JP2012207154A - Propylene resin composition - Google Patents
Propylene resin composition Download PDFInfo
- Publication number
- JP2012207154A JP2012207154A JP2011074813A JP2011074813A JP2012207154A JP 2012207154 A JP2012207154 A JP 2012207154A JP 2011074813 A JP2011074813 A JP 2011074813A JP 2011074813 A JP2011074813 A JP 2011074813A JP 2012207154 A JP2012207154 A JP 2012207154A
- Authority
- JP
- Japan
- Prior art keywords
- propylene
- mass
- ethylene
- less
- parts
- 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 153
- 239000011342 resin composition Substances 0.000 title claims abstract description 61
- 229920001155 polypropylene Polymers 0.000 claims abstract description 69
- 229920001971 elastomer Polymers 0.000 claims abstract description 45
- 239000000806 elastomer Substances 0.000 claims abstract description 33
- 238000010828 elution Methods 0.000 claims abstract description 19
- 230000001788 irregular Effects 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 13
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 239000000470 constituent Substances 0.000 claims abstract description 4
- 229920001577 copolymer Polymers 0.000 claims description 53
- 239000004711 α-olefin Substances 0.000 claims description 52
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 44
- 239000005977 Ethylene Substances 0.000 claims description 44
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- 239000012968 metallocene catalyst Substances 0.000 claims description 12
- 238000005194 fractionation Methods 0.000 claims description 5
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 description 89
- 229920000642 polymer Polymers 0.000 description 48
- -1 propylene-ethylene Chemical group 0.000 description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 43
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 40
- 229910052739 hydrogen Inorganic materials 0.000 description 37
- 239000001257 hydrogen Substances 0.000 description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 36
- 239000002002 slurry Substances 0.000 description 32
- 238000004519 manufacturing process Methods 0.000 description 29
- 239000003054 catalyst Substances 0.000 description 28
- 150000002430 hydrocarbons Chemical group 0.000 description 27
- 239000007789 gas Substances 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 19
- 239000007787 solid Substances 0.000 description 16
- 239000011949 solid catalyst Substances 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 239000004743 Polypropylene Substances 0.000 description 14
- 229920001400 block copolymer Polymers 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000003780 insertion Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 9
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- 150000008040 ionic compounds Chemical class 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 230000037431 insertion Effects 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 5
- 230000008016 vaporization Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- XPPWLXNXHSNMKC-UHFFFAOYSA-N phenylboron Chemical compound [B]C1=CC=CC=C1 XPPWLXNXHSNMKC-UHFFFAOYSA-N 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 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 description 4
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 3
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- MWHBZZADOGTHOW-UHFFFAOYSA-N 5-tert-butyl-1,3,3-trimethyl-2,6a-dihydro-1H-pentalene Chemical compound CC1CC(C)(C)C2=CC(=CC12)C(C)(C)C MWHBZZADOGTHOW-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- KOFGHHIZTRGVAF-UHFFFAOYSA-N n-ethyl-n-triethoxysilylethanamine Chemical compound CCO[Si](OCC)(OCC)N(CC)CC KOFGHHIZTRGVAF-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920001384 propylene homopolymer Polymers 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 125000005131 dialkylammonium group Chemical group 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- ZOICEQJZAWJHSI-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)boron Chemical compound [B]C1=C(F)C(F)=C(F)C(F)=C1F ZOICEQJZAWJHSI-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- VSYZXASVWVQEMR-UHFFFAOYSA-N 2-methylbuta-1,3-dienylalumane Chemical compound CC(=C[AlH2])C=C VSYZXASVWVQEMR-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- WBGJXNLILNRVBB-UHFFFAOYSA-N BBBBBBCBC Chemical compound BBBBBBCBC WBGJXNLILNRVBB-UHFFFAOYSA-N 0.000 description 1
- FOJJREBLHNCKQL-UHFFFAOYSA-N BBBBBCBBB Chemical compound BBBBBCBBB FOJJREBLHNCKQL-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- NSKVFTJEKYEULC-UHFFFAOYSA-N CCCCN(CCCC)CCCC.CCCCN(CCCC)CCCC.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O Chemical compound CCCCN(CCCC)CCCC.CCCCN(CCCC)CCCC.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O NSKVFTJEKYEULC-UHFFFAOYSA-N 0.000 description 1
- XGERXDAEUCZOMZ-UHFFFAOYSA-N CCCCN(CCCC)CCCC.CCCCN(CCCC)CCCC.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O Chemical compound CCCCN(CCCC)CCCC.CCCCN(CCCC)CCCC.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O XGERXDAEUCZOMZ-UHFFFAOYSA-N 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical group CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- QAHYSATYLGMNPK-UHFFFAOYSA-L [Cl-].[Cl-].C(C)(C)(C)C1=C(C=2CC3=CC(=CC=C3C2C=C1)C(C)(C)C)[Zr+2] Chemical compound [Cl-].[Cl-].C(C)(C)(C)C1=C(C=2CC3=CC(=CC=C3C2C=C1)C(C)(C)C)[Zr+2] QAHYSATYLGMNPK-UHFFFAOYSA-L 0.000 description 1
- AYYWWOWWADXQIA-UHFFFAOYSA-L [Cl-].[Cl-].C1(=CC=CC=C1)C(C1=CC=CC=C1)=[Zr+2](C1=CC(=CC=2C3=CC(=CC=C3CC1=2)C(C)(C)C)C(C)(C)C)C1C=C(C=C1C)C(C)(C)C Chemical compound [Cl-].[Cl-].C1(=CC=CC=C1)C(C1=CC=CC=C1)=[Zr+2](C1=CC(=CC=2C3=CC(=CC=C3CC1=2)C(C)(C)C)C(C)(C)C)C1C=C(C=C1C)C(C)(C)C AYYWWOWWADXQIA-UHFFFAOYSA-L 0.000 description 1
- BAAQZDCCXHWKDI-UHFFFAOYSA-L [Cl-].[Cl-].C1(=CC=CC=C1)C(C1=CC=CC=C1)=[Zr+2](C1=CC=CC=2C3=CC=CC=C3CC1=2)C1C=C(C=C1C)C(C)(C)C Chemical compound [Cl-].[Cl-].C1(=CC=CC=C1)C(C1=CC=CC=C1)=[Zr+2](C1=CC=CC=2C3=CC=CC=C3CC1=2)C1C=C(C=C1C)C(C)(C)C BAAQZDCCXHWKDI-UHFFFAOYSA-L 0.000 description 1
- YFNYHPMVZDTQSG-UHFFFAOYSA-L [Cl-].[Cl-].CC(=[Zr+2](C1(C(C(C(C2(CCC3C=4C=CC=CC=4CC3=C21)C)(C)C)(C)C)(C)C)C)C1C=C(C=C1C)C(C)(C)C)C1=CC=CC=C1 Chemical compound [Cl-].[Cl-].CC(=[Zr+2](C1(C(C(C(C2(CCC3C=4C=CC=CC=4CC3=C21)C)(C)C)(C)C)(C)C)C)C1C=C(C=C1C)C(C)(C)C)C1=CC=CC=C1 YFNYHPMVZDTQSG-UHFFFAOYSA-L 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000004305 biphenyl Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052800 carbon group element Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- SMKFCFKIYPLYNY-UHFFFAOYSA-K cerium(3+);trichloride;hydrate Chemical compound O.Cl[Ce](Cl)Cl SMKFCFKIYPLYNY-UHFFFAOYSA-K 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- CYKLGTUKGYURDP-UHFFFAOYSA-L copper;hydrogen sulfate;hydroxide Chemical compound O.[Cu+2].[O-]S([O-])(=O)=O CYKLGTUKGYURDP-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- GSQKXUNYYCYYKT-UHFFFAOYSA-N cyclo-trialuminium Chemical compound [Al]1[Al]=[Al]1 GSQKXUNYYCYYKT-UHFFFAOYSA-N 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- BOXSCYUXSBYGRD-UHFFFAOYSA-N cyclopenta-1,3-diene;iron(3+) Chemical compound [Fe+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 BOXSCYUXSBYGRD-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 125000005299 dibenzofluorenyl group Chemical group C1(=CC=CC2=C3C(=C4C=5C=CC=CC5CC4=C21)C=CC=C3)* 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-O dicyclohexylazanium Chemical compound C1CCCCC1[NH2+]C1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-O 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- UWAMTZZJXXCIOH-UHFFFAOYSA-M diethyl(phenoxy)alumane Chemical compound CC[Al+]CC.[O-]C1=CC=CC=C1 UWAMTZZJXXCIOH-UHFFFAOYSA-M 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- CBWJKNQKWLEEPG-UHFFFAOYSA-N dihydridoborate(1-) Chemical class [BH2-] CBWJKNQKWLEEPG-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- WNVQCJNZEDLILP-UHFFFAOYSA-N dimethyl(oxo)tin Chemical compound C[Sn](C)=O WNVQCJNZEDLILP-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 210000003195 fascia Anatomy 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- LJJQENSFXLXPIV-UHFFFAOYSA-N fluorenylidene Chemical group C1=CC=C2[C]C3=CC=CC=C3C2=C1 LJJQENSFXLXPIV-UHFFFAOYSA-N 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- ORECYURYFJYPKY-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine;2,4,6-trichloro-1,3,5-triazine;2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N.ClC1=NC(Cl)=NC(Cl)=N1.C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 ORECYURYFJYPKY-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- LKNLEKUNTUVOML-UHFFFAOYSA-L nickel(2+);sulfate;hydrate Chemical compound O.[Ni+2].[O-]S([O-])(=O)=O LKNLEKUNTUVOML-UHFFFAOYSA-L 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- QIIPQYDSKRYMFG-UHFFFAOYSA-N phenyl hydrogen carbonate Chemical group OC(=O)OC1=CC=CC=C1 QIIPQYDSKRYMFG-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000012899 standard injection Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- AHRSCNGWSKJKAW-UHFFFAOYSA-N tert-butylaluminum Chemical compound [Al].C[C](C)C AHRSCNGWSKJKAW-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- NDUUEFPGQBSFPV-UHFFFAOYSA-N tri(butan-2-yl)alumane Chemical compound CCC(C)[Al](C(C)CC)C(C)CC NDUUEFPGQBSFPV-UHFFFAOYSA-N 0.000 description 1
- URNNTTSIHDDFIB-UHFFFAOYSA-N tri(cyclooctyl)alumane Chemical compound C1CCCCCCC1[Al](C1CCCCCCC1)C1CCCCCCC1 URNNTTSIHDDFIB-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ZIYNWDQDHKSRCE-UHFFFAOYSA-N tricyclohexylalumane Chemical compound C1CCCCC1[Al](C1CCCCC1)C1CCCCC1 ZIYNWDQDHKSRCE-UHFFFAOYSA-N 0.000 description 1
- YGRHYJIWZFEDBT-UHFFFAOYSA-N tridecylaluminum Chemical compound CCCCCCCCCCCCC[Al] YGRHYJIWZFEDBT-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- YFDAMRSZJLWUSQ-UHFFFAOYSA-N tris(2-methylphenyl)borane Chemical compound CC1=CC=CC=C1B(C=1C(=CC=CC=1)C)C1=CC=CC=C1C YFDAMRSZJLWUSQ-UHFFFAOYSA-N 0.000 description 1
- AGOOAFIKKUZTEB-UHFFFAOYSA-N tris(3,5-difluorophenyl)borane Chemical compound FC1=CC(F)=CC(B(C=2C=C(F)C=C(F)C=2)C=2C=C(F)C=C(F)C=2)=C1 AGOOAFIKKUZTEB-UHFFFAOYSA-N 0.000 description 1
- OHSAEOPCBBOWPU-UHFFFAOYSA-N tris(3,5-dimethylphenyl)borane Chemical compound CC1=CC(C)=CC(B(C=2C=C(C)C=C(C)C=2)C=2C=C(C)C=C(C)C=2)=C1 OHSAEOPCBBOWPU-UHFFFAOYSA-N 0.000 description 1
- YPVVTWIAXFPZLS-UHFFFAOYSA-N tris(4-fluorophenyl)borane Chemical compound C1=CC(F)=CC=C1B(C=1C=CC(F)=CC=1)C1=CC=C(F)C=C1 YPVVTWIAXFPZLS-UHFFFAOYSA-N 0.000 description 1
- LEIHCYASDULBKZ-UHFFFAOYSA-N tris(4-methylphenyl)borane Chemical compound C1=CC(C)=CC=C1B(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LEIHCYASDULBKZ-UHFFFAOYSA-N 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- OSMBUUFIZBTSNO-UHFFFAOYSA-N tris[4-(fluoromethyl)phenyl]borane Chemical compound C1=CC(CF)=CC=C1B(C=1C=CC(CF)=CC=1)C1=CC=C(CF)C=C1 OSMBUUFIZBTSNO-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明はプロピレン系樹脂組成物に関する。 The present invention relates to a propylene-based resin composition.
プロピレン系重合体や、プロピレン系樹脂組成物は、日用雑貨、台所用品、包装用フィルム、家電製品、機械部品、電気部品、自動車部品等の様々な用途で用いられている。中でも、プロピレン系重合体や、プロピレン系樹脂組成物は、剛性や耐衝撃性が必要とされる用途、例えば自動車部品（自動車内装部品、自動車外装部品）、家電製品、機械部品、電気部品によく用いられている。 Propylene-based polymers and propylene-based resin compositions are used in various applications such as household goods, kitchenware, packaging films, home appliances, machine parts, electrical parts, and automobile parts. Among them, propylene-based polymers and propylene-based resin compositions are often used for applications that require rigidity and impact resistance, such as automobile parts (car interior parts, car exterior parts), home appliances, machine parts, and electrical parts. It is used.
プロピレン系重合体やプロピレン系樹脂組成物の剛性や耐衝撃性を改良するために、様々な提案が従来からされている。
特許文献１には、剛性と耐衝撃性とのバランスに優れたプロピレン系ブロック共重合体として、室温ｎ‐デカンに可溶な部分（Ｄsol）と室温ｎ‐デカンに不溶な部分（Ｄinsol）とから構成され、プロピレンと、エチレンおよび炭素数４以上のα‐オレフィンから選ばれる１種以上のオレフィンとから得られるプロピレン系重合体が開示されている。特許文献１に記載されたプロピレン系重合体は、ＤsolおよびＤinsolの分子量分布が４．０以下であること、Ｄinsolの融点が１５６℃以上であること、Ｄinsolの２，１−結合量と、１，３−結合量との和が０．０５モル％以下であることを要件とする重合体である。該プロピレン系重合体は、剛性および耐衝撃性のバランスには優れるが、その流動性については改良が望まれていた。
Various proposals have heretofore been made to improve the rigidity and impact resistance of propylene-based polymers and propylene-based resin compositions.
In Patent Document 1, as a propylene-based block copolymer having a good balance between rigidity and impact resistance, a part soluble in room temperature n-decane (D sol ) and a part insoluble in room temperature n-decane (D insol And a propylene-based polymer obtained from propylene and one or more olefins selected from ethylene and an α-olefin having 4 or more carbon atoms. The propylene-based polymer described in Patent Document 1 has a molecular weight distribution of D sol and D insol of 4.0 or less, a melting point of D insol of 156 ° C. or more, and a 2,1-bond of D insol . It is a polymer that requires the sum of the amount and the amount of 1,3-bond to be 0.05 mol% or less. The propylene-based polymer is excellent in the balance between rigidity and impact resistance, but improvement in its fluidity has been desired.
特許文献２には、剛性と低温での耐衝撃性に優れるプロピレン‐エチレンブロック共重合体として、結晶性ポリプロピレン部分６０〜８５重量％と、プロピレン‐エチレンランダム共重合体部分１５〜４０重量％とを含有するプロピレン‐エチレンブロック共重合体が開示されている。特許文献２に記載されたプロピレン‐エチレンブロック共重合体は、プロピレン‐エチレンランダム共重合体部分が、プロピレン‐エチレンランダム共重合体成分（ＥＰ）と、プロピレン‐エチレン‐ブテンランダム共重合体成分（ＥＰＢ）とを含有すること、ＥＰ、ＥＰＢがそれぞれ特定の極限粘度を有すること、プロピレン‐エチレンブロック共重合体のメルトフローレートが５〜１２０ｇ／１０分であること等を要件とする重合体である。該重合体は、剛性および低温での耐衝撃性のバランスには優れるが、その流動性については改良が望まれていた。 In Patent Document 2, as a propylene-ethylene block copolymer excellent in rigidity and impact resistance at low temperature, a crystalline polypropylene portion of 60 to 85% by weight, a propylene-ethylene random copolymer portion of 15 to 40% by weight, A propylene-ethylene block copolymer containing is disclosed. In the propylene-ethylene block copolymer described in Patent Document 2, the propylene-ethylene random copolymer portion is divided into a propylene-ethylene random copolymer component (EP) and a propylene-ethylene-butene random copolymer component ( EPB), EP and EPB have specific intrinsic viscosities, and the propylene-ethylene block copolymer has a melt flow rate of 5 to 120 g / 10 min. is there. The polymer is excellent in the balance between rigidity and impact resistance at low temperature, but improvement in fluidity has been desired.
特許文献３には、成形体にした場合に、剛性と耐衝撃性および低温耐衝撃性のバランスに優れるプロピレン系ブロック共重合体として、第一工程において、プロピレン系重合体成分（１）を製造し、第二工程において、成分（１）の存在下にプロピレン系共重合体成分（２）を製造し、第三工程において成分（１）および成分（２）の存在下にエチレン系共重合体成分（３）を製造して得られたプロピレン系ブロック共重合体が開示されている。特許文献３に記載されたプロピレン系ブロック共重合体は、成分（１）の融解温度が１５５℃以上であること、成分（２）の極限粘度が２．０ｄｌ／ｇ以上、８．０ｄｌ／ｇ以下であること、成分（３）の極限粘度が３．０ｄｌ／ｇ以上、８．０ｄｌ／ｇ以下であること、プロピレン系ブロック共重合体のガラス転移温度が−５５．０℃以下であること等を要件とする重合体である。該重合体は剛性と耐衝撃性および低温耐衝撃性のバランスには優れるが、その流動性については改良が望まれていた。 In Patent Document 3, a propylene-based polymer component (1) is produced in the first step as a propylene-based block copolymer having a good balance of rigidity, impact resistance and low-temperature impact resistance when formed into a molded body. In the second step, the propylene-based copolymer component (2) is produced in the presence of the component (1), and in the third step, the ethylene-based copolymer is present in the presence of the component (1) and the component (2). A propylene-based block copolymer obtained by producing the component (3) is disclosed. In the propylene-based block copolymer described in Patent Document 3, the melting temperature of component (1) is 155 ° C. or higher, and the intrinsic viscosity of component (2) is 2.0 dl / g or higher, 8.0 dl / g. The intrinsic viscosity of the component (3) is 3.0 dl / g or more and 8.0 dl / g or less, and the glass transition temperature of the propylene-based block copolymer is -55.0 ° C. or less. And the like. The polymer is excellent in the balance between rigidity, impact resistance and low temperature impact resistance, but improvement in fluidity has been desired.
