JPH01229063A - Elastomer composition having thermoplasticity - Google Patents
Elastomer composition having thermoplasticityInfo
- Publication number
- JPH01229063A JPH01229063A JP5501388A JP5501388A JPH01229063A JP H01229063 A JPH01229063 A JP H01229063A JP 5501388 A JP5501388 A JP 5501388A JP 5501388 A JP5501388 A JP 5501388A JP H01229063 A JPH01229063 A JP H01229063A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogenated
- block copolymer
- conjugated diene
- copolymer
- rubber
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 229920001971 elastomer Polymers 0.000 title claims abstract description 30
- 239000000806 elastomer Substances 0.000 title description 2
- 229920001400 block copolymer Polymers 0.000 claims abstract description 50
- -1 vinyl aromatic compounds Chemical class 0.000 claims abstract description 44
- 239000005060 rubber Substances 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 23
- 229920001577 copolymer Polymers 0.000 claims abstract description 22
- 150000002825 nitriles Chemical class 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 7
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 abstract description 11
- 238000009826 distribution Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 5
- 150000001993 dienes Chemical class 0.000 abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 27
- 238000000034 method Methods 0.000 description 17
- 239000003921 oil Substances 0.000 description 15
- 238000005984 hydrogenation reaction Methods 0.000 description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 239000005062 Polybutadiene Substances 0.000 description 8
- 229920002857 polybutadiene Polymers 0.000 description 8
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 229920000459 Nitrile rubber Polymers 0.000 description 6
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- DDXZFLFMKZXQOT-UHFFFAOYSA-N 2-fluoroprop-2-enenitrile Chemical compound FC(=C)C#N DDXZFLFMKZXQOT-UHFFFAOYSA-N 0.000 description 1
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- 238000003462 Bender reaction Methods 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920006170 Therban® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-ARJAWSKDSA-N angelic acid Chemical compound C\C=C(\C)C(O)=O UIERETOOQGIECD-ARJAWSKDSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- ILUAAIDVFMVTAU-UHFFFAOYSA-N cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CC=CCC1C(O)=O ILUAAIDVFMVTAU-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、水癌ブロック共重合体又は該変性物とα、β
−不飽和不飽和シトリルー共役ジエン共重合体又はその
水素添加物からなる、機械的特性に優れ、かつゴム弾性
・耐候性・耐熱性・耐油性に優ねた新規な熱可塑性エラ
ストマー組成物に関するものである。Detailed Description of the Invention (Industrial Field of Application) The present invention provides a water block copolymer or a modified product thereof and α, β
-Relating to a novel thermoplastic elastomer composition comprising an unsaturated unsaturated citrile-conjugated diene copolymer or its hydrogenated product and having excellent mechanical properties and excellent rubber elasticity, weather resistance, heat resistance, and oil resistance. It is.
（従来の技術及び問題点）
熱可塑性エラストマーは加硫を必要としないゴムとして
、近年、自動車部品・家電部品・履物・電線被榎・雑貨
等の分野で使用式れている。(Prior Art and Problems) Thermoplastic elastomers, as rubbers that do not require vulcanization, have recently been used in fields such as automobile parts, home appliance parts, footwear, electric wire coverings, and miscellaneous goods.
このうちスチレン系熱可塑性エラストマー、例エバスチ
レンーブタジェンブロック共重合体やスチレン−イソプ
レンブロック共重合体及びこれらのブロック共重合体の
水素添加物は、柔軟性に富み、常温で良好なゴム弾性を
有するため、粘接着剤・シーラントや熱可塑性樹脂との
コンパウンド等にも幅広く用いられている。Among these, styrenic thermoplastic elastomers, such as evastyrene-butadiene block copolymers, styrene-isoprene block copolymers, and hydrogenated products of these block copolymers, are highly flexible and have good rubber elasticity at room temperature. Because of this, it is widely used in adhesives, sealants, and compounds with thermoplastic resins.
しかし、このスチレン系熱可塑性エラストマーは、スチ
レン相の凝集による物理的架橋によって、そのゴム的性
質を持ち、スチレンのガラス転移点（約１００℃）を超
える温度では流動が生じてしま５ため、一般にはその温
度を超える環境での使用は困難であった。However, this styrenic thermoplastic elastomer has rubbery properties due to physical crosslinking caused by agglomeration of the styrene phase, and flows at temperatures exceeding the glass transition point of styrene (approximately 100°C)5, so it is generally not used. It was difficult to use it in environments exceeding that temperature.
又、このスチレン系熱可塑性エラストマーは、一般的に
は、炭化水素溶媒中での溶液１合で合成されることから
も明らかなように、オイル・ガソリン等の炭化水素系溶
剤に対する耐性に劣っていた。In addition, this styrene thermoplastic elastomer is generally synthesized in a single solution in a hydrocarbon solvent, and as is clear from this, it has poor resistance to hydrocarbon solvents such as oil and gasoline. Ta.
これらの改良方法としては、スチレン系熱可塑性エンス
トマーに、耐熱性・耐油性に優れる熱可塑性樹脂を混合
する方法（特開昭５８−７４４３号、特開昭５９−２７
９４２号、特開昭５９−２７９４％公報など）、加硫可
能なゴムを混合し共加硫する方法（％開昭６１−６０７
３９号公報など）等が提案妊れているが、これらによる
と、耐熱性や耐油性は改良されるものの、未だ改良の余
地を残しており、スチレン系熱可塑性エラストマーが本
来保有している良好なゴム弾性や加工性が損なわれる欠
点がある。As a method for improving these, a method of mixing a thermoplastic resin with excellent heat resistance and oil resistance with a styrene thermoplastic entomer (JP-A-58-7443, JP-A-59-27)
No. 942, Japanese Unexamined Patent Publication No. 59-2794, etc.), a method of mixing and co-vulcanizing vulcanizable rubber (Japanese Patent Application Laid-Open No. 61-607)
39 etc.), but according to these, although heat resistance and oil resistance are improved, there is still room for improvement, and the good properties originally possessed by styrene-based thermoplastic elastomers are still left. The disadvantage is that rubber elasticity and processability are impaired.
