JP6609650B2 - 架橋発泡体用熱可塑性エラストマー組成物およびその使用 - Google Patents
架橋発泡体用熱可塑性エラストマー組成物およびその使用 Download PDFInfo
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- JP6609650B2 JP6609650B2 JP2018009866A JP2018009866A JP6609650B2 JP 6609650 B2 JP6609650 B2 JP 6609650B2 JP 2018009866 A JP2018009866 A JP 2018009866A JP 2018009866 A JP2018009866 A JP 2018009866A JP 6609650 B2 JP6609650 B2 JP 6609650B2
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- copolymer
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- conjugated diene
- crosslinked foam
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- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
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- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
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- BLJHFERYMGMXSC-UHFFFAOYSA-N 3-[3-(hydrazinesulfonyl)phenyl]sulfonylbenzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC(S(=O)(=O)C=2C=C(C=CC=2)S(=O)(=O)NN)=C1 BLJHFERYMGMXSC-UHFFFAOYSA-N 0.000 description 2
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- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
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Description
本発明の架橋発泡体用熱可塑性エラストマー組成物は、主として:(A)エチレン系共重合体;(B)第1の共重合体;(C)第2の共重合体、ここに、成分(B)および(C)は、ビニル芳香族単量体および共役ジエン単量体を含む共重合体であり、第1の共重合体は、少なくとも80%の共役ジエン水素化率を有し、第2の共重合体は、10%以下の共役ジエン水素化率を有する;(D)有機過酸化物;および(E)発泡剤、ここに、成分(A):成分(B)および成分(C)の組合せの質量比(A/(B+C))は、95/5〜5/95であり、かつ、成分(B):成分(C)の質量比(B/C)は、9/1〜1/9、好ましくは、9/1〜5/5、より好ましくは、9/1〜7/3である、を含む。本発明の好ましい具体例において、種々の態様の物理的特性における良好なバランスを有する架橋発泡体に用いる熱可塑性エラストマー組成物の成分(B)および成分(C)は、12%〜50%の範囲の合計の「共役ジエン不飽和二重結合の含量」を有する。「共役ジエン不飽和二重結合の含量」の計算式は:
共役ジエン不飽和二重結合の含量(%)=(成分(B)の質量分率)/(成分(B)の質量分率+成分(C)の質量分率)×(100%−成分(B)の共役ジエン水素化率)+(成分(C)の質量分率)/(成分(B)の質量分率+成分(C)の質量分率)×(100%−成分(C)の共役ジエン水素化率)
である。
