JP2022135069A - Propylene-based resin composition and use of the same - Google Patents
Propylene-based resin composition and use of the same Download PDFInfo
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- JP2022135069A JP2022135069A JP2021034653A JP2021034653A JP2022135069A JP 2022135069 A JP2022135069 A JP 2022135069A JP 2021034653 A JP2021034653 A JP 2021034653A JP 2021034653 A JP2021034653 A JP 2021034653A JP 2022135069 A JP2022135069 A JP 2022135069A
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- Prior art keywords
- propylene
- mass
- ethylene
- sol
- resin composition
- Prior art date
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 167
- 239000011342 resin composition Substances 0.000 title claims abstract description 50
- 229920000642 polymer Polymers 0.000 claims abstract description 87
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000005977 Ethylene Substances 0.000 claims abstract description 79
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000005259 measurement Methods 0.000 claims abstract description 23
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920001384 propylene homopolymer Polymers 0.000 claims abstract description 15
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001155 polypropylene Polymers 0.000 claims description 26
- 239000000155 melt Substances 0.000 claims description 20
- 239000002667 nucleating agent Substances 0.000 claims description 16
- 229920000573 polyethylene Polymers 0.000 claims description 16
- 229920001038 ethylene copolymer Polymers 0.000 claims description 13
- 238000001746 injection moulding Methods 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 230000002087 whitening effect Effects 0.000 abstract description 16
- 239000004711 α-olefin Substances 0.000 abstract description 16
- 238000000465 moulding Methods 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 11
- 229920000089 Cyclic olefin copolymer Polymers 0.000 abstract description 3
- 229920005653 propylene-ethylene copolymer Polymers 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 description 62
- 239000003054 catalyst Substances 0.000 description 38
- 238000000034 method Methods 0.000 description 28
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- 239000010936 titanium Substances 0.000 description 21
- 150000001451 organic peroxides Chemical class 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 229910052719 titanium Inorganic materials 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000004898 kneading Methods 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- -1 polyethylene Polymers 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 230000003247 decreasing effect Effects 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 150000002902 organometallic compounds Chemical class 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 6
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 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
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 150000003961 organosilicon compounds Chemical class 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-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
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 3
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 3
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- OLGHJTHQWQKJQQ-UHFFFAOYSA-N 3-ethylhex-1-ene Chemical compound CCCC(CC)C=C OLGHJTHQWQKJQQ-UHFFFAOYSA-N 0.000 description 2
- YPVPQMCSLFDIKA-UHFFFAOYSA-N 3-ethylpent-1-ene Chemical compound CCC(CC)C=C YPVPQMCSLFDIKA-UHFFFAOYSA-N 0.000 description 2
- SUJVAMIXNUAJEY-UHFFFAOYSA-N 4,4-dimethylhex-1-ene Chemical compound CCC(C)(C)CC=C SUJVAMIXNUAJEY-UHFFFAOYSA-N 0.000 description 2
- KLCNJIQZXOQYTE-UHFFFAOYSA-N 4,4-dimethylpent-1-ene Chemical compound CC(C)(C)CC=C KLCNJIQZXOQYTE-UHFFFAOYSA-N 0.000 description 2
- OPMUAJRVOWSBTP-UHFFFAOYSA-N 4-ethyl-1-hexene Chemical compound CCC(CC)CC=C OPMUAJRVOWSBTP-UHFFFAOYSA-N 0.000 description 2
- SUWJESCICIOQHO-UHFFFAOYSA-N 4-methylhex-1-ene Chemical compound CCC(C)CC=C SUWJESCICIOQHO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 206010000496 acne Diseases 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- OYFUVZBROQZLCL-UHFFFAOYSA-K aluminum;4-tert-butylbenzoate;hydroxide Chemical compound [OH-].[Al+3].CC(C)(C)C1=CC=C(C([O-])=O)C=C1.CC(C)(C)C1=CC=C(C([O-])=O)C=C1 OYFUVZBROQZLCL-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 2
- ZHROMWXOTYBIMF-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C ZHROMWXOTYBIMF-UHFFFAOYSA-M 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 description 1
- GGQHNQQPLWRNHD-UHFFFAOYSA-N 1,3,7,9-tetratert-butyl-11-hydroxy-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP(O)(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C GGQHNQQPLWRNHD-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- PIYNPBVOTLQBTC-UHFFFAOYSA-N 1-[8-propyl-2,6-bis(4-propylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound O1C2C(CCC)OC(C=3C=CC(CCC)=CC=3)OC2C(C(O)CO)OC1C1=CC=C(CCC)C=C1 PIYNPBVOTLQBTC-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- UPMMYNHDIHLVEF-UHFFFAOYSA-N 2-tert-butylperoxy-4-methyl-1-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(C)C=C1OOC(C)(C)C UPMMYNHDIHLVEF-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- AZSQEXSKABOCGN-UHFFFAOYSA-M CC[Al+]CC.[Cl-].Cl.Cl.Cl Chemical compound CC[Al+]CC.[Cl-].Cl.Cl.Cl AZSQEXSKABOCGN-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-OUBTZVSYSA-N Carbon-13 Chemical compound [13C] OKTJSMMVPCPJKN-OUBTZVSYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229920003355 Novatec® Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 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
- 238000002835 absorbance Methods 0.000 description 1
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
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- 230000003078 antioxidant effect Effects 0.000 description 1
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- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
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Images
Landscapes
- Injection Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、剛性と耐衝撃性のバランスに優れ、成形収縮による白化が抑制された成形体を得るに好適なプロピレン樹脂組成物に関する。 TECHNICAL FIELD The present invention relates to a propylene resin composition suitable for obtaining a molded article having an excellent balance between rigidity and impact resistance and having suppressed whitening due to molding shrinkage.
ポリエチレンやポリプロピレンに代表されるポリオレフィン（オレフィン系重合体）は、生産に係るエネルギーが小さく、軽量かつリサイクル性にも優れることから、各産業界における、循環型社会を形成するための３Ｒ（Ｒｅｄｕｃｅ、Ｒｅｕｓｅ、Ｒｅｃｙｃｌｅ）への取り組みのなかで、更に注目が高まっている。ポリオレフィンは、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、自動車部品など、種々の分野で利用されている。 Polyolefins (olefin polymers) represented by polyethylene and polypropylene require little energy for production, are lightweight, and have excellent recyclability. Reuse, Recycle) is gaining more attention. Polyolefins are used in various fields such as daily necessities, kitchen utensils, packaging films, home electric appliances, machine parts, electric parts, and automobile parts.
オレフィン系重合体の中でも、ポリプロピレンは剛性、耐熱性に優れるが、ポリエチレンに比べると、耐寒性、耐衝撃性に劣ることから、ポリプロピレンの耐寒性、耐衝撃性を改良する方法が多々提案されている。 Among olefin polymers, polypropylene has excellent rigidity and heat resistance, but is inferior to polyethylene in cold resistance and impact resistance. Therefore, many methods have been proposed to improve the cold resistance and impact resistance of polypropylene. there is
例えば、特許文献１には、ポリプロピレンとして、２３０℃におけるメルトフローレートが２～８０ｇ／１０分、ホモ部立体規則性が０．９６０以上、且つ全エチレン含有量が２～１２重量％であるエチレン－プロピレンブロック共重合体を用い、当該ブロック共重合体６０～９９重量部と、１９０℃におけるメルトフローレートが１～６０ｇ／１０分、密度が０．８６０～０．９４０ｇ／ｃｍ3であるポリエチレン１～４０重量部とを混合することにより、食品分野、医療分野のキャップなどの小型の成形体の耐衝撃性、落下時に発生する白化を低減できることが示されている。 For example, in Patent Document 1, ethylene having a melt flow rate at 230° C. of 2 to 80 g/10 min, a homo-part stereoregularity of 0.960 or more, and a total ethylene content of 2 to 12% by weight is disclosed in Patent Document 1. a polyethylene block copolymer comprising 60 to 99 parts by weight of said block copolymer and having a melt flow rate at 190° C. of 1 to 60 g/10 min and a density of 0.860 to 0.940 g/cm 3 ; It is shown that by mixing 1 to 40 parts by weight, impact resistance of small moldings such as caps in the food and medical fields and whitening that occurs when dropped can be reduced.
また、特許文献２には、ポリプロピレンとして、２３０℃におけるメルトフローレートが２～２０（ｇ／１０分）でホモ部立体規則性が０．９６０以上で且つ全エチレン含有量が６～１２（重量％）であるエチレン－プロピレンブロック共重合体を用い、当該ブロック共重合体８５～９５重量部と、１９０℃におけるメルトフローレートが３０～６０（ｇ／１０分）、密度０．９５７～０．９６６（ｇ／ｃｍ3）である高密度ポリエチレン５～１５重量部とを混合することにより、飲料キャップなどの小型の成形体の耐衝撃性が改良されることが示されている。
Further, in
一方、コンテナやパレットのような大型の成形体は、その使用用途から、剛性や耐衝撃性といった物理的強度が高いレベルで要求されるため、リブ形状を持つ成形体であることが多い。ところが、リブ形状を持つ成形体は、成形時の成形体の収縮により生じる応力が起因となって、成形体の一部が白化する場合があることが分った。 On the other hand, large molded bodies such as containers and pallets are often rib-shaped molded bodies because they are required to have a high level of physical strength such as rigidity and impact resistance due to their intended use. However, it has been found that part of the rib-shaped molded body may be partially whitened due to stress caused by shrinkage of the molded body during molding.
本発明の目的は、リブ近傍での成形収縮により生じる応力が起因となって発生する白化(ヒケ白化)が抑制され、且つ、剛性、耐衝撃性のバランスに優れた成形体を得るに好適な、プロピレン系樹脂組成物、および当該組成物からなるコンテナやパレット等の大型成形体を得ることにある。 An object of the present invention is to suppress whitening (whitening of sink marks) caused by stress caused by molding shrinkage in the vicinity of ribs, and to obtain a molded article having an excellent balance between rigidity and impact resistance. , a propylene-based resin composition, and a large molded article such as a container or a pallet made of the composition.
さらに、本発明は、プロピレン系樹脂組成物の組成と配合するエチレン系重合体成分の最適化を図ることで、ヒケ白化の抑制を達成すると共に、コンテナやパレット等の大型成形体に要求される剛性と耐衝撃性のバランスの目標を達成できるプロピレン系樹脂組成物を提供することにある。 Furthermore, the present invention achieves suppression of whitening of sink marks by optimizing the composition of the propylene-based resin composition and the ethylene-based polymer component to be blended, and is required for large-sized molded articles such as containers and pallets. An object of the present invention is to provide a propylene-based resin composition capable of achieving a balance between rigidity and impact resistance.
また、本発明はこのプロピレン系樹脂組成物を用いたコンテナやパレット等の大型成形体を提供することを目的とする。 Another object of the present invention is to provide large molded articles such as containers and pallets using this propylene-based resin composition.
本発明は、下記要件（Ａ１）～（Ａ５）を満たすプロピレン系重合体（Ａ）を８５～９５質量部、および下記要件（Ｂ１）および（Ｂ２）を満たすエチレン系重合体（Ｂ）を５～１５質量部〔ただし、プロピレン系重合体（Ａ）とエチレン系重合体（Ｂ）の合計量を１００質量部とする。〕を含むことを特徴とするプロピレン系樹脂組成物に係る。
（Ａ１）ＪＩＳ Ｋ ７２１０に準拠して、測定温度２３０℃、荷重２．１６ｋｇで測定したメルトフローレート（ＭＦＲA）が、１～３０ｇ／１０分である。
（Ａ２）プロピレンを単独で重合させてなるプロピレン単独重合体セグメントと、プロピレンとエチレンを共重合させてなるプロピレン・エチレン共重合体セグメントを含む。
（Ａ３）室温ｎ－デカンに不溶な部分（Ｄinsol）を８６～９５質量％、および室温ｎ－デカンに可溶な部分（Ｄsol）を５～１４質量％〔ただし、（Ｄinsol）と（Ｄsol）の合計量を１００質量％とする。〕を含む。
（Ａ４）室温ｎ－デカンに可溶な部分（Ｄsol）のエチレンに由来する構成単位の含有量が２５質量％以上、４５質量％未満である。
（Ａ５）室温ｎ－デカンに可溶な部分（Ｄsol）の１３５℃デカリン中における極限粘度［η］が２．５～４．０ｄＬ／ｇである。
（Ｂ１）ＪＩＳ Ｋ ７２１０に準拠して、測定温度１９０℃、荷重２．１６ｋｇで測定したメルトフローレート（ＭＦＲB）が、１ｇ／１０分以上、３０ｇ／１０分未満である。
（Ｂ２）密度が９５０～９６６ｋｇ／ｍ3である。
The present invention comprises 85 to 95 parts by mass of a propylene polymer (A) that satisfies the following requirements (A1) to (A5), and 5 parts of an ethylene polymer (B) that satisfies the following requirements (B1) and (B2): up to 15 parts by mass [where the total amount of the propylene-based polymer (A) and the ethylene-based polymer (B) is 100 parts by mass. ] and relates to a propylene-based resin composition characterized by comprising
(A1) According to JIS K 7210, the melt flow rate (MFR A ) measured at a measurement temperature of 230° C. and a load of 2.16 kg is 1 to 30 g/10 minutes.
(A2) Contains a propylene homopolymer segment obtained by polymerizing propylene alone and a propylene/ethylene copolymer segment obtained by copolymerizing propylene and ethylene.
(A3) 86 to 95% by mass of a portion insoluble in room temperature n-decane (D insol ) and 5 to 14% by mass of a portion soluble in room temperature n-decane (D sol ) [provided that (D insol ) and Let the total amount of (D sol ) be 100% by mass. 〕including.
(A4) The content of structural units derived from ethylene in the portion (D sol ) soluble in n-decane at room temperature is 25% by mass or more and less than 45% by mass.
(A5) The portion soluble in n-decane at room temperature (D sol ) has an intrinsic viscosity [η] of 2.5 to 4.0 dL/g in decalin at 135°C.
(B1) According to JIS K 7210, the melt flow rate (MFR B ) measured at a measurement temperature of 190° C. and a load of 2.16 kg is 1 g/10 minutes or more and less than 30 g/10 minutes.
(B2) Density is 950-966 kg/m 3 .
本発明のプロピレン系樹脂組成物から得られる成形体は、リブ近傍での成形収縮により生じる応力が起因となって発生する白化(ヒケ白化)が抑制され、且つ、剛性、耐衝撃性のバランスに優れた成形体である。 The molded article obtained from the propylene-based resin composition of the present invention is inhibited from whitening (sink marks) caused by stress caused by molding shrinkage in the vicinity of the ribs, and has a good balance between rigidity and impact resistance. It is an excellent molded product.
＜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を構成する成分の一つであるプロピレン系重合体（Ａ）は、下記要件（Ａ１）～（Ａ５）を満たすプロピレン系重合体である。
<Propylene polymer (A)>
The propylene-based polymer (A), which is one of the components constituting the propylene-based resin composition of the present invention, is a propylene-based polymer that satisfies the following requirements (A1) to (A5).