一方、耐熱性・耐油性が優れるゴムにニトリルゴムがあ
るが、ニトリルゴムを他のゴム（例えば、ＫＰＭ、
ＥＰＤＭＸＥＶＡ ）と混合し加硫することにより、他
のゴムにニトリルゴムの特質、即ち耐熱性や耐油性等を
加える方法（％開昭５８−４０３３２号、特開昭６０−
１１２８３９号、特開昭６１−４０３４２号、特開昭６
１−２８３６３９号公報など）も提案笛れているが、こ
れらは加硫することが不可欠であり、加硫によりはじめ
てゴム弾性が生じる組成物であって、熱可塑性は完全に
失われている欠点がある。On the other hand, nitrile rubber is a rubber with excellent heat resistance and oil resistance, but nitrile rubber can be used with other rubbers (such as KPM,
A method of adding the properties of nitrile rubber, such as heat resistance and oil resistance, to other rubber by mixing it with EPDMXEVA and vulcanizing it (% 1987-40332, 1982-60-
No. 112839, JP-A-61-40342, JP-A-6
1-283639, etc.), but these require vulcanization, and are compositions that only develop rubber elasticity through vulcanization, and the drawback is that thermoplasticity is completely lost. There is.
スチレン系熱可塑性エラストマーとα、β−不飽和二ト
リル含有重合体からなる組成物（特開昭５３−１２４５
５９号、特開昭５３−１３８４５３号公報など）も提案
されているが、この組成物に含まれるα、β−不飽和二
トリル含有重合体は樹脂状重合体であり、この組成物は
ゴム弾性を持たない樹脂である。Composition consisting of styrenic thermoplastic elastomer and α,β-unsaturated nitrile-containing polymer (JP-A-53-1245
59, JP-A No. 53-138453, etc.), but the α,β-unsaturated nitrile-containing polymer contained in this composition is a resinous polymer, and this composition is a rubber-like polymer. It is a resin with no elasticity.
また、スチレン系熱可塑性エラストマーと共役ジエン及
びアクリロニトリルの共重合体から成る熱可塑性エラス
トマー組成物（特開昭４８−８０６４３号公報）も提案
されているが、この組成物にｔｌれる熱可塑性エラスト
マーはポリブタジェン鎖中に不飽和二重結合が存在する
ため、十分な耐候性を期待できない欠点を持つ。また、
この組成物に含まれる共役ジエン−ニトリル共重合体は
、結晶性を持つ樹脂状共重合体であり、この組成物では
スチレン系熱可塑性エラストマーの柔軟性、良好なゴム
弾性等がある程度犠牲になる。Furthermore, a thermoplastic elastomer composition (Japanese Unexamined Patent Application Publication No. 1983-80643) consisting of a styrene-based thermoplastic elastomer and a copolymer of a conjugated diene and acrylonitrile has been proposed, but the thermoplastic elastomer contained in this composition is Due to the presence of unsaturated double bonds in the polybutadiene chain, it has the disadvantage that sufficient weather resistance cannot be expected. Also,
The conjugated diene-nitrile copolymer contained in this composition is a resinous copolymer with crystallinity, and in this composition, the flexibility and good rubber elasticity of the styrenic thermoplastic elastomer are sacrificed to some extent. .
（問題を解決するための手段）
本発明者らは、スチレン系熱可塑性エラストマーの耐熱
性と耐油性を向上させた熱可塑性の組成物を得るべく鋭
意検討した結果、スチレン系熱可塑性エラストマーにニ
トリルゴム又はその水素添加物を加えることで均一な熱
可を性組成物が得られることを見出し、本発明に到達し
た。(Means for Solving the Problem) As a result of intensive studies to obtain a thermoplastic composition that improves the heat resistance and oil resistance of a styrene-based thermoplastic elastomer, the present inventors found that The inventors have discovered that a uniform thermoplastic composition can be obtained by adding rubber or its hydrogenated product, and have arrived at the present invention.
本発明は、スチレン系熱可塑性エラストマー、特に水添
ブロック共重合体又は該変性物にα、β−不飽和不飽和
シトリルー共役ジエン系共重合体ゴム又はその水素添加
物を配合することにより、上記の問題点を解決したもの
である。The present invention provides the above-mentioned method by blending an α,β-unsaturated citri-conjugated diene copolymer rubber or a hydrogenated product thereof into a styrenic thermoplastic elastomer, particularly a hydrogenated block copolymer or a modified product thereof. This problem was solved.
すなわち、本発明は、少なくとも１個のビニル芳香族化
合物を主体とする重合体ブロックＡと、少なくとも１個
の共役ジエン化合物を主体とする重合体ブロックＢより
なるブロック共重合体を水素添加して得られる水添ゾロ
ツク共重合体及び／又はカルボン酸基又はその誘導体基
を含有する該水添ブロック共重合体変性物（Ｉ）と、α
、β−不飽和ニトリル−共役ジエン系共重合体ゴム及び
／又はその水素添加物（ＩＩ）を含有し、（１）／（ｆ
ｆ）の重量比が９５１５〜５０１５０であり、更には、
少なくとも（…）を架橋してなることを特徴とする、機
械的特性に優れ、かつゴム弾性・耐候性・耐熱性・耐油
性に優れた新規な熱可塑性エラストマー組成物を提供す
るものである。That is, the present invention hydrogenates a block copolymer consisting of a polymer block A mainly composed of at least one vinyl aromatic compound and a polymer block B mainly composed of at least one conjugated diene compound. The obtained hydrogenated Zollock copolymer and/or the hydrogenated block copolymer modified product (I) containing a carboxylic acid group or a derivative group thereof, and α
, containing β-unsaturated nitrile-conjugated diene copolymer rubber and/or its hydrogenated product (II), (1)/(f
The weight ratio of f) is 9515 to 50150, and further,
The object of the present invention is to provide a novel thermoplastic elastomer composition which is characterized by being formed by crosslinking at least (...) and has excellent mechanical properties, as well as excellent rubber elasticity, weather resistance, heat resistance, and oil resistance.
以下、本発明に関して祥しく述べる。Hereinafter, the present invention will be described in detail.
