JP2020147622A - Resin composition and crosslinked molding - Google Patents
Resin composition and crosslinked molding Download PDFInfo
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- JP2020147622A JP2020147622A JP2019043725A JP2019043725A JP2020147622A JP 2020147622 A JP2020147622 A JP 2020147622A JP 2019043725 A JP2019043725 A JP 2019043725A JP 2019043725 A JP2019043725 A JP 2019043725A JP 2020147622 A JP2020147622 A JP 2020147622A
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- resin composition
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- copolymer
- ethylene
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- 239000011342 resin composition Substances 0.000 title claims abstract description 30
- 238000000465 moulding Methods 0.000 title abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 238000004132 cross linking Methods 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 15
- 150000008442 polyphenolic compounds Chemical class 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims description 46
- 150000004291 polyenes Chemical class 0.000 claims description 34
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 27
- 239000004711 α-olefin Substances 0.000 claims description 27
- 239000005977 Ethylene Substances 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 230000003712 anti-aging effect Effects 0.000 claims description 17
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 8
- 239000002683 reaction inhibitor Substances 0.000 claims description 8
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 4
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 4
- 238000007906 compression Methods 0.000 abstract description 6
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- 230000000607 poisoning effect Effects 0.000 abstract description 5
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 abstract 1
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- 238000012360 testing method Methods 0.000 description 17
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
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- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 125000005388 dimethylhydrogensiloxy group Chemical group 0.000 description 5
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 5
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 4
- 239000012744 reinforcing agent Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 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 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- 229920002857 polybutadiene Polymers 0.000 description 3
- 239000010734 process oil Substances 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
- 238000004073 vulcanization Methods 0.000 description 3
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- CZNRFEXEPBITDS-UHFFFAOYSA-N 2,5-bis(2-methylbutan-2-yl)benzene-1,4-diol Chemical compound CCC(C)(C)C1=CC(O)=C(C(C)(C)CC)C=C1O CZNRFEXEPBITDS-UHFFFAOYSA-N 0.000 description 2
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 2
- SZAQZZKNQILGPU-UHFFFAOYSA-N 2-[1-(2-hydroxy-3,5-dimethylphenyl)-2-methylpropyl]-4,6-dimethylphenol Chemical compound C=1C(C)=CC(C)=C(O)C=1C(C(C)C)C1=CC(C)=CC(C)=C1O SZAQZZKNQILGPU-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910003849 O-Si Inorganic materials 0.000 description 2
- 229910003872 O—Si Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000007788 liquid Substances 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
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- 229910052717 sulfur Inorganic materials 0.000 description 2
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- 238000009864 tensile test Methods 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000001993 wax Substances 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 1
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
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- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 1
- LKALLEFLBKHPTQ-UHFFFAOYSA-N 2,6-bis[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound OC=1C(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=CC(C)=CC=1CC1=CC(C)=CC(C(C)(C)C)=C1O LKALLEFLBKHPTQ-UHFFFAOYSA-N 0.000 description 1
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 description 1
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Landscapes
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Abstract
Description
本発明は、末端二重結合を有する重合体を含む樹脂組成物および該樹脂組成物を架橋してなる架橋成形体に関する。 The present invention relates to a resin composition containing a polymer having a terminal double bond and a crosslinked molded product obtained by cross-linking the resin composition.
エチレン・α−オレフィン・非共役ポリエンランダム共重合体などの末端二重結合を有する重合体を含む架橋可能なゴム組成物（例えば、特許文献１参照）のヒドロシリコーン架橋は、イオウ加硫や過酸化物架橋と比較して、低温で短時間の架橋が可能であり、揮発分が少ないなどの点で有用である。 Hydrosilicone cross-linking of a cross-linkable rubber composition (see, for example, Patent Document 1) containing a polymer having a terminal double bond such as ethylene / α-olefin / non-conjugated polyene random copolymer can be carried out by sulfur vulcanization or excess. Compared to oxide cross-linking, cross-linking is possible at low temperature for a short time, which is useful in that it has less volatile content.
しかしながら、ヒドロシリコーン架橋により得られる架橋物は、過酸化物架橋により得られる架橋物よりも圧縮永久歪み（ＣＳ）が劣るという課題がある。 However, the crosslinked product obtained by hydrosilicone cross-linking has a problem that the compressive permanent strain (CS) is inferior to that of the cross-linked product obtained by peroxide cross-linking.
上述したヒドロシリコーン架橋におけるＣＳ改善のために、過酸化物架橋で最もよく使用される老化防止剤である２−メルカプトベンズイミダゾールの使用を検討してみたが、ヒドロシリコーン架橋の場合、触媒被毒が生じるという問題が判明した。 In order to improve CS in the above-mentioned hydrosilicone crosslinking, we examined the use of 2-mercaptobenzimidazole, which is the most commonly used antioxidant in peroxide crosslinking, but in the case of hydrosilicone crosslinking, catalyst poisoning was considered. Turned out to be a problem.
本発明の課題は、触媒被毒が生じることなくヒドロシリコーン架橋が可能であり、かつ、圧縮永久歪みに優れた架橋成形体を得ることができる末端二重結合を有する重合体を含む樹脂組成物を提供することにある。 An object of the present invention is a resin composition containing a polymer having a terminal double bond, which enables hydrosilicone cross-linking without causing catalyst poisoning and can obtain a cross-linked molded product having excellent compression set. Is to provide.
本発明者らは、ポリフェノール系老化防止剤を用いることにより、上記課題を解決できることを見出し、本発明を完成するに至った。 The present inventors have found that the above problems can be solved by using a polyphenol-based antiaging agent, and have completed the present invention.
すなわち、本発明の樹脂組成物は、末端二重結合を有する重合体（Ａ）、ヒドロシリル基を１分子中に少なくとも２個持つヒドロシリル基含有化合物（Ｂ）、およびポリフェノール系老化防止剤（Ｃ）を含むことを特徴とする。 That is, the resin composition of the present invention comprises a polymer (A) having a terminal double bond, a hydrosilyl group-containing compound (B) having at least two hydrosilyl groups in one molecule, and a polyphenol-based antiaging agent (C). It is characterized by including.
本発明によれば、触媒被毒が生じることなくヒドロシリコーン架橋が可能であり、かつ、圧縮永久歪みに優れた架橋成形体を得ることができる末端二重結合を有する重合体を含む樹脂組成物および該樹脂組成物を架橋してなる架橋成形体を提供することができる。 According to the present invention, a resin composition containing a polymer having a terminal double bond, which enables hydrosilicone cross-linking without causing catalytic poisoning and can obtain a cross-linked molded product having excellent compression set. And a crosslinked molded article obtained by crosslinking the resin composition can be provided.
以下、本発明について詳細に説明する。
［樹脂組成物］
本発明に係る樹脂組成物は、末端二重結合を有する重合体（Ａ）、ヒドロシリル基を１分子中に少なくとも２個持つヒドロシリル基含有化合物（Ｂ）、およびポリフェノール系老化防止剤（Ｃ）を含むことを特徴とする。また、本発明の樹脂組成物は、必要に応じて、ヒドロシリコン用の白金系触媒（Ｄ）、反応抑制剤（Ｅ）およびその他の配合剤を含んでいてもよい。
Hereinafter, the present invention will be described in detail.
[Resin composition]
The resin composition according to the present invention comprises a polymer (A) having a terminal double bond, a hydrosilyl group-containing compound (B) having at least two hydrosilyl groups in one molecule, and a polyphenol-based antiaging agent (C). It is characterized by including. Further, the resin composition of the present invention may contain a platinum-based catalyst (D) for hydrosilicon, a reaction inhibitor (E) and other compounding agents, if necessary.
重合体（Ａ）
前記重合体（Ａ）としては、末端二重結合を有する重合体であれば制限なく用いることができ、１種単独で用いても、２種以上を組み合わせて用いてもよいが、後述するエチレン・α−オレフィン・非共役ポリエン共重合体（Ｓ）が好ましい。
Polymer (A)
As the polymer (A), any polymer having a terminal double bond can be used without limitation, and one type may be used alone or two or more types may be used in combination, but ethylene will be described later. The α-olefin / non-conjugated polyene copolymer (S) is preferable.
エチレン・α−オレフィン・非共役ポリエン共重合体（Ｓ）
本発明の成形体を製造する方法に用いるエチレン・α−オレフィン・非共役ポリエン共重合体（Ｓ）（以下「共重合体（Ｓ）」ともいう。）は、エチレン（ａ１）と、炭素原子数３〜２０のα−オレフィン（ａ２）と、下記一般式（Ｉ）および（II）からなる群から選ばれる部分構造を合計で分子中に２つ以上含む非共役ポリエン（ａ３）とに由来する構成単位を有する。
Ethylene / α-olefin / non-conjugated polyene copolymer (S)
The ethylene / α-olefin / non-conjugated polyene copolymer (S) (hereinafter, also referred to as “copolymer (S)”) used in the method for producing a molded product of the present invention contains ethylene (a1) and a carbon atom. Derived from α-olefins (a2) of numbers 3 to 20 and non-conjugated polyenes (a3) containing two or more partial structures selected from the group consisting of the following general formulas (I) and (II) in total. It has a structural unit to be used.
炭素原子数３〜２０のα−オレフィン（ａ２）としては、例えば、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、４−メチル−１−ペンテン、１−ヘプテン、１−オクテン、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−エイコセンなどが挙げられる。これらのうち、プロピレン、１−ブテン、１−ヘキセン、１−オクテンなどの炭素原子数３〜８のα−オレフィンが好ましく、特にプロピレンおよび１−ブテンが好ましい。このようなα−オレフィンは、原料コストが比較的安価であり、得られるエチレン・α−オレフィン・非共役ポリエン共重合体が優れた機械的性質を示し、さらにゴム弾性を持った成形体を得ることができるため好ましい。これらのα−オレフィンは一種単独で用いても、二種以上を用いてもよい。 Examples of the α-olefin (a2) having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and 1-. Examples thereof include decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene. Of these, α-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene, and 1-octene are preferable, and propylene and 1-butene are particularly preferable. As for such an α-olefin, the raw material cost is relatively low, the obtained ethylene / α-olefin / non-conjugated polyene copolymer exhibits excellent mechanical properties, and a molded product having rubber elasticity is obtained. It is preferable because it can be used. These α-olefins may be used alone or in combination of two or more.