〔要件（Ａ１）〕
ＪＩＳ Ｋ ７２１０に準拠して、測定温度２３０℃、荷重２．１６ｋｇで測定したメルトフローレート（ＭＦＲA）が、１～３０ｇ／１０分、好ましくは１～２０ｇ／１０分、より好ましくは１～１５ｇ／１０分である。
ＭＦＲAが上記範囲を下回ると、プロピレン系樹脂組成物を射出成形した際にショートショットが生じる虞がある。またＭＦＲAが上記範囲を上回ると、プロピレン系樹脂組成物から得られる成形体の機械的強度が低下する虞がある。
[Requirements (A1)]
According to JIS K 7210, the melt flow rate (MFR A ) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is 1 to 30 g / 10 minutes, preferably 1 to 20 g / 10 minutes, more preferably 1 to 15 g/10 minutes.
If the MFR A is below the above range, short shots may occur when the propylene-based resin composition is injection molded. On the other hand, if the MFR A exceeds the above range, the mechanical strength of the molded article obtained from the propylene-based resin composition may decrease.
〔要件（Ａ２）〕
プロピレンを単独で重合させてなるプロピレン単独重合体セグメントと、プロピレンとエチレンを共重合させてなるプロピレン・エチレン共重合体セグメントを含む。
本発明に係るプロピレン系重合体（Ａ）は、プロピレン単独重合体セグメントとプロピレン・エチレン共重合体セグメントを含むことにより、プロピレン系樹脂組成物から得られる成形体は、大型成形品に要求される剛性と耐衝撃性のバランスに優れる。
[Requirements (A2)]
It contains a propylene homopolymer segment obtained by polymerizing propylene alone and a propylene/ethylene copolymer segment obtained by copolymerizing propylene and ethylene.
Since the propylene-based polymer (A) according to the present invention contains a propylene homopolymer segment and a propylene/ethylene copolymer segment, molded articles obtained from the propylene-based resin composition are required for large molded articles. Excellent balance of rigidity and impact resistance.
〔要件（Ａ３）〕
室温ｎ－デカンに不溶な部分（Ｄinsol）を８６～９５質量％、好ましくは８６～９２質量％、より好ましくは８６～９０質量％、および室温ｎ－デカンに可溶な部分（Ｄsol）を５～１４質量％、好ましくは８～１４質量％、より好ましくは１０～１４質量％〔ただし、（Ｄinsol）と（Ｄsol）の合計量を１００質量％とする。〕を含む。
[Requirements (A3)]
86-95% by weight, preferably 86-92% by weight, more preferably 86-90% by weight of a portion insoluble in room temperature n-decane (D insol ), and a portion soluble in room temperature n-decane (D sol ) of 5 to 14% by mass, preferably 8 to 14% by mass, more preferably 10 to 14% by mass [where the total amount of (D insol ) and (D sol ) is 100% by mass. 〕including.
プロピレン系重合体（Ａ）において、ｎ－デカンに不溶な部分（Ｄinsol）とは、通常、主にプロピレン由来の構成単位からなる成分であり、結晶性を有し、高い剛性を示すと考えられる。ｎ－デカンに可溶な部分（Ｄsol）とは、通常、主にプロピレンおよびエチレン由来の構成単位からなる成分である。Ｄsol成分は結晶性を示さないか、もしくは結晶性が低い成分であり、ガラス転移温度が低く、耐衝撃性、およびエチレン・α－オレフィン共重合体（Ｂ）との相溶性を発現すると考えられる。これはゴム成分と言われることもある。プロピレン系重合体（Ａ）は、通常、ｎ－デカンに不溶な部分（Ｄinsol）およびｎ－デカンに可溶な部分（Ｄsol）を有するプロピレン系共重合体（いわゆるブロック共重合体）である。 In the propylene-based polymer (A), the n-decane-insoluble portion (D insol ) is usually a component mainly composed of structural units derived from propylene, and is considered to have crystallinity and high rigidity. be done. The portion soluble in n-decane (D sol ) is usually a component mainly composed of structural units derived from propylene and ethylene. The D sol component does not exhibit crystallinity or has low crystallinity, and is thought to exhibit low glass transition temperature, impact resistance, and compatibility with the ethylene/α-olefin copolymer (B). be done. This is sometimes referred to as the rubber component. The propylene-based polymer (A) is usually a propylene-based copolymer (so-called block copolymer) having a n-decane-insoluble portion (D insol ) and an n-decane-soluble portion (D sol ). be.
Ｄsolの割合が上記範囲を下回り、Ｄinsolの割合が上記範囲を上回ると、プロピレン系樹脂組成物から得られる成形体の耐衝撃性が低下し、またヒケ白化の改良効果が劣る傾向にある。これはＤsolの割合が減ることにより衝撃に対しての吸収エネルギーが低下し、また成形収縮時に生じる応力を分散し、吸収する効果が低くなるためと考えられる。 If the proportion of D sol is less than the above range and the proportion of D insol exceeds the above range, the impact resistance of the molded article obtained from the propylene-based resin composition tends to decrease, and the effect of improving whitening marks tends to be inferior. . This is thought to be due to the fact that the reduction in the ratio of D sol lowers the absorption energy against impact, and the effect of dispersing and absorbing the stress generated during molding shrinkage is lowered.
一方、Ｄinsolの割合が上記範囲を下回り、Ｄsolの割合が上記範囲を上回ると、プロピレン系樹脂組成物の高速での成形性が劣る場合があり、またプロピレン系樹脂組成物から得られる成形体の剛性が低下する傾向にある。これは剛性に寄与するＤinsolの成分が減少するためだと考えられる。
前記Ｄinsolの割合および前記Ｄsolの割合は、後述する実施例で採用した方法により測定した場合のものである。
On the other hand, when the ratio of D insol is below the above range and the ratio of D sol is above the above range, the high-speed moldability of the propylene-based resin composition may be poor. Body stiffness tends to decrease. It is believed that this is because the component of D insol that contributes to stiffness is reduced.
The ratio of D insol and the ratio of D sol are those measured by the method employed in the examples described later.
〔要件（Ａ４）〕
室温ｎ－デカンに可溶な部分（Ｄsol）のエチレンに由来する構成単位の含有量が２５質量％以上、４５質量％未満、好ましくは２７～４３質量％、より好ましくは３０～４０質量％である。なお、質量％は、Ｄsolにおけるエチレンに由来する構成単位の含有量とプロピレンに由来する構成単位の含有量の合計量を１００質量％とする量である。
室温ｎ－デカンに可溶な部分（Ｄsol）のエチレンに由来する構成単位の含有量はプロピレン単独重合体セグメントとプロピレン・エチレン共重合体セグメントの相溶性に寄与する。
[Requirements (A4)]
The content of structural units derived from ethylene in the portion soluble in room temperature n-decane (D sol ) is 25% by mass or more and less than 45% by mass, preferably 27 to 43% by mass, more preferably 30 to 40% by mass. is. The mass % is an amount based on 100% by mass of the total amount of the content of structural units derived from ethylene and the content of structural units derived from propylene in Dsol .
The content of structural units derived from ethylene in the room temperature n-decane soluble portion (D sol ) contributes to the compatibility between the propylene homopolymer segment and the propylene/ethylene copolymer segment.
エチレンに由来する構成単位の含有量が上記範囲を下回るとプロピレン系樹脂組成物から得られた成形体の剛性が劣る傾向がある。これはプロピレン単独重合体セグメントとプロピレン・エチレン共重合体セグメントの相溶性が高くなり、剛性に寄与するプロピレン単独重合体セグメントにプロピレン・エチレン共重合体セグメントに溶け込みが生じ、結晶性が低下するためと考えられる。一方、エチレンに由来する構成単位の含有量が上記範囲を上回ると、プロピレン系樹脂組成物から得られた成形体はブツが発生しやすくなり、耐衝撃性の低下や外観不良が発生しやすい傾向がある。これはプロピレン単独重合体セグメントとプロピレン・エチレン共重合体セグメントの相溶性が低くなり、分散不良を起こすためと考えられる。 If the content of structural units derived from ethylene is less than the above range, the rigidity of molded articles obtained from the propylene-based resin composition tends to be poor. This is because the compatibility between the propylene homopolymer segment and the propylene/ethylene copolymer segment increases, and the propylene homopolymer segment that contributes to rigidity melts into the propylene/ethylene copolymer segment, resulting in a decrease in crystallinity. it is conceivable that. On the other hand, if the content of the structural unit derived from ethylene exceeds the above range, the molded article obtained from the propylene-based resin composition tends to be more likely to have pimples, resulting in reduced impact resistance and poor appearance. There is This is presumably because the compatibility between the propylene homopolymer segment and the propylene/ethylene copolymer segment is low, resulting in poor dispersion.
〔要件（Ａ５）〕
室温ｎ－デカンに可溶な部分（Ｄsol）の１３５℃デカリン中における極限粘度［ηsol］が２．５～４．０ｄＬ／ｇ、好ましくは２．７～３．８ｄＬ／ｇ、より好ましくは２．９～３．６ｄＬ／ｇである。
前記極限粘度［ηsol］の値は、後述する実施例で採用した方法により測定した場合のものである。
[Requirements (A5)]
The intrinsic viscosity [η sol ] of the part soluble in room temperature n-decane (D sol ) in decalin at 135° C. is 2.5 to 4.0 dL/g, preferably 2.7 to 3.8 dL/g, more preferably is 2.9-3.6 dL/g.
The value of the intrinsic viscosity [η sol ] is the value measured by the method employed in the examples described later.
極限粘度［ηsol］が上記範囲を下回ると、プロピレン系樹脂組成物から得られた成形体の耐衝撃性が劣る傾向がある。これはＤsolの分子量が低下し、衝撃吸収エネルギーが低くなる為と考えられる。また極限粘度［ηsol］が上記範囲を上回ると、プロピレン系樹脂組成物から得られた成形体はブツが発生しやすくなり、耐衝撃性の低下や外観不良が発生しやすい傾向がある。これはＤsolの分子量が高く、分散不良を起こすためと考えられる。 If the intrinsic viscosity [η sol ] is below the above range, the impact resistance of the molded article obtained from the propylene-based resin composition tends to be poor. This is thought to be because the molecular weight of D sol is lowered and the impact absorption energy is lowered. If the intrinsic viscosity [η sol ] exceeds the above range, the molded article obtained from the propylene-based resin composition tends to be more likely to have pimples, resulting in lower impact resistance and poorer appearance. This is thought to be due to the high molecular weight of D sol causing poor dispersion.
本発明に係るプロピレン系重合体（Ａ）は、その製造方法に特に限定はないが、通常は、メタロセン化合物含有触媒存在下、またはチーグラーナッタ触媒存在下で、プロピレンおよびエチレンを共重合することにより得られる。 The propylene-based polymer (A) according to the present invention is not particularly limited in its production method, but usually by copolymerizing propylene and ethylene in the presence of a metallocene compound-containing catalyst or in the presence of a Ziegler-Natta catalyst. can get.
なお、本発明に係るプロピレン系重合体（Ａ）は、チーグラーナッタ触媒存在下で、プロピレンおよびエチレンを共重合することにより得られることが好ましい。分子量分布が広く成形性が良好な樹脂が得られ易い為である。 The propylene-based polymer (A) according to the present invention is preferably obtained by copolymerizing propylene and ethylene in the presence of a Ziegler-Natta catalyst. This is because a resin having a wide molecular weight distribution and good moldability can be easily obtained.
（メタロセン化合物含有触媒）
前記メタロセン化合物含有触媒としては、メタロセン化合物、並びに、有機金属化合物、有機アルミニウムオキシ化合物およびメタロセン化合物と反応してイオン対を形成することのできる化合物から選ばれる少なくとも１種以上の化合物、さらに必要に応じて粒子状担体とからなるメタロセン触媒を挙げることができ、好ましくはアイソタクチックまたはシンジオタクチック構造等の立体規則性重合をすることのできるメタロセン触媒を挙げることができる。前記メタロセン化合物の中では、国際公開第０１／２７１２４号に例示されている架橋性メタロセン化合物、国際公開第２０１０／７４００１号の［００６８］～［００７６］に記載のメタロセン化合物などが好ましい。また、有機金属化合物、有機アルミニウムオキシ化合物、および遷移金属化合物と反応してイオン対を形成する化合物、さらには必要に応じて用いられる粒子状担体としては、国際公開第０１／２７１２４号、特開平１１－３１５１０９号公報等に開示された化合物を制限無く使用することができる。
(Catalyst containing metallocene compound)
As the metallocene compound-containing catalyst, at least one compound selected from a metallocene compound, an organometallic compound, an organoaluminum oxy compound, and a compound capable of forming an ion pair by reacting with the metallocene compound, and, if necessary, A metallocene catalyst comprising a particulate carrier can be mentioned accordingly, and preferably a metallocene catalyst capable of stereoregular polymerization having an isotactic or syndiotactic structure can be mentioned. Among the metallocene compounds, preferred are the crosslinkable metallocene compounds exemplified in WO 01/27124 and the metallocene compounds described in [0068] to [0076] of WO 2010/74001. In addition, compounds that react with organometallic compounds, organoaluminum oxy compounds, and transition metal compounds to form ion pairs, and particulate carriers that are used as necessary are described in International Publication No. 01/27124, The compounds disclosed in Japanese Patent Application Laid-Open No. 11-315109 can be used without limitation.
（チーグラーナッタ触媒）
プロピレン系重合体（Ａ）は、高立体規則性チーグラーナッタ触媒を用いることにより製造することができる。前記高立体規則性チーグラーナッタ触媒としては、公知の種々の触媒が使用できる。たとえば、（ａ）マグネシウム、チタン、ハロゲンおよび電子供与体を含有する固体状チタン触媒成分と、（ｂ）有機金属化合物触媒成分と、（ｃ）シクロペンチル基、シクロペンテニル基、シクロペンタジエニル基およびこれらの誘導体からなる群から選ばれる少なくとも１種の基を有する有機ケイ素化合物触媒成分とからなる触媒を用いることができ、この触媒成分は公知の方法、たとえば国際公開第２０１０／７４００１号の［００７８］～［００９４］に記載の方法で製造することができる。
(Ziegler-Natta catalyst)
The propylene-based polymer (A) can be produced by using a highly stereoregular Ziegler-Natta catalyst. Various known catalysts can be used as the highly stereoregular Ziegler-Natta catalyst. For example, (a) a solid titanium catalyst component containing magnesium, titanium, a halogen and an electron donor, (b) an organometallic compound catalyst component, (c) a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, and A catalyst consisting of an organosilicon compound catalyst component having at least one group selected from the group consisting of these derivatives can be used, and this catalyst component is prepared by a known method, for example, [0078 ] to [0094].
上記のような固体状チタン触媒成分（ａ）、有機金属化合物触媒成分（ｂ）、および有機ケイ素化合物触媒成分（ｃ）からなる触媒を用いてプロピレンの重合を行うに際して、予め予備重合を行うこともできる。予備重合は、固体状チタン触媒成分（ａ）、有機金属化合物触媒成分（ｂ）、および必要に応じて有機ケイ素化合物触媒成分（ｃ）の存在下に、オレフィンを重合させる。 When propylene is polymerized using a catalyst comprising the solid titanium catalyst component (a), the organometallic compound catalyst component (b), and the organosilicon compound catalyst component (c) as described above, prepolymerization is carried out in advance. can also The prepolymerization polymerizes the olefin in the presence of the solid titanium catalyst component (a), the organometallic compound catalyst component (b), and optionally the organosilicon compound catalyst component (c).
