JP2018165310A - Ethylene copolymer composition - Google Patents
Ethylene copolymer composition Download PDFInfo
- Publication number
- JP2018165310A JP2018165310A JP2017063080A JP2017063080A JP2018165310A JP 2018165310 A JP2018165310 A JP 2018165310A JP 2017063080 A JP2017063080 A JP 2017063080A JP 2017063080 A JP2017063080 A JP 2017063080A JP 2018165310 A JP2018165310 A JP 2018165310A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- mass
- copolymer composition
- parts
- ethylene copolymer
- 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 60
- 229920001038 ethylene copolymer Polymers 0.000 title claims abstract description 34
- 229920001577 copolymer Polymers 0.000 claims abstract description 40
- 239000004711 α-olefin Substances 0.000 claims abstract description 32
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 19
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 19
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 8
- 238000007561 laser diffraction method Methods 0.000 claims abstract description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 35
- 239000005977 Ethylene Substances 0.000 claims description 35
- 239000004014 plasticizer Substances 0.000 claims description 13
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- 239000006229 carbon black Substances 0.000 claims description 10
- 239000012744 reinforcing agent Substances 0.000 claims description 9
- 150000001451 organic peroxides Chemical class 0.000 claims description 8
- 238000004438 BET method Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 abstract description 7
- 230000000704 physical effect Effects 0.000 abstract description 7
- 238000003878 thermal aging Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 17
- 230000032683 aging Effects 0.000 description 14
- 229920001971 elastomer Polymers 0.000 description 11
- 239000005060 rubber Substances 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 10
- 235000019241 carbon black Nutrition 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- -1 carbon black Chemical compound 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 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 5
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 5
- 150000004291 polyenes Chemical class 0.000 description 5
- 239000010734 process oil Substances 0.000 description 5
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-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
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 239000000126 substance Substances 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
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-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
- 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 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 2
- HBPSHRBTXIZBDI-UHFFFAOYSA-N 4-ethylidene-8-methylnona-1,7-diene Chemical compound C=CCC(=CC)CCC=C(C)C HBPSHRBTXIZBDI-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- NHLUYCJZUXOUBX-UHFFFAOYSA-N nonadec-1-ene Chemical compound CCCCCCCCCCCCCCCCCC=C NHLUYCJZUXOUBX-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 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
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 description 1
- SFTGRPFSYZGXQW-GQCTYLIASA-N (4e)-3-methylhexa-1,4-diene Chemical compound C\C=C\C(C)C=C SFTGRPFSYZGXQW-GQCTYLIASA-N 0.000 description 1
- JBVMSEMQJGGOFR-FNORWQNLSA-N (4e)-4-methylhexa-1,4-diene Chemical compound C\C=C(/C)CC=C JBVMSEMQJGGOFR-FNORWQNLSA-N 0.000 description 1
- UJNVTDGCOKFBKM-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)hexane Chemical compound CCCCCC(OOC(C)(C)C)OOC(C)(C)C UJNVTDGCOKFBKM-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- PPWUTZVGSFPZOC-UHFFFAOYSA-N 1-methyl-2,3,3a,4-tetrahydro-1h-indene Chemical compound C1C=CC=C2C(C)CCC21 PPWUTZVGSFPZOC-UHFFFAOYSA-N 0.000 description 1
- LPWUGKDQSNKUOQ-UHFFFAOYSA-N 12-ethyltetradec-1-ene Chemical compound CCC(CC)CCCCCCCCCC=C LPWUGKDQSNKUOQ-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- FEEIOCGOXYNQIM-UHFFFAOYSA-N 2,3-di(propan-2-ylidene)bicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(=C(C)C)C2=C(C)C FEEIOCGOXYNQIM-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
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- IILGVAQPFQYXIO-UHFFFAOYSA-N 2-methylhepta-2,5-diene Chemical compound CC=CCC=C(C)C IILGVAQPFQYXIO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RYDLGQCQPYTDKW-UHFFFAOYSA-N 4-ethylideneundeca-1,7-diene Chemical compound CCCC=CCCC(=CC)CC=C RYDLGQCQPYTDKW-UHFFFAOYSA-N 0.000 description 1
- NSCGBRZPOMAOIH-UHFFFAOYSA-N 5-(2-methylprop-1-enyl)bicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C(C)C)CC1C=C2 NSCGBRZPOMAOIH-UHFFFAOYSA-N 0.000 description 1
- KLAWFKRMCIXRFS-UHFFFAOYSA-N 5-ethenylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C=C)CC1C=C2 KLAWFKRMCIXRFS-UHFFFAOYSA-N 0.000 description 1
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- UGJBFMMPNVKBPX-UHFFFAOYSA-N 5-propan-2-ylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C(C)C)CC1C=C2 UGJBFMMPNVKBPX-UHFFFAOYSA-N 0.000 description 1
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- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
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- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、エチレン・α−オレフィン・非共役ポリエン共重合体および特定の酸化マグネシウムを含むエチレン系共重合体組成物およびその用途に関する。詳しくは、本発明は、エチレン・α−オレフィン・非共役ポリエン共重合体を含み、耐熱老化性に優れる架橋成形体を製造し得るエチレン系共重合体組成物、ならびに該エチレン系共重合体組成物を用いた架橋成形体に関する。 The present invention relates to an ethylene copolymer composition containing an ethylene / α-olefin / non-conjugated polyene copolymer and specific magnesium oxide and use thereof. Specifically, the present invention relates to an ethylene copolymer composition that can produce a cross-linked molded article having an excellent heat aging resistance, including an ethylene / α-olefin / non-conjugated polyene copolymer, and the ethylene copolymer composition. The present invention relates to a crosslinked molded article using the product.
エチレン・α−オレフィン共重合体やエチレン・α−オレフィン・非共役ポリエン共重合体などのエチレン系共重合体は、主鎖に不飽和結合を持たないため、ジエン系のゴムと比較して耐候性、耐熱性、耐オゾン性に優れ、自動車工業部品、工業用ゴム製品、電気絶縁材、土木建材用品、ゴム引布等のゴム製品等に広く用いられている。 Ethylene copolymers such as ethylene / α-olefin copolymers and ethylene / α-olefin / non-conjugated polyene copolymers have no unsaturated bonds in the main chain, so they have better weather resistance than diene rubbers. Excellent in heat resistance, heat resistance, and ozone resistance, it is widely used in rubber products such as automobile industrial parts, industrial rubber products, electrical insulation materials, civil engineering materials, and rubberized fabrics.
特に、エチレン・α−オレフィン・非共役ポリエン共重合体は、非共役ポリエンに由来する二重結合が架橋反応に関与でき、架橋反応を起こすことによりゴム製品においてより優れた強度とゴム弾性を達成することができるので、広く使用されている。 In particular, in ethylene / α-olefin / non-conjugated polyene copolymers, double bonds derived from non-conjugated polyenes can participate in the cross-linking reaction, resulting in superior strength and rubber elasticity in rubber products. Can be so widely used.