すなわち、前記共重合体（Ｓ）は、少なくとも１種の炭素原子数３〜２０のα−オレフィン（ａ２）に由来する構成単位を含んでおり、２種以上の炭素原子数３〜２０のα−オレフィン（ａ２）に由来する構成単位を含んでいてもよい。 That is, the copolymer (S) contains a structural unit derived from at least one kind of α-olefin (a2) having 3 to 20 carbon atoms, and two or more kinds of α having 3 to 20 carbon atoms. -It may contain a structural unit derived from the olefin (a2).
上記式（Ｉ）および（II）からなる群から選ばれる部分構造を合計で分子中に２つ以上含む非共役ポリエン（ａ３）としては、５−ビニル−２−ノルボルネン（ＶＮＢ）、ノルボルナジエン、１，４−ヘキサジエン、ジシクロペンタジエンなどが挙げられる。これらのうちでは、入手容易性が高く、ヒドロシリル架橋が良好で、重合体組成物の耐熱性が向上しやすいことから非共役ポリエン（ａ３）がＶＮＢを含むことが好ましく、非共役ポリエン（ａ３）がＶＮＢであることがより好ましい。非共役ポリエン（ａ３）は一種単独で用いても、二種以上を用いてもよい。 As the non-conjugated polyene (a3) containing two or more partial structures selected from the group consisting of the above formulas (I) and (II) in the molecule in total, 5-vinyl-2-norbornene (VNB), norbornadiene, 1 , 4-Hexadiene, dicyclopentadiene and the like. Among these, the non-conjugated polyene (a3) preferably contains VNB because it is easily available, has good hydrosilyl cross-linking, and easily improves the heat resistance of the polymer composition, and the non-conjugated polyene (a3). Is more preferably VNB. The non-conjugated polyene (a3) may be used alone or in combination of two or more.
前記非共役ポリエン（ａ４）としては、５−エチリデン−２−ノルボルネン（ＥＮＢ）、５−メチレン−２−ノルボルネン、５−（２−プロペニル）−２−ノルボルネン、５−（３−ブテニル）−２−ノルボルネン、５−（１−メチル−２−プロペニル）−２−ノルボルネン、５−（４−ペンテニル）−２−ノルボルネン、５−（１−メチル−３−ブテニル）−２−ノルボルネン、５−（５−ヘキセニル）−２−ノルボルネン、５−（１−メチル−４−ペンテニル）−２−ノルボルネン、５−（２，３−ジメチル−３−ブテニル）−２−ノルボルネン、５−（２−エチル−３−ブテニル）−２−ノルボルネン、５−（６−ヘプテニル）−２−ノルボルネン、５−（３−メチル−５−ヘキセニル）−２−ノルボルネン、５−（３，４−ジメチル−４−ペンテニル）−２−ノルボルネン、５−（３−エチル−４−ペンテニル）−２−ノルボルネン、５−（７−オクテニル）−２−ノルボルネン、５−（２−メチル−６−ヘプテニル）−２−ノルボルネン、５−（１，２−ジメチル−５−ヘキセニル）−２−ノルボルネン、５−（５−エチル−５−ヘキセニル）−２−ノルボルネン、５−（１，２，３−トリメチル−４−ペンテニル）−２−ノルボルネンなどが挙げられる。これらのうちでは、入手容易性が高く、ヒドロシリル架橋時の架橋速度を制御しやすく、良好な機械物性が得られやすいことからＥＮＢが好ましい。非共役ポリエン（ａ４）は一種単独で用いても、二種以上を用いてもよい。 Examples of the non-conjugated polyene (a4) include 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5- (2-propenyl) -2-norbornene, and 5- (3-butenyl) -2. -Norbornene, 5- (1-methyl-2-propenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (1-methyl-3-butenyl) -2-norbornene, 5-( 5-Hexenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, 5- (2,3-dimethyl-3-butenyl) -2-norbornene, 5- (2-ethyl-) 3-Butenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (3-methyl-5-hexenyl) -2-norbornene, 5- (3,4-dimethyl-4-pentenyl) -2-Norbornene, 5- (3-ethyl-4-pentenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene, 5- (2-methyl-6-heptenyl) -2-norbornene, 5 -(1,2-dimethyl-5-hexenyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- (1,2,3-trimethyl-4-pentenyl) -2 -Norbornene and the like. Of these, ENB is preferable because it is easily available, the crosslinking rate at the time of hydrosilyl crosslinking is easy to control, and good mechanical properties can be easily obtained. The non-conjugated polyene (a4) may be used alone or in combination of two or more.
前記共重合体（Ｓ）が、前記非共役ポリエン（ａ４）に由来する構成単位を含む場合、その割合は本発明の目的を損なわない範囲において特に限定されるものではないが、好ましくは０〜２０質量％、より好ましくは０〜８質量％、さらに好ましくは０．０１〜８質量％程度の質量分率で含む（ただし、（ａ１）、（ａ２）、（ａ３）および（ａ４）の質量分率の合計を１００質量％とする。）。 When the copolymer (S) contains a structural unit derived from the non-conjugated polyene (a4), the proportion thereof is not particularly limited as long as the object of the present invention is not impaired, but is preferably 0 to 0. It is contained in a mass fraction of about 20% by mass, more preferably 0 to 8% by mass, still more preferably 0.01 to 8% by mass (however, the masses of (a1), (a2), (a3) and (a4). The total of the fractions is 100% by mass.)
前記共重合体（Ｓ）は、上述の通り、エチレン（ａ１）と、炭素原子数３〜２０のα−オレフィン（ａ２）と、上記非共役ポリエン（ａ３）と、必要に応じて上記非共役ポリエン（ａ４）とに由来する構成単位を有する共重合体であって、下記（ｉ）〜（iv）の要件を満たすことが好ましい。 As described above, the copolymer (S) contains ethylene (a1), α-olefin (a2) having 3 to 20 carbon atoms, the non-conjugated polyene (a3), and the above-mentioned non-conjugated polyene (a3), if necessary. It is a copolymer having a structural unit derived from polyene (a4), and preferably satisfies the following requirements (i) to (iv).
（ｉ）エチレン（ａ１）／α−オレフィン（ａ２）のモル比が４０／６０〜９９．９／０．１である。
（ii）非共役ポリエン（ａ３）に由来する構成単位の質量分率が、前記共重合体（Ｓ）１００質量％中、０．０７質量％〜１０質量％である。
（iii）１００℃におけるムーニー粘度ＭＬ(1+4)１００℃が５〜２５０である。
（iv）１３５℃デカリン中で測定した極限粘度［η］が０．１〜５．０ｄｌ／ｇである。
(I) The molar ratio of ethylene (a1) / α-olefin (a2) is 40/60 to 99.9 / 0.1.
(Ii) The mass fraction of the structural unit derived from the non-conjugated polyene (a3) is 0.07% by mass to 10% by mass in 100% by mass of the copolymer (S).
(Iii) Mooney viscosity at 100 ° C. ML (1 + 4) 100 ° C. is 5 to 250.
(Iv) The ultimate viscosity [η] measured in 135 ° C. decalin is 0.1 to 5.0 dl / g.
本明細書において、前記（ｉ）〜（iv）をそれぞれ、要件（ｉ）〜（iv）とも記す。また、本明細書において、「炭素原子数３〜２０のα−オレフィン」を単に「α−オレフィン」とも記す。 In the present specification, the above (i) to (iv) are also referred to as requirements (i) to (iv), respectively. Further, in the present specification, "α-olefin having 3 to 20 carbon atoms" is also simply referred to as "α-olefin".
＜要件（ｉ）＞
要件（ｉ）は、前記共重合体（Ｓ）中のエチレン／α−オレフィンのモル比が４０／６０〜９９．９／０．１の範囲であることを特定するものである。前記モル比は、好ましくは５０／５０〜９０／１０、より好ましくは５５／４５〜８５／１５、さらに好ましくは５５／４５〜７８／２２である。このような共重合体（Ｓ）は、ヒドロシリル架橋して得られる成形体が優れたゴム弾性を示し、機械的強度および柔軟性に優れたものとなるため好ましい。
<Requirement (i)>
Requirement (i) specifies that the molar ratio of ethylene / α-olefin in the copolymer (S) is in the range of 40/60 to 99.9 / 0.1. The molar ratio is preferably 50/50 to 90/10, more preferably 55/45 to 85/15, and even more preferably 55/45 to 78/22. Such a copolymer (S) is preferable because the molded product obtained by hydrosilyl cross-linking exhibits excellent rubber elasticity and is excellent in mechanical strength and flexibility.
なお、前記共重合体（Ｓ）中のエチレン量（エチレン（ａ１）に由来する構成単位の含量）およびα−オレフィン量（α−オレフィン（ａ２）に由来する構成単位の含量）は、13Ｃ−ＮＭＲにより求めることができる。 The amount of ethylene (content of the structural unit derived from ethylene (a1)) and the amount of α-olefin (content of the structural unit derived from α-olefin (a2)) in the copolymer (S) are 13 C. It can be obtained by -NMR.
＜要件（ii）＞
要件（ii）は、前記共重合体（Ｓ）中において、非共役ポリエン（ａ３）に由来する構成単位の質量分率が、前記共重合体（Ｓ）１００質量％中（すなわち全構成単位の質量分率の合計１００質量％中）、０．０７質量％〜１０質量％の範囲であることを特定するものである。この非共役ポリエン（ａ３）に由来する構成単位の質量分率は、好ましくは０．１質量％〜８．０質量％、より好ましくは０．５質量％〜５．０質量％である。
<Requirement (ii)>
The requirement (ii) is that the mass fraction of the structural unit derived from the non-conjugated polyene (a3) in the copolymer (S) is 100% by mass of the copolymer (S) (that is, all the structural units). It is specified that the mass fraction is in the range of 0.07% by mass to 10% by mass) (in a total of 100% by mass). The mass fraction of the structural unit derived from this non-conjugated polyene (a3) is preferably 0.1% by mass to 8.0% by mass, and more preferably 0.5% by mass to 5.0% by mass.