予備重合するオレフィンとしては、炭素数２～８のα－オレフィンを用いることができる。具体的には、エチレン、プロピレン、１－ブテン、１－オクテンなどの直鎖状のオレフィン；３－メチル－１－ブテン、３－メチル－１－ペンテン、３－エチル－１－ペンテン、４－メチル－１－ペンテン、４－メチル－１－ヘキセン、４,４－ジメチル－１－ヘキセン、４,４－ジメチル－１－ペンテン、４－エチル－１－ヘキセン、３－エチル－１－ヘキセンなどの分岐構造を有するオレフィン等を用いることができる。これらは共重合させてもよい。 As the olefin to be prepolymerized, an α-olefin having 2 to 8 carbon atoms can be used. Specifically, linear olefins such as ethylene, propylene, 1-butene, 1-octene; 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, etc. An olefin having a branched structure of can be used. These may be copolymerized.
予備重合は、固体状チタン触媒成分（ａ）１ｇ当り０．１～１０００ｇ程度、好ましくは０．３～５００ｇ程度の重合体が生成するように行うことが望ましい。予備重合量が多すぎると、本重合における（共）重合体の生成効率が低下することがある。予備重合では、本重合における系内の触媒濃度よりもかなり高い濃度で触媒を用いることができる。 The prepolymerization is desirably carried out so that about 0.1 to 1000 g, preferably about 0.3 to 500 g of polymer is produced per 1 g of the solid titanium catalyst component (a). If the prepolymerization amount is too large, the production efficiency of the (co)polymer in the main polymerization may decrease. In the prepolymerization, the catalyst can be used at a much higher concentration than in the system in the main polymerization.
本重合の際には、固体状チタン触媒成分（ａ）（または予備重合触媒）を重合容積１Ｌ当りチタン原子に換算して約０．０００１～５０ミリモル、好ましくは約０．００１～１０ミリモルの量で用いることが望ましい。有機金属化合物触媒成分（ｂ）は、金属原子の量に換算して、重合系中のチタン原子１モルに対して約１～２０００モル、好ましくは約２～５００モル程度の量で用いることが望ましい。有機ケイ素化合物触媒成分（ｃ）は、有機金属化合物触媒成分（ｂ）の金属原子１モル当り約０．００１～５０モル、好ましくは約０．０１～２０モル程度の量で用いることが望ましい。 In the main polymerization, about 0.0001 to 50 millimoles, preferably about 0.001 to 10 millimoles of the solid titanium catalyst component (a) (or prepolymerization catalyst) is converted to titanium atoms per liter of polymerization volume. It is desirable to use it in quantity. The organometallic compound catalyst component (b) can be used in an amount of about 1 to 2000 mol, preferably about 2 to 500 mol, in terms of the amount of metal atoms, per 1 mol of titanium atoms in the polymerization system. desirable. The organosilicon compound catalyst component (c) is desirably used in an amount of about 0.001 to 50 mol, preferably about 0.01 to 20 mol, per 1 mol of the metal atom in the organometallic compound catalyst component (b).
〈プロピレン系重合体（Ａ）の製造方法〉
前記プロピレン系重合体（Ａ）は、前述のメタロセン化合物含有触媒存在下、またはチーグラーナッタ触媒存在下でプロピレンおよびエチレンを共重合することにより得られる。
<Method for Producing Propylene Polymer (A)>
The propylene-based polymer (A) is obtained by copolymerizing propylene and ethylene in the presence of the aforementioned metallocene compound-containing catalyst or in the presence of a Ziegler-Natta catalyst.
連続多段重合により前記プロピレン系重合体（Ａ）を製造する場合、各段においてはプロピレンを単独重合させるか、またはプロピレンとエチレンとを共重合させる。
重合は、気相重合法あるいは溶液重合法、懸濁重合法などの液相重合法いずれで行ってもよく、各段を別々の方法で行ってもよい。また連続式、半連続式のいずれの方式で行ってもよく、各段を複数の重合器たとえば２～１０器の重合器に分けて行ってもよい。工業的には連続式の方法で重合することが最も好ましく、この場合２段目以降の重合を２器以上の重合器に分けて行うことが好ましく、これによりゲルの発生を抑制することができる。
When the propylene-based polymer (A) is produced by continuous multi-stage polymerization, propylene is homopolymerized or propylene and ethylene are copolymerized in each stage.
The polymerization may be carried out by any of a gas phase polymerization method, a liquid phase polymerization method such as a solution polymerization method and a suspension polymerization method, and each stage may be carried out by a separate method. Further, the polymerization may be conducted by either a continuous system or a semi-continuous system, and each stage may be divided into a plurality of polymerization vessels, for example, 2 to 10 polymerization vessels. Industrially, it is most preferable to carry out polymerization by a continuous method. In this case, it is preferable to carry out the second and subsequent polymerizations in two or more polymerization vessels, thereby suppressing the generation of gel. .
重合媒体として、不活性炭化水素類を用いてもよく、また液状のプロピレンを重合媒体としてもよい。また各段の重合条件は、重合温度が約－５０～＋２００℃、好ましくは約２０～１００℃の範囲で、また重合圧力が常圧～１０ＭＰａ（ゲージ圧）、好ましくは約０．２～５ＭＰａ（ゲージ圧）の範囲内で適宜選択される。 As the polymerization medium, inert hydrocarbons may be used, and liquid propylene may be used as the polymerization medium. The polymerization conditions for each stage are such that the polymerization temperature is in the range of about −50 to +200° C., preferably about 20 to 100° C., and the polymerization pressure is normal pressure to 10 MPa (gauge pressure), preferably about 0.2 to 5 MPa. (gauge pressure).
プロピレン系重合体（Ａ）は、たとえば、２つ以上の重合器を直列につなげた反応装置で、次の二つの工程（［工程１］および［工程２］）を連続的に実施することによって得られる。プロピレン系重合体（Ａ）の製造の際には、二つ以上の反応機を直列に連結した重合装置を用いそれぞれの重合装置で［工程１］を行ってもよく、また二つ以上の反応機を直列に連結した重合装置を用いそれぞれの重合装置で［工程２］を行ってもよい。また、［工程１］と［工程２］とを別々に行い、それぞれで得られた重合体を単軸押出機、多軸押出機、ニーダー、バンバリーミキサーなどを用いて溶融混練し、プロピレン系重合体（Ａ）を製造してもよい。 The propylene-based polymer (A) can be prepared, for example, by continuously performing the following two steps ([step 1] and [step 2]) in a reactor in which two or more polymerization vessels are connected in series. can get. In the production of the propylene-based polymer (A), a polymerization apparatus in which two or more reactors are connected in series may be used and [Step 1] may be performed in each polymerization apparatus. [Step 2] may be performed in each of the polymerization apparatuses connected in series. Further, [Step 1] and [Step 2] are performed separately, and the polymers obtained in each are melt-kneaded using a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer, etc., and propylene-based polymer Coalescence (A) may be produced.
以下、［工程１］と［工程２］とを連続して実施することによりプロピレン系重合体（Ａ）を製造する方法について記載する。 A method for producing the propylene-based polymer (A) by continuously performing [Step 1] and [Step 2] will be described below.
［工程１］は、重合温度０～１００℃、重合圧力常圧～５ＭＰａゲージ圧で、プロピレンを重合させる工程であって、Ｄinsolの主成分となるプロピレン系重合体を製造する工程である。剛性に優れる成形体を得るにはプロピレンのみを重合させることが好ましく、また、必要に応じて水素ガスに代表される連鎖移動剤も導入し、［工程１］で生成される重合体の極限粘度［ηinsol］を調整してもよい。 [Step 1] is a step of polymerizing propylene at a polymerization temperature of 0 to 100° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure to produce a propylene-based polymer that is the main component of D insol . In order to obtain a molded article with excellent rigidity, it is preferable to polymerize only propylene, and if necessary, a chain transfer agent typified by hydrogen gas is also introduced to reduce the intrinsic viscosity of the polymer produced in [Step 1]. [η insol ] may be adjusted.
また、上記方法以外でも、重合で得られたプロピレン系重合体を有機過酸化物存在下で溶融混練処理することによりメルトフローレート（ＭＦＲ）（ＪＩＳ Ｋ ７２１０、測定温度２３０℃、荷重２．１６ｋｇ）を調整することができる。重合で得られたプロピレン系重合体を、有機過酸化物存在下での溶融混練処理を行うことにより該ＭＦＲは高くなり、有機過酸化物存在下での溶融混練処理を行う際の有機過酸化物の添加量を増やすことで該ＭＦＲはより高くなる。重合で得られたプロピレン系重合体を有機過酸化物存在下で溶融混練処理する場合、プロピレン系重合体１００質量部に対して有機過酸化物を０．００５から０．０５質量部の間で使用することが望ましい。また、上記有機過酸化物存在下での溶融混練処理は、下記後処理工程後に行ってもよい。 In addition to the above method, melt flow rate (MFR) (JIS K 7210, measurement temperature 230 ° C., load 2.16 kg) can be obtained by melt-kneading a propylene polymer obtained by polymerization in the presence of an organic peroxide. ) can be adjusted. By subjecting the propylene-based polymer obtained by polymerization to a melt-kneading treatment in the presence of an organic peroxide, the MFR increases, and when the melt-kneading treatment is performed in the presence of an organic peroxide, the organic peroxide The MFR becomes higher by increasing the addition amount of the compound. When the propylene-based polymer obtained by polymerization is melt-kneaded in the presence of an organic peroxide, 0.005 to 0.05 parts by mass of the organic peroxide is added to 100 parts by mass of the propylene-based polymer. It is preferable to use Moreover, the melt-kneading treatment in the presence of the organic peroxide may be performed after the following post-treatment step.
上記有機過酸化物存在下での溶融混練処理で使用することができる有機過酸化物としては、特に限定はされないが、ベンゾイルパーオキサイド、ｔ－ブチルパーベンゾエート、ｔ－ブチルパーアセテート、ｔ－ブチルパーオキシイソプロピルカーボネート、２，５－ジ－メチル－２，５－ジ－（ベンゾイルパーオキシ）ヘキサン、２，５－ジ－メチル－２，５－ジ－（ベンゾイルパーオキシ）ヘキシン－３、ｔ－ブチル－ジ－パーアジペート、ｔ－ブチルパーオキシ－３，５，５－トリメチルヘキサノエート、メチル－エチルケトンパーオキサイド、シクロヘキサノンパーオキサイド、ジ－ｔ－ブチルパーオキサイド、ジキユミルパーオキサイド、２，５－ジ－メチル－２，５－ジ－（ｔ－ブチルパーオキシ）ヘキサン、２，５－ジ－メチル－２，５－ジ－（ｔ－ブチルパーオキシ）ヘキシン－３、１，３－ビス－（ｔ－ブチルパーオキシイソプロピル）ベンゼン、ｔ－ブチルキユミルパーオキサイド、１，１－ビス－（ｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、１，１－ビス－（ｔ－ブチルパーオキシ）シクロヘキサン、２，２－ビス－（ｔ－ブチルパーオキシ）ブタン、ｐ－メンタンハイドロパーオキサイド、ジ－イソプロピルベンゼンハイドロパーオキサイド、キユメンハイドロパーオキサイド、ｔ－ブチルハイドロパーオキサイド、ｐ－サイメンハイドロパーオキサイド、１，１，３，３－テトラ－メチルブチルハイドロパーオキサイドもしくは２，５－ジ－メチル－２，５－ジ－（ハイドロパーオキシ）ヘキサンなどの有機過酸化物を例示できる。また、これらのうち、２，５－ジ－メチル－２，５－ジ－（ベンゾイルパーオキシ）ヘキサン、１，３－ビス－（ｔ－ブチルパーオキシイソプロピル）ベンゼンがより好ましい。 The organic peroxide that can be used in the melt-kneading treatment in the presence of the organic peroxide is not particularly limited, but benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl Peroxyisopropyl carbonate, 2,5-dimethyl-2,5-di-(benzoylperoxy)hexane, 2,5-dimethyl-2,5-di-(benzoylperoxy)hexyne-3, t -butyl-di-peradipate, t-butylperoxy-3,5,5-trimethylhexanoate, methyl-ethylketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dicumyl peroxide, 2 ,5-di-methyl-2,5-di-(t-butylperoxy)hexane, 2,5-di-methyl-2,5-di-(t-butylperoxy)hexyne-3, 1,3 -bis-(t-butylperoxyisopropyl)benzene, t-butylcymyl peroxide, 1,1-bis-(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis- (t-butylperoxy)cyclohexane, 2,2-bis-(t-butylperoxy)butane, p-menthane hydroperoxide, di-isopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide organic peroxides such as oxides, p-cymen hydroperoxide, 1,1,3,3-tetra-methylbutyl hydroperoxide or 2,5-di-methyl-2,5-di-(hydroperoxy)hexane I can exemplify things. Among these, 2,5-di-methyl-2,5-di-(benzoylperoxy)hexane and 1,3-bis-(t-butylperoxyisopropyl)benzene are more preferred.
［工程２］は、重合温度０～１００℃、重合圧力常圧～５ＭＰａゲージ圧で、プロピレンとエチレンとを共重合させる工程であって、プロピレンのフィード量に対するエチレンのフィード量の割合を［工程１］のときよりも大きくすることによって、Ｄsolの主成分となるプロピレン・エチレン共重合体（エラストマー）を製造する工程である。必要に応じて水素ガスに代表される連鎖移動剤も導入し、［工程２］で生成される重合体の極限粘度［ηsol］を調整してもよい。 [Step 2] is a step of copolymerizing propylene and ethylene at a polymerization temperature of 0 to 100° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure. 1] to produce a propylene-ethylene copolymer (elastomer), which is the main component of Dsol . If necessary, a chain transfer agent typified by hydrogen gas may be introduced to adjust the intrinsic viscosity [η sol ] of the polymer produced in [Step 2].
［工程１］は、重合温度０～１００℃、重合圧力常圧～５ＭＰａゲージ圧で、プロピレンを重合させる工程であって、Ｄinsolの主成分となるプロピレン単独重合体を製造する工程である。また、必要に応じて水素ガスに代表される連鎖移動剤も導入し、［工程１］で生成される重合体の極限粘度［ηinsol］を調整してもよい。 [Step 1] is a step of polymerizing propylene at a polymerization temperature of 0 to 100° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure to produce a propylene homopolymer, which is the main component of D insol . If necessary, a chain transfer agent typified by hydrogen gas may also be introduced to adjust the intrinsic viscosity [η insol ] of the polymer produced in [Step 1].
