JP2004323598A - Softening agent composition for thermoplastic elastomer, thermoplastic elastomer composition and molded item - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a readily manufacturable softening agent composition for a flexible thermoplastic elastomer, a gel-like thermoplastic elastomer composition having a hardness of at most 40A at room temperature (23°C) which exhibits an excellent moisture-retaining property and is almost free from oil bleeding, excellent in shock-absorbing property and excellently balanced with processability, and a vibration-damping material comprising the same. <P>SOLUTION: The softening agent composition for the thermoplastic elastomer comprises (a) 100 pts. wt. of a non-aromatic hydrocarbon softening agent for a rubber and (c) 1-50 pts. wt. of a hydroxy group-containing organic carboxylic acid. The gel-like thermoplastic elastomer composition having a hardness of at most 40A at room temperature (23°C) comprises the softening agent composition and (b) 3-110 pts. wt., based on 100 pts. wt. of the component (a), of a hydrogenated and/or partially hydrogenated block copolymer. The vibration-damping material is obtained by using the same. <P>COPYRIGHT: (C)2005,JPO&NCIPI

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]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a softener composition for a thermoplastic elastomer, a flexible thermoplastic elastomer composition and a molded product thereof, and more particularly to a gel (jelly) 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, has a unique jelly-like stiffness, has excellent shock absorption and vibration damping properties, and has a good balance between them. The present invention relates to an object and a vibration damping material comprising the same.
[0002]
[Prior art]
Conventionally, a thermoplastic elastomer resin composition having a predetermined hardness has been obtained by adding an oil as a softening agent to a styrene-based resin composition or an ethylene-propylene-based resin composition, and an olefin-based resin as a resin component. 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, heat resistance, weather resistance, mechanical strength, abrasion resistance, etc., decrease. .
[0003]
In addition, when obtaining a very soft thermoplastic resin composition, particularly a gel elastomer containing an elastomer and an oil component, when a conventional uncrosslinked oil is used, there is a problem that oil bleed occurs on the surface of the molded product, A satisfactory thermoplastic resin composition, in particular a gel elastomer, 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 amount) slightly more than three times, and when more oil is added, bleeding of oil occurs. Furthermore, when oil is blended with the thermoplastic resin composition, components other than oil are solid, whereas oil is liquid, which makes handling troublesome. There was a problem that equipment was required.
[0004]
Further, as a gel elastomer, a composition composed of a styrene-based thermoplastic elastomer and a paraffin is disclosed (for example, see Patent Document 1), but a high temperature is required during production and heating and melting. As a result, it is difficult to handle due to insufficient handling properties, and it is difficult to handle the gel, and the paraffins are likely to seep out and feel oily, possibly due to insufficient gel strength. Was.
[0005]
To solve the above problems, fatty acid esters such as isopropyl myristylate, isopropyl palmitate, butyl stearate, and isononyl isononanoate are blended, and the dissolution temperature of the styrene-based thermoplastic elastomer is lowered to make it transparent. An invention has been disclosed in which the property is increased and the feel is refreshed (for example, see Patent Document 2). However, although the effect of hue improvement is sufficiently exhibited, the oiliness is still strong, and the improvement of oiliness is insufficient particularly in fields requiring a lighter feel, such as foot care applications.
[0006]
In order to improve such oiliness, etc., the effect of adding fatty acid esters was examined, and the size of the alkyl group present between the ester groups and the proportion of branches were determined to affect the effect of adding the fatty acid ester. A gel elastomer composition comprising styrene-based thermoplastic elastomers, paraffins, and fatty acid esters (cetyl 2-ethylhexylate) has been proposed (see, for example, Patent Document 3). Further, as a gel composition having a shock absorbing performance, a gel composition obtained by swelling a triblock styrene elastomer in a softener (for example, see Patent Document 4), a triblock styrene elastomer and a diblock A gel composition comprising a styrenic elastomer and a softening agent (for example, see Patent Documents 5 and 6) has been proposed. However, these gel compositions also have a problem that the balance between oil bleed resistance, impact absorption, and moldability is extremely poor.
In addition, the composition described in the above prior art, particularly at the time of injection molding, has a cooling time which is abnormally long and sometimes requires about 25 minutes in some cases, and is extremely poor in productivity. .
[0007]
Therefore, the present inventors have excellent flexibility, heat deformation property, mechanical strength, excellent oil resistance and moldability, as a super-soft composition without stickiness, softener for non-aromatic hydrocarbon rubber, Compositions containing an organic peroxide, a crosslinking assistant, and a thermoplastic resin as an optional component (see, for example, Patent Document 7), styrene-based thermoplastic elastomers, softeners for non-aromatic hydrocarbon rubbers, and vinyl-aromatic resins , A composition containing a hydrogenated petroleum resin, an acrylic processing aid, and an organic peroxide (see, for example, Patent Document 8). Further, it is easy to handle, has no oil bleed, and has excellent mechanical strength. And a thermoplastic gel composition having abrasion resistance, comprising a softener for non-aromatic hydrocarbon rubber, a hydrogenated styrene-based thermoplastic elastomer, and an amorphous polyolefin. A plastic gel composition (for example, see Patent Document 9) has been proposed. However, a thermoplastic elastomer composition which is more excellent in moldability and impact absorption than these compositions, and which is more excellent in balance between moldability and various physical properties has not been obtained.