一般にエチレン・α−オレフィン・非共役ポリエン共重合体を各種用途に用いる場合は、エチレン・α−オレフィン・非共役ポリエン共重合体を単独で使用することはなく、例えば、加硫剤（架橋剤）として、硫黄、あるいは硫黄化合物など、加硫促進助剤として、酸化亜鉛、酸化マグネシウムなど、補強材としてカーボンブラックなど、あるいは可塑剤としてプロセスオイルなどが配合されている。 In general, when an ethylene / α-olefin / non-conjugated polyene copolymer is used for various purposes, the ethylene / α-olefin / non-conjugated polyene copolymer is not used alone, for example, a vulcanizing agent (crosslinking agent). ), Sulfur, sulfur compounds, etc., vulcanization accelerating aids such as zinc oxide and magnesium oxide, reinforcing materials such as carbon black, and plasticizers as process oils.
例えば、特許文献１には、エチレン・プロピレン・ジエン共重合体ゴムに、ＢＥＴ法により測定した比表面積が３０〜１３０ｍ2／ｇである酸化マグネシウムを配合することにより、未加硫ゴム組成物の貯蔵安定性、押出し加工性が改良されることが提案されている。 For example, Patent Document 1 discloses an unvulcanized rubber composition by blending an ethylene / propylene / diene copolymer rubber with magnesium oxide having a specific surface area measured by the BET method of 30 to 130 m 2 / g. It has been proposed that storage stability and extrusion processability be improved.
しかしながら、特許文献１の実施例および比較例に記載された粒度が大きい酸化マグネシウム（キョウワマグ１５０など）を用いて得られる組成物から得られる架橋成形体は、耐熱老化性に劣ることが判った。 However, it has been found that a crosslinked molded article obtained from a composition obtained by using a magnesium oxide having a large particle size (such as Kyowa Mug 150) described in Examples and Comparative Examples of Patent Document 1 is inferior in heat aging resistance.
本発明の課題は、さらに機械的物性および耐熱老化性が改良された架橋成形体を得るに好適なエチレン系共重合体組成物を得ることにある。 An object of the present invention is to obtain an ethylene copolymer composition suitable for obtaining a crosslinked molded article having further improved mechanical properties and heat aging resistance.
本発明者は、このような状況において鋭意検討した結果、特定の粒子径と比表面積の酸化マグネシウムとエチレン・α−オレフィン・非共役ポリエン共重合体を含む樹脂組成物を用いると、機械物性と耐熱老化性が改善された架橋成形体を製造し得ることを見出し、本発明を完成するに至った。 As a result of diligent examination in such a situation, the present inventor used a resin composition containing magnesium oxide having a specific particle diameter and specific surface area and an ethylene / α-olefin / non-conjugated polyene copolymer, It has been found that a crosslinked molded article having improved heat aging resistance can be produced, and the present invention has been completed.
すなわち、本発明はエチレン・α−オレフィン・非共役ポリエン共重合体（Ａ）：１００質量部およびレーザー回折法によって求められる平均粒径が（Ｄ５０）が０．４〜１．０μｍ、ＢＥＴ比表面積が１００〜２００ｍ2／ｇ以下の範囲にある酸化マグネシウム（Ｄ）：０．５〜２０質量部を含有することを特徴とするエチレン共重合体組成物に係る。 That is, the present invention relates to an ethylene / α-olefin / non-conjugated polyene copolymer (A): 100 parts by mass and an average particle size (D50) determined by a laser diffraction method of 0.4 to 1.0 μm, a BET specific surface area. Is contained in the range of 100 to 200 m 2 / g or less of magnesium oxide (D): 0.5 to 20 parts by mass.
本発明のエチレン共重合体組成物によれば、機械物性と耐熱老化性に優れた架橋成形体を製造することができる。本発明の架橋成形体は優れた耐熱老化性および耐疲労性を示し、高温下で用いる用途にも好適に用いることができ、自動車用、モーターバイク用、工業機械用、建設機械用または農業機械用等のホース、特にターボチャージャーホース等の用途に好適に用いることができる。 According to the ethylene copolymer composition of the present invention, a crosslinked molded article excellent in mechanical properties and heat aging resistance can be produced. The crosslinked molded article of the present invention exhibits excellent heat aging resistance and fatigue resistance, and can be suitably used for applications used at high temperatures. For automobiles, motorbikes, industrial machinery, construction machinery, or agricultural machinery For example, it can be suitably used for applications such as turbocharger hoses.
＜エチレン・α−オレフィン・非共役ポリエン共重合体（Ａ）＞
本発明に係るエチレン系共重合体組成物に含まれる成分の一つであるエチレン・α−オレフィン・非共役ポリエン共重合体（Ａ）〔以下、「共重合体（Ａ）」と呼称する場合がある。〕は、エチレンから導かれる構成単位と、炭素数３以上、好ましくは炭素数３〜２０のα−オレフィンから導かれる構成単位と、非共役ポリエンから導かれる構成単位を含む共重合体である。
<Ethylene / α-olefin / non-conjugated polyene copolymer (A)>
Ethylene / α-olefin / non-conjugated polyene copolymer (A) which is one of the components contained in the ethylene copolymer composition according to the present invention (hereinafter referred to as “copolymer (A)”) There is. ] Is a copolymer comprising a structural unit derived from ethylene, a structural unit derived from an α-olefin having 3 or more carbon atoms, preferably 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene.
本発明に係るエチレン・α−オレフィン・非共役ポリエン共重合体（Ａ）は、１種単独で用いてもよいし、２種類以上組み合わせて用いてもよい。該共重合体（Ａ）は、本発明の効果を奏する限り、トランス体やシス体など、構造異性体に何ら限定されない。 The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention may be used singly or in combination of two or more. The copolymer (A) is not limited to structural isomers such as trans isomers and cis isomers as long as the effects of the present invention are exhibited.
炭素数３以上のα−オレフィンとしては、具体的には、プロピレン、１−ブテン、４−メチル−１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−ノネン、１−デセン、１−ウンデセン、１−ドデセン、１−トリデセン、１−テトラデセン、１−ペンタデセン、１−ヘキサデセン、１−ヘプタデセン、１−ノナデセン、１−エイコセン、９−メチル−１−デセン、１４−メチル−１−ドデセンおよび１２−-エチル−１−テトラデセンなどが挙げられる。なかでも、炭素原子数３〜１０のα−オレフィンが好ましく、プロピレン、１−ブテン、４−メチル−１−ペンテン、１−ヘキセンおよび１−オクテンがより好ましく、特に、プロピレンおよび１−ブテンが好ましい。 Specific examples of the α-olefin having 3 or more carbon atoms include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 14-methyl-1- Examples include dodecene and 12-ethyl-1-tetradecene. Of these, α-olefins having 3 to 10 carbon atoms are preferable, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are more preferable, and propylene and 1-butene are particularly preferable. .
