JP6845001B2 - Polypropylene sheet, polypropylene sheet manufacturing method, and secondary molded product - Google Patents
Polypropylene sheet, polypropylene sheet manufacturing method, and secondary molded product Download PDFInfo
- Publication number
- JP6845001B2 JP6845001B2 JP2016239506A JP2016239506A JP6845001B2 JP 6845001 B2 JP6845001 B2 JP 6845001B2 JP 2016239506 A JP2016239506 A JP 2016239506A JP 2016239506 A JP2016239506 A JP 2016239506A JP 6845001 B2 JP6845001 B2 JP 6845001B2
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- JP
- Japan
- Prior art keywords
- polypropylene
- succinate
- sheet
- less
- mass
- 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.)
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- -1 Polypropylene Polymers 0.000 title claims description 179
- 239000004743 Polypropylene Substances 0.000 title claims description 133
- 229920001155 polypropylene Polymers 0.000 title claims description 133
- 238000004519 manufacturing process Methods 0.000 title claims description 54
- 239000000203 mixture Substances 0.000 claims description 98
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 55
- 239000005977 Ethylene Substances 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 42
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 39
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 38
- 239000003484 crystal nucleating agent Substances 0.000 claims description 38
- 229920000642 polymer Polymers 0.000 claims description 38
- 239000010936 titanium Substances 0.000 claims description 27
- 238000000465 moulding Methods 0.000 claims description 24
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000008096 xylene Substances 0.000 claims description 20
- 239000011949 solid catalyst Substances 0.000 claims description 16
- 238000002425 crystallisation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 15
- 238000003856 thermoforming Methods 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000009826 distribution Methods 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 230000005540 biological transmission Effects 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 238000009864 tensile test Methods 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 150000003890 succinate salts Chemical class 0.000 claims 2
- 238000006116 polymerization reaction Methods 0.000 description 32
- 239000000047 product Substances 0.000 description 28
- 239000001257 hydrogen Substances 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 239000000178 monomer Substances 0.000 description 16
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 16
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 14
- 239000002667 nucleating agent Substances 0.000 description 14
- 239000000600 sorbitol Substances 0.000 description 14
- 229960002920 sorbitol Drugs 0.000 description 14