In addition, when used as a floor rubbing prevention mat or industrial damper in the healthcare field, it is particularly necessary to be excellent in shock absorption and vibration absorption, and simply adding oil to a thermoplastic resin composition is not sufficient. At present, conventional polyurethane gels, silicone gels, and the like have no performance, require complicated steps in their production, and require more expensive materials.
In other words, conventional polyurethane-based gels and silicone-based gels are supplied to the user in a very greasy veil shape, cut into the desired size and sandwiched between polyethylene or polyurethane films, and are further cut into metal frames or the like. It was necessary to perform a very complicated work to fit the tools. Further, when it is fitted in a frame, the above materials have a problem of a reduction in vibration damping properties and shock absorbing properties (such as a rebound distance of an iron ball).
[0008]
[Patent Document 1]
U.S. Pat. No. 4,369,284
[Patent Document 2]
U.S. 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-A-2000-34389
[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 softener composition for a flexible thermoplastic elastomer that can be easily produced, and is 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, low in oil bleed, has a unique "strain", shock absorption, vibration damping properties (especially when the composition (eg, sheet) is framed) It is an object of the present invention to provide a thermoplastic elastomer composition excellent in balance with processability and a vibration damping material comprising the same.
[0010]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems, and as a result, using only a softener for a non-aromatic hydrocarbon rubber, when the addition amount is increased to a level at which sufficient fluidity and moldability are exhibited, The bleeding of the softener becomes remarkable, the composition has no stiffness, the shock absorption and vibration damping properties are poor, and the styrenic thermoplastic elastomer requires the blending of a polypropylene resin to form fluidity. Although it was difficult to avoid an increase in hardness accompanying this, an appropriate amount of fats and oils that were moderately compatible with the hydrogenated and / or partially hydrogenated block copolymer and the softener for non-aromatic hydrocarbon rubbers was used. It has been found that the addition of the compound improves the balance among flexibility, shock absorption, vibration damping, moldability and bleed resistance. Based on the results, a softener composition for a thermoplastic elastomer containing a specific amount of a hydroxyl group-containing organic carboxylic acid in a softener for a non-aromatic rubber, and a specific amount of hydrogenated and / or partially water-based The thermoplastic elastomer composition containing the added block copolymer becomes a gel in which a network is formed in the composition, is excellent in moisture retention, has a low oil bleed feeling, is excellent in shock absorption and vibration damping properties, and has excellent workability. It has been found that the composition can be excellent in balance with the present invention, and the present invention has been completed.
[0011]
That is, according to the first aspect of the present invention, (a) 100 parts by weight of a softener for a non-aromatic hydrocarbon rubber, and
(C) 1 to 50 parts by weight of a hydroxyl group-containing organic carboxylic acid
The softener composition for thermoplastic elastomers characterized by containing is provided.
[0012]
According to a second aspect of the present invention, in the first aspect, 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 a thermoplastic elastomer is provided.
[0013]
According to a third aspect of the present invention, there is provided the softener composition for a thermoplastic elastomer according to the first or second aspect, 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 composition for thermoplastic elastomer according to any one of the first to third aspects, wherein the component (c) is 12-hydroxystearic acid. Provided.
[0015]
Further, according to the fifth invention of the present invention, the softening agent composition for a thermoplastic elastomer according to any one of the first to fourth inventions,
(B) 3 to 110 parts by weight of hydrogenated and / or partially hydrogenated block copolymer
The thermoplastic elastomer composition characterized by containing is provided.
[0016]
According to a sixth aspect of the present invention, in the fifth aspect, 0.1 to 30 parts by weight of a surfactant (d) is further contained based on 100 parts by weight of the component (a). A thermoplastic elastomer composition is provided that features.
[0017]
According to a seventh aspect of the present invention, there is provided the thermoplastic elastomer composition according to the sixth aspect, wherein the component (d) is a nonionic, cationic or anionic surfactant. .
[0018]
According to the eighth invention of the present invention, in any one of the fifth to seventh inventions, (e) an antifoaming agent of 0.1 to 20 parts by weight per 100 parts by weight of the component (a). The thermoplastic elastomer composition characterized by containing is provided.
[0019]
According to a 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, or 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 the olefin resin based on 100 parts by weight of the component (a). A thermoplastic elastomer composition is provided.
[0021]
According to an eleventh aspect of the present invention, in any one of the fifth to tenth aspects, further, (g) 0.1 to 10 parts by weight of the organic peroxide with respect to 100 parts by weight of the component (a). The present invention provides a thermoplastic elastomer composition comprising:
[0022]
According to a twelfth aspect of the present invention, in any one of the fifth to eleventh aspects, (h) an ester-based crosslinking aid of 0.1 to 20 with respect to 100 parts by weight of the component (a). A thermoplastic elastomer composition is provided which contains parts by weight.
[0023]
According to a thirteenth aspect of the present invention, in any one of the fifth to twelfth aspects, the thermoplastic composition is a gel composition having a hardness at room temperature (23 ° C.) of 40 A or less. An elastomer composition is 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 of any one of the fifth to thirteenth aspects.