また、特許文献４には、柔軟性や耐衝撃性に優れ、ベタツキ感がなく、ブロッキング性が良好で、成形時のゲルの発生が少なく、線膨張率が低く、フローマークが出にくく、かつ重合パウダーの粉体性状がよいプロピレン系ブロック共重合体が開示されている。特許文献４に記載されたプロピレン系ブロック共重合体は、メタロセン触媒の存在下で、プロピレン単独重合体成分またはプロピレン共重合体成分（ＰＰ）を製造する工程と、該工程に続いて、気相重合により、プロピレンと、α‐オレフィンとの共重合体成分（ＣＰ）を製造する工程都からなる多段重合を連続的に行って得られるプロピレン系ブロック共重合体である。特許文献４に記載されたプロピレン系ブロック共重合体は、ＣＰ含有量が５０〜９９重量％であること、ＣＰ中のコモノマーの重合割合が４５モル％以上１００モル％未満であること、ＣＰの重量平均分子量が、１０〜２００万であること、プロピレン系ブロック共重合体の分子量５０００以下の成分量が、全体の２．０重量％以下であることを要件とする重合体である。 Further, Patent Document 4 is excellent in flexibility and impact resistance, has no stickiness, has a good blocking property, generates less gel during molding, has a low coefficient of linear expansion, is difficult to produce a flow mark, and A propylene-based block copolymer having a good powder property of the polymer powder is disclosed. The propylene-based block copolymer described in Patent Document 4 includes a step of producing a propylene homopolymer component or a propylene copolymer component (PP) in the presence of a metallocene catalyst, and a gas phase following the step. It is a propylene-based block copolymer obtained by continuously performing multistage polymerization comprising a process capital for producing a copolymer component (CP) of propylene and an α-olefin by polymerization. The propylene block copolymer described in Patent Document 4 has a CP content of 50 to 99% by weight, a comonomer polymerization ratio in CP of 45 mol% or more and less than 100 mol%, The polymer is required to have a weight average molecular weight of 102 to 2,000,000 and a propylene block copolymer having a molecular weight of 5000 or less and a component amount of 2.0% by weight or less.
従来から様々なプロピレン系重合体やプロピレン系樹脂組成物が提案されているが、伸び、耐衝撃性および低温耐衝撃性等の機械物性に優れ、かつ流動性に優れるプロピレン系樹脂組成物は、未だ提案されていなかった。 Various propylene-based polymers and propylene-based resin compositions have been proposed so far, but propylene-based resin compositions having excellent mechanical properties such as elongation, impact resistance and low-temperature impact resistance, and excellent fluidity are Not yet proposed.
これは、プロピレン系樹脂組成物の流動性が高くなる、すなわちＭＦＲが高くなると、一般に、伸び、耐衝撃性、低温耐衝撃性が低下するためである。ＭＦＲが高くなると、これらの機械物性に劣ることは、A. van der Wal, J.J. Mulder, J. Oderkerk and R.J. Gaymans , "Polypropylene-rubber blends: 1. The effect of the matrix properties on the impact behaviour", Polymer Vol.39 No.26, pp.6781-6787,1998 にも開示されている。 This is because when the fluidity of the propylene-based resin composition is increased, that is, when the MFR is increased, the elongation, impact resistance, and low temperature impact resistance are generally lowered. As the MFR increases, these mechanical properties are inferior due to A. van der Wal, JJ Mulder, J. Oderkerk and RJ Gaymans, "Polypropylene-rubber blends: 1. The effect of the matrix properties on the impact behavior", Polymer Vol.39 No.26, pp.6781-6787,1998 is also disclosed.
本発明は、従来技術では未だ達成されていない、伸び、耐衝撃性および低温耐衝撃性等の機械物性に優れ、かつ流動性に優れるプロピレン系樹脂組成物を提供することを目的とする。 An object of the present invention is to provide a propylene-based resin composition that is excellent in mechanical properties such as elongation, impact resistance, and low-temperature impact resistance, and excellent in fluidity, which has not yet been achieved in the prior art.
本発明者らは、前記課題を達成するために鋭意研究を重ねた結果、特定のプロピレン系重合体と、エラストマーとを、特定量で含有するプロピレン系樹脂組成物は、流動性と、伸び、耐衝撃性、低温耐衝撃性等の機械物性とのバランスが優れることを見出し、本発明を完成させた。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have obtained a propylene-based resin composition containing a specific propylene-based polymer and an elastomer in a specific amount, fluidity, elongation, The present invention has been completed by finding that the balance between mechanical properties such as impact resistance and low temperature impact resistance is excellent.
すなわち、本発明のプロピレン系樹脂組成物は、下記［１］〜［５］を同時に満たすプロピレン系重合体（Ａ）５５質量部以上、９８質量部以下と、エラストマー（Ｂ）２質量部以上、４５質量部以下（ただし、（Ａ）および（Ｂ）の合計は１００質量部である）とを含有する。 That is, the propylene-based resin composition of the present invention includes 55 parts by mass or more and 98 parts by mass or less of a propylene-based polymer (A) that simultaneously satisfies the following [1] to [5], and 2 parts by mass or more of an elastomer (B), 45 parts by mass or less (however, the sum of (A) and (B) is 100 parts by mass).
［１］ＡＳＴＭ−Ｄ１２３８に準拠し、２３０℃、２．１６ｋｇ荷重で測定したメルトフローレート（ＭＦＲ）が１００ｇ／１０分以上、１０００ｇ／１０分以下
［２］示差走査熱量計（ＤＳＣ）によって測定された融点が１５０℃以上、１６５℃以下
［３］13Ｃ−ＮＭＲスペクトルから求めた、全プロピレン構成単位中のプロピレンモノマーの２，１−結合に基づく位置不規則単位および１，３−結合に基づく位置不規則単位の合計が０．０％以上、１．０％以下
［４］分子量１００００以下の成分が７質量％以下
［５］ｏ−ジクロロベンゼンを用いたクロス分別クロマトグラフ（ＣＦＣ）により測定した溶出温度に対する溶出成分量のピーク半値幅が６．０℃以下であり、ピークトップ温度が１００℃以上、１３０℃以下
前記プロピレン系重合体（Ａ）が、メタロセン触媒存在下、プロピレンを単独重合もしくは、プロピレンと、エチレンおよび炭素数４〜１０のα‐オレフィンから選択される少なくとも１種のα‐オレフィンとを共重合して得られることが好ましい。
[1] Based on ASTM-D1238, melt flow rate (MFR) measured at 230 ° C. and 2.16 kg load is 100 g / 10 min or more and 1000 g / 10 min or less. [2] Measured by differential scanning calorimeter (DSC) The melting point was 150 ° C. or higher and 165 ° C. or lower. [3] The position irregular units and 1,3-bonds based on the 2,1-bonds of the propylene monomer in all propylene constituent units determined from the 13 C-NMR spectrum. [4] Components having molecular weight of 10,000 or less are 7% by mass or less. [5] By cross-fractionation chromatograph (CFC) using o-dichlorobenzene. The peak half-value width of the eluted component amount relative to the measured elution temperature is 6.0 ° C or lower, and the peak top temperature is 100 ° C or higher and 130 ° C or lower. In the presence of a metallocene catalyst, propylene homopolymerizes or copolymerizes propylene with at least one α-olefin selected from ethylene and an α-olefin having 4 to 10 carbon atoms. Is preferably obtained.
前記エラストマー（Ｂ）が、エチレンと、炭素数３〜１０のα−オレフィンから選択される少なくとも１種のα−オレフィンとの共重合体であり、下記［ｉ］〜［ｉｉ］を同時に満たすことが好ましい。 The elastomer (B) is a copolymer of ethylene and at least one α-olefin selected from α-olefins having 3 to 10 carbon atoms, and simultaneously satisfies the following [i] to [ii]. Is preferred.
［ｉ］エチレン含有量が１５ｍｏｌ％以上、９０ｍｏｌ％以下
［ｉｉ］極限粘度［η］が０．８ｄｌ／ｇ以上、４．０ｄｌ／ｇ以下
前記エラストマー（Ｂ）が、２種類以上のエチレンと、炭素数３〜１０のα−オレフィンから選択される少なくとも１種のα‐オレフィンとの共重合体からなることが好ましい。
[I] Ethylene content is 15 mol% or more and 90 mol% or less [ii] Intrinsic viscosity [η] is 0.8 dl / g or more and 4.0 dl / g or less The elastomer (B) is composed of two or more kinds of ethylene, It is preferably made of a copolymer with at least one α-olefin selected from α-olefins having 3 to 10 carbon atoms.
前記エラストマー（Ｂ）が、エチレン−プロピレン共重合体（Ｂ−１）および、エチレンと、炭素数４〜１０のα−オレフィンから選択される少なくとも１種のα‐オレフィンとの共重合体（Ｂ−２）の２種類の共重合体を含むことが好ましい。 The elastomer (B) is an ethylene-propylene copolymer (B-1) and a copolymer of ethylene and at least one α-olefin selected from α-olefins having 4 to 10 carbon atoms (B -2) two types of copolymers are preferably included.
前記エチレン−プロピレン共重合体（Ｂ−１）が、下記［Ｉ］〜［ＩＩ］を同時に満たし、前記エチレンと、炭素数４〜１０のα−オレフィンから選択される少なくとも１種のα‐オレフィンとの共重合体（Ｂ−２）が、下記［ＩＩＩ］〜［ＩＶ］を同時に満たし、プロピレン系樹脂組成物が、前記エチレン−プロピレン共重合体（Ｂ−１）を１質量部以上、４０質量部以下、前記エチレンと、炭素数４〜１０のα−オレフィンから選択される少なくとも１種のα‐オレフィンとの共重合体（Ｂ−２）を１質量部以上、４０質量部以下を含有することが好ましい。 The ethylene-propylene copolymer (B-1) simultaneously satisfies the following [I] to [II], and at least one α-olefin selected from the ethylene and an α-olefin having 4 to 10 carbon atoms (B-2) simultaneously satisfy the following [III] to [IV], and the propylene-based resin composition contains 1 part by mass or more of the ethylene-propylene copolymer (B-1), 40 1 part by mass or more and 40 parts by mass or less of a copolymer (B-2) of ethylene and at least one α-olefin selected from α-olefins having 4 to 10 carbon atoms It is preferable to do.
［Ｉ］エチレン含有量が１５ｍｏｌ％以上、５０ｍｏｌ％以下
［ＩＩ］極限粘度［η］が０．８ｄｌ／ｇ以上、４．０ｄｌ／ｇ以下
［ＩＩＩ］エチレン含有量が５０ｍｏｌ％以上、９０ｍｏｌ％以下
［ＩＶ］極限粘度［η］が０．８ｄｌ／ｇ以上、４．０ｄｌ／ｇ以下
[I] Ethylene content is 15 mol% or more and 50 mol% or less [II] Intrinsic viscosity [η] is 0.8 dl / g or more and 4.0 dl / g or less [III] Ethylene content is 50 mol% or more and 90 mol% or less [IV] Intrinsic viscosity [η] is 0.8 dl / g or more and 4.0 dl / g or less
本発明のプロピレン系樹脂組成物は、伸び、耐衝撃性および低温耐衝撃性等の機械物性に優れ、かつ流動性に優れる。 The propylene-based resin composition of the present invention is excellent in mechanical properties such as elongation, impact resistance and low temperature impact resistance, and is excellent in fluidity.
次に本発明について具体的に説明する。
本発明のプロピレン系樹脂組成物は、プロピレン系重合体（Ａ）５５質量部以上、９８質量部以下と、エラストマー（Ｂ）２質量部以上、４５質量部以下（ただし、（Ａ）および（Ｂ）の合計は１００質量部である）とを含有する。
Next, the present invention will be specifically described.
The propylene-based resin composition of the present invention comprises a propylene-based polymer (A) 55 parts by mass or more and 98 parts by mass or less, and an elastomer (B) 2 parts by mass or more and 45 parts by mass or less (however, (A) and (B ) Is 100 parts by mass).
〔プロピレン系重合体（Ａ）〕
本発明のプロピレン系樹脂組成物が含有するプロピレン系重合体（Ａ）は、下記［１］〜［５］を同時に満たす。
[Propylene polymer (A)]
The propylene polymer (A) contained in the propylene resin composition of the present invention satisfies the following [1] to [5] simultaneously.
［１］ＡＳＴＭ−Ｄ１２３８に準拠し、２３０℃、２．１６ｋｇ荷重で測定したメルトフローレート（ＭＦＲ）が１００ｇ／１０分以上、１０００ｇ／１０分以下
［２］示差走査熱量計（ＤＳＣ）によって測定された融点が１５０℃以上、１６５℃以下
［３］13Ｃ−ＮＭＲスペクトルから求めた、全プロピレン構成単位中のプロピレンモノマーの２，１−結合に基づく位置不規則単位および１，３−結合に基づく位置不規則単位の合計が０．０％以上、１．０％以下
［４］分子量１００００以下の成分が７質量％以下
［５］ｏ−ジクロロベンゼンを用いたクロス分別クロマトグラフ（ＣＦＣ）により測定した溶出温度に対する溶出成分量のピーク半値幅が６．０℃以下であり、ピークトップ温度が１００℃以上、１３０℃以下
[1] Based on ASTM-D1238, melt flow rate (MFR) measured at 230 ° C. and 2.16 kg load is 100 g / 10 min or more and 1000 g / 10 min or less. [2] Measured by differential scanning calorimeter (DSC) The melting point was 150 ° C. or higher and 165 ° C. or lower. [3] The position irregular units and 1,3-bonds based on the 2,1-bonds of the propylene monomer in all propylene constituent units determined from the 13 C-NMR spectrum. [4] Components having molecular weight of 10,000 or less are 7% by mass or less. [5] By cross-fractionation chromatograph (CFC) using o-dichlorobenzene. The peak half-value width of the eluted component with respect to the measured elution temperature is 6.0 ° C or lower, and the peak top temperature is 100 ° C or higher and 130 ° C or lower.
前記プロピレン系重合体（Ａ）は、前記［１］に示したように、ＭＦＲが１００ｇ／１０分以上、１０００ｇ／１０分以下であるが、好ましくは１２０ｇ／１０分以上、１０００ｇ／１０分以下であり、より好ましくは１４０ｇ／１０分以上、１０００ｇ／１０分以下であり、特に好ましくは１５０ｇ／１０分以上、１０００ｇ／１０分以下である。ＭＦＲが前記範囲内であると、本発明のプロピレン系樹脂組成物の流動性に優れるため好ましい。 The propylene polymer (A) has an MFR of 100 g / 10 min or more and 1000 g / 10 min or less, preferably 120 g / 10 min or more and 1000 g / 10 min or less, as shown in [1]. More preferably, it is 140 g / 10 min or more and 1000 g / 10 min or less, and particularly preferably 150 g / 10 min or more and 1000 g / 10 min or less. It is preferable for the MFR to be within the above range since the propylene resin composition of the present invention is excellent in fluidity.
前記プロピレン系重合体（Ａ）は、前記［２］に示したように、融点が１５０℃以上、１６５℃以下であるが、好ましくは１５２℃以上、１６５℃以下、より好ましくは１５４℃以上、１６５℃以下、特に好ましくは１５５℃以上、１６５℃以下である。融点が前記範囲内であると、本発明のプロピレン系樹脂組成物から得られる成形品の結晶化度が高くなり、良好な剛性を発現するため好ましい。 The propylene polymer (A) has a melting point of 150 ° C. or higher and 165 ° C. or lower as shown in [2], preferably 152 ° C. or higher and 165 ° C. or lower, more preferably 154 ° C. or higher. It is 165 ° C. or lower, particularly preferably 155 ° C. or higher and 165 ° C. or lower. It is preferable for the melting point to be within the above-mentioned range since the crystallinity of the molded product obtained from the propylene-based resin composition of the present invention is increased and good rigidity is exhibited.
前記プロピレン系重合体（Ａ）は、前記［３］に示したように、全プロピレン構成単位中のプロピレンモノマーの２，１−結合に基づく位置不規則単位および１，３−結合に基づく位置不規則単位の合計が０．０％以上、１．０％以下であるが、好ましくは０．０％以上、０．８％以下、より好ましくは０．０％以上、０．６％以下、特に好ましくは０．０％以上、０．４％以下である。なお、プロピレン系重合体（Ａ）のプロピレンの２，１−挿入結合量、１，３−挿入結合量が前記範囲よりも多い場合、プロピレン系樹脂組成物から得られる成形品の結晶構造に、欠陥が生じ、プロピレン系樹脂組成物が引っ張られた場合や衝撃が加わった際に、その欠陥が破壊の起点となる為、耐衝撃性、伸びが低下すると、本発明者らは推測している。 As shown in the above [3], the propylene-based polymer (A) is composed of a propylene monomer in all propylene structural units, a position irregular unit based on 2,1-bonds and a position disorder based on 1,3-bonds. The total of the regular units is 0.0% or more and 1.0% or less, preferably 0.0% or more and 0.8% or less, more preferably 0.0% or more and 0.6% or less, particularly Preferably they are 0.0% or more and 0.4% or less. When the propylene-based polymer (A) has a propylene 2,1-insertion bond amount and a 1,3-insertion bond amount larger than the above ranges, the crystal structure of the molded product obtained from the propylene-based resin composition When the propylene-based resin composition is pulled or an impact is applied when a defect is generated, the defect is a starting point of destruction, and therefore the inventors presume that the impact resistance and elongation are reduced. .
前記プロピレン系重合体（Ａ）は、前記［４］に示したように、分子量１００００以下の成分が７質量％以下であるが、好ましくは６．８質量％以下であり、より好ましくは６．６質量％以下であり、特に好ましくは６．５質量％以下である。分子量１００００以下の成分量は少ないほど好ましく、その下限としては特に限定はないが、通常前記プロピレン系重合体（Ａ）は分子量１００００以下の成分を、１．０質量％以上含む。 As shown in the above [4], the propylene polymer (A) has a component having a molecular weight of 10,000 or less in an amount of 7% by mass or less, preferably 6.8% by mass or less, more preferably 6. It is 6 mass% or less, Especially preferably, it is 6.5 mass% or less. The smaller the amount of the component having a molecular weight of 10,000 or less, the better. The lower limit thereof is not particularly limited, but the propylene polymer (A) usually contains 1.0% by mass or more of the component having a molecular weight of 10,000 or less.
前記プロピレン系重合体（Ａ）は、前記［５］に示したように、ＣＦＣにより測定した溶出温度に対する溶出成分量のピーク半値幅が６．０℃以下であり、ピークトップ温度が１００℃以上、１３０℃以下であるが、好ましくはピーク半値幅が５．８℃以下であり、ピークトップ温度が１０２℃以上、１３０℃以下であり、より好ましくはピーク半値幅が５．６℃以下であり、ピークトップ温度が１０４℃以上、１３０℃以下であり、特に好ましくはピーク半値幅が５．４℃以下であり、ピークトップ温度が１０５℃以上、１３０℃以下である。また、本願に用いるプロピレン系重合体（Ａ）のピーク半値幅は、通常は２．５℃以上である。また、通常の一般的なプロピレン系重合体のピーク半値幅は６．５℃以上である。 As shown in [5] above, the propylene polymer (A) has a peak half-value width of the eluted component amount with respect to the eluted temperature measured by CFC of 6.0 ° C. or lower, and a peak top temperature of 100 ° C. or higher. 130 ° C. or lower, preferably the peak half width is 5.8 ° C. or lower, the peak top temperature is 102 ° C. or higher and 130 ° C. or lower, more preferably the peak half width is 5.6 ° C. or lower. The peak top temperature is 104 ° C. or higher and 130 ° C. or lower, particularly preferably the peak half width is 5.4 ° C. or lower, and the peak top temperature is 105 ° C. or higher and 130 ° C. or lower. Moreover, the peak half width of the propylene polymer (A) used in the present application is usually 2.5 ° C. or more. In addition, the peak width at half maximum of a normal general propylene polymer is 6.5 ° C. or more.