前記共重合体（Ｓ）が、要件（ii）を満たすと、本発明の樹脂組成物が充分な硬度を有し、機械特性に優れたものとなるため好ましく、ヒドロシリル架橋した場合には、早い架橋速度を示すものとなり、前記共重合体（Ｓ）が、架橋成形体の製造に好適なものとなるため好ましい。 When the copolymer (S) satisfies the requirement (ii), the resin composition of the present invention has sufficient hardness and excellent mechanical properties, which is preferable, and when hydrosilyl cross-linking is performed, it is early. It shows the cross-linking rate, and the copolymer (S) is preferable because it is suitable for producing a cross-linked molded product.
なお、前記共重合体（Ｓ）中の非共役ポリエン（ａ３）量（非共役ポリエン（ａ３）に由来する構成単位の含量）は、13Ｃ−ＮＭＲにより求めることができる。 The amount of non-conjugated polyene (a3) in the copolymer (S) (content of structural units derived from non-conjugated polyene (a3)) can be determined by 13 C-NMR.
＜要件（iii）＞
要件（iii）は、前記共重合体（Ｓ）において、１００℃におけるムーニー粘度ＭＬ(1+4)１００℃が５〜２５０の範囲であることを特定するものである。前記ムーニー粘度ＭＬ(1+4)１００℃は、好ましくは６〜２００、より好ましくは８〜１５０、さらに好ましくは１０〜１００である。
<Requirement (iii)>
Requirement (iii) specifies that the Mooney viscosity ML (1 + 4) 100 ° C. at 100 ° C. is in the range of 5 to 250 in the copolymer (S). The Mooney viscosity ML (1 + 4) 100 ° C. is preferably 6 to 200, more preferably 8 to 150, and even more preferably 10 to 100.
前記共重合体（Ｓ）が、要件（iii）を満たす場合、加工性および流動性が良好であり、また良好な後処理品質（リボンハンドリング性）を示すと共に優れたゴム物性を有する共重合体が得られる。 When the copolymer (S) satisfies the requirement (iii), the copolymer has good processability and fluidity, exhibits good post-treatment quality (ribbon handleability), and has excellent rubber physical properties. Is obtained.
＜要件（iv）＞
要件（iv）は、前記共重合体（Ｓ）において、１３５℃デカリン中で測定した極限粘度［η］が０．１〜５．０ｄｌ／ｇの範囲であることを特定するものである。前記極限粘度［η］は、好ましくは０．２〜５．０ｄＬ／ｇ、より好ましくは０．５〜４．５ｄＬ／ｇ、さらに好ましくは０．９〜４．０ｄＬ／ｇである。
<Requirements (iv)>
Requirement (iv) specifies that in the copolymer (S), the ultimate viscosity [η] measured in decalin at 135 ° C. is in the range of 0.1 to 5.0 dl / g. The ultimate viscosity [η] is preferably 0.2 to 5.0 dL / g, more preferably 0.5 to 4.5 dL / g, and even more preferably 0.9 to 4.0 dL / g.
＜前記共重合体（Ｓ）の製造＞
前記共重合体（Ｓ）は、エチレン（ａ１）と、炭素原子数３〜２０のα−オレフィン（ａ２）と、前記非共役ポリエン（ａ３）と、必要に応じて前記非共役ポリエン（ａ４）とからなるモノマーを共重合してなる共重合体である。
<Production of the copolymer (S)>
The copolymer (S) includes ethylene (a1), α-olefin (a2) having 3 to 20 carbon atoms, the non-conjugated polyene (a3), and, if necessary, the non-conjugated polyene (a4). It is a copolymer obtained by copolymerizing a monomer composed of.
前記共重合体（Ｓ）は、前記の要件（ｉ）〜（iv）を満たす限りにおいて、どのような製法で調製されてもよいが、メタロセン化合物の存在下にモノマーを共重合して得られたものであることが好ましく、メタロセン化合物を含む触媒系の存在下にモノマーを共重合して得られたものであることがより好ましい。 The copolymer (S) may be prepared by any production method as long as the above requirements (i) to (iv) are satisfied, but it is obtained by copolymerizing a monomer in the presence of a metallocene compound. It is preferable that the compound is obtained by copolymerizing a monomer in the presence of a catalyst system containing a metallocene compound.
前記共重合体（Ｓ）は、具体的には、例えば、国際公開第２０１５／１２２４９５号パンフレット記載のメタロセン触媒に記載の方法を採用することにより製造することができる。 Specifically, the copolymer (S) can be produced, for example, by adopting the method described in the metallocene catalyst described in Pamphlet No. 2015/122495.
ヒドロシリル基含有化合物（Ｂ）
本発明で用いられるヒドロシリル基含有化合物（Ｂ）は、前記共重合体（Ｓ）と反応して架橋剤として作用する。このヒドロシリル基含有化合物（Ｂ）は、従来から製造・市販されている、例えば、線状、環状、分岐状の各構造あるいは三次元網目状構造の樹脂状物など、その構造においていずれでも使用可能であるが、本発明で用いるヒドロシリル基含有化合物（Ｂ）は、１分子中に少なくとも２個のヒドロシリル基を含んでいなければならない。
Hydrosilyl group-containing compound (B)
The hydrosilyl group-containing compound (B) used in the present invention reacts with the copolymer (S) and acts as a cross-linking agent. This hydrosilyl group-containing compound (B) can be used in any of the conventionally manufactured and commercially available structures, for example, a linear, cyclic, branched structure, or a resin-like substance having a three-dimensional network structure. However, the hydrosilyl group-containing compound (B) used in the present invention must contain at least two hydrosilyl groups in one molecule.
このようなヒドロシリル基含有化合物（Ｂ）は、通常、下記の一般組成式
Ｒ4 bＨcＳｉＯ(4-b-c)/2
で表わされる化合物を使用することができる。
Such a hydrosilyl group-containing compound (B) is usually produced by the following general composition formula R 4 b H c SiO (4-bc) / 2.
The compound represented by can be used.
上記一般組成式において、Ｒ4は、脂肪族不飽和結合を除く、炭素原子数１〜１０、特に炭素原子数１〜８の置換または非置換の１価炭化水素基であり、このような１価炭化水素基としては、メチル基やエチル基からはじまりノニル基やデシル基に至る、ｎ−、ｉｓｏ−、ｓｅｃ−、ｔｅｒｔ−などの異性体を含むアルキル基、フェニル基、ハロゲン置換のアルキル基、例えばトリフロロプロピル基を例示することができる。中でも、メチル基、エチル基、プロピル基、フェニル基、トリフロロプロピル基が好ましく、特にメチル基が好ましい。 In the above general composition formula, R 4 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, excluding the aliphatic unsaturated bond, and such 1 The valent hydrocarbon group includes an alkyl group containing isomers such as n-, iso-, sec-, and tert-, starting from a methyl group and an ethyl group, and reaching a nonyl group and a decyl group, a phenyl group, and a halogen-substituted alkyl group. For example, a trifluoropropyl group can be exemplified. Of these, a methyl group, an ethyl group, a propyl group, a phenyl group, and a trifluoropropyl group are preferable, and a methyl group is particularly preferable.
上記一般組成式において、ｂは、０．６＜ｂ＜３、好ましくは１≦ｂ＜２．２、特に好ましくは１．５≦ｂ≦２であり、ｃは、１≦ｃ≦３、好ましくは１＜ｃ＜２であり、かつ、ｂ＋ｃは、０＜ｂ＋ｃ≦３、好ましくは１．５＜ｂ＋ｃ≦２．７である。 In the above general composition formula, b is 0.6 <b <3, preferably 1 ≦ b <2.2, particularly preferably 1.5 ≦ b ≦ 2, and c is 1 ≦ c ≦ 3, preferably. Is 1 <c <2, and b + c is 0 <b + c ≦ 3, preferably 1.5 <b + c ≦ 2.7.
前記ヒドロシリル基含有化合物（Ｂ）は、１分子中のケイ素原子数が好ましくは２〜１０００個、特に好ましくは２〜３００個、最も好ましくは４〜２００個のオルガノハイドロジェンポリシロキサンであり、具体的には、１，１，３，３−テトラメチルジシロキサン、１，３，５，７−テトラメチルテトラシクロシロキサン、１，３，５，７，８−ペンタメチルペンタシクロシロキサン等のシロキサンオリゴマー、分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端シラノール基封鎖メチルハイドロジェンポリシロキサン、分子鎖両末端シラノール基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルポリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖メチルハイドロジェンポリシロキサン、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、Ｒ2 2（Ｈ）ＳｉＯ1/2 単位とＳｉＯ4/2単位とからなり、任意にＲ2 3ＳｉＯ1/2 単位、Ｒ2 2ＳｉＯ2/2 単位、Ｒ2（Ｈ）ＳｉＯ2/2単位、（Ｈ）ＳｉＯ3/2 またはＲ2ＳｉＯ3/2単位を含み得るシリコーンレジンなどを挙げることができる。 The hydrosilyl group-containing compound (B) is an organohydrogenpolysiloxane in which the number of silicon atoms in one molecule is preferably 2 to 1000, particularly preferably 2 to 300, and most preferably 4 to 200. Specifically, siloxane oligomers such as 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyltetracyclosiloxane, 1,3,5,7,8-pentamethylpentacyclosiloxane. , Molecular chain double-ended trimethylsiloxy group-blocked methylhydrogenpolysiloxane, Molecular chain double-ended trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, Molecular chain double-ended silanol group-blocked methylhydrogenpolysiloxane, Molecular chain both Terminal silanol group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain double-ended dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, molecular chain double-ended dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane, molecular chain double-ended dimethyl Hydrogensiloxy group-blocking dimethylsiloxane / methylhydrogensiloxane copolymer, consisting of R 2 2 (H) SiO 1/2 unit and SiO 4/2 unit, optionally R 2 3 SiO 1/2 unit, R 2 Examples thereof include silicone resins that may contain 2 SiO 2/2 units, R 2 (H) SiO 2/2 units, (H) SiO 3/2 or R 2 SiO 3/2 units.