[0025]
BEST MODE FOR CARRYING OUT THE INVENTION
1. Constituents of thermoplastic elastomer composition
(A) Softener for non-aromatic hydrocarbon rubber
The non-aromatic hydrocarbon-based rubber softener (a) used in the thermoplastic elastomer composition of the present invention includes a non-aromatic mineral oil or a liquid or low-molecular-weight synthetic softener. In general, a mineral oil softener for rubber is a mixture of an aromatic ring, a naphthene ring and a paraffin chain, wherein a saturated hydrocarbon chain having 50% or more of the total carbon number is a paraffinic or naphthenic ring carbon. Those having a number of 30 to 40% are called naphthenics, and those having an aromatic carbon number of 30% or more are called aromatics. The mineral oil softener for rubber used in the present invention is preferably the above-mentioned paraffin-based and naphthene-based. Aromatic softeners are not preferred because of poor dispersibility.
As the softener for the non-aromatic hydrocarbon rubber, a paraffinic mineral oil softener is particularly preferable, and among the paraffinic ones, those having a small aromatic ring component are particularly suitable.
[0026]
Examples of the compound constituting the paraffin softener include a paraffin compound having 4 to 155 carbon atoms, preferably a paraffin compound having 4 to 50 carbon atoms, and specifically, butane, pentane, and hexane. , Heptane, octane, nonane, decane, undecane, dodecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, docosane, trichosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosan, triacontan tria, triacontan tria N-paraffins (linear saturated hydrocarbons) such as contan, 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, isothiodecane 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 paraffin-based softeners that are liquid at room temperature (23 ° C.) include NA Solvent (isoparaffin-based hydrocarbon oil) manufactured by NOF Corporation and PW-90 (n-paraffin-based process manufactured by Idemitsu Kosan Co., Ltd.). Oil), IP-Solvent 2835 (synthetic isoparaffin-based hydrocarbon, 99.8 wt% or more isoparaffin) manufactured by Idemitsu Petrochemical Co., Ltd., and Neothiozole (n-paraffin-based process oil) manufactured by Sanko Chemical Industry Co., Ltd. .
[0028]
The non-aromatic hydrocarbon softener may contain a small amount of unsaturated hydrocarbon and a derivative thereof. Examples of the unsaturated hydrocarbon include ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-butene, 3-methyl-1-butene, and 2-methyl-2. -Butene, 1-hexene, 2,3-dimethyl-2-butene, 1-heptene, 1-octene, 1-nonene, 1-decene and other ethylene hydrocarbons, acetylene, methylacetylene, 1-butyne, 2- Acetylene-based hydrocarbons such as butyne, 1-pentyne, 1-hexyne, 1-octyne, 1-nonine and 1-decine can be mentioned.
[0029]
The specific gravity of the component (a) used in the present invention is preferably from 0.72 to 0.87, more preferably from 0.80 to 0.84. When the specific gravity is less than 0.72, the volatile component increases, and the mechanical properties further deteriorate. If it exceeds 0.87, the compatibility with the component (b) decreases, and the moldability further deteriorates.
[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.
Examples of the hydrogenated block copolymer include a block copolymer composed of 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. Examples thereof include hydrogenated block copolymers and 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, which can be used in the thermoplastic elastomer composition of the present invention. The hydrogenated block copolymer component obtained by hydrogenating the copolymer has 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 a single block copolymer. For example, a block copolymer of an aromatic vinyl compound-conjugated diene compound having a structure of AB, ABA, BABA, ABABA, or the like is hydrogenated. It is obtained by doing.
[0031]
The polymer block A mainly composed of an aromatic vinyl compound may be a polymer composed of only an aromatic vinyl compound or a copolymer of an aromatic vinyl compound and less than 50% by weight of a conjugated diene compound. Further, the polymer block B mainly composed of a conjugated diene compound may be a polymer composed of only 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 of styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene and the like can be selected, and among them, Styrene is preferred. Further, as the conjugated diene compound, for example, one or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like, and among them, butadiene, isoprene and These combinations are preferred.
[0033]
A hydrogenated block obtained by hydrogenating a block copolymer consisting of 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. The polymer component in the polymer block B mainly composed of a conjugated diene compound may have any hydrogenation rate, but is preferably 50% or more, more preferably 55% or more, and further preferably 60% or more. The microstructure is arbitrary. For example, when the block B is composed of butadiene alone, in the polybutadiene block, the 1,2-microstructure is preferably 20 to 50% by weight, and particularly preferably 25 to 45% by weight. % By weight. Further, a product obtained by selectively hydrogenating a 1,2-bond may be used. 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 the 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 an aliphatic double bond derived from isoprene. Preferably, 90% is hydrogenated.
[0035]
When a hydrogenated block copolymer is used depending on the application, preferably, the above hydrogenated product can be appropriately used according to the application.
[0036]
Further, the polymer block A is preferably present at a ratio of 5 to 70% by weight of the whole components. Further, the weight average molecular weight of the whole components is preferably 500,000 or less, more preferably 180,000 to 350,000. When the weight average molecular weight exceeds 500,000, moldability and mechanical properties deteriorate.