かかる（１）成分の一つとして用１ｘ５ろ水添ブロック
共重合体とは、少なくとも１個のビニル芳香族化合物を
主体とする重合体ブロックＡと、少なくとも１個の共役
ジエン化合物を生体とする重合体ブロックＢよりなる構
造を有するブロッ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−Ｂ−Ａ、 Ｂ−
Ａ−Ｂ−Ａ。The 1x5 hydrogenated block copolymer used as one of the components (1) is a polymer block A mainly composed of at least one vinyl aromatic compound and at least one conjugated diene compound. It is obtained by hydrogenating a block copolymer having a structure consisting of polymer block B, for example, A-B, A-B-A, B-
A-B-A.
（Ａ−Ｂ）ｎＸ（ｎ＝２〜４、Ｘはカップリング剤残基
）、（Ｂ−Ａ−Ｂ ）ｎｘ （ｎ−２〜４、Ｘはカップ
リング剤残基）及びこれらの混合物の水素添加された水
添ブロック共重合体である。また、この水添ブロック共
重合体はビニル芳香族化合物を５〜９５重ｆ％、好まし
くは１０〜６ＯｊＨｔ％含む。さらに好ましくは１５〜
４５３！童％において、かかる水添ブロック共重合体は
熱可塑性エラストマーとして優れた特性を示す。さらに
ブロック構造について言及すると、ビニル芳香族化合物
を主体とする重合体ブロックＡが、ビニル芳香族化合物
重合体ブロックまたは、ビニル芳香族化合物を５０ム黛
％をこえ、好１しくは７０重ｆ％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
合体ブロックの構造を有しており、そしてさらに、水素
重加された共役ジエン化合物を主体とする重合体ブロッ
クＢが、水素添加された共役ジエン化合物重合体ブロッ
クまたは、水素添加ちれた共役ジエン化合物を５０１ｉ
：ｔ％をこえ、好ましくは７０３ｉｉ％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
の共重合体ブロッ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重合体ブロッ
クＡ、水素添加婆れた共役ジエン化合物を主体とする重
合体ブロックＢは、各々の重合体ブロックにおける分子
鎖中の水素添加嘔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、チーバード（分子鎖に
沿ってモノマー分布が増加または減少するもの）、一部
ブロック状またはこれらの任意の組合せであってもよく
、該ビニル芳香族化合物を主体とする重合体ブロックＡ
１水素添加芒れた共役ジエン化合物を主体とする重合体
ブロックＢがそれぞれ２個以上ある場合は、各ブロック
はそれぞれ同一構造であってもよく、異なる構造であっ
てもよい。(A-B)nX (n=2 to 4, X is a coupling agent residue), (B-A-B)nx (n-2 to 4, X is a coupling agent residue) and mixtures thereof It is a hydrogenated block copolymer. Further, this hydrogenated block copolymer contains a vinyl aromatic compound in an amount of 5 to 95% by weight, preferably 10 to 6 OjHt%. More preferably 15~
453! %, such a hydrogenated block copolymer exhibits excellent properties as a thermoplastic elastomer. Furthermore, referring to the block structure, the polymer block A mainly composed of a vinyl aromatic compound is a vinyl aromatic compound polymer block or a vinyl aromatic compound containing more than 50% by weight, preferably 70% by weight. It has a structure of a copolymer block of the above-contained vinyl aromatic compound and a hydrogenated conjugated diene compound, and furthermore, a polymer block B mainly composed of a hydrogenated conjugated diene compound, Hydrogenated conjugated diene compound polymer block or hydrogenated conjugated diene compound 501i
: It has a structure of a copolymer block of a hydrogenated conjugated diene compound and a vinyl aromatic compound containing more than t%, preferably 703ii% or more. Also,
These polymer block A mainly consists of a vinyl aromatic compound, and the polymer block B mainly consists of a hydrogenated conjugated diene compound. The distribution of the compound or vinyl aromatic compound may be random, Cheebird (increasing or decreasing monomer distribution along the molecular chain), partially block-like, or any combination thereof, and the vinyl aromatic compound Polymer block A mainly composed of
When there are two or more polymer blocks B each consisting mainly of a conjugated diene compound with hydrogen added thereto, each block may have the same structure or may have a different structure.
水添ブロッ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、４−メ
チルスチレン、ビニルトルエン、４−第三ブチルスチレ
ン、１，１′−ジフェニルエチレンなどの内から１穐ま
たは２ａ１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
素添加前の共役ジエン化合物としては、例えば、ブタジ
ェン、イソプレン、１，６−ペンタジェン、２，６−シ
メチルー１，６−ブタジェン、１，３−へキサジエン等
の内から１福または２８以上が選択でき、中でもブタジ
ェン、イソプレン及びこわらの組合せが好ましい。そし
て、水素添加される前の共役ジエン化合物を主体とする
重合体ブロックＢは、そのブロック中におけるミクロ構
造を任意に選ぶことが出来るが、良好なゴム弾性を持つ
ためには、例えば、ポリブタジェンブロックにおいては
１゜２−ビニル結合量が、１０〜８０％、好ましくは、
２５〜４５％である。Examples of the vinyl aromatic compound constituting the hydrogenated block copolymer include styrene, α-methylstyrene, 4-methylstyrene, vinyltoluene, 4-tert-butylstyrene, 1,1'-diphenylethylene, etc. 1 or more than 2a1 can be selected, and among them, styrene is preferable. In addition, examples of the conjugated diene compound before hydrogenation constituting the hydrogenated conjugated diene compound include butadiene, isoprene, 1,6-pentadiene, 2,6-cymethyl-1,6-butadiene, 1,3- 1 or 28 or more can be selected from xadiene and the like, and among them, a combination of butadiene, isoprene, and kowara is preferred. The microstructure of the polymer block B, which is mainly composed of a conjugated diene compound before being hydrogenated, can be arbitrarily selected, but in order to have good rubber elasticity, it is necessary to In Genblock, the amount of 1°2-vinyl bond is 10 to 80%, preferably
It is 25-45%.
該水冷ブロック共重合体の数平均分子量は、５．０００
〜ｉ、ｏ ｏ ｏ、ｏ ｏ ｏ、好ましくは、１０．０
００〜８００．０００テあり、本発８Ａｍ成物の物性、
加工性とのバランスを保持する上からは３０．０００〜
３００，０００が更に好ましい範囲であり、分子量分布
〔１量平均分子量（Ｍｗ ）と数平均分子量（Ｍｎ ）
との比（Ｍｗ ／ Ｍｎ ） ］は１゜以下である。さ
らに水添ブロック共重合体の分子構造は、直鎖状、分岐
状、放射状あるいはこゎらの任意の組合せのいすねであ
ってもよい。The number average molecular weight of the water-cooled block copolymer is 5.000.