本発明のエチレン系共重合体は、単量体としてエチレンを含有するいずれかのホモ重合体または共重合体、例えば、ポリエチレン、エチレン/酢酸ビニル共重合体(EVA)、エチレン−α−オレフィン共重合体。(ブロックまたはランダム)である。一例として、ポリエチレン(PE)を挙げると、エチレン系共重合体は、好ましくは高密度ポリエチレン(HDPE)、超高分子量高密度ポリエチレン、低密度ポリエチレン(LDPE)、直鎖状低密度ポリエチレン(LLDPE)および超低密度ポリエチレン(ULDPE)等である。また、ポリエチレン系樹脂およびポリプロピレン系樹脂の混合物を用いることも可能である。エチレン、およびエチレン以外の2種の単量体を含む共重合体を用い得る。その例は、エチレン、α−オレフィンおよび不飽和カルボン酸(アクリル酸、メタクリル酸、マレイン酸等)を含有する共重合体を含み得る。本具体例において、エチレン−α−オレフィン系共重合体が好ましく;エチレンおよびC3−C10α−オレフィンを含有するエチレン−α−オレフィン系共重合体がより好ましく;エチレンおよびC3−C6α−オレフィンを含有するエチレン−α−オレフィン系共重合体が依然としてより好ましく;エチレンおよびプロピレンまたは1−ブテンを含有するエチレン−α−オレフィン系共重合体が、さらにより好ましい。
本発明の第1の共重合体(成分(B))は、ビニル芳香族単量体および共役ジエン単量体を含み、ここに、その共役ジエンは少なくとも80%、好ましくは少なくとも90%、より好ましくは少なくとも95%の水素化率を有する。本発明の第2の共重合体(成分(C))は、ビニル芳香族単量体および共役ジエン単量体を含み、ここに、その共役ジエンは、10%以下、好ましくは5%以下、より好ましくは0%(非水素化)の水素化率を有する。
本発明の成分(D)は、架橋効果を有するいずれかの有機過酸化物である。特定の例には、過酸化ジクミル、過酸化ジ−tert−ブチル、2,5−ジメチル−2,5−ジ(tert−ブチルペルオキシ)ヘキサン、2,5−ジ(tert−ブチルペルオキシ)−2,5−ジメチル−3−ヘキシン、ジ(tert−ブチルペルオキシイソプロピル)ベンゼン、1,1−ジ−(tert−ブチルペルオキシ)−3,3,5−トリメチルシクロヘキサン、4,4−ジ(ブチルペルオキシ)吉草酸ブチル、過酸化ベンゾイル、過酸化p−クロロベンゾイル、過酸化2,4−ジクロロベンゾイル、tert−ブチルペルオキシベンゾアート、tert−ブチルペルベンゾアート、イソプロピルtert−ブチルペルオキシカルボネート、過酸化ジアセチル、過酸化ラウロイル、過酸化tert−ブチルクミル等が含まれる。1または2、またはそれを超えるこれらの過酸化物を併用し得る。本発明の組成物中の成分(D)の含量は、成分(A)、(B)および(C)の合計の100質量部に対して、好ましくは0.01〜10質量部、より好ましくは0.05〜7質量部である。
本発明の成分(E)は、特に限定されず、いずれの公知の発泡剤も用いることができる。有機熱分解性発泡剤の特定の例には、アゾジカーボンアミド(ADCA)、N,N’−ジニトロソペンタメチレンテトラミン、4,4’−オキシビス(ベンゼンスルホニルヒドラジド)、ジフェニルスルホン−3,3’−ジスルホニルヒドラジド(DPSDSH)、p−トルエンスルホニルセミカルバジドまたはトリヒドラジノトリアジンが含まれ、無機熱分解性発泡剤の特定の例は、炭酸水素ナトリウム、炭酸ナトリウム、炭酸水素アンモニウムおよび炭酸アンモニウムである。前記発泡剤の中で、アゾジカーボンアミド(ADCA)および炭酸水素ナトリウムが好ましい。本発明の組成物中の成分(E)の含量は、成分(A)、(B)および(C)の合計の100質量部に対して、0.5〜20質量部、より好ましくは1〜12質量部である。
前記成分に加えて、本発明の架橋発泡体用熱可塑性エラストマー組成物は、必要ならば、有機金属化合物、架橋共助剤、充填剤、熱安定剤、耐候安定剤、難燃剤、塩酸吸収剤、色素等を含み得る。有機金属化合物の添加は、得られた架橋発泡体のゲル分率を増加させ、発泡した気孔を細かく、より均一にする。有機金属化合物は、周期表の2〜12族中の金属から選択される金属を含有する。例えば、亜鉛ジアクリレート(ZDA)、亜鉛ジメタクリレート(ZDMA)等である。架橋共助剤の添加は、架橋反応速度を促進する。架橋共助剤の例は、硫黄、p−キノンジオキシム、p,p’−ジベンゾイルキノンジオキシム、N−メチル−N−4−ジニトロソアニリン、ニトロソベンゼン、ジフェニルグアニジン、トリメチロールプロパン−N,N’−m−フェニレンジマレイミド、ジビニルベンゼン、シアヌル酸トリアリル(TAC)、トリアリルイソシアヌレート(TAIC)、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、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、ビニルブチレートおよびステアリン酸ビニルである。充填剤の例は、クレイ、二酸化チタン、二酸化ケイ素、酸化亜鉛、タルク、炭酸カルシウム等である。熱安定剤の例には、Irgafos 168のごときリン系熱安定剤、HP−136のごときラクトン系熱安定剤および硫黄系熱安定剤が含まれる。耐候安定剤の例には、ヒンダードフェノール系耐候安定剤、亜リン酸系耐候安定剤、チオエーテル系耐候安定剤等が含まれる。難燃剤の例には、赤リン系難燃剤、ハロゲン系難燃剤、有機リン酸系および無機系難燃剤等が含まれる。塩酸吸収剤の例には、ステアリン酸カルシウム等が含まれる。色素の例には、アゾ系色素、フタロシアニン系色素、酸化チタンのごとき酸化物系色素、クロム酸系色素、モリブデン酸系色素、硫化セレン化合物、フェリシアニド化合物およびカーボンブラックのごとき無機色素が含まれる。