When moldability is important, in addition to the above components, those having a weight average molecular weight of 50,000 to 150,000 can be used in combination. If the weight average molecular weight is 50,000 or less, the mechanical properties deteriorate 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 consisting of at least one polymer block A mainly containing an aromatic vinyl compound and at least one polymer block B mainly containing a conjugated diene compound. Numerous methods have been proposed as methods for producing the copolymer. Representative methods include, for example, using a lithium catalyst or a Ziegler-type catalyst by the method described in Japanese Patent Publication No. 40-23798. It can be obtained by block polymerization in an inert medium. The hydrogenation treatment of such a block copolymer can be performed by a known method in an inert solvent in the presence of a hydrogenation catalyst.
[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 And a block copolymer having a functional ethylene-butene block (CEBC). In the present invention, the hydrogenated product of the conjugated diene compound block copolymer may be used alone or as a mixture of two or more.
Further, 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. When the weight average molecular weight exceeds 150,000, moldability deteriorates.
[0040]
The compounding amount of the component (b) is 3 to 110 parts by weight, preferably 5 to 70 parts by weight based on 100 parts by weight of the component (a). When the amount of the component (b) is less than 3 parts by weight, oil bleed becomes remarkable from the thermoplastic elastomer composition, and the moldability deteriorates. When the amount exceeds 110 parts by weight, the hardness of the thermoplastic elastomer composition decreases. It becomes harder, and the shock absorption deteriorates.
[0041]
(C) hydroxyl-containing organic carboxylic acid
The hydroxyl group-containing organic carboxylic acid (c) used in the softener composition for a thermoplastic elastomer and the thermoplastic elastomer composition of the present invention is dispersed in the component (a) to form a light network structure. And a component (b) to form a network structure so as to more firmly associate with each other, improve the viscosity of the composition, and have a function of adjusting the hardness.
That is, in the conventional styrene-based thermoplastic elastomer, a crystalline resin such as polypropylene had to be blended to form a fluidized bed, and the increase in hardness due to the addition could not be avoided. However, when component (c) of the present invention is mixed with component (a) a softener for non-aromatic hydrocarbon rubber, heated and cooled, component (c) forms a network in component (a), Gel (jelly-like) without increasing the hardness. Therefore, the component (c) has both the effect of improving the fluidity of the styrene-based thermoplastic elastomer and the effect of imparting flexibility, the effect of exhibiting a vibration damping function by imparting a unique strain to the composition, and the impact absorption. This has the important feature of solving the problem of bleeding of a large amount of non-aromatic hydrocarbon rubber softener in the means of softening the 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 includes a saturated aliphatic, unsaturated aliphatic or aromatic hydroxyl-containing organic carboxylic acid, A hydroxyl group-containing fatty acid having 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, and α-hydroxyl. Tetraeicosanoic acid, α-hydroxyhexaeicosanoic acid, α-hydroxyoctaeicosanoic acid, α-hydroxytriacontanic acid, β-hydroxymyristic acid, 10-hydroxydecanoic acid, 15-hydroxypentadecanoic acid, 16-hydroxyhexadecane Acids, 12-hydroxystearic acid, ricinoleic acid and the like.
[0044]
Other aliphatic hydroxyl group-containing carboxylic acids include glycolic acid, lactic acid, hydroacrylic acid, α-hydroxybutyric acid, α-hydroxyisobutyric acid, δ-hydroxycaproic acid, α-hydroxydotricontanic acid, α-hydroxy Tetratriacontanic acid, α-hydroxyhexatriacontanic acid, α-hydroxyoctatriacontanic acid, α-hydroxytetracontanic acid, glyceric acid, tartronic acid, malic acid, citric acid and the like. Examples of the aromatic oxycarboxylic acid include salicylic acid, m-oxybenzoic acid, p-oxybenzoic acid, gallic acid, mandelic acid, trobic acid, sabininic acid, iprolic acid, yarapinolic acid, uniperic acid, ambritol acid, Alluritic acid, camlorenic acid, ferronic acid, cerebronic acid, 2-hydroxyoctadecanoic acid, 2-hydroxyhexadecanoic acid, 2-hydroxytetradecanoic acid, 18-hydroxyoctadecanoic acid, 9,10-dihydroxyoctadecanoic acid, 2-hydroxymyristinic acid , 2-hydroxypalmitic acid, 2-hydroxystearic acid, 18-hydroxystearic acid, 9,10-dihydroxystearic acid, and ricanoic acid. Among 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, and various methods have been industrially developed to increase the hydrolysis rate. For example, Twitchell method, medium pressure catalytic hydrolysis method, continuous high pressure hydrolysis method, enzymatic hydrolysis method, saponification hydrolysis method and the like can be mentioned. Above all, when a fatty acid is obtained from castor oil, the saponification hydrolysis method is preferable because it has a meaning that a hydroxyl group and a carboxyl group liberated at a high temperature react with each other to prevent re-esterification between molecules.
Hydrogenation of unsaturated hydroxyl group-containing fatty acids is mainly performed using a nickel catalyst, but the process is performed not only on the fatty acids obtained by hydrolyzing the fats and oils, but also on the fats and oils themselves before the hydrolysis. There is also.