~i, o o o, o o o, preferably 10.0
00 to 800.000 Te, the physical properties of the 8Am composition of the present invention,
30,000~ to maintain balance with workability
A more preferable range is 300,000, and molecular weight distribution [1 weight average molecular weight (Mw) and number average molecular weight (Mn)
(Mw/Mn)] is 1° or less. Furthermore, the molecular structure of the hydrogenated block copolymer may be linear, branched, radial, or any combination thereof.
これらの水添ブロッ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は、どの様な製法で得られ
るものであってもかまわない。例えは、特公昭４０−２
３７９８号公報に記載賂れた方法により、リチウム触媒
などを用いて不活性溶媒中でビニル芳香族化合物−共役
ジエン化合物ブロック共重合体を合成し、次いで、例え
ば特公昭４２−８７０４号公報、時分１１４３−６６３
６号公報に記載延れた方法、特に好ましくは特公昭６３
−４８４１号公報及び、特公昭６３−５４０１号公報に
記載葛れた方法により、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ック共重
合体を合成することが出来る。These hydrogenated block copolymers may be produced by any method as long as they have the above structure. For example, Tokuko 1977-2
A vinyl aromatic compound-conjugated diene compound block copolymer is synthesized in an inert solvent using a lithium catalyst using the method described in Japanese Patent Publication No. 3798, and then, for example, as described in Japanese Patent Publication No. 42-8704, Minutes 1143-663
The method described in Publication No. 6, particularly preferably the method described in Japanese Patent Publication No. 63
The hydrogenated block copolymer used in the present invention is synthesized by hydrogenation in the presence of a hydrogenation catalyst in an inert solvent by the method described in Japanese Patent Publication No. 4841 and Japanese Patent Publication No. 63-5401. I can do it.
その際、ビニル芳香族化合物−共役ジエン化合物ブロッ
ク共重合体の共役ジエン化合物に基づく脂肪族二ｌ結合
は少なくとも８０％を水素添加し、共役ジエン化合物を
主体とする重合体ブロックを形態的にオレフィン性化合
物重合体ブロックＢに変換させる。また、ビニル芳香族
化合物を主体とする重合体ブロックＡ及び、必要に応じ
て共役ジエン化合物を主体とする電合体ブロックＢに共
ム合されているビニル芳香族化合物に基づく芳香族二ｌ
結合の水素添加ｒＡＫついては特に制限はないが、水素
添加塞ｆ、２０％以下にするのが好ましい。At that time, at least 80% of the aliphatic di-l bonds based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer are hydrogenated, and the polymer block mainly composed of the conjugated diene compound is transformed into an olefin. The compound is converted into a polymer block B. In addition, an aromatic compound based on a vinyl aromatic compound co-combined with a polymer block A mainly composed of a vinyl aromatic compound and an electropolymer block B mainly composed of a conjugated diene compound as necessary.
Although there is no particular restriction on the hydrogenation rAK of the bond, it is preferable that the hydrogenation f is 20% or less.
該水添ブロック共重合体中に含まれる未水素添加の脂肪
族二重結合の量は、赤外分光光度計、核磁気共鳴装置な
どにより容易に知ることが出来る。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.
一方、（Ｉ）成分のもう一つとして用いることが出来る
水添ブロック共重合体変性物は、前記した水添ブロック
共重合体にカルボン酸基又はその誘碑体基金含有する分
子単位が結合したものである。On the other hand, a hydrogenated block copolymer modified product that can be used as another component (I) is a hydrogenated block copolymer having a molecular unit containing a carboxylic acid group or its derivative group bonded to the hydrogenated block copolymer described above. It is something.
かかる水添ブロック共重合体変性物は、前記の水添ブロ
ック共重合体に不飽和カルボン酸又はそのｖｊ２４体ヲ
、溶液状態又は溶融状態において、好ましくはラジカル
開始剤を使用して付加することによって得られる。かか
る付加変性に用いうろ水添ブロック共重合体は、前記に
規定したものであればいずれでも用いることが出来、又
、水添ブロック共重合体に付加きせる不飽和カルボン酸
又はその誘導体の例としては、マレイン酸、ハロゲン化
マレイン酸、イタコン酸、フマル酸、シトラコン酸、シ
ス−４−シクロヘキセン−１，２−ジカルボン酸、エン
ジ−シス−ビシクロ−〔２，２，１’：１−５−へブテ
ン−２，６−ジカルボン酸等やこれらジカルボン酸の無
水物、エステル、アミソ、イミｒ等及び、アクリル酸、
メタクリル酸、クロトン酸、インクロトン酸、メサコン
酸、アンゼリン酸等やこれらモノカルボン酸のエステル
、例えばメタクリル酸メチル、メタクリル酸グリシジル
やアミｒ１エーテル、ニトリル、チオール等の誘導体が
挙げられるが、これらの中では無水マレイン酸またはメ
タクリル酸グリシジルが特に好ましい。Such a modified hydrogenated block copolymer can be obtained by adding an unsaturated carboxylic acid or its vj24 derivative to the hydrogenated block copolymer in a solution or melt state, preferably using a radical initiator. can get. The hydrogenated block copolymer used for such addition modification can be any of those specified above, and examples of unsaturated carboxylic acids or derivatives thereof that can be added to the hydrogenated block copolymer include is maleic acid, halogenated maleic acid, itaconic acid, fumaric acid, citraconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, enedi-cis-bicyclo-[2,2,1':1-5- Hebutene-2,6-dicarboxylic acid, etc., anhydrides, esters, amiso, imir, etc. of these dicarboxylic acids, and acrylic acid,
Examples include methacrylic acid, crotonic acid, incrotonic acid, mesaconic acid, angelic acid, etc., and esters of these monocarboxylic acids, such as methyl methacrylate, glycidyl methacrylate, and derivatives such as amyl ether, nitrile, and thiol. Among these, maleic anhydride or glycidyl methacrylate is particularly preferred.
