, the surface interval in the present invention is the distance L of the layered repeating unit 2 in FIG. ₂ Say.
[0043]
The volume specific resistivity of the swellable layered silicate (organic modified clay) introduced with quaternary ammonium ions and anions used in the present invention is 10 ¹³ Ω · cm or less, preferably 10 ¹¹ Ω · cm or less, more preferably 10 ⁹ Ω · cm or less. The lower the volume resistivity of the organically modified layered silicate, the lower the volume resistivity of the resin when kneaded into the resin, and the smaller the amount used. Moreover, the volume resistivity of the organically modified layered silicate is 10 ¹³ If it exceeds Ω · cm, good antistatic properties cannot be obtained even if 30 parts by weight are used.
[0044]
In addition to the wet method as described above, the organically modified clay of the present invention can also be obtained by a dry method in which an organically modified clay previously treated with quaternary ammonium ions and an anionic compound are mixed with a Henschel mixer or the like.
[0045]
The swellable layered silicate into which quaternary ammonium ions and anions have been introduced, that is, organically modified clay, can be kneaded with a resin by a conventional molding method. For example, a thermoplastic layer, a swellable layered silicate into which a predetermined amount of quaternary ammonium ions and anions have been introduced, and, if necessary, a resin additive such as another antioxidant are blended in advance with a super mixer or tumbler. Kneading is possible by heating and kneading with a shaft extruder, a kneader, a mixing roll or the like. The kneaded resin composition can be pelletized by a pulverizer or a pelletizer and then molded into a mold, a film, a tube or the like using an injection molding machine or an extrusion molding machine depending on the purpose.
[0046]
Also, there is no problem in preparing resin pellets (masterbatch) kneaded with swellable layered silicate into which quaternary ammonium ions and anions have been introduced in high concentrations in advance, and diluting them to a predetermined concentration during molding. It can be used without.
[0047]
When the swellable layered silicate introduced with quaternary ammonium ions and anions was melt-kneaded with the resin, the swellable layered silicate introduced with quaternary ammonium ions and anions was previously swollen with an organic solvent such as toluene. If a material is used, it can be more efficiently dispersed in the resin.
[0048]
As the resin used in the present invention, a thermoplastic resin is suitable. A polyolefin resin, a polystyrene resin, a nitrile group-containing resin, a poly (meth) acrylic acid resin, a polyester resin, a polyamide resin, and these thermoplastic resins. A resin blend resin may be used. Of these, polypropylene resins are random resins of propylene and other α-olefins such as ethylene, butene-1,4-methylpentene-1, hexene-1, etc., in addition to polypropylene homopolymers. A copolymer or block copolymer can be used. Among these, a propylene homopolymer or a propylene copolymer in which 70% by weight or more of all constituent monomer components are propylene is preferable, and those having a melt flow of 0.1 to 100 g / 10 min are particularly preferable in view of moldability. In addition, the catalyst residue in the polypropylene resin used is a swellable layered silicate into which quaternary ammonium ions and anions of the present invention have been introduced, regardless of the type used during polymerization or the residual concentration after polymerization. It can mix | blend and can be used as an antistatic agent.
[0049]
In the resin composition of the present invention, 2 to 30 parts by weight of a swellable layered silicate organically modified with (a) an anionic compound and (b) quaternary ammonium ion in 100 parts by weight of resin,
(1) Primary aggregates and / or secondary aggregates having a minor axis of 500 nm or less, and
(2) The average distance between nearest neighbor particles is 500 nm or less,
The resin composition is characterized in that it is dispersed in the above-mentioned state, and is excellent in permanent antistatic properties.
[0050]
Although it is known to add an organic layered silicate modified with quaternary ammonium ions to a resin composition, as described above, (1) the primary aggregate and / or the minor axis of the aggregate is 500 nm or less. It is not known that the organically modified layered silicate is finely dispersed in the resin in the form of secondary aggregates and (2) the average distance between nearest neighbor particles is 500 nm or less. In the present invention, by using an anionic compound in combination with the modification with quaternary ammonium ions, fine dispersion as in the above (1) and (2) is realized, and even with a general-purpose mixer, such uniform fine dispersion is achieved. It has been found that dispersion can be easily obtained. Such a dispersion state can be confirmed by a method of an example described later.