- 239000000460 chlorine Substances 0.000 description 10
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- JGMMIGGLIIRHFV-UHFFFAOYSA-N nonane-1,2,3,4,5,6,7,8,9-nonol Chemical compound OCC(O)C(O)C(O)C(O)C(O)C(O)C(O)CO JGMMIGGLIIRHFV-UHFFFAOYSA-N 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 125000005234 alkyl aluminium group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 5
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 150000002681 magnesium compounds Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000003609 titanium compounds Chemical class 0.000 description 5
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000001174 ascending effect Effects 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 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 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- RUOKPLVTMFHRJE-UHFFFAOYSA-N benzene-1,2,3-triamine Chemical class NC1=CC=CC(N)=C1N RUOKPLVTMFHRJE-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920001384 propylene homopolymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- CQBVVSONJDUVEJ-UHFFFAOYSA-N 4-cyclohexyloxy-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OC1CCCCC1 CQBVVSONJDUVEJ-UHFFFAOYSA-N 0.000 description 2
- GFQUHXOKHFFPGI-UHFFFAOYSA-N CCC(CC)COC(=O)CCC(O)=O Chemical compound CCC(CC)COC(=O)CCC(O)=O GFQUHXOKHFFPGI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 2
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 2
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 2
- QWHNJUXXYKPLQM-UHFFFAOYSA-N dimethyl cyclopentane Natural products CC1(C)CCCC1 QWHNJUXXYKPLQM-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- RVOYYLUVELMWJF-UHFFFAOYSA-N magnesium;hexane Chemical compound [Mg+2].CCCCC[CH2-].CCCCC[CH2-] RVOYYLUVELMWJF-UHFFFAOYSA-N 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 150000002899 organoaluminium compounds Chemical class 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000007155 step growth polymerization reaction Methods 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 150000003900 succinic acid esters Chemical class 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- ASEHKQZNVUOPRW-UHFFFAOYSA-N tert-butyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C(C)(C)C ASEHKQZNVUOPRW-UHFFFAOYSA-N 0.000 description 2
- JHVNMGWNEQGGDU-UHFFFAOYSA-N tert-butyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C(C)(C)C)OCC JHVNMGWNEQGGDU-UHFFFAOYSA-N 0.000 description 2
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 2
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 2
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- 239000000811 xylitol Substances 0.000 description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 2
- 229960002675 xylitol Drugs 0.000 description 2
- 235000010447 xylitol Nutrition 0.000 description 2
