JPH0149423B2 - - Google Patents
Info
- Publication number
- JPH0149423B2 JPH0149423B2 JP60162964A JP16296485A JPH0149423B2 JP H0149423 B2 JPH0149423 B2 JP H0149423B2 JP 60162964 A JP60162964 A JP 60162964A JP 16296485 A JP16296485 A JP 16296485A JP H0149423 B2 JPH0149423 B2 JP H0149423B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- block copolymer
- parts
- composition
- hydrogenated block
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 vinyl aromatic compounds Chemical class 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 51
- 229920001400 block copolymer Polymers 0.000 claims description 47
- 229920001971 elastomer Polymers 0.000 claims description 27
- 238000007906 compression Methods 0.000 claims description 26
- 230000006835 compression Effects 0.000 claims description 26
- 239000005060 rubber Substances 0.000 claims description 26
- 229920000642 polymer Polymers 0.000 claims description 25
- 229920002554 vinyl polymer Polymers 0.000 claims description 18
- 229920001955 polyphenylene ether Polymers 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005672 polyolefin resin Polymers 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 238000005984 hydrogenation reaction Methods 0.000 description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 239000011256 inorganic filler Substances 0.000 description 8
- 229910003475 inorganic filler Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 description 6
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 1
- KUNNUNBSGQSGDY-UHFFFAOYSA-N 2-butyl-6-methylphenol Chemical compound CCCCC1=CC=CC(C)=C1O KUNNUNBSGQSGDY-UHFFFAOYSA-N 0.000 description 1
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
(産業上の利用分野)
本発明は、柔軟性に富み、高温圧縮永久歪、機
械的強度、成形加工性に優れ、各種成形物の素材
として利用できる高弾性な水添ブロツク共重合体
組成物に関するものである。
(従来の技術)
近年、ゴム的な軟質材料であつて加硫工程を必
要とせず、熱可塑性樹脂と同様な成形加工性を有
する熱可塑性エラストマーが、自動車部品、家電
部品、電線被覆、医療用部品、雑貨、履物等の分
野で有用されている。このような熱可塑性エラス
トマーのなかで、ビニル芳香族化合物―共役ジエ
ン化合物ブロツク共重合体の水素添加誘導体(以
下水添ブロツク共重合体と略記する)を用いたエ
ラストマー状組成物に関し、いくつかの提案がな
されている。例えば特開昭50−14742号、特開昭
52−65551号、特開昭58−206644号は、水添ブロ
ツク共重合体に炭化水素油およびオレフイン系重
合体を配合したエラストマー状組成物が開示され
ており、さらに特開昭59−131613号には、水添ブ
ロツク共重合体に炭化水素油およびオレフイン系
重合体、無機充填剤を配合したエラストマー状組
成物を有機パーオキサイドと架橋助剤により部分
架橋ならしめ、得られるエラストマー状組成物の
高温時のゴム弾性(圧縮永久歪)を改良する旨の
提案がなされている。
そしてさらに、特開昭54−88960号、特開昭59
−100159号、特公昭57−56941号には水添ブロク
共重合体とポリフエニレンエーテルを必須成分と
し、ポリオレフイン系樹脂、ポリスチレン系樹脂
から成る水添ブロツク共重合体の組成物が開示さ
れている。しかしながら、これらの提案は樹脂組
成物の改良を目的とするものであり、得られる組
成物は熱可塑性樹脂であり、先記した熱可塑性エ
ラストマーとしてはとうていなり得ず、エラスト
マー状組成物としてのゴム弾性を持たないもので
あつた。
(発明が解決しようとする問題点)
上記の提案で得られる水添ブロツク共重合体の
エラストマー状組成物は、70℃のゴム弾性(圧縮
永久歪)が優れるものの、100℃におけるゴム弾
性は70%以上と劣つており、従来加硫ゴム用途で
要求されている高温時の圧縮永久歪のレベルに到
達せず、熱可塑性エラストマーとしての特徴であ
るリサイクル成形性を有しながら、高温時のゴム
特性はいまだ不十分であるのが現状であり、また
これが当然とされていた。
(問題点を解決するための手段)
本発明は、上記した従来のエラストマー成形材
料では困難であつた問題点を解決すべくなされた
ものであつて、特に熱可塑性エラストマーとして
の加工性、リサイクル成形性と高温時のゴム弾性
(100℃における圧縮永久歪)のいまだかつて到達
できなかつた両性能を満足できる成形材料の要望
に基づいてなされたものであり、未だかつて到達
できなかつたこの要望を特定のエラストマー状組
成物を選択することによつて充分に達成し得るも
のであることを見い出し、さらにそれが実用的に
有用な組成物であることを見い出しなされたもの
である。
すなわち、本発明は、
(1) (a) 少なくとも2個のビニル芳香族化合物を
主体とする末端重合体ブロツクAと、少なく
とも1個の共役ジエン化合物を主体とする中
間重合体ブロツクBとからなるブロツク共重
合体を水素添加して得られる水添ブロツク共
重合体a100重量部
(b) 一般式
(ここで、R1,R2,R3およびR4はそれぞ
れ、水素、ハロゲン、炭化水素基からなる群
より選択される置換基を表らわし互に同一で
も異なつてもよい。)
で示される結合単位よりなり、0.5g/dlク
ロロホルム溶液において30℃で測定された還
元粘度が0.15〜0.70の範囲にあるホモ重合体
およびまたは共重合体であるポリフエニレン
エーテル樹脂bが前記aに対してa/b=
90/10〜30/70(重量比)
(c) 非芳香族系ゴム用軟化剤10〜300重量部
から成り、圧縮永久歪(100℃×22時間)が
65%以下の性能を有する高弾性な水添ブロツ
ク共重合体組成物を、また、
前記(a),(b),(c)および
(d) ポリオレフイン系樹脂5〜100重量部
から成り、圧縮永久歪(100℃×22時間)が
65%以下の性能を有する高弾性な水添ブロツ
ク共重合体組成物を
さらに実施態様として例えば前記(a),(b),
(c),(d)および
(e) 無機充填剤20〜300重量部
から成り、圧縮永久歪(100℃×22時間)が
65%以下の性能を有する高弾性な水添ブロツ
ク共重合体組成物を
またさらに、前記(a),(b),(c)および
(e) 無機充填剤20〜300重量部
から成り、圧縮永久歪(100℃×22時間)が
65%以下の性能を有する高弾性な水添ブロツ
ク共重合体組成物などを提供する。
以下、本発明に関して詳しく述べる。
本発明において、圧縮永久歪(100℃×22時間)
とはゴム弾性体としての高温圧縮永久歪であり、
JIS―K6301により、100℃×22時間、圧縮率25%
の条件で測定された値である。
本発明で(a)成分として用いられる水添ブロツク
共重合体は、少なくとも2個のビニル芳香族化合
物を主体とする末端重合体ブロツクAと、少なく