また、上記方法以外でも、重合で得られたプロピレン系重合体を有機過酸化物の存在下で溶融混練処理することによりＭＦＲAを調整することができる。重合で得られたプロピレン系重合体を、有機過酸化物存在下での溶融混練処理を行うことによりＭＦＲAは高くなり、有機過酸化物存在下での溶融混練処理を行う際の有機過酸化物の添加量を増やすことでＭＦＲAはより高くなる。重合で得られたプロピレン系重合体を有機過酸化物存在下で溶融混練処理する場合、有機過酸化物は、プロピレン系重合体１００質量部に対して０．００５～０．０５質量部使用することが望ましい。また、上記有機過酸化物存在下での溶融混練処理は、下記後処理工程後に行ってもよい。有機過酸化物としては、特に限定はなく、従来公知の有機過酸化物、たとえば２，５－ジ－メチル－２，５－ジ－（ベンゾイルパーオキシ）ヘキサン、および１，３－ビス－（ｔ－ブチルパーオキシイソプロピル）ベンゼン）が挙げられる。 In addition to the above method, the MFR A can also be adjusted by subjecting the propylene-based polymer obtained by polymerization to a melt-kneading treatment in the presence of an organic peroxide. By subjecting the propylene-based polymer obtained by polymerization to a melt-kneading treatment in the presence of an organic peroxide, the MFR A becomes higher, and the organic peroxide is reduced when the melt-kneading treatment is performed in the presence of an organic peroxide. The MFR A becomes higher by increasing the amount of additive added. When the propylene-based polymer obtained by polymerization is melt-kneaded in the presence of an organic peroxide, the organic peroxide is used in an amount of 0.005 to 0.05 parts by mass with respect to 100 parts by mass of the propylene-based polymer. is desirable. Moreover, the melt-kneading treatment in the presence of the organic peroxide may be performed after the following post-treatment step. The organic peroxide is not particularly limited, and conventionally known organic peroxides such as 2,5-di-methyl-2,5-di-(benzoylperoxy)hexane and 1,3-bis-( t-butylperoxyisopropyl)benzene).
要件（Ａ３）における前記Ｄinsolの割合および前記Ｄsolの割合は、上記［工程１］および［工程２］の重合時間を調整することにより、調整することが出来る。つまり、全重合時間に占める［工程１］の重合時間の割合を高めることで、Ｄinsolの割合を大きく、Ｄsolの割合を小さくすることが出来る。また、全重合時間に占める［工程２］の重合時間の割合を高めることで、Ｄinsolの割合を小さく、Ｄsolの割合を大きくすることが出来る。 The ratio of D insol and the ratio of D sol in requirement (A3) can be adjusted by adjusting the polymerization time in [Step 1] and [Step 2]. That is, by increasing the proportion of the polymerization time in [Step 1] in the total polymerization time, the proportion of D insol can be increased and the proportion of D sol can be decreased. Further, by increasing the ratio of the polymerization time of [Step 2] to the total polymerization time, the ratio of D insol can be decreased and the ratio of D sol can be increased.
要件（Ａ４）における前記Ｄsolに占めるエチレン由来の構成単位の割合は、［工程２］を行う際のプロピレンフィード量に対するエチレンフィード量の割合を調整することにより調整できる。つまり、このフィード量の割合を大きくすることにより、前記構成単位の割合を大きくすることができ、このフィード量の割合を小さくすることにより、前記構成単位の割合を小さくすることができる。 The ratio of ethylene-derived structural units in D sol in requirement (A4) can be adjusted by adjusting the ratio of the ethylene feed amount to the propylene feed amount when performing [Step 2]. That is, by increasing the feed rate, the proportion of the structural unit can be increased, and by decreasing the feed rate, the proportion of the structural unit can be decreased.
要件（Ａ５）における極限粘度［ηsol］は、［工程２］を行う際の連鎖移動剤として用いる水素ガスのフィード量により調整できる。つまり、モノマー（すなわち、プロピレンおよびエチレン）のフィード量に対する水素ガスのフィード量の割合を大きくすることにより極限粘度［ηsol］を小さくすることができ、モノマーのフィード量に対する水素ガスのフィード量の割合を小さくすることにより極限粘度［ηsol］を大きくすることができる。 The limiting viscosity [η sol ] in the requirement (A5) can be adjusted by adjusting the feed amount of hydrogen gas used as a chain transfer agent when performing [Step 2]. In other words, the limiting viscosity [η sol ] can be decreased by increasing the ratio of the hydrogen gas feed rate to the monomer (i.e., propylene and ethylene) feed rate, and the ratio of the hydrogen gas feed rate to the monomer feed rate is By decreasing the ratio, the intrinsic viscosity [η sol ] can be increased.
重合終了後、必要に応じて公知の触媒失活処理工程、触媒残渣除去工程、乾燥工程等の後処理工程を行うことにより、プロピレン系重合体（Ａ）がパウダーとして得られる。
また、プロピレン系重合体（Ａ）として市販品を使用してもよい。
After completion of the polymerization, the propylene-based polymer (A) is obtained as a powder by carrying out known post-treatment steps such as a catalyst deactivation treatment step, a catalyst residue removal step, a drying step, and the like, if necessary.
Moreover, you may use a commercial item as a propylene-type polymer (A).
＜エチレン系重合体（Ｂ）＞
本発明のプロピレン系樹脂組成物を構成する成分の一つであるエチレン系重合体（Ｂ）は、下記要件（Ｂ１）および（Ｂ２）を満たすエチレンの単独重合体またはエチレンとα－オレフィンとの共重合体である。
<Ethylene polymer (B)>
The ethylene-based polymer (B), which is one of the components constituting the propylene-based resin composition of the present invention, is an ethylene homopolymer or a mixture of ethylene and α-olefin that satisfies the following requirements (B1) and (B2). It is a copolymer.
前記α－オレフィンとしては炭素数３～２０のα－オレフィンが挙げられ、その例としてはプロピレン、１－ブテン、１－ペンテン、３－メチル－１－ブテン、１－ヘキセン、４－メチル－１－ペンテン、３－メチル－１－ペンテン、１－オクテン、１－デセン、１－ドデセン、１－テトラデセン、１－ヘキサデセン、１－オクタデセン、１－エイコセンなどが挙げられる。 Examples of the α-olefins include α-olefins having 3 to 20 carbon atoms, examples of which include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1 -pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like.
〔要件（Ｂ１）〕
ＪＩＳ Ｋ ７２１０に準拠して、測定温度１９０℃、荷重２．１６ｋｇで測定したメルトフローレート（ＭＦＲB）が、１ｇ／１０分以上、３０ｇ／１０分未満、好ましくは１～２０ｇ／１０分、より好ましくは１～１０ｇ／１０分である。
[Requirements (B1)]
According to JIS K 7210, the melt flow rate (MFR B ) measured at a measurement temperature of 190 ° C. and a load of 2.16 kg is 1 g / 10 minutes or more and less than 30 g / 10 minutes, preferably 1 to 20 g / 10 minutes, More preferably, it is 1 to 10 g/10 minutes.
エチレン系重合体（Ｂ）のＭＦＲが上記範囲を下回ると、プロピレン系樹脂組成物から得られた成形体の耐衝撃性が劣る傾向がある。これは分子量が高くなると、分散不良を起こすためと考えられる。上記範囲を上回ると、プロピレン系樹脂組成物から得られた成形体の耐衝撃性が劣る傾向がある。これは分子量が低くなると、衝撃に対しての吸収エネルギーが低くなるためと考えられる。 If the MFR of the ethylene-based polymer (B) is below the above range, the molded article obtained from the propylene-based resin composition tends to have poor impact resistance. It is considered that this is because the higher the molecular weight, the poorer the dispersion. When the above range is exceeded, the impact resistance of the molded article obtained from the propylene-based resin composition tends to be poor. It is considered that this is because the lower the molecular weight, the lower the absorption energy against impact.
〔要件（Ｂ２）〕
密度が９５０～９６６ｋｇ／ｍ3で、好ましくは９５５～９６６ｋｇ／ｍ3、より好ましくは９６０～９６６ｋｇ／ｍ3である。
[Requirements (B2)]
The density is 950-966 kg/m 3 , preferably 955-966 kg/m 3 , more preferably 960-966 kg/m 3 .
なお、エチレン系重合体（Ｂ）の密度の値は、エチレン系重合体（Ｂ）のＭＦＲ測定時に得られるストランドを、１２０℃で１時間熱処理し、１時間かけて室温まで徐冷したものをサンプルとして用い、密度勾配管法によって測定した場合のものである。
本発明に係るエチレン・α－オレフィン共重合体（Ｂ）は、従来公知の方法で製造することができる。
The value of the density of the ethylene polymer (B) is obtained by heat-treating the strand obtained when measuring the MFR of the ethylene polymer (B) at 120°C for 1 hour and slowly cooling it to room temperature over 1 hour. It was measured by the density gradient tube method using it as a sample.
The ethylene/α-olefin copolymer (B) according to the present invention can be produced by a conventionally known method.
要件（Ｂ１）におけるＭＦＲBは、エチレンあるいはエチレンおよびα－オレフィンを共重合してエチレン系重合体（Ｂ）を製造する際に、エチレンあるいはエチレンおよびα－オレフィンのフィード量に対する連鎖移動剤としての水素ガスのフィード量の割合を調整することにより調整できる。すなわち、この割合を大きくすることでＭＦＲBを高くすることができ、この割合を小さくすることでＭＦＲBを低くすることができる。 MFR B in requirement (B1) is a chain transfer agent for the feed amount of ethylene or ethylene and α-olefin when copolymerizing ethylene or ethylene and α-olefin to produce ethylene polymer (B) It can be adjusted by adjusting the ratio of the feed amount of hydrogen gas. That is, the MFR B can be increased by increasing this ratio, and the MFR B can be decreased by decreasing this ratio.
要件（Ｂ２）における密度は、エチレンあるいはエチレンおよびα－オレフィンを共重合してエチレン系重合体（Ｂ）を製造する際の、エチレンフィード量に対するα－オレフィンフィード量の割合を調整することにより調整できる。つまり、α－オレフィンのフィード量を大きくすることにより、密度を低くすることができ、α－オレフィンのフィード量を小さくすることにより、密度を高くすることができる。
また、エチレン系重合体（Ｂ）として市販品を使用してもよい。市販品の例としては、プライムポリマー社製のハイゼックスや日本ポリエチレン社製のノバテック等が挙げられる。
The density in the requirement (B2) is adjusted by adjusting the ratio of the α-olefin feed amount to the ethylene feed amount when ethylene or ethylene and α-olefin are copolymerized to produce the ethylene polymer (B). can. That is, the density can be lowered by increasing the feed amount of the α-olefin, and the density can be increased by decreasing the feed amount of the α-olefin.
Moreover, you may use a commercial item as an ethylene polymer (B). Examples of commercially available products include HI-ZEX manufactured by Prime Polymer Co., Ltd., Novatec manufactured by Nippon Polyethylene Co., Ltd., and the like.
＜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、上記プロピレン系重合体（Ａ）を８５～９５質量部、好ましくは８５～９４質量部、および上記エチレン系重合体（Ｂ）を５～１５質量部、好ましくは６～１５質量部〔ただし、プロピレン系重合体（Ａ）とエチレン系重合体（Ｂ）の合計量を１００質量部とする。〕を含む組成物である。
<Propylene resin composition>
The propylene-based resin composition of the present invention contains 85 to 95 parts by mass, preferably 85 to 94 parts by mass, of the propylene polymer (A), and 5 to 15 parts by mass, preferably 5 to 15 parts by mass, of the ethylene polymer (B). is 6 to 15 parts by mass [where the total amount of the propylene-based polymer (A) and the ethylene-based polymer (B) is 100 parts by mass. ] is a composition containing.
エチレン系重合体（Ｂ）の量が上記範囲を下回ると、プロピレン系樹脂組成物から得られた成形体のヒケ白化の改良効果が劣る傾向にある。これは成形収縮時に生じる応力を分散し、吸収する効果が低くなるためと考えられる。またエチレン系重合体（Ｂ）の量が上記範囲を上回ると、プロピレン系樹脂組成物から得られた成形体の剛性が劣る傾向にある。これは、剛性に寄与するプロピレン系重合体（Ａ）の成分が減少するためと考えられる。 If the amount of the ethylene-based polymer (B) is less than the above range, the effect of improving whitening of sink marks in the molded article obtained from the propylene-based resin composition tends to be inferior. It is considered that this is because the effect of dispersing and absorbing the stress generated during molding shrinkage is reduced. If the amount of the ethylene-based polymer (B) exceeds the above range, the molded article obtained from the propylene-based resin composition tends to have poor rigidity. It is considered that this is because the component of the propylene-based polymer (A) that contributes to rigidity is reduced.
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）およびエチレン系重合体（Ｂ）に加え、好ましくは、下記造核剤を、プロピレン系重合体（Ａ）およびエチレン系重合体（Ｂ）の合計量１００質量部に対して、０．０３～０．２質量部、０．０３～０．４質量部、より好ましくは０．０４～０．２５質量部、さらに好ましくは０．０５～０．１０質量部含む。 In the propylene-based resin composition of the present invention, in addition to the propylene-based polymer (A) and the ethylene-based polymer (B), preferably, the following nucleating agent is added to the propylene-based polymer (A) and the ethylene-based polymer ( 0.03 to 0.2 parts by mass, 0.03 to 0.4 parts by mass, more preferably 0.04 to 0.25 parts by mass, more preferably 0.04 to 0.25 parts by mass with respect to 100 parts by mass of the total amount of B). 05 to 0.10 parts by mass.
〔造核剤（Ｃ）〕
本発明のプロピレン系樹脂組成物に含まれる造核剤としては、特に限定はないが、ソルビトール系造核剤、リン系造核剤、カルボン酸金属塩系造核剤、ポリマー造核剤、無機化合物等が挙げられる。造核剤としては、ソルビトール系造核剤、リン系造核剤、ポリマー造核剤が好ましい。
[Nucleating agent (C)]
The nucleating agent contained in the propylene-based resin composition of the present invention is not particularly limited. compounds and the like. Preferred nucleating agents are sorbitol nucleating agents, phosphorus nucleating agents, and polymer nucleating agents.