また、本発明のプロピレン系重合体（Ａ）は、重量平均分子量（Ｍｗ）が、３万以上、２０万以下であることが好ましく、４万以上、１５万以下であることがより好ましい。
なお、前記［４］および前記重量平均分子量において、プロピレン系重合体（Ａ）の分子量は、標準ポリプロピレン（ＰＰ）換算の分子量である。
The propylene polymer (A) of the present invention preferably has a weight average molecular weight (Mw) of 30,000 or more and 200,000 or less, more preferably 40,000 or more and 150,000 or less.
In the above [4] and the weight average molecular weight, the molecular weight of the propylene polymer (A) is a molecular weight in terms of standard polypropylene (PP).
前記プロピレン系重合体（Ａ）の各物性は実施例に記載の方法で測定することができる。
本発明に用いるプロピレン系重合体（Ａ）は、前記［１］を満たすことにより流動性に優れる。なお、一般に重合体のＭＦＲが大きい、言い換えると流動性に優れる程、重合体の数平均分子量、重量平均分子量が小さくなる。なお、本発明に用いられるプロピレン系重合体（Ａ）は、比較的ＭＦＲが大きい。また、本発明に用いるプロピレン系重合体（Ａ）は、前記［４］に示すように分子量１００００以下の低分子量成分の量が少なく、前記［３］に示すように２，１−結合や１，３−結合に基づく位置不規則単位が少なく、さらに前記［５］に示すように立体規則性分布が狭いアイソタクチックポリプロピレンである。
Each physical property of the propylene polymer (A) can be measured by the methods described in Examples.
The propylene polymer (A) used in the present invention is excellent in fluidity by satisfying the above [1]. In general, the number average molecular weight and the weight average molecular weight of the polymer become smaller as the MFR of the polymer is larger, in other words, the better the fluidity. The propylene polymer (A) used in the present invention has a relatively large MFR. Further, the propylene-based polymer (A) used in the present invention has a low amount of low molecular weight components having a molecular weight of 10,000 or less as shown in [4], and 2,1-bond or 1 as shown in [3]. , 3-bond is an isotactic polypropylene with few positional irregular units and a narrow stereoregularity distribution as shown in [5].
本発明のプロピレン系樹脂組成物が、伸び、耐衝撃性および低温耐衝撃性等の機械物性に優れる理由は明らかではないが、本発明者らはこの理由をプロピレン系重合体（Ａ）が前記［４］を満たすため、前記［３］および［５］を満たすため、あるいは［３］〜［５］を満たすためであると推測している。 The reason why the propylene-based resin composition of the present invention is excellent in mechanical properties such as elongation, impact resistance, and low-temperature impact resistance is not clear, but the present inventors indicate that the propylene-based polymer (A) is the above-mentioned reason. It is presumed that [4] is satisfied, [3] and [5] are satisfied, or [3] to [5] are satisfied.
一般に伸び、耐衝撃性の発現に関与する分子量は絡み合い点間分子量の２倍以上であると言われている。プロピレン系重合体の絡み合い点間分子量は約５０００であることから（例えば LEWISE J. FETTERS, DAVID j. LOHSE, WILLIAM W. GRAESSLEY, "Chain Dimensions and Entanglement Spacings in Dense Macromolecular System", Journal of Polymer Science, 1999 参照）、プロピレン系重合体において、分子量１００００以下の低分子量成分の量が多い、即ち前記［４］を満たさない場合には、絡み合い点が少ない分子鎖が多くなり、伸び、耐衝撃性が低下してしまうと本発明者らは推測した。本発明のプロピレン系樹脂組成物は、プロピレン系重合体（Ａ）として、低分子量成分の量が少ないため、絡み合い点が少ない分子鎖の量を低減することが可能であり、本発明のプロピレン系樹脂組成物は、伸び、耐衝撃性に優れると推測した。 In general, it is said that the molecular weight involved in the expression of elongation and impact resistance is more than twice the molecular weight between entanglement points. Since the molecular weight between the entanglement points of the propylene polymer is about 5000 (for example, LEWISE J. FETTERS, DAVID j. LOHSE, WILLIAM W. GRAESSLEY, "Chain Dimensions and Entanglement Spacings in Dense Macromolecular System", Journal of Polymer Science, 1999)), when the amount of low molecular weight component having a molecular weight of 10000 or less is large in the propylene polymer, that is, when the above [4] is not satisfied, the number of molecular chains with few entanglement points increases, and the elongation and impact resistance are improved. The inventors speculated that it would decrease. Since the propylene-based resin composition of the present invention has a small amount of low molecular weight components as the propylene-based polymer (A), it is possible to reduce the amount of molecular chains with few entanglement points. The resin composition was presumed to be excellent in elongation and impact resistance.
プロピレン系重合体として、２，１−結合や１，３−結合に基づく位置不規則単位が多く存在する場合、即ち前記［３］を満たさない場合や、立体規則性分布が広い場合、即ち前記［５］を満たさない場合には、プロピレン系重合体の結晶構造に、欠陥が生じ、プロピレン系樹脂組成物が引っ張られた場合や衝撃が加わった際には、その欠陥が破壊の起点となると考えられる。本発明のプロピレン系樹脂組成物は、プロピレン系重合体（Ａ）として、位置不規則単位が少なく、立体規則性分布が狭いため、結晶構造に欠陥が少なく、本発明のプロピレン系樹脂組成物は、伸び、耐衝撃性に優れると推測した。 As a propylene polymer, when there are many regioregular units based on 2,1-bonds and 1,3-bonds, that is, when the above [3] is not satisfied, or when the stereoregularity distribution is wide, that is, When [5] is not satisfied, a defect occurs in the crystal structure of the propylene-based polymer, and when the propylene-based resin composition is pulled or subjected to an impact, the defect becomes a starting point of destruction. Conceivable. The propylene-based resin composition of the present invention has few positional irregular units and a narrow stereoregularity distribution as the propylene-based polymer (A), so that the crystal structure has few defects, and the propylene-based resin composition of the present invention is It was estimated that it was excellent in elongation and impact resistance.
また、本発明に用いるプロピレン系重合体（Ａ）としては、プロピレン単独重合体でもよく、プロピレンと他のモノマーとの共重合体でもよい。前記他のモノマーとしては、エチレンおよび炭素数４〜１０のα‐オレフィンから選択される少なくとも１種のα‐オレフィンが挙げられる。炭素数４〜１０のα‐オレフィンとしては、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−デセンが挙げられる。エチレンおよび炭素数４〜１０のα‐オレフィンから選択される少なくとも１種のα‐オレフィンとしては、エチレン、１−ブテンが好ましい。 The propylene polymer (A) used in the present invention may be a propylene homopolymer or a copolymer of propylene and another monomer. Examples of the other monomer include at least one α-olefin selected from ethylene and an α-olefin having 4 to 10 carbon atoms. Examples of the α-olefin having 4 to 10 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and 1-decene. The at least one α-olefin selected from ethylene and an α-olefin having 4 to 10 carbon atoms is preferably ethylene or 1-butene.
前記プロピレン系重合体（Ａ）が、プロピレンと他のモノマーとの共重合体である場合には、前記プロピレン系重合体（Ａ）が、前記他のモノマー由来の構成単位を３モル％以下の量で含むことが好ましい。また、プロピレン系重合体（Ａ）としては、剛性発現の観点からプロピレン単独重合体であることが好ましい。なお、プロピレン系重合体（Ａ）としては一種単独で用いても、二種以上を用いてもよい。 When the propylene polymer (A) is a copolymer of propylene and another monomer, the propylene polymer (A) contains 3 mol% or less of the structural unit derived from the other monomer. It is preferable to include by quantity. Moreover, as a propylene polymer (A), it is preferable that it is a propylene homopolymer from a viewpoint of rigidity expression. In addition, as a propylene polymer (A), it may use individually by 1 type, or may use 2 or more types.
また、前記プロピレン系重合体（Ａ）は、通常メタロセン触媒存在下で重合される。メタロセン触媒を用いることにより前記［１］〜［５］を満たすプロピレン系重合体を得ることができる。 The propylene polymer (A) is usually polymerized in the presence of a metallocene catalyst. By using a metallocene catalyst, a propylene polymer satisfying the above [1] to [5] can be obtained.
すなわち、前記プロピレン系重合体（Ａ）は、メタロセン触媒存在下、プロピレンを単独重合もしくは、プロピレンと、エチレンおよび炭素数４〜１０のα‐オレフィンから選択される少なくとも１種のα‐オレフィンとを共重合して得られることが好ましい。 That is, the propylene polymer (A) is obtained by homopolymerizing propylene in the presence of a metallocene catalyst, or propylene and at least one α-olefin selected from ethylene and an α-olefin having 4 to 10 carbon atoms. It is preferably obtained by copolymerization.
本発明に用いられるプロピレン系重合体（Ａ）は、例えば特定のメタロセン触媒を用いて調製される。本発明に用いることが可能なメタロセン触媒を形成するメタロセン化合物触媒成分としては例えば、下記一般式（１）で表わされる。 The propylene-based polymer (A) used in the present invention is prepared using, for example, a specific metallocene catalyst. The metallocene compound catalyst component that forms the metallocene catalyst that can be used in the present invention is represented, for example, by the following general formula (1).
また、一般式（１）において、置換基Ｒ5〜Ｒ12は隣接する置換基と相互に結合して環を形成してもよい。このような置換フルオレニル基としては、ベンゾフルオレニル基、ジベンゾフルオレニル基、オクタヒドロジベンゾフルオレニル基、オクタメチルオクタヒドロジベンゾフルオレニル基、オクタメチルテトラヒドロジシクロペンタフルオレニル基などを挙げることができる。 In the general formula (1), the substituents R 5 to R 12 may be bonded to adjacent substituents to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, octamethyloctahydrodibenzofluorenyl group, octamethyltetrahydrodicyclopentafluorenyl group, etc. Can be mentioned.
上記一般式（１）において、シクロペンタジエニル環に置換するＲ1、Ｒ2、Ｒ3、Ｒ4は水素原子または炭素原子数１〜２０の炭化水素基であることが好ましい。炭素原子数１〜２０の炭化水素基としては、前述の炭化水素基を例示することができる。さらに好ましくはＲ3が炭素数１〜２０の炭化水素基である。 In the general formula (1), R 1 , R 2 , R 3 and R 4 substituted on the cyclopentadienyl ring are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the above-described hydrocarbon groups. More preferably, R 3 is a hydrocarbon group having 1 to 20 carbon atoms.
上記一般式（１）において、フルオレン環に置換するＲ5〜Ｒ12は炭素原子数１〜２０の炭化水素基であることが好ましい。炭素原子数１〜２０の炭化水素基としては、前掲の炭化水素基を例示することができる。置換基Ｒ5〜Ｒ12は、隣接する置換基が相互に結合して環を形成してもよい。 In the said General formula (1), it is preferable that R < 5 > -R < 12 > substituted by a fluorene ring is a C1-C20 hydrocarbon group. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the hydrocarbon groups listed above. In the substituents R 5 to R 12 , adjacent substituents may be bonded to each other to form a ring.
上記一般式（１）において、シクロペンタジエニル環とフルオレニル環を架橋するＹは周期律表第１４族元素であることが好ましく、より好ましくは炭素、ケイ素、ゲルマニウムであり、さらに好ましくは炭素原子である。このＹに置換するＲ13、Ｒ14は炭素原子数１〜２０の炭化水素基が好ましい。これらは相互に同一でも異なっていてもよく、互いに結合して環を形成してもよい。炭素原子数１〜２０の炭化水素基としては、前掲の炭化水素基を例示することができる。さらに好ましくは、Ｒ14は炭素数６〜２０のアリール(ａｒｙｌ)基である。アリール基としては、前述の環状不飽和炭化水素基、環状不飽和炭化水素基の置換した飽和炭化水素基、ヘテロ原子含有環状不飽和炭化水素基を挙げることができる。また、Ｒ13、Ｒ14はそれぞれ同一でも異なっていてもよく、互いに結合して環を形成してもよい。このような置換基としては、フルオレニリデン基、１０−ヒドロアントラセニリデン基、ジベンゾシクロヘプタジエニリデン基などが好ましい。 In the general formula (1), Y that bridges the cyclopentadienyl ring and the fluorenyl ring is preferably a group 14 element of the periodic table, more preferably carbon, silicon, or germanium, and still more preferably a carbon atom. It is. R 13 and R 14 substituted on Y are preferably a hydrocarbon group having 1 to 20 carbon atoms. These may be the same as or different from each other, and may be bonded to each other to form a ring. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the hydrocarbon groups listed above. More preferably, R 14 is an aryl group having 6 to 20 carbon atoms. Examples of the aryl group include the above-mentioned cyclic unsaturated hydrocarbon group, a saturated hydrocarbon group substituted with a cyclic unsaturated hydrocarbon group, and a heteroatom-containing cyclic unsaturated hydrocarbon group. R 13 and R 14 may be the same or different, and may be bonded to each other to form a ring. As such a substituent, a fluorenylidene group, a 10-hydroanthracenylidene group, a dibenzocycloheptadienylidene group, and the like are preferable.
また、上記一般式（１）で表されるメタロセン化合物は、Ｒ1、Ｒ4、Ｒ5またはＲ12から選ばれる置換基と架橋部のＲ13またはＲ14が互いに結合して環を形成してもよい。
上記一般式（１）において、Ｍは好ましくは周期律表第４族遷移金属であり、さらに好ましくはＴi、Ｚr、Ｈfである。また、Ｑはハロゲン原子、炭化水素基、アニオン配位子または孤立電子対で配位可能な中性配位子から同一または異なる組合せで選ばれる。ｊは１〜４の整数であり、ｊが２以上のときは、Ｑは互いに同一でも異なっていてもよい。ハロゲン原子の具体例としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子であり、炭化水素基の具体例としては前掲と同様のものなどが挙げられる。アニオン配位子の具体例としては、メトキシ、ｔｅｒｔ−ブトキシ、フェノキシなどのアルコキシ基、アセテート、ベンゾエートなどのカルボキシレート基、メシレート、トシレートなどのスルホネート基等が挙げられる。孤立電子対で配位可能な中性配位子の具体例としては、トリメチルホスフィン、トリエチルホスフィン、トリフェニルホスフィン、ジフェニルメチルホスフィンなどの有機リン化合物、テトラヒドロフラン、ジエチルエーテル、ジオキサン、１，２−ジメトキシエタンなどのエーテル類等が挙げられる。Ｑは少なくとも１つがハロゲン原子またはアルキル基であることが好ましい。
Further, in the metallocene compound represented by the general formula (1), a substituent selected from R 1 , R 4 , R 5 or R 12 and R 13 or R 14 of the bridging part are bonded to each other to form a ring. May be.
In the general formula (1), M is preferably a Group 4 transition metal of the periodic table, more preferably Ti, Zr, or Hf. Q is selected from the same or different combinations from a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and specific examples of the hydrocarbon group include the same as those described above. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxy. And ethers such as ethane. It is preferable that at least one Q is a halogen atom or an alkyl group.
このような架橋メタロセン化合物としては、ジフェニルメチレン（３−ｔｅｒｔ−ブチル−５−メチル-シクロペンタジエニル）（フルオレニル）ジルコニウムジクロリド、ジフェニルメチレン（３−ｔｅｒｔ−ブチル−５−メチル-シクロペンタジエニル）（２，７−ジｔｅｒｔ−ブチルフルオレニル）ジルコニウムジクロリド、ジフェニルメチレン（３−ｔｅｒｔ−ブチル−５−メチル-シクロペンタジエニル）（３，６−ジｔｅｒｔ−ブチルフルオレニル）ジルコニウムジクロリド、（メチル）（フェニル）メチレン（３−ｔｅｒｔ−ブチル−５−メチル-シクロペンタジエニル）（オクタメチルオクタヒドロベンゾフルオレニル）ジルコニウムジクロリド、［３−（１'，１'，４'，４'，７'，７'，１０'，１０'−オクタメチルオクタヒドロジベンゾ［ｂ，ｈ］フルオレニル）（１，１，３−トリメチル−５−ｔｅｒｔ−ブチル−１，２，３，３ａ−テトラヒドロペンタレン）］ジルコニウムジクロライド（下記式（２）参照）などが好ましく挙げられる。 Such bridged metallocene compounds include diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl). ) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride (Methyl) (phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrobenzofluorenyl) zirconium dichloride, [3- (1 ′, 1 ′, 4 ′, 4 ', 7', 7 ', 10', 10'-octamethyloctahydro Benzo [b, h] fluorenyl) (1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride (see the following formula (2)) is preferred. It is done.
このような粒子状担体としては、ＳｉＯ2、Ａｌ2Ｏ3、Ｂ2Ｏ3、ＭｇＯ、ＺｒＯ2、ＣａＯ、ＴｉＯ2、ＺｎＯ、ＳｎＯ2、ＢａＯ、ＴｈＯなどの無機担体、ポリエチレン、プロピレン系ブロック共重合体、ポリ−１−ブテン、ポリ４−メチル−１−ペンテン、スチレン−ジビニルベンゼン共重合体などの有機担体を用いることができる。これらの粒子状担体は、１種単独で、または２種以上組合わせて用いることができる。 Examples of such particulate carriers include inorganic carriers such as SiO 2 , Al 2 O 3 , B 2 O 3 , MgO, ZrO 2 , CaO, TiO 2 , ZnO, SnO 2 , BaO, and ThO, polyethylene, and propylene-based blocks. An organic carrier such as a copolymer, poly-1-butene, poly-4-methyl-1-pentene, or a styrene-divinylbenzene copolymer can be used. These particulate carriers can be used alone or in combination of two or more.
本発明では前記メタロセン触媒の助触媒の一つとして、アルミノキサンを用いることができる。従来公知のようにアルミノキサンは、例えば下記のような方法によって製造することができる。 In the present invention, aluminoxane can be used as one of the promoters of the metallocene catalyst. As conventionally known, aluminoxane can be produced, for example, by the following method.
（１）吸着水を含有する化合物あるいは結晶水を含有する塩類、例えば塩化マグネシウム水和物、硫酸銅水和物、硫酸アルミニウム水和物、硫酸ニッケル水和物、塩化第１セリウム水和物などの炭化水素媒体懸濁液に、トリアルキルアルミニウムなどの有機アルミニウム化合物を添加して反応させる方法。 (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, and cerium chloride hydrate A method in which an organoaluminum compound such as trialkylaluminum is added to and reacted with a suspension of the above hydrocarbon medium.
（２）ベンゼン、トルエン、エチルエーテル、テトラヒドロフランなどの媒体中で、トリアルキルアルミニウムなどの有機アルミニウム化合物に直接水や氷や水蒸気を作用させる方法。 (2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
（３）デカン、ベンゼン、トルエンなどの媒体中でトリアルキルアルミニウムなどの有機アルミニウム化合物に、ジメチルスズオキシド、ジブチルスズオキシドなどの有機スズ酸化物を反応させる方法。 (3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.
