JP2004331707A - Resin composition for molding damping foam and damping foam - Google Patents
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、防音性、制振性が要求されるマンションなどの床材、運動靴、スポーツ用品のパッド等に使用される衝撃吸収性、制振性に優れる制振性発泡体が得られる制振性発泡体成形用樹脂組成物およびそれよりなる制振性発泡体に関する。
【０００２】
【従来の技術】
制振性発泡体は、柔軟でかつ振動をすばやく減衰させる性能（振動減衰能）の大きいことを利用して、防音、制振、衝撃吸収、振動吸収などの目的で運動靴、パッド等のスポーツ用品、床材やその他の建材、日曜品等へ使用されている。
【０００３】
ポリマーの制振性は、ガラス転移温度近辺やその温度以下の二次転移温度付近で分子鎖の内部摩擦により外部から与えられたエネルギーを消費することにより、振動減衰能が大きくなる現象を利用したものである。従来からポリウレタンで製造された制振発泡材料が使用され、例えば軟質ポリウレタンフォームを製造する際の整泡剤を特定量用いてなる制振性能及び吸音性能を兼備した天井、床等に用いる制振材料（例えば、特許文献１参照。）、有機ポリイソシアネートと特定のポリオールとを、発泡剤、触媒、整泡剤及び可塑効果を有する流動体等の存在下に発泡させて得られる防音・制振発泡体（例えば、特許文献２参照。）等が提案されている。これらのポリウレタンからなる制振発泡材料は、制振性に優れているが、耐候性、特に加水分解に起因する低い耐水性に欠点があった。また、ゴム系の制振性発泡体も提案されており、例えば制振性能に優れ、復元速度が遅くて衝撃吸収性に優れ、かつ熱可塑性樹脂と相溶性が良い１，２−ポリブタジエン発泡体の製造方法（例えば、特許文献３参照。）、制振性を有する１，２−ポリブタジエンと制振性を有するビニル結合−ポリイソプレン−ポリスチレンブロック共重合体との混合物の成形体を架橋発泡させる制振性の樹脂発泡体（例えば、特許文献４参照。）が提案されている。しかしながら、上記従来技術の１，２−ポリブタジエン系発泡体は、１，２−ポリブタジエンの側鎖にビニル基の二重結合炭素を有するので、側鎖間や側鎖と主鎖間で結合して架橋が起こり易く、これにより急激に硬化して、伸びと柔軟性が不足することが欠点であった。
【０００４】
この欠点を解決するために、ポリスチレンとビニル−ポリイソプレンが結合したトリブロック共重合体とポリエチレン系樹脂とを混合して加熱発泡させて制振性樹脂発泡体とすることが提案されている（例えば、特許文献５参照。）。
【０００５】
【特許文献１】
特公平０５−００８２０９号公報
【特許文献２】
特公平０７−０２５８６３号公報
【特許文献３】
特開平０７−０６２１３０号公報
【特許文献４】
特開平０８−２０８８６９号公報
【特許文献５】
特開平１１−３４９７１７号公報
【０００６】
【発明が解決しようとする課題】
しかしながら、特許文献５に提案された制振性樹脂発泡体は、制振性能に優れるポリスチレンとビニル−ポリイソプレンが結合したトリブロック共重合体のスチレン含量が２０ｗｔ％程度と多く、またポリエチレンと相溶しないポリイソプレン相からなっている。このため、高発泡体を得るために発泡剤を増量しても発泡体が発泡成形時に割れてしまい、高発泡倍率の製品が得られないという問題があった。
【０００７】
そこで、本発明は、前記したような課題を解消し、耐候性、耐水性、伸び及び柔軟性に優れ、かつ、高発泡倍率の製品が成形可能な制振性発泡体成形用樹脂組成物及びそれよりなる制振性発泡体を提供することにある。
【０００８】
【課題を解決するための手段】
本発明者は上記課題に関し鋭意検討した結果、スチレン−イソプレン−スチレントリブロック共重合体、水添スチレン−ブタジエン−スチレントリブロック共重合体及びポリエチレン系樹脂をそれぞれ特定の割合で配合してなる組成物が、耐候性、耐水性、伸び、柔軟性に優れ、かつ、高発泡倍率を有する制振性発泡体を与えうることを見出し、本発明を完成させるに至った。
【０００９】
即ち、本発明は、スチレン−イソプレン−スチレントリブロック共重合体５０〜８０重量％、水添スチレン−ブタジエン−スチレントリブロック共重合体５〜３０重量％及びポリエチレン系樹脂１５〜４５重量％からなることを特徴とする制振性発泡体成形用樹脂組成物及び該制振性発泡体成形用樹脂組成物を発泡させてなる制振性発泡体に関するものである。
【００１０】
以下に本発明を詳細に説明する。
【００１１】
本発明の制振性発泡体成形用樹脂組成物は、スチレン−イソプレン−スチレントリブロック共重合体５０〜８０重量％、水添スチレン−ブタジエン−スチレントリブロック共重合体５〜３０重量％及びポリエチレン系樹脂１５〜４５重量％からなる樹脂組成物である。
【００１２】
本発明において用いられるスチレン−イソプレン−スチレントリブロック共重合体とは、ポリスチレン単位とポリイソプレン単位が結合したトリブロック共重合体であり、室温領域にガラス転移温度（Ｔｇ）及び／又は損失正接係数（ｔａｎδ）のピークを有し、室温領域において高い制振性能を発揮する共重合体である。このようなスチレン−イソプレン−スチレントリブロック共重合体は、スチレン単量体とイソプレン単量体をイオン重合することにより製造することが可能であり、本発明においては市販のものを用いることも可能であり、その中でも特に制振性能に優れた制振性発泡体成形用樹脂組成物が得られることからポリスチレン単位を１０〜４０重量％含んでなるスチレン−イソプレン−スチレントリブロック共重合体であることが好ましい。また、スチレン−イソプレン−スチレントリブロック共重合体としては、水添触媒を用い水素添加を行った水添スチレン−イソプレン−スチレントリブロック共重合体であってもよい。
【００１３】
このようなスチレン−イソプレン−スチレントリブロック共重合体は、例えば（株）クラレ製、商品名ハイブラーとして入手することができる。
【００１４】
本発明において用いられる水添スチレン−ブタジエン−スチレントリブロック共重合体は、スチレン−イソプレン−スチレントリブロック共重合体とポリエチレン系樹脂とのバインダーとして作用する共重合体であり、このような水添スチレン−ブタジエン−スチレントリブロック共重合体は、スチレン単量体とブタジエン単量体をイオン重合することにより得られたスチレン−ブタジエン−スチレントリブロック共重合体を水添触媒を用いてポリブタジエン単位を水素添加することにより製造することが可能であり、本発明においては市販のものを用いることも可能である。