ソルビトール系造核剤の具体例としては、１，２，３－トリデオキシ－４，６：５，７－ビス－Ｏ－［（４－プロピルフェニル）メチレン］－ノニトール（該化合物を含む市販品として商品名「ミラッドＮＸ８０００」シリーズ、ミリケン社製（「ＮＸ８０００」は、上記化学物質＋蛍光増白剤＋ブルーミング剤、「ＮＸ８０００Ｋ」は「ＮＸ８０００」の蛍光増白剤抜き、「ＮＸ８０００Ｊ」は蛍光増白剤とブルーミング剤両方抜き）が挙げられる）、１，３，２，４－ジベンジリデンソルビトール、１，３，２，４－ジ－（ｐ－メチルベンジリデン）ソルビトール、１，３－ｐ－クロルベンジリデン－２，４－ｐ－メチルベンジリデンソルビトールが挙げられる。
Specific examples of sorbitol-based nucleating agents include 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonitol (commercially available products containing the compound Product name "Mirad NX8000" series, manufactured by Milliken ("NX8000" is the above chemical substance + fluorescent brightener + blooming agent, "NX8000K" is "NX8000" without fluorescent brightener, "NX8000J" is
リン系造核剤の具体例としては、ナトリウム－ビス－（４－ｔ－ブチルフェニル）フォスフェート、カリウム－ビス－（４－ｔ－ブチルフェニル）フォスフェート、ナトリウム－２，２'－エチリデン－ビス（４，６－ジ－ｔ－ブチルフェニル）フォスフェート、ナトリウム－２，２'－メチレン－ビス（４，６－ジ－ｔ－ブチルフェニル）フォスフェート、ビス（２，４，８，１０－テトラ－ｔ－ブチル－６－ヒドロキシ－１２Ｈ－ジベンゾ〔ｄ，ｇ〕〔１，３，２〕ジオキサホスホシン－６－オキシド）ナトリウム塩（商品名「アデカスタブ（登録商標）ＮＡ－１１」、（株）ＡＤＥＫＡ製）、ビス（２，４，８，１０－テトラ－ｔ－ブチル－６－ヒドロキシ－１２Ｈ－ジベンゾ〔ｄ，ｇ〕〔１，３，２〕ジオキサホスホシン－６－オキシド）水酸化アルミニウム塩を主成分とする複合物（商品名「アデカスタブＮＡ－２１」、（株）ＡＤＥＫＡ製）、リチウム－２，２'－メチレン－ビス（４，６－ジ－ｔ－ブチルフェニル）フォスフェートと１２－ヒドロキシステアリン酸とを含み、かつリチウムを必須性分として含む複合物（商品名「アデカスタブＮＡ－７１」、（株）ＡＤＥＫＡ製）が挙げられる。 Specific examples of phosphorus-based nucleating agents include sodium-bis-(4-t-butylphenyl) phosphate, potassium-bis-(4-t-butylphenyl) phosphate, sodium-2,2'-ethylidene- Bis(4,6-di-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis(4,6-di-t-butylphenyl) phosphate, bis(2,4,8,10 -tetra-t-butyl-6-hydroxy-12H-dibenzo[d,g][1,3,2]dioxaphosphocin-6-oxide) sodium salt (trade name “ADEKASTAB® NA-11”) , manufactured by ADEKA Corporation), bis(2,4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo[d,g][1,3,2]dioxaphosphosine-6- oxide) a composite mainly composed of aluminum hydroxide salt (trade name “ADEKA STAB NA-21” manufactured by ADEKA Corporation), lithium-2,2′-methylene-bis(4,6-di-t-butyl A complex containing phenyl)phosphate and 12-hydroxystearic acid and containing lithium as an essential component (trade name “ADEKA STAB NA-71”, manufactured by ADEKA Corporation) can be mentioned.
カルボン酸金属塩造核剤の具体例としては、ｐ－ｔ－ブチル安息香酸アルミニウム塩、ヒドロキシ－ジ（ｐ－ｔ－ブチル安息香酸）アルミニウム（商品名「ＡＬ－ＰＴＢＢＡ」、ジャパンケムテック製）、アジピン酸アルミニウム、安息香酸ナトリウムが挙げられる。 Specific examples of carboxylic acid metal salt nucleating agents include pt-butylbenzoic acid aluminum salt, hydroxy-di(pt-butylbenzoic acid) aluminum (trade name “AL-PTBBA”, manufactured by Japan Chemtech). , aluminum adipate, and sodium benzoate.
ポリマー造核剤としては分岐状α－オレフィン重合体が好適に用いられる。分岐状α－オレフィン重合体の例として、３－メチル－１－ブテン、３－メチル－１－ペンテン、３－エチル－１－ペンテン、４－メチル－１－ペンテン、４－メチル－１－ヘキセン、４，４－ジメチル－１－ヘキセン、４，４－ジメチル－１－ペンテン、４－エチル－１－ヘキセン、３－エチル－１－ヘキセンの単独重合体、あるいはそれら相互の共重合体、さらにはそれらと他のα－オレフィンとの共重合体を挙げることができる。低温耐衝撃性、剛性の特性が良好であること、および経済性の観点から、特に、３－メチル－１－ブテンの重合体が好ましい。 A branched α-olefin polymer is preferably used as the polymer nucleating agent. Examples of branched α-olefin polymers include 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene , 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene homopolymers, or copolymers thereof, and can include copolymers of them with other α-olefins. Polymers of 3-methyl-1-butene are particularly preferred from the viewpoints of good low-temperature impact resistance and rigidity properties, and economic efficiency.
無機化合物の具体例としては、タルク、マイカ、炭酸カルシウムが挙げられる。
これらの造核剤の中でも、ビス（２，４，８，１０－テトラ－ｔ－ブチル－６－ヒドロキシ－１２Ｈ－ジベンゾ〔ｄ，ｇ〕〔１，３，２〕ジオキサホスホシン－６－オキシド）ナトリウム塩、１，２，３－トリデオキシ－４，６：５，７－ビス－Ｏ－［（４－プロピフェニル）メチレン］－ノニトール、およびヒドロキシ－ジ（ｐ－ｔ－ブチル安息香酸）アルミニウムが好ましい。
Specific examples of inorganic compounds include talc, mica, and calcium carbonate.
Among these nucleating agents, bis(2,4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo[d,g][1,3,2]dioxaphosphosine-6- oxide) sodium salt, 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propiphenyl)methylene]-nonitol, and hydroxy-di(pt-butylbenzoic acid) Aluminum is preferred.
これらの造核剤は１種単独で用いてもよく、２種以上を併用してもよい。
本発明のプロピレン系樹脂組成物が、造核剤（Ｃ）を含有する場合は、当該組成物から形成されるコンテナやパレットなどの大型成形体の剛性に優れる。これは結晶化度の向上による高剛性化によると推定される。
These nucleating agents may be used singly or in combination of two or more.
When the propylene-based resin composition of the present invention contains the nucleating agent (C), the rigidity of large molded articles such as containers and pallets formed from the composition is excellent. It is presumed that this is due to the high rigidity due to the improvement of the degree of crystallinity.
本発明のプロピレン系樹脂組成物は、本発明の目的を損なわない範囲で適宜中和剤、酸化防止剤、熱安定剤、耐候剤、滑剤、紫外線吸収剤、帯電防止剤、アンチブロッキング剤、防曇剤、気泡防止剤、分散剤、難燃剤、抗菌剤、蛍光増白剤、架橋剤、架橋助剤等の添加剤；染料、顔料等の着色剤で例示される成分（以下「他の成分」と記載する。）を含んでいてもよい。 The propylene-based resin composition of the present invention may contain appropriate neutralizing agents, antioxidants, heat stabilizers, weathering agents, lubricants, ultraviolet absorbers, antistatic agents, antiblocking agents, anti-blocking agents, as long as the objects of the present invention are not impaired. Additives such as clouding agents, anti-foaming agents, dispersants, flame retardants, antibacterial agents, fluorescent brightening agents, cross-linking agents, cross-linking aids; ) may be included.
本発明のプロピレン系樹脂組成物が、他の成分を含む場合には、他の成分の量は、プロピレン系重合体（Ａ）およびエチレン系重合体（Ｂ）の合計１００質量部に対して、通常０．０１～５質量部である。 When the propylene-based resin composition of the present invention contains other components, the amount of the other components is It is usually 0.01 to 5 parts by mass.
本発明のプロピレン系樹脂組成物は、ＪＩＳ Ｋ ７２１０に準拠して、測定温度２３０℃、荷重２．１６ｋｇで測定されるメルトフローレート（以下、単に「ＭＦＲ」とも記載する。）が、通常、１～３０ｇ／１０分、好ましくは１～２０ｇ／１０分、より好ましくは１～１５ｇ／１０分である。 The propylene-based resin composition of the present invention has a melt flow rate (hereinafter also simply referred to as "MFR") measured at a measurement temperature of 230°C and a load of 2.16 kg in accordance with JIS K 7210. 1 to 30 g/10 minutes, preferably 1 to 20 g/10 minutes, more preferably 1 to 15 g/10 minutes.
《プロピレン系樹脂組成物の製造方法》
本発明のプロピレン系樹脂組成物の製造方法は特に限定されないが、該製造方法としては、例えば各成分を混練機で溶融混練して、プロピレン系樹脂組成物を製造する方法が挙げられる。混練機として、例えば単軸混練押出機、多軸混練押出機、ニーダー、バンバリーミキサー、ヘンシェルミキサー等が挙げられる。溶融混練条件は、混練時の剪断、加熱温度、剪断による発熱などによって溶融樹脂の劣化が起こらない限り、特に制限されない。溶融樹脂の劣化を防止する観点から、加熱温度を適正に設定したり、酸化防止剤や熱安定剤を添加したりすることは、効果的である。
<<Method for Producing Propylene-Based Resin Composition>>
The production method of the propylene-based resin composition of the present invention is not particularly limited, but examples of the production method include a method of melt-kneading each component in a kneader to produce a propylene-based resin composition. Examples of the kneader include a single-screw kneading extruder, a multi-screw kneading extruder, a kneader, a Banbury mixer, a Henschel mixer, and the like. Melt-kneading conditions are not particularly limited as long as the melted resin is not deteriorated by shearing during kneading, heating temperature, heat generation due to shearing, or the like. From the viewpoint of preventing deterioration of the molten resin, it is effective to appropriately set the heating temperature and add antioxidants and heat stabilizers.
＜成形体＞
本発明の成形体は、上述した本発明のプロピレン系樹脂組成物を含むことを特徴としている。その具体例としては、本発明のプロピレン系樹脂組成物を押出成形、圧縮成形、射出成形したものが挙げられる。これら成形体の中でも、射出成形体が好ましい。
<Molded body>
The molded article of the present invention is characterized by containing the propylene-based resin composition of the present invention described above. Specific examples thereof include extrusion molding, compression molding, and injection molding of the propylene-based resin composition of the present invention. Among these molded articles, injection molded articles are preferred.
本発明の成形体としては、容器、家電部品、住宅設備、日用品、コンテナ、パレットなどの物流用途等が挙げられる。中でも耐衝撃性および剛性の観点からコンテナ、パレットなどの大型成形体が挙げられる。 Examples of the molded article of the present invention include distribution applications such as containers, home appliance parts, housing equipment, daily necessities, containers, and pallets. Among them, large moldings such as containers and pallets are mentioned from the viewpoint of impact resistance and rigidity.
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。
実施例および比較例で用いた重合体の物性は、以下の方法により、測定した。
EXAMPLES Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these.
The physical properties of the polymers used in Examples and Comparative Examples were measured by the following methods.
＜プロピレン系重合体（Ａ）の物性＞
〔ＭＦＲA〕
プロピレン系重合体のペレットのメルトフローレイト（ＭＦＲA）は、ＪＩＳ Ｋ ７２１０（２３０℃、２．１６ｋｇ荷重）に準拠して測定した。
<Properties of propylene-based polymer (A)>
[ MFRA ]
The melt flow rate (MFR A ) of the propylene-based polymer pellets was measured according to JIS K 7210 (230° C., 2.16 kg load).
〔ＤinsolおよびＤsol量〕
プロピレン系重合体（Ａ）のＤinsolおよびＤsolの割合は以下の方法により求めた。
プロピレン系重合体（Ａ）のサンプル５ｇにｎ－デカン２００ｍＬを加え、１４５℃、３０分間加熱溶解を行い、溶液（１）を得る。
[D insol and D sol amounts]
The ratios of D insol and D sol of the propylene-based polymer (A) were obtained by the following method.
200 mL of n-decane is added to 5 g of a sample of the propylene-based polymer (A) and dissolved by heating at 145° C. for 30 minutes to obtain a solution (1).
次に約２時間かけて、溶液を室温２５℃まで冷却を行い、２５℃で３０分間放置し、析出物（α）を含む溶液（２）を得る。
その後、溶液（２）から析出物（α）を目開き約１５μｍの濾布でろ別し、析出物（α）を乾燥させた後、析出物（α）の質量を測定する。該析出物（α）の質量をサンプル質量（５ｇ）で除したものを、ｎ－デカン不溶部Ｄinsolの割合とする。
Next, the solution is cooled to room temperature of 25° C. over about 2 hours and allowed to stand at 25° C. for 30 minutes to obtain a solution (2) containing a precipitate (α).
After that, the precipitate (α) is separated from the solution (2) by filtration through a filter cloth having an opening of about 15 μm, dried, and then the mass of the precipitate (α) is measured. The ratio of the n-decane insoluble portion D insol is obtained by dividing the mass of the precipitate (α) by the sample mass (5 g).
また、析出物（α）をろ別した溶液（２）を、溶液（２）の約３倍量のアセトン中に入れ、ｎ－デカン中に溶解していた成分を析出させ、析出物（β）を得る。
その後、析出物（β）をガラスフィルター（Ｇ２、目開き約１００～１６０μｍ）でろ別し、乾燥させた後、析出物（β）の質量を測定する。
このときの析出物（β）の質量をサンプル質量（５ｇ）で除したものをｎ－デカン可溶部（Ｄsol）の割合とする。
Further, the solution (2) obtained by filtering the precipitate (α) is placed in about three times the amount of acetone of the solution (2) to precipitate the components dissolved in n-decane, and the precipitate (β ).
After that, the precipitate (β) is filtered through a glass filter (G2, opening about 100 to 160 μm), dried, and then the mass of the precipitate (β) is measured.
The ratio of the n-decane soluble portion (D sol ) is obtained by dividing the mass of the precipitate (β) at this time by the mass of the sample (5 g).
〔Ｄsolの、デカリン中１３５℃で測定した極限粘度［ηsol］〕
プロピレン系重合体（Ａ）の前記Ｄsolの、デカリン中１３５℃で測定した極限粘度［ηsol］は下記のようにして決定した。
サンプルは、前記のＤinsolおよびＤsolの割合を求めた際に得られた析出物（β）を用いた。
このサンプル約２５ｍｇをデカリン２５ｍＬに溶解し、１３５℃のオイルバス中で比粘度ηｓｐを測定する。
[Intrinsic viscosity of D sol measured at 135° C. in decalin [η sol ]]
The intrinsic viscosity [η sol ] of the D sol of the propylene-based polymer (A) measured in decalin at 135° C. was determined as follows.
The sample used was the precipitate (β) obtained when the ratio of D insol and D sol was determined.
About 25 mg of this sample is dissolved in 25 mL of decalin, and the specific viscosity ηsp is measured in an oil bath at 135°C.
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を測定する。
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、この値をＤsolの、デカリン中１３５℃で測定した極限粘度［ηsol］とした。
5 mL of decalin solvent is added to this decalin solution to dilute it, and then the specific viscosity ηsp is measured in the same manner.
This dilution operation is repeated twice, and the value of ηsp /C when the concentration (C) is extrapolated to 0 is obtained as the intrinsic viscosity. sol ].