分子鎖両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサンとしては、例えば下式で示される化合物、さらには下式においてメチル基の一部または全部をエチル基、プロピル基、フェニル基、トリフロロプロピル基等で置換した化合物などが挙げられる。
（ＣＨ3）3ＳｉＯ−（−ＳｉＨ（ＣＨ3）−Ｏ−）d−Ｓｉ（ＣＨ3）3
［式中のｄは２以上の整数である。］
Examples of the methylhydrogenpolysiloxane that blocks the trimethylsiloxy group at both ends of the molecular chain include a compound represented by the following formula, and a part or all of the methyl group in the following formula is an ethyl group, a propyl group, a phenyl group, or a trifluoropropyl group. Examples thereof include compounds substituted with or the like.
(CH 3 ) 3 SiO− (−SiH (CH 3 ) −O−) d− Si (CH 3 ) 3
[D in the formula is an integer of 2 or more. ]
分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体としては、下式で示される化合物、さらには下式においてメチル基の一部または全部をエチル基、プロピル基、フェニル基、トリフロロプロピル基等で置換した化合物などが挙げられる。
（ＣＨ3）3ＳｉＯ−（−Ｓｉ（ＣＨ3）2−Ｏ−）e−（−ＳｉＨ（ＣＨ3）−Ｏ−）f−Ｓｉ（ＣＨ3）3
［式中のｅは１以上の整数であり、ｆは２以上の整数である。］
As the dimethylsiloxane / methylhydrogensiloxane copolymer that blocks the trimethylsiloxy group at both ends of the molecular chain, the compound represented by the following formula, and further, a part or all of the methyl group in the following formula is an ethyl group, a propyl group, or a phenyl group. Examples thereof include compounds substituted with a trifluoropropyl group or the like.
(CH 3) 3 SiO - ( - Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) f -Si (CH 3) 3
[E in the equation is an integer of 1 or more, and f is an integer of 2 or more. ]
分子鎖両末端シラノール基封鎖メチルハイドロジェンポリシロキサンとしては、例えば下式で示される化合物、さらには下式においてメチル基の一部または全部をエチル基、プロピル基、フェニル基、トリフロロプロピル基等で置換した化合物などが挙げられる。
ＨＳｉ（ＣＨ3）2Ｏ−（−Ｓｉ（ＣＨ3）2−Ｏ−）e−Ｓｉ（ＣＨ3）2Ｈ
［式中のｅは１以上の整数である。］
Examples of the methylhydrogenpolysiloxane that blocks silanol groups at both ends of the molecular chain include a compound represented by the following formula, and a part or all of the methyl group in the following formula is an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group, or the like. Examples thereof include a compound substituted with.
HSi (CH 3) 2 O - (- Si (CH 3) 2 -O-) e -Si (CH 3) 2 H
[E in the formula is an integer of 1 or more. ]
分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖メチルハイドロジェンポリシロキサンとしては、例えば下式で示される化合物、さらには下式においてメチル基の一部または全部をエチル基、プロピル基、フェニル基、トリフロロプロピル基等で置換した化合物などが挙げられる。
ＨＳｉ（ＣＨ3）2Ｏ−（−ＳｉＨ（ＣＨ3）−Ｏ−）e−Ｓｉ（ＣＨ3）2Ｈ
［式中のｅは１以上の整数である。］
Examples of the methylhydrogenpolysiloxane that blocks the dimethylhydrogensiloxy group at both ends of the molecular chain include a compound represented by the following formula, and further, a part or all of the methyl group in the following formula is an ethyl group, a propyl group, a phenyl group, or a trifluororo. Examples thereof include compounds substituted with a propyl group or the like.
HSi (CH 3) 2 O - (- SiH (CH 3) -O-) e -Si (CH 3) 2 H
[E in the formula is an integer of 1 or more. ]
分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体としては、例えば下式で示される化合物、さらには下式においてメチル基の一部または全部をエチル基、プロピル基、フェニル基、トリフロロプロピル基等で置換した化合物などが挙げられる。
ＨＳｉ（ＣＨ3）2Ｏ−（−Ｓｉ（ＣＨ3）2−Ｏ−）e−（−ＳｉＨ（ＣＨ3）−Ｏ−）h−Ｓｉ（ＣＨ3）2Ｈ
［式中のｅおよびｈは、それぞれ１以上の整数である。］
Examples of the dimethylsiloxane / methylhydrogensiloxane copolymer that blocks dimethylhydrogensiloxy groups at both ends of the molecular chain include compounds represented by the following formulas, and further, some or all of the methyl groups in the following formulas are ethyl groups, propyl groups, and the like. Examples thereof include compounds substituted with a phenyl group, a trifluoropropyl group and the like.
HSi (CH 3) 2 O - (- Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) h -Si (CH 3) 2 H
[E and h in the equation are integers of 1 or more, respectively. ]
以上のような化合物は、公知の方法により製造することができ、例えばオクタメチルシクロテトラシロキサンおよび／またはテトラメチルシクロテトラシロキサンと、末端基となり得るヘキサメチルジシロキサンあるいは１，３−ジハイドロ−１，１，３，３−テトラメチルジシロキサンなどの、トリオルガノシリル基あるいはジオルガノハイドロジェンシロキシ基を含む化合物とを、硫酸、トリフルオロメタンスルホン酸、メタンスルホン酸等の触媒の存在下に、−１０℃〜＋４０℃程度の温度で平衡化させることによって容易に得ることができる。 The above compounds can be produced by known methods, for example, octamethylcyclotetrasiloxane and / or tetramethylcyclotetrasiloxane, and hexamethyldisiloxane or 1,3-dihydro-1, which can be a terminal group. Compounds containing a triorganosilyl group or diorganohydrogensiloxy group, such as 1,3,3-tetramethyldisiloxane, were added to the compound in the presence of a catalyst such as sulfuric acid, trifluoromethanesulfonic acid, methanesulfonic acid, etc. -10. It can be easily obtained by equilibrating at a temperature of about ° C. to + 40 ° C.
前記ヒドロシリル基含有化合物（Ｂ）は、前記重合体（Ａ）、好ましくは前記共重合体（Ｓ）１００質量部に対して、好ましくは０．１〜１００質量部、より好ましくは０．１〜５０質量部、さらに好ましくは０．２〜２０質量部、特に好ましくは０．５〜１０質量部、最も好ましくは１〜８質量部の範囲で用いられる。ヒドロシリル基含有化合物（Ｂ）の量が１００質量部を超えると、コスト的に不利になるので好ましくない。 The hydrosilyl group-containing compound (B) is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 1 parts by mass with respect to 100 parts by mass of the polymer (A), preferably the copolymer (S). It is used in the range of 50 parts by mass, more preferably 0.2 to 20 parts by mass, particularly preferably 0.5 to 10 parts by mass, and most preferably 1 to 8 parts by mass. If the amount of the hydrosilyl group-containing compound (B) exceeds 100 parts by mass, it is disadvantageous in terms of cost, which is not preferable.
ポリフェノール系老化防止剤（Ｃ）
本発明で用いられるポリフェノール系老化防止剤（Ｃ）としては、一分子中に複数のフェノール性水酸基を有する化合物からなる老化防止剤であれば特に限定されないが、例えば、ブチル化ビスフェノールＡ、２，２'−メチレン−ビス（４−メチル−６−ｔ−ブチルフェノール）、２，２'−メチレン−ビス（４−エチル−６−ｔ−ブチルフェノール）、２，２'−メチレン−ビス（４−メチル−６−ｔ−ノニルフェノール）、２，２'−イソブチリデン−ビス（４，６−ジメチルフェノール）、４，４'−ブチリデン−ビス（３−メチル−６−ｔ−ブチルフェノール）、４，４'−メチレン−ビス（２，６−ジ−ｔ−ブチルフェノール）、２，２'−チオ−ビス（４−メチル−６−ｔ−ブチルフェノール）、４，４'−チオ−ビス（３−メチル−６−ｔ−ブチルフェノール）、４，４'−チオ−ビス（２−メチル−６−ブチルフェノール）、４，４'−チオ−ビス（６−ｔ−ブチル−３−メチルフェノール）、ビス（３−メチル−４−ヒドロキシ−５−ｔ−ブチルベンゼン）スルフィド、２，２'−チオジエチル−ビス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、ビス［３，３−ビス（４−ヒドロキシ−３−ｔ−ブチルフェニル）酪酸］グリコールエステル、ビス［２−（２−ヒドロキシ−５−メチル−３−ｔ−ブチルベンゼン）−４−メチル−６−ｔ−ブチルフェニル］テレフタレート、１，３，５−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）イソシアヌレート、Ｎ，Ｎ'−ヘキサメチレン−ビス（３，５−ジ−ｔ−ブチル−４−ヒドロキシヒドロシンナムアミド）、テトラキス［メチレン−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］メタン、ペンタエリスリトール−テトラキス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、１，１'−ビス（４−ヒドロキシフェニル）シクロヘキサン、２，６−ビス（２−ヒドロキシ−３−ｔ−ブチル−５−メチルベンジル）−４−メチルフェノール、３，９−ビス［２−｛３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ｝−１，１−ジメチルエチル］−２，４，８，１０−テトラオキサスピロ［５．５］ウンデカン、２，５−ジ−ｔ−アミルハイドロキノン、２，５−ジ−ｔ−ブチルハイドロキノン、カテコール、ハイドロキノンなどが挙げられる。これらの中では、２，５−ジ−ｔ−アミルハイドロキノン、２，５−ジ−ｔ−ブチルハイドロキノンが好ましい。
このようなポリフェノール系老化防止剤（Ｃ）を用いることにより、触媒被毒が生じることなくヒドロシリコーン架橋が可能であり、かつ、圧縮永久歪みに優れた架橋成形体を得ることができる。
Polyphenol anti-aging agent (C)
The polyphenol-based anti-aging agent (C) used in the present invention is not particularly limited as long as it is an anti-aging agent composed of a compound having a plurality of phenolic hydroxyl groups in one molecule, but for example, butylated bisphenol A, 2, 2'-Methylene-bis (4-methyl-6-t-butylphenol), 2,2'-methylene-bis (4-ethyl-6-t-butylphenol), 2,2'-methylene-bis (4-methyl) -6-t-nonylphenol), 2,2'-isobutylidene-bis (4,6-dimethylphenol), 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), 4,4'- Methylene-bis (2,6-di-t-butylphenol), 2,2'-thio-bis (4-methyl-6-t-butylphenol), 4,4'-thio-bis (3-methyl-6-) t-butylphenol), 4,4'-thio-bis (2-methyl-6-butylphenol), 4,4'-thio-bis (6-t-butyl-3-methylphenol), bis (3-methyl- 4-Hydroxy-5-t-butylbenzene) sulfide, 2,2'-thiodiethyl-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4-Hydroxy-3-t-butylphenyl) butyric acid] glycol ester, bis [2- (2-hydroxy-5-methyl-3-t-butylbenzene) -4-methyl-6-t-butylphenyl] terephthalate , 1,3,5-Tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, N, N'-hexamethylene-bis (3,5-di-t-butyl-4-hydroxy) Hydrosinnumamide), tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, pentaerythritol-tetrakis [3- (3,5-di-t-butyl-) 4-Hydroxyphenyl) propionate], 1,1'-bis (4-hydroxyphenyl) cyclohexane, 2,6-bis (2-hydroxy-3-t-butyl-5-methylbenzyl) -4-methylphenol, 3 , 9-Bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [ 5.5] Undecane, 2,5-di-t-amylhydroquinone, 2,5-di-t-butylhydroquinone, catechol , Hydroquinone and the like. Among these, 2,5-di-t-amyl hydroquinone and 2,5-di-t-butyl hydroquinone are preferable.