これらα-オレフィンは、単独で、または２種以上組み合わせて用いられる。
非共役ポリエンとしては、具体的には、1,4-ヘキサジエン、3-メチル-1,4-ヘキサジエン、4-メチル-1,4-ヘキサジエン、5-メチル-1,4-ヘキサジエン、4,5-ジメチル-1,4-ヘキサジエン、7-メチル-1,6-オクタジエン、8-メチル-4-エチリデン-1,7-ノナジエンおよび4-エチリデン-1,7-ウンデカジエン等の鎖状非共役ジエン；メチルテトラヒドロインデン、5-エチリデン-2-ノルボルネン、5-メチレン-2-ノルボルネン、5-イソプロピリデン-2-ノルボルネン、5-ビニリデン-2-ノルボルネン、6-クロロメチル-5-イソプロペニル-2-ノルボルネン、5-ビニル-2-ノルボルネン、5-イソプロペニル-2-ノルボルネン、5-イソブテニル-2-ノルボルネン、シクロペンタジエンおよびノルボルナジエン等の環状非共役ジエン；2,3-ジイソプロピリデン-5-ノルボルネン、2-エチリデン-3-イソプロピリデン-5-ノルボルネン、2-プロペニル-2,2-ノルボルナジエン、4-エチリデン-8-メチル-1,7-ノナジエン等のトリエンなどが挙げられる。なかでも、１，４−ヘキサジエン、5-エチリデン-2-ノルボルネン、5-ビニル-2-ノルボルネン、５−エチリデン−２−ノルボルネンおよび５−ビニル−２−ノルボルネンの混合物が好ましく、５−エチリデン−２−ノルボルネン、５−ビニル−２−ノルボルネン、５−エチリデン−２−ノルボルネンおよび５−ビニル−２−ノルボルネンの混合物がより好ましい。
These α-olefins are used alone or in combination of two or more.
Specific examples of the non-conjugated polyene include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5 Chain non-conjugated dienes such as dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene and 4-ethylidene-1,7-undecadiene; Methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene Cyclic non-conjugated dienes such as 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene and norbornadiene; 2,3-diisopropylidene-5-norbornene, 2 -Ethylidene-3-isopropylide 5-norbornene, 2-propenyl-2,2-norbornadiene, etc. trienes and 4-ethylidene-8-methyl-1,7-nonadiene and the like. Of these, a mixture of 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene is preferable, and 5-ethylidene-2 More preferred are mixtures of -norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene.
これらの非共役ポリエンは、単独で、または２種類以上組み合わせて用いられる。
本発明に係るエチレン・α−オレフィン・非共役ポリエン共重合体（Ａ）は、好ましくは、下記要件（Ａ−１）〜（Ａ−３）を満たす。
These non-conjugated polyenes are used alone or in combination of two or more.
The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention preferably satisfies the following requirements (A-1) to (A-3).
（Ａ−１）
エチレンから導かれる構成単位を、７０質量％を超えて９９質量％以下、好ましくは７０〜９０質量％、より好ましくは７０〜８５質量％で含み、炭素数３以上のα−オレフィンから導かれる構成単位を、１質量％以上３０質量％未満、好ましくは１０〜３０質量％、より好ましくは１５〜３０質量％で含む〔ただし、エチレンから導かれる構成単位とα−オレフィンから導かれる構成単位の合計量を１００質量％とする。〕。
(A-1)
A constitutional unit derived from an ethylene-containing α-olefin having a constitutional unit derived from ethylene of more than 70% by mass and 99% by mass or less, preferably 70 to 90% by mass, more preferably 70 to 85% by mass. 1% or more and less than 30% by mass, preferably 10 to 30% by mass, more preferably 15 to 30% by mass [however, the total of the structural unit derived from ethylene and the structural unit derived from α-olefin The amount is 100% by mass. ].
非共役ポリエンから導かれる構成単位は、エチレンから導かれる構成単位とα−オレフィンから導かれる構成単位の合計量１００質量部に対して、通常１．０〜２０．０質量部であり、好ましくは３．０〜１５．０質量部、より好ましくは４．０〜１４．０質量部の量で含まれる。 The structural unit derived from the non-conjugated polyene is usually 1.0 to 20.0 parts by mass with respect to 100 parts by mass in total of the structural unit derived from ethylene and the structural unit derived from α-olefin, preferably It is contained in an amount of 3.0 to 15.0 parts by mass, more preferably 4.0 to 14.0 parts by mass.
本発明に係るエチレン・α−オレフィン・非共役ポリエン共重合体（Ａ）の組成は、たとえば、ＡＳＴＭ Ｄ ３９００およびＡＳＴＭ Ｄ ６０４７に準拠して、13Ｃ−ＮＭＲなどを用いて測定できる。 The composition of the ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention can be measured, for example, using 13 C-NMR in accordance with ASTM D 3900 and ASTM D 6047.
（Ａ−２）
本発明に係るエチレン・α−オレフィン・非共役ポリエン共重合体（Ａ）は、ＡＳＴＭ Ｄ １６４６に準じて測定して得られた、１００℃におけるムーニー粘度ＭＬ(1+4)（１００℃）が、１〜９０、より好ましくは１〜６０、さらに好ましくは１〜３０の範囲にある。ムーニー粘度が上記範囲にあると、良加工性および良物性を示すため好ましい。
(A-2)
The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention has a Mooney viscosity ML (1 + 4) (100 ° C.) at 100 ° C. obtained by measurement according to ASTM D 1646. 1 to 90, more preferably 1 to 60, and still more preferably 1 to 30. When the Mooney viscosity is in the above range, it is preferable because good processability and good physical properties are exhibited.
（Ａ−３）
本発明に係るエチレン・α−オレフィン・非共役ポリエン共重合体（Ａ）は、１３５℃、デカリン中で測定される極限粘度〔η〕が、１．０〜５．０ｄｌ／ｇ、好ましくは１．０〜４．０ｄｌ／ｇである。
(A-3)
The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 1.0 to 5.0 dl / g, preferably 1 0.0 to 4.0 dl / g.
