JP4163548B2 - Softener composition for thermoplastic elastomer, thermoplastic elastomer composition and molded article - Google Patents

Description

【００５２】
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１〜２０重量部である。配合量が３０重量部を超えるとブリードアウトが顕著になりベタツキが発生する。
【００５３】
（ｅ）消泡剤
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、（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組成物に添加することにより、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。
【００５４】
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。
【００５５】
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１〜１０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。
【００５６】
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。
【００５７】
（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。
【００５８】
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３〜１５重量部である。配合量が３０重量部を超えると、室温（２３℃）でのゲル状態（ゼリー状態）、成形性が悪化する。
【００５９】
（ｇ）有機過酸化物
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、（ｇ）有機過酸化物を用いることができる。成分（ｇ）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耐油性を向上することができ、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。
【００６０】
成分（ｇ）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。
【００６１】
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。
【００６２】
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１０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。
【００６３】
（ｈ）エステル系架橋助剤
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、（ｈ）エステル系架橋助剤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。
【００６４】
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。
【００６５】
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。
【００６６】
（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。
また、発泡剤（化学発泡、マイクロカプセル）としては、（ａ）１００重量部に対して、０．０１〜３重量部の範囲で添加し、成形品を軽量化することも可能であり、発泡剤としては、塩化ビニリデン・アクリロニトリルコポリマーを外殻とし、低沸点炭化水素（例えば、イソブタン）を内包した熱膨張性マイクロカプセルであるエクスパンセル（エクスパンセル社製）、あるいはマツモトマイクロスフィアー（松本油脂製薬社製）が好ましい。
【００６７】
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）、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）〜（ｃ）、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。
【００６８】
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。
【００６９】
本発明の熱可塑性エラストマー用軟化剤組成物及び熱可塑性エラストマー組成物は、上記の様に特定量を混合するだけで得られ、ウレタン系ゲルやシリコーン系ゲル、スチレン系エラストマーのみのゲルの製造におけるある種の反応を伴う必要のない簡単な方法で得ることができる。
【００７０】
３．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、保湿性に優れ、オイルブリード感が少なく、衝撃吸収性、制振性に優れる組成物であるので、様々な用途において使用可能である。
したがって、このようなゲル状の組成物を用いて下記に述べるような具体的な成形体の製造に当たっては、より簡単に、例えば、従来公知の成形方法の中でも設備をそれほど必要としない、特に注型成形、プレス成形等で容易に成形できるところに特徴がある。
【００７１】
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、型にはめ込んだときに、特に振動吸収特性の低下が少ないため、制振を必要とする用途、特に、防振シート、テープ、シール、チップ状等の防振部材、ゲーム機の制振パット、床ずれ防止マット、スポーツシューズ、ベッド等の制振材への応用が好ましい。
【００７２】
【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。
【００７３】
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、１８０℃、予熱２分／加圧２分、圧力５０ｋｇ／ｃｍ^２の熱プレスで得られた１３０×１６０×２ｍｍ厚のシートを用いて測定を行なった。
（２）硬さ：ＪＩＳ Ｋ ６２５３に準拠して測定した。１８０℃、予熱２分／加圧２分、圧力５０ｋｇ／ｃｍ^２の熱プレスで得られた１３０×１６０×２ｍｍ厚のシートを重ね合わせて４ｍｍ厚以上にして測定を行った。
なお、Ａ硬度測定範囲外の柔らかいサンプルの測定値は０で表した。
（３）オイルブリード：１８０℃、予熱２分／加圧２分、圧力５０ｋｇ／ｃｍ^２の熱プレスで得られた１３０×１６０×２ｍｍ厚の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、室温（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
○：クラフト紙にかすかにオイルブリードの痕跡が認められる
×：クラフト紙にオイルブリードの痕跡が認められる
（４）プレス成形性：１８０℃、予熱２分／加圧２分、圧力５０ｋｇ／ｃｍ^２の熱プレスで得られた１３０×１６０×５ｍｍ厚のシートを作成し、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）衝撃吸収性：上記（４）で得られたシートに３０ｃｍの高さからパチンコ玉を自然落下させ、撥ね具合を目視で観察し、次の基準で評価した。
○：全く跳ねない
△：シート上で１回だけ跳ねる
×：２回以上跳ねるか、シート外に飛び出す