とも1個の共役ジエン化合物を主体とする中間重
合体ブロツクBとからなるブロツク共重合体を水
素添加して得られるものであり、例えばA−B−
A、(A−B―)4Si,A−B−A−B−A、(A−
B―)Si−CH3等の構造を有するビニル芳香族化合
物―共役ジエン化合物ブロツク共重合体の水素添
加されたものである。この水添ブロツク共重合体
は、ビニル芳香族化合物を5〜60重量%、好まし
くは10〜50重量%含み、さらにブロツク構造につ
いて言及すると、ビニル芳香族化合物を主体とす
る末端重合体ブロツクAが、ビニル芳香族化合物
重合体ブロツクまたは、ビニル芳香族化合物を50
重量%を越え好ましくは70重量%以上含有するビ
ニル芳香族化合物と水素添加された共役ジエン化
合物との共重合体ブロツクの構造を有しており、
そしてさらに、水素添加された共役ジエン化合物
を主体とする中間重合体ブロツクBが、水素添加
された共役ジエン化合物重合体ブロツク、または
水素添加された共役ジエン化合物を50重量%を越
え好ましくは70重量%以上含有する水素添加され
た共役ジエン化合物とビニル芳香族化合物との共
重合体ブロツクの構造を有するものである。ま
た、これらのビニル芳香族化合物を主体とする末
端重合体ブロツクA、水素添加された共役ジエン
化合物を主体とする中間重合体ブロツクBは、そ
れぞれの重合体ブロツクにおける分子鎖中の水素
添加された共役ジエン化合物またはビニル芳香族
化合物の分布がランダム、テーパード(分子鎖に
沿つてモノマー成分が増加または減少するもの)、
一部ブロツク状またはこれらの任意の組合せで成
つていてもよく、該ビニル芳香族化合物を主体と
する重合体ブロツクおよび該水素添加された共役
ジエン化合物を主体とする重合体ブロツクがそれ
ぞれ2個以上ある場合は、各重合体ブロツクはそ
れぞれが同一構造であつてもよく、異なる構造で
あつてもよい。
水添ブロツク共重合体を構成するビニル芳香族
化合物としては、例えばスチレン、α―メチルス
チレン、ビニルトルエン、p―第3ブチルスチレ
ン等のうちから1種または2種以上が選択でき、
中でもスチレンが好ましい。また水素添加された
共役ジエン化合物を構成する水添前の共役ジエン
化合物としては、例えば、ブタジエン、イソプレ
ン、夫・3―ペンタジエン、2,3―ジメチル―
1,3―ブタジエン等のうちから1種または2種
以上が選ばれ、中でもブタジエン、イソプレンお
よびこれらの組合せが好ましい。そして、水添さ
れる前の共役ジエン化合物を主体とする重合体ブ
ロツクは、そのブロツクにおけるミクロ構造を任
意に選ぶことができ、例えばポリブタジエンブロ
ツクにおいては、1,2―ミクロ構造が20〜50
%、好ましくは25〜45%である。
また、上記した構造を有する本発明に供する水
添ブロツク共重合体の数平均分子量は5000〜
1000000、好ましくは10000〜800000、更に好まし
くは30000〜500000の範囲であり、分子量分布
〔重量平均分子量()と数平均分子量()
との(Mw/Mn)〕は10以下である。さらに水添
ブロツク共重合体の分子構造は、直鎖状、分岐
状、放射状あるいはこれらの任意の組合せのいず
れであつてもよい。
これらのブロツク共重合体の製造方法としては
上記した構造を有するものであればどのような製
造方法で得られるものであつてもかまわない。例
えば、特公昭40−23798号公報に記載された方法
により、リチウム触媒等を用いて不活性溶媒中で
ビニル芳香族化合物―共役ジエン化合物ブロツク
共重合体を合成し、次いで、例えば特公昭42−
8704号公報、特公昭43−6636号公報、あるいは特
開昭59−133203号公報に記載された方法により、
不活性溶媒中で水素添加触媒の存在下に水素添加
して、本発明に供する水添ブロツク共重合体を合
成することができる。その際ビニル芳香族化合物
―共役ジエン化合物ブロツク共重合体の共役ジエ
ン化合物に基づく脂肪族二重結合は少なくとも80
%を水素添加せしめ、共役ジエン化合物を主体と
する重合体ブロツクを形態的にオレフイン性化合
物重合体ブロツクに変換させることができる。ま
た、ビニル芳香族化合物を主体とする重合体ブロ
ツクAおよび必要に応じて共役ジエン化合物を主
体とする重合体ブロツクBに共重合されているビ
ニル芳香族化合物に基づく芳香族二重結合の水素
添加率については特に制限はないが、水素添加率
を20%以下にするのが好ましい。該水添ブロツク
共重合体中に含まれる未水添の脂肪族二重結合の
量は、赤外分光光度計、核磁気共鳴装置等により
容易に知ることができる。
つぎに、本発明の(b)成分として用いられるポリ
フエニレンエーテル樹脂は得られる組成物の圧縮
永久歪(100℃×22時間)を65%以下に改善する
ための必須成分であり、その分子鎖の結合単位が
一般式
(ここでR1,R2,R3およびR4はそれぞれ水
素、ハロゲン、炭化水素基からなる群より選択さ
れる置換基を表らわし互に同一でも異なつてもよ
い。)
よりなるホモ重合体及びまたは共重合体であり
0.5g/dlクロロホルム溶液において30℃で測定
された還元粘度が0.15〜0.70の範囲にあるものが
用いられ、より好ましくは0.20〜0.60の範囲のも
のが用いられる。このポリフエニレンエーテル樹
脂としては公知のものを用い得る。
具体的な例としてはポリ(2,6―ジメチル―
1,4―フエニレンエーテル、ポリ(2―メチル
―6エチル―1,4―フエニレン)エーテル、ポ
リ(2,6―ジフエニル―1,4―フエニレン)
エーテル、ポリ(2―メチル―6―フエニル―
1,4―フエニレン)エーテル、ポリ(2,6―
ジクロロ―1,4―フエニレン)エーテルなどが
あげられまた2,6―ジメチルフエノールと他の
フエノール類(例えば2,3,6―トリメチルフ
エノールや2―メチル―6―ブチルフエノール)
との共重合体のごときポリフエニレンエーテル共
重合体も挙げられる。なかでもポリ(2,6―ジ
メチル―1,4―フエニレン)エーテル、2,6
―ジメチルフエノールと2,3,6―トリメチル
フエノールとの共重合体が好ましく、さらに、ポ
リ(2,6―ジメチル―1,4―フエニレン)エ
ーテルが好ましい。
用いられるポリ(2,6―ジメチル―1,4―
フエニレンエーテル)の還元粘度(0.5g/dl、
クロロホルム溶液、30℃測定)は、0.15〜0.70の
範囲のものが好ましく、より好ましくは0.30〜
0.60の範囲である。
成分(b)の配合量は、成分(a)の水添ブロツク共重
合体/成分(b)のポリフエニレンエーテルの重量比
が90/10〜30/70の範囲で好適に選ぶことができ
る。該重量比が30/70未満の配合では得られるエ
ラストマー状組成物の硬度が高くなりすぎて柔軟
性が失なわれ樹脂状組成物となり、ゴム的感触の
製品が得られないばかりか、高温でのゴム弾性
〔圧縮永久歪(100℃×22時間)〕が65%を越え好
ましくない。また該重量比が90/10超の配合で
は、ポリフエニレンエーテルを添加する効果とし
ての高温でのゴム弾性(圧縮永久歪)の改良が認
められず好ましくない)。
本発明で(c)成分として用いられるゴム用軟化剤
は、得られる組成物を柔軟なゴム状組成物とする
ための必須成分であり、非芳香族系の鉱物油また
は液状もしくは低分子量の合成軟化剤が適してい
る。なかでも、一般にゴムの軟化、増容、加工性
向上に用いられるプロセスオイルまたはエクステ
ンダーオイルと呼ばれる鉱物油系ゴム用軟化剤
は、芳香族環、ナフテン環およびパラフイン鎖の
三者が組合わさつた混合物あつて、パラフイン鎖
の炭素数が全炭素中50%以上を占めるものがパラ
フイン系と呼ばれ、ナフテン環炭素数が30〜45%
のものがナフテン系、また、芳香族炭素数が30%
より多いものが芳香族系とされる。本発明の成分
(c)として用いられる鉱物油系ゴム軟化剤は、上記
の区分でナフテン系およびパラフイン系のものが
好ましく、芳香族炭素数が30%以上の芳香族系の
ものは、前記成分(a)との組成において分散性およ
び溶解性の点で好ましくない。これらの非芳香族
系ゴム用軟化剤の性状は、37.8℃における動粘度
が20〜500cst、流動点が−10〜−15℃および引火
点が170〜300℃を示す。合成軟化剤としては、ポ
リブテン、低分子量ポリブタジエン等が使用可能
であるが、上記鉱物油系ゴム用軟化剤の方が良好
な結果を与える。
成分(c)の軟化剤の配合量は、成分(a)の100重量
部に対して10〜300重量部であり、好ましくは20
〜250重量部である。300重量部を超えた配合のも
のは、軟化剤のブリードアウトを生じやすく、最
終製品に粘着性を生ずるおそれがあり、機械的性
質も低下せしめる。また10重量部未満の配合で
は、得られる組成物が樹脂組成物に近くなり、硬
度が増し、柔軟性を失なうほかに、経済性の点か
らも好ましくない。
つぎに、本発明の(d)成分として用いられるポリ
オレフイン系樹脂は得られる組成物の加工性、お
よびまたは耐熱性向上に有効であり、例えばポリ
エチレン、アイソタクチツクポリプロピレンや、