[0051]
The compounding amount of the organically modified clay in the composition of the present invention is 1 to 30 parts by weight, preferably 1 to 15 parts by weight, more preferably 1 with respect to 100 parts by weight of the resin for the purpose of antistatic effect. ~ 10 parts by weight. When the amount of the swellable layered silicate containing quaternary ammonium ions and anions is less than 1.0 part by weight, the antistatic effect is insufficient, and when it exceeds 30 parts by weight, the expression of the antistatic effect is saturated, Further, the effect of increasing the addition amount is lost, and adverse effects such as a decrease in resin physical properties occur, which is not preferable.
[0052]
On the other hand, when kneading organically modified clay at a high concentration in the resin, such as a masterbatch intended to be diluted with a virgin resin in a molding machine, There is no problem adding more than 30 parts by weight.
[0053]
In the present invention, a known surfactant-type antistatic agent can be used in combination as long as the effects of the present invention are not impaired, and the antistatic effect can be further improved. Antistatic agents used in combination include glycerin fatty acid esters, alkylamine ethylene oxide adducts, fatty acid diethanolamides, sorbitan fatty acid ester ethylene oxide adducts, sodium alkanesulfonates, etc. Can be used regardless. Moreover, the addition amount may be a commonly used addition amount, and the addition amount is 0.1 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
[0054]
In addition to the surfactant type antistatic agent, the resin composition of the present invention includes an antioxidant, an ultraviolet absorber, a lubricant, a flame retardant, a colorant, a dispersant, a release agent, glass fiber, talc, carbonic acid. Known resin additives, reinforcing agents, fillers and the like such as calcium can be added as necessary.
[0055]
Among the resin additives used here, phenolic compounds used in some antioxidants and ultraviolet absorbers may be colored by interaction with organically modified clay. For this reason, it is preferable to refrain from using these additives as much as possible. However, for antioxidants, etc., they can be replaced with phosphorus-based or sulfur-based antioxidants, or phosphorus-based or sulfur-based antioxidants and phenol-based antioxidants. Coloring can be suppressed by a method such as using an antioxidant together.
[0056]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and the like. “Parts” means “parts by weight” unless otherwise specified.
[0057]
Example 1
The swellable layered silicate introduced with quaternary ammonium ions and anions was prepared by the following procedure. 100 g of swellable layered silicate (trade name: Kunipia-F, manufactured by Kunimine Kogyo Co., Ltd.) was dissolved in 10 liters of 70 ° C. water in which 10 g of sodium alkylsulfonate (SAS) having an average carbon number of 14 was dissolved as an anionic compound. Add to disperse and dissolve. To this, 110 g of Cotamine 280GP (produced by Kao Co., Ltd.) having an effective content of 68% as a quaternary ammonium salt was dissolved in 300 ml of water / ethanol = 1/1 solution and stirred into the suspension of the swellable layered silicate. And added at 70 ° C. for 1 hour. The product is subjected to solid-liquid separation and washing to remove unreacted swellable layered silicate, ammonium salt, and by-product salts, and then dried and pulverized to introduce a swellable layered silicate into which quaternary ammonium ions and anions have been introduced. Obtained. The obtained swellable layered silicate into which quaternary ammonium ions and anions were introduced was kneaded into a polypropylene resin by the method described below, and performance evaluation was performed. In this example, Coatamine 280GP is an addition amount of 1.3 equivalent of the cation exchange capacity of the swellable layered silicate.
[0058]
Example 2
A swellable layered silicate having quaternary ammonium ions and anions introduced therein was prepared in the same manner as in Example 1 except that sodium pyrophosphate was used as the anionic compound, and the test piece was kneaded into the polypropylene resin by the method described later. Created and evaluated performance.
[0059]
Example 3
