JP4499394B2 - Polypropylene resin expanded particles and in-mold molded body using the same - Google Patents
Polypropylene resin expanded particles and in-mold molded body using the same Download PDFInfo
- Publication number
- JP4499394B2 JP4499394B2 JP2003339215A JP2003339215A JP4499394B2 JP 4499394 B2 JP4499394 B2 JP 4499394B2 JP 2003339215 A JP2003339215 A JP 2003339215A JP 2003339215 A JP2003339215 A JP 2003339215A JP 4499394 B2 JP4499394 B2 JP 4499394B2
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- JP
- Japan
- Prior art keywords
- propylene
- polymer
- polypropylene resin
- propylene polymer
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 229920001155 polypropylene Polymers 0.000 title claims description 223
- 239000002245 particle Substances 0.000 title claims description 157
- 229920005989 resin Polymers 0.000 title claims description 151
- 239000011347 resin Substances 0.000 title claims description 151
- -1 Polypropylene Polymers 0.000 title claims description 113
- 239000004743 Polypropylene Substances 0.000 title claims description 108
- 229920000642 polymer Polymers 0.000 claims description 113
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 97
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 87
- 238000002844 melting Methods 0.000 claims description 49
- 230000008018 melting Effects 0.000 claims description 49
- 239000011342 resin composition Substances 0.000 claims description 49
- 238000003780 insertion Methods 0.000 claims description 39
- 230000001788 irregular Effects 0.000 claims description 36
- 238000000465 moulding Methods 0.000 claims description 29
- 239000005977 Ethylene Substances 0.000 claims description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 22
- 239000004711 α-olefin Substances 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims description 8
- 230000037431 insertion Effects 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 description 48
- 239000002585 base Substances 0.000 description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- 238000000034 method Methods 0.000 description 36
- 239000000047 product Substances 0.000 description 32
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- 239000004088 foaming agent Substances 0.000 description 26
- 230000006835 compression Effects 0.000 description 25
- 238000007906 compression Methods 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000007789 gas Substances 0.000 description 21
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 19
- 238000006116 polymerization reaction Methods 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 18
- 238000005187 foaming Methods 0.000 description 18
- 238000002156 mixing Methods 0.000 description 15
- 239000006260 foam Substances 0.000 description 14
- 230000035699 permeability Effects 0.000 description 14
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 229920001384 propylene homopolymer Polymers 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 150000004696 coordination complex Chemical class 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000002685 polymerization catalyst Substances 0.000 description 8
- 230000035882 stress Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 230000004927 fusion Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229920005673 polypropylene based resin Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- 239000002667 nucleating agent Substances 0.000 description 6
- 239000011949 solid catalyst Substances 0.000 description 6
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 6
- 239000003570 air Substances 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 229910001872 inorganic gas Inorganic materials 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000012968 metallocene catalyst Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 4
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical group C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000004604 Blowing Agent Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 239000001282 iso-butane Substances 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 229920005629 polypropylene homopolymer Polymers 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-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
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052786 argon Inorganic materials 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
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 1
- JAGYXYUAYDLKNO-GGWOSOGESA-N (2e,5e)-hepta-2,5-diene Chemical compound C\C=C\C\C=C\C JAGYXYUAYDLKNO-GGWOSOGESA-N 0.000 description 1
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZRCFBHGCJAIXIH-UHFFFAOYSA-N 2-methylazulene Chemical compound C1=CC=CC2=CC(C)=CC2=C1 ZRCFBHGCJAIXIH-UHFFFAOYSA-N 0.000 description 1
- KGCRXHYTNRMHCF-UHFFFAOYSA-N 6-methyl-2-(2-methylpropyl)oxaluminane Chemical compound CC(C)C[Al]1CCCC(C)O1 KGCRXHYTNRMHCF-UHFFFAOYSA-N 0.000 description 1
- UCKITPBQPGXDHV-UHFFFAOYSA-N 7-methylocta-1,6-diene Chemical compound CC(C)=CCCCC=C UCKITPBQPGXDHV-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- JJDZBQREKCLIOM-UHFFFAOYSA-L CC1=CC(C=C1)[Zr](Cl)(Cl)(C1C=CC(C)=C1)=[Si](C)C Chemical compound CC1=CC(C=C1)[Zr](Cl)(Cl)(C1C=CC(C)=C1)=[Si](C)C JJDZBQREKCLIOM-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- CGELJBSWQTYCIY-UHFFFAOYSA-L [Cl-].[Cl-].CC1=Cc2ccccc2[C@H]1[Zr++]([C@@H]1C(C)=Cc2ccccc12)=[Si](C)C Chemical compound [Cl-].[Cl-].CC1=Cc2ccccc2[C@H]1[Zr++]([C@@H]1C(C)=Cc2ccccc12)=[Si](C)C CGELJBSWQTYCIY-UHFFFAOYSA-L 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003828 azulenyl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
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- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
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- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
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- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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Description
本発明は，低い成形温度にて表面外観及び機械的物性が優れた型内成形体を得ることができるポリプロピレン系樹脂発泡粒子，及びその型内成形体に関する。 The present invention relates to a low surface appearance at molding temperature and polypropylene resin foamed beads which can be mechanical properties provide excellent mold molding body, and a mold formed body.
ポリプロピレン系樹脂発泡粒子から得られる型内発泡成形体は，ポリスチレン系樹脂発泡粒子による成形体に比較して，耐薬品性，耐衝撃性，圧縮歪回復性等に優れていることから，自動車等のバンパー芯材や各種包装資材等として好適に使用されている。 In-mold foam molded products obtained from polypropylene resin expanded particles have superior chemical resistance, impact resistance, compression strain recovery, etc. compared to molded products made of polystyrene resin expanded particles. It is suitably used as a bumper core material and various packaging materials.
上記ポリプロピレン系樹脂発泡粒子は，基材樹脂としてのポリプロピレン系樹脂組成物と発泡剤とを含有してなる。
上記ポリプロピレン系樹脂組成物としては，その発泡適性等の面から，主としてプロピレンにエチレンや１−ブテン等のα−オレフィンを共重合させたプロピレン−α−オレフィンランダム共重合体等が用いられている。しかし，これらは共重合体であるがゆえに，重合体そのものの力学物性が低い。
そこで，上記ポリプロピレン系樹脂組成物の力学物性を向上させるために，共重合体中のコモノマー含量を低くする方法や，あるいはプロピレン−α−オレフィンランダム共重合体に直鎖状ポリエチレンを混合する方法（特許文献１参照）が提案されていた。しかし，このような方法によっても，成形体の力学物性を向上させるには限界があった。
The polypropylene resin expanded particles contain a polypropylene resin composition as a base resin and a foaming agent.
As the polypropylene resin composition, a propylene-α-olefin random copolymer obtained by copolymerizing propylene with an α-olefin such as ethylene or 1-butene is mainly used from the viewpoint of foamability and the like. . However, since these are copolymers, the mechanical properties of the polymer itself are low.
Therefore, in order to improve the mechanical properties of the polypropylene resin composition, a method of reducing the comonomer content in the copolymer or a method of mixing linear polyethylene with a propylene-α-olefin random copolymer ( Patent Document 1) has been proposed. However, even with such a method, there is a limit to improving the mechanical properties of the compact.
一方，ポリプロピレンは，本来それ自体が剛性等の力学特性が優れる合成樹脂である。そのため，ポリプロピレン単独重合体により発泡粒子を得ることができれば，剛性が充分に高い発泡粒子成形体を得ることができる。しかし，ポリプロピレン単独重合体からなる発泡粒子によって成形体を得ようとする場合には，発泡温度範囲や，成形範囲が非常に狭く，これら条件を精密に制御することは極めて困難である。そのため，得られた成形体には粒子間の融着不良が生じたり，成形体表面の外観が悪くなる等の不具合が生ずるという問題があった。それ故，実際の工業的生産においては，ポリプロピレン単独重合体より発泡成形体を得ることはできなかった。 On the other hand, polypropylene is a synthetic resin that is inherently excellent in mechanical properties such as rigidity. Therefore, if foamed particles can be obtained from a polypropylene homopolymer, a foamed particle molded body having sufficiently high rigidity can be obtained. However, when trying to obtain a molded body from expanded particles made of polypropylene homopolymer, the foaming temperature range and the molding range are very narrow, and it is extremely difficult to precisely control these conditions. For this reason, the obtained molded product has problems such as poor fusion between particles and the appearance of the molded product surface being deteriorated. Therefore, in actual industrial production, it was not possible to obtain a foamed molded product from a polypropylene homopolymer.
ところが，近年になって，いわゆるメタロセン系触媒を用いて得られたシンジオタクチック構造を有するポリプロピレンを発泡体の基材樹脂として用いる方法が提案された（特許文献２参照）。この提案により，プロピレン単独重合体による発泡体の製造が可能となった。
しかし，シンジオタクチック構造を有するポリプロピレンは，アイソタクチック構造を有するポリプロピレンに比較して融点が低く，機械的物性が劣るという問題があった。
However, in recent years, a method has been proposed in which polypropylene having a syndiotactic structure obtained using a so-called metallocene catalyst is used as a base resin for a foam (see Patent Document 2). This proposal made it possible to produce foams using propylene homopolymers.
However, polypropylene having a syndiotactic structure has a problem that its melting point is lower than that of polypropylene having an isotactic structure and mechanical properties are inferior.
また，後述する特許文献３においては，メタロセン系重合触媒を用いて重合されたアイソタクチックポリプロピレン系樹脂を基材樹脂とするポリプロピレン系樹脂発泡粒子が提案されている。
この場合には，発泡粒子の気泡径が比較的均一となるという特徴があるが，かかる発泡粒子を用いて得られる成形体は圧縮永久歪が大きいという問題があり，更なる改良が望まれていた。
Further, in Patent Document 3 to be described later, expanded polypropylene-based resin particles using an isotactic polypropylene-based resin polymerized using a metallocene-based polymerization catalyst as a base resin are proposed.
In this case, there is a feature that the bubble diameter of the expanded particles becomes relatively uniform, but the molded product obtained using the expanded particles has a problem that the compression set is large, and further improvement is desired. It was.
本発明は，かかる従来の問題点に鑑みてなされたもので，低い成形温度にて表面外観及び機械的物性が優れると共に圧縮永久歪が小さい型内成形体を得ることができるポリプロピレン系樹脂発泡粒子，及びその型内成形体を提供しようとするものである。 The present invention has been made in view of such conventional problems, and is a polypropylene-based resin expanded particle capable of obtaining an in-mold molded product having excellent surface appearance and mechanical properties at a low molding temperature and having a small compression set. And an in-mold molded product thereof.
第１の発明は，下記のプロピレン系重合体［Ａ］５〜９５重量％と，下記のプロピレン系重合体［Ｂ］９５〜５重量％（ただし，プロピレン系重合体［Ａ］とプロピレン系重合体［Ｂ］との合計量は１００重量％である）とを含有するポリプロピレン系樹脂組成物を基材樹脂として含有することを特徴とするポリプロピレン系樹脂発泡粒子にある。
プロピレン系重合体［Ａ］：下記の要件（ａ）及び（ｂ）を有するプロピレン系重合体。
（ａ）プロピレンから得られる構造単位が１００〜８５モル％，エチレン及び／又は炭素数４〜２０のα−オレフィンから得られる構造単位が０〜１５モル％存在すること（ただし，プロピレンから得られる構造単位と，エチレン及び／又は炭素数４〜２０のα−オレフィンから得られる構造単位との合計量は１００モル％である）。
（ｂ）１３Ｃ−ＮＭＲにて測定したときの，全プロピレン挿入中のプロピレンモノマー単位の２，１−挿入に基づく位置不規則単位の割合が０．５〜２．０％であり，かつプロピレンモノマー単位の１，３−挿入に基づく位置不規則単位の割合が０．００５〜０．４％であること。
プロピレン系重合体［Ｂ］：上記要件（ａ）及び（ｂ）のうち要件（ａ）だけを有するプロピレン系重合体。
The first invention includes the following propylene polymer [A] of 5 to 95% by weight and the following propylene polymer [B] of 95 to 5% by weight (provided that the propylene polymer [A] and the propylene polymer weight). The expanded polypropylene resin composition is characterized in that the base resin is a polypropylene resin composition containing a composite [B] in a total amount of 100% by weight.
Propylene polymer [A]: Help propylene-based polymer having a following requirements (a) and (b).
(A) The structural unit obtained from propylene is 100 to 85 mol%, and the structural unit obtained from ethylene and / or an α-olefin having 4 to 20 carbon atoms is present in an amount of 0 to 15 mol% (provided from propylene) The total amount of structural units and structural units obtained from ethylene and / or α-olefin having 4 to 20 carbon atoms is 100 mol%).
(B) the proportion of position irregular units based on 2,1-insertion of propylene monomer units in all propylene insertions as measured by 13C-NMR is 0.5 to 2.0%, and propylene monomers The percentage of irregularly located units based on 1,3-insertion of units is 0.005 to 0.4%.
Propylene polymer [B]: A propylene polymer having only requirement (a) among the above requirements (a) and (b).
上記ポリプロピレン系樹脂組成物は，上記（ａ）及び（ｂ）の要件を有するプロピレン系重合体［Ａ］５〜９５重量％と，上記（ａ）及び（ｂ）のうち要件（ａ）だけを有するプロピレン系重合体［Ｂ］９５〜５重量％とを含有している。そのため，上記ポリプロピレン系樹脂組成物は，機械的物性及び加工性に優れている。 The polypropylene resin composition comprises 5 to 95% by weight of the propylene polymer [A] having the above requirements (a) and (b), and only the requirement (a) among the above (a) and (b). And 95 to 5% by weight of a propylene-based polymer [B]. Therefore, the polypropylene resin composition is excellent in mechanical properties and processability.
また，上記ポリプロピレン系樹脂組成物は，これを基材樹脂として発泡粒子を作製すると，機械的物性に優れると共に成形時の発泡性（二次発泡性）に優れた発泡粒子を得ることができる。そのため，この発泡粒子を成形すると，表面外観及び機械的物性が優れる上，圧縮永久歪の小さな型内成形体を得ることができる。即ち，上記ポリプロピレン系樹脂組成物は，ポリプロピレン系樹脂発泡粒子の最適な基材樹脂として利用することができる。 Moreover, when the above-mentioned polypropylene resin composition is used as a base resin to produce expanded particles, it is possible to obtain expanded particles having excellent mechanical properties and excellent foamability (secondary foamability) during molding. Therefore, when this expanded particle is molded, it is possible to obtain an in-mold molded product having excellent surface appearance and mechanical properties and having a small compression set. That is, the polypropylene resin composition can be utilized as the optimum base resin of PP beads.
なお，ここに基材樹脂とは，発泡粒子を構成する基本となる樹脂成分を意味する。発泡粒子は，この基材樹脂と必要に応じて添加する他のポリマー成分或いは，発泡剤，触媒中和剤，滑剤，結晶核剤，その他の添加剤等の添加物からなる。但し，他のポリマー成分や添加物は，本発明の目的を阻害しない範囲内で，できる限り少量であることが望ましい。
即ち，プロピレン系重合体［Ａ］とプロピレン系重合体［Ｂ］の合計量を１００重量部とした場合，他のポリマー成分の添加量は４０重量部以下にすることが好ましい。より好ましくは，３０重量部以下がよく，さらに好ましくは１５重量部以下がよい。また，もっとも好ましくは５重量部以下がよい。
また，プロピレン系重合体［Ａ］とプロピレン系重合体［Ｂ］の合計量を１００重量部とした場合，上記添加物の添加量（発泡剤のように最終的に気散してなくなるものは除く）は，添加物の使用目的にもよるが４０重量部以下が好ましい。より好ましくは，３０重量部以下がよく，さらに好ましくは０〜１５重量部がよい。
Here, the base resin means a basic resin component constituting the foamed particles. The expanded particles are composed of the base resin and other polymer components added as necessary, or additives such as a foaming agent, a catalyst neutralizing agent, a lubricant, a crystal nucleating agent, and other additives. However, it is desirable that other polymer components and additives be as small as possible within the range not impairing the object of the present invention.
That is, when the total amount of the propylene polymer [A] and the propylene polymer [B] is 100 parts by weight, the amount of other polymer components added is preferably 40 parts by weight or less. More preferably, it is 30 parts by weight or less, and more preferably 15 parts by weight or less. Most preferably, it is 5 parts by weight or less.
In addition, when the total amount of the propylene polymer [A] and the propylene polymer [B] is 100 parts by weight, the amount of the additive added (those that are not finally diffused like a foaming agent) Is preferably 40 parts by weight or less, depending on the purpose of use of the additive. More preferably, it is 30 parts by weight or less, and more preferably 0 to 15 parts by weight.
上記第１の発明は，上記ポリプロピレン系樹脂組成物を基材樹脂として含有することを特徴とするポリプロピレン系樹脂発泡粒子にある。 The first aspect of the invention resides in a polypropylene resin expanded particle characterized by containing the polypropylene resin composition as a base resin .
本発明においては，上記ポリプロピレン系樹脂組成物を基材樹脂として用いているので，機械的物性に優れると共に成形時の発泡性に優れたポリプロピレン系樹脂発泡粒子を得ることができる。また，このポリプロピレン系樹脂発泡粒子を用いれば，圧縮強度，引張強度等の機械的物性，及び表面外観に優れた型内成形体を得ることができる。 In the present invention, because of the use of the polypropylene based resin composition as a base resin, it is possible to obtain polypropylene resin foamed beads excellent in foaming in molding excellent in mechanical properties. Moreover, if this polypropylene resin expanded particle is used, an in-mold molded article excellent in mechanical properties such as compressive strength and tensile strength, and surface appearance can be obtained.
第２の発明は，ポリプロピレン系樹脂発泡粒子を成形型内において成形してなり，密度０．５〜０．００８ｇ／ｃｍ3を有する型内成形体であって，
かつ上記ポリプロピレン系樹脂発泡粒子は，上記第１の発明のものを用いてなることを特徴とする型内成形体にある（請求項５）。
A second invention is an in-mold molded product having a density of 0.5 to 0.008 g / cm 3 formed by molding polypropylene resin expanded particles in a mold.
In addition, the polypropylene resin expanded particle is an in-mold molded product characterized by using the one according to the first invention (Claim 5 ).
本発明の型内成形体は，上記第１の発明のポリプロピレン系樹脂発泡粒子を用いて型内成形してなり，かつ上記密度を有している。
そのため，上記型内成形体は，圧縮強度，引張強度等の機械的物性に優れていると共に，平滑性，光沢性のような表面外観にも優れるものとなる。
尚，上記型内成形体の密度とは，ＪＩＳ Ｋ７２２２（１９９９年）で定義される見掛け全体密度を意味する。
The in-mold molded product of the present invention is molded in-mold using the polypropylene resin expanded particles of the first invention and has the above density.
Therefore, the in-mold molded body has excellent mechanical properties such as compressive strength and tensile strength, and also has excellent surface appearance such as smoothness and gloss.
The density of the in-mold molded product means the apparent overall density defined by JIS K7222 (1999).
請求項１の発明において，上記ポリプロピレン系樹脂組成物は，プロピレン系重合体［Ａ］とプロピレン系重合体［Ｂ］とを含有してなる。まず，上記プロピレン系重合体［Ａ］は，上記要件（ａ）及び（ｂ）を有するプロピレン系重合体である。以下に，プロピレン系重合体［Ａ］について説明する。 In the invention of claim 1, the polypropylene resin composition contains a propylene polymer [A] and a propylene polymer [B]. First, the propylene polymer [A] is a propylene polymer having the requirements (a) and (b). Hereinafter, the propylene polymer [A] will be described.
まず，上記要件（ａ）は，プロピレンから得られる構造単位が１００〜８５モル％，エチレン及び／又は炭素数４〜２０のα−オレフィンから得られる構造単位が０〜１５モル％存在することにある。
ここで，プロピレンから得られる構造単位と，エチレン及び／又は炭素数４〜２０のα−オレフィンから得られる構造単位との合計量は１００モル％である。
したがって，要件（ａ）を満たすプロピレン系重合体としては，プロピレン単独重合体（１００モル％）よりなるもの，或いはプロピレンと，エチレン及び／又は炭素数４〜２０のα−オレフィンとの共重合体よりなるものがある。
First, the requirement (a) is that the structural unit obtained from propylene is 100 to 85 mol%, and the structural unit obtained from ethylene and / or an α-olefin having 4 to 20 carbon atoms is present in an amount of 0 to 15 mol%. is there.
Here, the total amount of the structural unit obtained from propylene and the structural unit obtained from ethylene and / or an α-olefin having 4 to 20 carbon atoms is 100 mol%.
Therefore, as the propylene polymer satisfying the requirement (a), a propylene homopolymer (100 mol%) or a copolymer of propylene and ethylene and / or an α-olefin having 4 to 20 carbon atoms is used. There is something to do.