- YWEWWNPYDDHZDI-JJKKTNRVSA-N (1r)-1-[(4r,4ar,8as)-2,6-bis(3,4-dimethylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C1=C(C)C(C)=CC=C1C1O[C@H]2[C@@H]([C@H](O)CO)OC(C=3C=C(C)C(C)=CC=3)O[C@H]2CO1 YWEWWNPYDDHZDI-JJKKTNRVSA-N 0.000 description 1
- LVTPRIAGCBEGPW-UHFFFAOYSA-N (2-benzoyloxyphenyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1OC(=O)C1=CC=CC=C1 LVTPRIAGCBEGPW-UHFFFAOYSA-N 0.000 description 1
- CCLARULDIPFTCP-BOYHRMMASA-N (2r,3r,4r,5s)-heptane-1,2,3,4,5,6-hexol Chemical compound CC(O)[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO CCLARULDIPFTCP-BOYHRMMASA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- NENLYAQPNATJSU-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7,8,8a-decahydroisoquinoline Chemical compound C1NCCC2CCCCC21 NENLYAQPNATJSU-UHFFFAOYSA-N 0.000 description 1
- SLVYEMCIFUYCMB-UHFFFAOYSA-N 1,2-bis(2-methylpropyl)cyclohexane-1,2-dicarboxylic acid Chemical compound CC(C)CC1(C(O)=O)CCCCC1(CC(C)C)C(O)=O SLVYEMCIFUYCMB-UHFFFAOYSA-N 0.000 description 1
- PIYNPBVOTLQBTC-UHFFFAOYSA-N 1-[8-propyl-2,6-bis(4-propylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound O1C2C(CCC)OC(C=3C=CC(CCC)=CC=3)OC2C(C(O)CO)OC1C1=CC=C(CCC)C=C1 PIYNPBVOTLQBTC-UHFFFAOYSA-N 0.000 description 1
- JWRLWZWXJTXMFA-UHFFFAOYSA-N 2,2-bis(2,2-dimethylpropyl)-3-methoxybutanedioic acid Chemical compound CC(C)(C)CC(CC(C)(C)C)(C(C(=O)O)OC)C(=O)O JWRLWZWXJTXMFA-UHFFFAOYSA-N 0.000 description 1
- GTOFKXZQQDSVFH-UHFFFAOYSA-N 2-benzylsuccinic acid Chemical compound OC(=O)CC(C(O)=O)CC1=CC=CC=C1 GTOFKXZQQDSVFH-UHFFFAOYSA-N 0.000 description 1
- WGRZHLPEQDVPET-UHFFFAOYSA-N 2-methoxyethoxysilane Chemical compound COCCO[SiH3] WGRZHLPEQDVPET-UHFFFAOYSA-N 0.000 description 1
- ZSCLROYWHVMROC-UHFFFAOYSA-N 3,6-dimethyl-1,2-bis(2-methylpropyl)cyclohexane-1,2-dicarboxylic acid Chemical compound CC(C)CC1(C(C)CCC(C)C1(CC(C)C)C(O)=O)C(O)=O ZSCLROYWHVMROC-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- HWKNXXKPAYBMRC-UHFFFAOYSA-N 3-cyclohexyl-2,2-bis(2-methylpropyl)butanedioic acid Chemical compound CC(C)CC(CC(C)C)(C(C1CCCCC1)C(O)=O)C(O)=O HWKNXXKPAYBMRC-UHFFFAOYSA-N 0.000 description 1
- UJTSEBWFGIWPKU-UHFFFAOYSA-N 3-methoxy-2,2-bis(2-methylpropyl)butanedioic acid Chemical compound CC(C)CC(CC(C)C)(C(C(=O)O)OC)C(=O)O UJTSEBWFGIWPKU-UHFFFAOYSA-N 0.000 description 1
- CTTZQFZGUIRBLE-UHFFFAOYSA-N 4-(2,6-dimethyl-4-phenylheptan-4-yl)oxy-4-oxobutanoic acid Chemical compound CC(C)CC(CC(C)C)(C1=CC=CC=C1)OC(=O)CCC(=O)O CTTZQFZGUIRBLE-UHFFFAOYSA-N 0.000 description 1
- FNNOQGRXCHOBTE-UHFFFAOYSA-N 4-(2,6-dimethyl-4-propan-2-ylheptan-4-yl)oxy-4-oxobutanoic acid Chemical compound CC(C)CC(CC(C)C)(C(C)C)OC(=O)CCC(=O)O FNNOQGRXCHOBTE-UHFFFAOYSA-N 0.000 description 1
- RYJHSTNVHPTWRC-UHFFFAOYSA-N 4-(2-cyclohexyl-3,3-diethylcyclopentyl)oxy-4-oxobutanoic acid Chemical compound CCC1(CCC(C1C2CCCCC2)OC(=O)CCC(=O)O)CC RYJHSTNVHPTWRC-UHFFFAOYSA-N 0.000 description 1