A swellable lamellar silicate was prepared by introducing a quaternary ammonium ion and an anion in the same manner as in Example 1 except that Perex OTP (manufactured by Kao Corporation, sodium dialkylsulfosuccinate) was used as the anionic compound. The test piece was kneaded into a polypropylene resin by the method to evaluate the performance.
[0060]
Example 4
A swellable layered silicate into which quaternary ammonium ions and anions were introduced was prepared in the same manner as in Example 1 except that Coatamine D86 (manufactured by Kao Corporation, dioctadecyldimethylammonium chloride) was used as the quaternary ammonium salt. A test piece was kneaded into a polypropylene resin by the method described below to evaluate the performance.
[0061]
Example 5
Coatamine D86 (manufactured by Kao Corporation, dioctadecyldimethylammonium chloride) as the quaternary ammonium salt and C as the anionic compound ₁₂ A swellable layered silicate having quaternary ammonium ions and anions introduced therein was prepared in the same manner as in Example 1 except that monoalkyl phosphate (MAP) was used, and the test piece was kneaded into a polypropylene resin by the method described later. Created and evaluated performance.
[0062]
Example 6
A swellable layered silicate having quaternary ammonium ions and anions introduced therein was prepared in the same manner as in Example 1 except that polystyrene was used as the thermoplastic resin, and a test piece was prepared by kneading into the polystyrene resin by the method described later. Performance evaluation.
[0063]
Example 7
A swellable layered silicate was prepared by introducing quaternary ammonium ions and anions in the same manner as in Example 1 except that an ABS resin was used as the thermoplastic resin, and a test piece was kneaded into the ABS resin by the method described below. The performance was evaluated.
[0064]
Example 8
A swellable layered silicate in which quaternary ammonium ions and anions were introduced was prepared in the same manner as in Example 1 except that tetradecyl ammonium bromide (TDAB) (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the quaternary ammonium salt. A test piece was kneaded into a polypropylene resin by the method described later, and performance evaluation was performed.
[0065]
Example 9
A swellable layered silicate having quaternary ammonium ions and anions introduced therein was prepared in the same manner as in Example 8 except that sodium pyrophosphate was used as the anionic compound, and the test piece was kneaded into the polypropylene resin by the method described later. Created and evaluated performance.
[0066]
Example 10
The swellable layered silicate introduced with quaternary ammonium ions and anions was prepared by the following procedure. 100 g of swellable layered silicate (Kunimine Kogyo Co., Ltd., trade name: Kunipia-F) is added and dispersed in 10 liters of water at 70 ° C. To this, 110 g of Cotamine 280GP (produced by Kao Co., Ltd.) having an effective content of 68% as a quaternary ammonium salt was dissolved in 300 ml of water / ethanol = 1/1 solution and stirred into the suspension of the swellable layered silicate. And added at 70 ° C. for 1 hour. The product is subjected to solid-liquid separation and washing to remove unreacted swellable layered silicate, ammonium salt, and by-product salts, and then dried and pulverized to introduce a swellable layered silicate into which quaternary ammonium ions and anions have been introduced. Obtained. Next, 10 parts by weight of SAS of Example 1 as an anionic compound was dry-mixed with a Henschel mixer for 100 parts by weight of a swellable layered silicate into which quaternary ammonium ions and anions had been introduced, and modified with an anionic compound. It was. The obtained swellable layered silicate into which quaternary ammonium ions and anions were introduced was kneaded into a polypropylene resin by the method described below, and performance evaluation was performed.
[0067]
Comparative Example 1
Except not using an anionic compound, the swelling layered silicate which introduce | transduced the quaternary ammonium ion was prepared by the method similar to Example 1, and it knead | mixed to a polypropylene resin by the method mentioned later, and created a test piece, and evaluated performance Went.
[0068]
Comparative Example 2
Except not using an anionic compound, the swelling layered silicate which introduce | transduced the quaternary ammonium ion by the method similar to Example 4 was prepared, and it knead | mixed to a polypropylene resin by the method mentioned later, and created a test piece, and evaluated performance Went.
[0069]
Comparative Example 3
Except not using an anionic compound, the swelling layered silicate which introduce | transduced the quaternary ammonium ion was prepared by the method similar to Example 9, and it knead | mixed to a polypropylene resin by the method mentioned later, and created a test piece, and evaluated performance Went.