上記プロピレンと共重合されるコモノマーのエチレン及び／又は炭素数４〜２０のα−オレフィンとしては，具体的には，エチレン，１−ブテン，１−ペンテン，１−ヘキセン，１−オクテン，４−メチル−１−ブテン等を挙げることができる。 Specific examples of the ethylene comonomer copolymerized with propylene and / or the α-olefin having 4 to 20 carbon atoms include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4- Examples thereof include methyl-1-butene.
また，本発明では，上記プロピレン系重合体［Ａ］として，本発明の目的を阻害しない範囲内において，従来チーグラー／ナッタ触媒においては重合が困難であった他のモノマーをプロピレンに共重合させたものを使用することができる。この場合，上記他のモノマーから得られる構造単位は，上記プロピレン系重合体［Ａ］中で０．０１〜２０モル％が好ましく，０．０５〜１０モル％がより好ましい。
そして，このようなプロピレン系重合体を含有してなる上記ポリプロピレン系樹脂組成物は，発泡粒子を製造するための基材樹脂として用いることができる。
In the present invention, as the propylene-based polymer [A], other monomers that have been difficult to polymerize with conventional Ziegler / Natta catalysts are copolymerized with propylene within a range that does not impair the object of the present invention. Things can be used. In this case, the structural unit obtained from the other monomer is preferably 0.01 to 20 mol%, more preferably 0.05 to 10 mol% in the propylene polymer [A].
And the said polypropylene resin composition formed by containing such a propylene polymer can be used as base-material resin for manufacturing an expanded particle.
こうした上記他のモノマーとしては，例えば，シクロペンテン，ノルボルネン，１，４，５，８−ジメタノ−１，２，３，４，４ａ，８，８ａ，５−オクタヒドロナフタレン等の環状オレフィン，５−メチル−１，４−ヘキサジエン，７−メチル−１，６−オクタジエン等の非共役ジエン，スチレン，ジビニルベンゼン等の芳香族不飽和化合物などの一種又は二種以上を挙げることができる。 Examples of such other monomers include cyclic olefins such as cyclopentene, norbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 8,8a, 5-octahydronaphthalene, 5- One type or two or more types of non-conjugated dienes such as methyl-1,4-hexadiene and 7-methyl-1,6-octadiene, and aromatic unsaturated compounds such as styrene and divinylbenzene can be used.
本発明で用いるプロピレン系重合体［Ａ］は，上記要件（ａ），即ちプロピレン系重合体中のプロピレンから得られる構造単位を８５モル％〜１００モル％含有するプロピレン系（共）重合体樹脂であり，エチレン及び／又は炭素数４〜２０のα−オレフィン（コモノマー）から得られる構造単位が０〜１５モル％の割合で含有されていることが必要である。 The propylene-based polymer [A] used in the present invention is the propylene-based (co) polymer resin containing 85 mol% to 100 mol% of the structural unit obtained from the above requirement (a), ie, propylene in the propylene-based polymer. It is necessary that the structural unit obtained from ethylene and / or an α-olefin (comonomer) having 4 to 20 carbon atoms is contained in a proportion of 0 to 15 mol%.
コモノマーの構造単位の割合が１５モル％を越える場合には，上記ポリプロピレン系樹脂組成物の曲げ強度，引張強度などの機械的物性が大きく低下してしまう。そして，上記ポリプロピレン系樹脂組成物を基材樹脂として発泡粒子を作製しても，所望の発泡粒子を得ることができない。さらに，該発泡粒子を成形しても機械的強度と圧縮回復性に優れた，所望の型内成形体を得ることができない。 When the proportion of the comonomer structural unit exceeds 15 mol%, the mechanical properties such as bending strength and tensile strength of the polypropylene resin composition are greatly reduced. And even if it produces foamed particles by using the said polypropylene resin composition as base resin, a desired foamed particle cannot be obtained. Furthermore, even if the foamed particles are molded, a desired in-mold molded product having excellent mechanical strength and compression recovery cannot be obtained.
次に，上記要件（ｂ）に示すように，上記プロピレン系重合体［Ａ］は，１３Ｃ−ＮＭＲにて測定したときの，全プロピレン挿入中のプロピレンモノマー単位の２，１−挿入に基づく位置不規則単位の割合が０．５〜２．０％であり，かつプロピレンモノマー単位の１，３−挿入に基づく位置不規則単位の割合が０．００５〜０．４％のものである。
この要件（ｂ）はプロピレン系重合体の位置不規則単位の割合に関するものであり，かかる不規則単位は，プロピレン系重合体の結晶性を低下させる作用を有し，発泡適性を高める効果を示す。
Next, as shown in the requirement (b), the propylene polymer [A] is a position based on 2,1-insertion of propylene monomer units in all propylene insertions as measured by 13C-NMR. The proportion of irregular units is 0.5 to 2.0%, and the proportion of positional irregular units based on 1,3-insertion of propylene monomer units is 0.005 to 0.4%.
This requirement (b) relates to the proportion of position irregular units of the propylene polymer, and such irregular units have the effect of lowering the crystallinity of the propylene polymer and show the effect of improving foamability. .
上記２，１−挿入に基づく位置不規則単位の割合が０．５％未満の場合には，上記ポリプロピレン系樹脂組成物は，これを基材樹脂としたポリプロピレン系樹脂発泡粒子を型内成形するとき，得られる型内成形体の圧縮永久歪を小さくする効果が劣るという問題がある。一方，２．０％を越える場合には，基材樹脂としてのポリプロピレン系樹脂組成物の機械的物性，例えば曲げ強度や引張強度等が低下するため，発泡粒子及びそれから得られる型内成形体の強度が低くなるという問題がある。 The 2,1 If the ratio is less than 0.5% of the regio-irregular units based on insertion, the polypropylene-based resin composition, which is mold molding the polypropylene resin foamed particles as a base resin In some cases, there is a problem that the effect of reducing the compression set of the in-mold molded product obtained is inferior. On the other hand, if it exceeds 2.0%, the mechanical properties of the polypropylene resin composition as the base resin, such as bending strength and tensile strength, are reduced. There is a problem that the strength is lowered.
また，上記１，３−挿入に基づく位置不規則単位の割合が０．００５％未満の場合には，上記ポリプロピレン系樹脂組成物は，これを基材樹脂としたポリプロピレン系樹脂発泡粒子を型内成形するとき，得られる型内成形体の圧縮永久歪を小さくする効果が劣るという問題がある。一方，０．４％を越える場合には，基材樹脂としてのポリプロピレン系樹脂組成物の機械的物性，例えば曲げ強度や引張強度が低下するため，発泡粒子及びそれから得られる型内成形体の強度が低くなるという問題がある。 Further, when the ratio of the regio-irregular units based on the 1,3-insertion is less than 0.005%, the above polypropylene resin composition, which the mold the polypropylene resin foamed beads with the base resin When molding, there is a problem that the effect of reducing the compression set of the molded article in the mold obtained is inferior. On the other hand, if it exceeds 0.4%, the mechanical properties of the polypropylene resin composition as the base resin, such as bending strength and tensile strength, decrease, so that the strength of the expanded particles and the in-mold molded product obtained therefrom is reduced. There is a problem that becomes low.
上記要件（ｂ）における２，１−挿入に基づく位置不規則単位及び１，３−挿入に基づく位置不規則単位は，いずれも，これらの単位をその構造中に含有するポリプロピレン系樹脂の結晶性を低下させる効果を有する。さらに具体的には，これらの位置不規則単位は，ポリプロピレン系樹脂に対して，その融点を低下させる作用と，その結晶化度を低下させる作用とを有している。 The positional irregular unit based on 2,1-insertion and the positional irregular unit based on 1,3-insertion in the above requirement (b) are both crystalline of a polypropylene resin containing these units in its structure. Has the effect of lowering. More specifically, these position irregular units have an action to lower the melting point and an action to lower the crystallinity of the polypropylene resin.
これら２つの作用は，かかるポリプロピレン系樹脂を発泡に供した場合に，その発泡適性を高める効果を示すと共に得られる発泡体の圧縮永久歪を小さくする効果を示す。また，上記の位置不規則単位を有するプロピレン系重合体［Ａ］は，後述するプロピレン系重合体［Ｂ］との相溶性に優れるため両者を溶融混練した場合，非常によく混ざり合う。そのような樹脂組成物は，プロピレン系重合体［Ａ］の上記した特長に加え，発泡粒子に加工して型内成形した場合に二次発泡性が良好であるという効果を奏する。 These two actions show the effect of improving the foamability when such a polypropylene resin is subjected to foaming, and the effect of reducing the compression set of the obtained foam. Moreover, since the propylene polymer [A] having the above-mentioned position irregular unit is excellent in compatibility with the propylene polymer [B] to be described later, when the both are melt-kneaded, they are mixed very well. In addition to the above-described features of the propylene-based polymer [A], such a resin composition has an effect of good secondary foamability when processed into foamed particles and molded in-mold.
但し，ポリプロピレン系樹脂に含まれる位置不規則単位の割合が高すぎると，基材樹脂の融点や結晶化度が低下している度合いが高いがために，かかる樹脂をプロピレン系重合体［Ａ］として使用して発泡に供した場合には，得られる発泡樹脂粒子中の気泡径が粗大になってしまう，といった問題が生ずるおそれがあり，その場合には，かかる発泡樹脂粒子から得られる成形体の外観が損なわれる，という問題がある。さらに，上述した如く，かかる発泡粒子から得られる型内成形体の強度が低くなるという問題も生ずる。 However, if the proportion of the position irregular units contained in the polypropylene resin is too high, the melting point and crystallinity degree of the base resin is high, so that the resin is converted into the propylene polymer [A]. When used for foaming, there is a possibility that the bubble diameter in the resulting foamed resin particles becomes coarse, and in that case, a molded product obtained from such foamed resin particles. There is a problem that the appearance of is damaged. Further, as described above, there is a problem that the strength of the in-mold molded body obtained from the expanded particles is lowered.
ここで，プロピレン系重合体中のプロピレンから得られる構造単位，エチレン及び／又は炭素数４〜２０のα−オレフィンから得られる構造単位の分率，及び後述するアイソタクチックトリアッド分率は，１３Ｃ−ＮＭＲ法を用いて測定される値である。
１３Ｃ−ＮＭＲスペクトルの測定法は，例えば下記の通りである。
即ち，直径１０ｍｍφのＮＭＲ用サンプル管内に，３５０〜５００ｍｇ程度の試料を入れ，溶媒としてｏ−ジクロロベンゼン約２．０ｍｌ及びロック用に重水素化ベンゼン約０．５ｍｌを用いて完全に溶解させた後，１３０℃にてプロトン完全デカップル条件下に測定した。
Here, the structural unit obtained from propylene in the propylene-based polymer, the fraction of structural units obtained from ethylene and / or an α-olefin having 4 to 20 carbon atoms, and the isotactic triad fraction described later are: It is a value measured using 13 C-NMR method.
The measuring method of 13C-NMR spectrum is, for example, as follows.
That is, a sample of about 350 to 500 mg was placed in an NMR sample tube having a diameter of 10 mmφ and completely dissolved using about 2.0 ml of o-dichlorobenzene as a solvent and about 0.5 ml of deuterated benzene for locking. Thereafter, measurement was performed at 130 ° C. under the condition of complete proton decoupling.
測定条件としては，フリップアングル６５ｄｅｇ，パルス間隔 ５Ｔ１以上（但し，Ｔ１はメチル基のスピン格子緩和時間の内の最長の値）を選択した。プロピレン系重合体に於いては，メチレン基及びメチン基のスピン格子緩和時間はメチル基のそれよりも短い為，この測定条件では全ての炭素の磁化の回復は９９％以上である。
なお，１３C−ＮＭＲ法での位置不規則単位の検出感度は，通常０．０１％程度であるが，積算回数を増加することにより，これを高めることが可能である。
As measurement conditions, a flip angle of 65 deg and a pulse interval of 5T1 or more (where T1 is the longest value of the spin lattice relaxation time of the methyl group) were selected. In the propylene-based polymer, the spin lattice relaxation time of the methylene group and methine group is shorter than that of the methyl group, so that the recovery of the magnetization of all the carbons is 99% or more under these measurement conditions.
In addition, the detection sensitivity of the position irregular unit in the 13C-NMR method is usually about 0.01%, but it can be increased by increasing the number of integrations.
また，上記測定におけるケミカルシフトは，頭−尾結合しておりメチル分岐の方向が同一であるプロピレン単位５連鎖の第３単位目のメチル基のピークを２１．８ｐｐｍとして設定し，このピークを基準として他の炭素ピークのケミカルシフトを設定した。 In addition, the chemical shift in the above measurement was set with 21.8 ppm as the peak of the 3rd unit methyl group in the 5 units of propylene units that are head-to-tail bonded and have the same methyl branching direction. The chemical shifts of other carbon peaks were set as
この基準を用いると，下記式［化１］中のＰＰＰ［ｍｍ］で示されるプロピレン単位３連鎖中の第２単位目のメチル基に基づくピークは２１．３〜２２．２ｐｐｍの範囲に，ＰＰＰ［ｍｒ］で示されるプロピレン単位３連鎖中の第２単位目のメチル基に基づくピークは２０．５〜２１．３ｐｐｍの範囲に，ＰＰＰ［ｒｒ］で示されるプロピレン単位３連鎖中の第２単位目のメチル基に基づくピークは１９．７〜２０．５ｐｐｍの範囲に現れる。 Using this criterion, the peak based on the methyl group of the second unit in the three propylene units represented by PPP [mm] in the following formula [Chemical Formula 1] is in the range of 21.3 to 22.2 ppm. The peak based on the methyl group of the second unit in the three propylene units represented by [mr] is in the range of 20.5 to 21.3 ppm, and the second unit in the three propylene units represented by PPP [rr] The peak based on the methyl group of the eye appears in the range of 19.7 to 20.5 ppm.
ここで，ＰＰＰ［ｍｍ］，ＰＰＰ［ｍｒ］，及びＰＰＰ［ｒｒ］はそれぞれ下記のように示される。 Here, PPP [mm], PPP [mr], and PPP [rr] are respectively expressed as follows.
更に，本発明において，上記プロピレン系重合体［Ａ］は，プロピレンの２，１−挿入及び１，３−挿入に基づく位置不規則単位を含む下記の部分構造（Ι）及び（ΙΙ）を特定量含有するものである。 Furthermore, in the present invention, the propylene polymer [A] specifies the following partial structures (Ι) and (ΙΙ) including regioregular units based on 2,1-insertion and 1,3-insertion of propylene. It is contained in an amount.
この様な部分構造は，例えばメタロセン系触媒を用いて重合反応を行った場合に，プロピレン重合体の重合時に発生する位置不規則性により生ずると考えられている。
即ち，プロピレンモノマーは，通常，メチレン側が触媒中の金属成分と結合する方式，すなわち，いわゆる「１，２−挿入」にて反応するが，希には，「２，１−挿入」や「１，３−挿入」を起こすことがある。「２，１−挿入」は，「１，２−挿入」とは付加方向が逆となる反応形式であり，ポリマー鎖中に上記の部分構造（Ι）で表される構造単位を形成する。
Such a partial structure is considered to be caused by positional irregularities generated during the polymerization of the propylene polymer, for example, when a polymerization reaction is performed using a metallocene catalyst.
That is, the propylene monomer usually reacts by a method in which the methylene side is bonded to a metal component in the catalyst, that is, so-called “1,2-insertion”, but rarely “2,1-insertion” or “1” , 3-insertion ". “2,1-insertion” is a reaction mode in which the addition direction is opposite to “1,2-insertion”, and forms a structural unit represented by the above partial structure (構造) in the polymer chain.
また，「１，３−挿入」とは，プロピレンモノマーのＣ−１とＣ−３とでポリマー鎖中に取り込まれるものであり，その結果として直鎖状の構造単位，すなわち上記の部分構造（ΙΙ）を生ずるものである。 Further, “1,3-insertion” means that propylene monomers C-1 and C-3 are incorporated into a polymer chain, and as a result, a linear structural unit, that is, the above partial structure ( Ii).
上記の各位置不規則単位の割合が本発明の範囲にあるプロピレン系重合体［Ａ］は，適当な触媒を選定することにより得ることができる。具体的には，例えばヒドロアズレニル基を配位子として有するメタロセン系重合触媒等を用いて得ることができる。ここで，上記メタロセン系重合触媒とは，メタロセン構造を有する遷移金属化合物成分と，助触媒成分とからなるものである。各位置不規則単位の割合は，重合に用いる触媒の金属錯体成分の化学構造によって異なるが，一般には重合温度が高い方が大きくなる傾向にある。本発明においては，プロピレン系重合体［Ａ］における各位置不規則単位の割合を上記特定の範囲にするため，重合温度は０〜８０℃にすることが好ましい。 The propylene polymer [A] in which the ratio of each of the above-mentioned position irregular units is within the scope of the present invention can be obtained by selecting an appropriate catalyst. Specifically, it can be obtained using, for example, a metallocene polymerization catalyst having a hydroazurenyl group as a ligand. Here, the metallocene polymerization catalyst comprises a transition metal compound component having a metallocene structure and a promoter component. The proportion of each position irregular unit varies depending on the chemical structure of the metal complex component of the catalyst used in the polymerization, but generally the higher the polymerization temperature, the higher the tendency. In the present invention, the polymerization temperature is preferably 0 to 80 ° C. in order to bring the proportion of each position irregular unit in the propylene polymer [A] into the above specific range.
尚，金属錯体成分は，これをそのまま触媒成分として用いることもできるが，無機あるいは有機の，顆粒状ないしは微粒子状の固体である微粒子状担体に，上記金属錯体成分が担持された固体状触媒として用いてもよい。
微粒子状担体に金属錯体成分を担持させる場合，金属錯体成分の担持量は，担体１ｇあたり０．００１〜１０ｍｍｏｌであることが好ましく，より好ましくは，０．００１〜５ｍｍｏｌであることがよい。
The metal complex component can be used as a catalyst component as it is, but as a solid catalyst in which the metal complex component is supported on an inorganic or organic particulate carrier which is a granular or particulate solid. It may be used.
When the metal complex component is supported on the fine particle carrier, the amount of the metal complex component supported is preferably 0.001 to 10 mmol, more preferably 0.001 to 5 mmol, per 1 g of the carrier.
また，上記のヒドロアズレニル基を配位子として有するメタロセン触媒の中でも，金属原子として，チタン，ジルコニウム，ハフニウムを用いた触媒が好ましく，なかでも，ジルコニウムを有する錯体が，重合活性が高いという点で好ましい。
また，上記メタロセン系触媒の中でも，ジルコニウムジクロリド型の錯体が好適に使用されるが，その中でも，特に架橋型錯体を用いることが好ましい。
具体的には，メチレンビス｛１，１’−（２−メチル−４−フェニルジヒドロアズレニル）｝ジルコニウムジクロリド，メチレンビス｛１，１’−（２−エチル−４−フェニルジヒドロアズレニル）｝ジルコニウムジクロリド，メチレンビス｛１，１’−（４−フェニルジヒドロアズレニル）｝ジルコニウムジクロリド，メチレンビス｛１，１’−（４−ナフチルジヒドロアズレニル）｝ジルコニウムジクロリド，エチレンビス｛１，１’−（２−メチル−４−フェニルジヒドロアズレニル）｝ジルコニウムジクロリド，エチレンビス｛１，１’−（２−エチル−４−フェニルジヒドロアズレニル）｝ジルコニウムジクロリド，エチレンビス｛１，１’−（４−フェニルジヒドロアズレニル）｝ジルコニウムジクロリド，エチレンビス｛１，１’−（４−ナフチルジヒドロアズレニル）｝ジルコニウムジクロリド，イソプロピリデンビス｛１，１’−（２−メチル−４−フェニルジヒドロアズレニル）｝ジルコニウムジクロリド，イソプロピリデンビス｛１，１’−（２−エチル−４−フェニルジヒドロアズレニル）｝ジルコニウムジクロリド，イソプロピリデンビス｛１，１’−（４−フェニルジヒドロアズレニル）｝ジルコニウムジクロリド，イソプロピリデンビス｛１，１’−（４−ナフチルジヒドロアズレニル）｝ジルコニウムジクロリド，ジメチルシリレンビス｛１，１’−（２−メチル−４−フェニルジヒドロアズレニル）｝ジルコニウムジクロリド，ジメチルシリレンビス｛１，１’−（２−エチル−４−フェニルジヒドロアズレニル）｝ジルコニウムジクロリド，ジメチルシリレンビス｛１，１’−（４−フェニルジヒドロアズレニル）｝ジルコニウムジクロリド，ジメチルシリレンビス｛１，１’−（４−ナフチルジヒドロアズレニル）｝ジルコニウムジクロリド，ジフェニルシリレンビス｛１，１’−（２−メチル−４−フェニルジヒドロアズレニル）｝ジルコニウムジクロリド，ジフェニルシリレンビス｛１，１’−（２−エチル−４−フェニルジヒドロアズレニル）｝ジルコニウムジクロリド，ジフェニルシリレンビス｛１，１’−（４−フェニルジヒドロアズレニル）｝ジルコニウムジクロリド，ジフェニルシリレンビス｛１，１’−（４−ナフチルジヒドロアズレニル）｝ジルコニウムジクロリド，等が例示できる。
これらの中でも特に，ジメチルシリレンビス｛１，１’−（２−メチル−４−フェニルジヒドロアズレニル）｝ジルコニウムジクロリド，及びジメチルシリレンビス｛１，１’−（２−エチル−４−フェニルジヒドロアズレニル）｝ジルコニウムジクロリドを用いることが好ましい。この場合には，上記の各位置不規則単位の割合を容易に本発明の範囲内にコントロールすることができると共に，後述する要件（ｄ）を満足する（アイソタクチックトリアッド分率が９７％以上の）プロピレン重合体を容易に得ることができる。
Among the metallocene catalysts having the hydroazurenyl group as a ligand, a catalyst using titanium, zirconium, or hafnium as a metal atom is preferable, and a complex having zirconium is preferable because of its high polymerization activity. .