Fatty acids obtained from fats and oils are mixtures of various fatty acids, and therefore, when used, fatty acids having a high purity and a single composition are often separated from the mixed fatty acids. Representative low-pressure methods for this separation include fractional distillation, fractional crystallization (solventless method, solvent method, emulsification fractionation method), and liquid-liquid extraction.
[0046]
The 12-hydroxystearic acid preferably used in the present invention is obtained by hydrogenating ricinoleic acid, is a saturated fatty acid having an asymmetric hydroxyl group at the 12-position carbon, and is obtained by hydrogenating castor oil. It is produced by hydrolyzing oil and also obtained by hydrogenating castor oil fatty acid obtained by hydrolyzing castor oil. These can use a commercial item.
[0047]
The amount of the component (c) is 1 to 50 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of the component (b). If the compounding amount is less than 1 part by weight, the shock absorbing property is deteriorated, and if the compounding amount is more than 50 parts by weight, the molding processability is deteriorated and the oil bleed becomes remarkable. In addition, the shock absorption deteriorates.
[0048]
(D) surfactant
The thermoplastic elastomer composition of the present invention can contain (d) a surfactant, if necessary. 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 obtained composition. Component (d) may be any of nonionic, cationic and anionic surfactants. Among them, a nonionic surfactant is preferable. Examples of the nonionic surfactant include an ether type, an ether ester type, an ester type, and a nitrogen-containing nonionic surfactant.
Examples of the nonionic surfactant include polyoxyethylene higher alcohol ethers such as polyoxyethylene lauryl alcohol, polyoxyethylene lauryl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl Polyoxyethylene alkylaryl 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 phosphates, polyoxyethylene alkyl ether phosphorus Phosphoric acid esters such as esters, cellulose ethers are used.
Among them, alkyl and alkyl allyl polyoxyethylene ethers, alkyl allyl formaldehyde condensed polyoxyethylene ether, block polymers having polyoxypropylene as a base oil, ether type nonionic surfactants such as polyoxyethylene polyoxypropyl alkyl ether And 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 from 7 to 13, more preferably from 8 to 11. When the HLB is more than 13, the lipophilicity is reduced, and tackiness and stickiness are exhibited. On the other hand, when the HLB is less than 3, there is no effect of addition, and the tackiness and stickiness are also exhibited.
[0050]
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 the typical hydrophilic group and lipophilic group used in the calculation formula are used. The numbers are shown in the following formula (1) and Table 1 below.
HLB = 7 + S (the number of hydrophilic groups) + S (the number of lipophilic groups) (1)
[0051]
[Table 1]

[0052]
The amount of component (d) is 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of component (a). If the amount exceeds 30 parts by weight, bleed-out becomes remarkable and stickiness occurs.
[0053]
(E) Antifoaming agent
In the thermoplastic elastomer composition of the present invention, if necessary, (e) an antifoaming agent can be blended. The component (e) has the function of improving the miscibility of the thermoplastic elastomer composition and defoaming by being added to the thermoplastic elastomer composition. Therefore, by including the component, the moldability is extremely improved.
[0054]
Component (e) may be either a silicone compound or a non-silicone compound, and includes the following compounds.
Examples of the silicone compound include a polysiloxane copolymer having an HLB of 1 or more and less than 4.
Examples of the non-silicone compound include fatty acid ester compounds, urea resin compounds, paraffin compounds having an HLB of 1 or more and less than 4, polyoxyalkylene glycol compounds, acrylic ester copolymers, ester polymers, and ether compounds. Polymer, mineral oil emulsification type, polysiloxane adduct, fluorine compound, vinyl polymer, acetylene alcohol, acrylic polymer, special vinyl polymer, ethylene glycol, higher alcohol (octyl alcohol, cyclohexanol, etc.), HLB value Is at least 1 and less than 4, preferably at least 2 and less than 4 nonionic surfactants.
Among these, fatty acid ester compounds, urea resin compounds, paraffin compounds having an HLB of 1 or more and less than 4, polyoxyalkylene glycol compounds, and silicone compounds having an HLB of 1 or more and less than 4 are preferable. May be used alone or in combination of two or more.
[0055]
When added, the amount of the component (e) is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the component (a). When the amount is more than 20 parts by weight, the surface appearance of a molded article from the obtained thermoplastic elastomer composition is deteriorated.
[0056]
Compounds having the same compound name in the above components (d) and (e) can be distinguished by HLB according to the following criteria.
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-based resin can be blended if necessary.
As the component (f), a homopolymer of an α-olefin such as ethylene, propylene, butene-1, hexene-1, and 4-methyl-pentene-1, a copolymer of two or more thereof, or an α-olefin 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, alone or in combination of two or more. In addition, a hydrogenated product of a conjugated diene block copolymer (for example, CEBC: olefin crystal block-ethylene / butene random block-olefin crystal block) may be used as the olefin resin. Among these, ethylene homopolymers and copolymers of ethylene and other α-olefins are preferred, and particularly, ethylene-hexene-1 copolymer and ethylene-octene-1 polymerized using a single-site catalyst. Elastomer type ethylene copolymers having a copolymer as a main component and having improved impact resistance at low temperatures and the like are preferred.
[0058]
The amount of component (f), when mixed, is 1 to 30 parts by weight, preferably 3 to 15 parts by weight, per 100 parts by weight of component (a). If the amount exceeds 30 parts by weight, the gel state (jelly state) at room temperature (23 ° C.) and the moldability deteriorate.