（６）衝撃吸収性：上記（４）で得られたシートを２００×２００×５ｍｍに切ったうえ、金属の枠にはめ込んだ部品を作成し、３０ｃｍの高さからパチンコ玉を自然落下させ、撥ね具合を目視で観察し、次の基準で評価した。
なお、αゲルシートは、２ｍｍ厚と３ｍｍ厚を重ねて使用した。
○：全く跳ねない
△：シート上で１回だけ跳ねる
×：２回以上跳ねるか、シート外に飛び出す
（７）体積膨潤率（％）：ＪＩＳ Ｋ ６２５８に準拠し、上記（１）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。
【００７４】
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−１）（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−２）（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）水添ヒマシ油変性物成分：１２−ヒドロキシステアリン酸（ヒマシ硬化油のケン化分解物：伊藤製油（株）製）融点：７５〜７８℃、中和価：１７５〜１８５ｍｇＫＯＨ／ｇ、けん化価：１８０〜１９０ｍｇＫＯＨ／ｇ、ヨウ素価：３以下ｇＩ２／１００ｇ、水酸基価：１５３〜１６３ｍｇＫＯＨ／ｇ
（ｃ−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）
（ｃ−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）
（ｄ）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℃
（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）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）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（Ａｎｔｉｏｘｉｄａｎｔ）：ＨＰ２２１５（商標；チバスペシャリティケミカルズ社製）
【００７５】
実施例１〜４、比較例１〜９
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１８０℃で混錬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。
【００７６】
【表２】

【００７７】
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。
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（ゼリー状）でなくなり衝撃吸収性が悪化する。
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）が少ないと衝撃吸収性が悪化し、成分（ｃ）が多いと、オイルブリード性、プレス成形性、衝撃吸収性が悪化する。
比較例５〜８は、成分（ｃ）水酸基含有有機カルボン酸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、オイルブリードが悪化し、衝撃吸収性が悪化する。
比較例９は、株式会社ジェルテックのαゲルシートの衝撃吸収試験であるが、金属の枠にシートをはめ込むと衝撃吸収効果が低下した。
【００７８】
【発明の効果】
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以下でジェル状（ゼリー状）で存在し、保湿性に優れ、オイルブリード感が少なく、制振性に優れる組成物であるので、制振を必要とする用途、特に、防振シート、テープ、シール、チップ状等の防振部材、ゲーム機の制振パット等の制振材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 softening agent composition for a thermoplastic elastomer, a flexible thermoplastic elastomer composition, and a molded article thereof, and in particular, a gel-like (jelly-like) composition having a hardness of 40 A or less at room temperature (23 ° C.). Thermoplastic elastomer composition that can be easily manufactured, has excellent moisture retention, has little oil bleed, is jelly-like, has a unique strain, has excellent shock absorption and vibration damping properties, and is well balanced The present invention relates to an object and a vibration damping material made of the same.
[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 bleed resistance, impact absorption, and moldability is extremely inferior.
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 may take 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 7), 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 8), 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 9) is proposed. However, a thermoplastic elastomer composition excellent in molding processability and impact absorbability and excellent in balance between molding processability and various physical properties has not been obtained.
In addition, when used as a floor rubbing prevention mat or industrial damper in the health care field, it is particularly necessary to have excellent shock absorption and vibration absorption, and it is sufficient to simply add oil to the thermoplastic resin composition. In addition, conventional polyurethane-based gels, silicone-based gels, etc. do not have performance, and complicated processes are required for their production, and more expensive materials are required at present.