これら水添ブロック共重合体変性物の製造方法に関して
は、本発明においては特に限定はしないが、得られた水
糸ブロック共重合体変性物がデル等の好ましくない成分
を含んだり、その溶融粘度が著しく増大して加工性が悪
化したりする製造方法は好ましくない。好ましい方法と
しては、例えば、押出機中、ラジカル開始剤存在下で、
水添ブロック共重合体と不飽和カルボン酸又はその誘導
体とを反応させる方法がある。The method for producing these modified hydrogenated block copolymers is not particularly limited in the present invention; A manufacturing method in which the processability is deteriorated due to a significant increase in the amount is not preferable. As a preferable method, for example, in an extruder in the presence of a radical initiator,
There is a method of reacting a hydrogenated block copolymer with an unsaturated carboxylic acid or a derivative thereof.
不飽和カルボン酸又はその誘導体の水添ブロック共重合
体への付加量は、水添ブロック共重合体１００１に置部
あたり２０重量部以下が好ましく、１０！を部以下が更
に好ましい。付加量が２０１ｉＫ量部を超えても、それ
以下に比べて変性効果の増大は認められなり０本発明で
用いる不飽和カルボン酸又はその誘導体は、一種のみな
らず二種以上混合しても使用できる。The amount of unsaturated carboxylic acid or its derivative added to the hydrogenated block copolymer is preferably 20 parts by weight or less per part added to the hydrogenated block copolymer 1001, and 10! It is more preferable that the amount is less than 1 part. Even if the amount added exceeds 201 iK parts, no increase in the modification effect is observed compared to amounts less than 201 iK parts.The unsaturated carboxylic acids or derivatives thereof used in the present invention can be used not only alone but also as a mixture of two or more. can.
本発明の組成物にかかる（ＩＩ）成分として用いうるα
、β−不飽和ニトリル−共役ジエン系共重合体ゴム及び
／又はその水素添加物としては、α。α that can be used as component (II) in the composition of the present invention
, α as the β-unsaturated nitrile-conjugated diene copolymer rubber and/or its hydrogenated product.
β−不飽和二トリル／共役ジエンのＪｋ：ｆｔ比が１０
／９０〜８０／２０．好ましくは１５／８５〜５０１５
０で分子ｔ ｓ、ｏ ｏ ｃ＋〜２００，０００のもの
及び／又はその水素添加物が好ましい。Jk:ft ratio of β-unsaturated nitrile/conjugated diene is 10
/90~80/20. Preferably 15/85 to 5015
0 and molecules t s, o o c + ~200,000 and/or hydrogenated products thereof are preferred.
かかるα、β−不飽和不飽和シトリルー共役ジエン系共
重合体ゴムするα、β−不飽和二トリルの具体例として
は、アクリロニトリル、メタクリロニトリル、α−クロ
ロアクリロニトリル、α−フルオロアクリロニトリル、
エタクリロニトリル等が挙げられるが、これらの中でも
アクリロニトリルが特に好ましい。Specific examples of the α,β-unsaturated nitrile used in the α,β-unsaturated citrile-conjugated diene copolymer rubber include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile,
Examples include ethacrylonitrile, and among these, acrylonitrile is particularly preferred.
また、α、β−不飽和ニトリル−共役ジエン系共重合体
ゴムのもう一方の構成成分である共役ジエン化合物とし
ては、例えば、ブタジェン、イソプレン、１，３−ペン
タジェン、２，３−ジメチル−１，３−−７”タジエン
、１，３−へキサジエン等の内から１種または２種以上
が選択でき、中でもブタジェンが好ましい。In addition, examples of the conjugated diene compound which is the other component of the α,β-unsaturated nitrile-conjugated diene copolymer rubber include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1 , 3--7''tadiene, 1,3-hexadiene, etc., and butadiene is preferred among them.
またα、β−不飽和ニトリル−共役ジエン系共重合体ゴ
ム中の共役ジエン化合物に基づく部分が、完全にまたは
部分的に水Ｘ僑加されてｂてもかまわない。本発明にお
いて、α、β−不飽和不飽和シトリルー共役ジエン系共
重合体ゴムその水素添加物は、単独で用いてもよいし、
混合物として用いてもよいが、水添ブロック共重合体が
持つ耐候性を損なわなり点から、特に水素添加物を用い
ることが好ましい。Furthermore, the portion based on the conjugated diene compound in the α,β-unsaturated nitrile-conjugated diene copolymer rubber may be completely or partially added with water. In the present invention, the hydrogenated product of α,β-unsaturated citrile-conjugated diene copolymer rubber may be used alone, or
Although it may be used as a mixture, it is particularly preferable to use a hydrogenated product since the weather resistance of the hydrogenated block copolymer will be impaired.
該α、β−不飽和不飽和シトリルー共役ジエン系共重合
体ゴムえば、通常のラジカル１合触媒を用いた乳化１合
により製造することが出来る。また、該共重合体の水素
添加物は、例えば、特開昭４５−３９２７５号公報、特
開昭５０−７１６８１号公報などに記載された方法によ
って、該共重合体中の共役ジエン化合物単位部分を水素
添加して得られる。The α,β-unsaturated citrile-conjugated diene copolymer rubber can be produced by emulsion reaction using a conventional radical reaction catalyst. Further, the hydrogenated product of the copolymer can be obtained by, for example, the method described in JP-A-45-39275, JP-A-50-71681, etc. Obtained by hydrogenating.
本発明の組成物において、かかる（１）成分及び（ｎ）
成分の割合は、（１） ／ （Ｉｆ）の重量比が９５１
５〜５０１５０である。（１） ＋ （ｆｆ）にしめる
ＩＩ）の割合が５′ＩＬ−Ｉｋ％未溝では組成物が十分
な耐熱性・耐油性を示芒ず、又、５０１量％を超えると
組成物を架橋した際、加工性が悪化し良好な熱可塑性を
水石す、好ましくない。In the composition of the present invention, such component (1) and (n)
The ratio of the components is (1) / (If) weight ratio is 951
5 to 50150. (1) + (ff) If the proportion of II) was 5'IL-Ik%, the composition did not exhibit sufficient heat resistance and oil resistance, and when it exceeded 501% by weight, the composition was crosslinked. In this case, processability deteriorates and good thermoplasticity is lost, which is undesirable.