- APQSAVHZMIVHOP-UHFFFAOYSA-N 4-(2-cyclopentyl-4-ethylhexan-2-yl)oxy-4-oxobutanoic acid Chemical compound CCC(CC)CC(C)(C1CCCC1)OC(=O)CCC(=O)O APQSAVHZMIVHOP-UHFFFAOYSA-N 0.000 description 1
- HTZFWCKERCOKQL-UHFFFAOYSA-N 4-(3-cyclohexylhexan-3-yloxy)-4-oxobutanoic acid Chemical compound CCCC(CC)(C1CCCCC1)OC(=O)CCC(=O)O HTZFWCKERCOKQL-UHFFFAOYSA-N 0.000 description 1
- XWIMEAILKVOUBY-UHFFFAOYSA-N 4-(3-ethyl-2-methylpentan-2-yl)oxy-4-oxobutanoic acid Chemical compound CCC(CC)C(C)(C)OC(=O)CCC(=O)O XWIMEAILKVOUBY-UHFFFAOYSA-N 0.000 description 1
- KAXSCMJDJKSOSD-UHFFFAOYSA-N 4-(3-ethyl-3-methylpentan-2-yl)oxy-4-oxobutanoic acid Chemical compound CCC(C)(CC)C(C)OC(=O)CCC(=O)O KAXSCMJDJKSOSD-UHFFFAOYSA-N 0.000 description 1
- GKGGDGBREDAIRS-UHFFFAOYSA-N 4-(4-chloro-2,3-diethylphenoxy)-4-oxobutanoic acid Chemical compound CCC1=C(C=CC(=C1CC)Cl)OC(=O)CCC(=O)O GKGGDGBREDAIRS-UHFFFAOYSA-N 0.000 description 1
- LNFZQDBPJDGJHC-UHFFFAOYSA-N 4-(4-cyclohexyl-2,7-dimethyloctan-4-yl)oxy-4-oxobutanoic acid Chemical compound CC(C)CCC(CC(C)C)(C1CCCCC1)OC(=O)CCC(=O)O LNFZQDBPJDGJHC-UHFFFAOYSA-N 0.000 description 1
- YGQDZMVJSXFXEZ-UHFFFAOYSA-N 4-(4-tert-butyl-2,6-dimethylheptan-4-yl)oxy-4-oxobutanoic acid Chemical compound CC(C)CC(CC(C)C)(C(C)(C)C)OC(=O)CCC(=O)O YGQDZMVJSXFXEZ-UHFFFAOYSA-N 0.000 description 1
- HZXMLBSUEZTYHZ-UHFFFAOYSA-N 4-(cyclohexylmethoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OCC1CCCCC1 HZXMLBSUEZTYHZ-UHFFFAOYSA-N 0.000 description 1
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- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- RTYZQVDVGVAXSW-UHFFFAOYSA-N cyclohexylmethyl(diethoxy)silane Chemical compound CCO[SiH](OCC)CC1CCCCC1 RTYZQVDVGVAXSW-UHFFFAOYSA-N 0.000 description 1
- MUQCQZPQDMXYAA-UHFFFAOYSA-N cyclopentyl-dimethoxy-(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(OC)C1CCCC1 MUQCQZPQDMXYAA-UHFFFAOYSA-N 0.000 description 1
- JOUWRCGZMOSOCD-UHFFFAOYSA-N cyclopentyl-dimethoxy-propan-2-ylsilane Chemical compound CO[Si](OC)(C(C)C)C1CCCC1 JOUWRCGZMOSOCD-UHFFFAOYSA-N 0.000 description 1
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 description 1
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HVHRIKGOFGJBFM-UHFFFAOYSA-N di(butan-2-yl)-dimethoxysilane Chemical compound CCC(C)[Si](OC)(OC)C(C)CC HVHRIKGOFGJBFM-UHFFFAOYSA-N 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- VTZJFPSWNQFPCQ-UHFFFAOYSA-N dibutylaluminum Chemical compound CCCC[Al]CCCC VTZJFPSWNQFPCQ-UHFFFAOYSA-N 0.000 description 1
- RFUDQCRVCDXBGK-UHFFFAOYSA-L dichloro(propyl)alumane Chemical compound [Cl-].[Cl-].CCC[Al+2] RFUDQCRVCDXBGK-UHFFFAOYSA-L 0.000 description 1
- ZVMRWPHIZSSUKP-UHFFFAOYSA-N dicyclohexyl(dimethoxy)silane Chemical compound C1CCCCC1[Si](OC)(OC)C1CCCCC1 ZVMRWPHIZSSUKP-UHFFFAOYSA-N 0.000 description 1
- YXVDWNUMQJCHNL-UHFFFAOYSA-N dicyclohexyl(dimethoxy)silane silane Chemical compound [SiH4].C1(CCCCC1)[Si](OC)(OC)C1CCCCC1 YXVDWNUMQJCHNL-UHFFFAOYSA-N 0.000 description 1