[0070]
Comparative Example 4
In Comparative Example 1, when kneading the modified swellable layered silicate into the polypropylene resin, 0.5 parts by weight of SAS was added to create a test piece and performance evaluation was performed.
[0071]
Comparative Example 5
Without using a swellable layered silicate into which quaternary ammonium ions and anions were introduced, a test piece was made of a polypropylene resin and performance evaluation was performed.
[0072]
Comparative Example 6
Without using a swellable layered silicate introduced with quaternary ammonium ions and anions, a test piece was made of polystyrene resin and performance evaluation was performed.
[0073]
Comparative Example 7
Without using a swellable layered silicate into which quaternary ammonium ions and anions were introduced, test pieces were made of ABS resin and performance evaluation was performed.
[0074]
<Performance evaluation>
Using the organically modified swellable layered silicate obtained in Examples 1 to 10 above, performance evaluation was performed by kneading with a resin by the following method.
The kneading of the swellable layered silicate and the thermoplastic resin was performed as follows. As thermoplastic resins, polypropylene resins (propylene-ethylene random copolymer: Grand Polymer Co., Ltd., F357H), polystyrene resins (Asahi Kasei Co., Ltd., Stylac 666) and ABS resins (Asahi Kasei Co., Ltd., Stylac 182) is used, 100 parts of each thermoplastic resin is blended with 5 parts of organically modified swellable layered silicate in the combination of Tables 1-2, mixed with a super mixer, and then twin screw extruder (Toyo Seiki Co., Ltd., Lab Plast Mill ME type) kneaded and pelletized. A test piece of 50 × 100 × 1 mm was molded using this pellet, and the antistatic effect immediately after molding was measured. Moreover, the test piece was similarly prepared using the organic modified swelling layered silicate obtained in Comparative Examples 1 to 4, and the antistatic effect was measured. Further, in Comparative Examples 5 to 7, a test piece was prepared using only a resin, and the antistatic effect was measured.
[0075]
The antistatic effect was evaluated by measuring the surface and volume resistivity, charged half-life, and dirt chamber test in a constant temperature and humidity chamber adjusted to 25 ° C. and 50% RH.
The surface resistivity and the volume resistivity were measured using a high resistance measuring instrument (manufactured by ADVANTEST, R8340A).
The half-life of the charged voltage was measured at a applied voltage of 10 kV using a Static Honest Meter manufactured by Shishido Electrostatic Co., Ltd.
In the dirt chamber (DC) test, toluene was burned in a company-made dirt chamber tester compliant with ASTM, and a soot adhesion test was conducted. The evaluation criteria at this time are as follows.
○: No soot adhesion
Δ: Partially soot adhered
×: Overall soot adhesion
For evaluation of dispersibility, a transmission electron microscope (TEM) was used to count the number of aggregate particles of 500 nm or more present in 10 TEM images in an arbitrary 20 μm × 20 μm range, and the number Dispersibility was compared (dispersibility evaluation A). The evaluation criteria at this time are as follows.
○: Particles larger than 500nm are not recognized
Δ: 1 to 10 particles of 500 nm or more
×: 10 or more particles of 500 nm or more
Further, in the TEM image of dispersibility evaluation A, only the primary aggregates or secondary aggregate particles having the shortest diameter of 500 nm or less are picked up, and the area occupied by these organically modified layered silicate particle phases on the TEM screen , The total area occupied by the resin matrix phase on the TEM screen, and the density of both phases (g / cm ^Three From the above, it was determined whether the organically modified layered silicate particles satisfying the dispersity of 500 nm or less between the average nearest neighbor particles are in the range of 2 to 30 parts by weight with respect to 100 parts by weight of the resin. (Dispersibility evaluation B). The evaluation criteria at this time are as follows.
○: Satisfied with TEM image of 70% or more
Δ: Satisfied with TEM images of 50% or more and less than 70%
X: Satisfied with a TEM image of less than 50%
Furthermore, the surface spacing of the organically modified swellable layered silicate obtained in Examples 1 to 10 and Comparative Examples 1 to 3 was measured using a RU-200, CuK α-40kV X-ray diffractometer manufactured by Rigaku Corporation. Measured. These evaluation results are shown in Tables 1-2.
[0076]
[Table 1]

[0077]
[Table 2]

[0078]
【The invention's effect】
According to the present invention, the dispersibility in the resin is remarkably improved as compared with the conventional organically modified clay, and the dispersion in the resin becomes easy with a small kneading force. As a result, an antistatic resin composition capable of imparting an antistatic effect and high transparency can be obtained with a small addition amount. Furthermore, resin coloring after kneading can be suppressed.
[Brief description of the drawings]
FIG. 1 is a model diagram for explaining an interval between average closest particles in the present invention.
FIG. 2 is a model diagram illustrating a surface interval in the present invention.

Claims (17)

In 100 parts by weight of resin, (a) alkylsulfonate, alkylbenzenesulfonate, alkylnaphthalenesulfonate, naphthalenesulfonate formaldehyde condensate Na salt, dialkylsulfosuccinate ester, condensed phosphate, alkylsulfoacetic acid Salt, alkyl phosphate ester salt, N-acyl amino acid salt, alkyl ether carboxylate, α-olefin sulfonate, N-acyl methyl taurine, higher alcohol sulfate, alkyl ether sulfate, higher alcohol ethoxy sulfate, poly polyoxyethylene alkyl phenyl ether sulfate, monoglysulfate and an anionic compound selected from the group consisting of alkyl ether phosphate salt (b) swellable layered silicate organically modified by a quaternary ammonium ion 2 Itaru 30 parts by weight,
(1) Primary aggregates and / or secondary aggregates having a minor axis of 500 nm or less, and
(2) The average distance between nearest neighbor particles is 500 nm or less,
An antistatic resin composition characterized by being dispersed in the state of   The organically modified swellable layered silicate is 1 to 30 parts by weight of (a) anionic compound with respect to 100 parts by weight of the swellable layered silicate and 1.0 to 2.0 equivalents of the cation exchange capacity of the swellable layered silicate. 2. The resin composition according to claim 1, which is organically modified with (b) quaternary ammonium ions. (B) The resin composition according to claim 1 or 2 , wherein the quaternary ammonium ion is a quaternary ammonium ion having at least one alkyl group having 8 or more carbon atoms. The resin composition according to claim 3 , wherein the quaternary ammonium ion having at least one alkyl group having 8 or more carbon atoms is a quaternary ammonium ion represented by the following general formulas (I) to (VIII).

[Wherein R ¹ represents a branched saturated aliphatic alkyl group having 8 or more carbon atoms having at least one alkyl group having 1 or more carbon atoms in the side chain. R ² , R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and these may be all the same or different. ]

[Wherein, R ⁵ and R ⁶ each represent a saturated aliphatic alkyl group having 8 or more carbon atoms, and at least one of R ⁵ and R ⁶ has at least 1 alkyl group having 1 or more carbon atoms in the side chain. The branched aliphatic alkyl group which has this is shown. R ⁷ and R ⁸ represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and these may be all the same or different. ]

[Wherein R ⁹ , R ¹⁰ and R ¹¹ each represent a saturated aliphatic alkyl group having 8 or more carbon atoms, and at least one of R ⁹ , R ¹⁰ and R ¹¹ has 1 or more carbon atoms in the side chain. And a branched aliphatic alkyl group having at least one alkyl group. R ¹² represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. ]

[Wherein, R ¹³ and R ¹⁴ are the same or different and each represents an alkyl group having 12 or more carbon atoms which may have a substituent. ]

[Wherein, R ¹⁵ and R ¹⁶ are the same or different and each represents an optionally substituted alkyl group having 12 or more carbon atoms, and R ¹⁷ represents a hydrogen atom or a substituent. R ¹⁸ represents an optionally substituted alkyl group or aryl group having 2 to 7 carbon atoms, and R ¹⁸ represents a hydrogen atom or an optionally substituted alkyl group or aryl group having 1 to 7 carbon atoms. ]

[In the formula, R ¹⁹ , R ²⁰ and R ²¹ are the same or different and each represents an optionally substituted alkyl group having 8 or more carbon atoms, and R ²² represents a hydrogen atom or a substituent. An alkyl group or aryl group having 1 or more carbon atoms which may be used. ]

[In the formula, R ²³ represents an optionally substituted alkyl group having 8 or more carbon atoms, R ²⁴ represents an optionally substituted alkyl group having 1 to 11 carbon atoms, R ²⁵ and R ²⁶ are the same or different and each represents an optionally substituted alkyl group having 1 to 7 carbon atoms. ]

[Wherein R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ each represent a saturated aliphatic alkyl group having 6 to 12 carbon atoms. ] The quaternary ammonium ion is represented by the quaternary ammonium ion represented by the general formula (I) and / or the quaternary ammonium ion represented by the general formula (IV) and / or the general formula (VIII). The resin composition according to claim 4, which is a quaternary ammonium ion. (B) The resin composition according to claim 1 or 2 , wherein the quaternary ammonium ion is a quaternary ammonium ion having at least one group containing an oxyalkylene unit. The resin composition according to claim 6 , wherein the quaternary ammonium ion having at least one group containing an oxyalkylene unit is a quaternary ammonium ion represented by the following general formulas (1) to (3).