＜エチレン・α−オレフィン・非共役ポリエン共重合体（Ａ）の製造方法＞
本発明に係るエチレン・α−オレフィン・非共役ポリエン共重合体（Ａ）は、たとえば、チーグラー・ナッタ触媒やメタロセン触媒など公知の重合用触媒を用いて製造することができる。重合方法としても特に限定されず、溶液重合、懸濁重合、バルク重合法などの液相重合法、気相重合法、その他公知の重合方法で行うことができる。また、これらの共重合体は、本発明の効果を奏する限り限定されず、市販品としても入手可能である。市販品としては、たとえば、エクソンモービル社製のＶｉｓｔａｌｏｎ（登録商標）、住友化学（株）社製のエスプレン（登録商標）、三井化学（株）社製の三井ＥＰＴ（登録商標）が挙げられる。
<Method for producing ethylene / α-olefin / non-conjugated polyene copolymer (A)>
The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention can be produced using, for example, a known polymerization catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. It does not specifically limit as a polymerization method, It can carry out by liquid phase polymerization methods, such as solution polymerization, suspension polymerization, a bulk polymerization method, a gas phase polymerization method, and other well-known polymerization methods. In addition, these copolymers are not limited as long as the effects of the present invention are exhibited, and are also available as commercial products. Examples of commercially available products include Vistalon (registered trademark) manufactured by ExxonMobil, Espren (registered trademark) manufactured by Sumitomo Chemical Co., Ltd., and Mitsui EPT (registered trademark) manufactured by Mitsui Chemicals, Inc.
＜酸化マグネシウム（Ｄ）＞
本発明に係る共重合体組成物に含まれる成分の一つである酸化マグネシウム（Ｄ）は、レーザー回折法によって求められる平均粒径（Ｄ５０）が０．４〜１．０μｍの範囲、好ましくは０．５〜０．９μｍの範囲にある。
<Magnesium oxide (D)>
Magnesium oxide (D), which is one of the components contained in the copolymer composition according to the present invention, has an average particle diameter (D50) determined by a laser diffraction method in the range of 0.4 to 1.0 μm, preferably It is in the range of 0.5 to 0.9 μm.
平均粒径が上記範囲にある酸化マグネシウム（Ｄ）を用いることにより、機械的物性および耐熱老化性が改良された架橋成形体が得られうる。
本発明に係る酸化マグネシウム（Ｄ）は、好ましくは、ＢＥＴ法により測定した比表面積が１００〜２００ｍ2／ｇ、さらに好ましくは１００〜１３０ｍ2／ｇの範囲にある。
By using magnesium oxide (D) having an average particle size in the above range, a crosslinked molded article having improved mechanical properties and heat aging resistance can be obtained.
Magnesium oxide according to the present invention (D) is preferably the specific surface area measured by BET method is 100 to 200 m 2 / g, more preferably in the range of 100~130m 2 / g.
平均粒径が上記範囲にある酸化マグネシウムとしては、例えば、協和化学工業株式会社から商品名キョウワマグRＭＦ１５０、およびキョウワマグRＭＦ３０として販売されている。 Examples of magnesium oxide having an average particle size in the above range are sold by Kyowa Chemical Industry Co., Ltd. under the trade names Kyowa Mag R MF150 and Kyowa Mag R MF30.
＜エチレン系共重合体組成物＞
本発明のエチレン系共重合体組成物は、上記エチレン・α−オレフィン・非共役ポリエン共重合体（Ａ）：１００質量部に対し、上記酸化マグネシウム（Ｄ）を０．５〜２０質量部、好ましくは１〜１０質量部の範囲で含む。
<Ethylene copolymer composition>
The ethylene-based copolymer composition of the present invention is composed of 0.5 to 20 parts by mass of the magnesium oxide (D) with respect to 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer (A). Preferably it contains in 1-10 mass parts.
本発明のエチレン系共重合体組成物は、酸化マグネシウム（Ｄ）を上記範囲で含むことにより、機械的物性および耐熱老化性が改良された架橋成形体が得られうる。
本発明のエチレン系共重合体組成物は、好ましくは、上記酸化マグネシウム（Ｄ）に加え、さらに架橋剤（Ｂ）を０．１〜５質量部、より好ましくは１〜４質量部、および補強剤（Ｃ）を１０〜３００質量部、より好ましくは５０〜２００質量部含む。
When the ethylene copolymer composition of the present invention contains magnesium oxide (D) in the above range, a crosslinked molded article having improved mechanical properties and heat aging resistance can be obtained.
The ethylene-based copolymer composition of the present invention is preferably 0.1 to 5 parts by mass, more preferably 1 to 4 parts by mass, and reinforcement, in addition to the magnesium oxide (D), and further a crosslinking agent (B). The agent (C) is contained in an amount of 10 to 300 parts by mass, more preferably 50 to 200 parts by mass.
本発明のエチレン系共重合体組成物は、さらに好ましくは、上記（Ｄ）成分、（Ｂ）成分、および（Ｃ）成分に加え、エチレン・α−オレフィン・非共役ポリエン共重合体（Ａ）：１００質量部に対し、可塑剤（Ｅ）を１０〜８０質量部、より好ましくは２０〜７０質量部含む。 The ethylene-based copolymer composition of the present invention is more preferably an ethylene / α-olefin / non-conjugated polyene copolymer (A) in addition to the components (D), (B) and (C). : 10-80 mass parts of a plasticizer (E) is included with respect to 100 mass parts, More preferably, 20-70 mass parts is included.
《架橋剤（Ｂ）》
本発明に係る架橋剤(Ｂ)としては、種々公知の架橋剤、具体的には、例えば、有機過酸化物、フェノール樹脂、硫黄系化合物、ヒドロシリコーン系化合物、アミノ樹脂、キノンまたはその誘導体、アミン系化合物、アゾ系化合物、エポキシ系化合物、イソシアネート等のゴムを架橋する際に一般に使用される架橋剤が挙げられる。これらのうちでは、有機過酸化物、硫黄等の架橋剤（「加硫剤」とも言う。）が好適である。
これら架橋剤の中でも、有機過酸化物を用いると、特に耐熱老化性に優れる架橋成形体が得られうる。
<< Crosslinking agent (B) >>
As the crosslinking agent (B) according to the present invention, various known crosslinking agents, specifically, for example, organic peroxides, phenol resins, sulfur compounds, hydrosilicon compounds, amino resins, quinones or derivatives thereof, The crosslinking agent generally used when bridge | crosslinking rubber | gum, such as an amine compound, an azo compound, an epoxy compound, and isocyanate, is mentioned. Among these, organic peroxides, crosslinking agents such as sulfur (also referred to as “vulcanizing agents”) are preferable.
Among these crosslinking agents, when an organic peroxide is used, a crosslinked molded article having particularly excellent heat aging resistance can be obtained.