By using such a polyphenol-based antiaging agent (C), a crosslinked molded product that can be crosslinked with hydrosilicone without causing catalyst poisoning and has excellent compression set can be obtained.
前記ポリフェノール系老化防止剤（Ｃ）は、前記重合体（Ａ）、好ましくは前記共重合体（Ｓ）１００質量部に対して、好ましくは０．１〜３０質量部、より好ましくは０．２〜２０質量部、さらに好ましくは０．４〜１５質量部、特に好ましくは０．５〜１０質量部の範囲で用いられる。ポリフェノール系老化防止剤（Ｃ）を前記範囲で用いると、上述した効果が十分に得られる。 The polyphenol antiaging agent (C) is preferably 0.1 to 30 parts by mass, more preferably 0.2 parts by mass with respect to 100 parts by mass of the polymer (A), preferably the copolymer (S). It is used in the range of ~ 20 parts by mass, more preferably 0.4 to 15 parts by mass, and particularly preferably 0.5 to 10 parts by mass. When the polyphenol-based antiaging agent (C) is used in the above range, the above-mentioned effects can be sufficiently obtained.
白金系触媒（Ｄ）
本発明で必要に応じて用いられるヒドロシリコン架橋用の白金系触媒（Ｄ）は、付加反応触媒であり、末端二重結合を有する重合体、好ましくは前記共重合体（Ｓ）が有するアルケニル基と、ヒドロシリル基含有化合物（Ｂ）のヒドロシリル基との付加反応（アルケンのヒドロシリル化反応）を促進するものであれば、特に制限はなく使用することができる。
Platinum catalyst (D)
The platinum-based catalyst (D) for hydrosilicon cross-linking used as needed in the present invention is an addition reaction catalyst, and is an alkenyl group contained in a polymer having a terminal double bond, preferably the copolymer (S). And, as long as it promotes the addition reaction of the hydrosilyl group-containing compound (B) with the hydrosilyl group (hydrosilylation reaction of the alkene), it can be used without particular limitation.
具体的な白金系触媒は、通常、付加硬化型の硬化に使用される公知のものでよく、例えば米国特許第２，９７０，１５０号明細書に記載の微粉末金属白金触媒、米国特許第２，８２３，２１８号明細書に記載の塩化白金酸触媒、米国特許第３，１５９，６０１号公報明細書および米国特許第１５９，６６２号明細書に記載の白金と炭化水素との錯化合物、米国特許第３，５１６，９４６号明細書に記載の塩化白金酸とオレフィンとの錯化合物、米国特許第３，７７５，４５２号明細書および米国特許第３，８１４，７８０号明細書に記載の白金とビニルシロキサンとの錯化合物などが挙げられる。 The specific platinum-based catalyst may be a known one that is usually used for addition-curing type curing. For example, the fine powder metal platinum catalyst described in US Pat. No. 2,970,150, US Pat. No. 2, Ltd. , 823,218, Platinum Chloride Catalyst, US Pat. No. 3,159,601, US Pat. No. 3,159,662, US Pat. No. 3,159,662, US Pat. Complex compound of platinum chloride acid and olefin described in Japanese Patent No. 3,516,946, platinum described in US Pat. No. 3,775,452 and US Pat. No. 3,814,780. Examples include a complex compound of vinyl siloxane and vinyl siloxane.
より具体的には、白金の単体（白金黒）、塩化白金酸、白金−オレフィン錯体、白金−アルコール錯体、またはアルミナ、シリカ等の担体に白金の担体を担持させたものなどが挙げられる。 More specifically, a simple platinum (platinum black), platinum chloride acid, platinum-olefin complex, platinum-alcohol complex, or a carrier such as alumina or silica on which a platinum carrier is supported can be mentioned.
ヒドロシリコン架橋用の白金系触媒（Ｄ）は、前記重合体（Ａ）、好ましくは前記共重合体（Ｓ）１００質量部に対して、好ましくは０．１〜１００，０００質量ｐｐｍ、より好ましくは０．５〜５０，０００質量ｐｐｍ、さらに好ましくは１〜１０，０００質量ｐｐｍ、特に好ましくは５〜８，０００質量ｐｐｍの範囲で用いられる。０．１質量ｐｐｍ未満では架橋速度が遅くなる傾向にあり、また、１００，０００質量ｐｐｍを超えると、コスト的に不利になるので好ましくない。上記範囲内の割合でヒドロシリコン架橋用の白金系触媒（Ｄ）を用いることにより、架橋密度が適度で強度特性および伸び特性に優れる架橋成形体を形成できる。 The platinum-based catalyst (D) for hydrosilicon crosslinking is preferably 0.1 to 100,000 mass ppm, more preferably 0.1 to 100,000 mass ppm, based on 100 parts by mass of the polymer (A), preferably the copolymer (S). Is used in the range of 0.5 to 50,000 mass ppm, more preferably 1 to 10,000 mass ppm, and particularly preferably 5 to 8,000 mass ppm. If it is less than 0.1 mass ppm, the crosslinking rate tends to be slow, and if it exceeds 100,000 mass ppm, it is disadvantageous in terms of cost, which is not preferable. By using the platinum-based catalyst (D) for hydrosilicon cross-linking at a ratio within the above range, a cross-linked molded product having an appropriate cross-linking density and excellent strength characteristics and elongation characteristics can be formed.
反応抑制剤（Ｅ）
本発明で必要に応じて用いられる反応抑制剤（Ｅ）は、前記重合体（Ａ）、好ましくは前記共重合体（Ｓ）が有するアルケニル基と、ヒドロシリル基含有化合物（Ｂ）のヒドロシリル基との架橋反応（アルケンへのヒドロシリル化付加反応）を抑制する。この架橋反応の抑制は、混練時および成形時での加工性を安定にする点で好ましい。
Reaction inhibitor (E)
The reaction inhibitor (E) used as needed in the present invention includes the alkenyl group of the polymer (A), preferably the copolymer (S), and the hydrosilyl group of the hydrosilyl group-containing compound (B). Suppresses the cross-linking reaction (hydrosilylation addition reaction to alkenes). This suppression of the cross-linking reaction is preferable from the viewpoint of stabilizing the processability at the time of kneading and molding.
本発明で用いる反応抑制剤（Ｅ）は、ベンゾトリアゾール、エチニル基含有アルコール（たとえばエチニルシクロヘキサノール等）、アクリロニトリル、アミド化合物（たとえばN,N-ジアリルアセトアミド、N,N-ジアリルベンズアミド、N,N,N',N'-テトラアリル-ｏ-フタル酸ジアミド、N,N,N',N'-テトラアリル-ｍ-フタル酸ジアミド、N,N,N',N'-テトラアリル-ｐ-フタル酸ジアミドなど）、イオウ、リン、窒素、アミン化合物、イオウ化合物、リン化合物、スズ、スズ化合物、テトラメチルテトラビニルシクロテトラシロキサン、ハイドロパーオキサイド等の有機過酸化物などが挙げられる。 The reaction inhibitor (E) used in the present invention includes benzotriazole, an ethynyl group-containing alcohol (for example, ethynylcyclohexanol, etc.), acrylonitrile, and an amide compound (for example, N, N-diallyl acetamide, N, N-diallyl benzamide, N, N. , N', N'-tetraallyl-o-phthalic acid diamide, N, N, N', N'-tetraallyl-m-phthalic acid diamide, N, N, N', N'-tetraallyl-p-phthalic acid diamide Etc.), sulfur, phosphorus, nitrogen, amine compounds, sulfur compounds, phosphorus compounds, tin, tin compounds, tetramethyltetravinylcyclotetrasiloxane, organic peroxides such as hydroperoxide, and the like.