〔Ｄsol中のエチレンに由来する骨格の含有量〕
プロピレン系重合体（Ａ）の前記Ｄsol中のエチレンに由来する骨格の含有量は13ＣＮＭＲの測定に基づき下記のようにして測定・算出し決定した。
サンプルは、前記のＤinsolおよびＤsolの割合を求めた際に得られた析出物（α）および（β）を用いた。
この析出物（α）および（β）を試料として、下記条件にてそれぞれ13Ｃ－ＮＭＲの測定を行った。
[Content of skeleton derived from ethylene in D sol ]
The content of the skeleton derived from ethylene in the D sol of the propylene-based polymer (A) was measured and calculated as follows based on the measurement of 13 CNMR.
The samples used were precipitates (α) and (β) obtained when the proportions of D insol and D sol were determined.
Using the precipitates (α) and (β) as samples, 13 C-NMR measurements were carried out under the following conditions.
〈13Ｃ-ＮＭＲ測定条件〉
測定装置：日本電子製ＬＡ４００型核磁気共鳴装置
測定モード：ＢＣＭ（Ｂｉｌｅｖｅｌ Ｃｏｍｐｌｅｔｅ ｄｅｃｏｕｐｌｉｎｇ）
観測周波数：１００．４ＭＨｚ
観測範囲：１７００６．８Ｈｚ
パルス幅：Ｃ核４５°(７．８μ秒)
パルス繰り返し時間：５秒
試料管：５ｍｍφ
試料管回転数：１２Ｈｚ
積算回数：２００００回
測定温度：１２５℃
溶媒：１,２,４－トリクロロベンゼン：０．３５ｍＬ／重ベンゼン：０．２ｍＬ
試料量：約４０ｍｇ
< 13 C-NMR measurement conditions>
Measurement device: JEOL LA400 type nuclear magnetic resonance device Measurement mode: BCM (Bilevel Complete decoupling)
Observation frequency: 100.4MHz
Observation range: 17006.8Hz
Pulse width: C nucleus 45° (7.8 μs)
Pulse repetition time: 5 seconds Sample tube: 5 mmφ
Sample tube rotation speed: 12 Hz
Accumulation times: 20000 times Measurement temperature: 125°C
Solvent: 1,2,4-trichlorobenzene: 0.35 mL / deuterated benzene: 0.2 mL
Sample amount: about 40 mg
測定で得られたスペクトルより、下記文献（１）に準じて、モノマー連鎖分布（トリアッド（３連子）分布）の比率を決定し、前記のＤinsolおよびＤsol中のエチレンに由来する構成単位のモル分率（ｍｏｌ％）（以下Ｅ（ｍｏｌ％）と記す）およびプロピレンに由来する構成単位のモル分率（ｍｏｌ％）（以下Ｐ（ｍｏｌ％）と記す）を算出した。求められたＥ（ｍｏｌ％）およびＰ（ｍｏｌ％）から下記（式１）に従い質量％に換算しプロピレン系重合体の前記のＤinsolおよびＤsol中のエチレンに由来する構成単位の含有量（質量％）（以下Ｅ（ｗｔ％）と記す）を算出した。
Ｅ（ｗｔ％）＝Ｅ（ｍｏｌ％）×２８×１００／［Ｐ（ｍｏｌ％）×４２＋Ｅ（ｍｏｌ％）×２８］（式１）
文献（１）：Kakugo,M.; Naito,Y.; Mizunuma,K.; Miyatake,T., Carbon-13 NMR determination of monomer sequence distribution in ethylene-propylene copolymers preparedwith delta-titanium trichloride-diethylaluminum chloride. Macromolecules 1982, 15, (4), 1150-1152
From the spectrum obtained by the measurement, the ratio of the monomer chain distribution (triad (triad) distribution) was determined according to the following document (1), and the structural units derived from ethylene in the above D insol and D sol (hereinafter referred to as E (mol%)) and the molar fraction (mol%) of structural units derived from propylene (hereinafter referred to as P (mol%)) were calculated. The obtained E (mol%) and P (mol%) were converted to mass% according to the following (formula 1), and the content of structural units derived from ethylene in the above D insol and D sol of the propylene-based polymer ( mass%) (hereinafter referred to as E (wt%)) was calculated.
E (wt%) = E (mol%) x 28 x 100/[P (mol%) x 42 + E (mol%) x 28] (Formula 1)
Reference (1): Kakugo, M.; Naito, Y.; Mizunuma, K.; Miyatake, T., Carbon-13 NMR determination of monomer sequence distribution in ethylene-propylene copolymers prepared with delta-titanium trichloride-diethylaluminum chloride. Macromolecules 1982 , 15, (4), 1150-1152
＜エチレン系重合体（Ｂ）の物性＞
〔ＭＦＲB〕
ＪＩＳ Ｋ ７２１０（測定温度１９０℃、荷重２．１６ｋｇ）に従ってメルトフローレート（ＭＦＲB）を測定した。
<Physical properties of the ethylene polymer (B)>
[MFR B ]
The melt flow rate (MFR B ) was measured according to JIS K 7210 (measurement temperature 190° C., load 2.16 kg).
〔密度〕
メルトフローレート測定時（ＡＳＴＭ Ｄ－１２３８）に得られるストランドを、１２０℃で１時間熱処理し、１時間かけて室温まで徐冷したものをサンプルとして用い、密度勾配管法にて密度の測定を行い、エチレン系重合体の密度を決定した。
実施例で用いたプロピレン系重合体（Ａ）および比較例で用いたプロピレン系重合体（Ｅ）は、以下の製造方法で製造したプロピレン系重合体を用いた。
〔density〕
The strand obtained when measuring the melt flow rate (ASTM D-1238) was heat-treated at 120 ° C. for 1 hour and slowly cooled to room temperature over 1 hour, and the density was measured by the density gradient tube method. was performed to determine the density of the ethylene-based polymer.
The propylene-based polymer (A) used in the examples and the propylene-based polymer (E) used in the comparative examples were propylene-based polymers produced by the following production method.
〔プロピレン系重合体（Ａ－１）の製造〕
（１）固体触媒成分の調整
無水塩化マグネシウム９５．２ｇ、デカン４４２ｍＬおよび２－エチルヘキシルアルコール３９０．６ｇを１３０℃で２時間加熱反応を行って均一溶液とした後、この溶液中に無水フタル酸２１．３ｇを添加し、さらに１３０℃にて１時間攪拌混合を行い、無水フタル酸を溶解させた。
[Production of propylene-based polymer (A-1)]
(1) Preparation of Solid Catalyst Component 95.2 g of anhydrous magnesium chloride, 442 mL of decane and 390.6 g of 2-ethylhexyl alcohol were heated at 130° C. for 2 hours to form a homogeneous solution, and then 21 of phthalic anhydride was added to this solution. 3 g was added, and the mixture was further stirred and mixed at 130° C. for 1 hour to dissolve the phthalic anhydride.
このようにして得られた均一溶液を室温に冷却した後、－２０℃に保持した四塩化チタン２００ｍＬ中に、この均一溶液の７５ｍＬを１時間にわたって滴下装入した。装入終了後、この混合液の温度を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）５．２２ｇを添加し、これより２時間同温度にて攪拌保持した。 After the homogeneous solution thus obtained was cooled to room temperature, 75 mL of this homogeneous solution was dropped into 200 mL of titanium tetrachloride maintained at -20° C. over 1 hour. After the completion of charging, the temperature of the mixed solution was raised to 110°C over 4 hours, and when the temperature reached 110°C, 5.22 g of diisobutyl phthalate (DIBP) was added, followed by stirring at the same temperature for 2 hours. held.
２時間の反応終了後、熱濾過にて固体部を採取し、この固体部を２７５ｍＬ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。反応終了後、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にて溶液中に遊離のチタン化合物が検出されなくなるまで充分洗浄した。 After completion of the reaction for 2 hours, the solid portion was collected by hot filtration, resuspended in 275 mL of titanium tetrachloride, and heated again at 110° C. for 2 hours. After completion of the reaction, the solid portion was collected again by hot filtration and thoroughly washed with 110° C. decane and hexane until no free titanium compound was detected in the solution.
ここで、前記遊離チタン化合物の検出は次の方法で確認した。予め窒素置換した１００ｍＬの枝付きシュレンクに上記固体触媒成分の上澄み液１０ｍＬを注射器で採取し装入した。次に、窒素気流にて溶媒ヘキサンを乾燥し、さらに３０分間真空乾燥した。これに、イオン交換水４０ｍＬ、５０容量％硫酸１０ｍＬを装入し３０分間攪拌した。この水溶液をろ紙を通して１００ｍＬメスフラスコに移し、続いて鉄（ＩＩ）イオンのマスキング剤としてｃｏｎｃ．Ｈ3ＰＯ4 １ｍＬとチタンの発色試薬として３％Ｈ2Ｏ2水溶液 ５ｍＬを加え、さらにイオン交換水で１００ｍＬにメスアップした。このメスフラスコを振り混ぜ、２０分後にＵＶを用い４２０ｎｍの吸光度を観測し遊離チタンの検出を行った。この吸収が観測されなくなるまで遊離チタンの洗浄除去および遊離チタンの検出を行った。 Here, the detection of the free titanium compound was confirmed by the following method. 10 mL of the supernatant liquid of the solid catalyst component was collected with a syringe and charged into a 100 mL branched Schlenk tube previously purged with nitrogen. Next, the solvent hexane was dried with a stream of nitrogen, followed by vacuum drying for 30 minutes. 40 mL of ion-exchanged water and 10 mL of 50% by volume sulfuric acid were added thereto and stirred for 30 minutes. This aqueous solution was transferred to a 100 mL volumetric flask through filter paper, followed by conc. 1 mL of H 3 PO 4 and 5 mL of 3% H 2 O 2 aqueous solution as a coloring reagent for titanium were added, and ion-exchanged water was added to make up the volume to 100 mL. This volumetric flask was shaken, and after 20 minutes, free titanium was detected by observing absorbance at 420 nm using UV. Free titanium was washed away and free titanium was detected until this absorption was no longer observed.
上記のように調製された固体状チタン触媒成分（Ａ）は、デカンスラリーとして保存したが、この内の一部は触媒組成を調べる目的で乾燥した。このようにして得られた固体状チタン触媒成分（Ａ）の組成は、チタン２．３質量％、塩素６１質量％、マグネシウム１９質量％、ＤＩＢＰ １２．５質量％であった。 The solid titanium catalyst component (A) prepared as described above was stored as a decane slurry, part of which was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component (A) thus obtained was 2.3% by mass of titanium, 61% by mass of chlorine, 19% by mass of magnesium and 12.5% by mass of DIBP.
（２）予備重合触媒成分の調製
内容積５００ｍＬの攪拌機付きの三つ口フラスコを窒素ガスで置換した後、脱水処理したヘプタンを４００ｍＬ、トリエチルアルミニウム１９．２ｍｍｏｌ、ジシクロペンチルジメトキシシラン３．８ｍｍｏｌ、上記固体状チタン触媒成分（Ａ）４ｇを加えた。内温を２０℃に保持し、攪拌しながらプロピレンを導入した。１時間後、攪拌を停止し結果的に固体状チタン触媒成分（Ａ）１ｇ当たり２ｇのプロピレンが重合した予備重合触媒成分（Ｂ）を得た。
(2) Preparation of Prepolymerization Catalyst Components After purging a 500 mL three-necked flask equipped with a stirrer with nitrogen gas, 400 mL of dehydrated heptane, 19.2 mmol of triethylaluminum, 3.8 mmol of dicyclopentyldimethoxysilane, and the above were added. 4 g of solid titanium catalyst component (A) was added. The internal temperature was maintained at 20° C., and propylene was introduced while stirring. After 1 hour, stirring was stopped to obtain a prepolymerized catalyst component (B) in which 2 g of propylene was polymerized per 1 g of solid titanium catalyst component (A).
（３－１）重合－１（重合［工程１］）
内容積１０Ｌの攪拌機付きステンレス製オートクレーブを十分乾燥し、窒素置換の後、脱水処理したヘプタン６Ｌ、トリエチルアルミニウム１２．５ｍｍｏｌ、ジシクロペンチルジメトキシシラン０．６ｍｍｏｌを加えた。系内の窒素をプロピレンで置換した後に、水素を０．１７ＭＰａ－Ｇ装入した。
内温８０℃、全圧３．２ＭＰａ－Ｇに系内が安定した後、上記予備重合触媒成分（Ｂ）をＴｉ原子換算で０．１０ｍｍｏｌ含んだヘプタンスラリー２０．８ｍＬを加え、プロピレンを連続的に供給しながら８０℃で１時間重合を行った。
(3-1) Polymerization-1 (Polymerization [Step 1])
A 10-L stainless steel autoclave equipped with a stirrer was thoroughly dried and purged with nitrogen, and then 6 L of dehydrated heptane, 12.5 mmol of triethylaluminum, and 0.6 mmol of dicyclopentyldimethoxysilane were added. After replacing nitrogen in the system with propylene, 0.17 MPa-G of hydrogen was introduced.
After the inside of the system stabilized at an internal temperature of 80° C. and a total pressure of 3.2 MPa-G, 20.8 mL of a heptane slurry containing 0.10 mmol of the prepolymerization catalyst component (B) in terms of Ti atoms was added, and propylene was added continuously. Polymerization was carried out at 80° C. for 1 hour while supplying to .
（３－２）重合－２（重合［工程２］）
プロピレン単独重合体の重合終了後（前記［工程１］の後）、内温を３０℃まで降温し脱圧した。その後、水素／エチレン＝０．１０ｍ.ｒ.装入し、続いてエチレン／（エチレン＋プロピレン）＝０．４０ｍ.ｒ.の混合ガスを導入した。内温６０℃、全圧０．６０ＭＰａ－Ｇ（導入ガス量により変動）で５０分間プロピレン／エチレン共重合を行った。
(3-2) Polymerization-2 (Polymerization [Step 2])
After the completion of the polymerization of the propylene homopolymer (after the above [Step 1]), the internal temperature was lowered to 30°C and the pressure was released. After that, hydrogen/ethylene=0.10 m.r. was charged, and then a mixed gas of ethylene/(ethylene+propylene)=0.40 m.r. was introduced. Propylene/ethylene copolymerization was carried out for 50 minutes at an internal temperature of 60° C. and a total pressure of 0.60 MPa-G (varying depending on the amount of introduced gas).
所定時間経過したところで５０ｍＬのメタノールを添加し反応を停止し、降温、脱圧した。内容物を全量フィルター付きろ過槽へ移し６０℃に昇温し固液分離した。更に、６０℃のヘプタン６Ｌで固体部を２回洗浄した。このようにして得られたプロピレン・エチレン共重合体を真空乾燥した。 After a predetermined time, 50 mL of methanol was added to stop the reaction, and the temperature was lowered and the pressure was released. The content was transferred to a filtration tank with a total filter and heated to 60° C. for solid-liquid separation. Furthermore, the solid portion was washed twice with 6 L of heptane at 60°C. The propylene/ethylene copolymer thus obtained was vacuum dried.