アルミノキサンを調製する際に用いられる有機アルミニウム化合物としては、具体的には、トリメチルアルミニウム、トリエチルアルミニウム、トリプロピルアルミニウム、トリイソプロピルアルミニウム、トリｎ−ブチルアルミニウム、トリイソブチルアルミニウム、トリｓｅｃ−ブチルアルミニウム、トリｔｅｒｔ−ブチルアルミニウム、トリペンチルアルミニウム、トリヘキシルアルミニウム、トリオクチルアルミニウム、トリデシルアルミニウム等のトリアルキルアルミニウム、トリシクロヘキシルアルミニウム、トリシクロオクチルアルミニウム等のトリシクロアルキルアルミニウム、ジメチルアルミニウムクロリド、ジエチルアルミニウムクロリド、ジエチルアルミニウムブロミド、ジイソブチルアルミニウムクロリド等のジアルキルアルミニウムハライド、ジエチルアルミニウムハイドライド、ジイソブチルアルミニウムハイドライド等のジアルキルアルミニウムハイドライド、ジメチルアルミニウムメトキシド、ジエチルアルミニウムエトキシド等のジアルキルアルミニウムアルコキシド、ジエチルアルミニウムフェノキシド等のジアルキルアルミニウムアリーロキシドなどが挙げられる。これらのうち、トリアルキルアルミニウム、トリシクロアルキルアルミニウムが好ましく、トリメチルアルミニウムが特に好ましい。 Specific examples of organoaluminum compounds used in the preparation of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum, trialuminum. tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, trialkylaluminum such as tridecylaluminum, tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethyl Dia such as aluminum bromide, diisobutylaluminum chloride Kill aluminum halide, diethyl aluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride, dimethyl aluminum methoxide, dialkylaluminum alkoxides such as diethylaluminum ethoxide and dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide and the like. Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.
また、アルミノキサンを調製する際に用いられる有機アルミニウム化合物として、下記一般式で表されるイソプレニルアルミニウムを用いることもできる。アルミノキサンの溶液または懸濁液に用いられる溶媒としては、ベンゼン、トルエン、キシレン、クメン、シメンなどの芳香族炭化水素、ペンタン、ヘキサン、ヘプタン、オクタン、デカン、ドデカン、ヘキサデカン、オクタデカンなどの脂肪族炭化水素、シクロペンタン、シクロヘキサン、シクロオクタン、メチルシクロペンタンなどの脂環族炭化水素、ガソリン、灯油、軽油などの石油留分あるいは前記芳香族炭化水素、脂肪族炭化水素、脂環族炭化水素のハロゲン化物とりわけ、塩素化物、臭素化物などの炭化水素溶媒が挙げられる。 Moreover, the isoprenyl aluminum represented by the following general formula can also be used as an organoaluminum compound used when preparing an aluminoxane. Solvents used in aluminoxane solutions or suspensions include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, and aliphatic carbonization such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane. Hydrogen, cyclopentane, cyclohexane, cyclooctane, methylcyclopentane and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene and light oil, or halogens of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons Among them, hydrocarbon solvents such as chlorinated products and brominated products are mentioned.
その他、エチルエーテル、テトラヒドロフランなどのエーテル類を用いることもできる。これらの溶媒のうち特に芳香族炭化水素または脂肪族炭化水素が好ましい。
なお有機アルミニウムオキシ化合物は、少量のアルミニウム以外の金属の有機化合物成分を含有していてもよい。イオン化イオン性化合物としては、ルイス酸、イオン性化合物、ボラン化合物およびカルボラン化合物を例示することができる。
In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.
The organoaluminum oxy compound may contain a small amount of a metal organic compound component other than aluminum. Examples of ionized ionic compounds include Lewis acids, ionic compounds, borane compounds, and carborane compounds.
ルイス酸としては、ＢＲ3（式中、Ｒはフッ素原子、メチル基、トリフルオロメチル基などの置換基を有していてもよいフェニル基またはフッ素原子である。）で示される化合物が挙げられ、例えばトルフルオロボロン、トリフェニルボロン、トリス（４−フルオロフェニル）ボロン、トリス（３，５−ジフルオロフェニル）ボロン、トリス（４−フルオロメチルフェニル）ボロン、トリス（ペンタフルオロフェニル）ボロン、トリス（ｐ−トリル）ボロン、トリス（ｏ−トリル）ボロン、トリス（３，５−ジメチルフェニル）ボロンなどが挙げられる。 Examples of the Lewis acid include compounds represented by BR 3 (wherein R is a phenyl group or a fluorine atom which may have a substituent such as a fluorine atom, a methyl group or a trifluoromethyl group). For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris ( p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.
イオン性化合物としては、トリアルキル置換アンモニウム塩、Ｎ，Ｎ−ジアルキルアニリニウム塩、ジアルキルアンモニウム塩、トリアリールホスフォニウム塩などを挙げることができる。具体的に、トリアルキル置換アンモニウム塩としては、例えばトリエチルアンモニウムテトラ（フェニル）ホウ素、トリプロピルアンモニウムテトラ（フェニル）ホウ素、トリ（ｎ−ブチル）アンモニウムテトラ（フェニル）ホウ素などが挙げられる。ジアルキルアンモニウム塩としては、例えばジ（１−プロピル）アンモニウムテトラ（ペンタフルオロフェニル）ホウ素、ジシクロヘキシルアンモニウムテトラ（フェニル）ホウ素などが挙げられる。さらにイオン性化合物として、トリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレート、Ｎ，Ｎ−ジメチルアニリニウムテトラキス（ペンタフルオロフェニル）ボレート、フェロセニウムテトラ（ペンタフルオロフェニル）ボレートなどを挙げることもできる。 Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts. Specifically, examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, and tri (n-butyl) ammonium tetra (phenyl) boron. Examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron. Furthermore, examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate and the like.
ボラン化合物としては、デカボラン（１４）、ビス〔トリ（ｎ−ブチル）アンモニウム〕ノナボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕デカボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕ビス（ドデカハイドライドドデカボレート）ニッケル酸塩（ＩＩＩ）などの金属ボランアニオンの塩などが挙げられる。 Examples of borane compounds include decaborane (14), bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate ) Metal borane anion salts such as nickelate (III).
カルボラン化合物としては、４−カルバノナボラン（１４）、１，３−ジカルバノナボラン（１３）、ビス〔トリ（ｎ−ブチル）アンモニウム〕ビス（ウンデカハイドライド−７−カルバウンデカボレート）ニッケル酸塩（ＩＶ）などの金属カルボランアニオンの塩などが挙げられる。 Examples of the carborane compound include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate And salts of metal carborane anions such as (IV).
前記のようなイオン化イオン性化合物は、１種単独で、または２種以上組合わせて用いることができる。前記有機アルミニウムオキシ化合物またはイオン化イオン性化合物は、上述した粒子状担体に担持させて用いることもできる。 The ionized ionic compounds as described above can be used singly or in combination of two or more. The organoaluminum oxy compound or ionized ionic compound can also be used by being supported on the particulate carrier described above.
また、触媒を形成するに際しては、有機アルミニウムオキシ化合物またはイオン化イオン性化合物とともに以下のような有機アルミニウム化合物を用いてもよい。
有機アルミニウム化合物としては、分子内に少なくとも１個のＡ１−炭素結合を有する化合物が利用できる。このような化合物としては、例えば下記一般式で表される有機アルミニウム化合物が挙げられる。
Moreover, when forming a catalyst, you may use the following organoaluminum compounds with an organoaluminum oxy compound or an ionized ionic compound.
As the organoaluminum compound, a compound having at least one A1-carbon bond in the molecule can be used. Examples of such a compound include organoaluminum compounds represented by the following general formula.
（Ｒ1）ｍＡｌ（Ｏ（Ｒ2））ｎＨｐＸｑ
（式中、Ｒ1およびＲ2は、互いに同一でも異なっていてもよく、炭素原子数が通常１〜１５、好ましくは１〜４の炭化水素基を示し、Ｘはハロゲン原子を示し、ｍは０＜ｍ≦３、ｎは０≦ｎ＜３、ｐは０≦ｐ＜３、ｑは０≦ｑ＜３を満たす数であって、しかも、ｍ＋ｎ＋ｐ＋ｑ＝３である。）
(R 1 ) mAl (O (R 2 )) nHpXq
(In the formula, R 1 and R 2 may be the same or different from each other, and generally represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents (0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number satisfying 0 ≦ q <3, and m + n + p + q = 3)
本発明に用いるプロピレン系重合体（Ａ）は、前記したメタロセン触媒の存在下に、プロピレンを単独重合、あるいはプロピレンと他のモノマーとを共重合させることにより調製することができる。 The propylene polymer (A) used in the present invention can be prepared by homopolymerizing propylene or copolymerizing propylene and other monomers in the presence of the metallocene catalyst.
本発明に用いるプロピレン系重合体（Ａ）の重合工程は、通常、−５０〜２００℃、好ましくは５０〜１００℃の温度で、また通常、常圧〜１００ｋｇ／ｃｍ2、好ましくは約２〜５０ｋｇ／ｃｍ2の圧力下で行なわれる。プロピレン系重合体（Ａ）の重合は、回分式、半連続式、連続式の何れの方法においても行なうことができる。なお、前記メタロセン触媒を用い、かつ分子量調整剤として作用する水素を重合系内に存在させ、その水素濃度を調整することにより、本発明に用いるプロピレン系重合体（Ａ）は、前記[１]〜[５]を満たす。なお、本発明に用いるプロピレン系重合体（Ａ）を製造する際の重合機内の水素濃度は、従来公知のプロピレン系重合体を製造する際よりも、通常高濃度である。 The polymerization step of the propylene polymer (A) used in the present invention is usually at a temperature of −50 to 200 ° C., preferably 50 to 100 ° C., and usually at normal pressure to 100 kg / cm 2 , preferably about 2 to It is carried out under a pressure of 50 kg / cm 2 . The polymerization of the propylene polymer (A) can be carried out by any of batch, semi-continuous and continuous methods. The propylene-based polymer (A) used in the present invention is obtained by using the metallocene catalyst and allowing hydrogen acting as a molecular weight adjusting agent to be present in the polymerization system and adjusting the hydrogen concentration thereof. Satisfies [5]. The hydrogen concentration in the polymerization machine when producing the propylene-based polymer (A) used in the present invention is usually higher than when producing a conventionally known propylene-based polymer.
〔エラストマー（Ｂ）〕
本発明のプロピレン系樹脂組成物は、エラストマー（Ｂ）を含有する。
前記エラストマー（Ｂ）としては、通常エチレンと、α‐オレフィンとの共重合体が用いられ、エチレンと、炭素数３〜１０のα‐オレフィンから選択される少なくとも１種のα‐オレフィンとの共重合体であることが好ましい。
[Elastomer (B)]
The propylene-based resin composition of the present invention contains an elastomer (B).
As the elastomer (B), a copolymer of ethylene and an α-olefin is usually used, and a copolymer of ethylene and at least one α-olefin selected from α-olefins having 3 to 10 carbon atoms. A polymer is preferred.
前記エラストマー（Ｂ）としては、エチレンと、炭素数３〜１０のα‐オレフィンから選択される少なくとも１種のα‐オレフィンとの共重合体であり、下記［ｉ］〜［ｉｉ］を同時に満たすことが好ましい。 The elastomer (B) is a copolymer of ethylene and at least one α-olefin selected from α-olefins having 3 to 10 carbon atoms, and simultaneously satisfies the following [i] to [ii]: It is preferable.
［ｉ］エチレン含有量が１５ｍｏｌ％以上、９０ｍｏｌ％以下
［ｉｉ］極限粘度［η］が０．８ｄｌ／ｇ以上、４．０ｄｌ／ｇ以下
前記エラストマー（Ｂ）としては、一種単独で用いても、二種以上を用いてもよいが、剛性と常温・低温耐衝撃性および引張破断伸び発現の観点から、エラストマー（Ｂ）は、エチレンと、炭素数３〜１０のα‐オレフィンから選択される少なくとも１種のα‐オレフィンとの共重合体２種以上からなることが好ましい。なお、エラストマー（Ｂ）が二種類以上からなる場合には、それぞれの共重合体が、前記［ｉ］および［ｉｉ］を満たす。
[I] Ethylene content is 15 mol% or more and 90 mol% or less [ii] Intrinsic viscosity [η] is 0.8 dl / g or more and 4.0 dl / g or less The elastomer (B) may be used alone. Two or more types may be used, but the elastomer (B) is selected from ethylene and an α-olefin having 3 to 10 carbon atoms from the viewpoints of rigidity, normal temperature / low temperature impact resistance and tensile elongation at break. It is preferably composed of two or more copolymers with at least one α-olefin. In addition, when an elastomer (B) consists of two or more types, each copolymer satisfy | fills said [i] and [ii].
前記エラストマー（Ｂ）としては、エチレン−プロピレン共重合体（Ｂ−１）および、エチレンと、炭素数４〜１０のα−オレフィンから選択される少なくとも１種のα‐オレフィンとの共重合体（Ｂ−２）の２種類の共重合体を含むことが剛性と常温・低温耐衝撃性および引張破断伸び発現の観点から好ましい。炭素数４〜１０のα‐オレフィンとしては、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−デセンが挙げられ、１−ブテンが好ましい。 Examples of the elastomer (B) include an ethylene-propylene copolymer (B-1) and a copolymer of ethylene and at least one α-olefin selected from α-olefins having 4 to 10 carbon atoms ( It is preferable from the viewpoints of rigidity, normal temperature / low temperature impact resistance, and expression of tensile elongation at break. Examples of the α-olefin having 4 to 10 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and 1-decene. Is preferred.
前記エチレン−プロピレン共重合体（Ｂ−１）としては、下記［Ｉ］〜［ＩＩ］を同時に満たすことが好ましい。また、前記エチレンと、炭素数４〜１０のα−オレフィンから選択される少なくとも１種のα‐オレフィンとの共重合体（Ｂ−２）としては、下記［ＩＩＩ］〜［ＩＶ］を同時に満たすことが好ましい。
［Ｉ］エチレン含有量が１５ｍｏｌ％以上、５０ｍｏｌ％以下
［ＩＩ］極限粘度［η］が０．８ｄｌ／ｇ以上、４．０ｄｌ／ｇ以下
［ＩＩＩ］エチレン含有量が５０ｍｏｌ％以上、９０ｍｏｌ％以下
［ＩＶ］極限粘度［η］が０．８ｄｌ／ｇ以上、４．０ｄｌ／ｇ以下
The ethylene-propylene copolymer (B-1) preferably satisfies the following [I] to [II] simultaneously. The copolymer (B-2) of ethylene and at least one α-olefin selected from α-olefins having 4 to 10 carbon atoms simultaneously satisfies the following [III] to [IV]: It is preferable.
[I] Ethylene content is 15 mol% or more and 50 mol% or less [II] Intrinsic viscosity [η] is 0.8 dl / g or more and 4.0 dl / g or less [III] Ethylene content is 50 mol% or more and 90 mol% or less [IV] Intrinsic viscosity [η] is 0.8 dl / g or more and 4.0 dl / g or less
前記エラストマー（Ｂ）の製造方法としては、特に限定はないが、メタロセン触媒から得られるエラストマーが好ましい。
また、前記エラストマー（Ｂ）としては、市販品を用いてもよい。
Although there is no limitation in particular as a manufacturing method of the said elastomer (B), the elastomer obtained from a metallocene catalyst is preferable.
Moreover, you may use a commercial item as said elastomer (B).
〔プロピレン系樹脂組成物〕
本発明のプロピレン系樹脂組成物は、前述のように前記プロピレン系重合体（Ａ）５５質量部以上、９８質量部以下と、エラストマー（Ｂ）２質量部以上、４５質量部以下（ただし、（Ａ）および（Ｂ）の合計は１００質量部である）とを含有する。
[Propylene resin composition]
As described above, the propylene-based resin composition of the present invention is 55 parts by mass or more and 98 parts by mass or less of the propylene polymer (A) and 2 parts by mass or more and 45 parts by mass or less of the elastomer (B) (however, ( The sum of A) and (B) is 100 parts by mass).
本発明のプロピレン系樹脂組成物が、前記プロピレン系重合体（Ａ）を５８質量部以上、９５質量部以下と、前記エラストマー（Ｂ）を５質量部以上、４２質量部以下とを含有することが好ましく、前記プロピレン系重合体（Ａ）を６０質量部以上、９０質量部以下と、前記エラストマー（Ｂ）を１０質量部以上、４０質量部以下とを含有することがより好ましい。 The propylene resin composition of the present invention contains 58 parts by mass or more and 95 parts by mass or less of the propylene polymer (A) and 5 parts by mass or more and 42 parts by mass or less of the elastomer (B). It is preferable that the propylene polymer (A) contains 60 parts by mass or more and 90 parts by mass or less and the elastomer (B) contains 10 parts by mass or more and 40 parts by mass or less.
また、本発明のプロピレン系樹脂組成物が前記エラストマー（Ｂ）として、前記エチレン−プロピレン共重合体（Ｂ−１）および、前記エチレンと、炭素数４〜１０のα−オレフィンから選択される少なくとも１種のα‐オレフィンとの共重合体（Ｂ−２）の２種類の共重合体を含む場合には、通常前記エチレン−プロピレン共重合体（Ｂ−１）を１質量部以上、４０質量部以下、前記エチレンと、炭素数４〜１０のα−オレフィンから選択される少なくとも１種のα‐オレフィンとの共重合体（Ｂ−２）を１質量部以上、４０質量部以下を含有し、好ましくは前記エチレン−プロピレン共重合体（Ｂ−１）を１質量部以上、３５質量部以下、前記エチレンと、炭素数４〜１０のα−オレフィンから選択される少なくとも１種のα‐オレフィンとの共重合体（Ｂ−２）を１質量部以上、３５質量部以下を含有し、より好ましくは前記エチレン−プロピレン共重合体（Ｂ−１）を１質量部以上、３０質量部以下、前記エチレンと、炭素数４〜１０のα−オレフィンから選択される少なくとも１種のα‐オレフィンとの共重合体（Ｂ−２）を１質量部以上、３０質量部以下を含有する。 Moreover, the propylene-based resin composition of the present invention is at least selected from the ethylene-propylene copolymer (B-1), the ethylene, and an α-olefin having 4 to 10 carbon atoms as the elastomer (B). When two kinds of copolymers (B-2) with one kind of α-olefin are included, the ethylene-propylene copolymer (B-1) is usually 1 part by mass or more and 40 parts by mass. 1 part by mass or more and 40 parts by mass or less of the copolymer (B-2) of ethylene and at least one α-olefin selected from C 4-10 α-olefins. The ethylene-propylene copolymer (B-1) is preferably 1 part by mass or more and 35 parts by mass or less, and at least one α-olefin selected from the ethylene and an α-olefin having 4 to 10 carbon atoms. When 1 part by mass or more and 35 parts by mass or less of the copolymer (B-2), more preferably 1 part by mass or more and 30 parts by mass or less of the ethylene-propylene copolymer (B-1). And the copolymer (B-2) with the at least 1 sort (s) of alpha olefin selected from C4-C10 alpha olefin contains 1 mass part or more and 30 mass parts or less.