本発明の組成物においては、α、β−不飽和不飽和シト
リルー共役ジエン系共重合体ゴム剤等、例えば、有機過
酸化物等の架橋剤、アリル化合物、硫黄、オキシム類等
の架橋助剤、酸化亜鉛、酸化マグネシウム等の架橋促進
剤等を配合することも出来る。かかる架橋剤等の配合量
は、特に制限はないが、本組成物の熱可塑性を損なわな
ｌ、／′＞福度、すなわち、該α、β−不飽和不飽和シ
トリルー共役ジエン系共重合体ゴムにＲ適な配合量の７
０〜１００％が好ましい。In the composition of the present invention, α,β-unsaturated unsaturated citrile-conjugated diene copolymer rubber agents, etc., crosslinking agents such as organic peroxides, crosslinking aids such as allyl compounds, sulfur, oximes, etc. , a crosslinking accelerator such as zinc oxide, magnesium oxide, etc. can also be blended. The amount of the crosslinking agent, etc. to be blended is not particularly limited, but must be such that it does not impair the thermoplasticity of the composition, that is, the α,β-unsaturated citrile-conjugated diene copolymer 7, the appropriate amount of R for rubber
0 to 100% is preferred.
本発明の組成物には、必要に応じて、ポリエチレン、ポ
リプロぎレン等の熱可塑性樹脂、炭酸カルシウム、カー
ボンブラック、シリカ等の充＊斉艮オイル等を配合して
もよい。The composition of the present invention may optionally contain thermoplastic resins such as polyethylene and polypropylene, and filler oils such as calcium carbonate, carbon black, and silica.
本発明の組成物の混合に用いられる手段には、溶液ブレ
ンドなどの化学的混合法や機械的混合法、例えば、ロー
ル、押出機、プラベンダーなどが挙げられるが、もちろ
んこれらに限定するものではない。均一に混合するため
には、好ましくは１６０℃以上の条件を選択するのがよ
い。Means used to mix the compositions of the present invention include, but are of course not limited to, chemical mixing methods such as solution blending and mechanical mixing methods such as rolls, extruders, plastic benders, etc. do not have. In order to mix uniformly, it is preferable to select a temperature of 160° C. or higher.
また、（■）成分を架橋する場合、その方法は、特に制
限はないが、水添ブロック共重合体、α。In addition, when crosslinking component (■), the method is not particularly limited, but hydrogenated block copolymer, α.
β−不飽和ニトリル−共役ジエン系共重合体ゴムの混合
と同時、又は混合した後に（ｎ）成分の架橋剤等を加え
架橋させる方法が混合の良好な架橋組成物を得る上で好
ましい。In order to obtain a crosslinked composition with good mixing, it is preferable to add and crosslink component (n), such as a crosslinking agent, simultaneously with or after mixing the β-unsaturated nitrile-conjugated diene copolymer rubber.
（発明の効果）
本発明によれば、水添ブロック共重合体の優れた機械的
特性・ゴム弾性・耐候性と、ニトリルゴムの優れた耐熱
性・耐油性を兼ね備えた新規な熱可塑性エラストマー組
成物を得ることが出来、耐油性・耐熱性を必要とする各
種ホース類、各種ロール成型物等、例えば、自動車部品
、電気部品、各種工業部品等に極めて好適に使用するこ
とが出来る。(Effects of the Invention) According to the present invention, a novel thermoplastic elastomer composition has the excellent mechanical properties, rubber elasticity, and weather resistance of a hydrogenated block copolymer and the excellent heat resistance and oil resistance of nitrile rubber. It can be used very suitably for various hoses, various roll molded products, etc. that require oil resistance and heat resistance, such as automobile parts, electrical parts, and various industrial parts.
（実施例）
以下、実施例を挙げ本発明を更に具体的に説明するが、
本発明はその要旨を超えない限り、これらの実施例に制
限されるものではなり０鍵考例１ 水添ブロック共重合
体の合成（１，−１）特公昭６３−４８４１号公報記載
の方法にて、？リスチレンー水素添加されたポリブタジ
ェン−＆ １．１スチレンの構造を有し、結合スチレン
量３０％、水素添加前の？リプクジ１フ部の１゜２−ビ
ニル結合量３５％、数平均分子量１５０ 、０００、分
子量分布１．０４、ポリブタジェン部の水素添加率１０
０％の水添ブロック共重合体を合成した。(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples unless it exceeds the gist thereof. Key Example 1 Synthesis of hydrogenated block copolymer (1,-1) Method described in Japanese Patent Publication No. 4841/1983 At? Restyrene - Hydrogenated polybutadiene - Has a structure of 1.1 styrene, with a bound styrene content of 30%, before hydrogenation? Amount of 1°2-vinyl bonds in Lipukuji 1 part: 35%, number average molecular weight: 150,000, molecular weight distribution: 1.04, hydrogenation rate of polybutadiene part: 10
A 0% hydrogenated block copolymer was synthesized.
（１−２）（１−１）と両様にして、ポリスチレン−水
素添加されたポリイソプレン−ポリスチレンの構造を有
し、結合スチレン量６０％、水素添加前のポリインプレ
ン部の３，４−ビニル結合量３３％、数平均分子量１２
０，０００、分子量分布１．０４、ポリインプレン部の
水素添加率９９％の水添ブロック共重合体を合成した。(1-2) Similar to (1-1), it has a polystyrene-hydrogenated polyisoprene-polystyrene structure, with a bound styrene content of 60% and a 3,4- Vinyl bond amount 33%, number average molecular weight 12
0,000, a molecular weight distribution of 1.04, and a hydrogenation rate of 99% in the polyimprene portion.
（１−３）（１−１）と同様にして、水素添加嘔れたポ
リブタジェン−ポリスチレン−水素添加逼れたポリブタ
ジェン−ポリスチレンの構造を有し、結合スチレン量３
０％、水素添加前のポリブタジェン部の１，２−ビニル
結合１ｔ３５％、数平均分子量５０，０００、分子量分
布１．０４、ポリブタジェン部の水素添加率９９％の水
自ブロック共重合体を合成した。(1-3) Similar to (1-1), it has a structure of hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene-polystyrene, and the amount of bound styrene is 3.
0%, 1,2-vinyl bond 1t35% in the polybutadiene part before hydrogenation, number average molecular weight 50,000, molecular weight distribution 1.04, and a hydrogenation rate of 99% in the polybutadiene part. .