Among the metallocene catalysts, zirconium dichloride type complexes are preferably used, and among them, it is particularly preferable to use a crosslinked complex.
Specifically, methylenebis {1,1 ′-(2-methyl-4-phenyldihydroazulenyl)} zirconium dichloride, methylenebis {1,1 ′-(2-ethyl-4-phenyldihydroazulenyl)} zirconium dichloride. , Methylenebis {1,1 ′-(4-phenyldihydroazurenyl)} zirconium dichloride, methylenebis {1,1 ′-(4-naphthyldihydroazurenyl)} zirconium dichloride, ethylenebis {1,1 ′-(2- Methyl-4-phenyldihydroazurenyl)} zirconium dichloride, ethylenebis {1,1 ′-(2-ethyl-4-phenyldihydroazurenyl)} zirconium dichloride, ethylenebis {1,1 ′-(4-phenyldihydro) Azulenyl)} zirconium dichloride, ethylenebis {1,1 ′-(4 Naphthyldihydroazurenyl)} zirconium dichloride, isopropylidenebis {1,1 ′-(2-methyl-4-phenyldihydroazurenyl)} zirconium dichloride, isopropylidenebis {1,1 ′-(2-ethyl-4-) Phenyldihydroazurenyl)} zirconium dichloride, isopropylidenebis {1,1 ′-(4-phenyldihydroazurenyl)} zirconium dichloride, isopropylidenebis {1,1 ′-(4-naphthyldihydroazurenyl)} zirconium dichloride , Dimethylsilylenebis {1,1 ′-(2-methyl-4-phenyldihydroazulenyl)} zirconium dichloride, dimethylsilylenebis {1,1 ′-(2-ethyl-4-phenyldihydroazurenyl)} zirconium dichloride , Dimethylsilylenebis {1,1 ′-(4-Phenyldihydroazurenyl)} zirconium dichloride, dimethylsilylenebis {1,1 ′-(4-naphthyldihydroazurenyl)} zirconium dichloride, diphenylsilylenebis {1,1 ′-(2 -Methyl-4-phenyldihydroazurenyl)} zirconium dichloride, diphenylsilylenebis {1,1 ′-(2-ethyl-4-phenyldihydroazurenyl)} zirconium dichloride, diphenylsilylenebis {1,1 ′-(4 -Phenyldihydroazurenyl)} zirconium dichloride, diphenylsilylenebis {1,1 ′-(4-naphthyldihydroazurenyl)} zirconium dichloride, and the like.
Among these, dimethylsilylene bis {1,1 ′-(2-methyl-4-phenyldihydroazulenyl)} zirconium dichloride and dimethylsilylene bis {1,1 ′-(2-ethyl-4-phenyldihydroazule) are particularly preferred. Nil)} zirconium dichloride is preferably used. In this case, the ratio of each position irregular unit can be easily controlled within the scope of the present invention, and the later-described requirement (d) is satisfied (the isotactic triad fraction is 97%). The propylene polymer can be easily obtained.
また，上記助触媒成分としては，メチルアルミノキサン，イソブチルアルミノキサン，メチルイソブチルアルミノキサン等のアルミノキサン類，トリフェニルボラン，トリス（ペンタフルオロフェニル）ボラン，塩化マグネシウム等のルイス酸，ジメチルアニリニウムテトラキス（ペンタフルオロフェニル）ボレート等のイオン性化合物が例示できる。また，これらの助触媒成分を，他の有機アルミニウム化合物，例えば，トリメチルアルミニウム，トリエチルアルミニウム，トリイソブチルアルミニウム等のトリアルキルアルミニウムと併用して共存下に用いることも可能である。 The promoter component includes aluminoxanes such as methylaluminoxane, isobutylaluminoxane, methylisobutylaluminoxane, Lewis acid such as triphenylborane, tris (pentafluorophenyl) borane, magnesium chloride, dimethylanilinium tetrakis (pentafluorophenyl). ) An ionic compound such as borate can be exemplified. These promoter components can also be used in the presence of other organoaluminum compounds such as trialkylaluminum such as trimethylaluminum, triethylaluminum and triisobutylaluminum.
本発明に係わるプロピレン系重合体の全ポリマー連鎖中のｍｍ分率は，次の［数１］式で表される。ところで，部分構造（ΙΙ）では，１，３−挿入の結果として，プロピレンモノマーに由来するメチル基が１個相当分だけ消失している。 The mm fraction in the entire polymer chain of the propylene polymer according to the present invention is expressed by the following [Equation 1]. By the way, in the partial structure (ΙΙ), as a result of 1,3-insertion, only one methyl group derived from the propylene monomer has disappeared.
この式において，ΣΙＣＨ3は全メチル基（ケミカルシフトの１９〜２２ｐｐｍのピーク全て）の面積を示す。また，Ａ＜１＞，Ａ＜２＞，Ａ＜３＞，Ａ＜４＞，Ａ＜５＞，Ａ＜６＞，Ａ＜７＞，Ａ＜８＞及びＡ＜９＞は，それぞれ，４２．３ｐｐｍ，３５．９ｐｐｍ，３８．６ｐｐｍ，３０．６ｐｐｍ，３６．０ｐｐｍ，３１．５ｐｐｍ，３１．０ｐｐｍ，３７．２ｐｐｍ，２７．４ｐｐｍのピークの面積であり，部分構造（Ι）及び（ΙΙ）で示した炭素の存在量比を示す。
また，全プロピレン挿入に対する２，１−挿入したプロピレンの割合，及び１，３−挿入したプロピレンの割合は，下記の式で計算した。
In this formula, ΣΙCH 3 represents the area of all methyl groups (all peaks at 19-22 ppm of chemical shift). A <1>, A <2>, A <3>, A <4>, A <5>, A <6>, A <7>, A <8> and A <9> are respectively The peak areas of 42.3 ppm, 35.9 ppm, 38.6 ppm, 30.6 ppm, 36.0 ppm, 31.5 ppm, 31.0 ppm, 37.2 ppm, 27.4 ppm, and the partial structures (Ι) and (ΙΙ The abundance ratio of carbon indicated by) is shown.
The ratio of 2,1-inserted propylene and the ratio of 1,3-inserted propylene with respect to the total propylene insertion were calculated by the following equations.
次に，上記プロピレン系重合体［Ａ］は，該重合体の融点をＴｍ［℃］，また，該重合体をフィルムに成形した場合の水蒸気透過度をＹ［ｇ／ｍ2／２４ｈｒ］とした場合に，ＴｍとＹとが次の関係式（１）を満足するものであることが好ましい。
（−０．２０）・Ｔｍ＋３５≦Ｙ≦（−０．３３）・Ｔｍ＋６０・・式（１）
Next, the propylene polymer [A] is the melting point of the polymer Tm [° C.], also the water vapor permeability in the case of forming the polymer into a film and Y [g / m 2 / 24hr ] In this case, it is preferable that Tm and Y satisfy the following relational expression (1).
(−0.20) · Tm + 35 ≦ Y ≦ (−0.33) · Tm + 60 ·· Equation (1)
上記水蒸気透過度は，ＪＩＳ Ｋ７１２９（１９９２年）「プラスチックフィルム及びシートの水蒸気透過度試験方法」により測定することができる。この測定においては，試験方法は赤外センサー法が採用され，また試験条件としては，試験温度４０±０．５℃，相対湿度（９０±２）％ＲＨが採用される。 The water vapor permeability can be measured by JIS K7129 (1992) “Test method for water vapor permeability of plastic films and sheets”. In this measurement, an infrared sensor method is adopted as a test method, and a test temperature of 40 ± 0.5 ° C. and a relative humidity (90 ± 2)% RH are adopted as test conditions.
上記式（１）の範囲内にあるプロピレン系重合体［Ａ］は，適度の水蒸気透過性を示す。適度の水蒸気透過性は，型内成形時において，成形に使用される飽和スチームの発泡粒子内への浸透を助長し，これにより発泡粒子の二次発泡性が高まり，発泡粒子間の空隙のない又は少ない型内成形体の製造が容易となる。
また，ポリプロピレン系樹脂発泡粒子の製造方法としては，樹脂粒子を水に分散させつつ発泡剤を含浸させた後，高温高圧下から低圧下に放出して発泡粒子化する方法が一般的であるが，この際，適度の水蒸気透過性は，樹脂粒子への水及び発泡剤の浸透を行いやすくする。その結果，樹脂粒子内における水及び発泡剤の分散が均一となり，得られる発泡粒子の気泡径を均一にし，また，発泡倍率を向上させることができる。
上記水蒸気透過度（Ｙ）がプロピレン系重合体の融点（Ｔｍ）との関係で表現されているのは，発泡粒子の製造時の発泡温度や型内成形時の飽和スチーム温度が，一般的に基材樹脂であるプロピレン系重合体の融点（Ｔｍ）が高いほど高くなり，融点（Ｔｍ）が低いほど低くなることに基づいている。
The propylene-based polymer [A] within the range of the above formula (1) exhibits moderate water vapor permeability. Moderate water vapor permeability facilitates the penetration of saturated steam used for molding into the foamed particles during molding, thereby increasing the secondary foamability of the foamed particles and eliminating voids between the foamed particles. Alternatively, it becomes easy to produce a small number of in-mold molded bodies.
Also, as a method for producing polypropylene resin expanded particles, a method in which resin particles are dispersed in water and impregnated with a foaming agent and then discharged from high temperature and pressure to low pressure to form expanded particles. In this case, the proper water vapor permeability facilitates the penetration of water and the foaming agent into the resin particles. As a result, the water and the foaming agent are uniformly dispersed in the resin particles, the cell diameter of the obtained foamed particles can be made uniform, and the expansion ratio can be improved.
The water vapor permeability (Y) is expressed in relation to the melting point (Tm) of the propylene-based polymer because the foaming temperature during the production of the foamed particles and the saturated steam temperature during the in-mold molding are generally This is based on the fact that the higher the melting point (Tm) of the propylene-based polymer that is the base resin, the higher the melting point (Tm), and the lower the melting point (Tm).
上記水蒸気透過度（Ｙ）が［（−０．２０）・Ｔｍ＋３５］を下回る場合には，基材樹脂への水蒸気や発泡剤の浸透性が劣るようになり，逆に［（−０．３３）・Ｔｍ＋６０］を上回る場合には，基材樹脂への水蒸気の浸透性が良くなり過ぎて，いずれにしても，発泡粒子の製造過程で樹脂粒子内における水や発泡剤の分散が不均一となりやすく，得られる発泡粒子の気泡径の均一性が低下するおそれがある。特に，上記水蒸気透過度（Ｙ）が［（−０．３３）・Ｔｍ＋６０］を上回る場合は，得られる発泡粒子内に粗大気泡が混在するおそれがある。 When the water vapor permeability (Y) is lower than [(−0.20) · Tm + 35], the permeability of the water vapor or the foaming agent to the base resin becomes inferior, and conversely [(−0.33 ) · Tm + 60], the water vapor permeability into the base resin becomes too good, and in any case, the dispersion of water and foaming agent in the resin particles becomes uneven in the process of producing the foam particles. This tends to reduce the uniformity of the bubble diameter of the resulting expanded particles. In particular, when the water vapor permeability (Y) exceeds [(−0.33) · Tm + 60], there is a possibility that coarse bubbles are mixed in the obtained foamed particles.
融点（Ｔｍ）と水蒸気透過度（Ｙ）とが式（１）の関係を満たす様なプロピレン系重合体は，該重合体を製造するにあたって，適当な触媒を選定することにより得ることができる。具体的には，上記メタロセン系触媒の中でも，架橋型ビス｛１，１’−（４―ヒドロアズレニル）｝ジルコニウムジクロリドを金属錯体成分として用いることにより，好適に得ることが出来る。かかる金属錯体成分の好ましい例は，前述した通りである。 A propylene polymer in which the melting point (Tm) and the water vapor permeability (Y) satisfy the relationship of the formula (1) can be obtained by selecting an appropriate catalyst in producing the polymer. Specifically, among the above metallocene catalysts, it can be suitably obtained by using bridged bis {1,1 '-(4-hydroazurenyl)} zirconium dichloride as a metal complex component. Preferred examples of such metal complex components are as described above.
また，本発明において，プロピレン系重合体［Ａ］の上記融点（Ｔｍ）は，１２５℃〜１６５℃が一般的であるが，１３０℃〜１６０℃が好ましく，１３３℃〜１５８℃がより好ましい。
尚，上記融点（Ｔｍ）は，ＪＩＳ Ｋ７１２１（１９８７年）に記載の「一定の熱処理を行った後，融解温度を測定する場合」を採用し（試験片の状態調節における加熱速度と冷却速度は，いずれも，毎分１０℃を採用），熱流束ＤＳＣ装置を使用し，加熱速度毎分１０℃にてＤＳＣ曲線を描かせ，得られたＤＳＣ曲線上の融解ピークの頂点が採用される。尚，複数の頂点が観測された場合には，高温側のベースラインを基準に融解ピークの頂点が最も高いものが採用され，最も高い融解ピークの頂点が複数ある場合はそれらの相加平均値が採用される。
In the present invention, the melting point (Tm) of the propylene polymer [A] is generally 125 ° C. to 165 ° C., preferably 130 ° C. to 160 ° C., more preferably 133 ° C. to 158 ° C.
For the melting point (Tm), “when melting temperature is measured after performing a certain heat treatment” described in JIS K7121 (1987) is adopted (the heating rate and cooling rate in the condition adjustment of the test piece are , Both adopt 10 ° C./min), use a heat flux DSC apparatus to draw a DSC curve at a heating rate of 10 ° C./min, and adopt the peak of the melting peak on the obtained DSC curve. If multiple vertices are observed, the one with the highest melting peak based on the baseline on the high temperature side is adopted, and if there are multiple vertices with the highest melting peak, the arithmetic average value thereof is used. Is adopted.
次に，上記第１の発明における，上記プロピレン系重合体［Ｂ］について説明する。
上記プロピレン系重合体［Ｂ］は，上記の要件（ａ）及び（ｂ）のうち要件（ａ）だけを有するプロピレン系重合体である。即ち，上記プロピレン系重合体［Ｂ］は，プロピレンから得られる構造単位が１００〜８５モル％，エチレン及び／又は炭素数４〜２０のα−オレフィンから得られる構造単位が０〜１５モル％存在するという要件（ａ）を満たし，上記要件（ｂ）については満足しないものである。上記プロピレン系重合体［Ｂ］は，通常，上記（１）式も満足しない。このようなプロピレン系重合体［Ｂ］は，例えばチーグラー／ナッタ触媒等を用いて得ることができる。
上記要件（ａ）は，上記プロピレン系重合体［Ａ］の要件［ａ］と同様である。
Next, the propylene polymer [B] in the first invention will be described.
The propylene polymer [B] is a propylene polymer having only the requirement (a) among the requirements (a) and (b). That is, the propylene polymer [B] has 100 to 85 mol% of structural units obtained from propylene, and 0 to 15 mol% of structural units obtained from ethylene and / or an α-olefin having 4 to 20 carbon atoms. The requirement (a) to be satisfied is satisfied, and the requirement (b) is not satisfied. The propylene polymer [B] usually does not satisfy the formula (1). Such a propylene polymer [B] can be obtained using, for example, a Ziegler / Natta catalyst.
The requirement (a) is the same as the requirement [a] of the propylene polymer [A].
上記プロピレン系重合体［Ａ］に対して，上記プロピレン系重合体［Ｂ］を混合してなる樹脂組成物を基材樹脂として用いて得られる樹脂発泡粒子は，上記プロピレン系重合体［Ａ］を単独で用いて得られる樹脂発泡粒子に比べて，型内成形に於ける二次発泡性に優れ，したがって，成形体の表面外観が優れるものになるという特徴がある。 Resin foam particles obtained by using, as a base resin, a resin composition obtained by mixing the propylene polymer [B] with the propylene polymer [A] is the propylene polymer [A]. Compared to resin foam particles obtained by using the selenium alone, the secondary foamability in the in-mold molding is excellent, and therefore the surface appearance of the molded article is excellent.
この理由は必ずしも定かではないが，以下の如き機構によるものと推測される。
すなわち，上記プロピレン系重合体［Ａ］は，一般に狭い分子量分布を有し，一方，上記プロピレン系重合体［Ｂ］は，一般に広い分子量分布を有する。したがって，上記プロピレン系重合体［Ａ］に対して，上記プロピレン系重合体［Ｂ］を混合してなる樹脂組成物は広い分子量分布を有するものとなる。
The reason for this is not necessarily clear, but is presumed to be due to the following mechanism.
That is, the propylene polymer [A] generally has a narrow molecular weight distribution, while the propylene polymer [B] generally has a wide molecular weight distribution. Therefore, the resin composition obtained by mixing the propylene polymer [B] with the propylene polymer [A] has a wide molecular weight distribution.
また，樹脂粒子を発泡させて発泡粒子を製造する過程とは，樹脂部分を延伸する過程と見なすことができるため，樹脂が配向される過程と考えることができる。この配向の度合が高い場合には，配向した部分は，発泡粒子が加熱されたときに二次発泡を抑制する方向に作用すると考えられる。逆に，配向の程度が低いほど，型内成形においては二次発泡性が高くなると考えられる。
そして，一般に分子量分布が広い場合には，それが狭い場合に比べて配向される度合が低い。このことから，上記プロピレン系重合体［Ａ］に対して，上記プロピレン系重合体［Ｂ］を混合してなる樹脂組成物を用いて得られるポリプロピレン系樹脂発泡粒子は，上記プロピレン系重合体［Ａ］を単独で用いて得られる樹脂発泡粒子に比して，二次発泡力が高くなるものと推定される。
Further, the process of producing foamed particles by foaming the resin particles can be regarded as a process of stretching the resin portion, and thus can be considered as a process of orienting the resin. When the degree of orientation is high, the oriented part is considered to act in a direction to suppress secondary foaming when the foamed particles are heated. Conversely, the lower the degree of orientation, the higher the secondary foamability in in-mold molding.
In general, when the molecular weight distribution is wide, the degree of orientation is lower than when the molecular weight distribution is narrow. From this, the polypropylene resin expanded particles obtained by using the resin composition obtained by mixing the propylene polymer [B] with the propylene polymer [A] are the propylene polymer [A]. It is presumed that the secondary foaming power is higher than the resin foam particles obtained by using A] alone.
また，上記プロピレン系重合体［Ａ］と上記プロピレン系重合体［Ｂ］を混合してなる樹脂組成物を基材樹脂として用いて得られる樹脂発泡粒子は，上記プロピレン系重合体［Ｂ］を単独で用いて得られる樹脂発泡粒子に比べて，低温での成形が可能であり，更に得られる成形体の力学的特性，例えば，圧縮強度や曲げ強度に優れるという特徴がある。 Further, the resin expanded particles obtained by using as a base resin a resin composition obtained by mixing the propylene polymer [A] and the propylene polymer [B] is obtained by using the propylene polymer [B]. Compared to resin foam particles obtained by using alone, molding at a low temperature is possible, and further, mechanical properties of the obtained molded body, for example, excellent compressive strength and bending strength are characteristic.