- DODIKAULZAKDIN-UHFFFAOYSA-N diethyl 2,2-dimethylbutanedioate Chemical compound CCOC(=O)CC(C)(C)C(=O)OCC DODIKAULZAKDIN-UHFFFAOYSA-N 0.000 description 1
- AVLHXEDOBYYTGV-UHFFFAOYSA-N diethyl 2,3-bis(2-methylpropyl)butanedioate Chemical compound CCOC(=O)C(CC(C)C)C(CC(C)C)C(=O)OCC AVLHXEDOBYYTGV-UHFFFAOYSA-N 0.000 description 1
- WGFNXLQURMLAGC-UHFFFAOYSA-N diethyl 2,3-di(propan-2-yl)butanedioate Chemical compound CCOC(=O)C(C(C)C)C(C(C)C)C(=O)OCC WGFNXLQURMLAGC-UHFFFAOYSA-N 0.000 description 1
- DQNUPKXJISAAFG-UHFFFAOYSA-N diethyl 2,3-diethyl-2-propan-2-ylbutanedioate Chemical compound CCOC(=O)C(CC)C(CC)(C(C)C)C(=O)OCC DQNUPKXJISAAFG-UHFFFAOYSA-N 0.000 description 1
- YKNVJKQSCZQURF-UHFFFAOYSA-N diethyl 2-(3-methylbutyl)-2-(2-methylpropyl)butanedioate Chemical compound CCOC(=O)CC(CCC(C)C)(CC(C)C)C(=O)OCC YKNVJKQSCZQURF-UHFFFAOYSA-N 0.000 description 1
- TXRNMKWGVBBYLW-UHFFFAOYSA-N diethyl 2-benzyl-2-propan-2-ylbutanedioate Chemical compound CCOC(=O)CC(C(=O)OCC)(C(C)C)CC1=CC=CC=C1 TXRNMKWGVBBYLW-UHFFFAOYSA-N 0.000 description 1
- JZJPBADSXBZWAZ-UHFFFAOYSA-N diethyl 2-benzylbutanedioate Chemical compound CCOC(=O)CC(C(=O)OCC)CC1=CC=CC=C1 JZJPBADSXBZWAZ-UHFFFAOYSA-N 0.000 description 1
- GKCJIKJXEOGKJU-UHFFFAOYSA-N diethyl 2-butyl-2-phenylbutanedioate Chemical compound CCOC(=O)CC(CCCC)(C(=O)OCC)C1=CC=CC=C1 GKCJIKJXEOGKJU-UHFFFAOYSA-N 0.000 description 1
- OZTIOOUTDNFCJG-UHFFFAOYSA-N diethyl 2-ethyl-2-(2-methylpropyl)butanedioate Chemical compound CCOC(=O)CC(CC)(CC(C)C)C(=O)OCC OZTIOOUTDNFCJG-UHFFFAOYSA-N 0.000 description 1
- DJHQJVJMROPIHP-UHFFFAOYSA-N diethyl 2-ethyl-2-methylbutanedioate Chemical compound CCOC(=O)CC(C)(CC)C(=O)OCC DJHQJVJMROPIHP-UHFFFAOYSA-N 0.000 description 1
- MRWFEHLACVTKBG-UHFFFAOYSA-N diethyl 2-ethyl-2-tetradecylbutanedioate Chemical compound CCCCCCCCCCCCCCC(CC)(C(=O)OCC)CC(=O)OCC MRWFEHLACVTKBG-UHFFFAOYSA-N 0.000 description 1
- CNVQQORAGNTULF-UHFFFAOYSA-N diethyl 2-methyl-2-propan-2-ylbutanedioate Chemical compound CCOC(=O)CC(C)(C(C)C)C(=O)OCC CNVQQORAGNTULF-UHFFFAOYSA-N 0.000 description 1
- JVQDNCKPHSZFSO-UHFFFAOYSA-N diethyl 2-phenylbutanedioate Chemical compound CCOC(=O)CC(C(=O)OCC)C1=CC=CC=C1 JVQDNCKPHSZFSO-UHFFFAOYSA-N 0.000 description 1
- SSQLHHBLAVHVOU-UHFFFAOYSA-N diethyl 2-propan-2-ylbutanedioate Chemical compound CCOC(=O)CC(C(C)C)C(=O)OCC SSQLHHBLAVHVOU-UHFFFAOYSA-N 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- NHYFIJRXGOQNFS-UHFFFAOYSA-N dimethoxy-bis(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(CC(C)C)OC NHYFIJRXGOQNFS-UHFFFAOYSA-N 0.000 description 1
- JUESRADRPFMUCL-UHFFFAOYSA-N dimethoxy-methyl-(2-methylpropyl)silane Chemical compound CO[Si](C)(OC)CC(C)C JUESRADRPFMUCL-UHFFFAOYSA-N 0.000 description 1
- DIJRHOZMLZRNLM-UHFFFAOYSA-N dimethoxy-methyl-(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](C)(OC)CCC(F)(F)F DIJRHOZMLZRNLM-UHFFFAOYSA-N 0.000 description 1