プロピレンと他の少量のα―オレフイモの共重合
体、例えばプロピレン―エチレン共重合体、プロ
ピレン―1―ヘキセン共重合体、プロピレン―4
―メチル―1ペンテン共重合体、およびポリ4―
メチル―1―ペンテン、ポリブテン―1等を挙げ
ることができる。用いられるオレフイン系樹脂と
してポリプロピレンを使用する場合のMFR
(ASTM―D―1238―L条件、230℃)は0.1〜50
g/10分、とくに0.5〜30g/10分の範囲のもの
が好ましい。
成分(d)の配合量は、成分(a)100重量部に対し5
〜100重量部であり、好ましくは10〜70重量部で
ある。100重量部を超えた配合では、得られるエ
ラストマー状組成物の硬度が高くなりすぎて柔軟
性が失なわれ、ゴム的感触の製品が得られないば
かりでなく、高温でのゴム弾性(圧縮永久歪)が
極度に悪化し好ましくない。また、5重量部未満
の配合では、該ポリオレフイン系樹脂が未添加の
本発明の組成物と同等の加工性を発揮する。
さらに、本発明の実施態様の例として(e)成分と
して用いられる無機充填剤は増量剤として製品コ
ストの低下をはかることの利益があるばかりでな
く、品質改良(圧縮永久歪等)に積極的効果を付
与する。
無機充填剤としては、例えば炭酸カルシウム、
カーボンブラツク、タルク、水酸化マグネシウ
ム、マイカ、クレー、硫酸バリウム、天然けい
酸、合成けい酸(ホワイトカーボン)、酸化チタ
ン等があり、カーボンブラツクとしてはチヤンネ
ルブラツク、フアーネスブラツク等が使用でき
る。これらの無機充填剤のうち、タルク、炭酸カ
ルシウムおよびフアーネスブラツクは経済的にも
有利で好ましいものである。また導電性を付与す
るために導電性フイラーの添加も可能であり、例
えばケツチエンブラツク等の導電性カーボンを用
いてもかまわない。
無機充填剤の配合量は、成分(a)の水添ブロツク
共重合体100重量部に対し20〜300重量部であり、
好ましくは30〜250重量部である。300重量部を超
える配合では、組成物の機械的強度の低下が著し
く、かつ、硬度が高くなつて柔軟性が失なわれ、
ゴム的な感触の製品が得られなくなる。また20重
量部未満の配合では、該無機充填剤の未添加配合
で得られる本発明の組成物と同等の性能を発揮す
る。
本発明の高弾性エラストマー状組成物にさらに
必要に応じて難燃剤、ガラス繊維、カーボン繊
維、酸化防止剤、耐熱安定剤、紫外線吸収剤、ヒ
ンダードアミン系光安定剤、着色剤を加えること
ができる。
本発明の高弾性エラストマー状組成物の複合化
方法としては、通常の樹脂組成物の製造あるいは
ゴム組成物の製造に際して用いられる方法が採用
でき、単軸押出機、二軸押出機、バンバリーミキ
サー、加熱ロール、ブラベンダー、各種ニーダー
等の溶融混練機を用いて複合化することができ
る。この際、各成分の添加順序には制限が無く、
例えば全成分をヘンシエルミキサー、ブレンダー
等の混合機で予備混合し上記の混練機で予備混合
し上記の混練機で溶融複合化したり、任意の成分
を予備混合しマスターバツチ的に溶融複合化し、
さらに残りの成分を添加し溶融複合化する等の添
加方法が採用できる。
そして、複合化された本発明の組成物は、一般
に使用される熱可塑性樹脂成形機で成形すること
が可能であつて、射出成形、押出成形、ブロー成
形、カレンダー成形等の各種成形方法が適用可能
である。
(発明の効果)
本発明によつて得られる組成物は、柔軟性、耐
熱性、機械的強度、高温時のゴム弾性に優れか
つ、成形加工時、塗装性、および電気絶縁性に優
れるため、その使用分野としては、高ゴム弾性の
特徴を生かして各種電線被覆(絶縁、シース)、
家電部品、自動車部品、および各種工業部品に好
適に成形し用いることができる。具体的な用途と
しては、各種ガスケツト類、屈曲性チユーブ、ホ
ース被覆、ウエザーストリツプ、屈曲性バンパ
ー、サイドバンパー、モール、フイラーパネル、
ライプハウジング、ワイヤーケーブル被覆、エア
ーインテークホース、クツシヨンパネル等があ
る。
(実施例)
本発明を実施例によつて更に詳細に説明する
が、本発明がこれら実施例により限定されるもの
ではない。
なお、これらの実施例および比較例において、
各種の評価に用いられた試験法は以下のとおりで
ある。
(1) 硬度〔−〕
JIS―K6301、Aタイプ
(2) 引張強度〔Kg/cm2〕および引張伸度〔%〕
JIS―K―6301、試料は2mm厚のインジエク
シヨンシートを用い、試験片は3号形。
(3) 圧縮永久歪〔%〕
JIS―K―6301、70℃および100℃22時間、25
%変形。
また配合した各成分は以下のとおりである。
(1) 〈成分(a―1)〉
ポリスチレン―水素添加されたポリブタジエ
ン―ポリスチレンの構造を有し、結合スチレン
量27%、数平均分子量157000、分子量分布
1.07、水添前のポリブタジエンの1,2結合量
が34%、水添率98%の水添ブロツク共重合体を
特開昭59−133203号に記載されたTi系水添触
媒で合成し、成分(a―1)とした。
〈成分(a―2)〉
(ポリスチレン―水素添加されたポリブタジ
エン―)4Siの構造を有し、結合スチレン量36%、
数平均分子量379000、分子量分布1.35、水添前
のポリブタジエンの1,2結合量が27%、水添
率99%の水添ブロツク共重合体を特開昭59−
133203号に記載されたTi系水添触媒で合成し、
成分(a―2)とした。
〈成分(a―3)〉
シエル・ケミカル社製KRATON―G1651
〈成分(a―4)〉
シエル・ケミカル社製KRATON―G1650
(2) 成分(b)
出光典産社製ダイアナプロセスオイルPW―
380〔パラフイン系、動粘度;381.6cst(40℃)、
30.1cst(10℃)、平均分子量746、環分析;CN=
27%、CP=73%〕
(3) 成分(c)
旭化成社製ポリプロピレン樹脂、M―1300
〔MFR(230℃)4g/10分〕
(4) 成分(d)
白石カルシウム社製炭酸カルシウム、ホワイ
トインSB
(5) 成分(e)
ポリフエニレンエーテル樹脂として、ポリ
(2,6―ジメチル―1,4―フエニレン)エ
ーテル〈還元粘度;0.37、0.57〉を合成した。
実施例 1〜6
水添ブロツク共重合体として(a―1)〜(a
―3)を用い、またポリフエニレンエーテルとし
て還元粘度0.57のものを用い表―1に示す各成分
をヘンシエルミキサーで混合後、50mm径の二軸押
出機にて250℃の条件で溶融混練し熱可塑性エラ
ストマーのペレツトを得た。これを射出成形品と
して評価し、結果を表1に載せた。
この結果から、本発明のエラストマー状組成物
は100℃の圧縮永久歪が50%以下であり、高温時
のゴム弾性に優れることが明らかである。またさ
らにこれらの組成物は成形加工性にも優れてい
た。
(Field of Industrial Application) The present invention is a highly elastic hydrogenated block copolymer composition that is highly flexible, has excellent high-temperature compression set, mechanical strength, and moldability, and can be used as a material for various molded products. It is related to. (Prior art) In recent years, thermoplastic elastomers, which are rubber-like soft materials that do not require a vulcanization process and have moldability similar to thermoplastic resins, have been used for automobile parts, home appliance parts, electric wire coatings, and medical applications. It is useful in the fields of parts, miscellaneous goods, footwear, etc. Among such thermoplastic elastomers, there are some elastomeric compositions using hydrogenated derivatives of vinyl aromatic compound-conjugated diene compound block copolymers (hereinafter abbreviated as hydrogenated block copolymers). Suggestions have been made. For example, JP-A-50-14742, JP-A-Sho.