上記プロピレン系重合体［Ａ］と上記プロピレン系重合体［Ｂ］との配合比は，上記プロピレン系重合体［Ａ］５〜９５重量％に対して，上記プロピレン系重合体［Ｂ］９５〜５重量％（ただし，プロピレン系重合体［Ａ］とプロピレン系重合体［Ｂ］との合計量は１００重量％である）の範囲であることが必要である。
プロピレン系重合体［Ａ］の配合比が５重量％未満である場合には，プロピレン系重合体［Ｂ］が主たる成分であるために，得られる発泡粒子中の気泡径が小さなものとなる傾向があり，その力学特性が不十分となるおそれがある。また，かかる発泡樹脂粒子を型内成形するには高温の水蒸気が必要となるおそれがある。
一方，プロピレン系重合体［Ａ］の配合比が９５重量％を越える場合には，得られるポリプロピレン系樹脂発泡粒子は，その二次発泡性が不十分となるおそれがある。
The blending ratio of the propylene polymer [A] and the propylene polymer [B] is 5 to 95% by weight of the propylene polymer [A] and 95 to 95% of the propylene polymer [B]. It is necessary to be in the range of 5% by weight (however, the total amount of the propylene polymer [A] and the propylene polymer [B] is 100% by weight).
When the blending ratio of the propylene polymer [A] is less than 5% by weight, since the propylene polymer [B] is the main component, the bubble diameter in the obtained expanded particles tends to be small. There is a risk that its mechanical properties will be insufficient. In addition, high-temperature steam may be required to mold the foamed resin particles in the mold.
On the other hand, when the blending ratio of the propylene-based polymer [A] exceeds 95% by weight, the obtained polypropylene-based resin foamed particles may have insufficient secondary foamability.
上記プロピレン系重合体［Ａ］と上記プロピレン系重合体［Ｂ］との配合比は，好ましくは，上記プロピレン系重合体［Ａ］１０〜８０重量％に対して，上記プロピレン系重合体［Ｂ］９０〜２０重量％（ただし，プロピレン系重合体［Ａ］とプロピレン系重合体［Ｂ］との合計量は１００重量％）がよく，さらに好ましくは，上記プロピレン系重合体［Ａ］２０〜８０重量％に対して，上記プロピレン系重合体［Ｂ］８０〜２０重量％（ただし，プロピレン系重合体［Ａ］とプロピレン系重合体［Ｂ］との合計量は１００重量％）がよい。 The blending ratio of the propylene polymer [A] and the propylene polymer [B] is preferably 10 to 80% by weight of the propylene polymer [A]. ] 90 to 20% by weight (provided that the total amount of the propylene polymer [A] and the propylene polymer [B] is 100% by weight), more preferably the propylene polymer [A] 20 to The propylene polymer [B] is 80 to 20% by weight with respect to 80% by weight (however, the total amount of the propylene polymer [A] and the propylene polymer [B] is 100% by weight).
本発明においては，上記プロピレン系重合体［Ａ］は，更に下記の要件（ｄ）を有することが好ましい（請求項２）。
（ｄ）頭−尾結合からなるプロピレン単位連鎖部における，１３Ｃ−ＮＭＲで測定したときのアイソタクチックトリアッド分率は９７％以上であること。
この場合には，上記ポリプロピレン系樹脂組成物を基材樹脂として用いて得られる発泡粒子中の気泡径の均一性が，より高くなるという効果を得ることができる。
In the present invention, the propylene polymer [A] preferably further has the following requirement (d) (Claim 2).
(D) The isotactic triad fraction in the propylene unit chain part composed of head-to-tail bonds as measured by 13C-NMR is 97% or more.
In this case, the effect that the uniformity of the bubble diameter in the expanded particle obtained by using the said polypropylene resin composition as a base resin becomes higher can be acquired.
即ち，樹脂組成物の構成成分であるプロピレン系重合体［Ａ］として，既に述べた要件（ａ）及び（ｂ）に加えて，更に頭−尾結合からなるプロピレン単位連鎖部の，１３Ｃ−ＮＭＲ（核磁気共鳴法）で測定したアイソタクチックトリアッド分率（即ち，ポリマー鎖中の任意のプロピレン単位３連鎖のうち，各プロピレン単位が頭−尾で結合し，かつプロピレン単位中のメチル分岐の方向が同一であるプロピレン単位３連鎖の割合）が９７％以上であるものを用いる。 That is, as a propylene-based polymer [A] which is a constituent component of the resin composition, in addition to the requirements (a) and (b) already described, 13C-NMR of a propylene unit chain part further comprising a head-to-tail bond Isotactic triad fraction measured by (nuclear magnetic resonance method) (that is, propylene units are bonded head-to-tail out of three arbitrary propylene units in the polymer chain, and methyl branching in propylene units) The ratio of the three propylene unit chains having the same direction is 97% or more.
なお，アイソタクチックトリアッド分率を，以下適宜，ｍｍ分率と記載する。ｍｍ分率が９７％未満の場合には，上記ポリプロピレン系樹脂組成物の機械的物性が低下する。そのため，これを基材樹脂として用いて得られる発泡粒子からなる成形体の機械的物性も低下するおそれがある。
なお，更に好ましくは，上記ｍｍ分率は９８％以上である。
The isotactic triad fraction is hereinafter referred to as mm fraction as appropriate. When the mm fraction is less than 97%, the mechanical properties of the polypropylene resin composition are lowered. For this reason, there is a possibility that the mechanical properties of a molded article made of expanded particles obtained by using this as a base resin also deteriorate.
More preferably, the mm fraction is 98% or more.
次に，上記プロピレン系重合体［Ａ］は，更に下記の要件（ｅ）を有することが好ましい（請求項３）。
（ｅ）メルトフローレートが０．５〜１００ｇ／１０分であること。
Next, the propylene polymer [A] preferably further has the following requirement (e) (Claim 3).
(E) The melt flow rate is 0.5 to 100 g / 10 minutes.
この場合には，工業的に有用な製造効率を保ちつつ上記ポリプロピレン系樹脂組成物を生産することができる。さらに，これを基材樹脂として用いて得られる発泡粒子からなる成形体は，その力学物性が優れるという効果を得ることができる。 In this case, the polypropylene resin composition can be produced while maintaining industrially useful production efficiency. Furthermore, a molded body made of expanded particles obtained by using this as a base resin can obtain an effect that its mechanical properties are excellent.
上記メルトフローレート（ＭＦＲ）が，０．５ｇ／１０分未満の場合には，上記ポリプロピレン系樹脂組成物の製造効率，なかでも後述する溶融混練を行う際の生産性が低下するおそれがある。また，ＭＦＲが上記の１００ｇ／１０分を超える場合には，得られるポリプロピレン系樹脂組成物を基材樹脂として用いた発泡粒子をさらに成形して得られる成形体の圧縮強度，引張強度などの力学物性が低くなるおそれがある。なお，好ましくは，１．０〜５０ｇ／１０分，更には１．０〜３０ｇ／１０分である。上記ＭＦＲとは，ＪＩＳ Ｋ６９２１−２（１９９７年）の表３に記載された条件に従って測定されたメルトマスフローレイトを意味する。 When the melt flow rate (MFR) is less than 0.5 g / 10 minutes, the production efficiency of the polypropylene resin composition, particularly the productivity during melt kneading described later, may be reduced. When the MFR exceeds 100 g / 10 min, the mechanical properties such as compression strength and tensile strength of a molded product obtained by further molding expanded particles using the obtained polypropylene resin composition as a base resin. There is a risk that physical properties will be low. In addition, Preferably, it is 1.0-50 g / 10min, Furthermore, it is 1.0-30 g / 10min. The MFR means a melt mass flow rate measured according to the conditions described in Table 3 of JIS K6921-2 (1997).
次に，上記ポリプロピレン系樹脂組成物は，示差走査熱量計による測定で，実質上単独の融解ピークを示すことが好ましい（請求項４）。
「示差走査熱量計による測定で，実質上単独の融解ピークを示す」とは，上記融点（Ｔｍ）を測定する方法と同じ方法にて上記ポリプロピレン系樹脂組成物の融点を測定した場合において，１つの融解ピークとして観察されることを意味する場合のみならず，複数の融解ピークが観察された場合であっても，隣合う融解ピークの頂点間の温度差（高温側融解ピークの頂点−低温側融解ピークの頂点）が７℃以内の場合をも包含するが，その温度差は５℃以内であることが好ましく，３℃以内であることがより好ましい。
Next, the polypropylene resin composition preferably exhibits a substantially single melting peak as measured by a differential scanning calorimeter (Claim 4).
“A differential scanning calorimeter indicates a substantially single melting peak” means that when the melting point of the polypropylene resin composition is measured by the same method as the method of measuring the melting point (Tm), The difference in temperature between the vertices of adjacent melting peaks (top of the high-temperature side melting peak minus the low-temperature side), even when multiple melting peaks are observed. Although the case where the peak of the melting peak is within 7 ° C. is included, the temperature difference is preferably within 5 ° C., more preferably within 3 ° C.
ただし，この場合において，その温度差は，プロピレン系重合体［Ａ］及びプロピレン系重合体［Ｂ］の融点をそれぞれ単独で測定した際に得られる，それぞれの融解ピークの頂点の差（高温側融解ピークの頂点−低温側融解ピークの頂点）よりも小さくなければならない。
上記の隣合う融解ピークの頂点間の温度差が小さいほど，上記プロピレン系重合体［Ａ］と上記プロピレン系重合体［Ｂ］とが相互に高いレベルで溶解していることを意味し，樹脂組成物としての均一性が高いことを示す。その結果，かかるポリプロピレン系樹脂組成物を基材樹脂として用いて得られる発泡樹脂粒子においては，型内成形時の二次発泡性に優れるものとなる。
尚，本発明において，上記プロピレン系重合体［Ｂ］の融点は，使用される上記プロピレン系重合体［Ａ］の融点と同じであっても構わないが，両重合体の融点は２℃以上離れていることが好ましく，３℃以上離れていることが好ましく，５〜３０℃離れていることがより好ましい。
However, in this case, the temperature difference is the difference in the peak of each melting peak (high temperature side) obtained when the melting points of the propylene polymer [A] and the propylene polymer [B] are measured individually. The peak of the melting peak minus the peak of the low temperature side melting peak).
The smaller the temperature difference between the vertices of the adjacent melting peaks, the more the propylene polymer [A] and the propylene polymer [B] are dissolved at a higher level. It shows that the uniformity as a composition is high. As a result, in the foamed resin particles obtained using such a polypropylene resin composition as a base resin, the secondary foamability during in-mold molding is excellent.
In the present invention, the melting point of the propylene polymer [B] may be the same as the melting point of the propylene polymer [A] used, but the melting point of both polymers is 2 ° C. or higher. It is preferable that they are separated, preferably 3 ° C. or more, more preferably 5 to 30 ° C.
なお，本発明にかかるポリプロピレン系樹脂組成物は，これを基材樹脂としてポリプロピレン系樹脂発泡粒子を得るための材料などとして用いられる。さらに，このポリプロピレン系樹脂発泡粒子を成形型内に充填して，加熱することにより発泡させて，型内成形体を得ることもできる。 In addition, the polypropylene resin composition concerning this invention is used as a material etc. for obtaining a polypropylene resin expanded particle by using this as a base resin. Furthermore, the polypropylene resin expanded particles can be filled in a mold and foamed by heating to obtain an in-mold molded product.
次に，上記ポリプロピレン系樹脂発泡粒子は，下記の要件（ｆ）を満足する発泡剤を用いて発泡していることが好ましい。
（ｆ）上記発泡剤の臨界温度をＴｃ［℃］とした場合に，Ｔｃが下記の式（２）を満足すること。
−９０℃≦Ｔｃ≦４００℃ 式（２）
Next , it is preferable that the said polypropylene resin expanded particle is expanded using the foaming agent which satisfies the following requirements (f) .
(F) When the critical temperature of the blowing agent is Tc [° C.], Tc satisfies the following formula (2).
−90 ° C. ≦ Tc ≦ 400 ° C. Formula (2)
この場合には，得られるポリプロピレン系樹脂発泡粒子の気泡径が均一となる傾向があり，その結果として，かかる発泡粒子を用いて得られる型内発泡成形体の力学的特性が良好となる。 In this case, the cell diameter of the obtained polypropylene resin expanded particles tends to be uniform, and as a result, the mechanical properties of the in-mold expanded molded product obtained using such expanded particles are improved.
Ｔｃが−９０℃未満の場合には，得られるポリプロピレン系樹脂発泡粒子の気泡径の不均一さが顕著となるおそれがある。その理由は必ずしも定かではないが，発泡が急激に進行することに起因すると推定される。
一方，４００℃を越える場合には，高倍率，例えば嵩密度が０．１ｇ／ｃｍ3以下のポリプロピレン系樹脂発泡粒子を得ることが極めて困難となるおそれがある。
When Tc is less than −90 ° C., there is a possibility that the non-uniformity of the cell diameter of the obtained polypropylene resin foamed particles becomes remarkable. The reason is not necessarily clear, but it is presumed to be caused by the rapid progress of foaming.
On the other hand, when the temperature exceeds 400 ° C., it may be very difficult to obtain expanded polypropylene resin particles having a high magnification, for example, a bulk density of 0.1 g / cm 3 or less.
上記発泡剤の具体例としては，次の通りである。尚，物質名の後に臨界温度（℃）を併記する。メタン（−８２），エタン（３２），プロパン（９７），ブタン（１５２），イソブタン（１３５），ペンタン（１９７），ヘキサン（２３５），シクロペンタン（２３９），シクロヘキサン（２８０），等の鎖状または環状低級脂肪族炭化水素類，ジクロロジフルオロメタン（１１２），トリクロロモノフルオロメタン（１９８）等のハロゲン化炭化水素類，二酸化炭素（３１）等の無機ガス等が挙げられる。 Specific examples of the foaming agent are as follows. The critical temperature (° C) is also written after the substance name. Chains of methane (-82), ethane (32), propane (97), butane (152), isobutane (135), pentane (197), hexane (235), cyclopentane (239), cyclohexane (280), etc. And cyclic lower aliphatic hydrocarbons, halogenated hydrocarbons such as dichlorodifluoromethane (112) and trichloromonofluoromethane (198), and inorganic gases such as carbon dioxide (31).
また，上記の式（２）を満足する発泡剤の中でも，更に，下記の式（３）を満足する場合には，特にこれら発泡剤を取扱うにあたり，特殊な設備や装置を必要としないという利点がある。
０℃≦Ｔｃ≦３００℃ 式（３）
In addition, among the foaming agents that satisfy the above formula (2), when the following formula (3) is further satisfied, there is an advantage that special equipment and equipment are not particularly required when handling these foaming agents. There is.
0 ° C. ≦ Tc ≦ 300 ° C. Formula (3)
更に，下記式（４）を満足する場合には，前項に述べた工業的有用性に加え，得られる発泡粒子の気泡径が極めて均一になるという効果がある。
３０℃≦Ｔｃ≦２００℃ 式（４）
なお，上記発泡剤は，単独で使用してもよいし，また複数の発泡剤を組み合わせて用いてもよい。
Furthermore, when the following formula (4) is satisfied, in addition to the industrial utility described in the previous section, there is an effect that the bubble diameter of the obtained expanded particles becomes extremely uniform.
30 ° C. ≦ Tc ≦ 200 ° C. Formula (4)
In addition, the said foaming agent may be used independently and may be used combining several foaming agents.
また，上記発泡剤として，窒素，酸素，空気，二酸化炭素，水といったいわゆる無機ガスを発泡剤の全部として又は主成分として（発泡剤全体の５０モル％以上，好ましくは７０モル％以上，より好ましくは９０モル％以上。）使用した場合には，最終的な型内発泡成形体のエネルギー吸収量を高めることができる。これらの無機ガスの中でも，発泡粒子の見かけ密度の安定性，環境負荷やコストなどを考慮した場合，窒素，空気，二酸化炭素が特に好ましい。 Further, as the foaming agent, so-called inorganic gas such as nitrogen, oxygen, air, carbon dioxide and water is used as the whole foaming agent or as a main component (50 mol% or more, preferably 70 mol% or more of the entire foaming agent, more preferably 90 mol% or more.) When used, the energy absorption amount of the final in-mold foam-molded product can be increased. Among these inorganic gases, nitrogen, air, and carbon dioxide are particularly preferable in consideration of the stability of the apparent density of the expanded particles, environmental load, and cost.
次に，上記ポリプロピレン系樹脂発泡粒子においては，プロピレン系重合体［Ａ］とプロピレン系重合体［Ｂ］とからなる上記ポリプロピレン系樹脂組成物の基材樹脂に対し，前記の通り，本発明の効果を損なわない範囲であれば，他のポリマー成分や添加剤を混合することができる。 Next , in the polypropylene resin expanded particles, as described above, the base resin of the polypropylene resin composition comprising the propylene polymer [A] and the propylene polymer [B] is as described above. Other polymer components and additives can be mixed as long as the effects are not impaired.
上記，他のポリマー成分としては，例えば高密度ポリエチレン，低密度ポリエチレン，エチレンとα−オレフィン（炭素数４以上）の共重合体である直鎖状低密度ポリエチレン等のエチレン系樹脂；ポリブテン樹脂；エチレン−プロピレン系ゴム；エチレン−プロピレン−ジエン系ゴム；スチレン−ジエンブロック共重合体やスチレン−ジエンブロック共重合体のエチレン系二重結合の少なくとも一部を水素添加により飽和してなる水素添加ブロック共重合体等のスチレン系熱可塑性エラストマー；これら樹脂，エラストマー或いはゴムのアクリル酸系モノマーによるグラフト変成体等が挙げられる。本発明ではこれら樹脂，エラストマー，ゴム或いはそれら変成物を単独で又は２以上を組み合わせて使用することができる。 Examples of the other polymer components include high-density polyethylene, low-density polyethylene, and ethylene-based resins such as linear low-density polyethylene that is a copolymer of ethylene and α-olefin (4 or more carbon atoms); polybutene resin; Ethylene-propylene rubber; ethylene-propylene-diene rubber; hydrogenated block formed by saturating at least part of ethylene double bonds of styrene-diene block copolymer or styrene-diene block copolymer by hydrogenation Examples thereof include styrene-based thermoplastic elastomers such as copolymers; graft modified products of these resins, elastomers or rubbers with acrylic acid-based monomers. In the present invention, these resins, elastomers, rubbers or modified products thereof can be used alone or in combination of two or more.
上記添加剤としては，発泡核剤，着色剤，帯電防止剤，滑剤等の各種の添加剤を添加することができる。これらは，通常，後述する溶融混練の際に一緒に添加されて樹脂粒子中に含有される。
上記発泡核剤としては，タルク，炭酸カルシウム，シリカ，酸化チタン，石膏，ゼオライト，ホウ砂，ホウ酸亜鉛，水酸化アルミニウム等の無機化合物の他，カーボン，リン酸系核剤，フェノール系核剤，アミン系核剤等の有機系核剤が挙げられる。これら各種添加剤の添加量は，その添加目的により異なるが，上記基材樹脂１００重量部に対して１５重量部以下であり，好ましくは８重量部以下，更には５重量部以下が最も好ましい。
As said additive, various additives, such as a foam nucleating agent, a coloring agent, an antistatic agent, and a lubricant, can be added. These are usually added together during the melt kneading described later and contained in the resin particles.
The above foaming nucleating agents include inorganic compounds such as talc, calcium carbonate, silica, titanium oxide, gypsum, zeolite, borax, zinc borate, aluminum hydroxide, carbon, phosphate nucleating agent, phenolic nucleating agent. And organic nucleating agents such as amine nucleating agents. The addition amount of these various additives varies depending on the addition purpose, not more than 15 parts by weight relative to the base resin 100 parts by weight, preferably 8 parts by weight or less, and more most preferably 5 parts by weight or less.
本発明において，上記基材樹脂としてのプロピレン系重合体［Ａ］とプロピレン系重合体［Ｂ］とを混合するとき，及び，上記基材樹脂への上記その他の成分を混合するときには，固体混合により行うこともできるが，一般には溶融混練が利用される。即ち，例えばロール，スクリュー，バンバリーミキサー，ニーダー，ブレンダー，ミル等の各種混練機を使って，上記プロピレン系重合体同士，または上記基材樹脂とその他の成分等とを所望の温度で混練し，混練後は，発泡粒子の製造に適した大きさの樹脂粒子に成形する。 In the present invention, when mixing the propylene polymer [A] and the propylene polymer [B] as the base resin, and when mixing the other components to the base resin, solid mixing In general, melt-kneading is used. That is, for example, using various kneaders such as rolls, screws, Banbury mixers, kneaders, blenders, and mills, the propylene polymers or the base resin and other components are kneaded at a desired temperature, After kneading, it is molded into resin particles of a size suitable for the production of expanded particles.
また，押出機内で溶融混練した後に，押出機先端に取り付けた微***を有する口金より混練物を紐状に押出し，引取機を備えた切断機で規定の重量または大きさに切断し樹脂粒子を得る方法が好ましい。
また，一般に，樹脂粒子１個の重量が０．１〜２０ｍｇであれば発泡粒子の製造に支障はない。樹脂粒子１個の重量が０．２〜１０ｍｇの範囲にあって，更に粒子間の重量のばらつきが少であれば，発泡粒子の製造が容易になり，得られる発泡粒子の密度ばらつきも小となり，成形型内等への発泡樹脂粒子の充填性が良好となる。
In addition, after melt-kneading in the extruder, the kneaded product is extruded in a string form from a die having a micro hole attached to the tip of the extruder, and is cut into a specified weight or size with a cutting machine equipped with a take-off machine, and resin particles are removed. The obtaining method is preferred.