前記の各成分は、熱溶融し、適当な混練機中で混合して、本発明の熱可塑性エラストマー組成物を得ることもできる。その熱溶融および混合プロセスは、有機過酸化物(成分(D))および発泡剤(成分(E))が分解しない温度範囲にて実行されなければならず、好ましい温度範囲は、約100℃〜140℃である。混合中に各成分を添加する順序は特に限定されない。例えば、成分(A)、成分(B)および成分(C)は予め混合でき、次いで、成分(D)および成分(E)はさらに添加し得る。架橋発泡体用熱可塑性エラストマー組成物の形状は、特に限定されず、粒、シート/フィルム、糸、クラム(crumb)等であり得る。本発明の好ましい具体例は、混練後、それをペレタイザーでペレット化して、未架橋および未発泡状態の熱可塑性エラストマー組成物ペレットを調製することである。
前記の架橋発泡体用熱可塑性エラストマー組成物を架橋または発泡させて、架橋された発泡体が調製される。例えば、未発泡の熱可塑性エラストマー組成物ペレット(いずれかの他の適切な形態)は、融解および射出のために3〜20分間100℃〜200℃の範囲の型において処理し得る。発泡剤の架橋反応および分解の後、型を開けて組成物を発泡させて、一次架橋発泡体を完成する。一次架橋発泡体をさらに処理して、0.2〜0.3の比重に達するように型圧縮によって二次架橋発泡体を形成する。型圧縮の条件は特に限定されないが、100℃〜200℃の型温度、5分間〜60分間の圧縮時間、1.1〜3.0の圧縮比が好ましい。
三井化学によるTAFMER DF810(ポリオレフィンエラストマー、POE)を成分(A)として用い;TSRC社によるTaipol DP−6014を成分(B)として用い、それは99%の共役ジエン水素化率を有し;TSRC社によるTaipol 3206を成分(C)として用い、それは0%の共役ジエン水素化率を有し;過酸化ジクミルを成分(D)として用い;アゾジカーボンアミド成分(E)として用いた。80質量部の成分(A)、17質量部の成分(B)、3質量部の成分(C)、0.6質量部の成分(D)、および1.9質量部の成分(E)を120℃にて溶融および混練し、次いで、170℃〜174℃の射出成形条件下、架橋および発泡させた。一次架橋発泡体をさらに処理して、0.23の比重に達するように、型圧縮により二次架橋発泡体を形成した。二次架橋発泡体の物理的特性を測定した。
実施例1の組成物の共役ジエン不飽和二重結合の含量(%)=(17)/(17+3)×(100%−99%)+(3)/(17+3)×(100%−0%)=15.85%。
ピーク分子量(Mp):当業者によりよく知られた測定方法のゲル浸透クロマトグラフィーによる測定。
Claims (16)
- (A)エチレン系共重合体;
(B)第1の共重合体;
(C)第2の共重合体、ここに、成分(B)および(C)は、ビニル芳香族単量体および共役ジエン単量体を含む共重合体であり、第1の共重合体は、少なくとも80%の共役ジエン水素化率を有し、第2の共重合体は、10%以下の共役ジエン水素化率を有し、第2の共重合体は、ランダム共重合体ではなく、第1の共重合体および第2の共重合体は、12%〜50%の範囲の共役ジエン不飽和二重結合の合計の含量を有する;
(D)有機過酸化物;および
(E)発泡剤、
ここに、成分(A):成分(B)および成分(C)の組合せの質量比(A/(B+C))は、95/5〜5/95であり、かつ、成分(B):成分(C)の質量比(B/C)は、9/1〜1/9である、
を含む架橋発泡体用熱可塑性エラストマー組成物。 - ビニル芳香族単量体が独立して、スチレン、4−tert−ブチルスチレン、α−メチルスチレン、o−メチルスチレン、p−メチルスチレン、ジビニルベンゼン、1,1−ジフェニルエチレン、ビニルナフタレン、N,N−ジメチル−p−アミノエチルスチレン、N,N−ジエチル−p−アミノエチルスチレンおよびそれらのいずれかの組合せよりなる群から選択され;および