No. 52-65551 and JP-A No. 58-206644 disclose an elastomeric composition in which a hydrogenated block copolymer is blended with a hydrocarbon oil and an olefinic polymer, and JP-A No. 59-131613 discloses In this method, an elastomeric composition prepared by blending a hydrogenated block copolymer with a hydrocarbon oil, an olefinic polymer, and an inorganic filler is partially crosslinked with an organic peroxide and a crosslinking aid, and the resulting elastomeric composition is Proposals have been made to improve rubber elasticity (compression set) at high temperatures. Furthermore, JP-A-54-88960, JP-A-59
-100159 and Japanese Patent Publication No. 57-56941 disclose hydrogenated block copolymer compositions containing a hydrogenated block copolymer and polyphenylene ether as essential components and consisting of a polyolefin resin and a polystyrene resin. There is. However, these proposals are aimed at improving the resin composition, and the resulting composition is a thermoplastic resin, and cannot be used as the thermoplastic elastomer mentioned above, but rather a rubber composition as an elastomeric composition. It had no elasticity. (Problems to be Solved by the Invention) Although the elastomeric composition of the hydrogenated block copolymer obtained by the above proposal has excellent rubber elasticity (compression set) at 70°C, the rubber elasticity at 100°C is 70°C. % or more, and does not reach the level of compression set at high temperatures conventionally required for vulcanized rubber applications, and although it has the recyclable moldability that is a characteristic of thermoplastic elastomers, it is inferior to rubber at high temperatures. The current situation is that the characteristics are still insufficient, and this has been taken for granted. (Means for Solving the Problems) The present invention has been made to solve the problems that are difficult to solve with the conventional elastomer molding materials described above, and in particular, the processability as a thermoplastic elastomer, recycling moldability, etc. This was done based on the desire for a molding material that could satisfy both properties of rubber elasticity and rubber elasticity at high temperatures (compression set at 100℃), which had not been achieved before. The inventors have found that this can be fully achieved by selecting an elastomeric composition, and have further discovered that it is a practically useful composition. That is, the present invention comprises (1) (a) a terminal polymer block A mainly composed of at least two vinyl aromatic compounds and an intermediate polymer block B mainly composed of at least one conjugated diene compound; Hydrogenated block copolymer a obtained by hydrogenating block copolymer 100 parts by weight (b) General formula (Here, R 1 , R 2 , R 3 and R 4 each represent a substituent selected from the group consisting of hydrogen, halogen, and hydrocarbon group, and may be the same or different.) Polyphenylene ether resin b, which is a homopolymer and/or copolymer, is composed of bonding units of tea/b=
90/10 to 30/70 (weight ratio) (c) Consists of 10 to 300 parts by weight of a softener for non-aromatic rubber, and has a compression set (100℃ x 22 hours).
A highly elastic hydrogenated block copolymer composition having a performance of 65% or less, comprising 5 to 100 parts by weight of the polyolefin resins (a), (b), (c) and (d), is compressed. Permanent deformation (100℃ x 22 hours)
Further embodiments of the highly elastic hydrogenated block copolymer composition having a performance of 65% or less include the above-mentioned (a), (b),
(c), (d) and (e) Contains 20 to 300 parts by weight of inorganic filler, and has a compression set (100℃ x 22 hours).
A highly elastic hydrogenated block copolymer composition having a performance of 65% or less, further comprising 20 to 300 parts by weight of the above-mentioned (a), (b), (c) and (e) inorganic filler, is compressed. Permanent deformation (100℃ x 22 hours)
The present invention provides highly elastic hydrogenated block copolymer compositions having a performance of 65% or less. The present invention will be described in detail below. In the present invention, compression set (100°C x 22 hours)
is the high temperature compression set as a rubber elastic body,
According to JIS-K6301, 100℃ x 22 hours, compression rate 25%
This value was measured under the following conditions. The hydrogenated block copolymer used as component (a) in the present invention consists of a terminal polymer block A mainly composed of at least two vinyl aromatic compounds and an intermediate polymer block A mainly composed of at least one conjugated diene compound. It is obtained by hydrogenating a block copolymer consisting of a combined block B, for example, A-B-
A, (A-B-) 4 Si, A-B-A-B-A, (A-
B-) It is a hydrogenated vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as Si-CH 3 . This hydrogenated block copolymer contains 5 to 60% by weight, preferably 10 to 50% by weight of a vinyl aromatic compound, and furthermore, referring to the block structure, the terminal polymer block A mainly composed of a vinyl aromatic compound is , vinyl aromatic compound polymer block or vinyl aromatic compound 50
It has a structure of a copolymer block of a vinyl aromatic compound containing more than 70% by weight and preferably 70% by weight or more and a hydrogenated conjugated diene compound,
Furthermore, the intermediate polymer block B mainly composed of a hydrogenated conjugated diene compound contains more than 50% by weight of the hydrogenated conjugated diene compound polymer block or preferably 70% by weight of the hydrogenated conjugated diene compound. % or more of a hydrogenated conjugated diene compound and a vinyl aromatic compound. In addition, the terminal polymer block A mainly consists of these vinyl aromatic compounds and the intermediate polymer block B mainly consists of hydrogenated conjugated diene compounds. The distribution of the conjugated diene compound or vinyl aromatic compound is random, tapered (the monomer component increases or decreases along the molecular chain),
It may be partially block-shaped or in any combination thereof, and there may be two polymer blocks each consisting mainly of the vinyl aromatic compound and two polymer blocks mainly consisting of the hydrogenated conjugated diene compound. In the case where there are more than one, each polymer block may have the same structure or may have a different structure. As the vinyl aromatic compound constituting the hydrogenated block copolymer, one or more types can be selected from, for example, styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc.