本発明のプロピレン系樹脂組成物は、前記プロピレン系重合体（Ａ）およびエラストマー（Ｂ）を含有するが、必要に応じて、無機充填剤、耐熱安定剤、帯電防止剤、耐候安定剤、耐光安定剤、老化防止剤、酸化防止剤、脂肪酸金属塩、軟化剤、分散剤、充填剤、着色剤、滑剤、顔料などの他の添加剤を、本発明の目的を損なわない範囲で含有してもよい。 The propylene-based resin composition of the present invention contains the propylene-based polymer (A) and the elastomer (B), and if necessary, an inorganic filler, a heat-resistant stabilizer, an antistatic agent, a weather-resistant stabilizer, and a light-resistant agent. Contains other additives such as stabilizers, anti-aging agents, antioxidants, fatty acid metal salts, softeners, dispersants, fillers, colorants, lubricants, pigments, etc., as long as the object of the present invention is not impaired. Also good.
前記無機充填剤としては、具体的には、タルク、クレー、炭酸カルシウム、マイカ、けい酸塩類、炭酸塩類、ガラス織維などが挙げられる。これらの中では、タルク、炭酸カルシウムが好ましく、特にタルクが好ましい。タルクの平均粒径は、１〜５μｍ、好ましくは１〜３μｍの範囲内にあることが望ましい。また、無機充填剤は１種単独で用いても、２種以上を用いてもよい。本発明のプロピレン系樹脂組成物に無機充填剤が含まれる場合には、前記プロピレン系重合体（Ａ）およびエラストマー（Ｂ）の合計を１００質量部とすると、無機充填剤は、通常は１質量部以上、３０質量部以下、好ましくは１質量部以上、２５質量部以下含まれる。 Specific examples of the inorganic filler include talc, clay, calcium carbonate, mica, silicates, carbonates, and glass fiber. Among these, talc and calcium carbonate are preferable, and talc is particularly preferable. The average particle size of talc is 1 to 5 μm, preferably 1 to 3 μm. Moreover, an inorganic filler may be used individually by 1 type, or may use 2 or more types. When the inorganic filler is contained in the propylene resin composition of the present invention, the inorganic filler is usually 1 mass when the total of the propylene polymer (A) and the elastomer (B) is 100 parts by mass. Part by mass or more and 30 parts by mass or less, preferably 1 part by mass or more and 25 parts by mass or less.
前記酸化防止剤としては、従来公知のフェノール系、イオウ系またはリン系のいずれの酸化防止剤でも配合することができる。また、酸化防止剤は、１種単独で、あるいは２種以上組み合わせて用いることができる。本発明のプロピレン系樹脂組成物に酸化防止剤が含まれる場合には、前記プロピレン系重合体（Ａ）およびエラストマー（Ｂ）の合計を１００質量部とすると、酸化防止剤は、通常は０．０１質量部以上、２質量部以下、好ましくは０．０５質量部以上、２質量部以下含まれる。 As the antioxidant, any conventionally known phenol-based, sulfur-based or phosphorus-based antioxidant can be blended. Moreover, antioxidant can be used individually by 1 type or in combination of 2 or more types. When the propylene-based resin composition of the present invention contains an antioxidant, the amount of the antioxidant is usually 0.00 when the total of the propylene-based polymer (A) and the elastomer (B) is 100 parts by mass. 01 parts by mass or more and 2 parts by mass or less, preferably 0.05 parts by mass or more and 2 parts by mass or less.
前記耐光安定剤としては、例えばヒンダードアミン系光安定剤（ＨＡＬＳ）や紫外線吸収剤を挙げることができる。
ヒンダードアミン系光安定剤としては、具体的には、
テトラキス（１，２，２，６，６−ペンタメチル−４−ピペリジン）−１，２，３，４−ブタンテトラカルボキシレート（分子量＝８４７）、
アデカスタブＬＡ−５２〔分子量＝８４７、テトラキス（１，２，２，６，６−ペンタメチル−４−ピペリジン）−１，２，３，４−ブタンテトラカルボキシレート〕、
アデカスタブＬＡ−６２（分子量＝約９００）、
アデカスタブＬＡ−６７（分子量＝約９００）、
アデカスタブＬＡ−６３（分子量＝約２０００）、
アデカスタブＬＡ−６８ＬＤ（分子量＝約１９００）（いずれも旭電化工業（株）製、商標）、
キマソーブ（ＣＨＩＭＡＳＳＯＲＢ）９４４（分子量＝７２５００、チバ・スペシャルティ・ケミカルズ（株）社製、商標）などを挙げることができる。
Examples of the light-resistant stabilizer include hindered amine light stabilizers (HALS) and ultraviolet absorbers.
Specifically, as a hindered amine light stabilizer,
Tetrakis (1,2,2,6,6-pentamethyl-4-piperidine) -1,2,3,4-butanetetracarboxylate (molecular weight = 847),
ADK STAB LA-52 [molecular weight = 847, tetrakis (1,2,2,6,6-pentamethyl-4-piperidine) -1,2,3,4-butanetetracarboxylate],
ADK STAB LA-62 (molecular weight = about 900),
ADK STAB LA-67 (molecular weight = about 900),
ADK STAB LA-63 (molecular weight = about 2000),
ADK STAB LA-68LD (molecular weight = about 1900) (both manufactured by Asahi Denka Kogyo Co., Ltd., trademark),
CHIMASSORB 944 (molecular weight = 72500, manufactured by Ciba Specialty Chemicals Co., Ltd.).
また、紫外線吸収剤としては、具体的には、チヌビン３２６（分子量＝３１６）、チヌビン３２７（分子量＝３５７）、チヌビン１２０（分子量＝４３８）（いずれもチバ・スペシャルティ・ケミカルズ（株）社製、商標）などを挙げることができる。 Further, as the ultraviolet absorber, specifically, Tinuvin 326 (Molecular weight = 316), Tinuvin 327 (Molecular weight = 357), Tinuvin 120 (Molecular weight = 438) (all manufactured by Ciba Specialty Chemicals Co., Ltd.) Trademark).
これらの耐光安定剤は、１種単独で、あるいは２種以上組み合わせて用いることができる。本発明のプロピレン系樹脂組成物に耐光安定剤が含まれる場合には、前記プロピレン系重合体（Ａ）およびエラストマー（Ｂ）の合計を１００質量部とすると、耐光安定剤は、通常は０．０１質量部以上、２質量部以下、好ましくは０．０５質量部以上、２質量部以下含まれる。 These light stabilizers can be used singly or in combination of two or more. When the light-resistant stabilizer is contained in the propylene-based resin composition of the present invention, the light-resistant stabilizer is usually 0.00 when the total of the propylene-based polymer (A) and the elastomer (B) is 100 parts by mass. 01 parts by mass or more and 2 parts by mass or less, preferably 0.05 parts by mass or more and 2 parts by mass or less.
前記脂肪酸金属塩は、プロピレン系樹脂組成物中に含まれている触媒の中和剤、およびその樹脂組成物中に任意に配合される無機充填剤、顔料などの分散剤として機能する。本発明のプロピレン系樹脂組成物が前記脂肪酸金属塩を含有すると、優れた物性、例えば自動車内装部品として要求される強度などを備えた成形品が得られる。 The fatty acid metal salt functions as a neutralizing agent for the catalyst contained in the propylene-based resin composition, and as a dispersant for inorganic fillers, pigments and the like that are optionally blended in the resin composition. When the propylene-based resin composition of the present invention contains the fatty acid metal salt, a molded product having excellent physical properties such as strength required for automobile interior parts can be obtained.
前記脂肪酸金属塩としては、具体的には、ステアリン酸カルシウム、ステアリン酸マグネシウム、ステアリン酸リチウム、ステアリン酸亜鉛などが挙げられる。
本発明のプロピレン系樹脂組成物に脂肪酸金属塩が含まれる場合には、前記プロピレン系重合体（Ａ）およびエラストマー（Ｂ）の合計を１００質量部とすると、脂肪酸金属塩は、通常は０．０１質量部以上、２質量部以下、好ましくは０．０５質量部以上、２質量部以下含まれる。本発明のプロピレン系樹脂組成物が、脂肪酸金属塩を前記範囲で含有すると、中和剤および分散剤としての機能を充分に発揮させることができ、しかも、成形品からの昇華量も少なくすることができる。
Specific examples of the fatty acid metal salt include calcium stearate, magnesium stearate, lithium stearate, and zinc stearate.
When the fatty acid metal salt is contained in the propylene-based resin composition of the present invention, the fatty acid metal salt is usually 0.00 when the total of the propylene-based polymer (A) and the elastomer (B) is 100 parts by mass. 01 parts by mass or more and 2 parts by mass or less, preferably 0.05 parts by mass or more and 2 parts by mass or less. When the propylene-based resin composition of the present invention contains a fatty acid metal salt in the above range, the functions as a neutralizing agent and a dispersing agent can be sufficiently exerted, and the amount of sublimation from the molded product can be reduced. Can do.
前記顔料としては公知のものが使用でき、例えば金属の酸化物、硫化物、硫酸塩等の無機顔料；フタロシアニン系、キナクリドン系、ベンジジン系等の有機顔料などが挙げられる。本発明のプロピレン系樹脂組成物に顔料が含まれる場合には、前記プロピレン系重合体（Ａ）およびエラストマー（Ｂ）の合計を１００質量部とすると、顔料は、通常は０．０１質量部以上、２質量部以下、好ましくは０．０５質量部以上、２質量部以下含まれる。 Known pigments can be used, and examples thereof include inorganic pigments such as metal oxides, sulfides and sulfates; organic pigments such as phthalocyanine, quinacridone and benzidine. When a pigment is contained in the propylene-based resin composition of the present invention, when the total of the propylene-based polymer (A) and the elastomer (B) is 100 parts by mass, the pigment is usually 0.01 parts by mass or more. 2 parts by mass or less, preferably 0.05 parts by mass or more and 2 parts by mass or less.
本発明のプロピレン系樹脂組成物は、前記プロピレン系重合体（Ａ）、エラストマー（Ｂ）および必要に応じて用いられる添加剤を、バンバリーミキサー、単軸押出機、２軸押出機、高速２軸押出機などの混合装置により混合または溶融混練することにより得ることができる。
本発明のプロピレン系樹脂組成物は、伸び、耐衝撃性および低温耐衝撃性等の機械物性に優れ、かつ流動性に優れるため、各種用途に用いることができる。
In the propylene resin composition of the present invention, the propylene polymer (A), the elastomer (B) and additives used as necessary are prepared by using a Banbury mixer, a single screw extruder, a twin screw extruder, a high speed twin screw. It can be obtained by mixing or melt-kneading with a mixing device such as an extruder.
The propylene-based resin composition of the present invention is excellent in mechanical properties such as elongation, impact resistance, and low-temperature impact resistance, and is excellent in fluidity, and thus can be used for various applications.
〔用途〕
本発明のプロピレン系樹脂組成物は、従来からプロピレン系樹脂組成物が用いられてきた各種用途、例えば日用雑貨、台所用品、包装用フィルム、家電製品、機械部品、電気部品、自動車部品等の様々な用途で用いることができる。
[Use]
The propylene-based resin composition of the present invention is used in various applications in which the propylene-based resin composition has been used conventionally, such as daily goods, kitchenware, packaging films, home appliances, machine parts, electrical parts, automobile parts, etc. It can be used in various applications.
本発明のプロピレン系樹脂組成物は、伸び、耐衝撃性および低温耐衝撃性等の機械物性に優れるため、これらの機械物性が求められる用途に好適に用いることができる。
本発明のプロピレン系樹脂組成物は、自動車部品の原料として好適に用いることが可能である。自動車部品としては例えば、ドアトリム、インストルメントパネル等の自動車内装部品；サイドプロテクトモール、バンパー、ソフトフェイシア、マッドガード等の自動車外装部品が挙げられる。本発明のプロピレン系樹脂組成物の用途としては、自動車外装部品が流動性、伸び、耐衝撃性および低温耐衝撃性等の機械物性に優れるため好ましい。
Since the propylene-based resin composition of the present invention is excellent in mechanical properties such as elongation, impact resistance and low temperature impact resistance, it can be suitably used for applications requiring these mechanical properties.
The propylene-based resin composition of the present invention can be suitably used as a raw material for automobile parts. Examples of automobile parts include automobile interior parts such as door trims and instrument panels; automobile exterior parts such as side protect moldings, bumpers, soft fascias, mudguards, and the like. The use of the propylene-based resin composition of the present invention is preferable because automobile exterior parts are excellent in mechanical properties such as fluidity, elongation, impact resistance, and low-temperature impact resistance.
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。
各製造例、実施例、比較例における各物性は以下の方法で測定した。
EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.
Each physical property in each production example, example, and comparative example was measured by the following method.
（１）メルトフローレート（ＭＦＲ：〔ｇ／１０分〕）
プロピレン系重合体（Ａ）のＭＦＲおよびプロピレン系樹脂組成物のＭＦＲはそれぞれ、ＡＳＴＭ Ｄ１２３８Ｅに準拠し、２．１６ｋｇ荷重で測定した。測定温度は２３０℃とした。
(1) Melt flow rate (MFR: [g / 10 min])
The MFR of the propylene-based polymer (A) and the MFR of the propylene-based resin composition were each measured with a 2.16 kg load in accordance with ASTM D1238E. The measurement temperature was 230 ° C.
（２）融点（Ｔｍ：〔℃〕）
プロピレン系重合体（Ａ）のＴｍは、示差走査熱量計（ＤＳＣ、パーキンエルマー社製）を用いて測定を行った。ここで、第３ｓｔｅｐにおける吸熱ピークを融点（Ｔｍ）と定義した。
(2) Melting point (Tm: [° C])
Tm of the propylene polymer (A) was measured using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer). Here, the endothermic peak at the third step was defined as the melting point (Tm).
（測定条件）
第１ｓｔｅｐ ： １０℃／ｍｉｎで２４０℃まで昇温し、１０ｍｉｎ間保持する。
第２ｓｔｅｐ ： １０℃／ｍｉｎで６０℃まで降温する。
第３ｓｔｅｐ ： １０℃／ｍｉｎで２４０℃まで昇温する。
(Measurement condition)
First step: The temperature is raised to 240 ° C. at 10 ° C./min and held for 10 minutes.
Second step: The temperature is lowered to 60 ° C. at 10 ° C./min.
Third step: The temperature is raised to 240 ° C. at 10 ° C./min.
（３）２，１−結合に基づく位置不規則単位の量、１，３−結合に基づく位置不規則単位の量、１，２−結合に基づく構成単位の量
サンプル２０〜３０ｍｇを１，２，４−トリクロロベンゼン/重ベンゼン（２：１）溶液０．６ｍｌに溶解後、炭素核磁気共鳴分析（13Ｃ‐ＮＭＲ）を行った。ここで、２，１−挿入および１，３−挿入に基づく位置不規則単位を含む下記の部分構造は、下記（ｉ）および（ｉｉ）で表される。
(3) Amount of positional irregular units based on 2,1-linkage, Amount of positional irregular units based on 1,3-linkage, Amount of structural units based on 1,2-linkage , 4-trichlorobenzene / heavy benzene (2: 1) solution was dissolved in 0.6 ml, followed by carbon nuclear magnetic resonance analysis ( 13 C-NMR). Here, the following partial structures including position irregular units based on 2,1-insertion and 1,3-insertion are represented by the following (i) and (ii).
同様に、全プロピレン挿入に対する前記の部分構造（ｉｉ）で表される１，３−プロピレンモノマー挿入の頻度は、下記の式で計算した。 Similarly, the frequency of 1,3-propylene monomer insertion represented by the partial structure (ii) with respect to total propylene insertion was calculated by the following formula.
（４）プロピレン系重合体（Ａ）の分子量１００００以下の成分量、重量平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）を用い以下の条件で測定した。
ウォーターズ社製ＧＰＣ−１５０Ｃ Ｐｌｕｓを用い以下の様にして測定した。分離カラムは、ＴＳＫｇｅｌ ＧＭＨ６−ＨＴおよびＳＫｇｅｌ ＧＭＨ６−ＨＴＬであり、カラムサイズはそれぞれ内径７．５ｍｍ、長さ６００ｍｍであり、カラム温度は１４０℃とし、移動相にはｏ‐ジクロロベンゼン（和光純薬工業）および酸化防止剤としてＢＨＴ（和光純薬工業）０．０２５重量％を用い、１．０ｍｌ／分で移動させ、試料濃度は０．１重量％とし、試料注入量は５００マイクロリットルとし、検出器として示差屈折計を用いた。標準ポリスチレンは、分子量がＭｗ＜１０００およびＭｗ＞４×１０6については東ソー社製を用い、１０００≦Ｍｗ≦４×１０6についてはプレッシャーケミカル社製を用い、汎用較正法を用いてポリプロピレン（ＰＰ）に換算した。なお、ＰＰのＭａｒｋ−Ｈｏｕｗｉｎｋ係数はそれぞれ、文献（Ｊ． Ｐｏｌｙｍ． Ｓｃｉ．， Ｐａｒｔ Ａ−２， ８， １８０３ （１９７０）、Ｍａｋｒｏｍｏｌ． Ｃｈｅｍ．， １７７， ２１３ （１９７６））に記載の値を用いた。なお、分子量１万以下の成分量は、当該ＧＰＣ測定により算出した。
(4) The component amount and weight average molecular weight of the propylene polymer (A) having a molecular weight of 10,000 or less were measured under the following conditions using GPC (gel permeation chromatography).
It measured as follows using GPC-150C Plus by Waters. The separation columns are TSKgel GMH6-HT and SKgel GMH6-HTL, the column size is 7.5 mm in inner diameter and the length is 600 mm, the column temperature is 140 ° C., and the mobile phase is o-dichlorobenzene (Wako Pure Chemicals). Industrial) and 0.025 wt% BHT (Wako Pure Chemical Industries) as an antioxidant, moved at 1.0 ml / min, the sample concentration was 0.1 wt%, the sample injection volume was 500 microliters, A differential refractometer was used as a detector. Standard polystyrenes are manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 6 , and pressure chemicals are used for 1000 ≦ Mw ≦ 4 × 10 6 , and polypropylene (PP ). In addition, the Mark-Houwink coefficient of PP uses the value described in the literature (J. Polym. Sci., Part A-2, 8, 1803 (1970), Makromol. Chem., 177, 213 (1976)). It was. In addition, the amount of components having a molecular weight of 10,000 or less was calculated by the GPC measurement.
（５）ＣＦＣにより測定したピーク半値幅およびピークトップ温度
プロピレン系重合体（Ａ）のＣＦＣにより測定したピーク半値幅およびピークトップ温度は、以下の方法で行ったクロス分別クロマトグラフにより測定した溶出量を求め、ピーク半値幅は最大溶出量の半分の溶出量における溶出温度幅、ピークトップ温度は溶出量が最大となる温度と定義し求めた。
(5) Peak half-value width and peak top temperature measured by CFC The peak half-value width and peak top temperature measured by CFC of the propylene polymer (A) are the elution amounts measured by the cross fractionation chromatograph performed by the following method. The peak half-width was defined as the elution temperature width at half the maximum elution volume, and the peak top temperature was defined as the temperature at which the elution volume was maximum.
溶出量および溶出積分量を、三菱油化社製ＣＦＣ Ｔ−１５０Ａ型を用い以下のようにして測定した。
分離カラム：ＳｈｏｄｅｘＡＴ−８０６ＭＳ（３本）、
溶離液：ｏ−ジクロロベンゼン、
試料濃度：０．１５〜０．３ｗｔ／ｖｏｌ％、
注入量：０．５ｍｌ、
流速：１．０ｍｌ／ｍｉｎとした。
The elution amount and the elution integration amount were measured as follows using a CFC T-150A model manufactured by Mitsubishi Oil Chemical Co., Ltd.