- VXRHXYMVUBPPTO-UHFFFAOYSA-N dimethoxy-methyl-(4-methylphenyl)silane Chemical compound CO[Si](C)(OC)C1=CC=C(C)C=C1 VXRHXYMVUBPPTO-UHFFFAOYSA-N 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- KZLUHGRPVSRSHI-UHFFFAOYSA-N dimethylmagnesium Chemical compound C[Mg]C KZLUHGRPVSRSHI-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- YTHSGTQAXRQVOX-UHFFFAOYSA-N ethyl 1-(2-cyclohexyl-2-ethoxyacetyl)cyclohexane-1-carboxylate Chemical compound C1CCCCC1(C(=O)OCC)C(=O)C(OCC)C1CCCCC1 YTHSGTQAXRQVOX-UHFFFAOYSA-N 0.000 description 1
- JYEMURZLFONTNE-UHFFFAOYSA-N ethyl 1-(2-ethoxyacetyl)-2,6-dimethylcyclohexane-1-carboxylate Chemical compound CCOCC(=O)C1(C(=O)OCC)C(C)CCCC1C JYEMURZLFONTNE-UHFFFAOYSA-N 0.000 description 1
- REBFJHPJLSHCAF-UHFFFAOYSA-N ethyl hypochlorite;magnesium Chemical compound [Mg].CCOCl REBFJHPJLSHCAF-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- MYEJNNDSIXAGNK-UHFFFAOYSA-N ethyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](CC)(OC(C)C)OC(C)C MYEJNNDSIXAGNK-UHFFFAOYSA-N 0.000 description 1
- BBIDBFWZMCTRNP-UHFFFAOYSA-N ethylalumane Chemical class CC[AlH2] BBIDBFWZMCTRNP-UHFFFAOYSA-N 0.000 description 1
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 description 1
- YJCTUQFSSZSZPO-UHFFFAOYSA-L magnesium;chloride;phenoxide Chemical compound [Cl-].[Mg+]OC1=CC=CC=C1 YJCTUQFSSZSZPO-UHFFFAOYSA-L 0.000 description 1
- BJZBHTNKDCBDNQ-UHFFFAOYSA-L magnesium;dodecanoate Chemical compound [Mg+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BJZBHTNKDCBDNQ-UHFFFAOYSA-L 0.000 description 1
- DLPASUVGCQPFFO-UHFFFAOYSA-N magnesium;ethane Chemical compound [Mg+2].[CH2-]C.[CH2-]C DLPASUVGCQPFFO-UHFFFAOYSA-N 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- GBRJQTLHXWRDOV-UHFFFAOYSA-M magnesium;hexane;chloride Chemical compound [Mg+2].[Cl-].CCCCC[CH2-] GBRJQTLHXWRDOV-UHFFFAOYSA-M 0.000 description 1
- ZJOBTICDECBMMX-UHFFFAOYSA-N magnesium;octyl hypochlorite Chemical compound [Mg].CCCCCCCCOCl ZJOBTICDECBMMX-UHFFFAOYSA-N 0.000 description 1
- MHRHSHLWWOSEKQ-UHFFFAOYSA-N magnesium;propan-2-yl hypochlorite Chemical compound [Mg].CC(C)OCl MHRHSHLWWOSEKQ-UHFFFAOYSA-N 0.000 description 1
- RYEXTBOQKFUPOE-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].CC[CH2-] RYEXTBOQKFUPOE-UHFFFAOYSA-M 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- CPEULHAPWXMDDV-UHFFFAOYSA-N n-[3,5-bis(2,2-dimethylpropanoylamino)phenyl]-2,2-dimethylpropanamide Chemical compound CC(C)(C)C(=O)NC1=CC(NC(=O)C(C)(C)C)=CC(NC(=O)C(C)(C)C)=C1 CPEULHAPWXMDDV-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KOFGHHIZTRGVAF-UHFFFAOYSA-N n-ethyl-n-triethoxysilylethanamine Chemical compound CCO[Si](OCC)(OCC)N(CC)CC KOFGHHIZTRGVAF-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005673 polypropylene based resin Polymers 0.000 description 1