Among them, styrene is preferred. Further, examples of the conjugated diene compound before hydrogenation constituting the hydrogenated conjugated diene compound include butadiene, isoprene, 3-pentadiene, 2,3-dimethyl-
One or more types are selected from 1,3-butadiene and the like, and among them, butadiene, isoprene, and a combination thereof are preferred. The microstructure of a polymer block mainly composed of a conjugated diene compound before hydrogenation can be arbitrarily selected; for example, in a polybutadiene block, the 1,2-microstructure is 20 to 50%.
%, preferably 25-45%. Further, the number average molecular weight of the hydrogenated block copolymer used in the present invention having the above structure is 5000 to 5000.
1000000, preferably 10000 to 800000, more preferably 30000 to 500000, and the molecular weight distribution [weight average molecular weight () and number average molecular weight ()
(Mw/Mn)] is 10 or less. Furthermore, the molecular structure of the hydrogenated block copolymer may be linear, branched, radial, or any combination thereof. These block copolymers may be produced by any method as long as they have the above structure. For example, a vinyl aromatic compound-conjugated diene compound block copolymer is synthesized in an inert solvent using a lithium catalyst or the like by the method described in Japanese Patent Publication No. 40-23798, and then, for example,
By the method described in Japanese Patent Publication No. 8704, Japanese Patent Publication No. 43-6636, or Japanese Patent Application Publication No. 59-133203,
The hydrogenated block copolymer used in the present invention can be synthesized by hydrogenation in an inert solvent in the presence of a hydrogenation catalyst. In this case, the number of aliphatic double bonds based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer is at least 80.
% can be hydrogenated to morphologically convert a polymer block mainly composed of a conjugated diene compound into an olefinic compound polymer block. In addition, hydrogenation of aromatic double bonds based on vinyl aromatic compounds copolymerized into polymer block A mainly composed of vinyl aromatic compounds and, if necessary, polymer block B mainly composed of conjugated diene compounds. Although there is no particular restriction on the hydrogenation rate, it is preferable that the hydrogenation rate is 20% or less. The amount of unhydrogenated aliphatic double bonds contained in the hydrogenated block copolymer can be easily determined using an infrared spectrophotometer, nuclear magnetic resonance apparatus, or the like. Next, the polyphenylene ether resin used as component (b) of the present invention is an essential component for improving the compression set (100°C x 22 hours) of the resulting composition to 65% or less, and its molecular The bonding unit of the chain is a general formula (Here, R 1 , R 2 , R 3 and R 4 each represent a substituent selected from the group consisting of hydrogen, halogen, and hydrocarbon group, and may be the same or different.) is a combination and or copolymer
The reduced viscosity measured at 30° C. in a 0.5 g/dl chloroform solution is in the range of 0.15 to 0.70, more preferably in the range of 0.20 to 0.60. As this polyphenylene ether resin, known ones can be used. A specific example is poly(2,6-dimethyl-
1,4-phenylene ether, poly(2-methyl-6ethyl-1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene)
Ether, poly(2-methyl-6-phenyl-
1,4-phenylene)ether, poly(2,6-
Dichloro-1,4-phenylene) ether, etc., and 2,6-dimethylphenol and other phenols (e.g. 2,3,6-trimethylphenol and 2-methyl-6-butylphenol)
Also included are polyphenylene ether copolymers such as copolymers with. Among them, poly(2,6-dimethyl-1,4-phenylene) ether, 2,6
A copolymer of -dimethylphenol and 2,3,6-trimethylphenol is preferred, and poly(2,6-dimethyl-1,4-phenylene) ether is more preferred. Poly(2,6-dimethyl-1,4-
reduced viscosity (0.5 g/dl,
(chloroform solution, measured at 30°C) preferably ranges from 0.15 to 0.70, more preferably from 0.30 to 0.70.
It is in the range of 0.60. The amount of component (b) to be blended can be suitably selected so that the weight ratio of component (a) hydrogenated block copolymer/component (b) polyphenylene ether is in the range of 90/10 to 30/70. . If the weight ratio is less than 30/70, the hardness of the resulting elastomeric composition will be too high, resulting in a loss of flexibility and resulting in a resinous composition, which will not only result in a product with a rubbery feel, but also be difficult to handle at high temperatures. The rubber elasticity [compression set (100°C x 22 hours)] exceeds 65%, which is unfavorable. Furthermore, in a formulation where the weight ratio exceeds 90/10, no improvement in rubber elasticity (compression set) at high temperatures is observed as an effect of adding polyphenylene ether, which is not preferred). The rubber softener used as component (c) in the present invention is an essential component for making the resulting composition into a flexible rubber-like composition, and is a non-aromatic mineral oil, liquid or low molecular weight synthetic rubber softener. Softeners are suitable. Among these, mineral oil-based rubber softeners, called process oils or extender oils, which are generally used to soften, increase volume, and improve processability of rubber, are mixtures of aromatic rings, naphthenic rings, and paraffin chains. Those in which the number of carbon atoms in the paraffin chain accounts for 50% or more of the total carbons are called paraffin series, and the number of carbon atoms in the naphthene ring is 30 to 45%.
Those are naphthenic, and the number of aromatic carbons is 30%.
Those with a larger amount are considered aromatic. Components of the invention
The mineral oil-based rubber softener used as (c) is preferably a naphthene-based or paraffin-based one in the above category, and an aromatic one with an aromatic carbon number of 30% or more is the same as component (a). The composition is unfavorable in terms of dispersibility and solubility. The properties of these non-aromatic rubber softeners include a kinematic viscosity of 20 to 500 cst at 37.8°C, a pour point of -10 to -15°C, and a flash point of 170 to 300°C. As the synthetic softener, polybutene, low molecular weight polybutadiene, etc. can be used, but the above-mentioned mineral oil-based softeners for rubber give better results. The amount of the softener (component (c)) is 10 to 300 parts by weight, preferably 20 parts by weight, per 100 parts by weight of component (a).
~250 parts by weight. If the amount exceeds 300 parts by weight, the softener tends to bleed out, which may result in stickiness in the final product and also deteriorate mechanical properties. If the amount is less than 10 parts by weight, the resulting composition becomes close to a resin composition, increases in hardness, loses flexibility, and is also unfavorable from an economic point of view. Next, the polyolefin resin used as component (d) of the present invention is effective in improving the processability and/or heat resistance of the resulting composition, such as polyethylene, isotactic polypropylene,
Copolymers of propylene and small amounts of other α-olefins, such as propylene-ethylene copolymers, propylene-1-hexene copolymers, propylene-4
-Methyl-1-pentene copolymer and poly-4-
Examples include methyl-1-pentene and polybutene-1. MFR when using polypropylene as the olefin resin used
(ASTM-D-1238-L conditions, 230℃) is 0.1 to 50
g/10 minutes, particularly preferably in the range of 0.5 to 30 g/10 minutes. The blending amount of component (d) is 5 parts per 100 parts by weight of component (a).