In other words, conventional polyurethane gels, silicone gels, etc., are supplied to users in a very sticky veil, and the user cuts them into the desired size and sandwiches them between polyethylene and polyurethane films, and then uses metal or other frames and jigs. It was necessary to carry out very complicated work to fit in the tools. In addition, when it is fitted into a frame, the above-described material has a problem of a decrease in vibration damping and shock absorption (such as the rebound distance of the iron ball).
[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 2001-311012 A
[Patent Document 8]
JP 2000-34389 A
[Patent Document 9]
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 soft thermoplastic elastomer softener composition that can be easily manufactured, and a gel-like (jelly-like) composition having a hardness of 40 A or less at room temperature (23 ° C.). Manufacturable, easy to mold, excellent in moisture retention, less oil bleed, unique “strain”, shock absorption, vibration damping (especially when composition (eg, sheet) is framed) An object of the present invention is to provide a thermoplastic elastomer composition excellent in balance with workability and a vibration damping material comprising the same.
[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, The softening agent bleed becomes prominent, the composition is not fragile, the shock absorption and vibration damping properties are poor, and the styrenic thermoplastic elastomer requires blending of a polypropylene resin to form fluidity. Although it was difficult to avoid the increase in hardness associated therewith, an appropriate amount of fat and oil having a moderate compatibility with hydrogenated and / or partially hydrogenated block copolymers and non-aromatic hydrocarbon rubber softeners It was found that the balance of flexibility, shock absorption, vibration damping, molding processability, and bleed resistance can be improved by adding. Based on these results, a softening agent composition for thermoplastic elastomer containing a specific amount of a hydroxyl group-containing organic carboxylic acid in a non-aromatic rubber softening agent, and a specific amount of hydrogenation and / or partial water in the softening agent A thermoplastic elastomer composition containing a block copolymer becomes a gel with a network formed in the composition, has excellent moisture retention, less oil bleed, excellent shock absorption and vibration control, and processability The present inventors have found that the composition can be excellent in balance with the present invention and have completed the present invention.
[0011]
That is, according to the first invention of the present invention,
(A) 100 parts by weight of a non-aromatic hydrocarbon rubber softener, and
(C) 1 to 50 parts by weight of a hydroxyl group-containing organic carboxylic acid
It is characterized by containing Hydrogenation 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 For hydrogenated block copolymer or conjugated diene block copolymer A softener composition is provided (Hereinafter, the softener composition may be referred to as a thermoplastic elastomer softener composition.) .
[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, there is provided the softening agent composition for thermoplastic elastomer according to any one of the first to third aspects, wherein the component (c) is 12-hydroxystearic acid. Provided.
[0015]
According to the fifth aspect of the present invention, the thermoplastic elastomer softener composition according to any one of the first to fourth aspects of the present invention is prepared by adding 100 parts by weight of the component (a).
(B) 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 Hydrogenated product of copolymer or conjugated diene block copolymer 3 to 110 parts by weight
There is provided a thermoplastic elastomer composition characterized in that
[0016]
Moreover, according to the sixth invention of the present invention, in the fifth invention, it further comprises (d) 0.1 to 30 parts by weight of a surfactant with respect to 100 parts by weight of the component (a). A featured thermoplastic elastomer composition is provided.
[0017]
According to a seventh aspect of the present invention, there is provided a thermoplastic elastomer composition characterized in that, in the sixth aspect, the component (d) is a nonionic, cationic or anionic surfactant. .
[0018]
Moreover, according to the eighth invention of the present invention, in any one of the fifth to seventh inventions, further, (e) 0.1 to 20 parts by weight of the antifoaming agent with respect to 100 parts by weight of the component (a). There is provided a thermoplastic elastomer composition characterized in that
[0019]
According to the ninth aspect of the present invention, in the eighth aspect, the component (e) is a fatty acid ester-based, urea resin-based, paraffin-based, silicone-based, polyoxyalkylene glycol-based antifoaming agent. A thermoplastic elastomer composition is provided.