〈有機過酸化物〉
本発明に係る有機過酸化物としては、ジクミルペルオキシド、ジ−ｔｅｒｔ−ブチルペルオキシド、２，５−ジ−（ｔｅｒｔ−ブチルペルオキシ）ヘキサン、２，５−ジメチル−２，５−ジ−（ｔｅｒｔ−ブチルペルオキシ）ヘキサン、２，５−ジメチル−２，５−ジ−（ｔｅｒｔ−ブチルペルオキシ）ヘキシン−３、１，３−ビス（ｔｅｒｔ−ブチルペルオキシイソプロピル）ベンゼン、１，１−ビス（ｔｅｒｔ−ブチルペルオキシ）−３，３，５−トリメチルシクロヘキサン、ｎ−ブチル−４，４−ビス（ｔｅｒｔ−ブチルペルオキシ）バレレート、ベンゾイルペルオキシド、ｐ−クロロベンゾイルペルオキシド、２，４−ジクロロベンゾイルペルオキシド、ｔｅｒｔ−ブチルペルオキシベンゾエート、ｅｒｔ−ブチルペルオキシイソプロピルカーボネート、ジアセチルペルオキシド、ラウロイルペルオキシド、ｔｅｒｔ−ブチルクミルペルオキシド等が挙げられる。
<Organic peroxide>
Examples of the organic peroxide according to the present invention include dicumyl peroxide, di-tert-butyl peroxide, 2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert -Butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert- Butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl Peroxybenzoate, tert-butyl peroxyisop Pills carbonate, diacetyl peroxide, lauroyl peroxide, etc. tert- butyl cumyl peroxide.
このうちでは、２，５−ジ−（ｔｅｒｔ−ブチルペルオキシ）ヘキサン、２，５−ジメチル-２，５−ジ−（ｔｅｒｔ−ブチルペルオキシ）ヘキサン、２，５−ジメチル-２，５−ジ−（ｔｅｒｔ−ブチルペルオキシ）ヘキシン−３、１，３−ビス（ｔｅｒｔ−ブチルペルオキシイソプロピル）ベンゼン、１，１−ビス（ｔｅｒｔ−ブチルペルオキシ）−３，３，５−トリメチルシクロヘキサン、ｎ−ブチル−４,４−ビス（ｔｅｒｔ−ブチルペルオキシ）バレレート等の２官能性の有機過酸化物が好ましく、中でも、２，５−ジ−（ｔｅｒｔ−ブチルペルオキシ）ヘキサン、２，５−ジメチル−２，５−ジ−（ｔｅｒｔ−ブチルペルオキシ）ヘキサンが最も好ましい。 Among these, 2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (Tert-Butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4 Bifunctional organic peroxides such as 2,4-bis (tert-butylperoxy) valerate are preferred, among which 2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5- Most preferred is di- (tert-butylperoxy) hexane.
《補強剤（Ｃ）》
本発明に係る補強剤（Ｃ）は、ゴム組成物の補強剤として、通常用いられる補強剤である。補強剤の具体例としては、カーボンブラック、シランカップリング剤で表面処理したカーボンブラック、シリカ、微粉タルク、微粉ケイ酸などを例示できる。
これら補強剤として、カーボンブラックを用いる場合は、より機械的強度、耐熱老化性に優れる架橋成形体が得られうる。
<< Reinforcing agent (C) >>
The reinforcing agent (C) according to the present invention is a reinforcing agent that is usually used as a reinforcing agent for a rubber composition. Specific examples of the reinforcing agent include carbon black, carbon black surface-treated with a silane coupling agent, silica, fine talc, fine silicate, and the like.
When carbon black is used as the reinforcing agent, a cross-linked molded article having better mechanical strength and heat aging resistance can be obtained.
〈カーボンブラック〉
本発明に係るカーボンブラックとしては、各種の市販品を特に制限なく用いることができる。具体的には、旭＃１５ＨＳ、旭＃５０、旭＃５５Ｇ、旭＃５０ＨＧ、旭＃６０および旭＃６０Ｇ（商品名；旭カーボン社製）ならびにシースト（ＳＲＦ、ＧＰＦ、ＦＥＦ、ＭＡＦ、ＨＡＦ、ＩＳＡＦ、ＳＡＦ、ＦＴおよびＭＴなど）などのカーボンブラック（東海カーボン社製）あるいはこれらのカーボンブラックをシランカップリング剤などで表面処理したものが挙げられる。
これらカーボンブラック（Ｃ）は、一種単独でも、二種以上組み合わせて用いてもよい。
<Carbon black>
As the carbon black according to the present invention, various commercially available products can be used without particular limitation. Specifically, Asahi # 15HS, Asahi # 50, Asahi # 55G, Asahi # 50HG, Asahi # 60 and Asahi # 60G (trade name; manufactured by Asahi Carbon Co., Ltd.) and Seest (SRF, GPF, FEF, MAF, HAF, And carbon black (manufactured by Tokai Carbon Co., Ltd.) such as ISAF, SAF, FT and MT), or those obtained by surface treatment of these carbon blacks with a silane coupling agent.
These carbon blacks (C) may be used singly or in combination of two or more.
《可塑剤（Ｅ）》
本発明に係る可塑剤（Ｅ）は、種々公知の可塑剤であり、具体的には、プロセスオイル（例えば、ダイアナプロセスオイル ＰＷ−３８０、ダイアナプロセスオイル ＰＷ−１００（商品名；出光興産（株）製）、ダイアナプロセスオイル ＰＳ−４３０（商品名；出光興産社製））、潤滑油、パラフィン油、流動パラフィン、石油アスファルトおよびワセリンなどの石油系可塑剤；コールタールおよびコールタールピッチなどのコールタール系可塑剤；ヒマシ油、アマニ油、ナタネ油、大豆油およびヤシ油などの脂肪油系可塑剤；蜜ロウ、カルナウバロウおよびラノリンなどのロウ類；リシノール酸、パルミチン酸、ステアリン酸、ステアリン酸バリウム、ステアリン酸カルシウムおよびラウリン酸亜鉛などの脂肪酸またはその塩；ナフテン酸、パイン油およびロジンまたはその誘導体；テルペン樹脂、石油樹脂、アタクチックポリプロピレンおよびクマロンインデン樹脂などの合成高分子物質；ジオクチルフタレート、ジオクチルアジペートおよびジオクチルセバケートなどのエステル系可塑剤；その他、マイクロクリスタリンワックス、液状ポリブタジエン、変性液状ポリブタジエン、液状チオコール、炭化水素系合成潤滑油、トール油およびサブ（ファクチス）などが挙げられる。
これらのなかでも、石油系可塑剤が特に好ましい。本発明に係る可塑剤（Ｅ）は、一種単独で用いてもよいし、二種以上組み合わせて用いてもよい。
<< Plasticizer (E) >>
The plasticizer (E) according to the present invention is various known plasticizers, and specifically, process oils (for example, Diana process oil PW-380, Diana process oil PW-100 (trade name; Idemitsu Kosan Co., Ltd.). )), Diana Process Oil PS-430 (trade name; manufactured by Idemitsu Kosan Co., Ltd.)), petroleum-based plasticizers such as lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt and petroleum jelly; coal such as coal tar and coal tar pitch Tar plasticizers; fatty oil plasticizers such as castor oil, linseed oil, rapeseed oil, soybean oil and coconut oil; waxes such as beeswax, carnauba wax and lanolin; ricinoleic acid, palmitic acid, stearic acid, barium stearate , Fatty acids such as calcium stearate and zinc laurate or salts thereof; naphthenic acid Pine oil and rosin or derivatives thereof; synthetic polymer materials such as terpene resin, petroleum resin, atactic polypropylene and coumarone indene resin; ester plasticizers such as dioctyl phthalate, dioctyl adipate and dioctyl sebacate; other, microcrystalline wax , Liquid polybutadiene, modified liquid polybutadiene, liquid thiocol, hydrocarbon-based synthetic lubricating oil, tall oil, and sub (factis).