Separation column: ShodexAT-806MS (3),
Eluent: o-dichlorobenzene,
Sample concentration: 0.15-0.3 wt / vol%
Injection volume: 0.5 ml,
Flow rate: 1.0 ml / min.
試料を１３５℃で２時間加熱後、０℃まで１℃／ｍｉｎで降温した。さらに０℃で６０分間保持して試料をコーティングした。昇温溶出カラム容量は０．８６ｍｌ、配管容量は０．０６ｍｌであった。 The sample was heated at 135 ° C. for 2 hours and then cooled to 0 ° C. at 1 ° C./min. The sample was further coated at 0 ° C. for 60 minutes. The temperature rising elution column volume was 0.86 ml, and the pipe volume was 0.06 ml.
検出器はＦＯＸＢＯＲＯ社製赤外分光器ＭＩＲＡＮ １Ａ ＣＶＦ型（ＣａＦ2セル）を用い、応答時間１０秒の吸光度モードの設定で、３．４２μｍ（２９２４ｃｍ-1）の赤外光を検知した。溶出温度は０〜１３５℃までを２５〜３５フラクションに分け、特に溶出ピーク付近では２℃きざみのフラクションに分けた。温度表示は全て整数であり、例えば１２０℃の溶出画分とは、１１８〜１２０℃で溶出した成分のことを示す。ＣＦＣによる９０℃での溶出積分量は０〜９０℃までの溶出画分の合計とした。ＣＦＣによる１００℃での溶出積分量は０〜１００℃までの溶出画分の合計とした。０℃でもコーティングされなかった成分および各温度で溶出したフラクションの分子量を測定し、汎用較正曲線を使用して、ＰＰ換算分子量を求めた。ＳＥＣ温度：１３５℃、内標注入量：０．５ｍｌ、注入位置：３．０ｍｌ、データサンプリング時間：０．５０秒とした。 The detector was an infrared spectrometer MIRAN 1A CVF type (CaF 2 cell) manufactured by FOXBORO, and infrared light of 3.42 μm (2924 cm −1 ) was detected by setting the absorbance mode with a response time of 10 seconds. The elution temperature was divided into 25 to 35 fractions from 0 to 135 ° C., and in particular, fractions in increments of 2 ° C. in the vicinity of the elution peak. All temperature indications are integers. For example, an elution fraction at 120 ° C. indicates a component eluted at 118 to 120 ° C. The integrated amount of elution at 90 ° C. by CFC was the sum of the elution fractions from 0 to 90 ° C. The integrated amount of elution at 100 ° C. by CFC was the sum of the elution fractions from 0 to 100 ° C. The molecular weight of the components that were not coated even at 0 ° C. and the fraction eluted at each temperature were measured, and the molecular weight in terms of PP was determined using a general calibration curve. SEC temperature: 135 ° C., internal standard injection amount: 0.5 ml, injection position: 3.0 ml, data sampling time: 0.50 seconds.
なお、狭い温度範囲で溶出する成分が多すぎて、圧力異常が生じる場合には、試料濃度を０．１５ｗｔ／ｖｏｌ％未満とする場合もある。データ処理は、装置付属の解析プログラム「ＣＦＣデータ処理（バージョン１．５０）」で実施した。なお、クロス分別クロマトグラフ（ＣＦＣ）それ自身は、測定条件を厳密に同一にすれば高い分析精度でもって結果を再現する分析法であると言われているが、本発明の実施例においては測定を１回での値を記載した。 In addition, when there are too many components eluting in a narrow temperature range and a pressure abnormality occurs, the sample concentration may be less than 0.15 wt / vol%. Data processing was performed with the analysis program “CFC data processing (version 1.50)” attached to the apparatus. The cross-fractionation chromatograph (CFC) itself is said to be an analytical method that reproduces the result with high analytical accuracy if the measurement conditions are strictly the same, but in the examples of the present invention, the measurement is performed. The value at one time was described.
（６）エチレンに由来する構成単位の含量
エチレン‐プロピレン共重合体（Ｂ−１−１）およびエチレン‐ブテン共重合体ゴム（Ｂ−２−１）のエチレンに由来する構成単位の含量は、各重合体をサンプルとし、以下の方法で測定した。
(6) Content of structural units derived from ethylene The content of structural units derived from ethylene of the ethylene-propylene copolymer (B-1-1) and the ethylene-butene copolymer rubber (B-2-1) is: Each polymer was used as a sample and measured by the following method.
サンプル２０〜３０ｍｇを１，２，４−トリクロロベンゼン／重ベンゼン（２：１）溶液０．６ｍｌに溶解後、炭素核磁気共鳴分析（13Ｃ−ＮＭＲ）を行った。プロピレン、エチレン、ブテンの定量はダイアッド連鎖分布より求めた。 After dissolving 20-30 mg of sample in 0.6 ml of 1,2,4-trichlorobenzene / heavy benzene (2: 1) solution, carbon nuclear magnetic resonance analysis ( 13 C-NMR) was performed. Propylene, ethylene, and butene were quantitatively determined from the dyad chain distribution.
例えば、エチレン‐プロピレン共重合体（Ｂ−１−１）の場合、ＰＰ＝Ｓαα、ＥＰ＝Ｓαγ＋Ｓαβ、ＥＥ＝１／２（Ｓβδ＋Ｓδδ）＋１／４Ｓγδを用い、以下の計算式（Ｅｑ−１）および（Ｅｑ−２）により求めた。
プロピレン（ｍｏｌ％） ＝ （ＰＰ＋１／２ＥＰ）×１００／［（ＰＰ＋１／２ＥＰ）＋（１／２ＥＰ＋ＥＥ） …（Ｅｑ−１）
エチレン（ｍｏｌ％） ＝ （１／２ＥＰ＋ＥＥ）×１００／［（ＰＰ＋１／２ＥＰ）＋（１／２ＥＰ＋ＥＥ） …（Ｅｑ−２）
なお、エチレンに由来する構成単位の含量（エチレン含量）は、ｍｏｌ％で表記した。
For example, in the case of the ethylene-propylene copolymer (B-1-1), PP = Sαα, EP = Sαγ + Sαβ, EE = 1/2 (Sβδ + Sδδ) + 1 / 4Sγδ is used, and the following calculation formula (Eq-1) and It calculated | required by (Eq-2).
Propylene (mol%) = (PP + 1 / 2EP) × 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE) (Eq-1)
Ethylene (mol%) = (1 / 2EP + EE) × 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE) (Eq-2)
In addition, the content (ethylene content) of the structural unit derived from ethylene was described by mol%.
（７）極限粘度（［η］：〔ｄｌ／ｇ〕）
エチレン‐プロピレン共重合体（Ｂ−１−１）およびエチレン‐ブテン共重合体ゴム（Ｂ−２−１）の極限粘度は、各重合体をサンプルとし、以下の方法で求めた。
(7) Intrinsic viscosity ([η]: [dl / g])
The intrinsic viscosity of the ethylene-propylene copolymer (B-1-1) and the ethylene-butene copolymer rubber (B-2-1) was determined by the following method using each polymer as a sample.
極限粘度はデカリン溶媒を用いて、１３５℃で測定した。サンプル約２０ｍｇをデカリン１５ｍｌに溶解し、１３５℃のオイルバス中で比粘度ηｓｐを測定した。このデカリン溶液にデカリン溶媒を５ｍｌ追加して希釈後、同様にして比粘度ηｓｐを測定した。この希釈操作をさらに２回繰り返し、濃度（Ｃ）を０に外挿した時のηｓｐ／Ｃの値を極限粘度として求めた。
［η］＝ｌｉｍ（ηｓｐ／Ｃ） （Ｃ→０）
The intrinsic viscosity was measured at 135 ° C. using a decalin solvent. About 20 mg of the sample was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After diluting the decalin solution with 5 ml of decalin solvent, the specific viscosity ηsp was measured in the same manner. This dilution operation was further repeated twice, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity.
[Η] = lim (ηsp / C) (C → 0)
（８）引張破断伸び
プロピレン系樹脂組成物の引張破断伸びは、該組成物から作成した試験片を用いて、ＪＩＳ Ｋ７１６２に従い引張試験を行うことにより、下記の条件で測定した。
(8) Tensile elongation at break The tensile elongation at break of the propylene-based resin composition was measured under the following conditions by performing a tensile test according to JIS K7162 using a test piece prepared from the composition.
＜測定条件＞
試験片 ： ＪＩＳ Ｋ７１６２−ＢＡ ダンベル ； ５ｍｍ（幅）×２ｍｍ（厚さ）×７５ｍｍ（長さ）
引張速度 ： ２０ｍｍ／分
スパン間距離 ： ５８ｍｍ
<Measurement conditions>
Test piece: JIS K7162-BA dumbbell; 5 mm (width) x 2 mm (thickness) x 75 mm (length)
Tensile speed: 20 mm / min Distance between spans: 58 mm
（１０）曲げ強さ（ＦS：〔ＭＰａ〕）、曲げ弾性率（ＦＭ：〔ＭＰａ〕）
プロピレン系樹脂組成物の曲げ強さ、及び曲げ弾性率は、該組成物から作成した試験片を用いて、ＪＩＳ Ｋ７１７１に従って、下記の条件で測定した。
＜測定条件＞
試験片：１０ｍｍ（幅）×４ｍｍ（厚さ）×８０ｍｍ（長さ）
曲げ速度：２ｍｍ／分
曲げスパン：６４ｍｍ
(10) Bending strength (FS: [MPa]), flexural modulus (FM: [MPa])
The bending strength and the flexural modulus of the propylene-based resin composition were measured under the following conditions according to JIS K7171 using a test piece prepared from the composition.
<Measurement conditions>
Test piece: 10 mm (width) x 4 mm (thickness) x 80 mm (length)
Bending speed: 2 mm / min Bending span: 64 mm
（１１）シャルピー衝撃強度（〔ｋＪ／ｍ2〕）
プロピレン系樹脂組成物のシャルピー衝撃強度は、該組成物から作成した試験片を用いて、ＪＩＳ Ｋ７１１１に従いシャルピー衝撃試験を行うことにより、下記の条件で測定した。
＜試験条件＞
温度：２３℃、−３０℃
試験片：１０ｍｍ（幅）×４ｍｍ（厚さ）×８０ｍｍ（長さ）
ノッチは機械加工
(11) Charpy impact strength ([kJ / m 2 ])
The Charpy impact strength of the propylene-based resin composition was measured under the following conditions by performing a Charpy impact test according to JIS K7111, using a test piece prepared from the composition.
<Test conditions>
Temperature: 23 ° C, -30 ° C
Test piece: 10 mm (width) x 4 mm (thickness) x 80 mm (length)
Notch machined
（１２）加熱変形温度（ＨＤＴ：〔℃〕）
プロピレン系樹脂組成物の加熱変形温度は、ＪＩＳ Ｋ７１９１に従って、下記の条件で測定した。
＜測定条件＞
試験片：１０ｍｍ（幅）×４ｍｍ（厚さ）×８０ｍｍ（長さ）
荷重：０．４５ＭＰａ
＜溶融混練条件＞
単軸混練機：品番 ラボプラストミル１０Ｍ１００、東洋精機（株）製
混練温度：１９０℃
スクリュー回転数：６０ｒｐｍ
ホッパー内に窒素フロー有り
＜プレス成形条件＞
プレス成形温度：２００℃（加熱温度２００℃、予熱時間：２分）
プレス成形時間：１分
プレス成形後、２３℃程度の金型で１分間冷却
(12) Heat distortion temperature (HDT: [° C])
The heat deformation temperature of the propylene-based resin composition was measured under the following conditions in accordance with JIS K7191.
<Measurement conditions>
Test piece: 10 mm (width) x 4 mm (thickness) x 80 mm (length)
Load: 0.45 MPa
<Melting and kneading conditions>
Single-shaft kneader: Product No. Labo Plast Mill 10M100, manufactured by Toyo Seiki Co., Ltd. Kneading temperature: 190 ° C
Screw rotation speed: 60rpm
Nitrogen flow in hopper <Press molding conditions>
Press molding temperature: 200 ° C (heating temperature 200 ° C, preheating time: 2 minutes)
Press molding time: 1 minute After press molding, cool for 1 minute with a mold of about 23 ° C.
［製造例１］
（１）固体触媒担体の製造
内容量３０Ｌの攪拌機付き反応槽にトルエン１７ＬとＳｉＯ2（ＡＧＣエスアイテック製サンスフェアＨ１２２）６５０ｇを入れ、スラリー化した。次に、槽内温度４５℃に保ち、トリイソブチルアルミニウムトルエン溶液をトリイソブチルアルミニウム量として、６４ｇ装入し、１５分間攪拌した。槽内温度５０℃に保ち、ＭＡＯ（メチルアルミノキサン）−トルエン溶液（２０ｗｔ％溶液）２．２Ｌを約３０分かけて導入し、３０分間攪拌した。１時間で９５℃に昇温し、４時間反応を行った。反応終了後、６０℃まで冷却した。冷却後、上澄みトルエンを抜き出し、フレッシュなトルエンで、置換率が９５％になるまで、置換を行った。
[Production Example 1]
(1) Production of solid catalyst carrier 17 L of toluene and 650 g of SiO 2 (Sunsphere H122 manufactured by AGC S-Itech) were put into a slurry with a 30 L internal volume stirred tank. Next, while maintaining the temperature in the tank at 45 ° C., 64 g of triisobutylaluminum toluene solution was added as the amount of triisobutylaluminum and stirred for 15 minutes. While maintaining the temperature in the tank at 50 ° C., 2.2 L of MAO (methylaluminoxane) -toluene solution (20 wt% solution) was introduced over about 30 minutes and stirred for 30 minutes. The temperature was raised to 95 ° C. over 1 hour, and the reaction was performed for 4 hours. After completion of the reaction, it was cooled to 60 ° C. After cooling, the supernatant toluene was extracted and replaced with fresh toluene until the replacement rate reached 95%.
（２）固体触媒の製造（担体への金属触媒成分の担持）
内容量１４Ｌの攪拌機付き反応槽に（１）で調製したＭＡＯ／ＳｉＯ2／トルエンスラリー７．９Ｌ（固体成分として１０３０ｇ）を入れ、攪拌しながら温度を３０〜３５℃に保った。グローブボックス内にて、１Ｌフラスコに［３−（１’，１’，４’，４’，７’，７’，１０’，１０’−オクタメチルオクタヒドロジベンゾ［ｂ，ｈ］フルオレニル）（１，１，３−トリメチル−５−ｔｅｒｔ−ブチル−１，２，３，３ａ−テトラヒドロペンタレン）］ジルコニウムジクロライドを１５．５ｇ秤取った。フラスコを外へ出し、トルエン０．５リットルで希釈後、反応槽に加え、反応槽内液量を１０Ｌになるまでトルエンを加えた。６０分間攪拌し担持を行った。
(2) Production of solid catalyst (support of metal catalyst component on carrier)
7.9 L of MAO / SiO 2 / toluene slurry prepared in (1) (1030 g as a solid component) was placed in a reaction vessel equipped with a stirrer having an internal volume of 14 L, and the temperature was maintained at 30 to 35 ° C. while stirring. In the glove box, place the [3- (1 ′, 1 ′, 4 ′, 4 ′, 7 ′, 7 ′, 10 ′, 10′-octamethyloctahydrodibenzo [b, h] fluorenyl) ( 1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride was weighed in 15.5 g. The flask was taken out, diluted with 0.5 liter of toluene, added to the reaction tank, and toluene was added until the liquid volume in the reaction tank reached 10 L. The mixture was stirred for 60 minutes.
得られた［３−（１’，１’，４’，４’，７’，７’，１０’，１０’−オクタメチルオクタヒドロジベンゾ［ｂ，ｈ］フルオレニル）（１，１，３−トリメチル−５−ｔｅｒｔ−ブチル−１，２，３，３ａ−テトラヒドロペンタレン）］ジルコニウムジクロライド／ＭＡＯ／ＳｉＯ2／トルエンスラリーは、室温まで冷却した後、ｎ−ヘプタンにて９２％置換を行い、最終的なスラリー量を１０Ｌとした。 The obtained [3- (1 ′, 1 ′, 4 ′, 4 ′, 7 ′, 7 ′, 10 ′, 10′-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3- Trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride / MAO / SiO 2 / toluene slurry was cooled to room temperature and then 92% substituted with n-heptane, The final slurry volume was 10L.
（３）前重合触媒の製造
前記の（２）で調製した固体触媒成分１０４５ｇをあらかじめｎ−ヘプタン１８Ｌを入れておいた内容量２００Ｌの攪拌機付きオートクレーブに移液し、内温１５〜２０℃に保ち、トリイソブチルアルミニウム５５７ｇを入れ、ｎ−ヘプタンにて液量を６２Ｌに調整した。攪拌しながら、３０〜３５℃に保ち、エチレンを６３０ｇ／ｈで３１３５ｇ挿入し、３００分間攪拌しながら反応させた。
(3) Production of prepolymerization catalyst 1045 g of the solid catalyst component prepared in the above (2) was transferred to an autoclave with a stirrer having an internal capacity of 200 L in which 18 L of n-heptane had been put in advance, and the internal temperature was adjusted to 15 to 20 ° C. Then, 557 g of triisobutylaluminum was added, and the liquid volume was adjusted to 62 L with n-heptane. While stirring, the temperature was maintained at 30 to 35 ° C., 3135 g of ethylene was inserted at 630 g / h, and the reaction was allowed to proceed for 300 minutes with stirring.
重合終了後、固体成分を沈降させ、上澄み液の除去およびヘプタンによる洗浄を２回行った。得られた前重合触媒を精製ヘプタンに再懸濁して、固体触媒成分濃度で８ｇ／Ｌとなるよう、ヘプタンにより調整を行った。この前重合触媒は固体触媒成分１ｇ当りポリエチレンを３ｇ含んでいた。 After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 8 g / L. This prepolymerized catalyst contained 3 g of polyethylene per 1 g of the solid catalyst component.
（４）本重合
内容量１００Ｌの攪拌機付きベッセル重合器にプロピレンを１１９ｋｇ／時間、水素を気相部の水素濃度が０．４ｍｏｌ％になるように供給した。（３）で製造した触媒スラリーを固体触媒成分として１３．０ｇ／時間、トリエチルアルミニウム８．７ｍｌ／時間を連続的に供給した。重合温度７０℃、圧力は３．０ＭＰａ／Ｇであった。
(4) Main polymerization Propylene was supplied to a vessel polymerization vessel with a stirrer having an internal volume of 100 L so that 119 kg / hour of propylene and hydrogen were 0.4 mol% in the gas phase. The catalyst slurry produced in (3) was continuously supplied as a solid catalyst component at 13.0 g / hour and triethylaluminum 8.7 ml / hour. The polymerization temperature was 70 ° C., and the pressure was 3.0 MPa / G.
得られたスラリーは内容量１０００Ｌの攪拌機付きベッセル重合器へ送り、更に重合を行った。重合器へは、プロピレンを１７ｋｇ／時間、水素を気相部の水素濃度が０．４０ｍｏｌ％になるように供給した。重合温度６９℃、圧力２．９ＭＰａ／Ｇで重合を行った。 The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. Propylene was supplied to the polymerization vessel at 17 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.40 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 2.9 MPa / G.