[0020]
According to a tenth aspect of the present invention, in any one of the fifth to ninth aspects, the composition further comprises (f) 1 to 30 parts by weight of an olefin resin with respect to 100 parts by weight of the component (a). A thermoplastic elastomer composition is provided.
[0021]
According to the eleventh aspect of the present invention, in any one of the fifth to tenth aspects of the invention, (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.
[0022]
According to a twelfth aspect of the present invention, in any one of the fifth to eleventh aspects, further, (h) an ester-based crosslinking aid of 0.1-20 with respect to 100 parts by weight of component (a). A thermoplastic elastomer composition characterized by containing parts by weight is provided.
[0023]
According to a thirteenth aspect of the present invention, in any one of the fifth to twelfth 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.
[0024]
According to a fourteenth aspect of the present invention, there is provided a vibration damping material characterized by being molded using the thermoplastic elastomer composition according to any one of the fifth to thirteenth aspects.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
1. Components of thermoplastic elastomer composition
(A) Non-aromatic hydrocarbon rubber softener
Examples of the non-aromatic hydrocarbon rubber softener (a) used in the thermoplastic elastomer composition of the present invention include non-aromatic mineral oil or liquid or low molecular weight synthetic softener. 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.
[0026]
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.).
[0027]
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. .
[0028]
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.
[0029]
Further, 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.
[0030]
(B) Hydrogenated and / or partially hydrogenated block copolymer
The hydrogenated and / or partially hydrogenated block copolymer (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.
[0031]
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.
[0032]
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.
[0033]
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%.
[0034]
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.
[0035]
When a hydrogenated block copolymer is used depending on the application, the above hydrogenated product can be suitably used according to the application.
[0036]
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.
[0037]
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.
[0038]
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.
[0039]
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.
[0040]
The compounding quantity of a component (b) is 3-110 weight part with respect to 100 weight part of component (a), Preferably it is 5-70 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. When the amount exceeds 110 parts by weight, the hardness of the thermoplastic elastomer composition is low. It becomes hard and the shock absorption is deteriorated.
[0041]
(C) Hydroxyl group-containing organic carboxylic acid
The hydroxyl group-containing organic carboxylic acid (c) used in the thermoplastic elastomer softener composition and thermoplastic elastomer composition of the present invention is dispersed in the component (a) to form a light network structure, and the component (a) In order to improve the viscosity of the composition by forming a network structure so as to more firmly bind the component (b) and the component (b), it also functions to have an effect of adjusting the hardness.
That is, in the conventional styrenic thermoplastic elastomer, it is necessary to blend a crystalline resin such as polypropylene in order to form a fluidized bed, and the increase in hardness due to the addition cannot be avoided. However, when the component (c) of the present invention is mixed with the component (a) non-aromatic hydrocarbon rubber softener, heated and cooled, the component (c) forms a network in the component (a). It becomes a gel (jelly) without increasing the hardness. Therefore, the component (c) has both the fluidity improving effect and flexibility imparting effect of the styrenic thermoplastic elastomer, the damping function expression effect by giving the composition a unique strain, the impact absorbing property, and the conventional technology. Therefore, it has an important feature of solving the bleeding problem of a large amount of non-aromatic hydrocarbon rubber softener in the means of softening elastomer.
[0042]
The component (c) is not particularly limited as long as it is a compound having a carboxyl group and a hydroxyl group, and there are saturated aliphatic, unsaturated aliphatic or aromatic hydroxyl group-containing organic carboxylic acids. A hydroxyl group-containing fatty acid having 30 to 30 carbon atoms is preferable, and a hydroxyl group-containing saturated fatty acid having 10 to 30 carbon atoms is particularly preferable in that a weak gel is formed when a hot solution of a nonpolar solvent is cooled.