Of these, petroleum plasticizers are particularly preferred. The plasticizer (E) according to the present invention may be used alone or in combination of two or more.
《その他添加剤》
本発明のエチレン系共重合体組成物には、上記酸化マグネシウム（Ｄ）、架橋剤（Ｂ）、補強剤（Ｃ）および可塑剤（Ｅ）に加え、用途により、目的に応じて他の添加剤、例えば、加工助剤、活性剤、吸湿剤、さらに耐熱安定剤、耐候安定剤、帯電防止剤、着色剤、滑剤および増粘剤等を含んでいてもよい。
《Other additives》
In addition to the magnesium oxide (D), the cross-linking agent (B), the reinforcing agent (C) and the plasticizer (E), other additions are added to the ethylene copolymer composition of the present invention depending on the purpose. Agents such as processing aids, activators, hygroscopic agents, heat stabilizers, weathering stabilizers, antistatic agents, colorants, lubricants and thickeners may also be included.
《架橋成形体》
本発明の架橋成形体は、上記本発明のエチレン系共重合体組成物を必要に応じて成形し、架橋することにより得られる。架橋の際には、金型を用いても、用いなくてもよい。金型を用いない場合には、エチレン系共重合体組成物は、通常連続的に成形、架橋される。
<Crosslinked molded product>
The crosslinked molded product of the present invention can be obtained by molding and crosslinking the ethylene copolymer composition of the present invention as necessary. In the case of crosslinking, a mold may or may not be used. When a mold is not used, the ethylene copolymer composition is usually continuously molded and crosslinked.
エチレン系共重合体組成物を架橋させる方法としては、（ａ）エチレン系共重合体組成物を、通常、押出し成形、プレス成形、インジェクション成形等の成形法や、ロール加工により所望形状に予備成形し、成形と同時にまたは成形物を架橋槽内に導入して加熱する方法や、（ｂ）エチレン系共重合体組成物を上記と同様に予備成形し、次いで電子線を照射する方法等を例示することができる。 As a method of crosslinking the ethylene copolymer composition, (a) the ethylene copolymer composition is usually preformed into a desired shape by a molding method such as extrusion molding, press molding, injection molding, or roll processing. And a method of heating the molding simultaneously with molding or introducing the molded product into a crosslinking tank, and (b) a method of preforming an ethylene copolymer composition in the same manner as described above and then irradiating an electron beam. can do.
なお、（ａ）の方法では、加熱によりエチレン系共重合体組成物中の架橋剤（有機過酸化物）による架橋反応が起こり、架橋体が得られる。また、（ｂ）の方法では、電子線により架橋反応が起こり、架橋体が得られる。（ｂ）の方法においては通常、予備成形が施されたエチレン系共重合体組成物に、０．１〜１０ＭｅＶのエネルギーを有する電子線を、樹脂組成物の吸収線量が通常は０．５〜３６Ｍｒａｄ、好ましくは０．５〜２０Ｍｒａｄ、さらに好ましくは１〜１０Ｍｒａｄになるように照射する。 In the method (a), a crosslinking reaction is caused by heating with a crosslinking agent (organic peroxide) in the ethylene copolymer composition, whereby a crosslinked product is obtained. In the method (b), a crosslinking reaction is caused by an electron beam to obtain a crosslinked product. In the method (b), an electron beam having an energy of 0.1 to 10 MeV is usually applied to the pre-molded ethylene copolymer composition, and the absorbed dose of the resin composition is usually 0.5 to. Irradiation is performed at 36 Mrad, preferably 0.5 to 20 Mrad, more preferably 1 to 10 Mrad.
＜用途＞
本発明のエチレン系共重合体組成物は、低温特性、機械特性、押出し成形性、プレス成形性、インジェクション成形性等の成形性、およびロール加工性に非常に優れており、本発明のエチレン系共重合体組成物から、耐熱老化性、低温特性（低温での柔軟性、ゴム弾性等）、機械特性などに優れる成形体を好適に得ることができる。
<Application>
The ethylene copolymer composition of the present invention is very excellent in low temperature characteristics, mechanical properties, extrusion moldability, press moldability, moldability such as injection moldability, and roll processability, and the ethylene copolymer composition of the present invention. From the copolymer composition, a molded article having excellent heat aging resistance, low temperature characteristics (flexibility at low temperature, rubber elasticity, etc.), mechanical characteristics, and the like can be suitably obtained.
また、本発明のエチレン系共重合体組成物は、前述のエチレン・α−オレフィン・非共役ポリエン共重合体（Ａ）を含むことにより、成形性および架橋特性に優れ、耐熱安定性に優れた架橋体を製造することができるため、本発明のエチレン系共重合体組成物から得られた架橋成形体は、高温下での長期使用が見込まれる用途にも好適に使用することができる。 Moreover, the ethylene-based copolymer composition of the present invention is excellent in moldability and cross-linking properties and excellent in heat resistance stability by including the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer (A). Since a crosslinked body can be produced, the crosslinked molded body obtained from the ethylene-based copolymer composition of the present invention can be suitably used for applications that are expected to be used for a long time at high temperatures.