得られたプロピレン系重合体（Ａ－１）の、メルトフローレート（ＭＦＲ）（ＪＩＳ Ｋ ７２１０、測定温度２３０℃、荷重２．１６ｋｇ）は５.０ｇ／１０分、Ｄinsolは８８．０質量％、Ｄsolは１２.０質量％、極限粘度［ηsol］は３.３ｄＬ／ｇ、Ｄsol中のエチレンに由来する構成単位の質量が３３.０質量％であった。 The obtained propylene-based polymer (A-1) had a melt flow rate (MFR) (JIS K 7210, measurement temperature of 230°C, load of 2.16 kg) of 5.0 g/10 minutes and D insol of 88.0 mass. %, D sol was 12.0 mass %, the intrinsic viscosity [η sol ] was 3.3 dL/g, and the mass of structural units derived from ethylene in D sol was 33.0 mass %.
〔プロピレン系重合体（Ａ－２）の製造〕
（１）（２）の工程はプロピレン系重合体（Ａ－１）と同様である。
（３－１）重合－１（重合［工程１］）
内容積１０Ｌの攪拌機付きステンレス製オートクレーブを十分乾燥し、窒素置換の後、脱水処理したヘプタン６Ｌ、トリエチルアルミニウム１２．５ｍｍｏｌ、ジシクロペンチルジメトキシシラン０．６ｍｍｏｌを加えた。系内の窒素をプロピレンで置換した後に、水素を０．３５ＭＰａ－Ｇ装入した。
内温８０℃、全圧３．２ＭＰａ－Ｇに系内が安定した後、上記予備重合触媒成分（Ｂ）をＴｉ原子換算で０．１０ｍｍｏｌ含んだヘプタンスラリー２０．８ｍＬを加え、プロピレンを連続的に供給しながら８０℃で１時間重合を行った。
[Production of propylene-based polymer (A-2)]
The steps (1) and (2) are the same as those for the propylene-based polymer (A-1).
(3-1) Polymerization-1 (Polymerization [Step 1])
A 10-L stainless steel autoclave equipped with a stirrer was thoroughly dried and purged with nitrogen, and then 6 L of dehydrated heptane, 12.5 mmol of triethylaluminum, and 0.6 mmol of dicyclopentyldimethoxysilane were added. After replacing nitrogen in the system with propylene, 0.35 MPa-G of hydrogen was introduced.
After the inside of the system stabilized at an internal temperature of 80° C. and a total pressure of 3.2 MPa-G, 20.8 mL of a heptane slurry containing 0.10 mmol of the prepolymerization catalyst component (B) in terms of Ti atoms was added, and propylene was added continuously. Polymerization was carried out at 80° C. for 1 hour while supplying to .
（３－２）重合－２（重合［工程２］）
プロピレン単独重合体の重合終了後（前記［工程１］の後）、内温を３０℃まで降温し脱圧した。その後、水素／エチレン＝０．１０ｍ.ｒ.装入し、続いてエチレン／（エチレン＋プロピレン）＝０．４０ｍ.ｒ.の混合ガスを導入した。内温６０℃、全圧０．６０ＭＰａ－Ｇ（導入ガス量により変動）で５０分間プロピレン／エチレン共重合を行った。
(3-2) Polymerization-2 (Polymerization [Step 2])
After the completion of the polymerization of the propylene homopolymer (after the above [Step 1]), the internal temperature was lowered to 30°C and the pressure was released. After that, hydrogen/ethylene=0.10 m.r. was charged, and then a mixed gas of ethylene/(ethylene+propylene)=0.40 m.r. was introduced. Propylene/ethylene copolymerization was carried out for 50 minutes at an internal temperature of 60° C. and a total pressure of 0.60 MPa-G (varying depending on the amount of introduced gas).
所定時間経過したところで５０ｍＬのメタノールを添加し反応を停止し、降温、脱圧した。内容物を全量フィルター付きろ過槽へ移し６０℃に昇温し固液分離した。更に、６０℃のヘプタン６Ｌで固体部を２回洗浄した。このようにして得られたプロピレン・エチレン共重合体を真空乾燥した。 After a predetermined time, 50 mL of methanol was added to stop the reaction, and the temperature was lowered and the pressure was released. The content was transferred to a filtration tank with a total filter and heated to 60° C. for solid-liquid separation. Furthermore, the solid portion was washed twice with 6 L of heptane at 60°C. The propylene/ethylene copolymer thus obtained was vacuum dried.
得られたプロピレン系重合体（Ａ－２）の、メルトフローレート（ＭＦＲ）（ＪＩＳ Ｋ ７２１０、測定温度２３０℃、荷重２．１６ｋｇ）は１０ｇ／１０分、Ｄinsolは８８.０質量％、Ｄsolは１２．０質量％、極限粘度［ηsol］は３．４ｄＬ／ｇ、Ｄsol中のエチレンに由来する構成単位の質量が３３．０質量％であった。 The obtained propylene-based polymer (A-2) had a melt flow rate (MFR) (JIS K 7210, measurement temperature of 230°C, load of 2.16 kg) of 10 g/10 min, D insol of 88.0% by mass, The D sol was 12.0% by mass, the intrinsic viscosity [η sol ] was 3.4 dL/g, and the mass of structural units derived from ethylene in D sol was 33.0% by mass.
〔プロピレン系重合体（Ｅ－１）の製造〕
（１）（２）の工程はプロピレン系重合体（Ａ－１）と同様である。
（３－１）重合－１（重合［工程１］）
内容積１０Ｌの攪拌機付きステンレス製オートクレーブを十分乾燥し、窒素置換の後、脱水処理したヘプタン６Ｌ、トリエチルアルミニウム１２．５ｍｍｏｌ、ジシクロペンチルジメトキシシラン０．６ｍｍｏｌを加えた。系内の窒素をプロピレンで置換した後に、水素を０．１５ＭＰａ－Ｇ装入した。
内温８０℃、全圧３．２ＭＰａ－Ｇに系内が安定した後、上記予備重合触媒成分（Ｂ）をＴｉ原子換算で０．１０ｍｍｏｌ含んだヘプタンスラリー２０．８ｍＬを加え、プロピレンを連続的に供給しながら８０℃で１時間重合を行った。
[Production of propylene-based polymer (E-1)]
The steps (1) and (2) are the same as those for the propylene-based polymer (A-1).
(3-1) Polymerization-1 (Polymerization [Step 1])
A 10-L stainless steel autoclave equipped with a stirrer was thoroughly dried and purged with nitrogen, and then 6 L of dehydrated heptane, 12.5 mmol of triethylaluminum, and 0.6 mmol of dicyclopentyldimethoxysilane were added. After replacing nitrogen in the system with propylene, 0.15 MPa-G of hydrogen was introduced.
After the inside of the system stabilized at an internal temperature of 80° C. and a total pressure of 3.2 MPa-G, 20.8 mL of a heptane slurry containing 0.10 mmol of the prepolymerization catalyst component (B) in terms of Ti atoms was added, and propylene was added continuously. Polymerization was carried out at 80° C. for 1 hour while supplying to .
（３－２）重合－２（重合［工程２］）
プロピレン単独重合体の重合終了後（前記［工程１］の後）、内温を３０℃まで降温し脱圧した。その後、水素／エチレン＝０．２０ｍ.ｒ.装入し、続いてエチレン／（エチレン＋プロピレン）＝０．４０ｍ.ｒ.の混合ガスを導入した。内温６０℃、全圧０．６０ＭＰａ－Ｇ（導入ガス量により変動）で５０分間プロピレン／エチレン共重合を行った。
(3-2) Polymerization-2 (Polymerization [Step 2])
After the completion of the polymerization of the propylene homopolymer (after the above [Step 1]), the internal temperature was lowered to 30°C and the pressure was released. After that, hydrogen/ethylene=0.20 m.r. was charged, and then a mixed gas of ethylene/(ethylene+propylene)=0.40 m.r. was introduced. Propylene/ethylene copolymerization was carried out for 50 minutes at an internal temperature of 60° C. and a total pressure of 0.60 MPa-G (varying depending on the amount of introduced gas).
所定時間経過したところで５０ｍＬのメタノールを添加し反応を停止し、降温、脱圧した。内容物を全量フィルター付きろ過槽へ移し６０℃に昇温し固液分離した。更に、６０℃のヘプタン６Ｌで固体部を２回洗浄した。このようにして得られたプロピレン・エチレン共重合体を真空乾燥した。 After a predetermined time, 50 mL of methanol was added to stop the reaction, and the temperature was lowered and the pressure was released. The content was transferred to a filtration tank with a total filter and heated to 60° C. for solid-liquid separation. Furthermore, the solid portion was washed twice with 6 L of heptane at 60°C. The propylene/ethylene copolymer thus obtained was vacuum dried.
得られたプロピレン系重合体（Ｅ－１）の、メルトフローレート（ＭＦＲ）（ＪＩＳ Ｋ ７２１０、測定温度２３０℃、荷重２．１６ｋｇ）は５.０ｇ／１０分、Ｄinsolは８８．０質量％、Ｄsolは１２.０質量％、極限粘度［ηsol］は２.０ｄＬ／ｇ、Ｄsol中のエチレンに由来する構成単位の質量が３３.０質量％であった。 The obtained propylene-based polymer (E-1) had a melt flow rate (MFR) (JIS K 7210, measurement temperature of 230°C, load of 2.16 kg) of 5.0 g/10 min, and D insol of 88.0 mass. %, D sol was 12.0% by mass, the intrinsic viscosity [η sol ] was 2.0 dL/g, and the mass of structural units derived from ethylene in D sol was 33.0% by mass.
〔プロピレン系重合体（Ｅ－２）の製造〕
（１）（２）の工程はプロピレン系重合体（Ａ－１）と同様である。
（３－１）重合－１（重合［工程１］）
内容積１０Ｌの攪拌機付きステンレス製オートクレーブを十分乾燥し、窒素置換の後、脱水処理したヘプタン６Ｌ、トリエチルアルミニウム１２．５ｍｍｏｌ、ジシクロペンチルジメトキシシラン０．６ｍｍｏｌを加えた。系内の窒素をプロピレンで置換した後に、水素を０．１７ＭＰａ－Ｇ装入した。
内温８０℃、全圧３．２ＭＰａ－Ｇに系内が安定した後、上記予備重合触媒成分（Ｂ）をＴｉ原子換算で０．１０ｍｍｏｌ含んだヘプタンスラリー２０．８ｍＬを加え、プロピレンを連続的に供給しながら８０℃で１時間重合を行った。
[Production of propylene-based polymer (E-2)]
The steps (1) and (2) are the same as those for the propylene-based polymer (A-1).
(3-1) Polymerization-1 (Polymerization [Step 1])
A 10-L stainless steel autoclave equipped with a stirrer was thoroughly dried and purged with nitrogen, and then 6 L of dehydrated heptane, 12.5 mmol of triethylaluminum, and 0.6 mmol of dicyclopentyldimethoxysilane were added. After replacing nitrogen in the system with propylene, 0.17 MPa-G of hydrogen was introduced.
After the inside of the system stabilized at an internal temperature of 80° C. and a total pressure of 3.2 MPa-G, 20.8 mL of a heptane slurry containing 0.10 mmol of the prepolymerization catalyst component (B) in terms of Ti atoms was added, and propylene was added continuously. Polymerization was carried out at 80° C. for 1 hour while supplying to .
（３－２）重合－２（重合［工程２］）
プロピレン単独重合体の重合終了後（前記［工程１］の後）、内温を３０℃まで降温し脱圧した。その後、水素／エチレン＝０．１０ｍ.ｒ.装入し、続いてエチレン／（エチレン＋プロピレン）＝０．２１ｍ.ｒ.の混合ガスを導入した。内温６０℃、全圧０．６０ＭＰａ－Ｇ（導入ガス量により変動）で５０分間プロピレン／エチレン共重合を行った。
(3-2) Polymerization-2 (Polymerization [Step 2])
After the completion of the polymerization of the propylene homopolymer (after the above [Step 1]), the internal temperature was lowered to 30°C and the pressure was released. After that, hydrogen/ethylene=0.10 m.r. was charged, and then a mixed gas of ethylene/(ethylene+propylene)=0.21 m.r. was introduced. Propylene/ethylene copolymerization was carried out for 50 minutes at an internal temperature of 60° C. and a total pressure of 0.60 MPa-G (varying depending on the amount of introduced gas).
所定時間経過したところで５０ｍＬのメタノールを添加し反応を停止し、降温、脱圧した。内容物を全量フィルター付きろ過槽へ移し６０℃に昇温し固液分離した。更に、６０℃のヘプタン６Ｌで固体部を２回洗浄した。このようにして得られたプロピレン・エチレン共重合体を真空乾燥した。 After a predetermined time, 50 mL of methanol was added to stop the reaction, and the temperature was lowered and the pressure was released. The content was transferred to a filtration tank with a total filter and heated to 60° C. for solid-liquid separation. Furthermore, the solid portion was washed twice with 6 L of heptane at 60°C. The propylene/ethylene copolymer thus obtained was vacuum dried.
得られたプロピレン系重合体（Ｅ－２）の、メルトフローレート（ＭＦＲ）（ＪＩＳ Ｋ ７２１０、測定温度２３０℃、荷重２．１６ｋｇ）は５.０ｇ／１０分、Ｄinsolは８８．０質量％、Ｄsolは１２.０質量％、極限粘度［ηsol］は３.３ｄＬ／ｇ、Ｄsol中のエチレンに由来する構成単位の質量が２２.０質量％であった。 The obtained propylene-based polymer (E-2) had a melt flow rate (MFR) (JIS K 7210, measurement temperature of 230°C, load of 2.16 kg) of 5.0 g/10 min, and D insol of 88.0 mass. %, D sol was 12.0% by mass, the intrinsic viscosity [η sol ] was 3.3 dL/g, and the mass of structural units derived from ethylene in D sol was 22.0% by mass.
〔プロピレン系重合体（Ｅ－３）の製造〕
（１）（２）の工程はプロピレン形重合体（Ａ－１）と同様である。
（３－１）重合－１（重合［工程１］）
内容積１０Ｌの攪拌機付きステンレス製オートクレーブを十分乾燥し、窒素置換の後、脱水処理したヘプタン６Ｌ、トリエチルアルミニウム１２．５ｍｍｏｌ、ジシクロペンチルジメトキシシラン０．６ｍｍｏｌを加えた。系内の窒素をプロピレンで置換した後に、水素を０．２５ＭＰａ－Ｇ装入した。
内温８０℃、全圧３．２ＭＰａ－Ｇに系内が安定した後、上記予備重合触媒成分（Ｂ）をＴｉ原子換算で０．１０ｍｍｏｌ含んだヘプタンスラリー２０．８ｍＬを加え、プロピレンを連続的に供給しながら８０℃で１時間重合を行った。
[Production of propylene-based polymer (E-3)]
The steps (1) and (2) are the same as for the propylene polymer (A-1).
(3-1) Polymerization-1 (Polymerization [Step 1])
A 10-L stainless steel autoclave equipped with a stirrer was thoroughly dried and purged with nitrogen, and then 6 L of dehydrated heptane, 12.5 mmol of triethylaluminum, and 0.6 mmol of dicyclopentyldimethoxysilane were added. After replacing nitrogen in the system with propylene, 0.25 MPa-G of hydrogen was introduced.