[0043]
Examples of the aliphatic hydroxyl group-containing carboxylic acid having 10 to 30 carbon atoms include α-hydroxymyristic acid, α-hydroxypalmitic acid, α-hydroxystearic acid, α-hydroxyeicosanoic acid, α-hydroxydocosanoic acid, α-hydroxy Tetraeicosanoic acid, α-hydroxyhexaeicosanoic acid, α-hydroxyoctaeicosanoic acid, α-hydroxytriacontanoic acid, β-hydroxymyristic acid, 10-hydroxydecanoic acid, 15-hydroxypentadecanoic acid, 16-hydroxyhexadecane Examples include acid, 12-hydroxystearic acid, ricinoleic acid and the like.
[0044]
Other aliphatic hydroxyl group-containing carboxylic acids include glycolic acid, lactic acid, hydroacrylic acid, α-oxybutyric acid, α-hydroxyisobutyric acid, δ-hydroxycaproic acid, α-hydroxytriacontanoic acid, α-hydroxy Examples thereof include tetratriacontanoic acid, α-hydroxyhexatriacontanoic acid, α-hydroxyoctatriacontanoic acid, α-hydroxytetracontanic acid, glyceric acid, tartronic acid, malic acid, and citric acid. Examples of the aromatic oxycarboxylic acid include salicylic acid, m-oxybenzoic acid, p-oxybenzoic acid, gallic acid, mandelic acid, trovic acid, sabinic acid, iprolic acid, yalapinolic acid, uniperic acid, Aleurit acid, camlolenic acid, ferronic acid, cerebronic acid, 2-hydroxyoctadecanoic acid, 2-hydroxyhexadecanoic acid, 2-hydroxytetradecanoic acid, 18-hydroxyoctadecanoic acid, 9,10-dihydroxyoctadecanoic acid, 2-hydroxymyristic acid , 2-hydroxypalmitic acid, 2-hydroxystearic acid, 18-hydroxystearic acid, 9,10-dihydroxystearic acid and licanoic acid. Of these, 12-hydroxystearic acid is particularly preferred.
[0045]
Among the hydroxyl group-containing organic carboxylic acids, hydroxyl group-containing fatty acids are obtained by hydrolyzing fats and oils, but various methods have been developed industrially in order to increase the hydrolysis rate. For example, the Twitchel method, the medium pressure catalytic hydrolysis method, the continuous high pressure hydrolysis method, the enzyme hydrolysis method, the saponification hydrolysis method and the like can be mentioned. In particular, when fatty acid is obtained from castor oil, the saponification hydrolysis method is preferable because it can prevent the hydroxyl group and the carboxyl group liberated at high temperature from reacting and re-esterifying between molecules.
In addition, hydrogenation of unsaturated hydroxyl group-containing fatty acids is mainly performed using a nickel catalyst, but the process is performed on fatty acids obtained by hydrolyzing fats and oils, and on the fats and oils themselves before hydrolysis. There is also.
Since fatty acids obtained from fats and oils are a mixture of various fatty acids, in use, a single component fatty acid having a high purity is often separated from the mixed fatty acids. Representative low methods of this fractionation include fractional distillation, fractional crystallization (solvent-free method, solvent method, emulsion fractionation method), and liquid-liquid extraction.
[0046]
The 12-hydroxystearic acid preferably used in the present invention is a hydrogenated castor obtained by hydrogenating ricinoleic acid, a saturated fatty acid having an asymmetric hydroxyl group at the 12-position carbon, and obtained by hydrogenating castor oil. It is produced by hydrolyzing oil and can also be obtained by hydrogenating castor oil fatty acid obtained by hydrolyzing castor oil. These can use a commercial item.
[0047]
The compounding quantity of a component (c) is 1-50 weight part with respect to 100 weight part of component (b), Preferably it is 3-20 weight part. When the blending amount is less than 1 part by weight, the impact absorbability deteriorates. When the blending amount exceeds 50 parts by weight, the moldability deteriorates and oil bleed becomes remarkable. In addition, the shock absorption is deteriorated.