本発明のエチレン系共重合体組成物、該組成物から得られる架橋成形体は、様々な用途に用いることができる。具体的には、タイヤ用ゴム、Ｏ−リング、工業用ロール、パッキン（例えばコンデンサーパッキン）、ガスケット、ベルト（例えば、断熱ベルト、複写機ベルト、搬送ベルト）、自動車用ホースなどのホース類（例えば、ターボチャージャーホース、ウォーターホース、ブレーキリザーバーホース、ラジエターホース、エアーホース）、防振ゴム、防振材あるいは制振材（例えば、エンジンマウント、モーターマウント）、マフラーハンガー、スポンジ（例えば、ウェザーストリップスポンジ、断熱スポンジ、プロテクトスポンジ、微発泡スポンジ）、ケーブル（イグニッションケーブル、キャブタイヤケーブル、ハイテンションケーブル）、電線被覆材（高圧電線被覆材、低電圧電線被覆材、舶用電線被覆材）、グラスランチャネル、カラー表皮材、給紙ロール、ルーフィングシート等に好適に用いられる。 The ethylene-based copolymer composition of the present invention and the crosslinked molded product obtained from the composition can be used for various applications. Specifically, hoses such as rubber for tires, O-rings, industrial rolls, packing (for example, capacitor packing), gaskets, belts (for example, heat insulation belts, copying machine belts, conveyor belts), automobile hoses (for example, , Turbocharger hose, water hose, brake reservoir hose, radiator hose, air hose), anti-vibration rubber, anti-vibration material or damping material (eg engine mount, motor mount), muffler hanger, sponge (eg weather strip sponge) , Insulation sponge, protective sponge, fine foam sponge), cable (ignition cable, cabtyre cable, high tension cable), wire covering material (high voltage wire covering material, low voltage wire covering material, marine wire covering material), glass run channel, Kara Skin material, sheet feed roller, is suitably used in the roofing sheet.
次に本発明について実施例を示してさらに詳細に説明するが、本発明はこれらによって限定されるものではない。以下の実施例等の記載において、特に言及しない限り「部」は「質量部」を示す。 EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these. In the following description of Examples and the like, “parts” means “parts by mass” unless otherwise specified.
＜エチレン系共重合体組成物（未架橋）の物性の評価＞
（１）ムーニー粘度（ＭＬ（１＋４）１２５℃）
実施例および比較例におけるエチレン系共重合体組成物（組成物１）を用いて、１２５℃におけるムーニー粘度（ＭＬ（１＋４）１２５℃）は、ＪＩＳ Ｋ６３００に準拠して、ムーニー粘度計（（株）島津製作所製ＳＭＶ２０２型）を用いて、１２５℃の条件下で測定した。
<Evaluation of physical properties of ethylene copolymer composition (uncrosslinked)>
(1) Mooney viscosity (ML (1 + 4) 125 ° C)
Using the ethylene copolymer compositions (Composition 1) in Examples and Comparative Examples, the Mooney viscosity at 125 ° C. (ML (1 + 4) 125 ° C.) is in accordance with JIS K6300 (Mooney viscometer ) SMV202 type manufactured by Shimadzu Corporation) and measured at 125 ° C.
（２）加硫（架橋）誘導時間
実施例および比較例におけるエチレン系共重合体組成物（組成物２）を用いて、加硫測定装置：ＭＤＲ２０００（ＡＬＰＨＡ ＴＥＣＨＮＯＬＯＧＩＥＳ 社製）により、温度１８０℃および時間３０分の測定条件下で、誘導時間（ＴＳ１）を以下のとおり測定した。
(2) Vulcanization (crosslinking) induction time Using the ethylene copolymer compositions (composition 2) in the examples and comparative examples, a vulcanization measuring apparatus: MDR2000 (manufactured by ALPHA TECHNOLOGIES), a temperature of 180 ° C. and Under the measurement conditions for 30 minutes, the induction time (TS1) was measured as follows.
一定温度および一定のせん断速度の条件下で得られるトルク変化を測定した。最小トルク値からトルク１ｐｏｉｎｔ（１ｄＮｍ）上がるまでの時間を加硫誘導時間（ＴＳ１；分）とした。 The torque change obtained under conditions of constant temperature and constant shear rate was measured. The time from the minimum torque value until the torque increased by 1 point (1 dNm) was taken as the vulcanization induction time (TS1; minutes).
（３）加硫速度
実施例および比較例におけるエチレン系共重合体組成物（組成物２）を用いて、測定装置：ＭＤＲ２０００（ＡＬＰＨＡ ＴＥＣＨＮＯＬＯＧＩＥＳ 社製）により、温度１８０℃および時間３０分の測定条件下で、加硫速度（ＴＣ９０）を以下のとおり測定した。
(3) Vulcanization rate Using the ethylene copolymer composition (Composition 2) in Examples and Comparative Examples, measurement conditions: Measurement conditions: MDR2000 (manufactured by ALPHA TECHNOLOGIES), measurement conditions at a temperature of 180 ° C. and a time of 30 minutes Below, the vulcanization rate (TC90) was measured as follows.
一定温度および一定のせん断速度の条件下で得られるトルク変化を測定した。トルクの最大値と最小値との差の９０％のトルクに達成するまでの時間を加硫速度（ＴＣ９０；分）とした。 The torque change obtained under conditions of constant temperature and constant shear rate was measured. The time required to achieve 90% of the difference between the maximum value and the minimum value of the torque was defined as the vulcanization speed (TC90; minutes).
＜エチレン系共重合体組成物（架橋物）の物性＞
（１）硬さ試験（デュロ−Ａ硬度）
ＪＩＳ Ｋ ６２５３に従い、シートの硬度（タイプＡデュロメータ、ＨＡ）の測定は、平滑な表面をもっている２ｍｍの架橋物シート６枚を用いて、平らな部分を積み重ねて厚み約１２ｍｍとして行った。ただし、試験片に異物の混入したもの、気泡のあるもの、およびキズのあるものは用いなかった。また、試験片の測定面の寸法は、押針先端が試験片の端から１２ｍｍ以上離れた位置で測定できる大きさとした。
<Physical properties of ethylene copolymer composition (crosslinked product)>
(1) Hardness test (Duro-A hardness)
According to JIS K 6253, the hardness of the sheet (type A durometer, HA) was measured by stacking flat portions with a thickness of about 12 mm using six 2 mm cross-linked sheets having a smooth surface. However, those in which foreign matter was mixed in the test piece, those having bubbles, and those having scratches were not used. Moreover, the dimension of the measurement surface of the test piece was set to such a size that measurement was possible at a position where the tip of the push needle was 12 mm or more away from the end of the test piece.
（２）引張試験
実施例および比較例で得た架橋物シートを打抜いてＪＩＳ Ｋ ６２５１（２００１年）に記載されている３号形ダンベル試験片を調製した。この試験片を用いて同ＪＩＳ Ｋ ６２５１に規定される方法に従い、測定温度２５℃、引張速度５００ｍｍ／分の条件で引張り試験を行ない、２５％モジュラス（Ｍ２５）、５０％モジュラス（Ｍ５０）、１００％モジュラス（Ｍ１００）、２００％モジュラス（Ｍ２００）、３００％モジュラス（Ｍ３００）、引張破断点応力（ＴＢ）および引張破断点伸び（ＥＢ）を測定した。
(2) Tensile test No. 3 dumbbell test pieces described in JIS K 6251 (2001) were prepared by punching out the cross-linked products obtained in Examples and Comparative Examples. Using this test piece, according to the method defined in JIS K 6251, a tensile test was performed under the conditions of a measurement temperature of 25 ° C. and a tensile speed of 500 mm / min. 25% modulus (M25), 50% modulus (M50), 100 The% modulus (M100), 200% modulus (M200), 300% modulus (M300), tensile stress at break (TB) and tensile elongation at break (EB) were measured.