【００１５】
本発明において用いられるポリエチレン系樹脂は、本発明の制振性発泡体成形用樹脂組成物の発泡特性を決定する樹脂成分であり、該ポリエチレン系樹脂としては、例えば高圧法低密度ポリエチレン、高密度ポリエチレン、エチレン・α−オレフィン共重合体、エチレン・酢酸ビニル共重合体、メタロセン触媒を使用して重合されたポリエチレン系樹脂、バナジウム触媒を使用して重合されたポリエチレン系樹脂等が挙げられ、この中でも特に柔軟性に優れた制振性発泡体が得られることからメタロセン触媒、バナジウム触媒を使用して重合されたエチレン・α−オレフィン共重合体が好ましい。
【００１６】
そして、その中でもエチレン・α−オレフィン共重合体とは、エチレンとα−オレフィンを共重合したものであり、その際のα−オレフィンとしては、α−オレフィンの範疇に属するものであればいかなるものでもよく、特に均一気泡、柔軟性、強靭性に優れる制振性発泡体を得ることが可能となる制振性発泡体成形用樹脂組成物が得られることから、例えばプロピレン、ブテン−１、ヘキセン−１、オクテン−１、４−メチル−ペンテン−１等の炭素数３〜１２のα−オレフィンであることが好ましい。このようなエチレン・α−オレフィン共重合体は、一般的には直鎖状低密度ポリエチレンと称され、例えばエチレン・ブテン−１共重合体、エチレン・ヘキセン−１共重合体、エチレン・オクテン−１共重合体等が挙げられる。
【００１７】
また、このようなエチレン・α−オレフィン共重合体を製造する際の製造方法としては、例えば高圧法、溶液法、気相法等の各種製造方法を用いることができ、その製造の際に使用する触媒としては、例えばマグネシウムとチタンを含有する固体触媒成分及び有機アルミニウム化合物からなるチーグラー触媒、シクロペンタジエニル誘導体を含有する有機遷移金属化合物と、これと反応してイオン性錯体を形成する化合物及び／又は有機金属化合物からなるメタロセン触媒、バナジウム触媒等を挙げることができる。
【００１８】
本発明において、ポリエチレン系樹脂としてエチレン・α−オレフィン共重合体を用いる際には、特に柔軟性、クッション性に優れた制振性発泡体を生産効率良く製造することが可能となることから、ＪＩＳ Ｋ ６７６０を準拠し測定した密度が０．９４ｇ／ｃｍ３以下、１９０℃、２１６０ｇ荷重により測定したメルトフローレートが０．１〜３０ｇ／１０分間であるエチレン・α−オレフィン共重合体であることが好ましく、０．８７〜０．９０ｇ／ｃｍ３、０．１〜１０ｇ／１０分間であるエチレン・α−オレフィン共重合体がより好ましく、０．８７〜０．８９ｇ／ｃｍ３、０．１〜１０ｇ／１０分間であるエチレン・α−オレフィン共重合体が特に好ましい。さらに、本発明の制振性発泡体成形用樹脂組成物を制振性架橋発泡体とする際には、必要となる過酸化物の量、電離放射線の照射線量を低く抑えることが可能となることから、ゲル・パーミエイション・クロマトグラフィーにより１，２，４−トリクロロベンゼンを溶媒として用い直鎖ポリエチレン換算値として求められた重量平均分子量が６００００以上のエチレン・α−オレフィン共重合体であることが好ましい。
【００１９】
また、本発明におけるポリエチレン系樹脂としては、得られた制振性発泡体成形用樹脂組成物を制振性架橋発泡体とした際に、特に高発泡倍率を有する制振性架橋発泡体を得ることが可能となることから、エチレン・α−オレフィン共重合体１００重量部に対し、粘度平均分子量１００００以下のポリエチレン系ワックス０．１〜３０重量部を配合したポリエチレン系樹脂であることが好ましい。
【００２０】
本発明の制振性発泡体成形用樹脂組成物は、スチレン−イソプレン−スチレントリブロック共重合体５０〜８０重量％、水添スチレン−ブタジエン−スチレントリブロック共重合体５〜３０重量％及びポリエチレン系樹脂１５〜４５重量％からなるものである。ここで、スチレン−イソプレン−スチレントリブロック共重合体が５０重量％未満である場合、得られる組成物の制振性が不足する。一方、スチレン−イソプレン−スチレントリブロック共重合体が８０重量％を越える場合、得られた組成物を発泡成形に供した際に高発泡倍率を有する発泡体が得られない。また、水添スチレン−ブタジエン−スチレントリブロック共重合体が５重量％未満である場合、得られる組成物を構成するスチレン−イソプレン−スチレントリブロック共重合体とポリエチレン系樹脂の相溶性が劣り、このような組成物を発泡成形に供しても高発泡倍率を有する発泡体が得られない。一方、水添スチレン−ブタジエン−スチレントリブロック共重合体が３０重量％を越える場合、得られる組成物の制振性が不足する。ポリエチレン系樹脂が１５重量％未満である場合、得られる組成物は架橋発泡性に劣り、このような組成物を架橋発泡成形に供しても高発泡倍率を有する発泡体が得られない。一方、ポリエチレン系樹脂が４５重量％を越える場合、得られる組成物の制振性が不足する。
【００２１】
また、本発明の制振性発泡体成形用樹脂組成物は、制振性発泡体とする際により高発泡倍率を有する架橋発泡体を効率良く製造することが可能となることから、スチレン−イソプレン−スチレントリブロック共重合体５０〜８０重量％、水添スチレン−ブタジエン−スチレントリブロック共重合体５〜３０重量％及びポリエチレン系樹脂１５〜４５重量％からなる合計量１００重量部に対し、さらに発泡剤２〜２０重量部及び架橋剤０．１〜３重量部を含んでなることが好ましい。
【００２２】
本発明の制振性発泡体成形用樹脂組成物は、発泡成形に供することによりスチレン−イソプレン−スチレントリブロック共重合体５０〜８０重量％、水添スチレン−ブタジエン−スチレントリブロック共重合体５〜３０重量％及びポリエチレン系樹脂１５〜４５重量％からなる制振性に優れる発泡体とすることができる。
【００２３】
その際の制振性発泡体の製造方法としては、スチレン−イソプレン−スチレントリブロック共重合体５０〜８０重量％、水添スチレン−ブタジエン−スチレントリブロック共重合体５〜３０重量％及びポリエチレン系樹脂１５〜４５重量％からなる混合物を発泡することが可能であれば如何なる方法を用いることも可能であり、例えば１）スチレン−イソプレン−スチレントリブロック共重合体５０〜８０重量％、水添スチレン−ブタジエン−スチレントリブロック共重合体５〜３０重量％及びポリエチレン系樹脂１５〜４５重量％からなる混合物に発泡剤を添加し、加熱炉などにより発泡させ発泡体とする方法、２）スチレン−イソプレン−スチレントリブロック共重合体５０〜８０重量％、水添スチレン−ブタジエン−スチレントリブロック共重合体５〜３０重量％及びポリエチレン系樹脂１５〜４５重量％からなる混合物に発泡剤及び架橋剤を添加、混練して、両者の分解温度以下でシート状に成形したのちに、加熱炉などを利用して架橋剤と発泡剤の分解温度以上で加熱・発泡させ架橋発泡体とする方法、３）スチレン−イソプレン−スチレントリブロック共重合体５０〜８０重量％、水添スチレン−ブタジエン−スチレントリブロック共重合体５〜３０重量％及びポリエチレン系樹脂１５〜４５重量％からなる混合物に発泡剤を添加、混練して、電離放射線等を照射し架橋した後に、加熱炉などを利用して発泡剤の分解温度以上で加熱発泡させ架橋発泡体とする方法、等を挙げることができる。そして、本発明における制振性発泡体としては、特に高発泡倍率を有する制振性発泡体が容易に得られることからスチレン−イソプレン−スチレントリブロック共重合体５０〜８０重量％、水添スチレン−ブタジエン−スチレントリブロック共重合体５〜３０重量％及びポリエチレン系樹脂１５〜４５重量％からなる制振性架橋発泡体であることが好ましい。
【００２４】
ここで、発泡剤としては、発泡剤の範疇に属するものであればいかなるものでも用いることが可能であり、その中でも特に高発泡倍率を有する制振性発泡体、特に制振性架橋発泡体が効率よく得られることから、ポリエチレン系樹脂の溶融温度以上の分解温度を有する化学発泡剤が好ましく、例えばアゾジカルボンアミド、ジニトロソペンタメチレンテトラミン、ｐ，ｐ’−オキシビスベンゼンスルホニルヒドラジド等が挙げられる。さらに、発泡助剤を用いてもよく、該発泡助剤としては、例えば尿素を主成分とした化合物；酸化亜鉛、酸化鉛等の金属酸化物；サリチル酸、ステアリン酸等を主成分とする化合物、即ち高級脂肪酸あるいは高級脂肪酸の金属化合物などを挙げることができる。
【００２５】
また、制振性発泡体を高発泡倍率となる制振性架橋発泡体とする際の架橋法には架橋剤の添加、加熱処理による化学架橋、電子線照射による架橋等の方法があり、いずれの方法を用いることも可能であり、その中でも制振性架橋発泡体の架橋が均質に生じ、製品外観に優れる制振性架橋発泡体が得られることから架橋剤による架橋が好ましい。その際の架橋剤としては、加熱により分解され、遊離ラジカルを発生し樹脂分子間もしくは分子内に架橋結合を生じせしめるラジカル発生剤であるところの有機過酸化物が好ましく、例えばジクミルパーオキサイド、１，１−ジターシャリーブチルパーオキシ−３，３，５−トリメチルシクロヘキサン、２，５−ジメチル−２，５−ジターシャリーブチルパーオキシヘキサン、２，５−ジメチル−２，５−ジターシャリーブチルパーオキシヘキシン、α，α−ジターシャリーブチルパーオキシイソプロピルベンゼン、ターシャリーブチルパーオキシケトン、ターシャリーブチルパーオキシベンゾエート等が挙げられる。
【００２６】
本発明の制振性発泡体成形用樹脂組成物は、スチレン−イソプレン−スチレントリブロック共重合体、水添スチレン−ブタジエン−スチレントリブロック共重合体、ポリエチレン系樹脂、必要に応じて発泡剤、架橋剤、その他添加剤等を添加し、樹脂又はゴムの混練機として知られている例えば単軸押出機、２軸押出機、バンバリーミキサー、ニーダーミキサー、ロール、ミキシングロール、加圧式ニーダー等により加熱・混練することにより製造することが可能である。
【００２７】
また、本発明の制振性発泡体成形用樹脂組成物、制振性発泡体は、本発明の目的を逸脱しない限りにおいて物性の改良又は価格の低下を目的として、配合剤（充填剤）として、例えば酸化亜鉛、酸化チタン、酸化カルシウム、酸化マグネシウム、酸化ケイ素等の金属酸化物；炭酸マグネシウム、炭酸カルシウム等の炭酸塩；パルプ等の繊維物質；各種染料；顔料；蛍光物質；その他常用のゴム配合剤等を必要に応じて添加することができる。また、制振性の更なる向上を目的として、例えばポリイソプレン、イソプレン−スチレン共重合体、ポリイソブチレン、ブタジエン−アクリロニトリル共重合体、可塑化ポリ酢酸ビニル等を配合したものであってもよい。
【００２８】
また、本発明の制振性発泡体は、特にクッション性、柔軟性、防音性、制振性能に優れた発泡体となり、かつ連続したシート状の製品が得られることから常圧架橋発泡法で製造された発泡倍率１０〜５０倍を有する制振性架橋発泡体であることが好ましい。
【００２９】
【実施例】
以下に実施例を示し本発明を更に具体的に説明するが、本発明はこれら実施例により何等制限されるものではない。
【００３０】
〜反発弾性率の測定〜
実施例により得られた制振性発泡体の反ぱつ弾性は、ＪＩＳ Ｋ ６４０１に規定された試験方法により測定した。
【００３１】
５／８ｉｎ並球を用い、４６０ｍｍの高さから制振性発泡体に自然落下させた際の反発距離を測定し、該反発距離を落下距離で除した値を百分率で表わし、反発弾性率とした。
【００３２】
実施例１
スチレン−イソプレン−スチレントリブロック共重合体（株式会社クラレ製、商品名ハイブラー５１２５、ポリスチレン単位含有量２０重量％、ビニル結合量５５％、ガラス転移温度−１３℃）７０重量％、水添スチレン−ブタジエン−スチレントリブロック共重合体（クレイトンポリマー社製、商品名クレイトンＧ１６５７、ポリスチレン単位含有量１３重量％）１０重量％、直鎖状低密度ポリエチレン（デュポンダウエラストマー社製、商品名エンゲージ８２００、ＭＦＲ５．０ｇ／１０分、密度０．８７０ｇ／ｃｍ３、重量平均分子量７６０００）２０重量％からなる合計量１００重量部に対し、発泡剤としてアゾジカルボンアミド１０．０重量部、架橋剤としてジクミルパーオキサイド０．８重量部を配合し、１３０℃に設定したミキシングロールにて混練し、制振性発泡体成形用樹脂組成物を得た。
【００３３】
得られた制振性発泡体成形用樹脂組成物を１６０℃に加熱されたプレス内の金型（２００ｍｍ×２００ｍｍ×２ｍｍ）に充填し、２０分間加圧下で加熱した後除圧し制振性発泡性シートを作成した。該シートを２１０℃のオーブン中に静置して２０分間加熱して、制振性発泡体を得た。
【００３４】
得られた制振性発泡体は、発泡倍率２０倍、みかけ密度０．０４５ｇ／ｃｍ３、反発弾性率２０％を有し、制振性に優れるものであった。
【００３５】
実施例２
水添スチレン−イソプレン−スチレントリブロック共重合体（株式会社クラレ製、商品名ハイブラー７１２５、ポリスチレン単位含有量２０重量％、ガラス転移温度−１５℃）７０重量％、水添スチレン−ブタジエン−スチレントリブロック共重合体（クレイトンポリマー社製、商品名クレイトンＧ１６５７、ポリスチレン単位含有量１３重量％）１０重量％、直鎖状低密度ポリエチレン（デュポンダウエラストマー社製、商品名エンゲージ８２００、ＭＦＲ５．０ｇ／１０分、密度０．８７０ｇ／ｃｍ３、重量平均分子量７６０００）２０重量％からなる合計量１００重量部に対し、発泡剤としてアゾジカルボンアミド１０．０重量部、架橋剤としてジクミルパーオキサイド０．８重量部を配合し、１３０℃に調整したミキシングロールにて混練し、制振性発泡体成形用樹脂組成物を得た。
【００３６】
得られた制振性発泡体成形用樹脂組成物を１６０℃に加熱されたプレス内の金型（２００ｍｍ×２００ｍｍ×２ｍｍ）に充填し、２０分間加圧下で加熱した後除圧し、制振性発泡性シートを作成した。該シートを２１０℃のオーブン中に静置して２０分間加熱して、制振性発泡体を得た。
【００３７】
得られた制振性発泡体は、発泡倍率２０倍、みかけ密度０．０４５ｇ／ｃｍ３、反発弾性率１８％を有し、制振性に優れるものであった。
【００３８】
実施例３
スチレン−イソプレン−スチレントリブロック共重合体（株式会社クラレ製、商品名ハイブラー５１２７、ポリスチレン単位含有量２０重量％、ビニル結合量５５％、ガラス転移温度８℃）７０重量％、水添スチレン−ブタジエン−スチレントリブロック共重合体（クレイトンポリマー社製、商品名クレイトンＧ１６５７、ポリスチレン単位含有量１３重量％）１０重量％、直鎖状低密度ポリエチレン（デュポンダウエラストマー社製、商品名エンゲージ８２００、ＭＦＲ５．０ｇ／１０分、密度０．８７０ｇ／ｃｍ３、重量平均分子量７６０００）２０重量％からなる合計量１００重量部に対し、発泡剤としてアゾジカルボンアミド１０．０重量部、架橋剤としてジクミルパーオキサイド０．８重量部を配合し、１３０℃に調整したミキシングロールにて混練し、制振性発泡体成形用樹脂組成物を得た。
【００３９】
得られた制振性発泡体成形用樹脂組成物を１６０℃に加熱されたプレス内の金型（２００ｍｍ×２００ｍｍ×２ｍｍ）に充填し、２０分間加圧下で加熱した後除圧し、制振性発泡性シートを作成した。該シートを２１０℃のオーブン中に静置して２０分間加熱して、制振性発泡体を得た。
【００４０】
得られた制振性発泡体は、発泡倍率２０倍、みかけ密度０．０４５ｇ／ｃｍ３、反発弾性率１０％を有し、制振性に優れるものであった。
【００４１】
実施例４
水添スチレン−イソプレン−スチレントリブロック共重合体（株式会社クラレ製、商品名ハイブラー７１２５、ポリスチレン単位含有量２０重量％、ガラス転移温度−１５℃）７０重量％、水添スチレン−ブタジエン−スチレントリブロック共重合体（クレイトンポリマー社製、商品名クレイトンＧ１６５７、ポリスチレン単位含有量１３重量％）１０重量％、直鎖状低密度ポリエチレン（デュポンダウエラストマー社製、商品名エンゲージ８２００、ＭＦＲ５．０ｇ／１０分、密度０．８７０ｇ／ｃｍ３、重量平均分子量７６０００）２０重量％からなる合計量１００重量部に対し、発泡剤としてアゾジカルボンアミド２０．０重量部、架橋剤としてジクミルパーオキサイド１．０重量部、さらに直鎖状低密度ポリエチレン１００重量部に対しポリエチレンワックス（三井化学製、商品名ハイワックスＮＬ５００、粘土平均分子量４３００）１０重量部を配合し、１３０℃に調整したミキシングロールにて混練し、制振性発泡体成形用樹脂組成物を得た。
【００４２】
得られた制振性発泡体成形用樹脂組成物を１６０℃に加熱されたプレス内の金型（２００ｍｍ×２００ｍｍ×２ｍｍ）に充填し、２０分間加圧下で加熱した後除圧し、制振性発泡性シートを作成した。該シートを２１０℃のオーブン中に静置して２０分間加熱して、制振性発泡体を得た。
【００４３】
得られた制振性発泡体は、発泡倍率３８倍、みかけ密度０．０２３ｇ／ｃｍ３、反発弾性率２４％を有し、制振性に優れるものであった。
【００４４】
比較例１
実施例２において、直鎖状低密度ポリエチレン２０重量％を直鎖状低密度ポリエチレン３０重量％とし、水添スチレン−ブタジエン−スチレントリブロック共重合体を用いなかった以外は、実施例２と同様の方法により制振性発泡体の成形を試みたが、得られた発泡体は割れが発生し制振性発泡体とはならなかった。
【００４５】
比較例２
実施例２において、水添スチレン−ブタジエン−スチレントリブロック共重合体１０重量％を７０重量％、直鎖状低密度ポリエチレン２０重量％を直鎖状低密度ポリエチレン３０重量％とし、水添スチレン−イソプレン−スチレントリブロック共重合体を用いなかった以外は、実施例２と同様の方法により発泡体を得た。
【００４６】
得られた発泡体は、発泡倍率２０倍、みかけ密度０．０４６ｇ／ｃｍ３、反発弾性率５０％を有し、制振性に劣るものであった。
【００４７】
比較例３
実施例２において、水添スチレン−ブタジエン−スチレントリブロック共重合体１０重量％を３０重量％とし、直鎖状低密度ポリエチレンを用いなかった以外は、実施例２と同様の方法により発泡体の成形を試みたが、得られた発泡体は割れが発生し発泡体とはならなかった。
【００４８】
比較例４
実施例２において、水添スチレン−イソプレンースチレン共重合体７０重量％を水添スチレン−イソプレン−スチレン共重合体３０重量％とし、直鎖状低密度ポリエチレン２０重量％を直鎖状低密度ポリエチレン６０重量％とした以外は、実施例２と同様の方法により発泡体を得た。
【００４９】
得られた発泡体は、発泡倍率２２倍、みかけ密度０．０４３ｇ／ｃｍ３、反発弾性率６０％を有し、制振性に劣るものであった。
【００５０】
【発明の効果】
本発明の制振性発泡体成形用樹脂組成物及びそれよりなる制振性発泡体は、室温領域において高い制振性能を有し、高発泡倍率を有する発泡体となることから制振性、伸び、柔軟性、耐候性、耐水性、遮音性に優れ、運動靴等のスポーツ用品、床材等に有用である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention provides a vibration-damping foam having excellent shock-absorbing and vibration-damping properties for use in flooring materials such as condominiums, sports shoes, sports equipment pads, and the like, which require soundproofing and vibration-damping properties. The present invention relates to a resin composition for forming a vibration-damping foam and a vibration-damping foam comprising the same.
[0002]
[Prior art]
Utilizing the fact that the damping foam is flexible and has a large ability to rapidly attenuate vibration (vibration damping ability), sports shoes, pads and other sports are used for the purpose of soundproofing, damping, shock absorption and vibration absorption. Used for supplies, flooring and other building materials, Sunday goods, etc.
[0003]
The vibration damping property of the polymer is based on the phenomenon that the vibration damping ability is increased by consuming the energy given from outside due to the internal friction of the molecular chain around the glass transition temperature or near the secondary transition temperature below that temperature. Things. Conventionally, a vibration damping foam material made of polyurethane is used.For example, when a flexible polyurethane foam is manufactured, a specific amount of a foam stabilizer is used in a ceiling, a floor, etc., which has both a vibration damping performance and a sound absorbing performance. Sound insulation and vibration suppression obtained by foaming a material (for example, see Patent Document 1), an organic polyisocyanate and a specific polyol in the presence of a foaming agent, a catalyst, a foam stabilizer, a fluid having a plasticizing effect, and the like. Foams (for example, see Patent Document 2) have been proposed. Vibration damping foam materials made of these polyurethanes are excellent in vibration damping properties, but have drawbacks in weather resistance, especially low water resistance due to hydrolysis. Further, rubber-based damping foams have also been proposed. For example, 1,2-polybutadiene foam having excellent vibration damping performance, a low restoring speed, excellent shock absorption, and good compatibility with a thermoplastic resin. (For example, refer to Patent Document 3), a molded article of a mixture of 1,2-polybutadiene having damping properties and a vinyl bond-polyisoprene-polystyrene block copolymer having damping properties is crosslinked and foamed. A vibration damping resin foam (for example, see Patent Document 4) has been proposed. However, since the 1,2-polybutadiene-based foam of the prior art has a double bond carbon of a vinyl group in a side chain of 1,2-polybutadiene, it is bonded between side chains or between a side chain and a main chain. The disadvantage is that crosslinking is likely to occur, which causes rapid curing, resulting in insufficient elongation and flexibility.
[0004]
In order to solve this drawback, it has been proposed to mix a triblock copolymer in which polystyrene and vinyl-polyisoprene are combined with a polyethylene-based resin and heat-foam it to form a vibration-damping resin foam ( For example, see Patent Document 5.)
[0005]
[Patent Document 1]
Japanese Patent Publication No. 05-008209
[Patent Document 2]
Japanese Patent Publication No. 07-025863
[Patent Document 3]
JP-A-07-062130
[Patent Document 4]
JP 08-208869 A
[Patent Document 5]
JP-A-11-349717
[0006]
[Problems to be solved by the invention]
However, in the vibration damping resin foam proposed in Patent Document 5, the triblock copolymer in which polystyrene and vinyl-polyisoprene are excellent in vibration damping performance has a high styrene content of about 20% by weight, and also has a low styrene content. It consists of an insoluble polyisoprene phase. For this reason, even if the amount of the foaming agent is increased in order to obtain a high foam, the foam is broken at the time of foam molding, and there is a problem that a product having a high expansion ratio cannot be obtained.
[0007]
Therefore, the present invention has solved the above-mentioned problems, and has excellent weather resistance, water resistance, excellent elongation and flexibility, and a resin composition for molding a vibration damping foam capable of molding a product having a high expansion ratio. An object of the present invention is to provide a vibration-damping foam comprising the same.
[0008]
[Means for Solving the Problems]
The present inventor has conducted intensive studies on the above-mentioned problems, and as a result, a composition obtained by blending a styrene-isoprene-styrene triblock copolymer, a hydrogenated styrene-butadiene-styrene triblock copolymer, and a polyethylene resin in a specific ratio, respectively. It has been found that the product can provide a vibration-damping foam having excellent weather resistance, water resistance, elongation, flexibility, and a high expansion ratio, and completed the present invention.
[0009]
That is, the present invention comprises 50 to 80% by weight of a styrene-isoprene-styrene triblock copolymer, 5 to 30% by weight of a hydrogenated styrene-butadiene-styrene triblock copolymer, and 15 to 45% by weight of a polyethylene resin. The present invention relates to a vibration-damping foam molding resin composition and a vibration-damping foam obtained by foaming the vibration-damping foam molding resin composition.
[0010]
Hereinafter, the present invention will be described in detail.
[0011]
The resin composition for molding a vibration damping foam of the present invention comprises 50 to 80% by weight of a styrene-isoprene-styrene triblock copolymer, 5 to 30% by weight of a hydrogenated styrene-butadiene-styrene triblock copolymer, and polyethylene. It is a resin composition comprising 15 to 45% by weight of a base resin.
[0012]
The styrene-isoprene-styrene triblock copolymer used in the present invention is a triblock copolymer in which a polystyrene unit and a polyisoprene unit are bonded, and has a glass transition temperature (Tg) and / or a loss tangent coefficient in a room temperature region. It is a copolymer having a peak of (tan δ) and exhibiting high damping performance in a room temperature region. Such a styrene-isoprene-styrene triblock copolymer can be produced by ion-polymerizing a styrene monomer and an isoprene monomer, and a commercially available product can be used in the present invention. Among them, a styrene-isoprene-styrene triblock copolymer containing 10 to 40% by weight of a polystyrene unit because a resin composition for molding a vibration-damping foam having particularly excellent vibration-damping performance can be obtained. Is preferred. The styrene-isoprene-styrene triblock copolymer may be a hydrogenated styrene-isoprene-styrene triblock copolymer obtained by hydrogenation using a hydrogenation catalyst.
[0013]
Such a styrene-isoprene-styrene triblock copolymer can be obtained, for example, from Kuraray Co., Ltd. under the trade name Hibler.
[0014]
The hydrogenated styrene-butadiene-styrene triblock copolymer used in the present invention is a copolymer that acts as a binder between a styrene-isoprene-styrene triblock copolymer and a polyethylene resin, and such a hydrogenated styrene-butadiene-styrene triblock copolymer is used. The styrene-butadiene-styrene triblock copolymer is obtained by subjecting a styrene-butadiene-styrene triblock copolymer obtained by ion-polymerizing a styrene monomer and a butadiene monomer to polybutadiene units using a hydrogenation catalyst. It can be produced by hydrogenation, and in the present invention, a commercially available product can also be used.
[0015]
The polyethylene resin used in the present invention is a resin component that determines the foaming properties of the vibration-damping foam molding resin composition of the present invention. Examples of the polyethylene resin include a high-pressure low-density polyethylene and a high-density polyethylene. Polyethylene, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, polyethylene-based resin polymerized using a metallocene catalyst, polyethylene-based resin polymerized using a vanadium catalyst, and the like. Among them, an ethylene / α-olefin copolymer polymerized using a metallocene catalyst or a vanadium catalyst is preferable because a vibration damping foam having particularly excellent flexibility can be obtained.
[0016]
And, among them, the ethylene / α-olefin copolymer is a copolymer of ethylene and α-olefin, and the α-olefin at that time is any one as long as it belongs to the category of α-olefin. Since a resin composition for molding a vibration-damping foam capable of obtaining a vibration-damping foam excellent in uniform cells, flexibility and toughness can be obtained, for example, propylene, butene-1, hexene and the like can be obtained. It is preferably an α-olefin having 3 to 12 carbon atoms such as -1, octene-1, and 4-methyl-pentene-1. Such an ethylene / α-olefin copolymer is generally called a linear low-density polyethylene, for example, ethylene / butene-1 copolymer, ethylene / hexene-1 copolymer, ethylene / octene- 1 copolymer and the like.
[0017]
Further, as a production method for producing such an ethylene / α-olefin copolymer, various production methods such as a high pressure method, a solution method, and a gas phase method can be used. Examples of the catalyst include a solid catalyst component containing magnesium and titanium and a Ziegler catalyst comprising an organoaluminum compound, an organic transition metal compound containing a cyclopentadienyl derivative, and a compound which reacts with the compound to form an ionic complex. And / or metallocene catalysts and vanadium catalysts composed of organometallic compounds.
[0018]
In the present invention, when an ethylene-α-olefin copolymer is used as the polyethylene resin, in particular, flexibility, since it becomes possible to produce a vibration-damping foam excellent in cushioning property with high production efficiency, The density measured according to JIS K 6760 is 0.94 g / cm 3 Hereinafter, an ethylene / α-olefin copolymer having a melt flow rate measured at 190 ° C. and a load of 2160 g of 0.1 to 30 g / 10 minutes is preferable, and 0.87 to 0.90 g / cm. 3 , An ethylene / α-olefin copolymer having a viscosity of 0.1 to 10 g / 10 minutes is more preferable, and 0.87 to 0.89 g / cm. 3 And an ethylene / α-olefin copolymer having a viscosity of 0.1 to 10 g / 10 min. Furthermore, when the vibration-damping foam molding resin composition of the present invention is used as a vibration-damping crosslinked foam, the amount of peroxide required and the irradiation dose of ionizing radiation can be kept low. From this fact, the copolymer is an ethylene / α-olefin copolymer having a weight average molecular weight of 60,000 or more, which is determined by gel permeation chromatography using 1,2,4-trichlorobenzene as a solvent and converted into linear polyethylene. Is preferred.
[0019]
Further, as the polyethylene resin in the present invention, when the obtained resin composition for molding a damping foam is used as a damping crosslinked foam, a damping crosslinked foam having a particularly high expansion ratio is obtained. From the viewpoint of being able to do so, it is preferable to use a polyethylene resin in which 0.1 to 30 parts by weight of a polyethylene wax having a viscosity average molecular weight of 10,000 or less is blended with 100 parts by weight of the ethylene / α-olefin copolymer.
[0020]
The resin composition for molding a vibration damping foam of the present invention comprises 50 to 80% by weight of a styrene-isoprene-styrene triblock copolymer, 5 to 30% by weight of a hydrogenated styrene-butadiene-styrene triblock copolymer, and polyethylene. It is composed of 15 to 45% by weight of the base resin. Here, when the amount of the styrene-isoprene-styrene triblock copolymer is less than 50% by weight, the obtained composition has insufficient vibration damping properties. On the other hand, when the styrene-isoprene-styrene triblock copolymer exceeds 80% by weight, a foam having a high expansion ratio cannot be obtained when the obtained composition is subjected to foam molding. When the content of the hydrogenated styrene-butadiene-styrene triblock copolymer is less than 5% by weight, the compatibility between the styrene-isoprene-styrene triblock copolymer and the polyethylene resin constituting the obtained composition is poor, Even if such a composition is subjected to foam molding, a foam having a high expansion ratio cannot be obtained. On the other hand, when the amount of the hydrogenated styrene-butadiene-styrene triblock copolymer exceeds 30% by weight, the obtained composition has insufficient vibration damping properties. When the content of the polyethylene resin is less than 15% by weight, the composition obtained is inferior in cross-linking foaming properties, and a foam having a high expansion ratio cannot be obtained even when such a composition is subjected to cross-linking foam molding. On the other hand, when the content of the polyethylene resin exceeds 45% by weight, the obtained composition has insufficient vibration damping properties.
[0021]
Further, the resin composition for molding a vibration-damping foam of the present invention can efficiently produce a crosslinked foam having a high expansion ratio when the vibration-damping foam is used. -With respect to 100 parts by weight of a total amount of 50 to 80% by weight of a styrene triblock copolymer, 5 to 30% by weight of a hydrogenated styrene-butadiene-styrene triblock copolymer, and 15 to 45% by weight of a polyethylene resin, It preferably comprises 2 to 20 parts by weight of a foaming agent and 0.1 to 3 parts by weight of a crosslinking agent.
[0022]
The resin composition for molding a vibration damping foam of the present invention is subjected to foam molding to form a styrene-isoprene-styrene triblock copolymer 50 to 80% by weight, a hydrogenated styrene-butadiene-styrene triblock copolymer 5 It is possible to obtain a foam having excellent vibration damping properties, comprising up to 30% by weight and 15 to 45% by weight of a polyethylene resin.