[0059]
(G) Organic peroxide
In the thermoplastic elastomer composition of the present invention, (g) an organic peroxide can be used as necessary. The component (g) can improve oil resistance by cross-linking the component (b) of the obtained thermoplastic elastomer composition, is less likely to be plastically deformed at room temperature, and has the effect of improving oil bleed at high temperatures. Have.
[0060]
As the component (g), for example, 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, peroxysuccinate , 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 Benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butylcumyl peroxide and the like can be mentioned.
[0061]
Of these, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane (1 minute half-life temperature 147 ° C.), 2,2 5-dimethyl-2,5-di (tert-butylperoxy) hexane (1 minute half-life temperature 179 ° C.) and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexine-3 (1 minute (Half-life temperature 194 ° C.) and the like. In the case of the composition of the present invention, a low-temperature decomposable organic peroxide having a one-minute half-life temperature of 165 ° C. or less may be used.
[0062]
When compounded, the amount of component (g) is 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, per 100 parts by weight of component (a). When the amount exceeds 10 parts by weight, the decomposition reaction by the organic peroxide is prioritized, the odor becomes severe, and the moldability of the obtained thermoplastic elastomer composition is poor.
[0063]
(H) Ester-based crosslinking assistant
In the thermoplastic elastomer composition of the present invention, (h) an ester-based cross-linking aid can be blended, if necessary. The component (h) has an effect of performing a uniform and efficient cross-linking reaction during the cross-linking treatment with the organic peroxide component (g). As the component (h), for example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate having 9 to 14 ethylene glycol repeating units, and trimethylolpropanetriene Multifunctional methacrylate compounds such as methacrylate, allyl methacrylate, 2-methyl-1,8-octanediol dimethacrylate, 1,9-nonanediol dimethacrylate, polyethylene glycol diacrylate, ethoxylated cyclohexane dimethanol 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. These may be used alone or in combination of two or more. With such a compound, a uniform and efficient crosslinking reaction can be expected.
[0064]
Among the above crosslinking assistants, a polyfunctional methacrylate compound and a polyfunctional acrylate compound are preferable, 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 reduced.
[0065]
When compounded, 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). If the compounding amount exceeds 20 parts by weight, the crosslinking of the composition proceeds excessively, and the crosslinking aid is not partially dispersed, but the appearance can be deteriorated though it can be produced.
[0066]
(I) Other components
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 sealability are provided as long as the object of the present invention is not impaired. Agents, release agents such as stearic acid and silicone oil, lubricants such as polyethylene wax, coloring agents, pigments, inorganic fillers such as alumina, blowing agents (organic, inorganic, microcapsule), flame retardants (metal hydrate) Compound, red phosphorus, ammonium polyphosphate, antimony, silicone) and the like.
As the antioxidant, for example, 2,6-di-tert-p-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4,4- Examples include phenol-based antioxidants such as dihydroxydiphenyl and tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, phosphite-based antioxidants, and thioether-based antioxidants. Of these, phenolic antioxidants and phosphite antioxidants are particularly preferred.
Further, as a foaming agent (chemical foaming, microcapsule), it is possible to reduce the weight of a molded product by adding 0.01 to 3 parts by weight to 100 parts by weight of (a). As the agent, Expancel (manufactured by Expancel), which is a thermally expandable microcapsule having a vinylidene chloride-acrylonitrile copolymer as an outer shell and containing a low-boiling hydrocarbon (eg, isobutane), or Matsumoto Microsphere ( Matsumoto Yushi-Seiyaku Co., Ltd.) is preferred.
[0067]
2. Manufacturing of softener composition for thermoplastic elastomer, thermoplastic elastomer composition
The softener composition for a thermoplastic elastomer of the present invention can be easily obtained by blending the components (a) and (c), and other components as necessary, and mixing at room temperature with a mixing device. it can.
In addition, the thermoplastic elastomer composition of the present invention comprises the components (a) to (c) and, if necessary, other components, and is kneaded at a kneading temperature of 150 to 180 ° C. with a kneading apparatus. It can be obtained by melt mixing.
Furthermore, for simplicity, the thermoplastic elastomer composition of the present invention comprises components (a) to (c) and, if necessary, other components, and is mixed at 100 to 180 ° C. in a mixing device or a kneading device. , And the soup or sherbet-shaped composition is poured into a target mold and cooled, or the block obtained by cooling is directly subjected to press molding at 100 to 180 ° C. to thereby obtain a target thermoplastic resin. A molded article made of the elastomer composition can also be obtained.
[0068]
As the 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 method of kneading with a batch kneading apparatus such as a pressure kneader or a Banbury is good. In the case of performing continuously, a method in which a batch-type kneading device and an extruder are combined, for example, a method of kneading with a device in which a pressure kneader and an extruder are combined (batch supply type continuous extruder) is preferable.
[0069]
The softener composition and the thermoplastic elastomer composition for a thermoplastic elastomer of the present invention can be obtained only by mixing a specific amount as described above, and are used for producing a urethane gel, a silicone gel, and a styrene elastomer only gel. It can be obtained in a simple manner without having to involve certain reactions.