（３）耐熱老化試験
架橋物シートを、ＪＩＳ Ｋ ６２５７に従い、１６０℃で９６ｈ保持する熱老化試験を行った。熱老化試験後のシートの硬度、引張破断点応力、引張破断点伸びを、前記［硬度（Ｄｕｒｏｍｅｔｅｒ−Ａ）］の項目、前記［モジュラス、引張破断点応力、引張破断点伸び］の項目と同様の方法で測定した。
(3) Heat Aging Test A heat aging test was performed in which the cross-linked sheet was held at 160 ° C. for 96 hours according to JIS K 6257. The hardness, tensile breaking point stress, and tensile breaking point elongation of the sheet after the heat aging test are the same as the items of [Hardness (Durometer-A)] and [Modulus, tensile breaking point stress, tensile breaking point elongation]. It measured by the method of.
［実施例１］
第一段階として、ＢＢ−４型バンバリーミキサー（神戸製鋼所製）を用いて、三井ＥＰＴ(商標)２０６０Ｍ：１００質量部を１分間素練りし、次いでこれに、
キョーワマグMF150（酸化マグネシウム、協和化学工業株式会社）５質量部、
ステアリン酸（日油株式会社）１質量部、
旭#50 （SRFカーボン、旭カーボン株式会社）４５質量部、
旭#60 （FEFカーボン、旭カーボン株式会社）３０質量部、
旭#15HS（FTカーボン、旭カーボン株式会社）４０質量部、
Sunpar 2280（パラフィン系オイル、日本サン石油）４７質量部
を各々加え、１４０℃で２分間混練した。その後、ラムを上昇させ掃除を行ない、さらに、１分間混練を行ない、約１５０℃で排出し、第一段階の配合物（組成物１）を得た。
[Example 1]
As a first step, using a BB-4 type Banbury mixer (manufactured by Kobe Steel), 100 parts by mass of Mitsui EPT (trademark) 2060M: 100 parts by mass, then,
Kyowamag MF150 (magnesium oxide, Kyowa Chemical Industry Co., Ltd.) 5 parts by mass,
1 part by weight of stearic acid (NOF Corporation),
Asahi # 50 (SRF Carbon, Asahi Carbon Co., Ltd.) 45 parts by mass,
Asahi # 60 (FEF Carbon, Asahi Carbon Co., Ltd.) 30 parts by mass,
Asahi # 15HS (FT Carbon, Asahi Carbon Co., Ltd.) 40 parts by mass,
47 parts by mass of Sunpar 2280 (paraffinic oil, Nippon Sun Oil) were added and kneaded at 140 ° C. for 2 minutes. Thereafter, the ram was raised and cleaned, and further kneaded for 1 minute and discharged at about 150 ° C. to obtain a first-stage formulation (Composition 1).
次に、第二段階として、第一段階で得られた組成物１を、６インチロ−ル（日本ロール（株）社製、前ロールの表面温度５０℃、後ロールの表面温度５０℃、前ロールの回転数１６ｒｐｍ、後ロールの回転数１８ｒｐｍ）に巻き付けて、これに、Perhexa25B（100%）（ジアルキルパーオキサイド）、２質量部を加え１０分間混練して未架橋の共重合体組成物（組成物２）を得た。 Next, as a second stage, the composition 1 obtained in the first stage is a 6-inch roll (manufactured by Nippon Roll Co., Ltd., front roll surface temperature 50 ° C., rear roll surface temperature 50 ° C., front It was wound around a roll rotation speed of 16 rpm and a rear roll rotation speed of 18 rpm, and Perhexa25B (100%) (dialkyl peroxide), 2 parts by mass, and kneaded for 10 minutes to obtain an uncrosslinked copolymer composition ( Composition 2) was obtained.
得られた共重合体組成物を用いて、前記記載の方法で物性を評価した。
次いで、当該共重合体組成物をシート状に分出し、１００トンプレス成形機を用いて１８０℃で１０分間プレスし、厚み２ｍｍの架橋物のシートを調製した。得られた架橋物のシートを用いて、前記記載の方法で物性の評価を行った。
結果を表１に示す。
Using the obtained copolymer composition, the physical properties were evaluated by the method described above.
Next, the copolymer composition was dispensed into a sheet and pressed at 180 ° C. for 10 minutes using a 100-ton press molding machine to prepare a crosslinked sheet having a thickness of 2 mm. Using the obtained cross-linked sheet, physical properties were evaluated by the method described above.
The results are shown in Table 1.
［比較例１〜３］
実施例１において、第一段階および第二段階で配合する各配合物の種類および量を表１に示す通りとすること以外は、実施例１と同様にして、組成物１、組成物２、および架橋物のシートを得て、前記記載の方法で物性の評価を行った。
結果を表１に示す。
[Comparative Examples 1-3]
In Example 1, except that the types and amounts of the respective compounds to be blended in the first stage and the second stage are as shown in Table 1, composition 1, composition 2, And the sheet | seat of the crosslinked material was obtained, and the physical property was evaluated by the method of the said description.
The results are shown in Table 1.
Claims (5)
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| JPH02141418A (en) * | 1988-11-21 | 1990-05-30 | Kyowa Chem Ind Co Ltd | Highly dispersible magnesium oxide and its production |
| JP2009046636A (en) * | 2007-08-22 | 2009-03-05 | Yokohama Rubber Co Ltd:The | Rubber composition, fiber/rubber composite, and hose |
| JP2016106160A (en) * | 2013-03-25 | 2016-06-16 | 神島化学工業株式会社 | Magnesium oxide particle, resin composition, rubber composition and molding |
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| JPH02141418A (en) * | 1988-11-21 | 1990-05-30 | Kyowa Chem Ind Co Ltd | Highly dispersible magnesium oxide and its production |
| JP2009046636A (en) * | 2007-08-22 | 2009-03-05 | Yokohama Rubber Co Ltd:The | Rubber composition, fiber/rubber composite, and hose |
| JP2016106160A (en) * | 2013-03-25 | 2016-06-16 | 神島化学工業株式会社 | Magnesium oxide particle, resin composition, rubber composition and molding |
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| CN109291450A (en) * | 2018-09-13 | 2019-02-01 | 中北大学 | A kind of high-performance nano graphene foaming aluminum and preparation method thereof and prepare material |
| CN109291450B (en) * | 2018-09-13 | 2021-04-06 | 中北大学 | High-performance nano graphene foamed aluminum, and preparation method and preparation material thereof |
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