JP4250014B2 - Softener composition for thermoplastic elastomer, thermoplastic elastomer composition - Google Patents

Description

【００５０】
成分（ｄ）の配合量は、成分（ａ）１００重量部に対して、０．１〜３０重量部であり、好ましくは０．５〜２０重量部である。配合量が０．１重量部未満では、ベタツキを抑えスベスベ感を与える効果がなくフィルムとの密着性も低下し、３０重量部を超えるとブリードが顕著になりフィルムとの密着性も低下する。
【００５１】
（ｅ）消泡剤
本発明の熱可塑性エラストマー用軟化剤組成物および熱可塑性エラストマー組成物においては、必要に応じて、（ｅ）消泡剤を配合することができる。成分（ｅ）は、熱可塑性エラストマー用軟化剤組成物および熱可塑性エラストマー組成物に添加することにより、熱可塑性エラストマー用軟化剤組成物および熱可塑性エラストマー組成物の混和性向上と消泡機能を有する。そのため、当該成分を含むことにより、成形性が極めて良好となる。
【００５２】
成分（ｅ）としては、シリコーン系化合物、非シリコーン系化合物の何れでも良く、以下の化合物が挙げられる。
シリコーン系化合物としては、ＨＬＢが１以上、４未満のポリシロキサン共重合物等が挙げられる。
非シリコーン系化合物化合物としては、脂肪酸エステル系化合物、ウレア樹脂系化合物、ＨＬＢが１以上、４未満のパラフィン系化合物、ポリオキシアルキレングリコール系化合物、アクリルエステル共重合物、エステル系重合物、エーテル系重合物、ミネラルオイルの乳化タイプ、ポリシロキサンアダクト、フッ素系化合物、ビニル系重合物、アセチレンアルコール、アクリル系ポリマー、特殊ビニル系ポリマー、エチレングリコール、高級アルコール（オクチルアルコール、シクロヘキサノール等）、ＨＬＢ値は１以上、４未満、好ましくは２以上、４未満の非イオン系界面活性剤等が挙げられる。
これらの中では、脂肪酸エステル系化合物、ウレア樹脂系化合物、ＨＬＢが１以上、４未満のパラフィン系化合物、ポリオキシアルキレングリコール系化合物、ＨＬＢが１以上、４未満のシリコーン系化合物等が好ましく、これらは、単独でも、２種以上を併用して用いても良い。
【００５３】
成分（ｅ）の配合量は、添加する場合は、成分（ａ）１００重量部に対して、０．１〜２０重量部であり、好ましくは０．３〜１０重量部である。配合量が２０重量部を超えると、得られる熱可塑性エラストマー組成物からの成形品表面外観が悪化する。
【００５４】
なお、上記成分（ｄ）及び（ｅ）で重複する化合物名のものは、以下の基準でＨＬＢにより区別することが可能である。
重複成分の内、成分（ｄ）に属するものは、ＨＬＢが７〜１３であり、成分（ｅ）に属するものは、ＨＬＢが１以上、４未満である。
【００５５】
（ｆ）オレフィン系樹脂
本発明の熱可塑性エラストマー組成物においては、必要に応じて、（ｆ）オレフィン系樹脂を配合することができる。
成分（ｆ）としては、エチレン、プロピレン、ブテン−１、ヘキセン−１、４−メチル−ペンテン−１などのα−オレフィンの単独重合体、その２種以上の共重合体、あるいはα−オレフィンと他の重合性単量体との共重合体、例えば、エチレン−酢酸ビニル共重合体、エチレン−（メタ）アクリル酸共重合体、エチレン−（メタ）アクリレート共重合体（エチレン−アクリル酸メチル共重合体、エチレン−アクリル酸エチル共重合体、エチレン−メタクリル酸メチル共重合体等）等が挙げられ、単独でも、２種類以上を併用して用いることができる。その他、オレフィン系樹脂として共役ジエンブロック共重合体の水素添加物（例えば、ＣＥＢＣ：オレフィン結晶ブロック−エチレン・ブテンランダムのブロック−オレフィン結晶ブロック）が挙げられる。これらの中では、エチレンの単独重合体、エチレンと他のα−オレフィンの共重合体が好ましく、特に、シングルサイト触媒を用いて重合されたエチレン−ヘキセン−１共重合体、エチレン−オクテン−１共重合体を主成分とする低温下での耐衝撃性等が改良されたエラストマータイプのエチレン系共重合体が好ましい。
【００５６】
成分（ｆ）の配合量は、配合する場合は、成分（ａ）１００重量部に対して、１〜３０重量部、好ましくは３〜２０重量部である。配合量が３０重量部を超えると、室温でのゲル（ゼリー）状態、成形性が悪化する。
【００５７】
（ｇ）有機過酸化物
本発明の熱可塑性エラストマー用軟化剤組成物および熱可塑性エラストマー組成物においては、必要に応じて、（ｄ）有機過酸化物を含有させることができる。成分（ｄ）は、得られる熱可塑性エラストマー組成物の成分（ｂ）を架橋することにより、高度な耐油性を発現し、室温では塑性変形しにくくなり、高温でのオイルブリードを改善する効果を有する。
【００５８】
成分（ｄ）としては、例えば、１，１−ビス（ｔ−ヘキシルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、ベンゾイルパーオキサイド、ｍ−メチルベンゾイルパーオキサイド、ｍ−トルオイルパーオキサイド、ｔ−ヘキシルパーオキシベンゾエート、１，１−ビス（ｔ−ブチルパーオキシ）２−メチルシクロヘキサン、１，１−ビス（ｔ−ヘキシルパーオキシ）シクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、２，２−ビス（４，４−ジブチルパーオキシシクロヘキシル）プロパン、１，１−ビス（ｔ−ブチルパーオキシ）シクロドデカン、ｔ−ヘキシルパーオキシイソプロピルモノカーボネート、琥珀酸パーオキサイド、１−シクロヘキシル−１−メチルエチルパーオキシ−２−エチルヘキサノエート、ｔ−ヘキシルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ｍ−トルオイル及びベンゾイルパーオキサイド、ｔ−ブチルパーオキシイソブチレート、ｔ−ブチルパーオキシラウレート、２，５−ジメチル−２，５−ジ（ｍ−トルオイルパーオキシ）ヘキサン、ｔ−ブチルパーオキシイソプロピルモノカルボネート、ｔ−ブチルパーオキシ−２−エチルヘキシルモノカーボネート、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン、ｔ−ブチルパーオキシアセテート、２，２−ビス（ｔ−ブチルパーオキシ）ブタン、ジクミルパーオキサイド、ジ−ｔｅｒｔ−ブチルパーオキサイド、２，５−ジメチル−２，５−ジ−（ｔｅｒｔ−ブチルパーオキシ）ヘキサン、２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルペルオキシ）ヘキシン−３、１，３−ビス（ｔｅｒｔ−ブチルパーオキシイソプロピル）ベンゼン、１，１−ビス（ｔｅｒｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、ｎ−ブチル−４，４−ビス（ｔｅｒｔ−ブチルパーオキシ）バレレート、ベンゾイルパーオキサイド、ｐ−クロロベンゾイルパーオキサイド、２，４−ジクロロベンゾイルパーオキサイド、ｔｅｒｔ−ブチルパーオキシベンゾエート、ｔｅｒｔ−ブチルパーオキシイソプロピルカーボネート、ジアセチルパーオキサイド、ラウロイルパーオキサイド、ｔｅｒｔ−ブチルクミルパーオキサイドなどを挙げることができる。
【００５９】
これらのうち、臭気性、着色性、スコーチ安定性の点で、１，１−ビス（ｔ−ヘキシルパーオキシ）−３，３，５−トリメチルシクロヘキサン（１分半減期温度１４７℃）、２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルパーオキシ）ヘキサン（１分半減期温度１７９℃）および２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルペルオキシ）ヘキシン−３（１分半減期温度１９４℃）等が好ましい。本発明の組成物の場合は、１分半減期温度が１６５℃以下の低温分解型の有機過酸化物を使用しても良い。
【００６０】
成分（ｇ）の配合量は、配合する場合は、成分（ａ）１００重量部に対して、０．１〜１０重量部であり、好ましくは０．２〜５重量部である。配合量が５重量部を超えると有機過酸化物による分解反応が優先され、臭気も激しくなり、得られる熱可塑性エラストマー組成物の成形型加工性に劣る。配合量が０．１重量部未満では、耐熱変形性と耐油性などの改良効果がない。
【００６１】
（ｈ）エステル系架橋助剤
本発明の熱可塑性エラストマー用軟化剤組成物および熱可塑性エラストマー組成物においては、必要に応じて、エステル系架橋助剤成分（ｈ）を配合することができる。成分（ｈ）は、上記の有機過酸化物成分（ｇ）による架橋処理に際して、均一かつ効率的な架橋反応を行わせる効果を有する。成分（ｈ）としては、例えば、エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、エチレングリコールの繰り返し単位数が９〜１４のポリエチレングリコールジメタクリレート、トリメチロールプロパントリメタクリレート、アリルメタクリレート、２−メチル−１，８−オクタンジオールジメタクリレート、１，９−ノナンジオールジメタクリレートのような多官能性メタクリレート化合物、ポリエチレングリコールジアクリレート、エトキシ化シクロヘキサンジメタノールジアクリレート、１，６−ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート、プロピレングリコールジアクリレートのような多官能性アクリレート化合物、ビニルブチラート、ビニルステアレート、ジビニルベンゼン、トリアリルシアヌレートのような多官能性ビニル化合物を挙げることができる。これらは、単独あるいは２種類以上を組み合わせて用いても良い。このような化合物により、均一かつ効率的な架橋反応が期待できる。
【００６２】
上記の架橋助剤のうち、多官能性メタクリレート化合物および多官能性アクリレート化合物が好ましく、エトキシ化シクロヘキサンジメタノールジアクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、２−メチル−１，８−オクタンジオールジメタクリレート、１，９−ノナンジオールジメタクリレート、トリメチロールプロパントリメタクリレートが特に好ましく、特に、エトキシ化シクロヘキサンジメタノールジアクリレートを用いると透明性が低下しにくい。
【００６３】
成分（ｈ）の配合量は、配合する場合は、成分（ａ）１００重量部に対して、０．１〜２０重量部であり、好ましくは０．５〜１０重量部である。配合量が２０重量部を超えると組成物の架橋が進みすぎて架橋助剤が部分的に分散せず、製造出来るものの外観が悪くなる。