得られたスラリーは内容量５００Ｌの攪拌機付きベッセル重合器へ送り、更に重合を行った。重合器へは、プロピレンを８ｋｇ／時間、水素を気相部の水素濃度が０．３９ｍｏｌ％になるように供給した。重合温度６６℃、圧力２．９ＭＰａ／Ｇで重合を行った。 The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 8 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.39 mol%. Polymerization was performed at a polymerization temperature of 66 ° C. and a pressure of 2.9 MPa / G.
得られたスラリーは内容量５００Ｌの攪拌機付きベッセル重合器へ送り、更に重合を行った。重合器へは、プロピレンを７ｋｇ／時間、水素を気相部の水素濃度が０．４０ｍｏｌ％になるように供給した。重合温度６５．５℃、圧力２．８ＭＰａ／Ｇで重合を行った。 The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at 7 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.40 mol%. Polymerization was performed at a polymerization temperature of 65.5 ° C. and a pressure of 2.8 MPa / G.
得られたスラリーは内容量５００Ｌの攪拌機付きベッセル重合器へ送り、更に重合を行った。重合器へは、プロピレンを７ｋｇ／時間、水素を気相部の水素濃度が０．４０ｍｏｌ％になるように供給した。重合温度６４℃、圧力２．８ＭＰａ／Ｇで重合を行った。 The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at 7 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.40 mol%. Polymerization was performed at a polymerization temperature of 64 ° C. and a pressure of 2.8 MPa / G.
得られたスラリーを気化後、気固分離を行い、プロピレン系重合体（Ａ−１）を得た。プロピレン系重合体（Ａ−１）は、４２ｋｇ／ｈで得られた。プロピレン系重合体（Ａ−１）は、８０℃で真空乾燥を行った。 After vaporizing the obtained slurry, gas-solid separation was performed to obtain a propylene polymer (A-1). The propylene polymer (A-1) was obtained at 42 kg / h. The propylene polymer (A-1) was vacuum dried at 80 ° C.
［製造例２］
重合方法を以下の様に変えた以外は、製造例１と同様の方法で行った。
（１）本重合
内容量１００Ｌの攪拌機付きベッセル重合器にプロピレンを１１９ｋｇ／時間、水素を気相部の水素濃度が０．５６ｍｏｌ％になるように供給した。製造例１（３）で製造した触媒スラリーを固体触媒成分として１０．０ｇ／時間、トリエチルアルミニウム８．７ｍｌ／時間を連続的に供給した。重合温度７０℃、圧力は３．０ＭＰａ／Ｇであった。
[Production Example 2]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization Propylene was supplied to a vessel polymerization vessel with a stirrer with an internal volume of 100 L so that propylene was 119 kg / hour and hydrogen was 0.56 mol% in the gas phase. The catalyst slurry produced in Production Example 1 (3) was continuously supplied as a solid catalyst component at 10.0 g / hour and triethylaluminum 8.7 ml / hour. The polymerization temperature was 70 ° C., and the pressure was 3.0 MPa / G.
得られたスラリーは内容量１０００Ｌの攪拌機付きベッセル重合器へ送り、更に重合を行った。重合器へは、プロピレンを１７ｋｇ／時間、水素を気相部の水素濃度が０．５６ｍｏｌ％になるように供給した。重合温度６９℃、圧力２．９ＭＰａ／Ｇで重合を行った。 The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization reactor, propylene was supplied at 17 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.56 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 2.9 MPa / G.
得られたスラリーは内容量５００Ｌの攪拌機付きベッセル重合器へ送り、更に重合を行った。重合器へは、プロピレンを８ｋｇ／時間、水素を気相部の水素濃度が０．５６ｍｏｌ％になるように供給した。重合温度６６℃、圧力２．９ＭＰａ／Ｇで重合を行った。 The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at 8 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.56 mol%. Polymerization was performed at a polymerization temperature of 66 ° C. and a pressure of 2.9 MPa / G.
得られたスラリーは内容量５００Ｌの攪拌機付きベッセル重合器へ送り、更に重合を行った。重合器へは、プロピレンを７ｋｇ／時間、水素を気相部の水素濃度が０．５６ｍｏｌ％になるように供給した。重合温度６５℃、圧力２．８ＭＰａ／Ｇで重合を行った。 The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at 7 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.56 mol%. Polymerization was carried out at a polymerization temperature of 65 ° C. and a pressure of 2.8 MPa / G.
得られたスラリーは内容量５００Ｌの攪拌機付きベッセル重合器へ送り、更に重合を行った。重合器へは、プロピレンを７ｋｇ／時間、水素を気相部の水素濃度が０．５６ｍｏｌ％になるように供給した。重合温度６４℃、圧力２．８ＭＰａ／Ｇで重合を行った。 The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at 7 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.56 mol%. Polymerization was performed at a polymerization temperature of 64 ° C. and a pressure of 2.8 MPa / G.
得られたスラリーを気化後、気固分離を行い、プロピレン系重合体（Ａ−２）を得た。プロピレン系重合体（Ａ−２）は、４１ｋｇ／ｈで得られた。プロピレン系重合体（Ａ−２）は、８０℃で真空乾燥を行った。 After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene polymer (A-2). The propylene polymer (A-2) was obtained at 41 kg / h. The propylene polymer (A-2) was vacuum dried at 80 ° C.
［製造例３］
重合方法を以下の様に変えた以外は、製造例１と同様の方法で行った。
（１）本重合
内容量１００Ｌの攪拌機付きベッセル重合器にプロピレンを１１９ｋｇ／時間、水素を気相部の水素濃度が０．６２ｍｏｌ％になるように供給した。製造例１（３）で製造した触媒スラリーを固体触媒成分として９．５ｇ／時間、トリエチルアルミニウム８．７ｍｌ／時間を連続的に供給した。重合温度７０℃、圧力は３．０ＭＰａ／Ｇであった。
[Production Example 3]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization Propylene was supplied to a vessel polymerization vessel with an internal volume of 100 L with a stirrer so that propylene was 119 kg / hour and hydrogen was 0.62 mol% in the gas phase. The catalyst slurry produced in Production Example 1 (3) was continuously supplied as a solid catalyst component at 9.5 g / hour and triethylaluminum 8.7 ml / hour. The polymerization temperature was 70 ° C., and the pressure was 3.0 MPa / G.
得られたスラリーは内容量１０００Ｌの攪拌機付きベッセル重合器へ送り、更に重合を行った。重合器へは、プロピレンを１７ｋｇ／時間、水素を気相部の水素濃度が０．６２ｍｏｌ％になるように供給した。重合温度６９℃、圧力２．９ＭＰａ／Ｇで重合を行った。 The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization reactor, propylene was supplied at 17 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.62 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 2.9 MPa / G.
得られたスラリーは内容量５００Ｌの攪拌機付きベッセル重合器へ送り、更に重合を行った。重合器へは、プロピレンを８ｋｇ／時間、水素を気相部の水素濃度が０．６２ｍｏｌ％になるように供給した。重合温度６６℃、圧力２．９ＭＰａ／Ｇで重合を行った。 The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 8 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.62 mol%. Polymerization was performed at a polymerization temperature of 66 ° C. and a pressure of 2.9 MPa / G.
得られたスラリーは内容量５００Ｌの攪拌機付きベッセル重合器へ送り、更に重合を行った。重合器へは、プロピレンを７ｋｇ／時間、水素を気相部の水素濃度が０．６２ｍｏｌ％になるように供給した。重合温度６５℃、圧力２．８ＭＰａ／Ｇで重合を行った。 The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at 7 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.62 mol%. Polymerization was carried out at a polymerization temperature of 65 ° C. and a pressure of 2.8 MPa / G.
得られたスラリーは内容量５００Ｌの攪拌機付きベッセル重合器へ送り、更に重合を行った。重合器へは、プロピレンを７ｋｇ／時間、水素を気相部の水素濃度が０．６２ｍｏｌ％になるように供給した。重合温度６４℃、圧力２．８ＭＰａ／Ｇで重合を行った。 The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at 7 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.62 mol%. Polymerization was performed at a polymerization temperature of 64 ° C. and a pressure of 2.8 MPa / G.
得られたスラリーを気化後、気固分離を行い、プロピレン系重合体（Ａ−３）を得た。プロピレン系重合体（Ａ−３）は、４３ｋｇ／ｈで得られた。プロピレン系重合体（Ａ−３）は、８０℃で真空乾燥を行った。 After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene polymer (A-3). The propylene polymer (A-3) was obtained at 43 kg / h. The propylene polymer (A-3) was vacuum dried at 80 ° C.
［製造例４］
（１）固体状チタン触媒成分の調製
無水塩化マグネシウム９５２ｇ、デカン４４２０ｍｌおよび２−エチルヘキシルアルコール３９０６ｇを、１３０℃で２時間加熱して均一溶液とした。この溶液中に無水フタル酸２１３ｇを添加し、１３０℃にてさらに１時間攪拌混合を行って無水フタル酸を溶解させた。
[Production Example 4]
(1) Preparation of Solid Titanium Catalyst Component 952 g of anhydrous magnesium chloride, 4420 ml of decane and 3906 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to obtain a uniform solution. To this solution, 213 g of phthalic anhydride was added, and further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.
このようにして得られた均一溶液を２３℃まで冷却した後、この均一溶液の７５０ｍｌを、−２０℃に保持された四塩化チタン２０００ｍｌ中に１時間にわたって滴下した。滴下後、得られた混合液の温度を４時間かけて１１０℃に昇温し、１１０℃に達したところでフタル酸ジイソブチル（ＤＩＢＰ）５２．２ｇを添加し、これより２時間攪拌しながら同温度に保持した。次いで熱時濾過にて固体部を採取し、この固体部を２７５０ｍｌの四塩化チタンに再懸濁させた後、再び１１０℃で２時間加熱した。 After cooling the homogeneous solution thus obtained to 23 ° C., 750 ml of this homogeneous solution was dropped into 2000 ml of titanium tetrachloride maintained at −20 ° C. over 1 hour. After the dropwise addition, the temperature of the resulting mixture was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 52.2 g of diisobutyl phthalate (DIBP) was added, and the mixture was stirred at the same temperature for 2 hours. Held on. Subsequently, the solid part was collected by hot filtration, and the solid part was resuspended in 2750 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours.
加熱終了後、再び熱濾過にて固体部を採取し、１１０℃のデカンおよびヘキサンを用いて、洗浄液中にチタン化合物が検出されなくなるまで洗浄した。
前記の様に調製された固体状チタン触媒成分はヘキサンスラリーとして保存されるが、このうち一部を乾燥して触媒組成を調べた。固体状チタン触媒成分は、チタンを２質量％、塩素を５７質量％、マグネシウムを２１質量％およびＤＩＢＰを２０質量％の量で含有していた。
After the heating, the solid part was again collected by hot filtration, and washed with decane and hexane at 110 ° C. until no titanium compound was detected in the washing solution.
The solid titanium catalyst component prepared as described above was stored as a hexane slurry, and a part of the solid titanium catalyst component was dried to examine the catalyst composition. The solid titanium catalyst component contained 2% by mass of titanium, 57% by mass of chlorine, 21% by mass of magnesium and 20% by mass of DIBP.
（２）前重合触媒の製造
内容量１４Ｌの攪拌機付き反応槽にあらかじめヘプタン２Ｌを装入し、トリエチルアルミニウム６２．０ｍＬ、ジエチルアミノトリエトキシシラン１７．６ｍＬ、前記（１）で調製した遷移金属触媒成分６４ｇを装入し、ヘプタン量が９．１Ｌとなるようにヘプタンを追加した。内温１０℃以下に保ち、１０分攪拌した後、プロピレンを６４０ｇを約５０分かけて装入した後、６０分間攪拌しながら反応させた。重合終了後、固体成分を沈降させ、上澄み液の除去およびヘプタンによる洗浄を３回行った。得られた前重合触媒を内容量２００Ｌ攪拌機付き反応槽に移液した後、遷移金属触媒成分濃度で０．８ｇ／Ｌとなるよう、ヘプタンにより調整を行った。この前重合触媒は遷移金属触媒成分１ｇ当りポリプロピレンを１０ｇ含んでいた。
(2) Preparation of prepolymerization catalyst 2 L of heptane was charged in advance into a reaction tank with a stirrer having an internal volume of 14 L, 62.0 mL of triethylaluminum, 17.6 mL of diethylaminotriethoxysilane, and the transition metal catalyst component prepared in (1) above 64 g was charged, and heptane was added so that the amount of heptane was 9.1 L. After maintaining the internal temperature at 10 ° C. or lower and stirring for 10 minutes, 640 g of propylene was charged over about 50 minutes, and then reacted with stirring for 60 minutes. After completion of the polymerization, the solid component was allowed to settle, and the supernatant was removed and washed with heptane three times. The obtained prepolymerization catalyst was transferred to a reaction tank equipped with an internal volume 200 L stirrer and then adjusted with heptane so that the concentration of the transition metal catalyst component was 0.8 g / L. This prepolymerization catalyst contained 10 g of polypropylene per 1 g of the transition metal catalyst component.
（３）本重合
内容量５８Ｌのジャケット付循環式管状重合器にプロピレンを４０ｋｇ／時間、水素を１８６ＮＬ／時間、（２）で製造した触媒スラリーを固体触媒成分として０．３３ｇ／時間、トリエチルアルミニウム２．２ｍｌ／時間、ジエチルアミノトリエトキシシラン０．８８ｍｌ／時間を連続的に供給し、気相の存在しない満液の状態にて重合した。管状重合器の温度は６９℃であり、圧力は３．４ＭＰａ／Ｇであった。
(3) Main polymerization In a jacketed circulation tubular polymerizer with an internal capacity of 58 L, propylene is 40 kg / hour, hydrogen is 186 NL / hour, the catalyst slurry produced in (2) is 0.33 g / hour, using triethylaluminum as a solid catalyst component 2.2 ml / hour and diethylaminotriethoxysilane 0.88 ml / hour were continuously fed, and polymerization was carried out in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 69 ° C., and the pressure was 3.4 MPa / G.
得られたスラリーは内容量１００Ｌの攪拌機付きベッセル重合器へ送り、更に重合を行った。重合器へは、プロピレンを１５ｋｇ／時間、水素を気相部の水素濃度が６．０ｍｏｌ％になるように供給した。重合温度６９℃、圧力３．２ＭＰａ／Ｇで重合を行った。 The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 6.0 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 3.2 MPa / G.
得られたスラリーを気化後、気固分離を行い、プロピレン系重合体（Ａ’−１）を得た。プロピレン系重合体（Ａ’−１）は、１１ｋｇ／ｈで得られた。得られたプロピレン系重合体（Ａ’−１）は、８０℃で真空乾燥を行った。 After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene polymer (A′-1). The propylene polymer (A′-1) was obtained at 11 kg / h. The resulting propylene polymer (A′-1) was vacuum dried at 80 ° C.
［製造例５］
重合方法を以下の様に変えた以外は、製造例４と同様の方法で行った。
（３）本重合
内容量５８Ｌのジャケット付循環式管状重合器にプロピレンを４０ｋｇ／時間、水素を２３５ＮＬ／時間、（２）で製造した触媒スラリーを固体触媒成分として０．４３ｇ／時間、トリエチルアルミニウム２．９ｍｌ／時間、ジエチルアミノトリエトキシシラン１．２ｍｌ／時間を連続的に供給し、気相の存在しない満液の状態にて重合した。管状重合器の温度は６６℃であり、圧力は３．５ＭＰａ／Ｇであった。
[Production Example 5]
The polymerization was performed in the same manner as in Production Example 4 except that the polymerization method was changed as follows.
(3) Main polymerization Propylene is 40 kg / hour, hydrogen is 235 NL / hour in a jacketed circulating tubular polymerizer with an internal capacity of 58 L, and the catalyst slurry produced in (2) is 0.43 g / hour, using triethylaluminum as a solid catalyst component. 2.9 ml / hour and diethylaminotriethoxysilane 1.2 ml / hour were continuously fed, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular polymerizer was 66 ° C., and the pressure was 3.5 MPa / G.
得られたスラリーは内容量１００Ｌの攪拌機付きベッセル重合器へ送り、更に重合を行った。重合器へは、プロピレンを１５ｋｇ／時間、水素を気相部の水素濃度が９．６ｍｏｌ％になるように供給した。重合温度６７℃、圧力３．３ＭＰａ／Ｇで重合を行った。 The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 L and further polymerized. Propylene was supplied to the polymerization vessel at a rate of 15 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 9.6 mol%. Polymerization was performed at a polymerization temperature of 67 ° C. and a pressure of 3.3 MPa / G.
得られたスラリーを気化後、気固分離を行い、プロピレン系重合体（Ａ’−２）を得た。プロピレン系重合体（Ａ’−２）は、１４ｋｇ／ｈで得られた。得られたプロピレン系重合体（Ａ’−２）は、８０℃で真空乾燥を行った。
製造例１〜５で得られたプロピレン系重合体の物性を表１に示す。
After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene polymer (A′-2). The propylene polymer (A′-2) was obtained at 14 kg / h. The resulting propylene polymer (A′-2) was vacuum dried at 80 ° C.
Table 1 shows the physical properties of the propylene polymers obtained in Production Examples 1 to 5.
製造例１（１）で製造した固体触媒担体を用い、以下の方法により行った。
Using the solid catalyst carrier produced in Production Example 1 (1), the following method was used.
（１）固体触媒の製造（担体への金属触媒成分の担持）
グローブボックス内にて、５Ｌ４つ口フラスコにジフェニルメチレン（３−ｔ−ブチル−５−メチルシクロペンタジエニル）（２，７−ｔ−ブチルフルオレニル）ジルコニウムジクロリドを２．０ｇ秤取った。フラスコを外へ出し、トルエン０．４６リットルと（１）で調製したＭＡＯ／ＳｉＯ2／トルエンスラリー１．４リットルを窒素下で加え、３０分間攪拌し担持を行った。得られたジフェニルメチレン（３−ｔ−ブチル−５−メチルシクロペンタジエニル）（２，７−ｔ−ブチルフルオレニル）ジルコニウムジクロリド／ＭＡＯ／ＳｉＯ2／トルエンスラリーはｎ−ヘプタンにて９９％置換を行い、最終的なスラリー量を４．５リットルとした。この操作は、室温で行った。
(1) Production of solid catalyst (support of metal catalyst component on support)
In a glove box, 2.0 g of diphenylmethylene (3-t-butyl-5-methylcyclopentadienyl) (2,7-t-butylfluorenyl) zirconium dichloride was weighed in a 5 L four-necked flask. The flask was taken out, 0.46 liters of toluene and 1.4 liters of MAO / SiO 2 / toluene slurry prepared in (1) were added under nitrogen, and the mixture was stirred for 30 minutes to carry. The resulting diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-tert-butylfluorenyl) zirconium dichloride / MAO / SiO 2 / toluene slurry was 99% in n-heptane. Substitution was performed and the final slurry volume was 4.5 liters. This operation was performed at room temperature.