[0023]
At that time, the method for producing the vibration damping foam includes a styrene-isoprene-styrene triblock copolymer of 50 to 80% by weight, a hydrogenated styrene-butadiene-styrene triblock copolymer of 5 to 30% by weight, and a polyethylene-based material. Any method can be used as long as a mixture comprising 15 to 45% by weight of a resin can be foamed. For example, 1) 50 to 80% by weight of a styrene-isoprene-styrene triblock copolymer, hydrogenated styrene A method in which a foaming agent is added to a mixture of 5 to 30% by weight of a butadiene-styrene triblock copolymer and 15 to 45% by weight of a polyethylene resin, and the mixture is foamed by a heating furnace or the like to form a foam; 2) Styrene-isoprene -Styrene triblock copolymer 50-80% by weight, hydrogenated styrene-butadiene-styrene tribro A foaming agent and a cross-linking agent are added and kneaded to a mixture consisting of 5 to 30% by weight of a copolymer and 15 to 45% by weight of a polyethylene resin, and the mixture is formed into a sheet at a temperature not higher than the decomposition temperature of both. A method of heating and foaming at a temperature not lower than the decomposition temperature of the crosslinking agent and the foaming agent to form a crosslinked foam, 3) 50 to 80% by weight of styrene-isoprene-styrene triblock copolymer, hydrogenated styrene-butadiene- A foaming agent is added to a mixture of 5 to 30% by weight of a styrene triblock copolymer and 15 to 45% by weight of a polyethylene resin, kneaded, irradiated with ionizing radiation or the like, crosslinked, and then heated using a heating furnace or the like. A method of heating and foaming at a temperature not lower than the decomposition temperature of the foaming agent to form a crosslinked foam. As the damping foam in the present invention, particularly, a damping foam having a high expansion ratio can be easily obtained, so that 50 to 80% by weight of a styrene-isoprene-styrene triblock copolymer, hydrogenated styrene -A damping crosslinked foam comprising 5 to 30% by weight of a butadiene-styrene triblock copolymer and 15 to 45% by weight of a polyethylene resin is preferable.
[0024]
Here, as the foaming agent, any material can be used as long as it belongs to the category of the foaming agent. Among them, a damping foam having a high expansion ratio, particularly a damping cross-linked foam is preferred. A chemical foaming agent having a decomposition temperature equal to or higher than the melting temperature of the polyethylene resin is preferable because it can be efficiently obtained, and examples thereof include azodicarbonamide, dinitrosopentamethylenetetramine, and p, p'-oxybisbenzenesulfonylhydrazide. . Further, a foaming aid may be used. Examples of the foaming aid include compounds mainly containing urea; metal oxides such as zinc oxide and lead oxide; compounds mainly containing salicylic acid and stearic acid; That is, higher fatty acids or metal compounds of higher fatty acids can be mentioned.
[0025]
In addition, as a crosslinking method when the vibration-damping foam is a vibration-damping crosslinked foam having a high expansion ratio, there are methods such as addition of a crosslinking agent, chemical crosslinking by heat treatment, crosslinking by electron beam irradiation, and the like. It is also possible to use the method described above, and among them, crosslinking with a crosslinking agent is preferable because crosslinking of the damping crosslinked foam is uniformly generated and a damping crosslinked foam excellent in product appearance is obtained. As the cross-linking agent at that time, an organic peroxide which is a radical generator which is decomposed by heating and generates free radicals to cause cross-linking between resin molecules or within the molecule is preferable, for example, dicumyl peroxide, 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di-tert-butyl peroxyhexane, 2,5-dimethyl-2,5-di-tert-butyl peroxyhexane Oxyhexyne, α, α-di-tert-butylperoxyisopropylbenzene, tert-butyl peroxyketone, tert-butylperoxybenzoate and the like can be mentioned.
[0026]
The vibration-damping foam molding resin composition of the present invention is a styrene-isoprene-styrene triblock copolymer, a hydrogenated styrene-butadiene-styrene triblock copolymer, a polyethylene-based resin, a foaming agent if necessary, Add a cross-linking agent, other additives, etc. and heat with a resin or rubber kneading machine known as a single screw extruder, twin screw extruder, Banbury mixer, kneader mixer, roll, mixing roll, pressurized kneader, etc. -It can be manufactured by kneading.
[0027]
In addition, the vibration-damping foam molding resin composition and the vibration-damping foam of the present invention may be used as a compounding agent (filler) for the purpose of improving physical properties or lowering the price without departing from the object of the present invention. Metal oxides such as zinc oxide, titanium oxide, calcium oxide, magnesium oxide and silicon oxide; carbonates such as magnesium carbonate and calcium carbonate; fiber materials such as pulp; various dyes; pigments; fluorescent materials; Compounding agents and the like can be added as needed. Further, for the purpose of further improving the vibration damping property, for example, a composition containing polyisoprene, an isoprene-styrene copolymer, polyisobutylene, a butadiene-acrylonitrile copolymer, plasticized polyvinyl acetate, or the like may be used.
[0028]
In addition, the vibration-damping foam of the present invention is a foam particularly excellent in cushioning property, flexibility, soundproofing and vibration-damping performance, and a continuous sheet-like product is obtained. It is preferable that the manufactured vibration-damping crosslinked foam has an expansion ratio of 10 to 50 times.
[0029]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.
[0030]
~ Measurement of rebound resilience ~
The resilience of the damping foam obtained in the examples was measured by a test method specified in JIS K6401.
[0031]
Using a 5 / 8-inch side-by-side sphere, the rebound distance when naturally falling on the vibration-damping foam from a height of 460 mm was measured, and the value obtained by dividing the rebound distance by the drop distance was expressed as a percentage. did.
[0032]
Example 1
70% by weight of styrene-isoprene-styrene triblock copolymer (manufactured by Kuraray Co., Ltd., trade name: Hibler 5125, polystyrene unit content 20% by weight, vinyl bond amount 55%, glass transition temperature -13 ° C) 70% by weight, hydrogenated styrene 10% by weight of a butadiene-styrene triblock copolymer (manufactured by Clayton Polymer, trade name: Kraton G1657, polystyrene unit content: 13% by weight), linear low-density polyethylene (manufactured by Dupont Dow Elastomers, trade name: Engage 8200, MFR5) 0.0 g / 10 min, density 0.870 g / cm 3 , A weight average molecular weight of 76,000) 20 parts by weight of a total amount of 20 parts by weight, 10.0 parts by weight of azodicarbonamide as a foaming agent and 0.8 parts by weight of dicumyl peroxide as a crosslinking agent were blended. The mixture was kneaded with a set mixing roll to obtain a vibration-damping foam molding resin composition.
[0033]
The obtained resin composition for forming a vibration-damping foam is filled into a mold (200 mm × 200 mm × 2 mm) in a press heated to 160 ° C., heated under pressure for 20 minutes, and then depressurized to remove vibration. Sheet was created. The sheet was left standing in an oven at 210 ° C. and heated for 20 minutes to obtain a damping foam.
[0034]
The obtained damping foam had an expansion ratio of 20 times and an apparent density of 0.045 g / cm. 3 , A rebound resilience of 20%, and excellent vibration damping properties.