In general, if the weight of one resin particle is 0.1 to 20 mg, there is no problem in the production of expanded particles. If the weight of one resin particle is in the range of 0.2 to 10 mg and the variation in the weight between the particles is small, the production of the expanded particles is facilitated and the density variation of the obtained expanded particles is also small. , The filling property of the foamed resin particles into the mold is improved.
発泡粒子を得る方法としては，樹脂粒子に揮発性発泡剤を含浸した後，加熱発泡する方法，具体的には，例えば，特公昭４９−２１８３号公報，同５６−１３４４号公報，西ドイツ特開第１２８５７２２号公報，同第２１０７６８３号公報などに記載の方法を使用することができる。 As a method for obtaining expanded particles, a method in which resin particles are impregnated with a volatile foaming agent and then heated and foamed, specifically, for example, Japanese Patent Publication Nos. 49-2183 and 56-1344, West German Patent The methods described in Japanese Patent Nos. 1285722 and 2107683 can be used.
樹脂粒子に発泡剤を含浸した後，加熱発泡させる場合，密閉し開放できる圧力容器に揮発性発泡剤と共に樹脂粒子を入れ，基材樹脂の軟化温度以上に加熱すると共に，樹脂粒子に揮発性発泡剤を含浸させる。その後，密閉容器内の内容物を密閉容器から低圧の雰囲気に放出した後，乾燥処理する。これにより，発泡粒子が得られる。 When resin particles are impregnated with a foaming agent and then heated and foamed, the resin particles are placed in a pressure vessel that can be sealed and opened together with the volatile foaming agent and heated above the softening temperature of the base resin, and volatile foaming is applied to the resin particles. Impregnating agent. After that, the contents in the sealed container are discharged from the sealed container to a low-pressure atmosphere and then dried. Thereby, foamed particles are obtained.
本発明のポリプロピレン系樹脂発泡粒子は，示差走査熱量測定によって求められるＤＳＣ曲線（但し，発泡粒子２〜４ｍｇを示差走査熱量計によって１０℃／分の昇温速度で２０℃から２００℃まで昇温した時に得られるＤＳＣ曲線）において，基材樹脂に固有の吸熱ピークに加え，更にそれよりも高温の吸熱ピークを示すことが好ましい。 The expanded polypropylene resin particles of the present invention have a DSC curve obtained by differential scanning calorimetry (however, 2 to 4 mg of expanded particles are heated from 20 ° C. to 200 ° C. at a heating rate of 10 ° C./min by a differential scanning calorimeter. In addition to the endothermic peak inherent in the base resin, it is preferable that the endothermic peak at a higher temperature than the endothermic peak is obtained.
上記ＤＳＣ曲線に基材樹脂に固有の吸熱ピークに加え，更にそれよりも高温の吸熱ピークが現れる発泡粒子は，例えば特開２００２−２００６３５号公報等に記載された方法で製造することが可能であり，上記樹脂粒子を発泡させる際の条件，具体的には低圧の雰囲気に放出するまでの温度，圧力，時間等を制御することにより得られる。 In addition to the endothermic peak inherent in the base resin in the DSC curve, the expanded particles in which an endothermic peak higher than that can be produced can be produced, for example, by the method described in JP-A-2002-200355. Yes, it can be obtained by controlling the conditions for foaming the resin particles, specifically the temperature, pressure, time, etc. until the resin particles are released into a low-pressure atmosphere.
尚，前記の密閉容器内の内容物を密閉容器から低圧の雰囲気に放出して発泡粒子を製造する方法において，樹脂粒子中に予め分解型発泡剤を練り込んでおけば圧力容器中に発泡剤を配合しなくとも，上記発泡粒子を得ることが可能である。
上記分解型発泡剤としては，樹脂粒子の発泡温度で分解してガスを発生するものであれば使用することができる。具体的には，たとえば重炭酸ナトリウム，炭酸アンモニウム，アジド化合物，アゾ化合物等が挙げられる。
In the method of producing foamed particles by releasing the contents in the sealed container from the sealed container to a low-pressure atmosphere, if the decomposable foaming agent is kneaded in advance in the resin particles, the foaming agent is put into the pressure container. Even without blending, it is possible to obtain the expanded particles.
As the above decomposable foaming agent, any gas can be used as long as it decomposes at the foaming temperature of the resin particles to generate gas. Specifically, sodium bicarbonate, ammonium carbonate, an azide compound, an azo compound, etc. are mentioned, for example.
また，加熱発泡時には，樹脂粒子の分散媒として，水，アルコールなどを使用することが好ましい。更に樹脂粒子が分散媒に均一に分散する様に，酸化アルミニウム，第三リン酸カルシウム，ピロリン酸マグネシウム，酸化亜鉛，カオリン，アムスナイト，マイカ，クレーなどの難水溶性の無機物質，ポリビニルピロリドン，ポリビニルアルコール，メチルセルロースなどの水溶性高分子系保護コロイド剤，ドデシルベンゼンスルホン酸ナトリウム，アルカンスルホン酸ナトリウム等のアニオン性界面活性剤を単独または２以上混合して使用するのが好ましい。 Further, at the time of heating and foaming, it is preferable to use water, alcohol or the like as a dispersion medium for the resin particles. Furthermore, poorly water-soluble inorganic substances such as aluminum oxide, tricalcium phosphate, magnesium pyrophosphate, zinc oxide, kaolin, amusnite, mica, clay, etc., polyvinyl pyrrolidone, polyvinyl alcohol, so that the resin particles are uniformly dispersed in the dispersion medium It is preferable to use a water-soluble polymeric protective colloid agent such as methylcellulose, an anionic surfactant such as sodium dodecylbenzenesulfonate, sodium alkanesulfonate, or a mixture of two or more.
更に，上記分散媒には，分散剤の分散力を強化する（分散剤の添加量を少なくしても容器内で樹脂粒子の融着を防止する）分散強化剤を添加してもよい。特に，見かけ密度が１００ｇ／Ｌ以上という低発泡の発泡粒子を製造する場合には，分散強化剤を使用することが好ましい。
このような分散強化剤としては，４０℃の水１００ｃｃに対して少なくとも１ｍｇ以上溶解し得る無機物質であって，該化合物の陰イオンまたは陽イオンの少なくとも一方が２価または３価のものを用いることができる。このような無機物質としては，たとえば，塩化マグネシウム，硝酸マグネシウム，硫酸マグネシウム，塩化アルミニウム，硝酸アルミニウム，硫酸アルミニウム，塩化鉄，硫酸鉄，硝酸鉄等が例示される。
Furthermore, a dispersion strengthening agent that strengthens the dispersing power of the dispersing agent (which prevents the resin particles from being fused in the container even if the amount of the dispersing agent added is small) may be added to the dispersion medium. In particular, when producing low-expanded expanded particles having an apparent density of 100 g / L or more, it is preferable to use a dispersion strengthening agent.
As such a dispersion strengthening agent, an inorganic substance that can be dissolved in at least 1 mg or more in 100 cc of water at 40 ° C., wherein at least one of the anion or cation of the compound is divalent or trivalent, is used. be able to. Examples of such inorganic substances include magnesium chloride, magnesium nitrate, magnesium sulfate, aluminum chloride, aluminum nitrate, aluminum sulfate, iron chloride, iron sulfate, and iron nitrate.
低圧の雰囲気に樹脂粒子を放出する際には，当該放出を容易にするため，前記と同様な無機ガス又は揮発性発泡剤を外部より密閉容器に導入することにより密閉容器内の圧力を一定に保持することが好ましい。 When releasing resin particles to a low-pressure atmosphere, in order to facilitate the release, the same pressure as in the above is introduced by introducing the same inorganic gas or volatile foaming agent into the sealed container from the outside. It is preferable to hold.
上記した方法によって得られたポリプロピレン系樹脂発泡粒子は，大気圧下で熟成した後，必要に応じて気泡内圧を高めてから，水蒸気や熱風を用いて加熱することによって，より高発泡倍率の発泡粒子とすることが可能である。 Polypropylene resin foam particles obtained by the above-mentioned method are expanded at a higher expansion ratio by aging at atmospheric pressure and then increasing the internal pressure of the bubbles as necessary, followed by heating with steam or hot air. It can be a particle.
次に，本発明のポリプロピレン系樹脂発泡粒子は，様々な条件の金型を使用して成形される。例えば，大気圧または減圧下の凹凸一対の金型よりなるキャビティー内へポリプロピレン系樹脂発泡粒子を充填した後に，金型キャビティー体積を５〜７０％減少する様に圧縮し，次いでスチーム等の熱媒をキャビティー内に導入してポリプロピレン系樹脂発泡粒子を加熱融着させる圧縮成型法が挙げられる（例えば特公昭４６−３８３５９号公報）。 Next, the expanded polypropylene resin particles of the present invention are molded using molds under various conditions. For example, after filling polypropylene resin foam particles into a cavity consisting of a pair of concave and convex molds under atmospheric pressure or reduced pressure, the mold cavity volume is compressed to reduce by 5 to 70%, and then steam or the like is used. There is a compression molding method in which a heat medium is introduced into a cavity and polypropylene resin foam particles are heated and fused (for example, Japanese Patent Publication No. 46-38359).
また，揮発性発泡剤または無機ガスの１種または２種以上で予め発泡樹脂粒子を処理して発泡樹脂粒子の二次発泡力を高め，次いでその二次発泡力を保持しつつ大気圧または減圧下の凹凸一対の金型よりなるキャビティー内に発泡樹脂粒子を充填した後，金型キャビティー内に熱媒を導入して発泡樹脂粒子を加熱融着させる加圧熟成法もある（例えば特公昭５１−２２９５１号公報）。 Also, the foamed resin particles are pretreated with one or more volatile foaming agents or inorganic gases to increase the secondary foaming power of the foamed resin particles, and then the atmospheric pressure or reduced pressure is maintained while maintaining the secondary foaming power. There is also a pressure aging method in which foamed resin particles are filled into a cavity composed of a pair of concave and convex lower molds, and then a heat medium is introduced into the mold cavity to heat-fuse the foamed resin particles (for example, a special technique). (Publication No. 51-22951).
また，圧縮ガスにより大気圧以上に加圧した金型キャビティーに，当該圧力以上に加圧した発泡樹脂粒子を充填した後，金型キャビティー内にスチーム等の熱媒を導入して発泡樹脂粒子を加熱融着させる圧縮充填法もある（例えば特公平４−４６２１７号公報）。 In addition, after filling the mold cavity pressurized above the atmospheric pressure with compressed gas with foamed resin particles pressurized above the pressure, a heating medium such as steam is introduced into the mold cavity and the foamed resin is introduced. There is also a compression filling method in which particles are heated and fused (for example, Japanese Patent Publication No. 4-46217).
更に，特殊な条件にて得られる二次発泡力の高い発泡樹脂粒子を使用して大気圧または減圧下の凹凸一対の金型よりなるキャビティー内に発泡樹脂粒子を充填し，次いで，金型キャビティー内にスチーム等の熱媒を導入して発泡樹脂粒子を加熱融着させる常圧充填法もある（例えば特公平６−４９７９５号公報）。また，上記の方法の組合わせによっても成形できる（例えば特公平６−２２９１９号公報参照）。 Furthermore, the foamed resin particles having high secondary foaming power obtained under special conditions are filled into the cavity formed by a pair of concave and convex molds under atmospheric pressure or reduced pressure, and then the mold There is also a normal pressure filling method in which a heat medium such as steam is introduced into the cavity to heat-fuse the foamed resin particles (for example, Japanese Patent Publication No. 6-49795). Moreover, it can also shape | mold by the combination of said method (for example, refer to Japanese Patent Publication No. 6-22919).
また，上記発泡成形体には，必要に応じてフィルムをラミネートすることができる。ラミネートするフィルムは特に制限が無く，例えば，ＯＰＳ（２軸延伸ポリスチレンシート），耐熱ＯＰＳ，ＨＩＰＳなどのポリスチレン系樹脂フィルム，ＣＰＰ（無延伸ポリプロピレンフィルム），ＯＰＰ（２軸延伸ポリプロピレンフィルム）等のポリプロピレン系樹脂のフィルムあるいはポリエチレン系樹脂フィルム，ポリエステル系樹脂フィルム等が用いられる。 Moreover, a film can be laminated on the foamed molded article as necessary. The film to be laminated is not particularly limited. For example, polypropylene such as OPS (biaxially stretched polystyrene sheet), heat-resistant OPS, HIPS and other polystyrene resin films, CPP (unstretched polypropylene film), and OPP (biaxially stretched polypropylene film). A resin film, a polyethylene resin film, a polyester resin film, or the like is used.
また，ラミネートするフィルムの厚さには制限はないが，通常は１５μｍ〜１５０μｍのフィルムが用いられる。これらのフィルムには必要に応じて印刷が施されてもよい。また，ラミネートを行う場合，発泡粒子の加熱融着成形と同時に行ってもよい。また，一旦成形した成形体にラミネートを行ってもよい。尚，必要に応じてホットメルト系の接着剤を用いてラミネーションを行うこともできる。 Moreover, although there is no restriction | limiting in the thickness of the film to laminate, Usually, a film of 15 micrometers-150 micrometers is used. These films may be printed as necessary. Further, when laminating, it may be performed simultaneously with the heat-fusion molding of the foamed particles. Moreover, you may laminate to the molded object once shape | molded. If necessary, lamination can be performed using a hot-melt adhesive.
次に，上記第２の発明の型内成形体において，上記型内成形体の密度は０．００８〜０．５ｇ／ｃｍ3である。型内成形体の密度が０．５ｇ／ｃｍ3より大きくなると，軽量性，衝撃吸収性，断熱性といった発泡体の好ましい特性が充分に発揮されなくなり，低発泡倍率であるがゆえにコスト上の不利を招くおそれがある。
一方，密度が０．００８ｇ／ｃｍ3よりも小さくなると，独立気泡率が小さくなる傾向にあり，曲げ強度，圧縮強度等の機械的物性が不充分となるおそれがある。
本発明の型内成形体は，例えば包装容器，玩具，自動車部品，ヘルメット芯材，緩衝包装材等に好適である。
Next, in the in-mold molded body of the second invention, the density of the in-mold molded body is 0.008 to 0.5 g / cm 3 . If the density of the molded body in the mold exceeds 0.5 g / cm 3 , the desirable properties of the foam, such as lightness, impact absorption, and heat insulation, will not be sufficiently exerted, and the low foaming ratio is disadvantageous in terms of cost. May be incurred.
On the other hand, when the density is smaller than 0.008 g / cm 3 , the closed cell ratio tends to be small, and mechanical properties such as bending strength and compressive strength may be insufficient.
The in-mold molded product of the present invention is suitable for, for example, a packaging container, a toy, an automobile part, a helmet core material, a buffer packaging material, and the like.
次に，本発明の実施例につき説明する。 Next, examples of the present invention will be described.
［プロピレン系重合体の製造］
まず，ポリプロピレン系樹脂組成物を構成するプロピレン系重合体［Ａ］及び［Ｂ］を，下記の製造例１〜８に示す方法で合成した。
[Production of propylene polymer]
First, the propylene polymers [A] and [B] constituting the polypropylene resin composition were synthesized by the methods shown in the following Production Examples 1 to 8.
製造例１
（ｉ）［ジメチルシリレンビス｛１，１’−（２−メチル−４−フェニル−４−ヒドロアズレニル）｝ジルコニウムジクロリド］の合成
以下の反応は全て不活性ガス雰囲気で行い，また，反応には予め乾燥精製した溶媒を用いた。
Production Example 1
(I) Synthesis of [dimethylsilylenebis {1,1 ′-(2-methyl-4-phenyl-4-hydroazurenyl)} zirconium dichloride] The following reactions are all carried out in an inert gas atmosphere. A dried and purified solvent was used.
（ａ）ラセミ・メソ混合物の合成
特開昭６２−２０７２３２号公報に記載の方法に従って合成した２−メチルアズレン２．２２ｇをヘキサン３０ｍＬに溶解し，フェニルリチウムのシクロヘキサン−ジエチルエーテル溶液１５．６ｍＬ（１．０当量）を０℃にて少量ずつ添加した。
この溶液を室温で１時間撹拌した後，−７８℃に冷却し，テトラヒドロフラン３０ｍＬを加えた。
(A) Synthesis of racemic / meso mixture 2.22 g of 2-methylazulene synthesized according to the method described in JP-A-62-207232 was dissolved in 30 mL of hexane, and 15.6 mL of cyclohexane-diethyl ether solution of phenyllithium ( 1.0 equivalent) was added in small portions at 0 ° C.
The solution was stirred at room temperature for 1 hour, cooled to -78 ° C, and 30 mL of tetrahydrofuran was added.
次いで，ジメチルジクロロシラン０．９５ｍＬを加えた後，室温まで昇温し，更に５０℃で９０分間加熱した。この後，塩化アンモニウム飽和水溶液を加え，有機層を分離後，硫酸ナトリウムで乾燥し，溶媒を減圧下に留去した。 Subsequently, after adding 0.95 mL of dimethyldichlorosilane, it heated up to room temperature, and also heated at 50 degreeC for 90 minutes. Thereafter, a saturated aqueous solution of ammonium chloride was added, the organic layer was separated, dried over sodium sulfate, and the solvent was distilled off under reduced pressure.
得られた粗生成物をシリカゲルカラムクロマトグラフィー（ヘキサン−：ジクロロメタン＝５：１）で精製することにより，ビス｛１，１’−（２−メチル−４−フェニル−１，４−ジヒドロアズレニル）ジメチルシラン１．４８ｇを得た。
上記で得られたビス｛１，１’−（２−メチル−４−フェニル−１，４−ジヒドロアズレニル）ジメチルシラン７８６ｍｇをジエチルエーテル１５ｍＬに溶解し，−７８℃でｎ−ブチルリチウムのヘキサン溶液（１．６８ｍｏｌ／Ｌ）１．９８ｍＬを滴加し，徐々に室温に昇温し，その後室温にて１２時間撹拌した。溶媒を減圧留去して得られた固体をヘキサンで洗浄し，減圧乾固した。
The obtained crude product was purified by silica gel column chromatography (hexane: dichloromethane = 5: 1) to give bis {1,1 ′-(2-methyl-4-phenyl-1,4-dihydroazurenyl). ) 1.48 g of dimethylsilane was obtained.
786 mg of the bis {1,1 ′-(2-methyl-4-phenyl-1,4-dihydroazurenyl) dimethylsilane obtained above was dissolved in 15 mL of diethyl ether, and hexane of n-butyllithium was added at −78 ° C. 1.98 mL of the solution (1.68 mol / L) was added dropwise, the temperature was gradually raised to room temperature, and then the mixture was stirred at room temperature for 12 hours. The solid obtained by distilling off the solvent under reduced pressure was washed with hexane and dried under reduced pressure.
更に，トルエン−ジエチルエーテル混合溶媒（４０：１）を２０ｍＬ加え，−６０℃にて四塩化ジルコニウム３２５ｍｇを加え，徐々に昇温して室温で１５分間撹拌した。
得られた溶液を減圧下に濃縮し，ヘキサンを加えて再沈殿させることにより，ジメチルシリレンビス｛１，１’−（２−メチル−４−フェニル−４−ヒドロアズレニル）｝ジルコニウムジクロリドよりなる，ラセミ／メソ混合物１５０ｍｇを得た。
Furthermore, 20 mL of a toluene-diethyl ether mixed solvent (40: 1) was added, 325 mg of zirconium tetrachloride was added at −60 ° C., the temperature was gradually raised, and the mixture was stirred at room temperature for 15 minutes.
The resulting solution was concentrated under reduced pressure, and reprecipitated by adding hexane, whereby racemic dimethylsilylenebis {1,1 ′-(2-methyl-4-phenyl-4-hydroazurenyl)} zirconium dichloride was prepared. A 150 mg / meso mixture was obtained.
（ｂ）ラセミ体の分離
上記の反応を繰り返して得たラセミ／メソ混合物８８７ｍｇをガラス容器に入れ，ジクロロメタン３０ｍＬに溶解し，高圧水銀ランプで３０分間光照射した。その後ジクロロメタンを減圧下に留去し，黄色固体を得た。
この固体にトルエン７ｍＬを添加して撹拌後，静置することにより，黄色固体が沈殿として分離した。上澄みを除去し，固体を減圧乾固して，ジメチルシリレンビス｛１，１’−（２−メチル−４−フェニル−４−ヒドロアズレニル）｝ジルコニウムジクロリドよりなる，ラセミ体を４３７ｍｇ得た。
(B) Separation of racemic body 887 mg of a racemic / meso mixture obtained by repeating the above reaction was put in a glass container, dissolved in 30 mL of dichloromethane, and irradiated with a high pressure mercury lamp for 30 minutes. Thereafter, dichloromethane was distilled off under reduced pressure to obtain a yellow solid.