（２）前重合触媒の製造
前記（１）で調製した固体触媒成分４０４ｇ、トリエチルアルミニウム２１８ｍＬ、ヘプタン１００Ｌを内容量２００Ｌの攪拌機付きオートクレーブに挿入し、内温１５〜２０℃に保ちエチレンを６０６ｇ挿入した後、１８０分間攪拌しながら反応させた。重合終了後、固体成分を沈降させ、上澄み液の除去し、ヘプタンで２回洗浄した。得られた前重合触媒を精製ヘプタンに再懸濁して、固体触媒成分濃度で６ｇ／Ｌとなるよう、ヘプタンにより調整を行った。この前重合触媒は固体触媒成分１ｇ当りポリエチレンを３ｇ含んでいた。
(2) Production of prepolymerization catalyst 404 g of the solid catalyst component prepared in (1) above, 218 mL of triethylaluminum, and 100 L of heptane were inserted into an autoclave equipped with a stirrer with an internal volume of 200 L, and the internal temperature was maintained at 15 to 20 ° C., and 606 g of ethylene was inserted. Then, the reaction was carried out with stirring for 180 minutes. After completion of the polymerization, the solid component was settled, the supernatant was removed, and washed twice with heptane. The obtained prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 6 g / L. This prepolymerized catalyst contained 3 g of polyethylene per 1 g of the solid catalyst component.
（３）本重合
充分に窒素置換し、１０℃にした内容量３０ＬのＳＵＳ製オートクレーブに液体プロピレン９ｋｇを装入し、エチレンを分圧として０．６ＭＰａ装入した。充分に撹拌しながら４５℃まで加温し、触媒挿入用ポットから、固体触媒成分として０．６ｇ／ヘプタン３００ｍｌとトリエチルアルミニウム０．５ｍｌの混合溶液を窒素でオートクレーブに加圧挿入した。６０℃で、２０分間重合を行った後、メタノールを添加し重合を停止した。重合終了後、プロピレンをパージし、充分窒素置換をし、プロピレン−エチレン共重合体（Ｂ−１−１）を分別した。得られたプロピレン−エチレン共重合体（Ｂ−１−１）を８０℃で真空乾燥した。
(3) Main polymerization 9 kg of liquid propylene was charged into a 30-liter SUS autoclave sufficiently purged with nitrogen and brought to 10 ° C., and 0.6 MPa was charged with ethylene as a partial pressure. The mixture was heated to 45 ° C. with sufficient stirring, and a mixed solution of 0.6 g / 300 ml of heptane and 0.5 ml of triethylaluminum as a solid catalyst component was pressure-inserted into the autoclave with nitrogen from the catalyst insertion pot. After carrying out the polymerization at 60 ° C. for 20 minutes, methanol was added to stop the polymerization. After completion of the polymerization, the propylene was purged and sufficiently purged with nitrogen to fractionate the propylene-ethylene copolymer (B-1-1). The resulting propylene-ethylene copolymer (B-1-1) was vacuum dried at 80 ° C.
製造例６で得られたプロピレン−エチレン共重合体（Ｂ−１−１）、後述の実施例、比較例で用いたエチレン−ブテン共重合体ゴム（Ｂ−２−１）の物性を表２に示す。 Table 2 shows the physical properties of the propylene-ethylene copolymer (B-1-1) obtained in Production Example 6 and the ethylene-butene copolymer rubber (B-2-1) used in Examples and Comparative Examples described later. Shown in
製造例１で製造されたプロピレン系重合体（Ａ−１）６８質量部、製造例６で製造されたプロピレン−エチレン共重合体（Ｂ−１−１）８質量部、エチレン−ブテン共重合体ゴム（Ｂ−２−１）（タフマーＡ０５５０Ｓ（三井化学（株）、商標）２４質量部、耐熱安定剤ＩＲＧＡＮＯＸ１０１０（チバガイギー（株）商標）０．１質量部、耐熱安定剤ＩＲＧＡＦＯＳ１６８（チバガイギー（株）商標）０．１質量部、耐熱安定剤ＩＲＧＡＮＯＸ１０７６（チバガイギー（株）商標）０．１質量部、ステアリン酸カルシウム０．１質量部をタンブラーにて混合後、二軸押出機にて溶融混練してペレット状のプロピレン系樹脂組成物を調製、射出成形機にて試験片（小型試験片）を作成した。成形品の機械物性を表３に示す。
68 parts by mass of the propylene-based polymer (A-1) produced in Production Example 1, 8 parts by mass of the propylene-ethylene copolymer (B-1-1) produced in Production Example 6, and an ethylene-butene copolymer Rubber (B-2-1) (Tuffmer A0550S (Mitsui Chemicals, Inc., trademark) 24 parts by mass, heat stabilizer IRGANOX 1010 (Ciba Geigy) trademark), 0.1 parts by mass, heat stabilizer IRGAFOS168 (Ciba Geigy) Trademark) 0.1 parts by mass, heat stabilizer IRGANOX 1076 (Ciba Geigy Co., Ltd.) 0.1 parts by mass, calcium stearate 0.1 parts by mass are mixed in a tumbler, and then melt-kneaded in a twin screw extruder and pellets A test piece (small test piece) was prepared using an injection molding machine, and the mechanical properties of the molded product are shown in Table 3.
＜溶融混練条件＞
同方向二軸混練機：品番 ＫＺＷ１５ＴＷ−４５ＭＧ−ＮＨ、（株）テクノベル社製
混練温度：１９０℃
スクリュー回転数：５００ｒｐｍ
フィーダー回転数：４０ｒｐｍ
＜ＪＩＳ小型試験片／射出成形条件＞
射出成形機：品番 ＥＣ４０、東芝機械（株）製
シリンダー温度：１９０℃
金型温度：４０℃
射出時間−保圧時間：１３秒（一次充填時間：１秒）
冷却時間：１５秒
<Melting and kneading conditions>
Same-direction biaxial kneader: Product number KZW15TW-45MG-NH, manufactured by Technobel Co., Ltd. Kneading temperature: 190 ° C
Screw rotation speed: 500rpm
Feeder rotation speed: 40 rpm
<JIS small test piece / injection molding conditions>
Injection molding machine: Part number EC40, manufactured by Toshiba Machine Co., Ltd. Cylinder temperature: 190 ° C
Mold temperature: 40 ℃
Injection time-pressure holding time: 13 seconds (primary filling time: 1 second)
Cooling time: 15 seconds
［実施例２］
実施例１において、プロピレン系重合体（Ａ−１）７１質量部、製造例６で製造されたプロピレン−エチレン共重合体（Ｂ−１−１）７質量部、エチレン−ブテン共重合体ゴム（Ｂ−２−１）（タフマーＡ０５５０Ｓ（三井化学（株）商標）２２質量部、を使用した以外は同様に行った。成形品の機械物性を表３に示す。
[Example 2]
In Example 1, 71 parts by mass of propylene-based polymer (A-1), 7 parts by mass of propylene-ethylene copolymer (B-1-1) produced in Production Example 6, ethylene-butene copolymer rubber ( B-2-1) (Tuffmer A0550S (trademark of Mitsui Chemicals Co., Ltd.)) was used in the same manner except that 22 parts by mass were used.
［実施例３］
実施例１において、プロピレン系重合体（Ａ−２）６８質量部、製造例６で製造されたプロピレン−エチレン共重合体（Ｂ−１−１）８質量部、エチレン−ブテン共重合体ゴム（Ｂ−２−１）（タフマーＡ０５５０Ｓ（三井化学（株）商標）２４質量部、を使用した以外は同様に行った。成形品の機械物性を表３に示す。
[Example 3]
In Example 1, 68 parts by mass of propylene-based polymer (A-2), 8 parts by mass of propylene-ethylene copolymer (B-1-1) produced in Production Example 6, ethylene-butene copolymer rubber ( B-2-1) (Tuffmer A0550S (trade name, Mitsui Chemicals, Inc.) 24 parts by mass was used in the same manner. Table 3 shows the mechanical properties of the molded product.
［実施例４］
実施例１において、プロピレン系重合体（Ａ−２）７１質量部、製造例６で製造されたプロピレン−エチレン共重合体（Ｂ−１−１）７質量部、エチレン−ブテン共重合体ゴム（Ｂ−２−１）（タフマーＡ０５５０Ｓ（三井化学（株）商標）２２質量部、を使用した以外は同様に行った。成形品の機械物性を表３に示す。
[Example 4]
In Example 1, 71 parts by mass of propylene-based polymer (A-2), 7 parts by mass of propylene-ethylene copolymer (B-1-1) produced in Production Example 6, ethylene-butene copolymer rubber ( B-2-1) (Tuffmer A0550S (trademark of Mitsui Chemicals Co., Ltd.)) was used in the same manner except that 22 parts by mass were used.
［実施例５］
実施例１において、プロピレン系重合体（Ａ−３）６８質量部、製造例６で製造されたプロピレン−エチレン共重合体（Ｂ−１−１）８質量部、エチレン−ブテン共重合体ゴム（Ｂ−２−１）（タフマーＡ０５５０Ｓ（三井化学（株）商標）２４質量部、を使用した以外は同様に行った。成形品の機械物性を表３に示す。
[Example 5]
In Example 1, 68 parts by mass of the propylene-based polymer (A-3), 8 parts by mass of the propylene-ethylene copolymer (B-1-1) produced in Production Example 6, and ethylene-butene copolymer rubber ( B-2-1) (Tuffmer A0550S (trade name, Mitsui Chemicals, Inc.) 24 parts by mass was used in the same manner. Table 3 shows the mechanical properties of the molded product.
［比較例１］
実施例１において、プロピレン系重合体（Ａ’−１）６８質量部、製造例６で製造されたプロピレン−エチレン共重合体（Ｂ−１−１）８質量部、エチレン−ブテン共重合体ゴム（Ｂ−２−１）（タフマーＡ０５５０Ｓ（三井化学（株）商標）２４質量部、を使用した以外は同様に行った。成形品の機械物性を表３に示す。
[Comparative Example 1]
In Example 1, 68 parts by mass of the propylene-based polymer (A′-1), 8 parts by mass of the propylene-ethylene copolymer (B-1-1) produced in Production Example 6, and ethylene-butene copolymer rubber (B-2-1) (Tuffmer A0550S (trade name, Mitsui Chemicals, Inc.) 24 parts by mass was used in the same manner. Table 3 shows the mechanical properties of the molded product.
［比較例２］
実施例１において、プロピレン系重合体（Ａ’−２）６８質量部、製造例６で製造されたプロピレン−エチレン共重合体（Ｂ−１−１）８質量部、エチレン−ブテン共重合体ゴム（Ｂ−２−１）（タフマーＡ０５５０Ｓ（三井化学（株）商標）２４質量部、を使用した以外は同様に行った。成形品の機械物性を表３に示す。
[Comparative Example 2]
In Example 1, 68 parts by mass of the propylene-based polymer (A′-2), 8 parts by mass of the propylene-ethylene copolymer (B-1-1) produced in Production Example 6, and ethylene-butene copolymer rubber (B-2-1) (Tuffmer A0550S (trade name, Mitsui Chemicals, Inc.) 24 parts by mass was used in the same manner. Table 3 shows the mechanical properties of the molded product.
Claims (6)
エラストマー（Ｂ）２質量部以上、４５質量部以下（ただし、（Ａ）および（Ｂ）の合計は１００質量部である）とを含有するプロピレン系樹脂組成物。
［１］ＡＳＴＭ−Ｄ１２３８に準拠し、２３０℃、２．１６ｋｇ荷重で測定したメルトフローレート（ＭＦＲ）が１００ｇ／１０分以上、１０００ｇ／１０分以下
［２］示差走査熱量計（ＤＳＣ）によって測定された融点が１５０℃以上、１６５℃以下
［３］13Ｃ−ＮＭＲスペクトルから求めた、全プロピレン構成単位中のプロピレンモノマーの２，１−結合に基づく位置不規則単位および１，３−結合に基づく位置不規則単位の合計が０．０％以上、１．０％以下
［４］分子量１００００以下の成分が７質量％以下
［５］ｏ−ジクロロベンゼンを用いたクロス分別クロマトグラフ（ＣＦＣ）により測定した溶出温度に対する溶出成分量のピーク半値幅が６．０℃以下であり、ピークトップ温度が１００℃以上、１３０℃以下 55 parts by mass or more and 98 parts by mass or less of a propylene polymer (A) that simultaneously satisfies the following [1] to [5]:
A propylene-based resin composition containing 2 parts by mass or more and 45 parts by mass or less (however, the sum of (A) and (B) is 100 parts by mass) of the elastomer (B).
[1] Based on ASTM-D1238, melt flow rate (MFR) measured at 230 ° C. and 2.16 kg load is 100 g / 10 min or more and 1000 g / 10 min or less. [2] Measured by differential scanning calorimeter (DSC) The melting point was 150 ° C. or higher and 165 ° C. or lower. [3] The position irregular units and 1,3-bonds based on the 2,1-bonds of the propylene monomer in all propylene constituent units determined from the 13 C-NMR spectrum. [4] Components having molecular weight of 10,000 or less are 7% by mass or less. [5] By cross-fractionation chromatograph (CFC) using o-dichlorobenzene. The peak half-value width of the eluted component with respect to the measured elution temperature is 6.0 ° C or lower, and the peak top temperature is 100 ° C or higher and 130 ° C or lower.
［ｉ］エチレン含有量が１５ｍｏｌ％以上、９０ｍｏｌ％以下
［ｉｉ］極限粘度［η］が０．８ｄｌ／ｇ以上、４．０ｄｌ／ｇ以下 The elastomer (B) is a copolymer of ethylene and at least one α-olefin selected from α-olefins having 3 to 10 carbon atoms, and simultaneously satisfies the following [i] to [ii]. The propylene-based resin composition according to claim 1 or 2.
[I] Ethylene content is 15 mol% or more and 90 mol% or less [ii] Intrinsic viscosity [η] is 0.8 dl / g or more and 4.0 dl / g or less
前記エチレンと、炭素数４〜１０のα−オレフィンから選択される少なくとも１種のα‐オレフィンとの共重合体（Ｂ−２）が、下記［ＩＩＩ］〜［ＩＶ］を同時に満たし、
プロピレン系樹脂組成物が、前記エチレン−プロピレン共重合体（Ｂ−１）を１質量部以上、４０質量部以下、前記エチレンと、炭素数４〜１０のα−オレフィンから選択される少なくとも１種のα‐オレフィンとの共重合体（Ｂ−２）を１質量部以上、４０質量部以下を含有する、請求項５に記載のプロピレン系樹脂組成物。
［Ｉ］エチレン含有量が１５ｍｏｌ％以上、５０ｍｏｌ％以下
［ＩＩ］極限粘度［η］が０．８ｄｌ／ｇ以上、４．０ｄｌ／ｇ以下
［ＩＩＩ］エチレン含有量が５０ｍｏｌ％以上、９０ｍｏｌ％以下
［ＩＶ］極限粘度［η］が０．８ｄｌ／ｇ以上、４．０ｄｌ／ｇ以下 The ethylene-propylene copolymer (B-1) satisfies the following [I] to [II] simultaneously,
A copolymer (B-2) of ethylene and at least one α-olefin selected from α-olefins having 4 to 10 carbon atoms simultaneously satisfies the following [III] to [IV],
The propylene-based resin composition is at least one selected from the ethylene-propylene copolymer (B-1) from 1 part by mass to 40 parts by mass, the ethylene, and an α-olefin having 4 to 10 carbon atoms. The propylene-type resin composition of Claim 5 containing 1 mass part or more and 40 mass parts or less of the copolymer (B-2) with (alpha) -olefin.
[I] Ethylene content is 15 mol% or more and 50 mol% or less [II] Intrinsic viscosity [η] is 0.8 dl / g or more and 4.0 dl / g or less [III] Ethylene content is 50 mol% or more and 90 mol% or less [IV] Intrinsic viscosity [η] is 0.8 dl / g or more and 4.0 dl / g or less
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011074813A JP5684024B2 (en) | 2011-03-30 | 2011-03-30 | Propylene resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011074813A JP5684024B2 (en) | 2011-03-30 | 2011-03-30 | Propylene resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2012207154A true JP2012207154A (en) | 2012-10-25 |
| JP5684024B2 JP5684024B2 (en) | 2015-03-11 |
Family
ID=47187176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011074813A Active JP5684024B2 (en) | 2011-03-30 | 2011-03-30 | Propylene resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5684024B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020523437A (en) * | 2017-06-29 | 2020-08-06 | ボレアリス エージー | Polypropylene composition having excellent impact performance |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006028449A (en) * | 2004-07-21 | 2006-02-02 | Mitsui Chemicals Inc | Propylene-based polymer |
| WO2006068308A1 (en) * | 2004-12-22 | 2006-06-29 | Mitsui Chemicals, Inc. | Propylene polymer, composition containing the polymer, and molded objects obtained from these |
| JP2008115262A (en) * | 2006-11-02 | 2008-05-22 | Mitsui Chemicals Inc | Automotive part comprising propylene-based resin composition |
-
2011
- 2011-03-30 JP JP2011074813A patent/JP5684024B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006028449A (en) * | 2004-07-21 | 2006-02-02 | Mitsui Chemicals Inc | Propylene-based polymer |
| WO2006068308A1 (en) * | 2004-12-22 | 2006-06-29 | Mitsui Chemicals, Inc. | Propylene polymer, composition containing the polymer, and molded objects obtained from these |
| JP2008115262A (en) * | 2006-11-02 | 2008-05-22 | Mitsui Chemicals Inc | Automotive part comprising propylene-based resin composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020523437A (en) * | 2017-06-29 | 2020-08-06 | ボレアリス エージー | Polypropylene composition having excellent impact performance |
| US11186708B2 (en) | 2017-06-29 | 2021-11-30 | Borealis Ag | Polypropylene composition with outstanding impact performance |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5684024B2 (en) | 2015-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5000070B2 (en) | Auto parts made of polypropylene resin composition | |
| KR101007482B1 (en) | Propylene random block copolymer, resin compositions containing the copolymer, and moldings of both | |
| JP6420335B2 (en) | Heterophase copolymer | |
| US9902847B2 (en) | 4-methyl-1-pentene (co)polymer composition, and film and hollow molded product composed of the composition | |
| EP1829903B1 (en) | Propylene polymer, composition containing the polymer, and molded objects obtained from these | |
| US9771448B2 (en) | Olefin-based resin, method for producing same and propylene-based resin composition | |
| CN111032707B (en) | Polypropylene composition with low shrinkage at wide application temperature range | |
| JP6253765B2 (en) | Olefin resin and process for producing the same | |
| JP2017502163A (en) | Heterophase polypropylene polymer | |
| JP3530143B2 (en) | Polyolefin resin composition | |
| CN111527140B (en) | Heterophasic polypropylene composition with high flexibility and high softness | |
| JP4414513B2 (en) | Propylene-based resin composition and method for producing the same | |
| TW200400225A (en) | Impact-resistant polyolefin compositions | |
| TW200401800A (en) | Impact-resistant polyolefin compositions | |
| EP1987098A1 (en) | Propylene polymers for injection molding applications | |
| JP2024050994A (en) | Propylene-based resin composition, molded article and propylene polymer | |
| WO2020048794A1 (en) | Polypropylene based composition with improved paintability | |
| JP2017222850A (en) | Propylene-based resin composition and method for producing the same, and molded body using the propylene-based resin composition | |
| JP2008231266A (en) | Polypropylene composition and molded product of the same | |
| JP5684024B2 (en) | Propylene resin composition | |
| JP2017066200A (en) | Olefin resin and manufacturing method therefor, composition and molded body | |
| JP6666089B2 (en) | Propylene resin composition and molded article | |
| KR20170035711A (en) | Polypropylene resin composition having improved whitening resistance and high impact resistance | |
| JP6615554B2 (en) | Olefin-based resin, production method and composition thereof, and molded article | |
| JP7483392B2 (en) | Propylene-based resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20130904 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20140227 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140311 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140512 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20141216 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150114 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5684024 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |