JP6847203B2 - 成形外観に優れた熱可塑性エラストマー組成物及びその成形体 - Google Patents
成形外観に優れた熱可塑性エラストマー組成物及びその成形体 Download PDFInfo
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- JP6847203B2 JP6847203B2 JP2019509158A JP2019509158A JP6847203B2 JP 6847203 B2 JP6847203 B2 JP 6847203B2 JP 2019509158 A JP2019509158 A JP 2019509158A JP 2019509158 A JP2019509158 A JP 2019509158A JP 6847203 B2 JP6847203 B2 JP 6847203B2
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- thermoplastic elastomer
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- rubber
- olefin
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims description 105
- 239000000203 mixture Substances 0.000 title claims description 53
- 229920001971 elastomer Polymers 0.000 claims description 76
- 239000005060 rubber Substances 0.000 claims description 72
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 60
- 229920001577 copolymer Polymers 0.000 claims description 41
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 30
- 239000005977 Ethylene Substances 0.000 claims description 30
- 239000004711 α-olefin Substances 0.000 claims description 28
- 229920005672 polyolefin resin Polymers 0.000 claims description 27
- 238000001746 injection moulding Methods 0.000 claims description 26
- 238000000465 moulding Methods 0.000 claims description 26
- 229920003023 plastic Polymers 0.000 claims description 16
- 239000004033 plastic Substances 0.000 claims description 15
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 8
- 229920001400 block copolymer Polymers 0.000 claims description 8
- 239000000806 elastomer Substances 0.000 claims description 4
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 description 40
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 39
- 239000005011 phenolic resin Substances 0.000 description 34
- 239000003431 cross linking reagent Substances 0.000 description 33
- 229920001155 polypropylene Polymers 0.000 description 30
- 239000004743 Polypropylene Substances 0.000 description 26
- -1 polypropylene Polymers 0.000 description 26
- 238000004132 cross linking Methods 0.000 description 19
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- 238000000034 method Methods 0.000 description 15
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 14
- 238000002347 injection Methods 0.000 description 13
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- 239000000126 substance Substances 0.000 description 13
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- 238000004898 kneading Methods 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
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- 239000000178 monomer Substances 0.000 description 10
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- 238000001125 extrusion Methods 0.000 description 8
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- 125000004432 carbon atom Chemical group C* 0.000 description 7
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical group 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
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- 239000011787 zinc oxide Substances 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
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- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- 239000004971 Cross linker Substances 0.000 description 4
- 229920002633 Kraton (polymer) Polymers 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
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- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 4
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- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 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 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229920005549 butyl rubber Polymers 0.000 description 3
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- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 2
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 2
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 2
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
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- 229920002943 EPDM rubber Polymers 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- FMGUJLASXUBMOP-UHFFFAOYSA-N N-Methyl-N,4-dinitrosoaniline Chemical compound O=NN(C)C1=CC=C(N=O)C=C1 FMGUJLASXUBMOP-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- WMVSVUVZSYRWIY-UHFFFAOYSA-N [(4-benzoyloxyiminocyclohexa-2,5-dien-1-ylidene)amino] benzoate Chemical compound C=1C=CC=CC=1C(=O)ON=C(C=C1)C=CC1=NOC(=O)C1=CC=CC=C1 WMVSVUVZSYRWIY-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
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- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 2
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- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
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- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
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- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
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- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
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- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
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- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- DOMHCBYZLIWUHE-UHFFFAOYSA-N 2-(chloromethyl)-3-prop-1-en-2-ylbicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(C(=C)C)C2CCl DOMHCBYZLIWUHE-UHFFFAOYSA-N 0.000 description 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
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- B60R21/00—Arrangements or fittings on vehicles for protecting or preventing injuries to occupants or pedestrians in case of accidents or other traffic risks
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- B60R21/20—Arrangements for storing inflatable members in their non-use or deflated condition; Arrangement or mounting of air bag modules or components
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- C08L2205/00—Polymer mixtures characterised by other features
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Description
(1)ポリオレフィン樹脂(A)10〜80質量部、スチレン系熱可塑性エラストマー(B)10〜80質量部、及び少なくとも一部が架橋されたゴム(C)1〜20質量部(成分(A)、(B)及び(C)の合計量は100質量部である)を含む組成物であり、JIS K6253に準拠するタイプD硬度(瞬間値)が35以上かつ70以下である熱可塑性エラストマー組成物。
(2)成分(A)、(B)及び(C)の合計量100質量部に対して、可塑剤(D)を0質量部以上、10質量部以下含む前記(1)に記載の熱可塑性エラストマー組成物。
(3)前記ゴム(C)がエチレン・α−オレフィン共重合体ゴム及び/又はエチレン・α−オレフィン・非共役ポリエン共重合体ゴムを含む前記(1)又は(2)に記載の熱可塑性エラストマー組成物。
(4)前記(1)〜(3)のいずれかに記載の熱可塑性エラストマー組成物を成形して得られる熱可塑性エラストマー成形体。
(5)前記(1)〜(3)のいずれかに記載の熱可塑性エラストマー組成物を射出成形して得られる熱可塑性エラストマー成形体。
(6)成形時の樹脂流動方向に直交する向きの成形体厚みの最も厚い部分(L1)と最も薄い部分(L2)との比率(L1/L2)が2〜50である前記(4)又は(5)に記載の熱可塑性エラストマー成形体。
(7)前記(4)〜(6)のいずれかに記載の熱可塑性エラストマー成形体を含む自動車部品。
(8)エアバッグカバーである前記(7)に記載の自動車部品。
本発明の熱可塑性エラストマー組成物は、ポリオレフィン樹脂(A)、スチレン系熱可塑性エラストマー(B)、及び少なくとも一部が架橋されたゴム(C)を含有している。
本発明に用いるポリオレフィン樹脂(A)としては、好ましくはオレフィン系プラスチックが挙げられ、架橋剤として有機ペルオキシドを用いる場合は、特にペルオキシド分解型オレフィン系プラスチックが好ましい。
(1)プロピレン単独重合体
(2)プロピレンと10モル%以下の他のα−オレフィンとのランダム共重合体
(3)プロピレンと30モル%以下の他のα−オレフィンとのブロック共重合体
(4)1−ブテン単独重合体
(5)1−ブテンと10モル%以下の他のα−オレフィンとのランダム共重合体
(6)4−メチル−1−ペンテン単独重合体
(7)4−メチル−1−ペンテンと20モル%以下の他のα−オレフィンとのランダム共重合体
本発明に用いるポリオレフィン樹脂(A)としては、ポリプロピレンが特に好ましい。
本発明に用いるスチレン系熱可塑性エラストマー(B)としては、好ましくは、エチレンと炭素数3〜20のα−オレフィンを主体としたエチレン・α−オレフィン系共重合体であり、スチレン/エチレン・α−オレフィン比(質量比)は通常5/95〜75/25、好ましくは10/90〜70/30の範囲である。
本発明に用いる少なくとも一部が架橋されたゴム(C)としては、特に制限はないが、好ましくは、ペルオキシド架橋型オレフィン系共重合体ゴム及びフェノール樹脂架橋型オレフィン系共重合体ゴムが挙げられる。
(1)エチレン・α−オレフィン共重合体ゴム
[エチレン/α−オレフィン(モル比)=約95/5〜50/50]
(2)エチレン・α−オレフィン・非共役ポリエン共重合体(好ましくは、エチレン・α−オレフィン・非共役ジエン共重合体ゴム)
[エチレン/α−オレフィン(モル比)=約95/5〜50/50]
本発明の熱可塑性エラストマー組成物は、必要に応じて、可塑剤(軟化剤)(D)を含むことができる。
前記のポリオレフィン樹脂(A)及び少なくとも一部が架橋されたゴム(C)は、ポリオレフィン系の完全又は部分架橋熱可塑性エラストマーに存在してもよい。
(1)(a)ペルオキシド架橋型オレフィン系共重合体ゴムと、(b)ペルオキシド分解型オレフィン系プラスチック(ポリオレフィン樹脂(A))とからなる混合物、又は(a)ペルオキシド架橋型オレフィン系共重合体ゴムと、(b)ペルオキシド分解型オレフィン系プラスチック(ポリオレフィン樹脂(A))と、(c)ペルオキシド非架橋型ゴム状物質及び/又は(d)鉱物油系軟化剤とからなる混合物を、有機ペルオキシドの存在下に動的に熱処理して得られた、部分的に架橋された熱可塑性エラストマー、
(2)(a)ペルオキシド架橋型オレフィン系共重合体ゴムと、(b)ペルオキシド分解型オレフィン系プラスチック(ポリオレフィン樹脂(A))と、(c)ペルオキシド非架橋型ゴム状物質及び/又は(d)鉱物油系軟化剤とからなる混合物を、有機ペルオキシド(もしくはフェノール樹脂系架橋剤)の存在下に動的に熱処理して得られた架橋されたゴム組成物に、(e)ポリオレフィン樹脂(A)を均一に配合せしめた、部分的に架橋された熱可塑性エラストマー(及び完全に架橋された熱可塑性エラストマー)等が挙げられる。
本発明の熱可塑性エラストマー組成物は、ポリオレフィン樹脂(A)10〜80質量部、スチレン系熱可塑性エラストマー(B)10〜80質量部、及び少なくとも一部が架橋されたゴム(C)1〜20質量部(成分(A)、(B)及び(C)の合計量は100質量部である)を含み、好ましくはポリオレフィン樹脂(A)20〜70質量部、スチレン系熱可塑性エラストマー(B)20〜70質量部、及び少なくとも一部が架橋されたゴム(C)1〜15質量部(成分(A)、(B)及び(C)の合計量は100質量部である)を含み、更に好ましくはポリオレフィン樹脂(A)30〜60質量部、スチレン系熱可塑性エラストマー(B)30〜60質量部、及び少なくとも一部が架橋されたゴム(C)1〜10質量部(成分(A)、(B)及び(C)の合計量は100質量部である)を含む。前記の割合で成分(A)、(B)及び(C)を配合することにより、エアバッグカバーのような厚肉部と薄肉部が存在する成形体を射出成形で製造する場合でも、薄肉部の厚さを変えずに外観を向上させることができる。例えば、成形時の樹脂流動方向に直交する向きの成形体厚みの最も厚い部分(L1)と最も薄い部分(L2)との比率(L1/L2)が通常2以上、50以下(下限値が好ましくは3以上、より好ましくは5以上、上限値が好ましくは20以下、より好ましくは10以下)である成形体を射出成形で製造する場合でも、薄肉部の厚さを変えずに外観を向上させることができる。
成形方法:カレンダー成形又はTダイからの押出成形
積層方法:ポリオレフィン系基材層からなるシートを発泡成形した後に表面層を基材層に積層する逐次法、又は、Tダイ押出成形の場合は同時多層押出成形を行う。
成形方法:多層押出成形
積層方法:ポリオレフィン系基材層と表面層の同時多層押出成形を行う。
成形方法:逐次又は同時射出成形
積層方法:ポリオレフィン系基材層を射出発泡した後に、表面層である熱可塑性エラストマー組成物を射出し、金型内で積層する逐次射出成形、又は、いわゆるサンドウィッチ成形により基材層と表面層を同時に射出し、積層部品を成形する同時法を行う。
本発明の熱可塑性エラストマー組成物は、種々公知の成形方法、具体的には、例えば、押出成形、プレス成形、射出成形、カレンダー成形、中空成形棟の各種の成形方法により、熱可塑性エラストマー成形体とすることができる。更に、前記成形方法で得られたシートなど成形体を熱成形などで二次加工することができる。
本発明の熱可塑性エラストマー成形体の使用しえる自動車部品としては、自動車内装部品、自動車外装部品があり、例えば、ウェザーストリップ材、バンパーモール、サイドモール、エアスポイラー、エアダクトホース、ワイヤーハーネスグロメット、ラックアンドピニオンブーツ、サスペンションカバーブーツ、ガラスガイド、インナーベルトラインシール、コーナーモールディング、グラスエンキャプシュレーション、フードシール、グラスランチャンネル、セカンダリーシール、各種パッキン類、ホース、エアバッグカバー等を例示でき、中でも本発明の熱可塑性エラストマー組成物は、射出成形や射出発泡成形性に優れるため、射出成形や射出発泡成形で得られる成形品が特に好ましい。
本発明の熱可塑性エラストマー成形体の使用しえる土木・建材用品としては、例えば、地盤改良用シート、上水板、騒音防止等の土木資材や建材、土木・建築用各種ガスケット及びシート、止水材、目地材、建築用窓枠などを例示できる。中でも本発明の熱可塑性エラストマー組成物は、射出成形や射出発泡成形性に優れるため、射出成形や射出発泡成形で得られる成形品が特に好ましい。
本発明の熱可塑性エラストマー成形体の使用しえる電気・電子部品としては、例えば、電線被覆材、コネクター、キャップ、プラグ等の電気・電子部品などを例示でき、中でも本発明の熱可塑性エラストマー組成物は、射出成形や射出発泡成形性に優れるため、射出成形や射出発泡成形で得られる成形品が特に好ましい。
本発明の熱可塑性エラストマー成形体の使用しえる衛生用品としては、例えば生理用品、使い捨ておむつ、歯ブラシ用グリップ等の衛生用品などを例示でき、中でも本発明の熱可塑性エラストマー組成物は、射出成形や射出発泡成形性に優れるため、射出成形や射出発泡成形で得られる成形品が特に好ましい。
本発明の熱可塑性エラストマー成形体の使用しえるフィルム・シートとしては、例えば、輸液バッグ、医療容器、自動車内外装材、飲料ボトル、衣装ケース、食品包材、食品容器、レトルト容器、パイプ、透明基盤、シーラントなどを例示でき、中でも本発明の熱可塑性エラストマー組成物は、射出成形や射出発泡成形性に優れるため、射出成形や射出発泡成形で得られる成形品が特に好ましい。
本発明の熱可塑性エラストマー成形体の使用しえるその他用途としては、例えば、靴底、サンダル等の履物、水泳用フィン、水中メガネ、ゴルフクラブグリップ、野球バットグリップ等のレジャー用品、ガスケット、防水布、ベルト、ガーデンホース、階段用滑り止めテープ、物流用パレットの滑り止めテープなどを例示できる。
(1)引張強度試験
JIS K6251に準拠して、射出成形にて試験片(JIS 3号ダンベル、厚み2mm)を作成し、引張強さ(TB)(単位:MPa)と破断伸び(EB)(単位:%)を23℃又は−35℃の雰囲気下にて引張速度500mm/分にて測定した。
(2)メルトフローレート(MFR)
ISO1133(又はASTM D1238)に準拠し、230℃、2.16kg荷重で測定した。
(3)ショアー硬度測定
(a)ショアーD硬度
ISO7619(JIS K6253)に準拠して、厚さ3mmの射出成形角板を用い、厚み6mm(厚み3mm片の2枚重ね)の積層されたシートを用いてショアーD硬度計により測定した。ショアーD硬度については、瞬間値を求めた。
(b)ショアーA硬度
JIS K6253に準拠して、厚さ2mmの射出成形角板を用い、厚み6mm(厚み2mm片の3枚重ね)の積層されたシートを用いてショアーA硬度計により測定した。ショアーA硬度については、瞬間値を求めた。
(4)外観
射出成形により、図1に示すような厚肉部(3mm)と薄肉部(0.5mm)が存在する成形体を作成し、成形後に肉厚差がある部分に発生するティアライン(エアバッグ動作時にカバーが裂ける線)部のグロス変化を肉眼により観察し、下記の基準で評価した。
1.差が顕著である、2.わずかだか差がある、3.差が見分けられない
<使用材料>
(A)ポリオレフィン樹脂としては以下のものを使用した。
・ブロックポリプロピレン(PP−1)
メルトフローレート10g/10分(230℃、2.16kg荷重)
エチレン単位含量14モル%
・ブロックポリプロピレン(PP−2)
メルトフローレート(ISO1133、230℃、2.16kg荷重)50g/10分
密度(ISO1183)0.90g/cm3
引張弾性率(ISO527)1450MPa
シャルピー衝撃強さ(ISO179、23℃)10kJ/m2
荷重たわみ温度(ISO75、1.8MPa)55℃
スチレン/エチレン・ブチレン共重合体(B−1)
メルトフローレート(ISO1133,230℃、2.16kg荷重)20g/10分
A硬度(ISO7619)70
密度(ISO1183)0.89g/cm3
スチレン/エチレン・ブチレン比(質量比)=20/80
油展エチレン・プロピレン・5−エチリデン−2−ノルボルネン共重合体ゴム(C−1)エチレン単位含量78モル%
ヨウ素価13
極限粘度[η]3.4dl/g
油展量:ゴム100質量部に対して、可塑剤(ダイアナプロセスオイルPW−380、出光興産製)を40質量部配合
油展エチレン・プロピレン・5−エチリデン−2−ノルボルネン共重合体ゴム(C−1)50質量部と、ブロックポリプロピレン(PP−1)50質量部と、架橋剤として有機ペルオキシド(パーヘキサ25B、日本油脂(株)製)0.3質量部と、架橋助剤としてジビニルベンゼン0.3質量部と、酸化防止剤としてフェノール系酸化防止剤(イルガノックス1010、BASF(株)製)0.1質量部とをヘンシェルミキサーで充分に混合し、下記条件下で押出混練した。
押出機(品番 KTX−46、神戸製鋼(株)製、シリンダー温度:C1〜C2 120℃、C3〜C4 140℃、C5〜C14 200℃、ダイス温度:200℃、スクリュー回転数:400rpm、押出量:80kg/h)
押出機:品番 KTX−46、神戸製鋼(株)製
シリンダー温度:C1〜C2 120℃、C3〜C4 140℃、C5〜C14 200℃
ダイス温度:200℃
スクリュー回転数:400rpm
押出量:80kg/h
ポリオレフィン樹脂(A)(ブロックポリプロピレン(PP−1)、ブロックポリプロピレン(PP−2))、スチレン/エチレン・ブチレン共重合体(B−1)及びエチレン・プロピレン・5−エチリデン−2−ノルボルネン共重合体ゴム(C−1)の質量比を表1に示すように変更する以外は、実施例1と同様にして、熱可塑性エラストマー組成物を得た。
ゴム成分(エチレン・プロピレン・5−エチリデン−2−ノルボルネン共重合体ゴム(C−1))を配合せず、ポリオレフィン樹脂(A)(ブロックポリプロピレン(PP−1)、ブロックポリプロピレン(PP−2))及びスチレン/エチレン・ブチレン共重合体(B−1)の質量比を表1に示すように変更する以外は、実施例1と同様にして、熱可塑性エラストマー組成物を得た。
実施例1〜2及び比較例1の物性評価の結果を表2に示す。
Claims (8)
- ポリオレフィン樹脂(A)10〜80質量部、JIS K6253に準拠するタイプA硬度(瞬間値)が96以下であるスチレン系熱可塑性エラストマー(B)10〜80質量部、及び少なくとも一部が架橋されたゴム(C)1〜15質量部(成分(A)、(B)及び(C)の合計量は100質量部である)を含み、更に成分(A)、(B)及び(C)の合計量100質量部に対して、可塑剤(D)を0質量部以上、10質量部以下含む組成物であり、JIS K6253に準拠するタイプD硬度(瞬間値)が35以上かつ70以下である熱可塑性エラストマー組成物であって、(a)スチレン又はその誘導体の重合体ブロックと、(b)イソプレン重合体ブロック又はイソプレン・ブタジエン共重合体ブロックであって、全イソプレン単位に対する1,2−位及び3,4−位で結合しているイソプレン単位含有量が40%以上である重合体又は共重合体ブロックとからなる水素添加されていてもよいブロック共重合体を含有しない熱可塑性エラストマー組成物。
- 前記スチレン系熱可塑性エラストマー(B)がスチレン/エチレン・ブチレン共重合体である請求項1記載の熱可塑性エラストマー組成物。
- 前記ゴム(C)がエチレン・α−オレフィン共重合体ゴム及び/又はエチレン・α−オレフィン・非共役ポリエン共重合体ゴムを含む請求項1又は2に記載の熱可塑性エラストマー組成物。
- 請求項1〜3のいずれか1項に記載の熱可塑性エラストマー組成物を成形して得られる熱可塑性エラストマー成形体。
- 請求項1〜3のいずれか1項に記載の熱可塑性エラストマー組成物を射出成形して得られる熱可塑性エラストマー成形体。
- 成形時の樹脂流動方向に直交する向きの成形体厚みの最も厚い部分(L1)と最も薄い部分(L2)との比率(L1/L2)が2以上、50以下である請求項4又は5記載の熱可塑性エラストマー成形体。
- 請求項4〜6のいずれか1項に記載の熱可塑性エラストマー成形体を含む自動車部品。
- エアバッグカバーである請求項7記載の自動車部品。
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