[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, low oil bleeding, 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, a special molding method which does not require much equipment among conventionally known molding methods. It is characterized in that it can be easily molded by molding, press molding, or the like.
[0071]
Specific applications include, for example, an insulator for vibration isolation (with bolts), a bolt penetrating bush, a (concavo-convex) vibration isolation sheet, a tape, a seal, a chip-shaped vibration isolation member, a cushioning material for a bag (eg, a shoulder bag for a school bag) Parts, handbags, etc.), armrests and wrist rests for personal computers (applied to mouse pads), paper feed rollers, audio-related members (turntables, insulators, spacers, etc.), vibration-proof rubber feet for cases, and shoe esthetics Doll face (skin, etc.), tennis racket, heat insulation sheet, waterproof sheet for electric pole protection, etc., bedsore prevention mat, etc., film sealing products (for example, hip protector for elderly people's thigh fracture prevention, post-operative body shape auxiliary material, Rider suits, gloves (for soccer keeper, golf, ski, rider), rifle jackets (eg shoulder ), Sports shoes, beds, high-temperature and high-pressure molding machine cushion (ceramic molding, etc.), heat-conducting gel sheet (for example, for the outer periphery of CPU core for heat dissipation, etc.), vibration damping pads for game machines, health care related, automobile parts (win Cushioning material for do packing, etc.), shock absorbers for car doors (sides, etc.), insoles for shoes, foot care shock absorbers to relieve pain caused by hallux valgus and ingrown nails, bumpers and helmets Miscellaneous goods such as shock absorbers, beds, mattresses, pillows, cushions and cushions, shock absorbers as bedding, elbow pads, knee pads, saddle prevention of horse back by saddle, ski shoes, toe shoes, ballet shoes, Sports-related shock absorbers such as gloves, shock absorbers in the transport of luggage, protects against fractures, injuries and injuries, and prevents prostheses and skin from rubbing Shock absorbers for medical use, people whose breasts have been cut off with breast cancer, breast pads for swimwear and breast augmentation, false baits for fishing, etc., and dust and debris from desks, chairs, personal computers, bookshelves, floors, and other household items It can be applied to cleaning products that absorb odors, and cosmetics such as packs, compresses, and fragrances using the sustained release of oils.
Above all, when fitted into a mold, there is little decrease in vibration absorption characteristics, so applications that require vibration damping, especially vibration damping members such as vibration damping sheets, tapes, seals, chips, and game machine damping It is preferably applied to vibration damping materials such as pads, bedsore prevention mats, sports shoes, and beds.
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【Example】
Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation methods and materials used in the examples are shown below.
[0073]
1. Evaluation method of thermoplastic elastomer composition
(1) Specific gravity: 180 ° C., preheating 2 minutes / pressing 2 minutes, pressure 50 kg / cm according to JIS K 7112 ² The measurement was carried out using a sheet having a thickness of 130 × 160 × 2 mm obtained by the hot press.
(2) Hardness: Measured according to JIS K6253. 180 ° C, 2 minutes preheating / 2 minutes pressurization, 50 kg / cm pressure ² The sheets having a thickness of 130 × 160 × 2 mm obtained by the hot pressing were superposed and measured to have a thickness of 4 mm or more.
In addition, the measured value of the soft sample outside the A hardness measurement range was represented by 0.
(3) Oil bleed: 180 ° C, preheating 2 minutes / pressurization 2 minutes, pressure 50 kg / cm ² A sheet having a thickness of 130 × 160 × 2 mm obtained by the hot press described above is sandwiched between kraft papers, a 500 g weight having a disk shape of 70 mm in diameter is placed thereon, and the state of the kraft paper is visually observed after being left at room temperature (23 ° C.) for 168 hours. And evaluated according to the following criteria.
◎: No trace of oil bleed is found on kraft paper
：: Traces of oil bleed are slightly observed on kraft paper
×: Traces of oil bleed are found on kraft paper
(4) Press formability: 180 ° C., preheating 2 minutes / pressing 2 minutes, pressure 50 kg / cm ² A sheet having a thickness of 130 × 160 × 5 mm obtained by hot pressing was prepared, the surface appearance and shape were observed, and evaluated according to the following criteria.
：: The surface is smooth and there are no bubbles
：: The presence of air bubbles is observed even when the surface is smooth
Δ: Surface is not smooth, but no bubbles
×: The surface is not smooth and bubbles are present.
(5) Impact absorption: The pachinko balls were allowed to fall naturally from the height of 30 cm onto the sheet obtained in (4) above, and the repellency was visually observed, and evaluated according to the following criteria.
○: Does not bounce at all
△: Bouncing only once on the sheet
×: Bouncing two or more times or jumping out of the seat
(6) Shock absorbency: Cut the sheet obtained in (4) above into 200 × 200 × 5 mm, make a part fitted in a metal frame, and let the pachinko balls fall naturally from a height of 30 cm. The degree of splashing was visually observed and evaluated according to the following criteria.
The α gel sheet was used by stacking a 2 mm thickness and a 3 mm thickness.
○: Does not bounce at all
△: Bouncing only once on the sheet
×: Bouncing two or more times or jumping out of the seat
(7) Volume swelling ratio (%): Based on JIS K6258, the product taken out in the above (1) was used, and the swelling ratio after immersion in IRM # 902 at 70 ° C. for 72 hours was measured.