反応抑制剤（Ｅ）は、前記重合体（Ａ）、好ましくは前記共重合体（Ｓ）１００質量部に対して、好ましくは０．０５〜５質量部、より好ましくは０．０６〜４．５質量部、さらに好ましくは０．０８〜４．０質量部、特に好ましくは０．１〜３．０質量部、最も好ましくは０．１〜２．０質量部の割合で用いられる。０．０５質量部未満では架橋速度が速すぎる虞があり、また、５質量部を超えると、反応抑制の効果が大きく架橋が起こりにくくなる虞がある。 The reaction inhibitor (E) is preferably 0.05 to 5 parts by mass, more preferably 0.06 to 4. by mass, based on 100 parts by mass of the polymer (A), preferably the copolymer (S). It is used in a proportion of 5 parts by mass, more preferably 0.08 to 4.0 parts by mass, particularly preferably 0.1 to 3.0 parts by mass, and most preferably 0.1 to 2.0 parts by mass. If it is less than 0.05 parts by mass, the cross-linking rate may be too fast, and if it exceeds 5 parts by mass, the effect of suppressing the reaction is large and cross-linking may be difficult to occur.
その他の配合剤
本発明の樹脂組成物は、本発明の効果を損なわない範囲で、必要に応じて、上記成分以外の配合剤として、補強剤、無機充填剤、軟化剤、前記成分（Ｃ）以外の老化防止剤（安定剤）、加工助剤、活性剤、シランカップリング剤、界面活性剤、帯電防止剤、発泡剤、発泡助剤、可塑剤、着色剤、他のゴム配合剤、ゴム、樹脂などを含有してもよい。これらの配合剤は、用途に応じて、その種類および含有量が適宜選択されるが、これらのうちでも特に補強剤、軟化剤などを用いることが好ましい。
Other Blending Agents The resin composition of the present invention contains a reinforcing agent, an inorganic filler, a softener, and the above-mentioned component (C) as a compounding agent other than the above-mentioned components, if necessary, as long as the effects of the present invention are not impaired. Other than anti-aging agents (stabilizers), processing aids, activators, silane coupling agents, surfactants, antistatic agents, foaming agents, foaming aids, plasticizers, colorants, other rubber compounding agents, rubber , Resin and the like may be contained. The type and content of these compounding agents are appropriately selected depending on the intended use, and among these, it is particularly preferable to use a reinforcing agent, a softening agent, or the like.
＜補強剤＞
前記補強剤としては、例えば、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、炭酸カルシウム、活性化炭酸カルシウム、微粉タルク、微分ケイ酸が挙げられる。
<Reinforcing agent>
Examples of the reinforcing agent include carbon black, carbon black surface-treated with a silane coupling agent, silica, calcium carbonate, activated calcium carbonate, fine powder talc, and differential silicic acid.
＜軟化剤＞
前記軟化剤としては、例えば、プロセスオイル、潤滑油、パラフィン油、流動パラフィン、石油アスファルト、ワセリン等の石油系軟化剤；コールタール等のコールタール系軟化剤；ヒマシ油、アマニ油、ナタネ油、大豆油、ヤシ油等の脂肪油系軟化剤；蜜ロウ、カルナウバロウ等のロウ類；ナフテン酸、パイン油、ロジンまたはその誘導体；テルペン樹脂、石油樹脂、クマロンインデン樹脂等の合成高分子物質；ジオクチルフタレート、ジオクチルアジペート等のエステル系軟化剤；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、炭化水素系合成潤滑油、トール油、サブ（ファクチス）が挙げられ、これらのうちでは、石油系軟化剤が好ましく、プロセスオイルが特に好ましい。
<Softener>
Examples of the softener include petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and vaseline; and hydrocarbon-based softeners such as coal tar; castor oil, flaxseed oil, and rapeseed oil. Fatty oil-based softeners such as soybean oil and coconut oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin or derivatives thereof; synthetic polymer substances such as terpene resin, petroleum resin and kumaron inden resin; Ester-based softeners such as dioctylphthalate and dioctyl adipate; other examples include microcrystallin wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oil, tall oil, and sub (factis). Among these, petroleum-based Softeners are preferred, process oils are particularly preferred.
＜樹脂＞
本発明で必要に応じて用いられる樹脂としては、ポリエチレン、ポリプロピレン、ポリスチレンなどの汎用樹脂が挙げられる。また、本発明では、必要に応じて用いられるゴムとしては、シリコーンゴム、エチレン・プロピレンランダム共重合体ゴム（ＥＰＲ）、天然ゴム、スチレン−ブタジエンゴム、イソプレンゴム、ブタジエンゴム、クロロプレンゴムなどをブレンドして用いることができる。また、前記共重合体（Ｓ）とは異なるが類似するゴム（ＥＰＴ）を用いることもできる。
<Resin>
Examples of the resin used as needed in the present invention include general-purpose resins such as polyethylene, polypropylene, and polystyrene. Further, in the present invention, as the rubber used as needed, silicone rubber, ethylene / propylene random copolymer rubber (EPR), natural rubber, styrene-butadiene rubber, isoprene rubber, butadiene rubber, chloroprene rubber and the like are blended. Can be used. Further, a rubber (EPT) different from the copolymer (S) but similar to the copolymer (S) can also be used.
＜樹脂組成物の調製方法＞
本発明の樹脂組成物は、混練−成形加工する際の５０〜１３０℃の比較的低い温度では、架橋反応が抑制されるので、押出し成形性、プレス成形性、射出成形性等の成形性、およびロール加工性などの加工性に優れており、しかも、架橋温度である１５０〜２００℃では、短時間で架橋し得るという架橋特性にも優れている。したがって、下記、種々公知の成形方法を採用することにより、機械特性、耐熱安定性などに優れる成形体を従来の樹脂組成物に比べ、高速で成形することができる。
<Preparation method of resin composition>
Since the cross-linking reaction of the resin composition of the present invention is suppressed at a relatively low temperature of 50 to 130 ° C. during kneading-molding, moldability such as extrusion moldability, press moldability, injection moldability, etc. It is also excellent in processability such as roll processability, and is also excellent in cross-linking property that it can be cross-linked in a short time at a cross-linking temperature of 150 to 200 ° C. Therefore, by adopting various known molding methods described below, it is possible to mold a molded product having excellent mechanical properties, heat resistance stability, etc. at a higher speed than that of a conventional resin composition.
［架橋成形体］
本発明に係る架橋成形体は、上述した本発明の樹脂組成物をヒドロシリル化反応により架橋させてなることを特徴とする。
[Cross-linked molded product]
The crosslinked molded article according to the present invention is characterized in that the above-mentioned resin composition of the present invention is crosslinked by a hydrosilylation reaction.
＜架橋成形体の製造方法＞
本発明の架橋成形体の製造方法としては、公知の一般的なゴム配合物の加工方法（成形方法）を採用し得る。具体的には、以下の通りである。
<Manufacturing method of crosslinked molded article>
As a method for producing the crosslinked molded article of the present invention, a known general processing method (molding method) for a rubber compound can be adopted. Specifically, it is as follows.
バンバリーミキサー、ニーダー、インターミックスのようなインターナルミキサー類を用いて、例えば、前記重合体（Ａ）およびフェノール系老化防止剤（Ｃ）、ならびに、必要に応じて他の配合剤などを８０〜１７０℃の温度で３〜１０分間混練した後、ヒドロシリル基含有化合物（Ｂ）、ならびに、必要に応じて白金系触媒（Ｄ）、反応抑制剤（Ｅ）および他の配合剤などを加えて、オープンロールなどのロール類あるいはニーダーを用いて、ロール温度５０〜１３０℃で５〜３０分間混練した後、分出しすることにより調製することができる。このようにして、リボン状またはシート状の組成物が得られる。 Using internal mixers such as Banbury mixer, kneader, and intermix, for example, the polymer (A) and the phenolic anti-aging agent (C), and if necessary, other compounding agents, etc., 80 to 80 to After kneading at a temperature of 170 ° C. for 3 to 10 minutes, the hydrosilyl group-containing compound (B) and, if necessary, a platinum-based catalyst (D), a reaction inhibitor (E) and other compounding agents are added. It can be prepared by kneading with a roll such as an open roll or a kneader at a roll temperature of 50 to 130 ° C. for 5 to 30 minutes and then dispensing. In this way, a ribbon-shaped or sheet-shaped composition is obtained.
得られた組成物は、例えば、押出成形機、カレンダーロール、プレス、射出成形機、トランスファー成形機など種々の成形法によって所望の形状に予備成形され、成形と同時に、または成形物を加硫槽内に導入した後、加熱して架橋することにより、架橋成形体を得ることができる。 The obtained composition is preformed into a desired shape by various molding methods such as an extrusion molding machine, a calendar roll, a press, an injection molding machine, and a transfer molding machine, and at the same time as molding, or the molded product is placed in a sulfide tank. A crosslinked molded product can be obtained by heating and cross-linking after introducing the product.
加熱する方法としては、公知の方法が制限無く用いることができるが、特に、熱空気、ガラスビーズ流動床、ＵＨＦ（極超短波電磁波）、スチーム、ＬＣＭ（熱溶融塩槽）などの加熱形態の加熱槽を用いて、１５０〜２００℃の温度で１〜３０分間加熱することが好ましい。成形および架橋に際しては、金型を用いてもよく、または金型を用いないでもよい。金型を用いない場合、樹脂組成物は連続的に成形および架橋される。 As a heating method, known methods can be used without limitation, but in particular, heating in a heating form such as hot air, glass bead fluidized bed, UHF (ultra high frequency electromagnetic wave), steam, LCM (heat molten salt tank), etc. It is preferable to heat at a temperature of 150 to 200 ° C. for 1 to 30 minutes using a tank. Molds may or may not be used for molding and cross-linking. If no mold is used, the resin composition is continuously molded and crosslinked.