-100 parts by weight, preferably 10-70 parts by weight. If the amount exceeds 100 parts by weight, the hardness of the resulting elastomeric composition becomes too high, resulting in a loss of flexibility and a product with a rubbery feel. (distortion) becomes extremely bad, which is undesirable. Furthermore, when the amount is less than 5 parts by weight, the polyolefin resin exhibits the same processability as the composition of the present invention to which it is not added. Furthermore, as an example of an embodiment of the present invention, the inorganic filler used as component (e) not only has the benefit of reducing product cost as an extender, but also has the advantage of actively improving quality (compression set, etc.). Add effect. Examples of inorganic fillers include calcium carbonate,
Carbon black, talc, magnesium hydroxide, mica, clay, barium sulfate, natural silicic acid, synthetic silicic acid (white carbon), titanium oxide, etc. are available, and as carbon black, channel black, furnace black, etc. can be used. Among these inorganic fillers, talc, calcium carbonate and furnace black are economically advantageous and preferred. It is also possible to add a conductive filler to impart conductivity; for example, conductive carbon such as ketchen black may be used. The blending amount of the inorganic filler is 20 to 300 parts by weight per 100 parts by weight of the hydrogenated block copolymer of component (a),
Preferably it is 30 to 250 parts by weight. When the amount exceeds 300 parts by weight, the mechanical strength of the composition decreases significantly, and the hardness increases and flexibility is lost.
It becomes impossible to obtain a product with a rubbery feel. Furthermore, when the amount is less than 20 parts by weight, the composition exhibits the same performance as the composition of the present invention obtained when the inorganic filler is not added. If necessary, flame retardants, glass fibers, carbon fibers, antioxidants, heat stabilizers, ultraviolet absorbers, hindered amine light stabilizers, and colorants can be added to the highly elastic elastomeric composition of the present invention. As a method for compounding the highly elastic elastomeric composition of the present invention, methods used in the production of ordinary resin compositions or rubber compositions can be adopted, such as a single screw extruder, a twin screw extruder, a Banbury mixer, Composite composition can be performed using a melt kneader such as a heating roll, Brabender, or various kneaders. At this time, there is no restriction on the order of addition of each component,
For example, all components are premixed in a mixer such as a Henschel mixer or a blender, premixed in the above-mentioned kneading machine, and melted and composited in the abovementioned kneading machine, or arbitrary components are premixed and melted and composited in a master batch.
Furthermore, an addition method such as adding the remaining components and melting and compounding them can be adopted. The composite composition of the present invention can be molded using a commonly used thermoplastic resin molding machine, and various molding methods such as injection molding, extrusion molding, blow molding, and calendar molding can be applied. It is possible. (Effects of the Invention) The composition obtained by the present invention has excellent flexibility, heat resistance, mechanical strength, and rubber elasticity at high temperatures, as well as excellent coating properties and electrical insulation properties during molding processing. Its fields of use include various electric wire coatings (insulation, sheathing), making use of its high rubber elasticity,
It can be suitably molded and used for home appliance parts, automobile parts, and various industrial parts. Specific applications include various gaskets, flexible tubes, hose coverings, weather strips, flexible bumpers, side bumpers, moldings, filler panels,
Includes life housing, wire cable covering, air intake hose, cushion panel, etc. (Examples) The present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, in these Examples and Comparative Examples,
The test methods used for various evaluations are as follows. (1) Hardness [-] JIS-K6301, A type (2) Tensile strength [Kg/cm 2 ] and tensile elongation [%] JIS-K-6301, test using a 2 mm thick in-die extension sheet as a sample. The piece is size 3. (3) Compression set [%] JIS-K-6301, 70℃ and 100℃ 22 hours, 25
% deformation. The ingredients blended are as follows. (1) <Component (a-1)> Polystyrene-hydrogenated polybutadiene-polystyrene structure, bound styrene content 27%, number average molecular weight 157000, molecular weight distribution
1.07, a hydrogenated block copolymer with a 1,2 bond content of polybutadiene before hydrogenation of 34% and a hydrogenation rate of 98% was synthesized using a Ti-based hydrogenation catalyst described in JP-A-59-133203, It was designated as component (a-1). <Component (a-2)> (Polystyrene - hydrogenated polybutadiene) Has a structure of 4 Si, with a bound styrene content of 36%,
A hydrogenated block copolymer with a number average molecular weight of 379,000, a molecular weight distribution of 1.35, a 1,2 bond content of polybutadiene before hydrogenation of 27%, and a hydrogenation rate of 99% was produced in JP-A-59-
Synthesized using the Ti-based hydrogenation catalyst described in No. 133203,
It was designated as component (a-2). <Ingredient (a-3)> KRATON-G1651 manufactured by Ciel Chemical Co., Ltd. <Ingredient (a-4)> KRATON-G1650 manufactured by Ciel Chemical Company (2) Ingredient (b) Diana Process Oil PW manufactured by Idemitsu Norisan Co., Ltd.
380 [paraffinic, kinematic viscosity; 381.6cst (40℃),
30.1cst (10℃), average molecular weight 746, ring analysis; C N =
27%, C P = 73%] (3) Component (c) Polypropylene resin manufactured by Asahi Kasei Co., Ltd., M-1300
[MFR (230℃) 4g/10 minutes] (4) Component (d) Calcium carbonate manufactured by Shiraishi Calcium Co., Ltd., Whitein SB (5) Component (e) Poly(2,6-dimethyl-) as polyphenylene ether resin 1,4-phenylene) ether (reduced viscosity: 0.37, 0.57) was synthesized. Examples 1 to 6 Hydrogenated block copolymers (a-1) to (a
-3) and polyphenylene ether with a reduced viscosity of 0.57. After mixing each component shown in Table-1 in a Henschel mixer, melt-knead at 250℃ in a 50 mm diameter twin screw extruder. Pellets of thermoplastic elastomer were obtained. This was evaluated as an injection molded product, and the results are listed in Table 1. From these results, it is clear that the elastomeric composition of the present invention has a compression set of 50% or less at 100°C and is excellent in rubber elasticity at high temperatures. Furthermore, these compositions also had excellent moldability.
【表】
比較例 1〜7
水添ブロツク共重合体として(a―1)〜(a
―3)を用い、またポリフエニレンエーテルとし
て還元粘度0.57のものを用い、表2に示す各成分
を実施例1〜6と同様の方法で混練し、さらに成
形して評価した。結果を表2に載せた。
この結果から、本発明の範囲外の組成物は、70
℃の圧縮永久歪に優れるものの、100℃の圧縮永
久歪は極度に悪化し、高温時のゴム弾性に劣るこ
とが明らかとなつた。また市販の水添ブロツク共
重合体のエラストマー状組成物であるKRATON
―G2705、G―7720、G―7820(いずれもシエ
ル・ケミカル社製)は組成は不明だが、100℃の
圧縮永久歪は悪く、高温時のゴム弾性に劣ること
が明らかとなつた。[Table] Comparative Examples 1 to 7 Hydrogenated block copolymers (a-1) to (a
-3) and a polyphenylene ether with a reduced viscosity of 0.57, the components shown in Table 2 were kneaded in the same manner as in Examples 1 to 6, and further molded and evaluated. The results are listed in Table 2. From this result, it can be seen that compositions outside the scope of the present invention have a
Although it has excellent compression set at 100°C, it has become clear that the compression set at 100°C is extremely poor and its rubber elasticity at high temperatures is poor. Additionally, KRATON is a commercially available elastomeric composition of hydrogenated block copolymers.
- Although the composition of G2705, G-7720, and G-7820 (all manufactured by Ciel Chemical) is unknown, it has been revealed that the compression set at 100°C is poor and the rubber elasticity at high temperatures is poor.