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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) (trade name; 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) (trade name, 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 component: 12-hydroxystearic acid (saponified hydrolyzed castor oil: manufactured by Ito Oil Co., Ltd.) Melting point: 75-78 ° C, neutralization value: 175-185 mgKOH / g, saponification value: 180 to 190 mg KOH / g, iodine value: 3 or less gI2 / 100 g, hydroxyl value: 153 to 163 mg KOH / g
(C-2) Butyl stearate: manufactured by NOF Corporation, lubricant for plastic, HLB = 5.5 (comparative component)
(C-3) Cetyl 2-ethylhexanoate: Exepearl HO (manufactured by Kao) Iodine value 1 or less, hydroxyl value 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 to 8, specific gravity: 0.93, flash point: 228 ° C
(E) Defoamer component: Deform 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-based 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 to obtain 1 minute half life: 147.1 ° C
(H) Ester-based crosslinking auxiliary component: CHD-4E (ethoxylated cyclohexane dimethanol diacrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.) Viscosity: 50 mPa · s, specific gravity: 1.062, molecular weight: 636
(I) Hindered phenol / phosphite / lactone complex antioxidant (Antioxidant): HP2215 (trademark; manufactured by Ciba Specialty Chemicals)
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Examples 1-4, Comparative Examples 1-9
The components (a) to (i) were added at the component ratios shown in Table 2, and the mixture was kneaded at a kneading temperature of 180 ° C. using a mixer or an autoclave to obtain a thermoplastic elastomer composition. The physical properties of the obtained composition were measured. Table 2 shows the results.
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[Table 2]

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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, in Comparative Examples 1 and 2, the component (b) was out of the range. When the amount of the component (b) is small, stickiness becomes remarkable, and press formability deteriorates. If the amount of the component (b) is too large, the hardness becomes too hard to be gel-like (jelly-like) and the shock absorbing property deteriorates.
Comparative Examples 3 and 4 have component (c) out of range. If the amount of the component (c) is too small, the shock absorbing property is deteriorated. If the amount of the component (c) is too large, the oil bleeding property, press formability and shock absorbing property are deteriorated.
In Comparative Examples 5 to 8, butyl stearate, which is generally used as a plastic lubricant, and cetyl 2-ethylhexanoate were used instead of the component (c) the hydroxyl group-containing organic carboxylic acid. When butyl stearate or cetyl 2-ethylhexanoate is used, stickiness becomes remarkable, oil bleeding deteriorates, and shock absorption deteriorates.
Comparative Example 9 is a shock absorption test of an α gel sheet manufactured by Geltech Co., Ltd. When the sheet was fitted in a metal frame, the shock absorption effect was reduced.
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【The invention's effect】
The thermoplastic elastomer composition of the present invention preferably has a hardness at room temperature (23 ° C.) of 40 A or less and is in a gel (jelly) form, has excellent moisture retention, has a low oil bleed feeling, and has a vibration damping property. Because it is a composition excellent in vibration resistance, it is suitable for use as a vibration damping material such as a vibration damping sheet, a tape, a seal, a vibration damping member such as a chip, and a vibration damping pad for a game machine. Can be.

Claims (14)

A softener composition for a thermoplastic elastomer, comprising (a) 100 parts by weight of a softener for a non-aromatic hydrocarbon rubber and (c) 1 to 50 parts by weight of a hydroxyl group-containing organic carboxylic acid. The softener composition for a thermoplastic elastomer according to claim 1, wherein the component (a) is a mixture of a linear saturated hydrocarbon having 4 to 155 carbon atoms and / or a branched saturated hydrocarbon. The softener composition for a thermoplastic elastomer according to claim 1 or 2, wherein the component (a) is liquid at room temperature. The component (c) is 12-hydroxystearic acid, The softener composition for thermoplastic elastomers as described in any one of Claims 1-3 characterized by the above-mentioned. The softener composition for a thermoplastic elastomer according to any one of claims 1 to 4, based on 100 parts by weight of the component (a).
(B) A thermoplastic elastomer composition containing 3 to 110 parts by weight of a hydrogenated and / or partially hydrogenated block copolymer. The thermoplastic elastomer composition according to claim 5, further comprising (d) 0.1 to 30 parts by weight of a surfactant based on 100 parts by weight of the component (a). 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 based on 100 parts by weight of the component (a). Composition. 9. 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 (f) 1 to 30 parts by weight of the olefin resin based on 100 parts by weight of the component (a). . The thermoplastic according to any one of claims 5 to 10, further comprising (g) 0.1 to 10 parts by weight of an organic peroxide with respect to 100 parts by weight of the component (a). Elastomer composition. The heat according to any one of claims 5 to 11, further comprising (h) 0.1 to 20 parts by weight of an ester cross-linking aid with respect to 100 parts by weight of the component (a). Plastic elastomer composition. The thermoplastic elastomer composition according to any one of claims 5 to 12, wherein the composition is a gel-like (jelly-like) composition having a hardness at room temperature (23 ° C) of 40A or less. A vibration damping material formed by using the thermoplastic elastomer composition according to claim 5.