共役ジエン単量体が独立して、1,3−ブタジエン、イソプレン、2,3−ジメチル−1,3−ブタジエン、2−フェニル−1,3−ブタジエン、1,3−ペンタジエン、2−メチル−1,3−ペンタジエン、1,3−ヘキサジエン、4,5−ジエチル−1,3−オクタジエン、3−ブチル−1,3−オクタジエンおよびそれらのいずれかの組合せよりなる群から選択される請求項1記載の組成物。 - 第1の共重合体が、少なくとも90%の共役ジエン水素化率を有する、または第1の共重合体が、少なくとも95%の共役ジエン水素化率を有する請求項1記載の組成物。
- 第2の共重合体が、5%以下の共役ジエン水素化率を有する、または第2の共重合体が、非水素化されている請求項1記載の組成物。
- 成分(B):成分(C)の質量比(B/C)が、9/1〜5/5である、または成分(B):成分(C)の質量比(B/C)が、9/1〜7/3である請求項1記載の組成物。
- 第1の共重合体が、10重量%〜50重量%のビニル芳香族単量体含量を有し;および第2の共重合体が、10重量%〜50重量%のビニル芳香族単量体含量を有する請求項1記載の組成物。
- 第1の共重合体が、30重量%〜80重量%の1,2−ビニル結合含量を有し;および第2の共重合体が、5重量%〜80重量%の1,2−ビニル結合含量を有する請求項1記載の組成物。
- 第1の共重合体が、50,000〜300,000のピーク分子量(Mp)を有し;および第2の共重合体が、50,000〜300,000のピーク分子量(Mp)を有する請求項1記載の組成物。
- 成分(A)がエチレン−α−オレフィン共重合体である請求項1記載の組成物。
- 動的粘弾性測定(1Hzにて測定)によって決定された第1の共重合体の損失正接(tan δ)ピーク温度が、−65℃〜−35℃または−50℃〜−35℃の範囲にある請求項1記載の組成物。
- 動的粘弾性測定(1Hzにて測定)によって決定された第2の共重合体の損失正接(tan δ)ピーク温度が、−80℃〜−40℃または−80℃〜−60℃の範囲にある請求項1記載の組成物。
- 工程(a):請求項1〜11のいずれかに記載の架橋発泡体用熱可塑性エラストマー組成物を提供する;および
工程(b):架橋発泡体用熱可塑性エラストマー組成物を架橋および発泡させる
を含むことを特徴とする、架橋発泡体の製造方法。 - 請求項1〜11のいずれかに記載の架橋発泡体用熱可塑性エラストマー組成物を架橋および発泡させることにより製造された架橋発泡体。
- 架橋発泡体が、45C〜60Cの硬度、0.2〜0.3の比重および少なくとも3.3kg/cmの割裂き強度を有する請求項13記載の架橋発泡体。
- 架橋発泡体が、1.4〜1.6の膨張比、55%〜70%の反発弾性および55%以下の圧縮永久歪みを有する請求項14記載の架橋発泡体。
- 架橋発泡体が、30kg/cm2〜60kg/cm2の引張破断強度、少なくとも450%の破断時の伸びおよび少なくとも10kg/cmの引裂き強度を有する請求項15記載の架橋発泡体。
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TWI439478B (zh) * | 2009-08-28 | 2014-06-01 | Tsrc Corp | 部份氫化聚合物及其方法 |
JP5637765B2 (ja) | 2010-08-06 | 2014-12-10 | 旭化成ケミカルズ株式会社 | 変性水添ブロック共重合体組成物及びこれを用いた成形体 |
US20140004288A1 (en) * | 2010-12-13 | 2014-01-02 | Keiji Wakayama | Impact-absorbing material and sealing material comprising same |
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JP6153788B2 (ja) | 2013-07-01 | 2017-06-28 | リケンテクノス株式会社 | 発泡熱可塑性エラストマー組成物、及び複合成形体 |
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US20150257473A1 (en) * | 2014-03-13 | 2015-09-17 | Sunko Ink Co., Ltd. | Integrated shoe and method of making the same |
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