本発明の樹脂組成物から得られる架橋成形体としては、例えば、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、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、防振材または制振材（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。これらのうちでも、自動車用内外装部品や耐熱性を求められる用途に好適に用いられる。 Examples of the crosslinked molded product obtained from the resin composition of the present invention include tire rubber, O-ring, industrial roll, packing (for example, condenser packing), gasket, belt (for example, heat insulating belt, copying machine belt, and transporting). Belts), hoses such as automobile hoses (eg water hoses, brake reservoir hoses, radiator hoses, air hoses), anti-vibration rubber, anti-vibration or anti-vibration materials (eg engine mounts, motor mounts), muffler hangers , Sponge (for example, weather strip sponge, heat insulating sponge, protect sponge, slightly foamed sponge), cable (ignition cable, cab tire cable, high tension cable), wire coating material (high pressure wire coating material, low voltage wire coating material, marine use) (Electric wire coating material), glass run channel, color skin material, paper feed roll, roofing sheet, etc. are preferably used. Among these, it is suitably used for interior / exterior parts for automobiles and applications that require heat resistance.
以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
後述する製造例、実施例および比較例で行った評価は以下の方法で行った。
Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.
The evaluations performed in the production examples, examples, and comparative examples described later were performed by the following methods.
＜エチレン・α−オレフィン・非共役ポリエン共重合体の組成＞
エチレン・α−オレフィン・非共役ポリエン共重合体の、各構成単位の質量分率（質量％）およびエチレンとα−オレフィンのモル比は、13Ｃ−ＮＭＲによる測定値により求めた。測定値は、ＥＣＸ４００Ｐ型核磁気共鳴装置（日本電子製）を用いて、測定温度：１２０℃、測定溶媒：オルトジクロロベンゼン／重水素化ベンゼン＝４／１、積算回数：８０００回にて、共重合体の13Ｃ−ＮＭＲのスペクトルを測定して得た。
<Composition of ethylene / α-olefin / non-conjugated polyene copolymer>
The mass fraction (mass percentage) of each structural unit and the molar ratio of ethylene to α-olefin of the ethylene / α-olefin / non-conjugated polyene copolymer were determined by the values measured by 13 C-NMR. The measured values were measured using an ECX400P type nuclear magnetic resonance device (manufactured by JEOL Ltd.) at a measurement temperature of 120 ° C., a measurement solvent: orthodichlorobenzene / deuterated benzene = 4/1, and an integration number of 8000 times. It was obtained by measuring the 13 C-NMR spectrum of the polymer.
＜極限粘度［η］＞
極限粘度［η］（ｄｌ／ｇ）は、（株）離合社製全自動極限粘度計を用いて、温度：１３５℃、測定溶媒：デカリンにて測定した。
<Ultimate viscosity [η]>
The ultimate viscosity [η] (dl / g) was measured using a fully automatic ultimate viscometer manufactured by Rigo Co., Ltd. at a temperature of 135 ° C. and a measurement solvent of decalin.
＜ムーニー粘度＞
ムーニー粘度ＭＬ(1+4)１００℃は、ムーニー粘度計「ＳＭＶ−２０２」（（株）島津製作所製）を用いて、ＪＩＳ Ｋ６３００（１９９４）に準じて１００℃で測定した。
<Moony viscosity>
Mooney viscosity ML (1 + 4) 100 ° C. was measured at 100 ° C. using a Mooney viscometer "SMV-202" (manufactured by Shimadzu Corporation) according to JIS K6300 (1994).
＜加硫速度＞
ＭＤＲ２０００（アルファテクノロジーズ製）を用い、加硫曲線を測定し、当該加硫曲線から得られるトルクの最低値Ｓ’ｍｉｎ［ｄＮｍ］と最高値Ｓ’ｍａｘ［ｄＮｍ］の差：Ｓ’ｍａｘ−Ｓ’ｍｉｎ［ｄＮｍ］、測定試料のトルクが最低値Ｓ’ｍｉｎ到達後にトルクが１［ｄＮｍ］上昇した時の時間：ｔｓ１［ｍｉｎ］、トルクの最低値Ｓ’ｍｉｎを０％、最高値Ｓ’ｍａｘを１００％として、測定試料のトルクが９０％に到達したときの時間［ｍｉｎ］：ｔｃ９０、およびＭＣＲ［ｄＮｍ／ｍｉｎ］を求めた。
<Vulcanization rate>
A vulcanization curve is measured using MDR2000 (manufactured by Alpha Technologies), and the difference between the minimum torque value S'min [dNm] and the maximum torque value S'max [dNm] obtained from the vulcanization curve: S'max-S. 'min [dNm], the time when the torque rises by 1 [dNm] after reaching the minimum value S'min of the measurement sample: ts1 [min], the minimum torque value S'min is 0%, the maximum value S' With max as 100%, the time [min]: tk90 and MCR [dNm / min] when the torque of the measurement sample reached 90% were determined.
＜硬さ試験（デュロ−Ａ硬度）＞
ＪＩＳ Ｋ ６２５３に従い、架橋シートの硬度（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。
<Hardness test (DULO-A hardness)>
According to JIS K 6253, the hardness of the crosslinked sheets (type A durometer, HA) was measured by stacking flat portions to a thickness of about 12 mm using six 2 mm crosslinked sheets having a smooth surface. However, the test pieces containing foreign matter, air bubbles, and scratches were not used. The size of the measurement surface of the test piece was set so that the tip of the push needle could be measured at a position 12 mm or more away from the end of the test piece.
＜引張り試験＞
ＪＩＳ Ｋ ６２５１に従い、測定温度２３℃、引張速度５００ｍｍ／分の条件で引張試験を行い、シートの破断強度（ＴＢ）〔ＭＰａ〕および破断伸び（ＥＢ）〔％〕を測定した。すなわち、シート状の架橋成形体を打抜いて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、伸び率が２５％であるときの引張応力〔２５％モジュラス（Ｍ２５）〕、伸び率が５０％であるときの引張応力〔５０％モジュラス（Ｍ５０）〕、伸び率が１００％であるときの引張応力〔１００％モジュラス（Ｍ１００）〕、伸び率が２００％であるときの引張応力〔２００％モジュラス（Ｍ２００）〕、引張破断点応力（ＴＢ）および引張破断点伸び（ＥＢ）を測定した。
<Tension test>
A tensile test was conducted under the conditions of a measurement temperature of 23 ° C. and a tensile speed of 500 mm / min according to JIS K 6251, and the breaking strength (TB) [MPa] and breaking elongation (EB) [%] of the sheet were measured. That is, a sheet-shaped crosslinked molded product was punched out to prepare a No. 3 dumbbell test piece described in JIS K 6251 (2001). Using this test piece, a tensile test was conducted under the conditions of a measurement temperature of 25 ° C. and a tensile speed of 500 mm / min according to the method specified in JIS K 6251, and a tensile stress [25% modulus] when the elongation rate was 25%. (M25)], tensile stress when the elongation rate is 50% [50% modulus (M50)], tensile stress when the elongation rate is 100% [100% modulus (M100)], elongation rate is 200%. The tensile stress [200% modulus (M200)], the tensile breaking point stress (TB), and the tensile breaking point elongation (EB) were measured.
＜架橋密度＞
架橋密度νは下記の平衡膨潤を利用したFlory-Rehnerの式（ａ）から算出した。式（ａ）中のＶRは架橋した２ｍｍシートを３７℃×７２ｈの条件でトルエン抽出して求めた。
<Crosslink density>
The crosslink density ν was calculated from the Flory-Rehner equation (a) using the following equilibrium swelling. V R in the formula (a) were determined by toluene extraction in the conditions of 37 ° C. × 72h a 2mm sheet crosslinked.
＜圧縮永久歪み（架橋シート２ｍｍ）＞
２０×２０ｍｍの試料を作製し、５枚重ねて試験片とする。
試料高さは１枚ずつ測寸した５枚の合計を高さとし、荷重をかける前の試験片高さ(約１０ｍｍ)に対して２５％圧縮し、圧縮板保持具ごと指定温度のオーブン中にセットして指定時間熱処理した。次いで試験片を開放、３０分間放冷後、試験片の高さを測定し以下の計算式で圧縮永久歪み（％）を算出した。
圧縮永久歪み（％）＝｛（ｔ0−ｔ1）／（ｔ0−ｔ2）｝×１００
ｔ0：試験片の試験前の高さ
ｔ1：試験片を熱処理し３０分間放冷した後の高さ
ｔ2：試験片の測定金型に取り付けた状態での高さ
<Compressed permanent strain (crosslinked sheet 2 mm)>
A sample of 20 × 20 mm is prepared, and 5 sheets are stacked to form a test piece.
The height of the sample is the total of 5 samples measured one by one, compressed by 25% of the height of the test piece (about 10 mm) before applying the load, and placed in the oven at the specified temperature together with the compression plate holder. It was set and heat-treated for a specified time. Next, the test piece was opened, allowed to cool for 30 minutes, the height of the test piece was measured, and the compression set (%) was calculated by the following formula.
Compressed permanent strain (%) = {(t0-t1) / (t0-t2)} x 100
t0: Height of the test piece before the test t1: Height after the test piece is heat-treated and allowed to cool for 30 minutes t2: Height of the test piece when attached to the measurement mold
＜耐熱老化性＞
厚さ２ｍｍの加硫ゴムシートを、ＪＩＳ Ｋ ６２５７に従い、１５０℃で１６８ｈ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（ＴＢ）、引張破断点伸び（ＥＢ）を、前記と同様の方法で測定し、老化前後の硬度の変化（ＡＨ）、老化前後のＴＢの変化率［Ａｃ（ＴＢ）］、老化前後のＥＢの変化率［Ａｃ（ＥＢ）］を求めた。
<Heat aging property>
A heat aging test was carried out in which a vulcanized rubber sheet having a thickness of 2 mm was held at 150 ° C. for 168 hours according to JIS K 6257. The hardness of the sheet after the heat aging test, the tensile breaking point stress (TB), and the tensile breaking point elongation (EB) were measured by the same method as described above, and the change in hardness before and after aging (AH) and the TB before and after aging were measured. The rate of change [Ac (TB)] and the rate of change of EB before and after aging [Ac (EB)] were determined.