【表】【table】
【表】
実施例7〜9比較例8〜10
水添ブロツク共重合体として(a―4)を用
い、またポリフエニレンエーテルとして還元粘度
が0.37のものを用い、表3に示す各成分を実施例
1〜6と同様の方法で混練し、さらに成形して評
価した。結果を表3に載せた。
この結果から、(a―4)を用いた水添ブロツ
ク共重合体組成物(比較例8〜10)は70℃の圧縮
永久歪が極度に悪化しているのにもかかわらず、
ポリフエニレンエーテルを添加した本発明の水添
ブロツク共重合体組成物は、70℃の圧縮永久歪お
よび100℃の圧縮永久歪が大巾に改善され、高温
時のゴム弾性が改良されていることが明らかとな
つた。[Table] Examples 7 to 9 Comparative Examples 8 to 10 Using (a-4) as the hydrogenated block copolymer and having a reduced viscosity of 0.37 as the polyphenylene ether, each component shown in Table 3 was added. The mixture was kneaded in the same manner as in Examples 1 to 6, and then molded and evaluated. The results are listed in Table 3. From this result, even though the hydrogenated block copolymer compositions (Comparative Examples 8 to 10) using (a-4) had extremely deteriorated compression set at 70°C,
The hydrogenated block copolymer composition of the present invention to which polyphenylene ether is added has greatly improved compression set at 70°C and compression set at 100°C, and has improved rubber elasticity at high temperatures. It became clear.
【表】
実施例 10
水添ブロツク共重合体として(a―1)を用
い、ポリフエニレンエーテル樹脂として、2,
3,6―トリメチルフエノールを5%含む2,6
―ジメチルフエノールを重合し、2,6―ジメチ
ルフエノール/2,3,6―トリメチルフエノー
ル共重合体(還元粘度0.51)を得て用いたほか
は、実施例4と同じ配合でテストピースを作り、
評価したところ、硬度75、孔張強度180Kg/cm2、
伸び390%、圧縮永久歪(100℃×22HRS)38%
の特性を有する高弾性な水添ブロツク共重合体組
成物が得られた。
実施例 11
ポリスチレン―ポリ(スチレン/ブタジエン=
10/90重量%)―ポリ(スチレン/ブタジエン=
10/90重量%)―ポリ(スチレン/ブタジエン=
10/90重量%)―ポリスチレンの構造を有し、該
ポリ(スチレン/ブタジエン=10/90重量%)部
分でスチレンが漸増するテーパーブロツクを3個
有する全結合スチレン量37%、ブロツクスチレン
量30%、数平均分子量156000、分子量分布1.05、
1,2結合量が35%のブロツク共重合体を合成
し、さらに特開昭59―133203号公報に記載された
Ti系水添触媒で水素添加反応を行ない、水添率
99%の水添ブロツク共重合体を得た。
この水添ブロツク共重合体を用いたほかは実施
例5と同様の組成で配合し、同様の混練、射出成
形し評価したところ、硬度74、引張強度100Kg/
cm2、伸び400%、圧縮永久歪(100℃×22HRS)
42%の特性を有する高弾性な水添ブロツク共重合
体組成物が得られた。[Table] Example 10 (a-1) was used as the hydrogenated block copolymer, 2,
2,6 containing 5% 3,6-trimethylphenol
-A test piece was made with the same formulation as in Example 4, except that dimethylphenol was polymerized to obtain a 2,6-dimethylphenol/2,3,6-trimethylphenol copolymer (reduced viscosity 0.51).
When evaluated, the hardness was 75, the pore tensile strength was 180Kg/cm 2 ,
Elongation 390%, compression set (100℃×22HRS) 38%
A highly elastic hydrogenated block copolymer composition having the following properties was obtained. Example 11 Polystyrene-poly(styrene/butadiene=
10/90% by weight) - poly(styrene/butadiene =
10/90% by weight) - poly(styrene/butadiene =
10/90% by weight) - has a polystyrene structure, and has three tapered blocks in which styrene gradually increases in the poly(styrene/butadiene = 10/90% by weight) part, with a total bound styrene content of 37% and a block styrene content of 30%. %, number average molecular weight 156000, molecular weight distribution 1.05,
A block copolymer with a 1,2 bond content of 35% was synthesized, and was further described in JP-A-59-133203.
A hydrogenation reaction is carried out using a Ti-based hydrogenation catalyst, and the hydrogenation rate is
A 99% hydrogenated block copolymer was obtained. Except for using this hydrogenated block copolymer, it was blended with the same composition as in Example 5, kneaded and injection molded in the same manner, and evaluated. The hardness was 74, and the tensile strength was 100 kg/
cm2 , elongation 400%, compression set (100℃×22HRS)
A highly elastic hydrogenated block copolymer composition with properties of 42% was obtained.
Claims (1)
主体とする末端重合体ブロツクAと、少なくと
も1個の共役ジエン化合物を主体とする中間重
合体ブロツクBとからなるブロツク共重合体を
水素添加して得られる水添ブロツク共重合体
a100重量部 (b) 一般式 (ここで、R1,R2,R3およびR4はそれぞ
れ、水素、ハロゲン、炭化水素基からなる群か
ら選択される置換基を表わし互に同一でも異つ
てもよい) で示される結合単位からなり0.5g/dlクロロ
ホルム溶液において30℃で測定された還元粘度
が0.15〜0.70の範囲にあるホモ重合体およびま
たは共重合体であるポリフエニレンエーテル樹
脂bが前記aに対してa/b=90/10〜30/70
(重量比) (c) 非芳香族系ゴム用軟化剤10〜300重量部から
成り、圧縮永久歪(100℃×22時間)が65%以
下の性能を有する高弾性な水添ブロツク共重合
体組成物。 2 (a) 少なくとも2個のビニル芳香族化合物を
主体とする末端重合体ブロツクAと、少なくと
も1個の共役ジエン化合物を主体とする中間重
合体ブロツクBとからなるブロツク共重合体を
水素添加して得られる水添ブロツク共重合体
a100重量部 (b) 一般式 (ここで、R1,R2,R3およびR4はそれぞ
れ、水素、ハロゲン、炭化水素基からなる群か
ら選択される置換基を表わし互に同一でも異つ
てもよい) で示される結合単位からなり、0.5g/dlクロ
ロホルム溶液において30℃で測定された還元粘
度が0.15〜0.70の範囲にあるホモ重合体および
または共重合体であるポリフエニレンエーテル
樹脂bが前記aに対してa/b=90/10〜30/
70(重量比) (c) 非芳香族系ゴム用軟化剤10〜300重量部 (d) ポリオレフイン系樹脂5〜100重量部から成
り、圧縮永久歪(100℃×22時間)が65%以下
の性能を有する高弾性な水添ブロツク共重合体
組成物。[Scope of Claims] 1 (a) A block combination consisting of a terminal polymer block A mainly composed of at least two vinyl aromatic compounds and an intermediate polymer block B mainly composed of at least one conjugated diene compound. Hydrogenated block copolymer obtained by hydrogenating a polymer
a100 parts by weight (b) General formula (Here, R 1 , R 2 , R 3 and R 4 each represent a substituent selected from the group consisting of hydrogen, halogen, and hydrocarbon group, and may be the same or different.) Polyphenylene ether resin b, which is a homopolymer and/or copolymer and has a reduced viscosity in the range of 0.15 to 0.70 measured in a 0.5 g/dl chloroform solution at 30°C, is a/b for the above a/b. =90/10~30/70
(Weight ratio) (c) A highly elastic hydrogenated block copolymer consisting of 10 to 300 parts by weight of a non-aromatic rubber softener and having a compression set (100°C x 22 hours) of 65% or less. Composition. 2 (a) Hydrogenating a block copolymer consisting of a terminal polymer block A mainly composed of at least two vinyl aromatic compounds and an intermediate polymer block B mainly composed of at least one conjugated diene compound. Hydrogenated block copolymer obtained by
a100 parts by weight (b) General formula (Here, R 1 , R 2 , R 3 and R 4 each represent a substituent selected from the group consisting of hydrogen, halogen, and hydrocarbon group, and may be the same or different.) Polyphenylene ether resin b, which is a homopolymer and/or copolymer, has a reduced viscosity in the range of 0.15 to 0.70 measured in a 0.5 g/dl chloroform solution at 30°C, and has a/ b=90/10~30/