7 mL of toluene was added to this solid, stirred, and allowed to stand to separate a yellow solid as a precipitate. The supernatant was removed, and the solid was dried under reduced pressure to obtain 437 mg of a racemate consisting of dimethylsilylene bis {1,1 ′-(2-methyl-4-phenyl-4-hydroazurenyl)} zirconium dichloride.
（ｉｉ）触媒の合成
（ａ）触媒担体の処理
脱塩水１３５ｍＬと硫酸マグネシウム１６ｇをガラス製容器に入れ，撹拌し溶液とした。この溶液にモンモリロナイト（クニミネ工業製「クニピア−Ｆ」）２２．２ｇを加えた後，昇温し，８０℃で１時間保持した。
次いで，脱塩水３００ｍＬを加えた後に濾過により，固形分を分離した。この固形分に，脱塩水４６ｍＬと硫酸２３．４ｇ及び硫酸マグネシウム２９．２ｇを加えた後，昇温し，加熱還流下に２時間処理した後，脱塩水２００ｍＬを加え，濾過した。
更に脱塩水４００ｍＬを加えて濾過する，という操作を２回実施した。その後，固体を１００℃で乾燥し，触媒担体としての化学処理モンモリロナイトを得た。
(Ii) Catalyst synthesis (a) Treatment of catalyst carrier 135 mL of demineralized water and 16 g of magnesium sulfate were placed in a glass container and stirred to obtain a solution. After adding 22.2 g of montmorillonite (“Kunipia-F” manufactured by Kunimine Kogyo Co., Ltd.) to this solution, the temperature was raised and kept at 80 ° C. for 1 hour.
Next, after adding 300 mL of demineralized water, the solid content was separated by filtration. After adding 46 mL of demineralized water, 23.4 g of sulfuric acid, and 29.2 g of magnesium sulfate to this solid content, the temperature was raised and the mixture was heated and refluxed for 2 hours, and then 200 mL of demineralized water was added and filtered.
Further, 400 mL of demineralized water was added and filtration was performed twice. Thereafter, the solid was dried at 100 ° C. to obtain chemically treated montmorillonite as a catalyst support.
（ｂ）触媒成分の調製
内容積１リットルの撹拌式オートクレーブ内をプロピレンで十分に置換した後，脱水ヘプタン２３０ｍＬを導入し，系内温度を４０℃に保持した。
ここに，上記にて調製した，触媒担体としての化学処理モンモリロナイト１０ｇを２００ｍＬのトルエンに懸濁させて添加した。
(B) Preparation of catalyst component After the inside of a stirring autoclave having an internal volume of 1 liter was sufficiently substituted with propylene, 230 mL of dehydrated heptane was introduced, and the system temperature was maintained at 40 ° C.
Here, 10 g of the chemically treated montmorillonite prepared as described above as a catalyst support was suspended in 200 mL of toluene and added.
更に，別容器中に調製した，ジメチルシリレンビス｛１，１’−（２−メチル−４−フェニル−４−ヒドロアズレニル）｝ジルコニウムジクロリドのラセミ体（０．１５ｍｍｏｌ）と，トリイソブチルアルミニウム（３ｍｍｏｌ）とを，トルエン（計２０ｍＬ）中にて混合したものをオートクレーブ内に添加した。 Further, a racemic dimethylsilylene bis {1,1 ′-(2-methyl-4-phenyl-4-hydroazurenyl)} zirconium dichloride prepared in a separate container (0.15 mmol) and triisobutylaluminum (3 mmol) Were mixed in toluene (total 20 mL) and added to the autoclave.
その後，プロピレンを１０ｇ／ｈｒの速度で１２０分間導入し，更にその後に１２０分間，重合反応を継続した後，窒素雰囲気下に溶媒を留去，乾燥して固体触媒成分を得た。この触媒成分は，固体成分１ｇあたり，１．９ｇの重合体を含有するものであった。 Thereafter, propylene was introduced at a rate of 10 g / hr for 120 minutes, and then the polymerization reaction was continued for 120 minutes. Then, the solvent was distilled off under a nitrogen atmosphere and dried to obtain a solid catalyst component. This catalyst component contained 1.9 g of polymer per 1 g of the solid component.
（ｉｉｉ）プロピレンの重合（プロピレン系重合体Ａの製造）
内容積２００Ｌの撹拌式オートクレーブ内をプロピレンで十分に置換した後，十分に脱水した液化プロピレン４５ｋｇを導入した。これに，トリイソブチルアルミニウムのヘキサン溶液５００ｍＬ（０．１２ｍｏｌ），及び水素（３ＮＬ）を導入し，オートクレーブ内を７０℃に昇温した。
その後，上記固体触媒成分（１．７ｇ）をアルゴンで圧入して重合を開始させ，３時間重合反応を行った。
(Iii) Polymerization of propylene (production of propylene-based polymer A)
After sufficiently replacing the inside of the stirring type autoclave with an internal volume of 200 L with propylene, 45 kg of sufficiently dehydrated liquefied propylene was introduced. To this, 500 mL (0.12 mol) of hexane solution of triisobutylaluminum and hydrogen (3NL) were introduced, and the temperature inside the autoclave was raised to 70 ° C.
Thereafter, the solid catalyst component (1.7 g) was injected with argon to start polymerization, and a polymerization reaction was carried out for 3 hours.
その後，反応系にエタノール１００ｍＬを圧入して反応を停止させ，残存ガス成分をパージすることで，１４．１ｋｇのポリマーを得た。
このポリマーは，プロピレンから得られる構造単位が１００モル％であり，即ちプロピレン単独重合体である。これは上記要件（ａ）を満たす。
Thereafter, 100 mL of ethanol was injected into the reaction system to stop the reaction, and the residual gas component was purged to obtain 14.1 kg of polymer.
This polymer has a structural unit obtained from propylene of 100 mol%, that is, a propylene homopolymer. This satisfies the requirement (a).
また，このポリマーはＭＦＲ（メルトフローレート）＝１０ｇ／１０分，アイソタクチックトリアッド分率が９９．７％，融点（Ｔｍ）が１４６℃であり，上記要件（ｄ）及び（ｅ）を満たしている。さらに，２，１−挿入に基づく位置不規則単位の割合が１．３２％，１，３−挿入に基づく位置不規則単位の割合が０．０８％であり，上記要件（ｂ）を満たしている。
以下，ここで得られたポリプロピレン系重合体を「ポリマー１」と称する。
Further, this polymer has MFR (melt flow rate) = 10 g / 10 min, an isotactic triad fraction of 99.7%, a melting point (Tm) of 146 ° C., and the above requirements (d) and (e) are satisfied. Satisfies. Furthermore, the ratio of the position irregular unit based on 2,1-insertion is 1.32%, and the ratio of the position irregular unit based on 1,3-insertion is 0.08%, which satisfies the above requirement (b). Yes.
Hereinafter, the polypropylene polymer obtained here is referred to as “polymer 1”.
（ｉｖ）水蒸気透過度の測定
上記で得られたポリマー１を厚み２５ミクロンのフィルムに成形し，ＪＩＳ Ｋ７１２９に記載の方法に従って水蒸気透過度Ｙを測定した（以下の製造例も同じ）結果，１０．５（ｇ／ｍ2／２４ｈｒ）であった。
なお，ポリマー１は，上記のように融点Ｔｍが１４６℃であるため，上記式（１）からＹは５．８≦Ｙ≦１１．８の範囲内にあるべきところ，その範囲内に入っていた。
(Iv) Measurement of water vapor permeability The polymer 1 obtained above was formed into a film having a thickness of 25 microns, and the water vapor permeability Y was measured according to the method described in JIS K7129 (the same is true for the following production examples). was .5 (g / m 2 / 24hr ).
Since the melting point Tm of the polymer 1 is 146 ° C. as described above, Y should be within the range of 5.8 ≦ Y ≦ 11.8 from the above formula (1). It was.
製造例２（プロピレン系重合体［Ａ］の製造，プロピレン単独重合）
内容積２００Ｌの撹拌式オートクレーブ内をプロピレンで十分に置換した後，十分に脱水した液化プロピレン４５ｋｇを導入した。これに，トリイソブチルアルミニウムのヘキサン溶液５００ｍＬ（０．１２ｍｏｌ），及び水素（３ＮＬ）を導入し，オートクレーブ内を４０℃に昇温した。
その後，上記固体触媒成分（３．０ｇ）をアルゴンで圧入して重合を開始させ，３時間重合反応を行った。
Production Example 2 (Production of propylene polymer [A], propylene homopolymerization)
After sufficiently replacing the inside of the stirring type autoclave with an internal volume of 200 L with propylene, 45 kg of sufficiently dehydrated liquefied propylene was introduced. To this, 500 mL (0.12 mol) of a hexane solution of triisobutylaluminum and hydrogen (3NL) were introduced, and the temperature inside the autoclave was raised to 40 ° C.
Thereafter, the solid catalyst component (3.0 g) was injected with argon to initiate polymerization, and a polymerization reaction was carried out for 3 hours.
その後，反応系にエタノール１００ｍＬを圧入して反応を停止させ，残存ガス成分をパージすることで，４．４ｋｇのポリマーを得た。
このポリマーは，プロピレンから得られる構造単位が１００モル％であり，即ちプロピレン単独重合体である。これは，上記要件（ａ）を満たす。
Thereafter, 100 mL of ethanol was injected into the reaction system to stop the reaction, and the remaining gas component was purged to obtain 4.4 kg of polymer.
This polymer has a structural unit obtained from propylene of 100 mol%, that is, a propylene homopolymer. This satisfies the above requirement (a).
また，このポリマーはＭＦＲ＝２，アイソタクチックトリアッド分率が９９．８％，融点（Ｔｍ）が１５２℃であり，上記要件（ｄ）及び（ｅ）を満たしている。さらに，２，１−挿入に基づく位置不規則単位の割合が０．８９％，１，３−挿入に基づく位置不規則単位の割合が０．００５％であり，上記要件（ｂ）を満たしている。
以下，ここで得られた重合体を「ポリマー２」と称する。
Further, this polymer has an MFR = 2, isotactic triad fraction of 99.8% and a melting point (Tm) of 152 ° C., which satisfies the above requirements (d) and (e). Furthermore, the ratio of the position irregular unit based on 2,1-insertion is 0.89%, and the ratio of the position irregular unit based on 1,3-insertion is 0.005%, which satisfies the requirement (b). Yes.
Hereinafter, the polymer obtained here is referred to as “polymer 2”.
また，上記ポリマー２について，上記ポリマー１と同様にして，フィルムに成形したときの水蒸気透過度Ｙを調べたところ，９．５（ｇ／ｍ2／２４ｈｒ）であった。
なお，ポリマー２は，上記のように融点Ｔｍが１５２℃であるため，上記式（１）からＹは４．６≦Ｙ≦９．８の範囲内にあるべきところ，その範囲内に入っていた。
As for the polymer 2, as in the polymer 1 was examined the water vapor transmission rate Y when molded into a film was 9.5 (g / m 2 / 24hr ).
Since the melting point Tm of the polymer 2 is 152 ° C. as described above, Y should be within the range of 4.6 ≦ Y ≦ 9.8 from the above formula (1). It was.
製造例３（プロピレン系重合体［Ａ］の製造，プロピレン／エチレン共重合）
内容積２００Ｌの撹拌式オートクレーブ内をプロピレンで十分に置換した後，精製したｎ−ヘプタン６０Ｌを導入し，トリイソブチルアルミニウムのヘキサン溶液５００ｍＬ（０．１２ｍｏｌ）を添加し，オートクレーブ内を７０℃に昇温した。その後，上記固体触媒成分（９．０ｇ）を添加し，プロピレンとエチレンの混合ガス（プロピレン：エチレン＝９７．５：２．５；但し重量比）を圧力が０．７ＭＰａとなるように導入して重合を開始させ，本条件下に３時間重合反応を行った。
Production Example 3 (Production of propylene polymer [A], propylene / ethylene copolymer)
After thoroughly replacing the inside of the stirred autoclave with an internal volume of 200 L with propylene, introduce 60 L of purified n-heptane, add 500 mL (0.12 mol) of hexane solution of triisobutylaluminum, and raise the inside of the autoclave to 70 ° C. Warm up. Thereafter, the solid catalyst component (9.0 g) was added, and a mixed gas of propylene and ethylene (propylene: ethylene = 97.5: 2.5; weight ratio) was introduced so that the pressure became 0.7 MPa. Then, the polymerization was started, and the polymerization reaction was carried out for 3 hours under these conditions.
その後，反応系にエタノール１００ｍＬを圧入して反応を停止させ，残存ガス成分をパージすることで，９．３ｋｇのポリマーを得た。
このポリマーには，プロピレンから得られる構造単位が９７．０モル％，エチレンから得られる構造単位が３．０モル％存在している。これは，上記要件（ａ）を満たす。
Thereafter, 100 mL of ethanol was injected into the reaction system to stop the reaction, and the residual gas component was purged to obtain 9.3 kg of polymer.
In this polymer, 97.0 mol% of structural units obtained from propylene and 3.0 mol% of structural units obtained from ethylene are present. This satisfies the above requirement (a).
また，このポリマーはＭＦＲ＝１４，エチレン含量＝２．０ｗｔ％，アイソタクチックトリアッド分率が９９．２％，融点（Ｔｍ）が１４１℃であり，上記要件（ｄ）及び（ｅ）を満たしている。さらに，２，１−挿入に基づく位置不規則単位の割合が１．０６％，１，３−挿入に基づく位置不規則単位の割合が０．１６％であり，上記要件（ｂ）を満たしている。
以下，ここで得られた重合体を「ポリマー３」と称する。
This polymer has MFR = 14, ethylene content = 2.0 wt%, isotactic triad fraction 99.2%, melting point (Tm) 141 ° C., and the above requirements (d) and (e) are satisfied. Satisfies. Further, the ratio of the position irregular unit based on 2,1-insertion is 1.06%, and the ratio of the position irregular unit based on 1,3-insertion is 0.16%, which satisfies the above requirement (b). Yes.
Hereinafter, the polymer obtained here is referred to as “polymer 3”.
また，ポリマー３について，上記ポリマー１及びポリマー２と同様にして，フィルムに成形した後の水蒸気透過度Ｙを調べたところ，１２．０（ｇ／ｍ2／２４ｈｒ）であった。
なお，ポリマー３は，上記のように融点Ｔｍが１４１℃であるため，上記式（１）からＹは６．８≦Ｙ≦１３．５の範囲内にあるべきところ，その範囲内に入っていた。
Further, the polymer 3, in the same manner as in the polymer 1 and polymer 2, was examined water vapor transmission rate Y after molding into a film was 12.0 (g / m 2 / 24hr ).
In addition, since the melting point Tm of the polymer 3 is 141 ° C. as described above, Y should be within the range of 6.8 ≦ Y ≦ 13.5 from the above formula (1). It was.
製造例４（プロピレン系重合体［Ａ］の製造，プロピレン／１−ブテン共重合）
内容積２００Ｌの撹拌式オートクレーブ内をプロピレンで十分に置換した後，精製したｎ−ヘプタン６０Ｌを導入し，トリイソブチルアルミニウムのヘキサン溶液５００ｍＬ（０．１２ｍｏｌ）を添加し，オートクレーブ内を７０℃に昇温した。その後，上記固体触媒成分（９．０ｇ）を添加し，プロピレンと１−ブテンの混合ガス（プロピレン：１−ブテン＝９０：１０）を圧力が０．６ＭＰａとなるように導入して重合を開始させ，本条件下に３時間重合反応を行った。
Production Example 4 (Production of propylene polymer [A], propylene / 1-butene copolymer)
After thoroughly replacing the inside of the stirred autoclave with an internal volume of 200 L with propylene, introduce 60 L of purified n-heptane, add 500 mL (0.12 mol) of hexane solution of triisobutylaluminum, and raise the inside of the autoclave to 70 ° C. Warm up. Thereafter, the solid catalyst component (9.0 g) was added, and a mixed gas of propylene and 1-butene (propylene: 1-butene = 90: 10) was introduced so that the pressure became 0.6 MPa, and polymerization was started. The polymerization reaction was carried out for 3 hours under these conditions.
その後，反応系にエタノール１００ｍＬを圧入して反応を停止させ，残存ガス成分をパージすることで，８．６ｋｇのポリマーを得た。
このポリマーには，プロピレンから得られる構造単位が９５．４モル％，１−ブテンから得られる構造単位が４．６モル％存在している。これは上記要件（ａ）を満たしている。
Thereafter, 100 mL of ethanol was injected into the reaction system to stop the reaction, and the residual gas component was purged to obtain 8.6 kg of polymer.
In this polymer, 95.4 mol% of structural units obtained from propylene and 4.6 mol% of structural units obtained from 1-butene are present. This satisfies the requirement (a).
また，このポリマーはＭＦＲ＝６，１−ブテン含量＝６．０ｗｔ％，融点（Ｔｍ）が１４２℃，アイソタクチックトリアッド分率が９９．３％であり，上記要件（ｄ）及び（ｅ）を満たしている。さらに，２，１−挿入に基づく位置不規則単位の割合が１．２３％，１，３−挿入に基づく位置不規則単位の割合が０．０９％であり，上記要件（ｂ）を満たしている。ここで得られた重合体を「ポリマー４」と称する。 Further, this polymer has MFR = 6,1-butene content = 6.0 wt%, melting point (Tm) is 142 ° C., isotactic triad fraction is 99.3%, and the above requirements (d) and (e ) Is satisfied. Further, the ratio of the position irregular unit based on 2,1-insertion is 1.23%, and the ratio of the position irregular unit based on 1,3-insertion is 0.09%, which satisfies the above requirement (b). Yes. The polymer obtained here is referred to as “Polymer 4”.
ポリマー４を上記ポリマー１〜３と同様にしてフィルムに成形し，水蒸気透過度Ｙを調べたところ，１１．５（ｇ／ｍ2／２４ｈｒ）であった。
なお，ポリマー４は，上記のように融点Ｔｍが１４２℃であるため，上記式（１）からＹは６．６≦Ｙ≦１３．１の範囲内にあるべきところ，その範囲内に入っていた。
Polymer 4 was formed into a film in the same manner as in the polymer 1 to 3, were examined water vapor transmission rate Y, it was 11.5 (g / m 2 / 24hr ).
In addition, since the melting point Tm of the polymer 4 is 142 ° C. as described above, Y should be within the range of 6.6 ≦ Y ≦ 13.1 from the above formula (1). It was.
製造例５（プロピレン系重合体［Ｂ］の製造，プロピレン単独重合）
内容積２００Ｌの撹拌式オートクレーブ内をプロピレンで十分に置換した後，精製したｎ−ヘプタン６０Ｌを導入し，ジエチルアルミニウムクロリド（４５ｇ），丸紅ソルベー社製三塩化チタン触媒１１．５ｇをプロピレン雰囲気下に導入した。更に気相部の水素濃度を７．０容量％に保持しながら，オートクレーブ内温６０℃にて，プロピレンを９ｋｇ／ｈｒの速度にて４時間にわたり，オートクレーブ内に導入した。
Production Example 5 (Production of propylene polymer [B], propylene homopolymerization)
After fully replacing the inside of the stirred autoclave with an internal volume of 200 L with propylene, 60 L of purified n-heptane was introduced, and diethylaluminum chloride (45 g) and 11.5 g of Marubeni Solvay's titanium trichloride catalyst were placed in a propylene atmosphere. Introduced. Further, propylene was introduced into the autoclave at a rate of 9 kg / hr over 4 hours at an autoclave internal temperature of 60 ° C. while maintaining the hydrogen concentration in the gas phase at 7.0 vol%.
プロピレン導入を停止した後，更に１時間反応を継続し，反応系にブタノール１００ｍＬを添加して反応を停止させ，残存ガス成分をパージすることで，２６ｋｇのポリマーを得た。ここで得られたポリマーを「ポリマー５」と称する。
このポリマーは，プロピレンから得られる構造単位が１００モル％であり，即ちプロピレン単独重合体である。これは，上記要件（ａ）を満たす。
After stopping the introduction of propylene, the reaction was continued for an additional hour, 100 mL of butanol was added to the reaction system to stop the reaction, and the residual gas component was purged to obtain 26 kg of polymer. The polymer obtained here is referred to as “Polymer 5”.
This polymer has a structural unit obtained from propylene of 100 mol%, that is, a propylene homopolymer. This satisfies the above requirement (a).
このポリマーは，ＭＦＲ＝７，融点（Ｔｍ）１６５℃，アイソタクチックトリアッド分率が９７．６％，２，１−挿入に基づく位置不規則単位の割合が０％，１，３−挿入に基づく位置不規則単位の割合が０％であった。
即ち，このものは，上記要件（ｂ）を満足しないものである。
This polymer has an MFR = 7, a melting point (Tm) of 165 ° C., an isotactic triad fraction of 97.6%, a proportion of regioregular units based on 2,1-insertion of 0%, 1,3-insertion. The ratio of the position irregular units based on was 0%.