（１−４）（１−１）と同様にして、（ポリスチレン−
水素添加されたポリブタジェン）４Ｓ１の構造を有し、
結合スチレン量３０％、水素添加前のポリブタジェン部
の１，２−ビニル結合量６５％、数平均分子ｉ ７０，
０００、分子量分布１．０４、ポリブタジェン部の水素
添加名９６％の水添ブロック共重合体を合成した。(1-4) Similarly to (1-1), (polystyrene-
Hydrogenated polybutadiene) has a structure of 4S1,
The amount of bound styrene is 30%, the amount of 1,2-vinyl bond in the polybutadiene part before hydrogenation is 65%, the number average molecular i is 70,
000, a molecular weight distribution of 1.04, and a hydrogenated block copolymer having a hydrogenation rate of 96% in the polybutadiene moiety.
参考例２ 変性水添ブロック共重合体の合成（２−１）
（１−１）で得られた水添ブロック共重合体１００重量
部あたり、無水マレイン酸１重蓋部、２，５−ジメチル
−２，５−ジ（第三ブチルパーオキシ）ヘキサンｏ、ｉ
ｉｎ部を混合し、２５０°ＯＫ設定した５０肩冨ダ径
の二軸押出機で付加変性反応を行った。得られた変性水
添ブロック共重合体は無水マレイン酸が０．７５１（置
部付加したものであった。Reference Example 2 Synthesis of modified hydrogenated block copolymer (2-1)
Per 100 parts by weight of the hydrogenated block copolymer obtained in (1-1), 1 part maleic anhydride, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane o, i
The in part was mixed and an addition modification reaction was performed in a twin screw extruder with a diameter of 50 mm and set at 250° OK. The obtained modified hydrogenated block copolymer was one in which 0.751 portions of maleic anhydride were added.
（２−２） （１−３）で得られた水添ブロック共重合
体ｉｏｏｍｔ部あたり、無水マレイン１２１１Ｌ量部、
２，５−ジメチル−２，５−ジ（第三ブチルパーオキシ
）ヘキサン０．１ ｉｔ部を混合し、２５０°ＯＫ設定
した５０ｍｍ径の二軸押出機で付加変性反応を行った。(2-2) 1211 L parts of anhydrous maleic per ioomt part of the hydrogenated block copolymer obtained in (1-3),
0.1 part of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane was mixed and an addition modification reaction was carried out in a 50 mm diameter twin screw extruder set at 250° OK.
得られた変性水添ブロック共重合体は無水マレイン酸が
０．５５重量部付加したものであった。The obtained modified hydrogenated block copolymer had 0.55 parts by weight of maleic anhydride added thereto.
（２−３）（１−３）で得られた水添ブロック共重合体
１００！童部あたり、メタクリル酸グリシジル２．５１
量部、ジー第三ブチルパーオキサイぜ０．５重量部を混
合し、１９０℃に設定した４５ｉｎｍのベント付き二軸
押出機で、真空ポンプを用いて強制ベント（減圧度：
７５０ｍＥｇＧ ）を打込ながら変性反応を行った。得
られた変性水添ブロック共重合体はメタクリル酸グリシ
ジルが１．５重量部付加したものであった。(2-3) Hydrogenated block copolymer obtained in (1-3) 100! Glycidyl methacrylate 2.51 per Dobe
and 0.5 parts by weight of di-tert-butyl peroxide were mixed, and in a 45-inch vented twin-screw extruder set at 190°C, forced venting was performed using a vacuum pump (degree of vacuum:
The denaturation reaction was performed while injecting 750 mEgG). The obtained modified hydrogenated block copolymer had 1.5 parts by weight of glycidyl methacrylate added thereto.
実施例１〜３９、及び比較例１〜２７
表１〜８に示した配合割合の熱可塑性エラストマー組成
物ｔ−１８０°Ｃのロールにより調製し、厚嘔約２１０
Ｅのシートに１８０℃で圧縮成形した後、下記の試験に
供した。Examples 1 to 39 and Comparative Examples 1 to 27 Thermoplastic elastomer compositions having the compounding ratios shown in Tables 1 to 8 were prepared using a roll at t-180°C.
After compression molding a sheet of E at 180° C., it was subjected to the following test.
耐熱性：
Ｊ工５Ｋ６３０１ｒ加硫ゴムの物理試験方法」Ｋ準じて
上記の圧縮成形したシート（以下プレスシートと呼ぶ）
をダンベル状３号型試験片に打ち抜いたものを用いて２
５℃、７０°Ｃ，１００°Ｃにおける引張強度を測定し
、２５℃における引張強度が、７０°Ｃで７０％以上保
持葛れ、かつ１００°Ｃで５０％以上保持されるものを
○、その値を下回るものを×として評価した。Heat resistance: The above compression molded sheet (hereinafter referred to as press sheet) according to "J-K5K6301R Physical Test Method for Vulcanized Rubber" K
2 using a dumbbell-shaped No. 3 test piece punched out.
The tensile strength at 5℃, 70℃, and 100℃ is measured, and the tensile strength at 25℃ is 70% or more at 70℃ and 50% or more at 100℃. Those below that value were evaluated as ×.
耐油性：
Ｊ工５ｘ６３０１ｒ加硫ゴムの物理試験方法」に準じて
上記のプレスシートをダンベル状３号型試験片に打ち抜
いたものを３１８６号オイル中に７０゛Ｃで１時間浸漬
した後取り出し、浸漬前後で表面に変化が生ぜず、かつ
浸漬前後の重量変化が２０％以下のものを○、表面が変
化したものまたは重量変化がこの値を上回るものを×と
して評価した。Oil resistance: The above press sheet was punched out into a dumbbell-shaped No. 3 test piece according to "Physical test method for vulcanized rubber J-K5x6301R" and was immersed in No. 3186 oil at 70°C for 1 hour, then taken out. Those with no change in the surface before and after immersion and a weight change of 20% or less before and after immersion were evaluated as ○, and those with surface changes or weight changes exceeding this value were evaluated as ×.