After the inside of the system stabilized at an internal temperature of 80° C. and a total pressure of 3.2 MPa-G, 20.8 mL of a heptane slurry containing 0.10 mmol of the prepolymerization catalyst component (B) in terms of Ti atoms was added, and propylene was added continuously. Polymerization was carried out at 80° C. for 1 hour while supplying to .
（３－２）重合－２（重合［工程２］）
プロピレン単独重合体の重合終了後（前記［工程１］の後）、内温を３０℃まで降温し脱圧した。その後、水素／エチレン＝０．０４ｍ.ｒ.装入し、続いてエチレン／（エチレン＋プロピレン）＝０．３３ｍ.ｒ.の混合ガスを導入した。内温６０℃、全圧０．６０ＭＰａ－Ｇ（導入ガス量により変動）で７０分間プロピレン／エチレン共重合を行った。
(3-2) Polymerization-2 (Polymerization [Step 2])
After the completion of the polymerization of the propylene homopolymer (after the above [Step 1]), the internal temperature was lowered to 30°C and the pressure was released. After that, hydrogen/ethylene=0.04 m.r. was charged, and then a mixed gas of ethylene/(ethylene+propylene)=0.33 m.r. was introduced. Propylene/ethylene copolymerization was carried out for 70 minutes at an internal temperature of 60° C. and a total pressure of 0.60 MPa-G (varying depending on the amount of introduced gas).
所定時間経過したところで５０ｍＬのメタノールを添加し反応を停止し、降温、脱圧した。内容物を全量フィルター付きろ過槽へ移し６０℃に昇温し固液分離した。更に、６０℃のヘプタン６Ｌで固体部を２回洗浄した。このようにして得られたプロピレン・エチレン共重合体を真空乾燥した。 After a predetermined time, 50 mL of methanol was added to stop the reaction, and the temperature was lowered and the pressure was released. The content was transferred to a filtration tank with a total filter and heated to 60° C. for solid-liquid separation. Furthermore, the solid portion was washed twice with 6 L of heptane at 60°C. The propylene/ethylene copolymer thus obtained was vacuum dried.
得られたプロピレン系重合体（Ｅ－３）の、メルトフローレート（ＭＦＲ）（ＪＩＳ Ｋ ７２１０、測定温度２３０℃、荷重２．１６ｋｇ）は５.０ｇ／１０分、Ｄinsolは８５．０質量％、Ｄsolは１５.０質量％、極限粘度［ηsol］は４．５ｄＬ／ｇ、Ｄsol中のエチレンに由来する構成単位の質量が２９.０質量％であった。 The obtained propylene-based polymer (E-3) had a melt flow rate (MFR) (JIS K 7210, measurement temperature of 230°C, load of 2.16 kg) of 5.0 g/10 minutes and D insol of 85.0 mass. %, D sol was 15.0% by mass, the intrinsic viscosity [η sol ] was 4.5 dL/g, and the mass of structural units derived from ethylene in D sol was 29.0% by mass.
実施例および比較例で用いたエチレン系重合体を以下に示す。
〔エチレン系重合体（Ｂ－１）〕
密度９６４ｋｇ／ｍ3、ＭＦＲ（１９０℃）５．２ｇ／１０分（プライムポリマー製、商品名 ハイゼックス：２２００Ｊ）
〔エチレン系重合体（Ｅ－１）〕
密度９０４ｋｇ／ｍ3、ＭＦＲ（１９０℃）３．８ｇ／１０分（プライムポリマー製、商品名 エボリュー：ＳＰ０５４０）
The ethylene-based polymers used in Examples and Comparative Examples are shown below.
[Ethylene polymer (B-1)]
Density 964 kg/m 3 , MFR (190°C) 5.2 g/10 minutes (made by Prime Polymer, trade name Hi-Zex: 2200J)
[Ethylene polymer (E-1)]
Density 904 kg/m 3 , MFR (190° C.) 3.8 g/10 min (made by Prime Polymer, trade name EVOLUE: SP0540)
実施例および比較例で用いたプロピレン系樹脂組成物は、以下の方法で調整した。
（１）造粒
表１（実施例・比較例）に示す配合にて、プロピレン系重合体と、エチレン系重合体を所定の量を配合し、添加剤として、フェノール系酸化防止剤のＩｒｇａｎｏｘ１０１０（商品名、ＢＡＳＦ社製）を０.０５質量部、リン系酸化防止剤のＩｒｇａｆｏｓ１６８（商品名、ＢＡＳＦ社製）を０.０５質量部、中和剤のステアリン酸カルシウム（日東化成社製）を０．１０質量部、造核剤としてＡＬ－ＰＴＢＢＡ（商品名、ＤＩＣ社製）を０．１０質量部配合し、ヘンシェルミキサーにて攪拌混合した。
The propylene-based resin compositions used in Examples and Comparative Examples were prepared by the following method.
(1) Granulation A propylene-based polymer and an ethylene-based polymer were blended in predetermined amounts according to the formulation shown in Table 1 (Examples and Comparative Examples). 0.05 parts by mass of phosphorus antioxidant Irgafos168 (trade name, manufactured by BASF), 0.05 parts by mass of calcium stearate neutralizing agent (manufactured by Nitto Kasei Co., Ltd.) 0.10 parts by mass of AL-PTBBA (trade name, manufactured by DIC) as a nucleating agent was blended, and mixed by stirring with a Henschel mixer.
得られた混合物を東芝機械株式会社製の二軸押出機（ＴＥＭ３５ＢＳ）を用いて下記条件にて溶融混練してストランド状のプロピレン系樹脂組成物を得た。
型式：ＴＥＭ３５ＢＳ（３５ｍｍ二軸押出機）
スクリュー回転数：３００ｒｐｍ
吐出量：３０ｋｇ／ｈ
スクリーンメッシュ：＃２００
樹脂温度：２３０℃
The resulting mixture was melt-kneaded under the following conditions using a twin-screw extruder (TEM35BS) manufactured by Toshiba Machine Co., Ltd. to obtain a strand-shaped propylene-based resin composition.
Model: TEM35BS (35mm twin screw extruder)
Screw rotation speed: 300 rpm
Discharge rate: 30kg/h
Screen mesh: #200
Resin temperature: 230°C
得られたストランドを水冷後ペレタイザーにて切断することにより、プロピレン系樹脂組成物のペレットを得た。
実施例および比較例で得られた成形体の評価は以下の方法で行った。
The resulting strand was cooled with water and then cut with a pelletizer to obtain pellets of the propylene-based resin composition.
The molded bodies obtained in Examples and Comparative Examples were evaluated by the following methods.
〔ヒケ白化評価〕
プロピレン系樹脂組成物のペレットを用いて、以下の方法で容器を成形した。
[Sink whitening evaluation]
Using pellets of the propylene-based resin composition, a container was molded by the following method.
型締め力１４０トンの電動射出成形機（日精樹脂工業社製ＮＥＸ１４０ ＩＶ－１８Ｅ）を用いて、シリンダー温度２３０℃、金型温度２０℃、射出１次圧力１００ＭＰａ、射出速度３０ｍｍ／ｓｅｃ、射出充填時間２．５ｓｅｃ、保持圧力、５５ＭＰａ、保圧時間１２．５ｓｅｃ、冷却時間６０ｓｅｃの条件で、プロピレン系樹脂組成物のペレットを射出成形し、図１に示した成形体を射出成形した。 Using an electric injection molding machine with a mold clamping force of 140 tons (NEX140 IV-18E manufactured by Nissei Plastic Industry Co., Ltd.), cylinder temperature 230 ° C., mold temperature 20 ° C., primary injection pressure 100 MPa, injection speed 30 mm / sec, injection filling Pellets of the propylene-based resin composition were injection-molded under conditions of 2.5 seconds of holding pressure, 55 MPa of holding pressure, 12.5 seconds of holding pressure, and 60 seconds of cooling time to form the molded body shown in FIG.
リブ形状の裏側のヒケ白化を目視で評価し、下記のような５段階の評点で判定した。
１：白化が非常に目立つ
２：白化が目立つ
３：白化がやや目立つ
４：白化がほとんど目立たない
５：白化してない
The whitening of sink marks on the back side of the rib shape was visually evaluated, and judged on the following 5-grade scale.
1: Very conspicuous whitening 2: Conspicuous whitening 3: Slightly conspicuous whitening 4: Hardly conspicuous whitening 5: No whitening
〔引張弾性率〕
射出成形法により試験片を成形し、成形後に室温２３±５℃、相対湿度５０±５％に調節された恒温室に７２時間放置した後、ＪＩＳ Ｋ ７１６１に準拠して求めた。
[Tensile modulus]
A test piece was molded by injection molding, and after molding, it was left for 72 hours in a constant temperature room adjusted to a room temperature of 23±5° C. and a relative humidity of 50±5%.
〔シャルピー衝撃強さ（ノッチ有、２３℃）〕
射出成形法により試験片を成形し、成形後に室温２３±５℃、相対湿度５０±５％に調節された恒温室に７２時間放置した後、ＪＩＳ Ｋ ７１１１に準拠して求めた。
[Charpy impact strength (with notch, 23°C)]
A test piece was molded by injection molding, and after molding, it was left for 72 hours in a constant temperature room adjusted to a room temperature of 23±5° C. and a relative humidity of 50±5%.
〔実施例１〕
上記製造方法で得たプロピレン系重合体（Ａ－１）９４質量部および上記エチレン系重合体（Ｂ－１）６質量部を配合し、上記記載の方法で造粒してプロピレン系樹脂組成物を得た後、上記記載の方法で成形体および試験片を作製し、上記記載の方法で物性を測定した。
結果を表１に示す。
[Example 1]
94 parts by mass of the propylene-based polymer (A-1) obtained by the above production method and 6 parts by mass of the ethylene-based polymer (B-1) are blended and granulated by the above-described method to obtain a propylene-based resin composition. After obtaining, a molded article and a test piece were produced by the method described above, and the physical properties were measured by the method described above.
Table 1 shows the results.
〔実施例２、３〕
実施例１で用いたプロピレン系樹脂組成物に替えて、プロピレン系重合体（Ａ－１）およびエチレン系重合体（Ｂ－１）の配合量を表１に示す配合量に替える以外は実施例１と同様に行い成形体および試験片を作製し、上記記載の方法で物性を測定した。
結果を表１に示す。
[Examples 2 and 3]
Examples except that the propylene-based resin composition used in Example 1 was replaced with the blending amounts of the propylene-based polymer (A-1) and the ethylene-based polymer (B-1) as shown in Table 1. A molded article and a test piece were prepared in the same manner as in 1, and the physical properties were measured by the methods described above.
Table 1 shows the results.
〔実施例４〕
実施例２で用いたプロピレン系重合体（Ａ－１）に替えて、プロピレン系重合体（Ａ－２）を用いる以外は実施例２と同様に行い成形体および試験片を作製し、上記記載の方法で物性を測定した。
結果を表１に示す。
[Example 4]
A molded article and a test piece were prepared in the same manner as in Example 2 except that the propylene polymer (A-2) was used instead of the propylene polymer (A-1) used in Example 2. The physical properties were measured by the method of
Table 1 shows the results.
〔比較例１〕
実施例１で用いたプロピレン系樹脂組成物に替えて、プロピレン系重合体（Ａ－１）を単独で用いる以外は実施例１と同様に行い成形体および試験片を作製し、上記記載の方法で物性を測定した。
結果を表１に示す。
[Comparative Example 1]
A molded article and a test piece were prepared in the same manner as in Example 1 except that the propylene-based polymer (A-1) was used alone instead of the propylene-based resin composition used in Example 1, and the method described above was used. The physical properties were measured with
Table 1 shows the results.
〔比較例２～６〕
実施例１で用いたプロピレン系樹脂組成物に替えて、表１に示すプロピレン系重合体およびエチレン系重合体を用い、且つその配合量を表１に示す量で用いる以外は実施例１と同様に行い成形体および試験片を作製し、上記記載の方法で物性を測定した。
結果を表１に示す。
[Comparative Examples 2 to 6]
Same as Example 1 except that the propylene-based polymer and ethylene-based polymer shown in Table 1 were used in place of the propylene-based resin composition used in Example 1, and the amounts shown in Table 1 were used. A molded body and a test piece were prepared by the above-described method, and the physical properties were measured by the method described above.
Table 1 shows the results.
Claims (5)
（Ａ１）ＪＩＳ Ｋ ７２１０に準拠して、測定温度２３０℃、荷重２．１６ｋｇで測定したメルトフローレート（ＭＦＲA）が、１～３０ｇ／１０分である。
（Ａ２）プロピレンを単独で重合させてなるプロピレン単独重合体セグメントと、プロピレンとエチレンを共重合させてなるプロピレン・エチレン共重合体セグメントを含む。
（Ａ３）室温ｎ－デカンに不溶な部分（Ｄinsol）を８６～９５質量％、および室温ｎ－デカンに可溶な部分（Ｄsol）を５～１４質量％〔ただし、（Ｄinsol）と（Ｄsol）の合計量を１００質量％とする。〕を含む。
（Ａ４）室温ｎ－デカンに可溶な部分（Ｄsol）のエチレンに由来する構成単位の含有量が２５質量％以上、４５質量％未満である。
（Ａ５）室温ｎ－デカンに可溶な部分（Ｄsol）の１３５℃デカリン中における極限粘度［η］が２．５～４．０ｄＬ／ｇである。
（Ｂ１）ＪＩＳ Ｋ ７２１０に準拠して、測定温度１９０℃、荷重２．１６ｋｇで測定したメルトフローレート（ＭＦＲB）が、１ｇ／１０分以上、３０ｇ／１０分未満である。
（Ｂ２）密度が９５０～９６６ｋｇ／ｍ3である。 85 to 95 parts by mass of a propylene polymer (A) that satisfies the following requirements (A1) to (A5), and 5 to 15 parts by mass of an ethylene polymer (B) that satisfies the following requirements (B1) and (B2): [However, the total amount of the propylene-based polymer (A) and the ethylene-based polymer (B) shall be 100 parts by mass. ] A propylene-based resin composition characterized by comprising:
(A1) According to JIS K 7210, the melt flow rate (MFR A ) measured at a measurement temperature of 230° C. and a load of 2.16 kg is 1 to 30 g/10 minutes.
(A2) Contains a propylene homopolymer segment obtained by polymerizing propylene alone and a propylene/ethylene copolymer segment obtained by copolymerizing propylene and ethylene.
(A3) 86 to 95% by mass of a portion insoluble in room temperature n-decane (D insol ) and 5 to 14% by mass of a portion soluble in room temperature n-decane (D sol ) [provided that (D insol ) and Let the total amount of (D sol ) be 100% by mass. 〕including.
(A4) The content of structural units derived from ethylene in the portion (D sol ) soluble in n-decane at room temperature is 25% by mass or more and less than 45% by mass.
(A5) The portion soluble in n-decane at room temperature (D sol ) has an intrinsic viscosity [η] of 2.5 to 4.0 dL/g in decalin at 135°C.
(B1) According to JIS K 7210, the melt flow rate (MFR B ) measured at a measurement temperature of 190° C. and a load of 2.16 kg is 1 g/10 minutes or more and less than 30 g/10 minutes.
(B2) Density is 950-966 kg/m 3 .
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