【００６４】
（ｉ）その他の成分
なお、本発明の熱可塑性エラストマー組成物においては、本発明の目的を損なわない範囲で、熱安定剤、酸化防止剤、光安定剤、紫外線吸収剤、結晶核剤、ブロッキング防止剤、シール性改良剤、ステアリン酸、シリコーンオイル等の離型剤、ポリエチレンワックス等の滑剤、着色剤、顔料、アルミナ等の無機充填剤、発泡剤（有機系、無機系、マイクロカプセル系）難燃剤（水和金属化合物、赤燐、ポリりん酸アンモニウム、アンチモン、シリコーン）などを配合することができる。
酸化防止剤としては、例えば、２，６−ジ−ｔｅｒｔ−ｐ−ブチル−ｐ−クレゾール、２，６−ジ−ｔｅｒｔ−ブチルフェノール、２，４−ジメチル−６−ｔｅｒｔ−ブチルフェノール、４，４−ジヒドロキシジフェニル、トリス（２−メチル−４−ヒドロキシ−５−ｔｅｒｔ−ブチルフェニル）ブタン等のフェノール系酸化防止剤、ホスファイト系酸化防止剤、チオエーテル系酸化防止剤等が挙げられる。このうちフェノール系酸化防止剤、ホスファイト系酸化防止剤が特に好ましい。
【００６５】
２．熱可塑性エラストマー用軟化剤組成物、熱可塑性エラストマー組成物の製造本発明の熱可塑性エラストマー用軟化剤組成物は、成分（ａ）、（ｃ）、（ｄ）、および、必要に応じてその他の成分を配合し、室温で、混合装置にて混合して簡単に得ることができる。
また、本発明の熱可塑性エラストマー組成物は、成分（ａ）〜（ｄ）、および、必要に応じてその他の成分を配合し、１５０〜１８０℃の混練温度で、混練装置にて溶融混練または溶融混合して得ることができる。
さらにまた、簡易的には本発明の熱可塑性エラストマー組成物は、成分（ａ）〜（ｃ）、および、必要に応じてその他の成分を配合し、１００〜１８０℃で、混合装置または混練装置にて混合し、スープ状またはシャーベット状になった組成物を目的の型に流し込み冷却するか、もしくは冷却で得られたブロックを１００〜１８０℃でプレス成形を行うこと等により直接目的の熱可塑性エラストマー組成物からなる成形体を得ることもできる。
本願の組成物において発泡は、溶融混練時あるいは溶融成形時でもよいし、混練・成形時に発泡させず溶融成形後さらに加熱しその際に発泡させても良い。その中でも溶融混練時に発泡させることが均一で高倍率の発泡体が得られる点で好ましい。
【００６６】
例えば、熱膨張マイクロカプセルの膨張開始温度より２０℃以上低い温度で組成物を熱処理し、次の成形段階で膨張開始温度より２０℃以上高い温度で処理すれば発泡をさせることができる。
【００６７】
本発明で使用する混練装置としては、オートクレーブ、加圧ニーダー、バンバリーミキサー、単軸押出機、２軸押出機、多軸押出機等を使用することが出来る。好ましくは、加圧ニーダー、バンバリー等のバッチ式混練装置で混練する方法が良い。連続的に行う場合には、バッチ式混練装置と押出機とが組み合わされた、例えば、加圧ニーダーと押出機が組合わさった装置（バッチ供給型連続押出装置）で混練する方法が良い。
【００６８】
３．熱可塑性エラストマー用軟化剤組成物、熱可塑性エラストマー組成物
本発明の熱可塑性エラストマー用軟化剤組成物は、柔軟な熱可塑性エラストマー組成物の形成に用いられ、特にジェル状で存在する熱可塑性エラストマー組成物のジェル用軟化組成物として用いることができる。
また、本発明の熱可塑性エラストマー組成物は、室温（２３℃）での硬さは、好ましくは４０Ａ以下、より好ましくは１０Ａ以下であって、ジェル状（ゼリー状）で存在する。
また、本発明の熱可塑性エラストマー組成物は、成形時に加熱し、溶融ジェル化と同時に発泡して発泡体成形体となるため、容易に製造ができ、成形も容易で、保湿性に優れ、オイルブリード感が少なく、比重が０．８以下の軽量で、消音性等に優れる発泡性組成物であるので、様々な用途において使用可能である。
【００６９】
具体的な用途としては、例えば、防振用（ボルト付き）インシュレーター、ボルト貫通ブッシュ、（凹凸）防振シート、テープ、シール、チップ状等の防振部材、鞄の緩衝材（例えばランドセルの肩掛け部、手提げ部等）、パソコン用アームレストやリストレスト（マウスパットにも応用）、紙送りローラ、オーディオ関係部材（ターンテーブル、インシュレーター、スぺーサー等）、ケース用防振ゴム足、靴エステ用人形の顔（皮膚等）、テニスラケット、断熱用シート、電柱保護用等の防水シート、床ずれ防止マット等、フィルムシーリング品（例えば老人大腿部骨折防止ヒッププロテクター、術後の身体形状補助材、ライダー用スーツ、グローブ（サッカーのキーパー、ゴルフ、スキー、ライダー用）、ライフルジャケット（例えば肩パット）、スポーツシューズ、ベッド、高温高圧成形機クッション（セラミック成形等）、熱伝導ゲルシート（例えば、放熱用ＣＰＵコア外周用等）、ゲーム機の制振パット、ヘルスケア関係、自動車部材（ウインドーパッキンの緩衝材等）、自動車ドアの衝撃吸収材（側面等）、靴の中敷き、靴にあたると痛い外反母趾や巻き爪等による痛みを緩和するためのフットケア用衝撃吸収剤、バンパーやヘルメットの衝撃吸収剤、ベット、マットレス、枕、クッション、座布団などの雑貨、寝具類としての衝撃吸収剤、肘あて、膝あて、鞍による馬の背中の鞍ずれ防止、スキー靴、トゥ・シューズ、バレエシューズ、グローブのようなスポーツ関係の衝撃吸収剤、荷物の輸送での衝撃吸収剤、骨折、怪我や傷を守り、義足と皮膚がこすれないための医療用衝撃吸収剤、乳がん等で乳房を切り取った人、水着や豊胸用の胸パット、魚つり用等の疑似餌、また、机や椅子、パソコン、本棚、床等の生活用品の埃やゴミを吸着する掃除用品、さらに油剤の徐放性を利用してパック等の化粧品や湿布、芳香剤等に応用が可能である。
中でも、ヘルスケア関係への応用が好ましい。
【００７０】
【実施例】
以下、実施例及び比較例により本発明を更に説明するが、本発明はこれに限定されるものではない。なお、実施例における評価方法及び使用した材料を以下に示す。
【００７１】
１．熱可塑性エラストマー組成物の評価方法
（１）比重：ＪＩＳ Ｋ ７１１２に準拠し、溶融混練直後２１５×１４５×２ｍｍ厚のＳＵＳ３０４ステンレスバットに流込むか塗込めたものの上に重さ５００ｇの２１５×１４５ｍｍのステンレス板をかぶせ、２４時間以上放置して冷却したシートを用いて測定を行なった。
（２）硬さ：ＪＩＳ Ｋ ６２５３に準拠し、溶融混練直後２１５×１４５×２ｍｍ厚のＳＵＳ３０４ステンレスバットに流込むか塗込めたものの上に重さ５００ｇの２１５×１４５ｍｍのステンレス板をかぶせ、２４時間以上放置して冷却したシートを重ね合わせて４ｍｍ厚以上にして測定を行った。
（３）オイルブリードとスベスベ・さらさら感：溶融混練直後２１５×１４５×２ｍｍ厚のＳＵＳ３０４ステンレスバットに流込むか塗込めたものの上に重さ５００ｇの２１５×１４５ｍｍのステンレス板をかぶせ、２４時間以上放置して冷却したシートをクラフト紙に挟んで、直径７０ｍｍ円盤状の５００ｇの重りをのせ、常温（２３℃）で１６８時間放置後のクラフト紙の状態を目視で観察し、次の基準で評価した。
◎：クラフト紙にオイルブリードの痕跡が認められない
○：クラフト紙にオイルブリードの痕跡が認められるが、スベスベ・さらさら感がある
×：クラフト紙にオイルブリードの痕跡が認められ、ベトツキ感がある
（４）成形性：溶融混練直後２１５×１４５×２ｍｍ厚のＳＵＳ３０４ステンレスバットに流込むか塗込めたものの上に重さ５００ｇの２１５×１４５ｍｍのステンレス板をかぶせ、２４時間以上放置して冷却したシートを作成し、表面外観や形状を観察し、次の基準で評価した。
◎：表面は平滑で、気泡もない
○：表面の平滑でも、気泡の存在が認められる
△：表面の平滑でないが、気泡はない
×：表面は平滑でなく、気泡も存在する
（５）歪維持性：上記（４）で得られたシートに直径７０ｍｍ円筒状の５００ｇの重りを１時間のせた後、重りを取り除き、歪の維持具合を目視で観察し、次の基準で評価した。
○：１分では回復せず、３０分で徐々に回復する
△：１分では回復せず、３０分でも回復しない
×：１分で回復する
（６）体積膨潤率（％）：ＪＩＳ Ｋ ６２５８に準拠し、上記（４）で取り出した製品を使用し、７０℃×７２時間、ＩＲＭ＃９０２浸漬後の膨潤率を測定した。
（７）フィルム（ポリエチレン）シートとの密着性：（５）の成形時、本発明の組成物とＳＵＳ３０４ステンレスバットとの間に０．１ｍｍ厚のポリエチレンフィルムをはさみ、同様の条件で成形を行い、以下の基準で評価した。
◎：表面は平滑で、気泡もない
△：表面の平滑でも、気泡の存在が認められる
×：表面は平滑でなく、気泡も存在する
【００７２】
２．材料
（ａ）非芳香族系ゴム用軟化剤成分：ＮＡソルベント ＮＡＳ−５Ｈ （日本油脂（株）製）比重：０．８２３、種類：イソパラフィン系炭化水素油、粘度（４０℃）：１１．０ｃＳｔ、引火点：１４６℃
（ｂ−１）水添ブロック共重合体成分： セプトン４０７７（ＳＥＰＳ）（商標；クラレ株式会社製）、スチレン含有量３０重量％、数平均分子量２６０，０００、重量平均分子量３２０，０００、分子量分布１．２３、水素添加率９０％以上
（ｂ−２）水添ブロック共重合体成分： セプトン４０３３（ＳＥＰＳ）（商標；クラレ株式会社製）、スチレン含有量３０重量％、数平均分子量１３０，０００、重量平均分子量１００，０００、分子量分布１．３０、水素添加率９０％以上
（ｃ−１）熱膨張性マイクロカプセル成分：エクスパンセル ０９２ＤＵＸ１２０（エクスパンセル社製）、粒子径；２８〜３８μｍ、膨張開始温度；１１６〜１２６℃、膨張終了温度；２３０〜２４０℃
（ｃ−２）熱膨張性マイクロカプセル成分：エクスパンセル ０９８ＤＵＸ１２０（エクスパンセル社製）、粒子径；２８〜４５μｍ、膨張開始温度；１５０〜１７０℃、膨張終了温度；２５０〜２６５℃
（ｄ−１）界面活性剤成分：ノニオン Ｅ−２０５Ｓ（日本油脂社製）、ポリエチレングリコール オレイルエーテル、ＨＬＢ：９．０、ｐＨ：５〜８、比重：０．９３、引火点：２２８℃
（ｄ−２）ブチルステアレート：日本油脂製、プラスチック用滑剤、ＨＬＢ＝５．５（比較成分）
（ｄ−３）２−エチルヘキサン酸セチル：エキセパールＨＯ（花王製）ヨウ素価１以下、水酸基価３以下、ＨＬＢ＝６（比較成分）
（ｅ）消泡剤成分：ディスホームＢＦ−７５（ポリアルキレングリコール（商標；日本油脂（株）社製）、動粘度（４０℃）：４０ｍｍ^２／ｓ、ｐＨ：７．０〜１０．０、比重：０．９１、引火点：１８６℃、ＨＬＢ＝３