[Wherein R ³¹ represents a mono- or polyoxyalkylene group composed of an oxyalkylene unit having 2 to 4 carbon atoms, and R ³² and R ³³ may be the same or different and each may have a substituent. The substituent selected from the group of the mono or polyoxyalkylene group which consists of a C1-C30 alkyl group and a C2-C4 oxyalkylene unit is shown. The added mole number of the oxyalkylene unit is 1 to 50. R ³⁴ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group which may have a substituent. ]

[In the formula, R ³⁵ represents an alkyl mono- or polyoxyalkylene group, a hydrogen atom or a substituent, each consisting of an optionally substituted alkyl unit having 1 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms. An alkylphenyl mono- or polyoxyalkylene group comprising an alkyl unit having 1 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms, or a substituent having 2 or more carbon atoms An acyl mono- or polyoxyalkylene group composed of an acyl unit and an oxyalkylene unit having 2 to 4 carbon atoms, wherein R ³⁶ and R ³⁷ are the same or different and each may have a substituent group having 1 to 30 carbon atoms; A mono- or polyoxyalkylene group consisting of an oxyalkylene unit having 2 to 4 carbon atoms , An alkyl mono- or polyoxyalkylene group composed of an alkyl unit having 1 or more carbon atoms which may have a substituent and an oxyalkylene unit having 2 to 4 carbon atoms, a hydrogen atom or a carbon which may have a substituent An alkylphenyl mono- or polyoxyalkylene group composed of an alkyl unit having 1 or more and an oxyalkylene unit having 2 to 4 carbon atoms, an acyl unit having 2 or more carbon atoms which may have a substituent, and 2 to 2 carbon atoms 4 represents a substituent selected from the group of acyl mono or polyoxyalkylene groups composed of 4 oxyalkylene units. The added mole number of the oxyalkylene unit is 1 to 50. R ³⁸ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group which may have a substituent. ]

[Wherein, R ³⁹ , R ⁴⁰ and R ⁴¹ are the same or different and each is a monovalent alkyl group having 1 to 30 carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms which may have a substituent. Or a polyoxyalkylene group, an alkyl mono- or polyoxyalkylene group composed of an optionally substituted alkyl unit having 1 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms, a hydrogen atom, or a substituent. An alkylphenyl mono- or polyoxyalkylene group comprising an alkyl unit having 1 or more carbon atoms and an oxyalkylene unit having 2 to 4 carbon atoms, and an acyl unit having 2 or more carbon atoms which may have a substituent And a substituent selected from the group of acyl mono or polyoxyalkylene groups consisting of oxyalkylene units having 2 to 4 carbon atoms Are shown, R ⁴² is a hydrogen atom, an alkyl group or an aryl group which has having 1 to carbon atoms which may 8 have a substituent. The added mole number of the oxyalkylene unit is 1 to 50.
Also, Y, Z, of the W, at least _{one, -CH 2 O -, - CH} 2 COO -, - CH 2 CH 2 COO -, - CH 2 OCO -, - CH 2 CH 2 OCO -, - A linking group selected from the group of (CH ₂ ) _m NHCO— and — (CH ₂ ) _m NHCO—CH ₂ O— represents a single bond directly bonded to the nitrogen atom of the ammonium group. m represents an integer of 1 to 4. ] The resin composition according to any one of claims 1 to 7 , wherein the swellable layered silicate is a smectite-based layered silicate having a cation exchange capacity of 50 meq / 100 g or more. The resin composition according to any one of claims 1 to 8 , wherein the organically modified swellable layered silicate has a volume resistivity of 10 ¹³ Ω · cm or less. The resin composition according to claim 9 , wherein the resin is a thermoplastic resin. The resin composition according to claim 9 , wherein the resin is a polyolefin-based resin. The resin composition according to claim 9 , wherein the resin is a polystyrene resin. The resin composition according to claim 9 , wherein the resin is a nitrile group-containing resin. The resin composition according to claim 9 , wherein the resin is a poly (meth) acrylic acid resin. The resin composition according to claim 9 , wherein the resin is a polyester resin. The resin composition according to claim 9 , wherein the resin is a polyamide-based resin. The resin composition according to claim 9, wherein the resin is a blend resin of a thermoplastic resin.

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