That is, this does not satisfy the requirement (b).
ポリマー５について，上記ポリマー１〜４と同様にして，フィルムに成形した後の水蒸気透過度Ｙを調べたところ，７．８（ｇ／ｍ2／２４ｈｒ）であった。
なお，ポリマー５は，上記のように融点Ｔｍが１６５℃であるため，上記式（１）からＹは２．０≦Ｙ≦５．６の範囲内にあるべきところ，その範囲内に入っていない。
For Polymer 5, in the same manner as in the above polymers 1 to 4, were examined water vapor transmission rate Y after molding into a film was 7.8 (g / m 2 / 24hr ).
Since the melting point Tm of the polymer 5 is 165 ° C. as described above, Y should be within the range of 2.0 ≦ Y ≦ 5.6 from the above formula (1). Absent.
製造例６（プロピレン系重合体［Ｂ］の製造，プロピレン／エチレン共重合）
内容積２００Ｌの撹拌式オートクレーブ内をプロピレンで十分に置換した後，精製したｎ−ヘプタン６０Ｌを導入し，ジエチルアルミニウムクロリド（４０ｇ），丸紅ソルベー社製三塩化チタン触媒７．５ｇをプロピレン雰囲気下に導入した。更に気相部の水素濃度を７．０容量％に保持しながら，オートクレーブ内温６０℃にて，プロピレンとエチレンの混合ガス（プロピレン：エチレン＝９７．５：２．５；但し重量比）を圧力が０．７ＭＰａとなるように導入した。
Production Example 6 (Production of propylene polymer [B], propylene / ethylene copolymer)
After thoroughly replacing the inside of the stirred autoclave with an internal volume of 200 L with propylene, 60 L of purified n-heptane was introduced, and 7.5 g of diethylaluminum chloride (40 g) and a titanium trichloride catalyst manufactured by Marubeni Solvay Co. were placed in a propylene atmosphere. Introduced. Further, while maintaining the hydrogen concentration in the gas phase at 7.0% by volume, a mixed gas of propylene and ethylene (propylene: ethylene = 97.5: 2.5; weight ratio) at an autoclave internal temperature of 60 ° C. It introduced so that a pressure might be set to 0.7 Mpa.
混合ガス導入を停止した後，更に１時間反応を継続し，反応系にブタノール１００ｍＬを添加して反応を停止させ，残存ガス成分をパージすることで，３２ｋｇのポリマーを得た。本ポリマーを「ポリマー６」と称する。
このポリマーには，プロピレンから得られる構造単位が９６．１モル％，エチレンから得られる構造単位が３．９モル％存在している。これは，上記要件（ａ）を満たす。
After the introduction of the mixed gas was stopped, the reaction was continued for another hour, 100 mL of butanol was added to the reaction system to stop the reaction, and the remaining gas components were purged to obtain 32 kg of polymer. This polymer is referred to as “Polymer 6”.
In this polymer, 96.1 mol% of structural units obtained from propylene and 3.9 mol% of structural units obtained from ethylene are present. This satisfies the above requirement (a).
また，このポリマー６はＭＦＲ＝１２，融点（Ｔｍ）１４６℃，アイソタクチックトリアッド分率が９６％，２，１−挿入に基づく位置不規則単位の割合が０％，１，３−挿入に基づく位置不規則単位の割合が０％であった。
即ち，ポリマー６は，上記要件（ｂ）を満足しないものである。
In addition, this polymer 6 has MFR = 12, melting point (Tm) 146 ° C., isotactic triad fraction 96%, 2,1-positioned
That is, the polymer 6 does not satisfy the requirement (b).
また，ポリマー６について，上記ポリマー１〜５と同様にして，フィルムに成形した後の水蒸気透過度Ｙを調べたところ，１５．０（ｇ／ｍ2／２４ｈｒ）であった。
なお，ポリマー６は，融点Ｔｍが１４６℃であるため，上記式（１）からＹは５．８≦Ｙ≦１１．８の範囲内にあるべきところ，その範囲内に入っていない。
Further, the polymer 6, in the same manner as in the above polymers 1 to 5, were examined water vapor transmission rate Y after molding into a film was 15.0 (g / m 2 / 24hr ).
In addition, since the melting point Tm of the polymer 6 is 146 ° C., Y should be within the range of 5.8 ≦ Y ≦ 11.8 from the above formula (1), but does not fall within the range.
製造例７（プロピレン系重合体［Ｂ］の製造，プロピレン単独重合）
特開平６−２４００４１号公報の実施例中の［基材樹脂の製造１］に記載の方法を適用して実施した。
すなわち，内容積２００Ｌの撹拌式オートクレーブ内をプロピレンで十分に置換した後，精製したｎ−ヘプタン６０Ｌを導入し，東ソーアクゾ社製のメチルアルモキサン（平均オリゴマー度１６）を１２０ｇ，特開平４−２６８３０７号公報に記載の方法で合成したｒａｃ−ジメチルシリレンビス（２−メチルインデニル）ジルコニウムジクロリド（１５０ｍｇ）をプロピレン雰囲気下に導入した。更に気相部の水素濃度を０．５容量％に保持しながら，オートクレーブ内温４０℃にて，プロピレンを７ｋｇ／ｈｒの速度にて３時間にわたり，オートクレーブ内に導入した。
Production Example 7 (Production of propylene polymer [B], propylene homopolymerization)
This was carried out by applying the method described in [Production of base resin 1] in the examples of JP-A-6-240041.
That is, after the inside of a stirring autoclave having an internal volume of 200 L is sufficiently substituted with propylene, 60 L of purified n-heptane is introduced, and 120 g of methylalumoxane (average oligomer degree 16) manufactured by Tosoh Akzo Co., Ltd. is disclosed. Rac-dimethylsilylenebis (2-methylindenyl) zirconium dichloride (150 mg) synthesized by the method described in Japanese Patent No. 268307 was introduced under a propylene atmosphere. Further, propylene was introduced into the autoclave at a rate of 7 kg / hr for 3 hours at an autoclave internal temperature of 40 ° C. while maintaining the hydrogen concentration in the gas phase at 0.5% by volume.
プロピレン導入を停止した後，更に１時間反応を継続し，反応系にブタノール１００ｍＬを添加して反応を停止させ，残存ガス成分をパージすることで，９．４ｋｇのポリマーを得た。本ポリマーを「ポリマー７」と称する。
このポリマー７は，ＭＦＲ＝９，融点（Ｔｍ）１５０℃，アイソタクチックトリアッド分率が９４．４％，２，１−挿入に基づく位置不規則単位の割合が０．２５％，１，３−挿入に基づく位置不規則単位の割合は検出限界以下，すなわち０．００５％未満であった。即ち，このものは，上記要件（ｂ）を満足しないものである。
なお，後述する表２においては，ポリマー７の１，３挿入に基づく位置不規則単位の割合は０％として表記した。
After stopping the introduction of propylene, the reaction was continued for another hour, 100 mL of butanol was added to the reaction system to stop the reaction, and the residual gas component was purged to obtain 9.4 kg of polymer. This polymer is referred to as “Polymer 7”.
This polymer 7 has an MFR = 9, a melting point (Tm) of 150 ° C., an isotactic triad fraction of 94.4%, a ratio of regioregular units based on 2,1-insertion of 0.25%, 3- The percentage of irregular units based on insertion was below the detection limit, ie less than 0.005%. That is, this does not satisfy the requirement (b).
In Table 2, which will be described later, the ratio of position irregular units based on 1,3 insertion of polymer 7 is shown as 0%.
また，ポリマー７について，上記ポリマー１〜６と同様にして，フィルムに成形した後の水蒸気透過度Ｙを調べたところ，４．８（ｇ／ｍ2／２４ｈｒ）であった。
なお，このポリマー７は，融点Ｔｍが１５０℃であるため，上記式（１）からＹは５．０≦Ｙ≦１０．５の範囲内にあるべきところ，その範囲外であった。
Also, for the polymer 7, in the same manner as in the above polymers 1 to 6, were examined water vapor transmission rate Y after molding into a film was 4.8 (g / m 2 / 24hr ).
Since this polymer 7 has a melting point Tm of 150 ° C., Y was outside the range where Y should be within the range of 5.0 ≦ Y ≦ 10.5 from the above formula (1).
製造例８（プロピレン系重合体［Ｂ］の製造，プロピレン単独重合）
内容積２００Ｌの撹拌式オートクレーブ内をプロピレンで十分に置換した後，精製したｎ−ヘプタン６０Ｌを導入し，東ソーアクゾ社製のメチルアルモキサン（平均オリゴマー度１６）を１２０ｇ，公知の方法［エイチ．ヤマザキ他（H.Yamazaki et.al），「ケミストリー レターズ」（“Chemistry Letters”），日本国，１９８９年，第１８巻，ｐ．１８５３］で合成したｒａｃ−ジメチルシリレンビス（３−メチルシクロペンタジエニル）ジルコニウムジクロリド（１００ｍｇ）をプロピレン雰囲気下に導入した。更に気相部の水素濃度を０．５容量％に保持しながら，オートクレーブ内温４０℃にて，プロピレンを７ｋｇ／ｈｒの速度にて３時間にわたり，オートクレーブ内に導入した。
Production Example 8 (Production of propylene polymer [B], propylene homopolymerization)
After sufficiently replacing the interior of the stirred autoclave with an internal volume of 200 L with propylene, 60 L of purified n-heptane was introduced, and 120 g of methylalumoxane (average oligomer degree 16) manufactured by Tosoh Akzo Co., Ltd., a known method [H. H. Yamazaki et.al, “Chemistry Letters”, Japan, 1989, Vol. 18, p. Rac-dimethylsilylene bis (3-methylcyclopentadienyl) zirconium dichloride (100 mg) synthesized in 1853] was introduced in a propylene atmosphere. Further, propylene was introduced into the autoclave at a rate of 7 kg / hr for 3 hours at an autoclave internal temperature of 40 ° C. while maintaining the hydrogen concentration in the gas phase at 0.5% by volume.
プロピレン導入を停止した後，更に１時間反応を継続し，反応系にブタノール１００ｍＬを添加して反応を停止させ，残存ガス成分をパージすることで，５．６ｋｇのポリマーを得た。本ポリマーを「ポリマー８」と称する。
このポリマー８は，ＭＦＲ＝２０，融点１４１℃，アイソタクチックトリアッド分率が９１．５％，２，１−挿入に基づく位置不規則単位の割合が２．１％，１，３−挿入に基づく位置不規則単位の割合は０．４５％であった。
即ち，このものは，上記要件（ｂ）を満足しないものである。
After stopping the introduction of propylene, the reaction was continued for an additional hour, 100 mL of butanol was added to the reaction system to stop the reaction, and the residual gas component was purged to obtain 5.6 kg of polymer. This polymer is referred to as “polymer 8”.
This polymer 8 has an MFR = 20, a melting point of 141 ° C., an isotactic triad fraction of 91.5%, a ratio of position irregular units based on 2,1-insertion of 2.1%, and 1,3-insertion. The ratio of the position irregular units based on was 0.45%.
That is, this does not satisfy the requirement (b).
また，ポリマー８について，上記ポリマー１〜７と同様にして，フィルムに成形した後の水蒸気透過度Ｙを調べたところ，１３．８（ｇ／ｍ2／２４ｈｒ）であった。
なお，このポリマー８は，融点Ｔｍが１４１℃であるため，上記式（１）からＹは６．８≦Ｙ≦１３．５の範囲内にあるべきところ，その範囲外であった。
以上の製造例１〜８の結果を表１及び表２に示す。
Also, for the polymer 8, in the same manner as in the above polymers 1 to 7, were examined water vapor transmission rate Y after molding into a film was 13.8 (g / m 2 / 24hr ).
Since this polymer 8 has a melting point Tm of 141 ° C., Y should be within the range of 6.8 ≦ Y ≦ 13.5 from the above formula (1), but was outside the range.
The results of the above Production Examples 1 to 8 are shown in Tables 1 and 2.
表１からも知られるごとく，ポリマー１〜ポリマー４は，上記要件（ａ）及び（ｂ）を満たし，上記プロピレン系重合体［Ａ］に相当するものである。また，ポリマー１〜ポリマー４は，上記要件（ｄ）及び（ｅ）をも満足する。
一方，表２より，ポリマー５〜ポリマー８は，上記要件（ａ）を満たしているが，上記要件（ｂ）を満足していないことが分かる。即ち，ポリマー５〜ポリマー８は，上記プロピレン系重合体［Ｂ］に相当するものである。
As is also known from Table 1, Polymers 1 to 4 satisfy the requirements (a) and (b) and correspond to the propylene polymer [A]. Polymers 1 to 4 also satisfy the above requirements (d) and (e).
On the other hand, it can be seen from Table 2 that polymers 5 to 8 satisfy the requirement (a) but do not satisfy the requirement (b). That is, polymer 5 to polymer 8 correspond to the propylene polymer [B].
次に，上記製造例１〜８により得られた各種プロピレン系重合体（ポリマー１〜８）を用いて，ポリプロピレン系樹脂組成物及びポリプロピレン系樹脂発泡粒子を製造し，さらに該ポリプロピレン系樹脂発泡粒子を用いて型内成形体を作製した実施例につき説明する。 Next, using the various propylene polymers (Polymers 1 to 8) obtained in Production Examples 1 to 8, a polypropylene resin composition and polypropylene resin expanded particles are manufactured, and the polypropylene resin expanded particles are further produced. An example in which an in-mold molded body was produced using the above will be described.
実施例１
製造例１で得たポリマー１（プロピレン系重合体［Ａ］）と製造例５で得たポリマー５（プロピレン系重合体［Ｂ］）とを９０：１０（重量比）で混合し，この混合物に酸化防止剤（吉富製薬（株）製 商品名「ヨシノックスＢＨＴ」０．０５ｗｔ％，及びチバガイギー製 商品名「イルガノックス１０１０」０．１０ｗｔ％）を加えて６５ｍｍφ単軸押出機で直径１ｍｍのストランド状に押し出し，水槽にて冷却後，長さ２ｍｍにカットして，ポリプロピレン系樹脂組成物の細粒ペレットを得た。
Example 1
Polymer 1 (propylene polymer [A]) obtained in Production Example 1 and polymer 5 (propylene polymer [B]) obtained in Production Example 5 were mixed at a ratio of 90:10 (weight ratio). Addition of antioxidant (trade name “Yoshinox BHT” 0.05 wt% made by Yoshitomi Pharmaceutical Co., Ltd. and Ciba Geigy trade name “Irganox 1010” 0.10 wt%) to a strand with a diameter of 1 mm using a 65 mmφ single screw extruder After being extruded into a shape and cooled in a water tank, it was cut to a length of 2 mm to obtain a fine pellet of a polypropylene resin composition.
こうして得られたポリプロピレン系樹脂組成物のＤＳＣ測定を行ったところ，一つの吸熱ピークを示し，ピーク温度（融点）は１５３℃であった。 When the DSC measurement of the polypropylene resin composition thus obtained was performed, it showed one endothermic peak and the peak temperature (melting point) was 153 ° C.
次に，このポリプロピレン系樹脂組成物を基材樹脂として用いて，ポリプロピレン系樹脂発泡粒子を以下のようにして作製する。
まず，ペレット状のポリプロピレン系樹脂組成物１０００ｇを水２５００ｇ，第三リン酸カルシウム２００ｇ，ドデシルベンゼンスルホン酸ナトリウム０．２ｇと共に内容積５リットルのオートクレーブに入れ，更に上記発泡剤としてのイソブタン１２０ｇを加えて，１４０℃迄６０分間で昇温した後，この温度で３０分間保持した。
Next, this polypropylene resin composition is used as a base resin to produce polypropylene resin expanded particles as follows.
First, 1000 g of a pellet-shaped polypropylene resin composition was put in an autoclave having an internal volume of 5 liters together with 2500 g of water, 200 g of tribasic calcium phosphate and 0.2 g of sodium dodecylbenzenesulfonate, and 120 g of isobutane as a foaming agent was further added. After raising the temperature to 140 ° C. over 60 minutes, the temperature was maintained for 30 minutes.
その後，オートクレーブ内の圧力をゲージ圧２．３ＭＰａに保持するために外部より圧縮窒素ガスを加えながら，オートクレーブ底部のバルブを開き内容物を大気下へ放出した。
以上の操作によりポリプロピレン系樹脂発泡粒子を得た。
また，このポリプロピレン系樹脂発泡粒子を乾燥後，嵩密度を測定したところ，４２ｇ／Ｌであった。また，ポリプロピレン系樹脂発泡粒子の気泡は，その平均径が２５０μｍであり，非常に均一なものであった。
Thereafter, in order to maintain the pressure in the autoclave at a gauge pressure of 2.3 MPa, the valve at the bottom of the autoclave was opened while the compressed nitrogen gas was added from the outside, and the contents were released to the atmosphere.
Polypropylene resin expanded particles were obtained by the above operation.
Moreover, when the polypropylene resin foamed particles were dried and the bulk density was measured, it was 42 g / L. Further, the bubbles of the polypropylene resin expanded particles had an average diameter of 250 μm and were very uniform.
なお，上記ポリプロピレン系樹脂発泡粒子の平均径は，無作為に選んだ発泡粒子のほぼ中心部を通るように切断した発泡粒子の断面を顕微鏡にて観察して得られる顕微鏡写真又はこの断面を画面上に映し出し，無作為に５０点の気泡について各気泡の直径（最大長さ）を測定し，その平均値を示したものである。 The average diameter of the expanded polypropylene resin particles is a micrograph obtained by observing a cross section of the expanded particles cut through almost the center of the randomly selected expanded particles with a microscope or a screen showing this cross section. The diameter (maximum length) of each bubble is measured on 50 bubbles at random, and the average value is shown.
次に，上記ポリプロピレン系樹脂発泡粒子を用いて，以下のように型内成形体を作製する。
まず，上記で得られたポリプロピレン系樹脂発泡粒子をホッパーにより圧縮空気を用いて逐次的にアルミニウム製の成形用金型に圧縮しながら充填した。その後，金型のチャンバにゲージ圧０．３０ＭＰａのスチーム（下記の表中では「成形蒸気圧」と表示）を通じて加熱成形し，型内成形体を得た。
Next, an in-mold molded body is produced as follows using the polypropylene resin expanded particles.
First, the polypropylene resin expanded particles obtained above were filled while being compressed sequentially into a mold made of aluminum using compressed air using a hopper. Thereafter, the mold chamber was heat-formed through steam having a gauge pressure of 0.30 MPa (shown as “molding vapor pressure” in the table below) to obtain an in-mold molded body.
この型内成形体は密度０．０６０ｇ／ｃｍ3（６０ｇ／Ｌ），縦３００ｍｍ，横３００ｍｍ，厚み５０ｍｍであり，表面の間隙も少なく，凹凸も無い表面外観が優れた成形体であった。また，型内成形体の中央部より破断し，その断面の融着度を測定したところ，９０％であった。 This in-mold molded body had a density of 0.060 g / cm 3 (60 g / L), a length of 300 mm, a width of 300 mm and a thickness of 50 mm, and had a small surface gap and an excellent surface appearance with no irregularities. Moreover, it fractured | ruptured from the center part of the in-mold molded object, and it was 90% when the fusion degree of the cross section was measured.
なお，上記融着度は，成形体を割断し，その断面における粒子破壊の数と粒子間破壊の数とを目視にて計測し，両者の合計数に対する粒子破壊の数の割合で表した。 The degree of fusion was expressed by the ratio of the number of particle fractures to the total number of both, when the compact was cut and the number of particle fractures and the number of interparticle fractures in the cross section were visually measured.
また，同一成形条件で成形した別の成形体から，縦５０ｍｍ，横５０ｍｍ，厚さ２５ｍｍの試験片を作成し，ＪＩＳ Ｋ７２２０（１９９９年）に従って，試験片温度２３℃，圧縮速度１０ｍｍ／分の条件にて圧縮試験を実施したところ，５０％圧縮時（５０％歪時と同義）の応力が７．５ｋｇｆ／ｃｍ2であった。更に，同じ大きさの試験片を用い，同じくＪＩＳ Ｋ６７６７（１９７６年）に記載の方法により，圧縮永久歪を測定したところ，１１％であった。 In addition, a test piece having a length of 50 mm, a width of 50 mm, and a thickness of 25 mm was prepared from another molded body molded under the same molding conditions, and the test piece temperature was 23 ° C. and the compression speed was 10 mm / min in accordance with JIS K7220 (1999). When the compression test was performed under the conditions, the stress at 50% compression (synonymous with 50% strain) was 7.5 kgf / cm 2 . Furthermore, the compression set was measured by the method described in JIS K6767 (1976) using a test piece of the same size, and it was 11%.