耐候性：
Ｊ工８に１４１５ ｒプラスチック建築材料の促進暴露
試験方法」に準じて上記のプレスシートをダンベル状３
号型試験片に打ち抜いたものをブラックパネル温度６３
°Ｃ１スプレーサイクル１２分／６０分のサンシャイン
ウニずオメータ中で５００時間！Ｗした後取り出し、暴
露前後における引張強度の保持ふが９５％以上で、かつ
暴露前後で表面状態に変化のないものを○、保持基がこ
の値を下回るものまたは表面状態が変化したものを×と
して評価した。Weather resistance: The above press sheet was pressed into a dumbbell shape 3 according to ``Accelerated Exposure Test Method for Plastic Building Materials'' (1415 r) to J-8.
Black panel temperature 63
500 hours in the Sunshine Unizu Ometer with a 12 minute/60 minute spray cycle at °C! When taken out after W treatment, those with tensile strength retention of 95% or more before and after exposure and no change in surface condition before and after exposure are ○, and those with retention groups below this value or whose surface condition has changed are ×. It was evaluated as
熱可塑性：
Ｊ工５ｘ７２１０ 「熱可塑性プラスチックの流れ試験
方法」に準じて各熱可塑性エラストマー組成物のメルト
フローレイト（ＭＦＲ）を条件１４（試験温度２６０°
Ｃ１試験向！２．１６ゆで）で測定し、ＭＦＲが０．１
以上のものを○、この値を下回るものを×として評価し
た。Thermoplasticity: J Engineering 5x7210 The melt flow rate (MFR) of each thermoplastic elastomer composition was determined under condition 14 (test temperature 260°
For C1 exam! 2.16 boiled), MFR is 0.1
Those above were evaluated as ○, and those below this value were evaluated as ×.
表１〜８において１）〜１２）は以下の通りである。In Tables 1 to 8, 1) to 12) are as follows.
１）：参考例で合成したエラストマー、及び５ｈｅ１１
社製Ｋｒａｔｏｎ Ｇ １６５２２）：水添ニトリルゴ
ム（Ａ） ｍ Ｂａｙｅｒ社製Ｔｈｅｒｂａｎ １７
０７
水添二トリルプム（Ｂ）−日本ゼオン社製ｚｅｔｐｏ１
２０１０
ニトリルゴム 請日本ゼオン社製Ｎ１ｐＯ１１０
４２
６）：旭化成工業社製旭化成ポリプロＨ−１１００４）
：出光興産社製ＰＷ３８０
５）ニトリアリルイソシアヌレート
６）二日本油脂社製ペロキシモンＦ′４０７）：ジオク
チルセバケー） （ＤＯ８）８）ニトリメチロール ト
リス−（β−チオプロピオネート）
９）：テトラメテルチウラムジサルファイド（ＴＭＴＤ
）
１０）：テトラエチルチウラムジサルファイド（ＴＥＴ
Ｄ ）
１１） ： ２−メルカプトベンゾチアゾール（ＭＢＴ
）１２）：へキサメチレンテトラミン（Ｈ）表
２
表 ３1): Elastomer synthesized in Reference Example and 5he11
Kraton G 16522): Hydrogenated nitrile rubber (A) m Bayer Therban 17
07 Hydrogenated nitrile pum (B) - zetpo1 manufactured by Nippon Zeon Co., Ltd.
2010 Nitrile rubber N1pO110 manufactured by Nippon Zeon Co., Ltd.
42 6): Asahi Kasei Polypro H-11004) manufactured by Asahi Kasei Industries, Ltd.
: PW380 manufactured by Idemitsu Kosan 5) Nitriallyl isocyanurate 6) Peroximone F'407 manufactured by Nippon Oil & Fats Co., Ltd.): Dioctyl sebaque) (DO8) 8) Nitrimethylol tris-(β-thiopropionate) 9): Tetra Metelthiuram disulfide (TMTD)
) 10): Tetraethylthiuram disulfide (TET
D) 11): 2-mercaptobenzothiazole (MBT
)12): Hexamethylenetetramine (H) table
2 Table 3
Claims (2)
る重合体ブロックＡと、少なくとも１個の共役ジエン化
合物を主体とする重合体ブロックＢよりなるブロック共
重合体を水素添加して得られる水添ブロック共重合体及
び／又はカルボン酸基又はその誘導体基を含有する該水
添ブロック共重合体変性物（ I ）と、α，β−不飽和
ニトリル−共役ジエン系共重合体ゴム及び／又はその水
素添加物（II）を必須の成分とし、（ I ）／（II）の
重量比が９５／５〜５０／５０である熱可塑性エラスト
マー組成物。(1) Water obtained by hydrogenating a block copolymer consisting of a polymer block A mainly composed of at least one vinyl aromatic compound and a polymer block B mainly composed of at least one conjugated diene compound The hydrogenated block copolymer modified product (I) containing an added block copolymer and/or a carboxylic acid group or its derivative group, and an α,β-unsaturated nitrile-conjugated diene copolymer rubber and/or A thermoplastic elastomer composition containing the hydrogenated compound (II) as an essential component and having a weight ratio of (I)/(II) of 95/5 to 50/50.
記載の熱可塑性エラストマー組成物。(2) The thermoplastic elastomer composition according to claim 1, obtained by crosslinking at least (II).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5501388A JPH0692521B2 (en) | 1988-03-10 | 1988-03-10 | Elastomer composition having thermoplasticity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5501388A JPH0692521B2 (en) | 1988-03-10 | 1988-03-10 | Elastomer composition having thermoplasticity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01229063A true JPH01229063A (en) | 1989-09-12 |
| JPH0692521B2 JPH0692521B2 (en) | 1994-11-16 |
Family
ID=12986777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5501388A Expired - Lifetime JPH0692521B2 (en) | 1988-03-10 | 1988-03-10 | Elastomer composition having thermoplasticity |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0692521B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1161493A1 (en) * | 1999-07-13 | 2001-12-12 | Nitriflex S/A Industria E. Comércio | Composition containing nbr and thermoplastic elastomer |
-
1988
- 1988-03-10 JP JP5501388A patent/JPH0692521B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1161493A1 (en) * | 1999-07-13 | 2001-12-12 | Nitriflex S/A Industria E. Comércio | Composition containing nbr and thermoplastic elastomer |
| EP1161493A4 (en) * | 1999-07-13 | 2004-06-23 | Nitriflex S A Ind E Com | Composition containing nbr and thermoplastic elastomer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0692521B2 (en) | 1994-11-16 |
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