70 (weight ratio) (c) 10 to 300 parts by weight of a non-aromatic rubber softener (d) 5 to 100 parts by weight of a polyolefin resin, with a compression set (100°C x 22 hours) of 65% or less A highly elastic hydrogenated block copolymer composition with excellent performance.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16296485A JPS6225149A (en) | 1985-07-25 | 1985-07-25 | Highly elastic hydrogenated block copolymer composition |
EP86109956A EP0209874B2 (en) | 1985-07-19 | 1986-07-18 | Hydrogenated block copolymer compositions |
ES8600373A ES2001020A6 (en) | 1985-07-19 | 1986-07-18 | Hydrogenated block copolymer compositions. |
DE8686109956T DE3675095D1 (en) | 1985-07-19 | 1986-07-18 | HYDRATED BLOCK COPOLYMER COMPOSITIONS. |
US06/886,601 US4772657A (en) | 1985-07-19 | 1986-07-18 | Hydrogenated block copolymer compositions |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16296485A JPS6225149A (en) | 1985-07-25 | 1985-07-25 | Highly elastic hydrogenated block copolymer composition |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2308611A Division JPH0670162B2 (en) | 1990-11-16 | 1990-11-16 | Highly elastic hydrogenated block copolymer composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6225149A JPS6225149A (en) | 1987-02-03 |
JPH0149423B2 true JPH0149423B2 (en) | 1989-10-24 |
Family
ID=15764625
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP16296485A Granted JPS6225149A (en) | 1985-07-19 | 1985-07-25 | Highly elastic hydrogenated block copolymer composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6225149A (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63251457A (en) * | 1987-04-06 | 1988-10-18 | Asahi Chem Ind Co Ltd | Polyphenylene ether resin composition |
JP2727190B2 (en) * | 1988-03-18 | 1998-03-11 | 旭化成工業株式会社 | Block copolymer composition |
JP2754723B2 (en) * | 1989-05-19 | 1998-05-20 | ジェイエスアール株式会社 | Hydrogenated diene copolymer and composition thereof |
JP2764746B2 (en) * | 1989-05-19 | 1998-06-11 | ジェイエスアール株式会社 | Hydrogenated diene copolymer, modified hydrogenated diene copolymer and composition thereof |
JP4574150B2 (en) * | 2003-09-19 | 2010-11-04 | Sabicイノベーティブプラスチックスジャパン合同会社 | Resin composition with excellent flexibility |
WO2009125623A1 (en) * | 2008-04-09 | 2009-10-15 | 住友電気工業株式会社 | Flame-retardant tube and heat-shrinkable tube made by using the same |
JP6368189B2 (en) * | 2014-08-07 | 2018-08-01 | 旭化成株式会社 | A mixture having no stickiness and excellent long-term storage stability, a method for mixing the mixture, and a method for producing a thermoplastic resin composition by melt-kneading the mixture |
CN109312132B (en) * | 2016-07-04 | 2020-04-24 | 住友橡胶工业株式会社 | Rubber composition |
US11453773B2 (en) | 2017-01-24 | 2022-09-27 | Asahi Kasei Kabushiki Kaisha | Thermoplastic elastomer composition, plug body and container |
JP7017293B2 (en) * | 2020-06-12 | 2022-02-08 | 三菱ロジスネクスト株式会社 | Vehicle approach notification device and forklift equipped with the device |
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JPS5371158A (en) * | 1976-12-03 | 1978-06-24 | Gen Electric | Polyphenylene ether and styrene resin preblended polymer composition and composition of block copolymer of vinyl aromatic compound and olefinntype elastomer |
JPS5373248A (en) * | 1976-12-13 | 1978-06-29 | Gen Electric | Flame retardant shockkresistant polyphenylene ether compound |
JPS5488960A (en) * | 1977-10-03 | 1979-07-14 | Gen Electric | Highhimpact thermoplastic composition |
US4313864A (en) * | 1980-01-21 | 1982-02-02 | General Electric Company | Polyphenylene oxide/plasticizer/hydrogenated radial teleblock copolymer blends |
US4322507A (en) * | 1980-03-13 | 1982-03-30 | General Electric Company | Molded article of polyphenylene ether and hydrogenated block copolymer |
JPS58103557A (en) * | 1981-12-01 | 1983-06-20 | ゼネラル・エレクトリツク・カンパニイ | Polyphenylene ether resin composition containing large quantity of polyolefin |
JPS58141233A (en) * | 1982-02-16 | 1983-08-22 | Asahi Chem Ind Co Ltd | Thermoplastic polymer composition |
JPS6076547A (en) * | 1983-07-29 | 1985-05-01 | ゼネラル・エレクトリツク・カンパニイ | Polyphenylene ether resin composition containing large quantity of polyolefin |
US4529652A (en) * | 1983-05-04 | 1985-07-16 | General Electric Company | Flame retardant polyphenylene ether composition |
-
1985
- 1985-07-25 JP JP16296485A patent/JPS6225149A/en active Granted
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5071742A (en) * | 1973-08-13 | 1975-06-13 | ||
JPS5371158A (en) * | 1976-12-03 | 1978-06-24 | Gen Electric | Polyphenylene ether and styrene resin preblended polymer composition and composition of block copolymer of vinyl aromatic compound and olefinntype elastomer |
JPS5373248A (en) * | 1976-12-13 | 1978-06-29 | Gen Electric | Flame retardant shockkresistant polyphenylene ether compound |
JPS5488960A (en) * | 1977-10-03 | 1979-07-14 | Gen Electric | Highhimpact thermoplastic composition |
US4166055A (en) * | 1977-10-03 | 1979-08-28 | General Electric Company | Composition of a polyphenylene ether, a block copolymer of a vinyl aromatic compound and a conjugated diene and a polyolefin |
US4313864A (en) * | 1980-01-21 | 1982-02-02 | General Electric Company | Polyphenylene oxide/plasticizer/hydrogenated radial teleblock copolymer blends |
US4322507A (en) * | 1980-03-13 | 1982-03-30 | General Electric Company | Molded article of polyphenylene ether and hydrogenated block copolymer |
JPS58103557A (en) * | 1981-12-01 | 1983-06-20 | ゼネラル・エレクトリツク・カンパニイ | Polyphenylene ether resin composition containing large quantity of polyolefin |
JPS58141233A (en) * | 1982-02-16 | 1983-08-22 | Asahi Chem Ind Co Ltd | Thermoplastic polymer composition |
US4529652A (en) * | 1983-05-04 | 1985-07-16 | General Electric Company | Flame retardant polyphenylene ether composition |
JPS6076547A (en) * | 1983-07-29 | 1985-05-01 | ゼネラル・エレクトリツク・カンパニイ | Polyphenylene ether resin composition containing large quantity of polyolefin |
Also Published As
Publication number | Publication date |
---|---|
JPS6225149A (en) | 1987-02-03 |
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