[0048]
(D) Surfactant
In the thermoplastic elastomer composition of this invention, (d) surfactant can be contained as needed. In the thermoplastic elastomer composition of the present invention, the component (d) surfactant, which is an optional component, can be made smooth by suppressing the stickiness of the surface feel in the resulting composition. 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.
[0049]
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 stickiness are also exhibited.
[0050]
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)
[0051]
[Table 1]

[0052]
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 1-20 weight part. When the blending amount exceeds 30 parts by weight, bleeding out becomes remarkable and stickiness is generated.
[0053]
(E) Antifoam agent
In the thermoplastic elastomer composition of this invention, (e) an antifoamer can be mix | blended as needed. By adding the component (e) to the thermoplastic elastomer composition, the component (e) has a miscibility improvement and a defoaming function of the thermoplastic elastomer composition. Therefore, the moldability becomes extremely good by including the component.
[0054]
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.
[0055]
When added, the amount of component (e) is 0.1 to 20 parts by weight, preferably 1 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.
[0056]
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.
[0057]
(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.
[0058]
When blended, the amount of component (f) is 1 to 30 parts by weight, preferably 3 to 15 parts by weight, per 100 parts by weight of component (a). When the amount exceeds 30 parts by weight, the gel state (jelly state) and moldability at room temperature (23 ° C.) are deteriorated.
[0059]
(G) Organic peroxide
In the thermoplastic elastomer composition of the present invention, (g) an organic peroxide can be used as necessary. Component (g) can improve oil resistance by cross-linking component (b) of the resulting thermoplastic elastomer composition, is less susceptible to plastic deformation at room temperature, and has the effect of improving oil bleed at high temperatures. Have.
[0060]
Examples of the component (g) 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.
[0061]
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.
[0062]
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 10 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.
[0063]
(H) Ester-based crosslinking aid
In the thermoplastic elastomer composition of the present invention, (h) an ester-based crosslinking aid 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.
[0064]
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.
[0065]
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.
[0066]
(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.
In addition, as a foaming agent (chemical foaming, microcapsule), (a) it can be added in the range of 0.01 to 3 parts by weight with respect to 100 parts by weight to reduce the weight of the molded product. As an agent, EXPANSEL (manufactured by EXPANSEL), which is a thermally expandable microcapsule containing vinylidene chloride / acrylonitrile copolymer as an outer shell and encapsulating a low boiling point hydrocarbon (for example, isobutane), or Matsumoto Microsphere ( Matsumoto Yushi Seiyaku Co., Ltd.) is preferred.
[0067]
2. Production of softener composition for thermoplastic elastomer and thermoplastic elastomer composition
The softening agent composition for thermoplastic elastomer of the present invention can be easily obtained by blending components (a), (c) and other components as necessary, and mixing them at room temperature with a mixing device. it can.
In addition, the thermoplastic elastomer composition of the present invention comprises components (a) to (c) and other components as necessary, and is melt kneaded 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.
[0068]
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.
[0069]
The softening agent composition for thermoplastic elastomer and the thermoplastic elastomer composition of the present invention can be obtained by mixing a specific amount as described above, and in the production of a urethane gel, a silicone gel, or a gel containing only a styrene elastomer. It can be obtained in a simple manner without the need for some kind of reaction.
[0070]
3. Thermoplastic elastomer composition
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 a composition having excellent moisture retention, less oil bleed feeling, excellent shock absorption and vibration damping properties, and can be used in various applications.
Therefore, in the production of a specific molded article as described below using such a gel-like composition, it is easier to use, for example, less equipment is required in a conventionally known molding method. It is characterized in that it can be easily molded by mold molding, press molding, or the like.
[0071]
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 or wound nails, etc. Shock absorbers, beds, mattresses, pillows, cushions, cushions and other miscellaneous goods, shock absorbers as 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 whose breasts have been removed due to breast cancer, swimsuits, breast pads for breast augmentation, simulated foods for fishing, etc., and dust and trash on household items such as desks, chairs, computers, bookshelves, floors, etc. Can be applied to cosmetics such as packs, poultices, fragrances, etc. by utilizing the sustained release of oil, especially when it is fitted into a mold, there is little decrease in vibration absorption characteristics Therefore, for applications requiring vibration suppression, especially vibration damping sheets, tapes, seals, chip-like vibration damping members, vibration damping pads for game machines, floor slip prevention mats, sports shoes, beds, etc. Application is preferred.