（ｆ）オレフィン系樹脂成分：：ＰＥ、Ｅｎｇａｇｅ ＥＧ８４０１（Ｄｕｐｏｎｔ Ｄｏｗ Ｅｌａｓｔｏｍｅｒ社製）比重：０．８８５、硬さ：８５（ＳｈｏｒｅＡ）、ムーニー粘度ＭＬ_１＋４（１２１℃）：５以下、重量平均分子量：１００，０００
（ｇ）有機過酸化物成分：パーヘキサＴＭＨ（１，１−ビス（ｔ−ヘキシルパーオキシ）−３，３，５−トリメチルシクロヘキサン）（商標；日本油脂株式会社製）、活性酸素量：７．５２％、分子量：３５８．５７、１分間半減期を得るための分解温度：１４７．１℃
（ｈ）エステル系架橋助剤成分：ＣＨＤ−４Ｅ（エトキシ化シクロヘキサンジメタノールジアクリレート；新中村化学株式会社製）粘度：５０ｍＰａ・ｓ、比重：１．０６２、分子量：６３６
（ｉ）酸化防止剤：ヒンダードフェノール／フォスファイト／ラクトン系複合酸化防止剤：ＨＰ２２１５（商標；チバスペシャリティケミカルズ社製）
【００７３】
実施例１〜４、比較例１〜１０
表２に示す成分比で、成分（ａ）〜（ｉ）を加えて、ミキサーまたはオートクレーブにて、混練温度１６０℃で混練を行い熱可塑性エラストマー組成物を得た。得られた組成物の物性を測定した。その結果を表２に示す。
【００７４】
【表２】

【００７５】
表２から明らかなように、本発明の熱可塑性エラストマー組成物である実施例１〜４の組成物は、いずれも良好な結果を示した。
特に熱膨張温度の高い熱膨張剤を用いた実施例４は、未膨張のまま溶融混練直後に２１５×１４５×２ｍｍ厚のＳＵＳ３０４ステンレスバットに流込むか塗込めたものの上に重さ５００ｇの２１５×１４５ｍｍのステンレス板をかぶせ、２４時間以上放置して冷却したシートを作成した後、２００℃オーブン中に１０分間放置して評価を行った結果である。
一方、比較例１と２は、成分（ｂ）を範囲外にしたものである。成分（ｂ）が少ないと、ベタツキが顕著になり、プレス成形性、歪維持性が悪化する。成分（ｂ）が多いと、硬さが硬くなりすぎてジェル状でなくなり、歪維持性が悪化する。
比較例３と４は、成分（ｃ）を範囲外にしたものである。成分（ｃ）が少ないと歪維持性が悪化し、成分（ｃ）が多いと、発泡剤の凝集が顕著になりシートの崩壊が認められ、プレス成形性、歪維持性が悪化する。
比較例５〜８は、成分（ｄ）を範囲外にしたものである。成分（ｄ）を用いないと、オイルブリードとさらさら感、フィルムシートとの密着性が悪化し、成分（ｄ）が多いと、オイルブリード、フィルムシートとの密着性が悪化する。
比較例９と１０は、成分（ｄ）界面活性剤の代わりに一般にプラスチック用滑剤として使われるブチルステアレート、２−エチルヘキサン酸セチルを用いたものである。ブチルステアレート、２−エチルヘキサン酸セチルを用いると、ベタツキが顕著になり、オイルがブリードしさらさら感がなくなる。また、フィルムとの密着性も悪化する。
【００７６】
【発明の効果】
本発明の熱可塑性エラストマー組成物は、成形時に加熱し、溶融ジェル化と同時に発泡して発泡体成形体となるため、容易に製造ができ、成形も容易で、保湿性に優れ、オイルブリード感が少なく、比重が０．８以下の軽量で、消音性等に優れる発泡性組成物であるので、床ずれ防止マット、老人大腿部骨折防止ヒッププロテクター、術後の身体形状補助材等のヘルスケア関係の材料として好適に用いることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a softener composition for a thermoplastic elastomer, a flexible thermoplastic elastomer composition, and a foamed molded article comprising the same, and in particular, a gel-like (jelly-like) composition having a hardness of 40 A or less at room temperature (23 ° C.). Thermoplastic elastomer with a specific gravity of 0.8 or less that can be easily manufactured, has excellent moisture retention, has little oil bleed, has excellent strain retention characteristics, has a smooth and smooth feel, and is not sticky The present invention relates to a composition and a foamed molded article comprising the composition.
[0002]
[Prior art]
Conventionally, a thermoplastic elastomer resin composition having a predetermined hardness has been obtained by adding oil as a softening agent and olefin resin as a resin component to a styrene resin composition or an ethylene-propylene resin composition, Paraffin oil is often used as the oil. However, the addition of oil makes it possible to reduce the hardness, but since a resin having a lower molecular weight than other resin components is used, the heat resistance, weather resistance, mechanical strength, wear resistance, etc. are reduced. .
[0003]
In addition, when obtaining a very soft thermoplastic resin composition, particularly a gel elastomer containing an elastomer and an oil component, there is a problem that oil bleed occurs on the surface of the molded product when a conventional uncrosslinked oil is used. Satisfactory thermoplastic resin compositions, especially gel elastomers, cannot be obtained. That is, in general, the amount of oil that can be absorbed by the thermoplastic resin composition has an upper limit of oil amount / thermoplastic resin composition = a little more than three times, and when more oil is added, oil bleeding occurs. Furthermore, when oil is blended in the thermoplastic resin composition, the components other than oil are solid, whereas the oil is liquid, which makes it difficult to handle and is used exclusively for pumps and the like to blend oil. There was a problem that equipment was necessary.
[0004]
Furthermore, a composition composed of styrene-based thermoplastic elastomers and paraffins is disclosed as a gel elastomer (see, for example, Patent Document 1), but a high temperature is required during production and heat dissolution. For this reason, there is also a problem that the paraffins ooze out and feel oily because the gel is browned and solidified immediately when molded, the handling property is insufficient and difficult to handle, and the structural strength of the gel is insufficient. It was.
[0005]
In order to solve the above problems, isopropyl myristate, isopropyl palmitate, butyl stearate, and isononyl isononanoate are blended to lower the melting temperature of styrenic thermoplastic elastomers. An invention has been disclosed in which the nature is increased and the feel is refreshed (see, for example, Patent Document 2). However, although the effect of improving the hue is sufficiently exerted, the oiliness is still strong, and the improvement of oiliness is insufficient particularly in the field where a refreshing feel such as foot care use is required.
[0006]
In order to improve such oily feeling, etc., the effect of addition of fatty acid esters was studied, and the size of the alkyl group existing between the ester groups and the ratio of branching influence the effect of adding the fatty acid ester. A gel elastomer composition composed of styrene-based thermoplastic elastomers, paraffins, and fatty acid esters (cetyl 2-ethylhexylate) has been proposed (for example, see Patent Document 3). Furthermore, as a gel-like composition imparted with shock absorbing performance, a gel-like composition obtained by swelling a triblock styrene elastomer in a softening agent (see, for example, Patent Document 4), a triblock styrene elastomer and diblock A gel-like composition (for example, see Patent Documents 5 and 6) composed of a type styrene elastomer and a softening agent has been proposed.
However, these gel-like compositions also have a problem that the balance of oil bleeding and moldability is remarkably inferior, and in terms of a smooth surface and film sealing products, films such as polyethylene and polyurethane are used. The adhesiveness with was not considered.
Furthermore, a gel (for example, Patent Document 7) obtained by foaming a gel composition composed of a triblock styrene elastomer, a diblock styrene elastomer and a softening agent has been proposed.
However, these gel-like compositions also have problems such as severe oil bleed and a remarkably poor balance of moldability, and are difficult to adapt to the human body when using a conventional polyurethane foam bed cushion. In applications that do not use a film on the surface (for example, armrests, pillows, etc.), the smoothness of the surface that affects comfort is not considered in order to improve the likelihood of bedsores. It was. Similarly, many industrial applications that do not use a film on the surface cannot be used due to surface tackiness (stickiness) and oil bleeding.
In addition, in film sealing products etc., the excessive adhesiveness and poor oil bleedability of the gel composition worsen the adhesion with a film such as polyethylene or polyurethane instead of bubbles entering between the films, It was a thing causing bed slip.
In addition, the compositions described in the above prior arts are particularly inferior in productivity because the cooling time is abnormally long especially in injection molding, and in some cases, it takes about 25 minutes.
[0007]
Therefore, the present inventors have a softening agent for non-aromatic hydrocarbon rubber as a super-soft composition which is rich in flexibility, excellent in heat distortion characteristics, mechanical strength, oil resistance and molding processability and has no stickiness, Compositions containing organic peroxides, crosslinking aids, thermoplastic resins as optional components (see, for example, Patent Document 8), styrenic thermoplastic elastomers, softeners for non-aromatic hydrocarbon rubbers, vinyl aromatic resins , A hydrogenated petroleum resin, an acrylic processing aid, and a composition containing an organic peroxide (see, for example, Patent Document 9), easy handling, no oil bleed, and excellent mechanical strength As a thermoplastic gel composition having wear resistance, a thermoplastic resin containing a softener for non-aromatic hydrocarbon rubber, a hydrogenated styrene thermoplastic elastomer, and an amorphous polyolefin. A plastic gel composition (see, for example, Patent Document 10) is proposed. However, a thermoplastic elastomer composition excellent in molding processability and having a good balance between molding processability and various physical properties has not been obtained.
In addition, when used in cushioning materials such as automobile parts, building materials, and household appliance parts, it must be lightweight and have excellent sound deadening properties. Simply adding oil to a thermoplastic resin composition will give sufficient performance. Furthermore, the conventional polyurethane foam is light in weight but inferior in delay elasticity, requires a complicated process for its production, and requires expensive materials such as those used for PHARMAEDICS Control Pillow. It is.
[0008]
[Patent Document 1]
US Pat. No. 4,369,284
[Patent Document 2]
US Pat. No. 5,558,872
[Patent Document 3]
JP 2000-281850 A
[Patent Document 4]
JP-A-8-73696
[Patent Document 5]
JP 2001-151979 A
[Patent Document 6]
JP 2001-151980 A
[Patent Document 7]
JP 2001-342283 A
[Patent Document 8]
JP 2001-311012 A
[Patent Document 9]
JP 2000-34389 A
[Patent Document 10]
Japanese Patent Application No. 2001-388697
[0009]
[Problems to be solved by the invention]
In view of the above problems, the present invention is a flexible heat-softenable elastomer softener composition that can be easily produced, a gel-like (jelly-like) composition having a hardness of 40 A or less at room temperature, and can be easily produced. A thermoplastic elastomer composition that is easy to mold, has excellent moisture retention, has very little oil bleed, has excellent strain retention characteristics, has a smooth and smooth feel, is light and has excellent sound deadening properties, and the like. It aims at providing a foaming molding.
[0010]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventor has increased the amount of addition up to a level at which sufficient fluidity and moldability can be expressed by using only the non-aromatic hydrocarbon rubber softener, Bleeding of the softening agent becomes prominent, and flexibility, molding processability and bleed resistance can be improved by mixing the hydrogenated and / or partially hydrogenated block copolymer with the softener for non-aromatic hydrocarbon rubber. It turns out that the balance can be improved. Based on these results, a foamable thermoplastic elastomer composition containing a specific amount of hydrogenated and / or partially hydrogenated block copolymer and a foaming agent in a non-aromatic rubber softener is foamed, A gel-like (jelly-like) composition having a hardness of 40 A or less at room temperature (23 ° C.), which can be easily produced, is easy to mold, has excellent moisture retention, has little oil bleed, and has a specific gravity of 0.8 or less. The present invention has been completed by finding that it is a very soft elastic body that is light in weight and excellent in noise reduction.
[0011]
That is, according to the first invention of the present invention, (a) 100 parts by weight of a non-aromatic hydrocarbon rubber softener,
(C) 0.1 to 30 parts by weight of a foaming agent, and
(D) 0.1-30 parts by weight of surfactant
A softener composition for a thermoplastic elastomer is provided.
[0012]
According to the second invention of the present invention, in the first invention, the component (a) is a mixture of a linear saturated hydrocarbon and / or a branched saturated hydrocarbon having 4 to 155 carbon atoms. A softener composition for thermoplastic elastomers is provided.
[0013]
According to a third invention of the present invention, there is provided the softener composition for thermoplastic elastomer according to the first or second invention, wherein the component (a) is liquid at room temperature (23 ° C.). Provided.
[0014]
According to a fourth aspect of the present invention, in any one of the first to third aspects, the component (c) is a thermal expansion microcapsule, a chemical foaming agent, or a physical foaming agent. A softener composition for a thermoplastic elastomer is provided.
[0015]
According to a fifth aspect of the present invention, in the thermoplastic elastomer according to any one of the first to fourth aspects, the component (d) is a nonionic, cationic or anionic surfactant. A softener composition is provided.
[0016]
According to the sixth invention of the present invention, the thermoplastic elastomer softener composition of any one of the first to fifth inventions, and further, with respect to 100 parts by weight of component (a),
(B) Hydrogenated and / or partially hydrogenated block copolymer 3 to 110 parts by weight
A thermoplastic elastomer composition is provided.
[0017]
Moreover, according to the seventh invention of the present invention, in the sixth invention, it further comprises (e) 0.1 to 20 parts by weight of an antifoaming agent with respect to 100 parts by weight of the component (a). A featured thermoplastic elastomer composition is provided.
[0018]
According to the eighth invention of the present invention, in the seventh invention, the component (e) is a fatty acid ester-based, urea resin-based, paraffin-based, silicone-based, or polyoxyalkylene glycol-based antifoaming agent. A thermoplastic elastomer composition is provided.
[0019]
According to the ninth aspect of the present invention, in any one of the sixth to seventh aspects, the component (a) further contains 1 to 30 parts by weight of an olefin-based resin with respect to 100 parts by weight. A thermoplastic elastomer composition is provided.
[0020]
According to the tenth aspect of the present invention, in any one of the sixth to ninth aspects, (g) an organic peroxide is 0.1 to 10 weights per 100 weight parts of the component (a). A thermoplastic elastomer composition characterized by containing a part is provided.
[0021]
According to an eleventh aspect of the present invention, in any one of the sixth to tenth aspects of the invention, (h) an ester-based crosslinking aid of 0.1 to 20 with respect to 100 parts by weight of component (a). A thermoplastic elastomer composition characterized by containing parts by weight is provided.
[0022]
According to a twelfth aspect of the present invention, in any one of the sixth to eleventh aspects, the thermoplastic resin is a gel composition having a hardness at room temperature (23 ° C.) of 40 A or less. Elastomeric compositions are provided.
[0023]
According to a thirteenth aspect of the present invention, there is provided a foamed molded article formed by using the thermoplastic elastomer composition according to any one of the sixth to twelfth aspects.
[0024]
DETAILED DESCRIPTION OF THE INVENTION
1. Softener composition for thermoplastic elastomer, component of thermoplastic elastomer composition
(A) Softener component for non-aromatic hydrocarbon rubber
The non-aromatic hydrocarbon rubber softener component (a) used in the thermoplastic elastomer softener composition and thermoplastic elastomer composition of the present invention is a non-aromatic mineral oil or liquid, or has a low molecular weight. Synthetic softeners may be mentioned. Generally, a mineral oil softener for rubber is a mixture of an aromatic ring, a naphthene ring and a paraffin chain, and has a saturated hydrocarbon chain carbon number of 50% or more of the total carbon number. Those that occupy 30 to 40% are called naphthenes, and those that occupy 30% or more aromatic carbons are called aromatics. The mineral oil softener for rubber used in the present invention is preferably the paraffinic and naphthenic types described above. Aromatic softeners are not preferred because of their poor dispersibility.
As the non-aromatic hydrocarbon rubber softening agent, a paraffinic mineral oil softening agent is particularly preferable, and paraffinic ones having a small aromatic ring component are particularly suitable.
[0025]
Examples of the compound constituting the paraffinic softener include paraffinic compounds having 4 to 155 carbon atoms, preferably paraffinic compounds having 4 to 50 carbon atoms, specifically, butane, pentane, hexane. , Heptane, octane, nonane, decane, undecane, dodecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosan, heneicosan, docosan, tricosan, tetracosan, pentacosan, hexacosan, heptacosan, octacosan, triacotan, henakosan, triacontane, N-paraffins (linear saturated hydrocarbons) such as Kontan, Dotriacontane, Pentatriacontane, Hexacontane, Heptacontane, Isobutane, Isopentane, Neopentane, Isohexane, Pentane, neohexane, 2,3-dimethylbutane, 2-methylhexane, 3-methylhexane, 3-ethylpentane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3, 3-dimethylpentane, 2,2,3-trimethylbutane, 3-methylheptane, 2,2-dimethylhexane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,4 -Dimethylhexane, 2,2,3-trimethylpentane, isooctane, 2,3,4-trimethylpentane, 2,3,3-trimethylpentane, 2,3,4-trimethylpentane, isononane, 2-methylnonane, isodecane, Isoundecane, isododecane, isotridecane, isotetradecane, isopentadecane, isoeo Tadekan, Isonanodekan, isoeicosane, 4-ethyl-5-isoparaffins methyl octane (branched saturated hydrocarbons) and can include derivatives of these saturated hydrocarbons. These paraffins are used in a mixture and are preferably liquid at room temperature (23 ° C.).
[0026]
Commercially available paraffinic softeners that are liquid at room temperature (23 ° C.) include NA Solvent (isoparaffinic hydrocarbon oil) manufactured by Nippon Oil & Fats Co., Ltd., and PW-90 (n-paraffinic process manufactured by Idemitsu Kosan Co., Ltd.). Oil), IP-solvent 2835 (synthetic isoparaffinic hydrocarbon, 99.8 wt% or more isoparaffin) manufactured by Idemitsu Petrochemical Co., Ltd., neothiozole (n-paraffinic process oil) manufactured by Sanko Chemical Co., Ltd., and the like. .
[0027]
Moreover, a small amount of unsaturated hydrocarbons and derivatives thereof may coexist in the non-aromatic hydrocarbon softener. Unsaturated hydrocarbons include ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2 -Ethylene hydrocarbons such as butene, 1-hexene, 2,3-dimethyl-2-butene, 1-heptene, 1-octene, 1-nonene, 1-decene, acetylene, methylacetylene, 1-butyne, 2- Examples thereof include acetylene hydrocarbons such as butyne, 1-pentyne, 1-hexyne, 1-octyne, 1-nonine and 1-decyne.
[0028]
In addition, the specific gravity of the component (a) used in the present invention is preferably 0.72 to 0.87, more preferably 0.80 to 0.84. When the specific gravity is less than 0.72, the volatile components increase, and the mechanical properties further deteriorate. Moreover, when it exceeds 0.87, compatibility with a component (b) will fall and a moldability will deteriorate.
[0029]
(B) Hydrogenated and / or partially hydrogenated block copolymer component
The hydrogenated and / or partially hydrogenated block copolymer component (b) used in the thermoplastic elastomer composition of the present invention is used for adjusting flexibility.
The hydrogenated block copolymer is a block copolymer comprising at least one polymer block A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound. Mention may be made, for example, of hydrogenated block copolymers or conjugated diene block copolymers obtained by hydrogenation.
A block comprising at least one polymer block A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound that can be used in the thermoplastic elastomer composition of the present invention. The hydrogenated block copolymer component obtained by hydrogenating the copolymer contains at least one polymer block A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound. It is a polymer obtained by hydrogenating one block copolymer. For example, a hydrogenated block copolymer of an aromatic vinyl compound-conjugated diene compound having a structure such as A-B, A-B-A, B-A-B-A, or A-B-A-B-A Is obtained.
[0030]
The polymer block A mainly composed of an aromatic vinyl compound may be a polymer composed only of an aromatic vinyl compound or a copolymer of an aromatic vinyl compound and less than 50% by weight of a conjugated diene compound. The polymer block B mainly composed of a conjugated diene compound may be a polymer composed solely of a conjugated diene compound or a copolymer of a conjugated diene compound and less than 50% by weight of an aromatic vinyl compound.
[0031]
As the aromatic vinyl compound constituting the hydrogenated block copolymer, for example, one or more kinds can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc. Styrene is preferred. In addition, as the conjugated diene compound, for example, one or two or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc., among which butadiene, isoprene and These combinations are preferred.
[0032]
Hydrogenated block obtained by hydrogenating a block copolymer comprising at least one polymer block A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound In the polymer block B mainly composed of a conjugated diene compound, the hydrogenation rate of the polymer component is arbitrary, but it is preferably 50% or more, more preferably 55% or more, and still more preferably 60% or more. Further, the microstructure is arbitrary. For example, when the block B is composed of butadiene alone, the polybutadiene block preferably has a 1,2-microstructure of 20 to 50% by weight, particularly preferably 25 to 45%. % By weight. Moreover, the thing which hydrogenated the 1, 2- bond selectively may be sufficient. When block B is composed of a mixture of isoprene and butadiene, the 1,2-microstructure is preferably less than 50%, more preferably less than 25%, and even more preferably less than 15%.
[0033]
When block B is composed of isoprene alone, in the polyisoprene block, preferably 70 to 100% by weight of isoprene has a 1,4-microstructure, and preferably at least aliphatic double bonds derived from isoprene. 90% hydrogenated is preferred.
[0034]
When a hydrogenated block copolymer is used depending on the application, the above hydrogenated product can be suitably used according to the application.
[0035]
Moreover, it is preferable that the polymer block A exists in the ratio of 5-70 weight% of the whole component. Furthermore, the weight average molecular weight of the whole component is preferably 500,000 or less, more preferably 180,000 to 350,000. If the weight average molecular weight exceeds 500,000, molding processability and mechanical properties deteriorate.
When emphasizing moldability, in addition to the above components, those having a weight average molecular weight of 50,000 to 150,000 can be used in combination. When the weight average molecular weight is 50,000 or less, the mechanical properties are deteriorated and oil bleed becomes remarkable.
[0036]
Specific examples of the hydrogenated block polymer component include styrene-ethylene / butadiene copolymer (SEB), styrene-ethylene / propylene copolymer (SEP), styrene-ethylene / butadiene-styrene copolymer (SEBS), Styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS), styrene-butadiene-butylene-styrene copolymer (partially hydrogenated styrene-butadiene-styrene copolymer) Polymer, SBBS) and the like.
[0037]
A block obtained by hydrogenating a block copolymer comprising at least one polymer block A mainly composed of these aromatic vinyl compounds and at least one polymer block B mainly composed of a conjugated diene compound. As a method for producing a copolymer, a number of methods have been proposed. As a typical method, for example, a lithium catalyst or a Ziegler type catalyst is used by the method described in JP-B-40-23798. It can be obtained by block polymerization in an inert medium. Such a hydrogenation treatment of the block copolymer can be performed by a known method in the presence of a hydrogenation catalyst in an inert solvent.
[0038]
Examples of the hydrogenated conjugated diene block copolymer that can be used in the thermoplastic elastomer composition of the present invention include, for example, a crystalline ethylene block obtained by hydrogenating a butadiene block copolymer and an amorphous block. And a block copolymer (CEBC) having a functional ethylene-butene block. In the present invention, the hydrogenated product of the conjugated diene compound block copolymer may be used alone or in combination of two or more.
Moreover, the weight average molecular weight of the hydrogenated product of the conjugated diene block copolymer is 150,000 or less, and preferably 30,000 to 120,000. If the weight average molecular weight exceeds 150,000, the moldability deteriorates.
[0039]
The compounding quantity of a component (b) is 3-110 weight part with respect to 100 weight part of component (a), Preferably it is 5-60 weight part. When the amount of the component (b) is less than 3 parts by weight, oil bleed becomes conspicuous from the thermoplastic elastomer composition and molding processability deteriorates. If it exceeds 110 parts by weight, the gel shape (jelly shape) cannot be maintained and it becomes hard.
[0040]
(C) Foaming agent
The softening agent composition for thermoplastic elastomer of the present invention, the foaming agent (c) used in the thermoplastic elastomer composition has the property of imparting functions such as weight reduction of products, sound insulation by foaming during molding, Examples of the component (c) include thermal expansion microcapsules, chemical foaming agents, physical foaming agents and the like.
[0041]
The thermal expansion microcapsule is a foaming agent that exhibits an effect of causing volume expansion by thermal expansion and reducing specific gravity. That is, it is a foaming agent that encloses a thermally expandable substance in a microcapsule and expands the thermally expandable substance by heating to expand the volume, and a uniform fine cell can be obtained.
The thermal expansion temperature of the thermally expandable microcapsule used in the present invention is preferably 120 to 300 ° C, more preferably 140 to 260 ° C. When the thermal expansion temperature of the thermally expandable microcapsule is less than 120 ° C., the outer shell components such as methylmethacrylic acid (MMA) and acrylonitrile (AN) are softened by the component (b) surfactant, Not only is the shell broken, but the heat resistance of the resulting foamable thermoplastic elastomer composition is deteriorated. When it exceeds 300 ° C., it does not thermally expand within the molding processing temperature range of the foamable thermoplastic elastomer composition.
Here, as a thermally expandable microcapsule that expands at a temperature of 120 to 300 ° C., an average particle diameter of 1 to 50 μm is necessary. If it is less than 1 μm, dispersion in the composition becomes insufficient, and above 50 μm The strength of the molded product obtained from the composition is greatly reduced. Further, the expansion ratio is preferably 10 to 100 times, and if it is less than 10 times, a sufficient foaming ratio cannot be obtained, and if it exceeds 100 times, uniform fine cells are hardly obtained. As such a heat-expandable microcapsule, EXPANSEL having a vinylidene chloride / acrylonitrile copolymer as an outer shell and encapsulating a low boiling point hydrocarbon (for example, isobutane) is commercially available from EXPANCEL. A similar product is Matsumoto Microsphere (Matsumoto Yushi Seiyaku).
[0042]
The chemical foaming agent is a foaming agent that decomposes upon heating to generate foaming gas, and includes an organic chemical foaming agent and an inorganic chemical foaming agent.
Examples of the organic chemical foaming agent include nitroso compounds such as N, N′-dimethyl-N, N′-dinitrosoterephthalamide and N, N′-dinitrosopentamethylenetetramine; diethyl azocarboxylate, azodicarbonamide Azo compounds such as azobisisobutyronitrile, azocyclohexyl nitrile, azodiaminobenzene, barium azodicarboxylate; hydrazine compounds such as hydrazine, trihydrazine triazine; benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, 4,4′-oxybis ( Benzenesulfonyl hydrazide), sulfonyl hydrazide compounds such as diphenylsulfone-3,3′-disulfonyl hydrazide; terephthalazide, calcium azide, 4,4′-diphenylsulfonyl azide, p-toluenesulfo Azide compounds such as Ruajido; p, p'-oxybis (benzenesulfonyl semicarbazide); oxalate derivatives. These foaming agents can be used singly or in combination.
Examples of the inorganic chemical foaming agent include sodium hydrogen carbonate, sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate, ammonium nitrite and the like. These foaming agents can be used singly or in combination.
Furthermore, the foaming effect can be further enhanced by using a foaming aid in combination. As the foaming aid, zinc oxide, lead sulfate, urea, zinc stearate and the like are used. When the foaming agent is dinitrosopentamethylenetetramine, salicylic acid, phthalic acid, boric acid, urea resin, or the like is used as the foaming aid.
[0043]
The physical foaming agent is a foaming agent that expands and foams a foaming agent enclosed in a foamed body by heat operation or pressure operation. For example, volatile hydrocarbons such as pentane and butane, halogenated hydrocarbons, Nitrogen gas, carbon dioxide gas, water, etc. are mentioned.
[0044]
The compounding quantity of a component (c) is 0.1-30 weight part with respect to 100 weight part of component (a), Preferably it is 0.5-15 weight part. If the amount of component (c) exceeds 30 parts by weight, the mechanical properties and strain-maintaining properties of the product deteriorate due to aggregation of component (c), and if it is less than 0.1 part by weight, a sufficient foamed product cannot be obtained. Sufficient strain maintaining characteristics cannot be obtained.
[0045]
(D) Surfactant
(D) Surfactant used in the thermoplastic elastomer softener composition and thermoplastic elastomer composition of the present invention suppresses bleeding of the softener from the composition and simultaneously imparts a smooth feeling to the composition surface. Thus, in applications where no film is used on the surface (for example, armrests, pillows, etc.), it has the effect of dramatically improving the usability. That is, it has the effect of eliminating the need to attach a polyethylene film or polyurethane film to the surface of the composition in order to improve the feel of the composition having a sticky feeling as in the prior art. Moreover, in film sealing products etc., it has the effect that adhesiveness with films, such as polyethylene and a polyurethane, improves markedly.
[0046]
The component (d) may be any nonionic, cationic or anionic surfactant. Among these, nonionic surfactants are preferable. Examples of nonionic surfactants include ether type, ether ester type, ester type, and nitrogen-containing type nonionic surfactants.
Examples of the nonionic surfactant include polyoxyethylene higher alcohol ethers such as polyoxyethylene lauryl alcohol, polyoxyethylene lauryl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl Polyoxyethylene alkyl aryl ethers such as ethers; Polyoxyethylene acyl esters such as polyoxyethylene glycol monostearate; Polypropylene glycol ethylene oxide adducts; Polyoxyethylene sorbitan monolaurate, Polyoxyethylene sorbitan monostearate, etc. Polyoxyethylene sorbitan aliphatic esters; alkyl phosphate esters, polyoxyethylene alkyl ether phosphorus Phosphoric acid esters such as esters, cellulose ethers are used.
Among them, ether-type nonionic surfactants such as alkyl and alkylallyl polyoxyethylene ether, alkylallyl formaldehyde condensed polyoxyethylene ether, block polymer having polyoxypropylene as a base oil, polyoxyethylene polyoxypropyl alkyl ether, etc. These may be used alone or in combination of two or more.
[0047]
The HLB (balance between hydrophilic group and lipophilic group) of the surfactant used in the composition of the present invention is preferably 7 to 13, and more preferably 8 to 11. When the HLB exceeds 13, the lipophilicity is lowered, and tackiness and stickiness are exhibited. On the other hand, when the HLB is less than 3, there is no effect of addition, and tackiness and tackiness are exhibited.
[0048]
Although there are various methods for calculating the HLB value from the chemical structure, among them, the calculation formula of the HLB value used in the present invention, and typical hydrophilic groups and lipophilic groups used in the calculation formulas. The radix is shown in the following formula (1) and the following Table 1.
HLB = 7 + S (the number of hydrophilic groups) + S (the number of lipophilic groups) (1)
[0049]
[Table 1]

[0050]
The compounding quantity of a component (d) is 0.1-30 weight part with respect to 100 weight part of component (a), Preferably it is 0.5-20 weight part. If the blending amount is less than 0.1 parts by weight, there is no effect of suppressing stickiness and giving a smooth feeling, and the adhesion to the film is lowered, and if it exceeds 30 parts by weight, bleeding is remarkable and the adhesion to the film is also lowered.
[0051]
(E) Antifoam agent
In the softener composition for thermoplastic elastomers and the thermoplastic elastomer composition of the present invention, (e) an antifoaming agent can be blended as necessary. Component (e) has a function of improving the miscibility and defoaming function of the softener composition for thermoplastic elastomer and the thermoplastic elastomer composition by adding to the softener composition for thermoplastic elastomer and the thermoplastic elastomer composition. . Therefore, the moldability becomes extremely good by including the component.
[0052]
Component (e) may be either a silicone compound or a non-silicone compound, and examples thereof include the following compounds.
Examples of the silicone compound include polysiloxane copolymers having an HLB of 1 or more and less than 4.
Non-silicone compound compounds include fatty acid ester compounds, urea resin compounds, paraffinic compounds having an HLB of 1 or more and less than 4, polyoxyalkylene glycol compounds, acrylic ester copolymers, ester polymers, ether compounds. Polymer, emulsion type of mineral oil, polysiloxane adduct, fluorine compound, vinyl polymer, acetylene alcohol, acrylic polymer, special vinyl polymer, ethylene glycol, higher alcohol (octyl alcohol, cyclohexanol, etc.), HLB value Includes 1 or more and less than 4, preferably 2 or more and less than 4 nonionic surfactants.
Among these, fatty acid ester compounds, urea resin compounds, paraffinic compounds having an HLB of 1 or more and less than 4, polyoxyalkylene glycol compounds, silicone compounds having an HLB of 1 or more and less than 4, etc. are preferred. May be used alone or in combination of two or more.
[0053]
The amount of component (e), when added, is 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, per 100 parts by weight of component (a). When the amount exceeds 20 parts by weight, the surface appearance of the molded product from the resulting thermoplastic elastomer composition deteriorates.
[0054]
In addition, the thing of the compound name which overlaps with the said component (d) and (e) can be distinguished by HLB on the following references | standards.
Among the overlapping components, those belonging to the component (d) have an HLB of 7 to 13, and those belonging to the component (e) have an HLB of 1 or more and less than 4.
[0055]
(F) Olefin resin
In the thermoplastic elastomer composition of the present invention, (f) an olefin resin can be blended as necessary.
As the component (f), a homopolymer of α-olefin such as ethylene, propylene, butene-1, hexene-1, 4-methyl-pentene-1, two or more copolymers thereof, or α-olefin and Copolymers with other polymerizable monomers, for example, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylate copolymer (ethylene-methyl acrylate copolymer) Polymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, etc.) and the like, and can be used alone or in combination of two or more. In addition, examples of the olefin resin include hydrogenated conjugated diene block copolymers (for example, CEBC: olefin crystal block-ethylene / butene random block-olefin crystal block). Among these, ethylene homopolymers and copolymers of ethylene and other α-olefins are preferred, and in particular, ethylene-hexene-1 copolymer polymerized using a single site catalyst, ethylene-octene-1 An elastomer-type ethylene-based copolymer having a copolymer as a main component and improved impact resistance at low temperatures and the like is preferable.
[0056]
When blended, the amount of component (f) is 1 to 30 parts by weight, preferably 3 to 20 parts by weight, per 100 parts by weight of component (a). If the blending amount exceeds 30 parts by weight, the gel (jelly) state at room temperature and the moldability deteriorate.
[0057]
(G) Organic peroxide
In the softening agent composition for thermoplastic elastomer and the thermoplastic elastomer composition of the present invention, (d) an organic peroxide can be contained as required. Component (d) has the effect of improving the oil bleed at a high temperature by developing a high level of oil resistance by crosslinking the component (b) of the resulting thermoplastic elastomer composition, making it difficult to plastically deform at room temperature. Have.
[0058]
Examples of the component (d) include 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -3,3,5- Trimethylcyclohexane, benzoyl peroxide, m-methylbenzoyl peroxide, m-toluoyl peroxide, t-hexylperoxybenzoate, 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (T-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-dibutylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) Oxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, oxalic acid peroxide 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, m-toluoyl and benzoyl Peroxide, t-butylperoxyisobutyrate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate , T-butylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) Butane, dicumyl peroxide, di-tert-butyl peroxide, 2,5 Dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) ) Benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chloro Examples thereof include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide and the like.
[0059]
Of these, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane (1 minute half-life temperature 147 ° C.), 2, in terms of odor, colorability and scorch stability 5-dimethyl-2,5-di (tert-butylperoxy) hexane (1 minute half-life temperature 179 ° C.) and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3 (1 minute) A half-life temperature of 194 ° C.) is preferable. In the case of the composition of the present invention, a low-temperature decomposition type organic peroxide having a 1 minute half-life temperature of 165 ° C. or less may be used.
[0060]
The compounding amount of the component (g) is 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the component (a). When the blending amount exceeds 5 parts by weight, the decomposition reaction by the organic peroxide is prioritized, the odor becomes intense, and the moldability of the resulting thermoplastic elastomer composition is inferior. When the blending amount is less than 0.1 parts by weight, there are no improvement effects such as heat distortion resistance and oil resistance.
[0061]
(H) Ester-based crosslinking aid
In the softening agent composition for thermoplastic elastomer and the thermoplastic elastomer composition of the present invention, an ester-based crosslinking aid component (h) can be blended as necessary. The component (h) has an effect of performing a uniform and efficient crosslinking reaction in the crosslinking treatment with the organic peroxide component (g). Examples of the component (h) include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate having 9 to 14 repeating units of ethylene glycol, and trimethylolpropane tri Polyfunctional methacrylate compounds such as methacrylate, allyl methacrylate, 2-methyl-1,8-octanediol dimethacrylate, 1,9-nonanediol dimethacrylate, polyethylene glycol diacrylate, ethoxylated cyclohexanedimethanol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate Multifunctional acrylate compounds such as, vinyl butyrate, vinyl stearate, divinylbenzene can be mentioned polyfunctional vinyl compounds such as triallyl cyanurate. You may use these individually or in combination of 2 or more types. By such a compound, a uniform and efficient crosslinking reaction can be expected.
[0062]
Of the above crosslinking aids, polyfunctional methacrylate compounds and polyfunctional acrylate compounds are preferred, and ethoxylated cyclohexanedimethanol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 2-methyl-1,8- Octanediol dimethacrylate, 1,9-nonanediol dimethacrylate, and trimethylolpropane trimethacrylate are particularly preferred. In particular, when ethoxylated cyclohexanedimethanol diacrylate is used, the transparency is hardly lowered.
[0063]
When blended, the amount of component (h) is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of component (a). When the blending amount exceeds 20 parts by weight, the crosslinking of the composition proceeds so much that the crosslinking aid is not partially dispersed, and the appearance of what can be produced deteriorates.
[0064]
(I) Other ingredients
In the thermoplastic elastomer composition of the present invention, a heat stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a crystal nucleating agent, an antiblocking agent, and an improvement in sealing properties are within the range not impairing the object of the present invention. Agent, mold release agent such as stearic acid, silicone oil, lubricant such as polyethylene wax, colorant, pigment, inorganic filler such as alumina, foaming agent (organic, inorganic, microcapsule) flame retardant (hydrated metal) Compound, red phosphorus, ammonium polyphosphate, antimony, silicone) and the like.
Examples of the antioxidant include 2,6-di-tert-p-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4,4- Examples thereof include phenolic antioxidants such as dihydroxydiphenyl and tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, phosphite antioxidants, thioether antioxidants, and the like. Of these, phenolic antioxidants and phosphite antioxidants are particularly preferred.
[0065]
2. Softener composition for thermoplastic elastomer, production of thermoplastic elastomer composition The softener composition for thermoplastic elastomer of the present invention comprises components (a), (c), (d), and other components as required. It can be easily obtained by blending the components and mixing them with a mixing device at room temperature.
In addition, the thermoplastic elastomer composition of the present invention comprises components (a) to (d) and other components as necessary, and melt kneading or kneading in a kneading apparatus at a kneading temperature of 150 to 180 ° C. It can be obtained by melt mixing.
Furthermore, simply, the thermoplastic elastomer composition of the present invention comprises components (a) to (c) and other components as necessary, and a mixing device or kneading device at 100 to 180 ° C. The composition is made in a soup or sorbet form, and poured into a target mold for cooling, or the block obtained by cooling is subjected to press molding at 100 to 180 ° C. to directly achieve the target thermoplasticity. A molded body made of the elastomer composition can also be obtained.
In the composition of the present application, foaming may be performed at the time of melt kneading or melt molding, or may be further heated after melt molding without being foamed at the time of kneading / molding, and may be foamed at that time. Among these, foaming at the time of melt-kneading is preferable because a uniform and high-magnification foam can be obtained.
[0066]
For example, foaming can be achieved by heat-treating the composition at a temperature 20 ° C. or more lower than the expansion start temperature of the thermal expansion microcapsule and processing at a temperature 20 ° C. or higher higher than the expansion start temperature in the next molding step.
[0067]
As a kneading apparatus used in the present invention, an autoclave, a pressure kneader, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi-screw extruder, or the like can be used. Preferably, a kneading method using a batch kneader such as a pressure kneader or a Banbury is good. When performing continuously, the method of kneading | mixing with the apparatus (batch supply type | mold continuous extrusion apparatus) with which the batch type kneading apparatus and the extruder were combined, for example, the pressure kneader and the extruder was combined is good.
[0068]
3. Softener composition for thermoplastic elastomer, thermoplastic elastomer composition
The softening agent composition for a thermoplastic elastomer of the present invention is used for forming a flexible thermoplastic elastomer composition, and can be used as a gel softening composition for a thermoplastic elastomer composition present in a gel state.
In addition, the thermoplastic elastomer composition of the present invention has a hardness at room temperature (23 ° C.) of preferably 40 A or less, more preferably 10 A or less, and exists in a gel form (jelly form).
In addition, the thermoplastic elastomer composition of the present invention is heated at the time of molding and foamed at the same time as melted gel to form a foamed molded body. Therefore, the thermoplastic elastomer composition can be easily manufactured, molded easily, has excellent moisture retention, Since it is a foamable composition that is less bleed, has a specific gravity of 0.8 or less, and is excellent in silence, etc., it can be used in various applications.
[0069]
Specific applications include, for example, insulators for vibration isolation (with bolts), bolt through bushes, (unevenness) vibration isolation sheets, vibration isolation members such as tapes, seals, chips, and bag cushioning materials (eg, school bag shoulders) Parts, handbags, etc.) PC armrests and wrist rests (also applied to mouse pads), paper feed rollers, audio-related materials (turntables, insulators, spacers, etc.), anti-vibration rubber feet for cases, shoe esthetics Doll's face (skin, etc.), tennis racket, insulation sheet, waterproofing sheet for protection of utility poles, floor slip prevention mats, etc., film sealing products (eg hip protectors for preventing thigh fractures in the elderly, postoperative body shape aids, Rider suits, gloves (soccer keeper, golf, ski, rider), rifle jackets (eg shoulders) ), Sports shoes, beds, high-temperature and high-pressure molding machine cushions (ceramic molding, etc.), heat conductive gel sheets (for example, for the outer periphery of the CPU core for heat dissipation), game machine damping pads, health care-related, automobile parts (win) Shock absorbers for automobiles, shock absorbers for automobile doors (sides, etc.), insoles for shoes, shock absorbers for foot care to relieve pain caused by hallux valgus and wound nails, etc. Shock absorbers, beds, mattresses, pillows, cushions, cushions and other miscellaneous goods, shock absorbers for bedding, elbow pads, knee pads, prevention of horse back slipping by heels, ski shoes, toe shoes, ballet shoes, Sport-related shock absorbers such as gloves, shock absorbers for transporting luggage, protecting against fractures, injuries and injuries, and preventing prosthetic legs and skin from rubbing Medical shock absorbers, people who have had their breasts removed due to breast cancer, breast pads for swimsuits and breast augmentation, artificial food for fishing, etc., and dust and debris from household items such as desks, chairs, computers, bookshelves and floors It can be applied to cosmetics such as packs, poultices, fragrances, etc. by using the cleaning product that adsorbs spills, and the sustained release of oil.
Of these, application to healthcare is preferred.
[0070]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further, this invention is not limited to this. In addition, the evaluation method and the used material in an Example are shown below.
[0071]
1. Method for evaluating thermoplastic elastomer composition
(1) Specific gravity: In accordance with JIS K 7112, immediately after melting and kneading, a 215 × 145 × 2 mm thick SUS304 stainless steel bat is poured or coated onto a 215 × 145 mm stainless steel plate with a weight of 24 hours. The measurement was performed using the sheet that had been allowed to cool as described above.
(2) Hardness: In accordance with JIS K 6253, immediately after melting and kneading, a 215 × 145 × 2 mm thick SUS304 stainless steel bat is poured or coated onto a 215 × 145 mm stainless steel plate with a weight of 24 g. The measurement was performed by stacking sheets that had been allowed to stand for more than an hour and cooling them to a thickness of 4 mm or more.
(3) Oil bleed and smooth / smooth feeling: Immediately after melting and kneading, a 215 × 145 × 2 mm thick SUS304 stainless steel bat is poured or coated onto a 215 × 145 mm stainless steel plate, covering 24 hours or more The sheet cooled by standing is sandwiched between kraft paper, and a weight of 500 g in a disk shape of 70 mm diameter is put on it. The condition of the kraft paper after standing at room temperature (23 ° C.) for 168 hours is visually observed and evaluated according to the following criteria. did.
◎: No trace of oil bleed on kraft paper
○: Marks of oil bleed are recognized on kraft paper, but there is smooth and smooth feeling
×: Traces of oil bleed are recognized on the kraft paper, and there is a sticky feeling
(4) Formability: Immediately after melt-kneading, a 215 × 145 mm stainless steel plate weighing 500 g is placed on a 215 × 145 × 2 mm thick SUS304 stainless steel vat and coated, and allowed to cool for 24 hours or longer. Sheets were prepared, surface appearance and shape were observed, and evaluated according to the following criteria.