また，同一成形条件で成形した別の成形体から，縦５０ｍｍ，横５０ｍｍ，厚み２５ｍｍの試験片を作製し，ＪＩＳ Ｋ７２２０（１９９９年）に従って，試験片温度２３℃，圧縮速度１０ｍｍ／分の条件にて圧縮試験を行って図１に示すような応力−歪線図を得て，下記式（５）により単位体積当たりのエネルギー吸収量を求め，これをＪ（ジュール）／Ｌ（リッター）単位に換算することによって成形体のエネルギー吸収量を求めたところ，２７６Ｊ／Ｌであった。
単位体積当たりのエネルギー吸収量（ｋｇｆ／ｃｍ／ｃｍ3）＝５０％歪時の応力（ｋｇｆ／ｃｍ2）×５０％歪時までのエネルギー吸収効率×０．５（ｃｍ／ｃｍ）・・・式（５）
尚，式（５）中の「５０％歪時までのエネルギー吸収効率」とは，図１中の「ＯＡＢの面積（斜線部の面積）／四角形ＯＡＢＣの面積」で表される面積割合である。
これらの結果を下記の表３に示す。
In addition, a test piece having a length of 50 mm, a width of 50 mm, and a thickness of 25 mm was prepared from another molded body molded under the same molding conditions, and in accordance with JIS K7220 (1999), the test piece temperature was 23 ° C. and the compression speed was 10 mm / min. 1 to obtain a stress-strain diagram as shown in FIG. 1, and obtain the energy absorption amount per unit volume by the following equation (5), which is expressed in J (joule) / L (liter) units. It was 276 J / L when the energy absorption amount of the molded object was calculated | required by converting into.
Energy absorption amount per unit volume (kgf / cm / cm 3 ) = stress at 50% strain (kgf / cm 2 ) × energy absorption efficiency up to 50% strain × 0.5 (cm / cm) Formula (5)
Note that “energy absorption efficiency up to 50% strain” in equation (5) is an area ratio represented by “area of OAB (area of hatched portion) / area of quadrangular OABC” in FIG. .
These results are shown in Table 3 below.
実施例２〜８及び比較例１〜５
次に，ポリプロピレン系樹脂発泡粒子の基材樹脂として用いるポリプロピレン系樹脂組成物の組成を変え，他は実施例１と同様にして，ポリプロピレン系樹脂発泡粒子及び型内成形体を作製した。
基材樹脂としては，上記製造例１〜８で得た「ポリマー１」〜「ポリマー８」を表３又は表４に記載の組成にて配合したポリプロピレン系樹脂組成物を使用した。
その他は，実施例１と同様にして，上記ポリピロピレン系樹脂組成物を用いてポリプロピレン系樹脂発泡粒子及び型内成形体を作製し，これらの評価を行った。
その結果を表３及び表４に示した。尚，表３〜表５における成形体外観の評価基準は次の通りである。
○ 表面の間隙が少なく，凹凸も無い表面外観が優れた成形体。
△ 表面の間隙がやや認められる又は表面凹凸がやや認められる表面外観が多少劣る成形体。
× 表面の間隙が多い又は表面凹凸が多い表面外観不良の成形体。
Examples 2-8 and Comparative Examples 1-5
Next, the composition of the polypropylene resin composition used as the base resin of the polypropylene resin expanded particles was changed, and the other components were produced in the same manner as in Example 1 to produce polypropylene resin expanded particles and in-mold molded bodies.
As the base resin, a polypropylene resin composition prepared by blending “Polymer 1” to “Polymer 8” obtained in Production Examples 1 to 8 with the composition shown in Table 3 or Table 4 was used.
Others were made in the same manner as in Example 1 to produce polypropylene resin expanded particles and in-mold molded articles using the above-described polypyropylene resin composition, and evaluated them.
The results are shown in Tables 3 and 4. In addition, the evaluation criteria of the molded object external appearance in Table 3-Table 5 are as follows.
○ Molded body with excellent surface appearance with few gaps on the surface and no irregularities.
Δ: A molded article having a slightly inferior surface appearance in which surface gaps are slightly recognized or surface irregularities are slightly recognized.
X A molded article having a poor surface appearance with many surface gaps or many surface irregularities.
実施例９
製造例３で得たポリマー３（プロピレン系重合体［Ａ］）と製造例５で得たポリマー５（プロピレン系重合体［Ｂ］）とを６５：３５（重量比）で混合し，他は実施例１と同様にして，ポリプロピレン系樹脂組成物の細粒ペレットを得た。
Example 9
Polymer 3 (propylene polymer [A]) obtained in Production Example 3 and polymer 5 (propylene polymer [B]) obtained in Production Example 5 were mixed at 65:35 (weight ratio). In the same manner as in Example 1, a fine pellet of the polypropylene resin composition was obtained.
次に，このポリプロピレン系樹脂組成物を基材樹脂として用いて，ポリプロピレン系樹脂発泡粒子を以下のようにして作製する。
まず，ペレット状のポリプロピレン系樹脂組成物１００ｋｇを，水２２０Ｌ，ドデシルベンゼンスルホン酸ナトリウム（界面活性剤）５ｇ，カオリン（分散剤）３００ｇ，粉末硫酸アルミニウム１０ｇ（分散強化剤）と共に内容積４００Ｌのオートクレーブに入れて密閉した。続いて，発泡剤としての炭酸ガスをオートクレーブ内圧力が０．４９ＭＰａ（ゲージ圧）となるように圧入した後，攪拌しながら１６２℃まで昇温した。
Next, this polypropylene resin composition is used as a base resin to produce polypropylene resin expanded particles as follows.
First, 100 kg of a pellet-shaped polypropylene resin composition was mixed with 220 L of water, 5 g of sodium dodecylbenzenesulfonate (surfactant), 300 g of kaolin (dispersant), 10 g of powdered aluminum sulfate (dispersion strengthener), and an autoclave with an internal volume of 400 L. And sealed. Subsequently, carbon dioxide gas as a blowing agent was injected so that the pressure in the autoclave was 0.49 MPa (gauge pressure), and then the temperature was increased to 162 ° C. while stirring.
次いで，オートクレーブの内圧力が３．１４ＭＰａ（ゲージ圧）になるまで炭酸ガスを圧入しつつその温度で１５分間保持した。その後，オートクレーブの一端を開放してオートクレーブ内容物を大気圧下に放出して発泡粒子を得た。尚，樹脂粒子をオートクレーブから放出する間のオートクレーブ内圧力が，放出直前のオートクレーブ内圧力に保たれるように，オートクレーブ内に窒素ガスを供給しながら放出を行った。得られた発泡粒子を水洗し遠心分離機にかけたのち，２４時間大気圧下に放置して養生した後，発泡粒子の嵩密度等を測定した。
また，得られた発泡粒子について実施例１と同様にして気泡径を測定した。これらの結果を表５に示す。
Next, carbon dioxide gas was injected and held at that temperature for 15 minutes until the internal pressure of the autoclave reached 3.14 MPa (gauge pressure). Thereafter, one end of the autoclave was opened, and the contents of the autoclave were released under atmospheric pressure to obtain expanded particles. The release was performed while supplying nitrogen gas into the autoclave so that the pressure inside the autoclave during the release of the resin particles from the autoclave was maintained at the pressure inside the autoclave immediately before the release. The foamed particles thus obtained were washed with water, centrifuged, and allowed to stand at atmospheric pressure for 24 hours, and then the bulk density and the like of the foamed particles were measured.
Further, the bubble diameter of the obtained expanded particles was measured in the same manner as in Example 1. These results are shown in Table 5.
次に，上記ポリプロピレン系樹脂発泡粒子を用いて，実施例１と同様にして型内成形体を作製し，得られた成形体について，表面外観，融着度，５０％圧縮時の応力，圧縮永久歪，エネルギー吸収量等の評価を行った。その結果を表５に示す。 Next, using the above-mentioned polypropylene resin expanded particles, an in-mold molded product was produced in the same manner as in Example 1. The resulting molded product was subjected to surface appearance, degree of fusion, 50% compression stress, and compression. Permanent strain, energy absorption, etc. were evaluated. The results are shown in Table 5.
表３及び表５より知られるごとく，本発明にかかる実施例１〜９は，いずれもポリプロピレン系樹脂発泡粒子の気泡が非常に均一で，またそれを用いた型内成形体は，低い成形蒸気圧で加熱されたにもかかわらず，融着度も高く，更に表面外観も優れていることが分る。また，機械的物性についても圧縮強度（５０％圧縮時の応力）が高く，圧縮永久歪が小さいものであった。
また，発泡剤としてイソブタンを使用した実施例８と二酸化炭素を使用した実施例９との比較より，両者は同じ組成物を使用して同じ密度の成形体を得たものであるが，二酸化炭素を使用した実施例９の方が得られた成形体のエネルギー吸収量に優れていることが分かる。
As is known from Tables 3 and 5, in Examples 1 to 9 according to the present invention, the bubbles of the polypropylene resin foamed particles are very uniform, and the in-mold molded body using the same has a low molding vapor. Despite being heated by pressure, the degree of fusion is high and the surface appearance is also excellent. The mechanical properties were high in compressive strength (stress at 50% compression) and small in compression set.
Further, from the comparison between Example 8 using isobutane as a blowing agent and Example 9 using carbon dioxide, both obtained molded bodies having the same density using the same composition. It can be seen that the energy absorption of the molded product obtained in Example 9 using No. is excellent.
これに対して，表４に示す通り，上記製造例１にて得られたポリマー１を単独で用いた場合には，得られたポリプロピレン系樹脂発泡粒子を用いて成形した型内成形体の表面外観が多少劣る部分と著しく劣る不良部分を含むものであった（比較例３）。
また，上記製造例５により得たポリマー５を単独で用いた場合には，得られたポリプロピレン系樹脂発泡粒子は，気泡のバラツキが大きく，そのポリプロピレン系樹脂発泡粒子を用いて成形した型内成形体は，内部の融着度が低く，更に型内成形体の表面外観が悪く，圧縮強度（５０％圧縮時の応力）についても不十分なものであった（比較例４）。
On the other hand, as shown in Table 4, when the polymer 1 obtained in Production Example 1 was used alone, the surface of the in-mold molded product molded using the obtained polypropylene resin expanded particles. It contained a part with a slightly inferior appearance and a defective part that was remarkably inferior (Comparative Example 3).
In addition, when the polymer 5 obtained in Production Example 5 is used alone, the obtained polypropylene resin foamed particles have a large variation in air bubbles and are molded using the polypropylene resin foamed particles. The body had a low degree of internal fusion, the surface appearance of the in-mold molded body was poor, and the compressive strength (stress at 50% compression) was insufficient (Comparative Example 4).
また，ポリマー７とポリマー５とを混合してなる比較例１は，プロピレン重合体［Ａ］を含有しないため，得られたポリプロピレン系樹脂発泡粒子は，気泡のバラツキが大きいものとなった。そして，このポリプロピレン系樹脂発泡粒子を用いて成形した型内成形体は，内部の融着度が低く，更に型内成形体の表面外観が悪く，圧縮強度（５０％圧縮時の応力）の割りに圧縮永久歪が大きいものであった。
また，ポリマー８とポリマー５とを混合してなる比較例２は，プロピレン重合体［Ａ］を含有しないため，得られたポリプロピレン系樹脂発泡粒子には，粗大気泡が存在した。そして，このポリプロピレン系樹脂発泡粒子を用いて成形した型内成形体は，表面外観がやや悪く，圧縮強度（５０％圧縮時の応力）についても不十分なものであった。
Moreover, since the comparative example 1 which mixed the polymer 7 and the polymer 5 does not contain a propylene polymer [A], the obtained polypropylene resin expanded particle became a thing with large variation of a bubble. An in-mold molded product molded using the polypropylene resin expanded particles has a low degree of internal fusion, a poor surface appearance of the in-mold molded product, and a compression strength (stress at 50% compression). In addition, the compression set was large.
Moreover, since the comparative example 2 formed by mixing the polymer 8 and the polymer 5 does not contain the propylene polymer [A], coarse bubbles were present in the obtained polypropylene resin expanded particles. The in-mold molded body molded using the polypropylene resin expanded particles had a slightly poor surface appearance and an insufficient compressive strength (stress at 50% compression).
更に，ポリマー７を単独で用いた比較例５は，プロピレン重合体［Ａ］を含有しないため，得られたポリプロピレン系樹脂発泡粒子は，気泡のバラツキが大きいものとなった。そして，このポリプロピレン系樹脂発泡粒子を用いて成形した型内成形体は，表面外観がやや悪く，圧縮強度（５０％圧縮時の応力）の割りに圧縮永久歪が大きいものであった。 Furthermore, since Comparative Example 5 using the polymer 7 alone did not contain the propylene polymer [A], the obtained polypropylene-based resin expanded particles had a large variation in bubbles. The in-mold molded product molded using the polypropylene resin expanded particles had a slightly poor surface appearance and a large compression set for the compressive strength (stress at 50% compression).
尚，製造例１と製造例２は，同じメタロセン系重合触媒を使用してプロピレン単独重合体を製造した例を示すが，得られたプロピレン単独重合体の性質が異なる。この理由は，重合温度の相違に基づくものである。即ち，重合温度が高い製造例１の方が得られるプロピレン単独重合体の各位置不規則単位の割合が高い。
また，製造例５及び６は，メタロセン系重合触媒とは異なるチーグラー／ナッタ触媒を使用したことにより，得られたプロピレン系重合体に位置不規則単位が形成されなかった例を示すものである。
Production Example 1 and Production Example 2 show examples in which a propylene homopolymer was produced using the same metallocene polymerization catalyst, but the properties of the obtained propylene homopolymer were different. The reason is based on the difference in polymerization temperature. That is, the ratio of each position irregular unit of the propylene homopolymer obtained in Production Example 1 having a higher polymerization temperature is high.
In addition, Production Examples 5 and 6 show examples in which position irregular units were not formed in the obtained propylene polymer by using a Ziegler / Natta catalyst different from the metallocene polymerization catalyst.
また，製造例７は，製造例１とは異なるメタロセン系重合触媒を使用してプロピレン単独重合体を製造して例を示すが，公知文献に記載された条件では各位置不規則単位の割合が本発明の範囲を下回ることが分かる。なお，製造例７においては，重合温度が４０℃であったが，重合温度を例えば７０℃又はそれ以上に高めた場合には，得られるプロピレン単独重合体は位置不規則単位が本発明の範囲内に入ると予想されるが，その一方で，［ｍｍ］分率は製造例７のプロピレン単独重合体よりも更に低下するものと予想される。
また，製造例８は，製造例１及び製造例７とは異なるメタロセン系重合触媒を使用してプロピレン単独重合体を製造した例を示すが，使用されたメタロセン系重合触媒の金属錯体成分が適当でなかったため各位置不規則単位の割合が本発明の範囲を上回ったものである。
Further, Production Example 7 shows an example in which a propylene homopolymer is produced using a metallocene polymerization catalyst different from Production Example 1, but the ratio of each position irregular unit is under the conditions described in the publicly known literature. It can be seen that it is below the scope of the present invention. In Production Example 7, the polymerization temperature was 40 ° C. However, when the polymerization temperature is increased to, for example, 70 ° C. or higher, the resulting propylene homopolymer has position irregular units within the scope of the present invention. On the other hand, the [mm] fraction is expected to be lower than that of the propylene homopolymer of Production Example 7.
Production Example 8 shows an example of producing a propylene homopolymer using a metallocene polymerization catalyst different from Production Example 1 and Production Example 7, but the metal complex component of the metallocene polymerization catalyst used is appropriate. Therefore, the ratio of each position irregular unit exceeds the range of the present invention.
Claims (5)
プロピレン系重合体［Ａ］：下記の要件（ａ）及び（ｂ）を有するプロピレン系重合体。
（ａ）プロピレンから得られる構造単位が１００〜８５モル％，エチレン及び／又は炭素数４〜２０のα−オレフィンから得られる構造単位が０〜１５モル％存在すること（ただし，プロピレンから得られる構造単位と，エチレン及び／又は炭素数４〜２０のα−オレフィンから得られる構造単位との合計量は１００モル％である）。
（ｂ）１３Ｃ−ＮＭＲにて測定したときの，全プロピレン挿入中のプロピレンモノマー単位の２，１−挿入に基づく位置不規則単位の割合が０．５〜２．０％であり，かつプロピレンモノマー単位の１，３−挿入に基づく位置不規則単位の割合が０．００５〜０．４％であること。
プロピレン系重合体［Ｂ］：上記要件（ａ）及び（ｂ）のうち要件（ａ）だけを有するプロピレン系重合体。 5 to 95% by weight of the following propylene polymer [A] and 95 to 5% by weight of the following propylene polymer [B] (provided that the propylene polymer [A] and the propylene polymer [B] A polypropylene resin expanded particle comprising: a polypropylene resin composition containing: 100% by weight as a base resin .
Propylene polymer [A]: Help propylene-based polymer having a following requirements (a) and (b).
(A) The structural unit obtained from propylene is 100 to 85 mol%, and the structural unit obtained from ethylene and / or an α-olefin having 4 to 20 carbon atoms is present in an amount of 0 to 15 mol% (provided from propylene) The total amount of structural units and structural units obtained from ethylene and / or α-olefin having 4 to 20 carbon atoms is 100 mol%).
(B) the proportion of position irregular units based on 2,1-insertion of propylene monomer units in all propylene insertions as measured by 13C-NMR is 0.5 to 2.0%, and propylene monomers The percentage of irregularly located units based on 1,3-insertion of units is 0.005 to 0.4%.
Propylene polymer [B]: A propylene polymer having only requirement (a) among the above requirements (a) and (b).
（ｄ）頭−尾結合からなるプロピレン単位連鎖部における，１３Ｃ−ＮＭＲで測定したときのアイソタクチックトリアッド分率は９７％以上であること。 The expanded polypropylene resin particle according to claim 1, wherein the propylene polymer [A] further has the following requirement (d).
(D) The isotactic triad fraction in the propylene unit chain part composed of head-to-tail bonds as measured by 13C-NMR is 97% or more.
（ｅ）メルトフローレートが０．５〜１００ｇ／１０分であること。 3. The expanded polypropylene resin particle according to claim 1, wherein the propylene polymer [A] further has the following requirement (e):
(E) The melt flow rate is 0.5 to 100 g / 10 minutes.
かつ上記ポリプロピレン系樹脂発泡粒子は，上記請求項１〜４のいずれか一項に記載のものを用いてなることを特徴とする型内成形体。 An in-mold molded product having a density of 0.008 to 0.5 g / cm 3 formed by molding polypropylene resin expanded particles in a molding die ,
And the said polypropylene resin expanded particle uses the thing as described in any one of the said Claims 1-4, The in-mold molded object characterized by the above-mentioned .
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| JP5281333B2 (en) * | 2008-08-15 | 2013-09-04 | 株式会社カネカ | Process for producing polypropylene resin pre-expanded particles and polypropylene resin pre-expanded particles |
| CN102292383B (en) | 2009-01-27 | 2013-08-21 | 株式会社钟化 | Polypropylene resin pre-foamed particle and method for producing same, and polypropylene resin in-mold foaming molded article |
| JP5177247B2 (en) * | 2011-03-07 | 2013-04-03 | 株式会社カネカ | Polypropylene-based resin pre-expanded particles, in-mold foam molded product, and method for producing the same |
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| WO1999028374A1 (en) * | 1997-12-01 | 1999-06-10 | Jsp Corporation | Expandable polypropylene resin beads and products of in-mold expansion |
| JP2001240711A (en) * | 2000-03-01 | 2001-09-04 | Japan Polychem Corp | Thermally shrinkable stretched polypropylene film |
| JP2003327740A (en) * | 2002-05-13 | 2003-11-19 | Jsp Corp | Polypropylene resin foaming particle and in-mold molded product using the same |
| WO2003095539A1 (en) * | 2002-05-13 | 2003-11-20 | Jsp Corporation | Expandable polypropylene resin particle and molded object obtained therefrom by in-mold molding |
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| JP4058159B2 (en) * | 1998-04-21 | 2008-03-05 | 日本ポリプロ株式会社 | Propylene resin composition for injection molding |
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| JP4374629B2 (en) * | 1998-06-05 | 2009-12-02 | 三菱化学株式会社 | Propylene resin composition |
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| WO1999028374A1 (en) * | 1997-12-01 | 1999-06-10 | Jsp Corporation | Expandable polypropylene resin beads and products of in-mold expansion |
| JP2001240711A (en) * | 2000-03-01 | 2001-09-04 | Japan Polychem Corp | Thermally shrinkable stretched polypropylene film |
| JP2003327740A (en) * | 2002-05-13 | 2003-11-19 | Jsp Corp | Polypropylene resin foaming particle and in-mold molded product using the same |
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