[0072]
【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.
[0073]
1. Method for evaluating thermoplastic elastomer composition
(1) Specific gravity: According to JIS K 7112, 180 ° C., preheating 2 minutes / pressurization 2 minutes, pressure 50 kg / cm ² Measurement was performed using a sheet of 130 × 160 × 2 mm thickness obtained by the hot press.
(2) Hardness: Measured according to JIS K 6253. 180 ° C, preheating 2 minutes / pressurization 2 minutes, pressure 50 kg / cm ² Measurement was carried out by superposing sheets of 130 × 160 × 2 mm thickness obtained by hot pressing in 4 mm thickness or more.
In addition, the measured value of the soft sample outside A hardness measurement range was represented by 0.
(3) Oil bleed: 180 ° C., preheating 2 minutes / pressurization 2 minutes, pressure 50 kg / cm ² The sheet of 130x160x2mm thickness obtained by the heat press is sandwiched between kraft papers, and a weight of 70g disk-shaped 500g is put on it, and the state of kraft papers after standing at room temperature (23 ° C) for 168 hours visually And evaluated according to the following criteria.
◎: No trace of oil bleed on kraft paper
○: Trace of oil bleed is recognized on kraft paper
×: Traces of oil bleed are observed on kraft paper
(4) Press formability: 180 ° C., preheating 2 minutes / pressurization 2 minutes, pressure 50 kg / cm ² A sheet of 130 × 160 × 5 mm thickness obtained by hot pressing was prepared, and the 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) Impact absorbability: Pachinko balls were naturally dropped from a height of 30 cm onto the sheet obtained in (4) above, and the repelling condition was visually observed and evaluated according to the following criteria.
○: No jump at all
Δ: Jump once on the sheet
×: bouncing twice or more or jumping out of the seat
(6) Impact absorption: After cutting the sheet obtained in (4) above to 200 × 200 × 5 mm, create a part fitted in a metal frame, let the pachinko ball fall naturally from a height of 30 cm, The repellency was visually observed and evaluated according to the following criteria.
In addition, the α gel sheet was used by overlapping 2 mm thickness and 3 mm thickness.
○: No jump at all
Δ: Jump once on the sheet
×: bouncing twice or more or jumping out of the seat
(7) Volume swelling ratio (%): Based on JIS K 6258, the product taken out in (1) above was used, and the swelling ratio after immersion in IRM # 902 was measured at 70 ° C. for 72 hours.
[0074]
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-1) (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, hydrogenation rate 90% or more
(B-2) Hydrogenated block copolymer component: Septon 4033 (SEPS-2) (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, hydrogenation rate 90% or more
(C-1) Hydrogenated castor oil modified product component: 12-hydroxystearic acid (saponified decomposition product of castor hydrogenated oil: manufactured by Ito Oil Co., Ltd.) Melting point: 75-78 ° C, neutralization value: 175-185 mgKOH / g, Saponification value: 180 to 190 mgKOH / g, Iodine value: 3 or less gI2 / 100 g, Hydroxyl value: 153 to 163 mgKOH / g
(C-2) Butyl stearate: manufactured by NOF Corporation, plastic lubricant, HLB = 5.5 (comparative component)
(C-3) Cetyl 2-ethylhexanoate: Exepearl HO (manufactured by Kao) Iodine value of 1 or less, hydroxyl value of 3 or less, HLB = 6 (comparative component)
(D) 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
(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) Hindered phenol / phosphite / lactone composite antioxidant (Antioxidant): HP2215 (trademark; manufactured by Ciba Specialty Chemicals)
[0075]
Examples 1-4, Comparative Examples 1-9
Components (a) to (i) were added at the component ratios shown in Table 2, and kneading was carried out at a kneading temperature of 180 ° 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.