A: The surface is smooth and there are no bubbles
○: Even if the surface is smooth, the presence of bubbles is recognized.
Δ: The surface is not smooth, but there are no bubbles
X: The surface is not smooth and there are bubbles
(5) Strain maintainability: After placing a cylindrical weight of 70 g on the sheet obtained in (4) above for 1 hour, the weight is removed, and the strain maintenance condition is visually observed. evaluated.
○: No recovery in 1 minute, gradually recovery in 30 minutes
Δ: No recovery in 1 minute, no recovery in 30 minutes
×: Recovery in 1 minute
(6) Volume swelling ratio (%): Based on JIS K 6258, the product taken out in (4) above was used, and the swelling ratio after immersion in IRM # 902 was measured at 70 ° C. for 72 hours.
(7) Adhesion with film (polyethylene) sheet: At the time of molding (5), a 0.1 mm thick polyethylene film was sandwiched between the composition of the present invention and a SUS304 stainless steel bat, and molding was performed under the same conditions. The evaluation was based on the following criteria.
A: The surface is smooth and there are no bubbles
Δ: The presence of bubbles is recognized even when the surface is smooth.
X: The surface is not smooth and there are bubbles
[0072]
2. material
(A) Softener component for non-aromatic rubber: NA solvent NAS-5H (manufactured by NOF Corporation) Specific gravity: 0.823, Type: Isoparaffin hydrocarbon oil, Viscosity (40 ° C.): 11.0 cSt, Flash point: 146 ° C
(B-1) Hydrogenated block copolymer component: Septon 4077 (SEPS) (trademark; manufactured by Kuraray Co., Ltd.), styrene content 30% by weight, number average molecular weight 260,000, weight average molecular weight 320,000, molecular weight distribution 1.23, 90% or higher hydrogenation rate
(B-2) Hydrogenated block copolymer component: Septon 4033 (SEPS) (trademark; manufactured by Kuraray Co., Ltd.), styrene content 30% by weight, number average molecular weight 130,000, weight average molecular weight 100,000, molecular weight distribution 1.30, over 90% hydrogenation rate
(C-1) Thermally expandable microcapsule component: EXPANSEL 092DUX120 (manufactured by EXPANSEL), particle size: 28-38 μm, expansion start temperature: 116-126 ° C., expansion end temperature: 230-240 ° C.
(C-2) Thermally expandable microcapsule component: EXPANSEL 098DUX120 (manufactured by EXPANSEL), particle size: 28-45 μm, expansion start temperature: 150-170 ° C., expansion end temperature: 250-265 ° C.
(D-1) Surfactant component: Nonion E-205S (manufactured by NOF Corporation), polyethylene glycol oleyl ether, HLB: 9.0, pH: 5-8, specific gravity: 0.93, flash point: 228 ° C
(D-2) Butyl stearate: manufactured by NOF Corporation, plastic lubricant, HLB = 5.5 (comparative component)
(D-3) Cetyl 2-ethylhexanoate: Exepearl HO (manufactured by Kao) Iodine value 1 or less, hydroxyl value 3 or less, HLB = 6 (comparative component)
(E) Antifoam component: Dishome BF-75 (polyalkylene glycol (trademark; manufactured by NOF Corporation), kinematic viscosity (40 ° C.): 40 mm ² / S, pH: 7.0 to 10.0, specific gravity: 0.91, flash point: 186 ° C., HLB = 3
(F) Olefin resin component :: PE, Engage EG8401 (manufactured by Dupont Dow Elastomer) Specific gravity: 0.885, Hardness: 85 (Shore A), Mooney viscosity ML _{1 + 4} (121 ° C.): 5 or less, weight average molecular weight: 100,000
(G) Organic peroxide component: Perhexa TMH (1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane) (trademark; manufactured by NOF Corporation), active oxygen content: 7. 52%, molecular weight: 358.57, decomposition temperature for obtaining a half-life of 1 minute: 147.1 ° C
(H) Ester-based crosslinking assistant component: CHD-4E (ethoxylated cyclohexanedimethanol diacrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.) Viscosity: 50 mPa · s, specific gravity: 1.062, molecular weight: 636
(I) Antioxidant: hindered phenol / phosphite / lactone complex antioxidant: HP2215 (trademark; manufactured by Ciba Specialty Chemicals)
[0073]
Examples 1-4, Comparative Examples 1-10
Components (a) to (i) were added at the component ratios shown in Table 2, and kneaded at a kneading temperature of 160 ° C. in a mixer or an autoclave to obtain a thermoplastic elastomer composition. The physical properties of the obtained composition were measured. The results are shown in Table 2.
[0074]
[Table 2]

[0075]
As is clear from Table 2, the compositions of Examples 1 to 4 which are the thermoplastic elastomer compositions of the present invention all showed good results.
In particular, Example 4 using a thermal expansion agent having a high thermal expansion temperature was 215 × 145 × 2 mm thick SUS304 stainless steel vat which was not expanded yet and poured into a SUS304 stainless steel bat having a weight of 500 g. This is a result of evaluation by making a sheet covered with a × 145 mm stainless steel plate and allowing it to cool for 24 hours or longer and then leaving it in an oven at 200 ° C. for 10 minutes.
On the other hand, Comparative Examples 1 and 2 are components (b) outside the range. When there are few components (b), stickiness will become remarkable and press moldability and distortion maintenance property will deteriorate. When there is much component (b), hardness will become hard too much and it will not become a gel form, and distortion maintenance property will deteriorate.
In Comparative Examples 3 and 4, the component (c) is out of the range. When the amount of component (c) is small, the strain maintaining property is deteriorated. When the amount of component (c) is large, the foaming agent is remarkably aggregated and the sheet is collapsed, and press formability and strain maintaining property are deteriorated.
In Comparative Examples 5 to 8, the component (d) is out of the range. If the component (d) is not used, the oil bleed and smooth feeling and the adhesion between the film sheet are deteriorated, and if the component (d) is large, the adhesion between the oil bleed and the film sheet is deteriorated.
In Comparative Examples 9 and 10, butyl stearate and cetyl 2-ethylhexanoate, which are generally used as plastic lubricants, are used in place of the component (d) surfactant. When butyl stearate or cetyl 2-ethylhexanoate is used, the stickiness becomes remarkable, the oil bleeds and the smooth feeling is lost. Moreover, the adhesiveness with a film also deteriorates.
[0076]
【The invention's effect】
The thermoplastic elastomer composition of the present invention is heated at the time of molding and foamed at the same time as melted gel to form a foamed molded body. Therefore, the thermoplastic elastomer composition can be easily manufactured, easily molded, has excellent moisture retention, and has an oil bleed feeling. It is a foaming composition that has a low weight and a specific gravity of 0.8 or less, and is excellent in sound deadening, etc. It can be suitably used as a related material.

Claims (13)

(A) 100 parts by weight of a non-aromatic hydrocarbon rubber softener,
(C) 0.1-30 weight part of foaming agents, and (d) 0.1-30 weight part of surfactant, The following softener composition for thermoplastic elastomers characterized by the above-mentioned .
Thermoplastic elastomer: obtained by hydrogenating a block copolymer comprising at least one polymer block A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound. Hydrogenated block copolymer or conjugated diene block copolymer.   The component (a) is a mixture of a linear saturated hydrocarbon having 4 to 155 carbon atoms and / or a branched saturated hydrocarbon, and the softener composition for a thermoplastic elastomer according to claim 1.   The softener composition for a thermoplastic elastomer according to claim 1 or 2, wherein the component (a) is liquid at room temperature.   The softener composition for a thermoplastic elastomer according to any one of claims 1 to 3, wherein the component (c) is a thermal expansion microcapsule, a chemical foaming agent, or a physical foaming agent.   The softener composition for thermoplastic elastomer according to any one of claims 1 to 4, wherein component (d) is a nonionic, cationic or anionic surfactant. To the softener composition for thermoplastic elastomer according to any one of claims 1 to 5, with respect to 100 parts by weight of component (a),
Hydrogenated block obtained by hydrogenating a block copolymer comprising at least one polymer block A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound A thermoplastic elastomer composition comprising 3 to 110 parts by weight of a hydrogenated product of a copolymer or a conjugated diene block copolymer .   Furthermore, 0.1-20 weight part of (e) antifoamer is contained with respect to 100 weight part of component (a), The thermoplastic elastomer composition of Claim 6 characterized by the above-mentioned. The component (e) is at least one selected from the group consisting of fatty acid ester-based, urea resin-based, paraffin-based, silicone-based, and polyoxyalkylene glycol-based antifoaming agents. A thermoplastic elastomer composition.   The thermoplastic elastomer composition according to any one of claims 6 to 7, further comprising 1 to 30 parts by weight of (f) an olefin resin with respect to 100 parts by weight of the component (a). .   Furthermore, 0.1 to 10 weight part of (g) organic peroxide is contained with respect to 100 weight part of component (a), The thermoplastic of any one of Claims 6-9 characterized by the above-mentioned. Elastomer composition.   Furthermore, 0.1 to 20 weight part of (h) ester type crosslinking adjuvant is contained with respect to 100 weight part of components (a), The heat of any one of Claims 6-10 characterized by the above-mentioned. Plastic elastomer composition.   The thermoplastic elastomer composition according to any one of claims 6 to 11, which is a gel-like (jelly-like) composition having a hardness at room temperature of 40 A or less.   A foamed molded article formed by using the thermoplastic elastomer composition according to any one of claims 6 to 12.