〔製造例１〕
攪拌翼を備えた容積３００Ｌの重合器を用いて、連続的に、エチレン、ブテン、５−ビニル−２−ノルボルネン（ＶＮＢ）の重合反応を９５℃にて行った。重合溶媒としてはヘキサン（フィード量：２３．６Ｌ／ｈ）を用いて、連続的に、エチレンフィード量が４．５ｋｇ／ｈ、ブテン量が１４．４ｋｇ／ｈ、ＶＮＢフィード量が４２０ｇ／ｈおよび水素フィード量が４０．０ＮＬ／ｈとなるように、重合器に連続供給した。
[Manufacturing Example 1]
A polymerization reaction of ethylene, butene, and 5-vinyl-2-norbornene (VNB) was continuously carried out at 95 ° C. using a polymerizer having a volume of 300 L equipped with a stirring blade. Hexane (feed amount: 23.6 L / h) was used as the polymerization solvent, and the ethylene feed amount was 4.5 kg / h, the butene amount was 14.4 kg / h, and the VNB feed amount was 420 g / h. The hydrogen feed amount was continuously supplied to the polymerizer so as to be 40.0 NL / h.
重合圧力を１．６ＭＰａＧ、重合温度を９５℃に保ちながら、主触媒としてジ（ｐ−トリル）メチレン（シクロペンタジエニル）（オクタメチルオクタヒドロジベンゾフルオレニル）ジルコニウムジクロリドを用いて、フィード量０．００５２ｍｍｏｌ／ｈとなるよう、重合器に連続的に供給した。また、共触媒として(Ｃ6Ｈ5)3ＣＢ(Ｃ6Ｆ5)4（ＣＢ−３）をフィード量０．０２６ｍｍｏｌ／ｈ、有機アルミニウム化合物としてトリイソブチルアルミニウム（ＴＩＢＡ）をフィード量２０ｍｍｏｌ／ｈとなるように、それぞれ重合器に連続的に供給した。 Feed amount using di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride as the main catalyst while maintaining the polymerization pressure at 1.6 MPaG and the polymerization temperature at 95 ° C. It was continuously supplied to the polymerizer so as to be 0.0052 mmol / h. In addition, (C 6 H 5 ) 3 CB (C 6 F 5 ) 4 (CB-3) as a cocatalyst has a feed amount of 0.026 mmol / h, and triisobutylaluminum (TIBA) as an organoaluminum compound has a feed amount of 20 mmol / h. Each was continuously supplied to the polymerizer so as to be.
このようにして、エチレン、ブテンおよびＶＮＢから形成されたエチレン・ブテン・ＶＮＢ共重合体を２０質量％含む溶液が得られた。重合器下部から抜き出した重合反応液中に少量のメタノールを添加して重合反応を停止させ、スチームストリッピング処理にてエチレン・ブテン・ＶＮＢ共重合体を溶媒から分離した後、８０℃で一昼夜減圧乾燥した。 In this way, a solution containing 20% by mass of an ethylene-butene-VNB copolymer formed from ethylene, butene and VNB was obtained. A small amount of methanol was added to the polymerization reaction solution extracted from the lower part of the polymer to stop the polymerization reaction, the ethylene / butene / VNB copolymer was separated from the solvent by steam stripping treatment, and then the pressure was reduced at 80 ° C. for 24 hours. It was dry.
以上の操作によって、エチレン、ブテンおよびＶＮＢから形成されたエチレン・ブテン・ＶＮＢ共重合体（ＶＮＢ−ＥＢＴ）が、毎時５．０ｋｇの速度で得られた。得られた共重合体（ＶＮＢ−ＥＢＴ）の物性を測定した。結果を表１に示す。 By the above operation, an ethylene-butene-VNB copolymer (VNB-EBT) formed from ethylene, butene and VNB was obtained at a rate of 5.0 kg / h. The physical properties of the obtained copolymer (VNB-EBT) were measured. The results are shown in Table 1.
［実施例１］
第一段階として、Ｍｉｘｔｒｏｎ ＢＢ−４型ミキサー（神戸製鋼所製）を用いて、製造例１で得たエチレン・ブテン・ＶＮＢ共重合体（ＶＮＢ−ＥＢＴ）１００質量部を１分間素練りし、次いでこれに、カーボンブラック（旭＃６０ＵＧ、旭カーボン（株）社製）４０質量部、パラフィン系プロセスオイル（ダイアナプロセスＰＷ−３８０、出光興産（株）製）４０質量部、およびポリフェノール系老化防止剤（ノクラックＮＳ−７、大内新興化学（株）製）２質量部を加え、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、第一段階の配合物を得た。
[Example 1]
As a first step, 100 parts by mass of the ethylene / butene / VNB copolymer (VNB-EBT) obtained in Production Example 1 was kneaded for 1 minute using a Mixtron BB-4 type mixer (manufactured by Kobe Steel). Next, 40 parts by mass of carbon black (Asahi # 60UG, manufactured by Asahi Carbon Co., Ltd.), 40 parts by mass of paraffin-based process oil (Diana Process PW-380, manufactured by Idemitsu Kosan Co., Ltd.), and polyphenol-based anti-aging 2 parts by mass of an agent (Nocrack NS-7, manufactured by Ouchi Shinko Kagaku Co., Ltd.) was added, and the mixture was kneaded at 140 ° C. for 2 minutes. Then, the ram was raised and cleaned, and further kneaded for 1 minute and discharged at about 150 ° C. to obtain the first-stage formulation.
次に、第二段階として、第一段階で得られた配合物を、８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、ヒドロシリル基含有化合物［信越化学（株）製「Ｘ−９３−１３４６」：(CH3)3SiO-(SiH(CH3)-O-)6-Si(CH3)2-O-Si(C6H6)2-O-Si(CH3)3］４質量部、白金系触媒［信越化学（株）製「Ｘ−９３−１４１０」：塩化白金酸+［CH2=CH(Me)SiO］4錯体］０．４質量部および反応抑制剤（信越化学（株）製「Ｘ−９３−１０３６」：３，５−ジメチル−１−ヘキシル−３−オール）０．８質量部を加え１０分間混練して未架橋の樹脂組成物を得た。この樹脂組成物の粘度を評価した。 Next, as the second step, the compound obtained in the first step is subjected to 8-inch roll (manufactured by Nippon Roll Co., Ltd., front roll surface temperature 50 ° C., rear roll surface temperature 50 ° C., front roll. wound rotational speed 16 rpm, the rotational speed 18 rpm) of the rear roll, to which hydrosilyl group-containing compound [manufactured by Shin-Etsu chemical Co., Ltd., "X-93-1346" :( CH 3) 3 SiO- (SiH (CH 3 ) -O-) 6 -Si (CH 3 ) 2 -O-Si (C 6 H 6 ) 2 -O-Si (CH 3 ) 3 ] 4 parts by mass, platinum-based catalyst [Shinetsu Chemical Co., Ltd. "X" -93-1410 ": Platinum chloride acid + [CH 2 = CH (Me) SiO] 4 complex] 0.4 parts by mass and reaction inhibitor ("X-93-1036" manufactured by Shin-Etsu Chemical Co., Ltd .: 3,5 -Dimethyl-1-hexyl-3-ol) 0.8 parts by mass was added and kneaded for 10 minutes to obtain an uncrosslinked resin composition. The viscosity of this resin composition was evaluated.
得られた樹脂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１５分間プレスし、厚み２ｍｍの架橋ゴムシートを得た。これを用いて、架橋成形体の各種物性の評価を行った。結果を表２に示す。 The obtained resin composition was dispensed into a sheet and pressed at 180 ° C. for 15 minutes using a 100-ton press molding machine to obtain a crosslinked rubber sheet having a thickness of 2 mm. Using this, various physical properties of the crosslinked molded article were evaluated. The results are shown in Table 2.
［比較例１〜２］
表２に示すように、比較例１では老化防止剤を用いなかったこと、比較例２ではポリフェノール系老化防止剤の代わりにイオウ系老化防止剤（Irganox 1010、ＢＡＳＦ社製）を用いたこと以外は実施例１と同様にして、樹脂組成物および架橋ゴムシートを得て評価を行った。結果を表２に示す。
[Comparative Examples 1-2]
As shown in Table 2, except that the anti-aging agent was not used in Comparative Example 1 and the sulfur-based anti-aging agent (Irganox 1010, manufactured by BASF) was used instead of the polyphenol-based anti-aging agent in Comparative Example 2. In the same manner as in Example 1, a resin composition and a crosslinked rubber sheet were obtained and evaluated. The results are shown in Table 2.
Claims (6)
下記（ｉ）〜（iv）の要件を満たすことを特徴とするエチレン・α−オレフィン・非共役ポリエン共重合体（Ｓ）である請求項１〜４のいずれか１項に記載の樹脂組成物。
（ii）非共役ポリエン（ａ３）に由来する構成単位の質量分率が、エチレン・α−オレフィン・非共役ポリエン共重合体（Ｓ）１００質量％中、０．０７質量％〜１０質量％である。
（iii）１００℃におけるムーニー粘度ＭＬ(1+4)１００℃が５〜２５０である。
（iv）１３５℃デカリン中で測定した極限粘度［η］が０．１〜５．０ｄｌ／ｇである The polymer (A) is a total of partial structures selected from the group consisting of ethylene (a1), α-olefin (a2) having 3 to 20 carbon atoms, and the following general formulas (I) and (II). It has a structural unit derived from a non-conjugated polyene (a3) containing two or more in the molecule.
The resin composition according to any one of claims 1 to 4, which is an ethylene / α-olefin / non-conjugated polyene copolymer (S), which satisfies the following requirements (i) to (iv). ..
(Ii) The mass fraction of the structural unit derived from the non-conjugated polyene (a3) is 0.07% by mass to 10% by mass in 100% by mass of the ethylene / α-olefin / non-conjugated polyene copolymer (S). is there.
(Iii) Mooney viscosity at 100 ° C. ML (1 + 4) 100 ° C. is 5 to 250.
(Iv) The ultimate viscosity [η] measured in 135 ° C. decalin is 0.1 to 5.0 dl / g.
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