[0076]
[Table 2]

[0077]
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.
On the other hand, Comparative Examples 1 and 2 are those in which the component (b) is out of the range. When there are few components (b), stickiness will become remarkable and press moldability will deteriorate. When there are many components (b), hardness will become hard too much and it will not become gel form (jelly form), but shock absorption will deteriorate.
In Comparative Examples 3 and 4, the component (c) is out of the range. If the component (c) is small, the impact absorbability deteriorates, and if the component (c) is large, the oil bleed property, press moldability, and impact absorbability deteriorate.
In Comparative Examples 5 to 8, butyl stearate and cetyl 2-ethylhexanoate, which are generally used as a lubricant for plastics, are used in place of the component (c) hydroxyl group-containing organic carboxylic acid. When butyl stearate or cetyl 2-ethylhexanoate is used, stickiness becomes remarkable, oil bleed deteriorates, and impact absorbability deteriorates.
Comparative Example 9 is an impact absorption test of an gel gel manufactured by Geltech Co., Ltd. When the sheet was fitted into a metal frame, the impact absorption effect was reduced.
[0078]
【The invention's effect】
The thermoplastic elastomer composition of the present invention has a gel-like (jelly-like) hardness at a room temperature (23 ° C.) of preferably 40 A or less, excellent moisturizing property, little oil bleed feeling, and vibration damping properties. Because it is an excellent composition, it is preferably used as a vibration damping material for vibration damping sheets, vibration damping members such as vibration damping sheets, tapes, seals, chips, and game machine vibration damping pads. Can do.

Claims (14)

(A) 100 parts by weight of a non-aromatic hydrocarbon-based rubber softener, and (c) 1-50 parts by weight of a hydroxyl group-containing organic carboxylic acid, comprising at least one aromatic vinyl compound as a main component Hydrogenated block copolymer or conjugated diene block copolymer obtained by hydrogenating a block copolymer comprising a polymer block A and at least one polymer block B mainly composed of a conjugated diene compound A softener composition for hydrogenated products. Component (a), softening agent composition according to claim 1, characterized in that a mixture of linear saturated hydrocarbons and / or branched saturated hydrocarbons 4-155 carbon atoms. Component (a), softening agent composition according to claim 1 or 2 characterized in that it is a liquid at room temperature. Softening agent composition according to any one of claims 1 to 3, wherein the component (c) is 12-hydroxystearic acid. A softening agent composition according to any one of claims 1 to 4, with respect to component (a) 100 parts by weight of,
(B) 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 hydrogenated block copolymer or conjugated diene block copolymer .   Furthermore, 0.1-30 weight part of (d) surfactant is contained with respect to 100 weight part of component (a), The thermoplastic-elastomer composition of Claim 5 characterized by the above-mentioned.   The thermoplastic elastomer composition according to claim 6, wherein the component (d) is a nonionic, cationic or anionic surfactant.   The thermoplastic elastomer according to any one of claims 5 to 7, further comprising (e) 0.1 to 20 parts by weight of an antifoaming agent with respect to 100 parts by weight of the component (a). Composition.   The thermoplastic elastomer composition according to claim 8, wherein the component (e) is a fatty acid ester-based, urea resin-based, paraffin-based, silicone-based, or polyoxyalkylene glycol-based antifoaming agent.   The thermoplastic elastomer composition according to any one of claims 5 to 9, 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 5-10 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 component (a), The heat of any one of Claims 5-11 characterized by the above-mentioned. Plastic elastomer composition.   The thermoplastic elastomer composition according to any one of claims 5 to 12, which is a gel-like (jelly-like) composition having a hardness at room temperature (23 ° C) of 40 A or less.   A vibration damping material, which is molded using the thermoplastic elastomer composition according to any one of claims 5 to 13.