[0035]
Example 2
70% by weight of hydrogenated styrene-isoprene-styrene triblock copolymer (trade name: Hibler 7125, manufactured by Kuraray Co., Ltd., polystyrene unit content 20% by weight, glass transition temperature -15 ° C), hydrogenated styrene-butadiene-styrene triblock 10% by weight of block copolymer (manufactured by Clayton Polymer Co., Ltd., trade name Clayton G1657, polystyrene unit content: 13% by weight), linear low-density polyethylene (manufactured by Dupont Dow Elastomer Co., Ltd., trade name: Engage 8200, MFR 5.0 g / 10) Min, density 0.870g / cm 3 , A weight average molecular weight of 76,000) 20 parts by weight of a total amount of 20 parts by weight, 10.0 parts by weight of azodicarbonamide as a foaming agent and 0.8 parts by weight of dicumyl peroxide as a crosslinking agent were blended. The mixture was kneaded with the adjusted mixing roll to obtain a vibration-damping foam molding resin composition.
[0036]
The obtained resin composition for forming a vibration-damping foam was filled into a mold (200 mm × 200 mm × 2 mm) in a press heated to 160 ° C., heated under pressure for 20 minutes, and then depressurized. A foam sheet was prepared. The sheet was left standing in an oven at 210 ° C. and heated for 20 minutes to obtain a damping foam.
[0037]
The obtained damping foam had an expansion ratio of 20 times and an apparent density of 0.045 g / cm. 3 And had a rebound resilience of 18% and was excellent in vibration damping properties.
[0038]
Example 3
70% by weight of styrene-isoprene-styrene triblock copolymer (manufactured by Kuraray Co., Ltd., trade name: Hibler 5127, polystyrene unit content: 20% by weight, vinyl bond amount: 55%, glass transition temperature: 8 ° C.), hydrogenated styrene-butadiene 10% by weight of a styrene triblock copolymer (trade name: Clayton G1657, trade name: Clayton G1657, polystyrene unit content: 13% by weight), linear low-density polyethylene (trade name: Engage 8200, trade name: MFR5. 0 g / 10 min, density 0.870 g / cm 3 , A weight average molecular weight of 76,000) 20 parts by weight of a total amount of 20 parts by weight, 10.0 parts by weight of azodicarbonamide as a foaming agent and 0.8 parts by weight of dicumyl peroxide as a crosslinking agent were blended. The mixture was kneaded with the adjusted mixing roll to obtain a vibration-damping foam molding resin composition.
[0039]
The obtained resin composition for forming a vibration-damping foam was filled into a mold (200 mm × 200 mm × 2 mm) in a press heated to 160 ° C., heated under pressure for 20 minutes, and then depressurized. A foam sheet was prepared. The sheet was left standing in an oven at 210 ° C. and heated for 20 minutes to obtain a damping foam.
[0040]
The obtained damping foam had an expansion ratio of 20 times and an apparent density of 0.045 g / cm. 3 , A rebound resilience of 10%, and excellent vibration damping properties.
[0041]
Example 4
70% by weight of hydrogenated styrene-isoprene-styrene triblock copolymer (trade name: Hibler 7125, manufactured by Kuraray Co., Ltd., polystyrene unit content 20% by weight, glass transition temperature -15 ° C), hydrogenated styrene-butadiene-styrene triblock 10% by weight of block copolymer (manufactured by Clayton Polymer Co., Ltd., trade name Clayton G1657, polystyrene unit content: 13% by weight), linear low-density polyethylene (manufactured by Dupont Dow Elastomer Co., Ltd., trade name: Engage 8200, MFR 5.0 g / 10) Min, density 0.870g / cm 3 20.0 parts by weight of azodicarbonamide as a foaming agent, 1.0 part by weight of dicumyl peroxide as a crosslinking agent, and a linear low density 10 parts by weight of polyethylene wax (manufactured by Mitsui Chemicals, trade name: High Wax NL500, clay average molecular weight: 4300) is blended with 100 parts by weight of polyethylene and kneaded with a mixing roll adjusted to 130 ° C. to form a vibration damping foam. A resin composition was obtained.
[0042]
The obtained resin composition for forming a vibration-damping foam was filled into a mold (200 mm × 200 mm × 2 mm) in a press heated to 160 ° C., heated under pressure for 20 minutes, and then depressurized. A foam sheet was prepared. The sheet was left standing in an oven at 210 ° C. and heated for 20 minutes to obtain a damping foam.
[0043]
The obtained damping foam had an expansion ratio of 38 times and an apparent density of 0.023 g / cm. 3 , A rebound resilience of 24%, and excellent vibration damping properties.
[0044]
Comparative Example 1
In the same manner as in Example 2, except that 20% by weight of the linear low-density polyethylene was changed to 30% by weight of the linear low-density polyethylene and the hydrogenated styrene-butadiene-styrene triblock copolymer was not used. An attempt was made to form a vibration-damping foam by the above method, but the resulting foam cracked and did not become a vibration-damping foam.
[0045]
Comparative Example 2
In Example 2, 10% by weight of hydrogenated styrene-butadiene-styrene triblock copolymer was 70% by weight, and 20% by weight of linear low-density polyethylene was 30% by weight of linear low-density polyethylene. A foam was obtained in the same manner as in Example 2 except that the isoprene-styrene triblock copolymer was not used.
[0046]
The obtained foam had an expansion ratio of 20 times and an apparent density of 0.046 g / cm. 3 , A rebound resilience of 50%, and poor vibration damping properties.
[0047]
Comparative Example 3
In the same manner as in Example 2, except that 10% by weight of the hydrogenated styrene-butadiene-styrene triblock copolymer was changed to 30% by weight and no linear low-density polyethylene was used. Molding was attempted, but the resulting foam cracked and did not become a foam.
[0048]
Comparative Example 4
In Example 2, 70% by weight of hydrogenated styrene-isoprene-styrene copolymer was changed to 30% by weight of hydrogenated styrene-isoprene-styrene copolymer, and 20% by weight of linear low-density polyethylene was changed to linear low-density polyethylene. A foam was obtained in the same manner as in Example 2, except that the amount was 60% by weight.
[0049]
The obtained foam had an expansion ratio of 22 times and an apparent density of 0.043 g / cm. 3 , A rebound resilience of 60%, and poor vibration damping properties.
[0050]
【The invention's effect】
The resin composition for molding a vibration-damping foam of the present invention and the vibration-damping foam comprising the same have a high vibration-damping performance in a room temperature region, and provide a foam having a high expansion ratio. It excels in elongation, flexibility, weather resistance, water resistance and sound insulation, and is useful for sports equipment such as athletic shoes, flooring materials and the like.
Claims (7)
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