- 238000009725 powder blending Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- OBRKWFIGZSMARO-UHFFFAOYSA-N propylalumane Chemical class [AlH2]CCC OBRKWFIGZSMARO-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 235000012046 side dish Nutrition 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 description 1
- AQPCDBILXLZJIX-UHFFFAOYSA-N tert-butyl-dimethoxy-[(2-methylpropan-2-yl)oxy]silane Chemical compound CO[Si](OC)(C(C)(C)C)OC(C)(C)C AQPCDBILXLZJIX-UHFFFAOYSA-N 0.000 description 1
- CFWAESPQSRZDQT-UHFFFAOYSA-N tert-butyl-dimethoxy-propylsilane Chemical compound CCC[Si](OC)(OC)C(C)(C)C CFWAESPQSRZDQT-UHFFFAOYSA-N 0.000 description 1
- PSWKAZOCOHMXCW-UHFFFAOYSA-N tert-butyl-ethyl-dimethoxysilane Chemical compound CC[Si](OC)(OC)C(C)(C)C PSWKAZOCOHMXCW-UHFFFAOYSA-N 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- OJAJJFGMKAZGRZ-UHFFFAOYSA-N trimethyl(phenoxy)silane Chemical compound C[Si](C)(C)OC1=CC=CC=C1 OJAJJFGMKAZGRZ-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明はポリプロピレン組成物、該ポリプロピレン組成物からなるポリプロピレン製シート、該ポリプロピレン製シートの製造方法、および該ポリプロピレン製シートの二次成形体に関する。 The present invention relates to a polypropylene composition, a polypropylene sheet made of the polypropylene composition, a method for producing the polypropylene sheet, and a secondary molded product of the polypropylene sheet.
ポリプロピレンは、安価で剛性、耐湿性、および耐熱性に優れており、食品包装や繊維包装などに用いられるシートの材料として好適である。例えば、耐熱性を有する食品容器としてポリプロピレンを使用した容器が使用されているが強度面で課題が残り、それを補うため、厚みを持たせたり、多くのリブを入れて対応しているが、コスト増や内容物が見辛くなるといった問題が生じる。また、食品容器には内容物を確認することができるように透明性が要求されるが、ポリプロピレンは結晶性樹脂でありそのままでは半透明のシートとなるため、その改善策として結晶核剤の添加が知られている。しかし、それでも十分な透明性を得ることは難しい。また、近年では冷凍状態での流通に対応するために−３０℃の低温でも耐衝撃性を有することが求められる。 Polypropylene is inexpensive, has excellent rigidity, moisture resistance, and heat resistance, and is suitable as a material for sheets used in food packaging, fiber packaging, and the like. For example, a container made of polypropylene is used as a food container with heat resistance, but there is still a problem in terms of strength, and in order to make up for it, it is possible to increase the thickness or add many ribs. Problems such as increased costs and unsightly contents arise. In addition, transparency is required for food containers so that the contents can be confirmed, but polypropylene is a crystalline resin and becomes a translucent sheet as it is, so as a remedy, addition of a crystal nucleating agent It has been known. However, it is still difficult to obtain sufficient transparency. Further, in recent years, in order to cope with distribution in a frozen state, it is required to have impact resistance even at a low temperature of −30 ° C.
ポリプロピレン組成物の成形品の透明性を改善するために、例えば特許文献１には結晶核剤を添加する方法が提案されている。また、ポリプロピレンの剛性や透明性を向上させる手法として延伸する方法は公知である（特許文献２）。さらに、剛性と透明性のバランスを向上させるために、ポリプロピレン組成物の組み合わせを利用する方法も公知である（特許文献３）。しかし、このようにして得たポリプロピレン組成物の成形体は、低温で使用する場合に耐衝撃性が低下するという問題があった。これを改善するために、例えばエチレン系コポリマーをポリプロピレンに添加することが提案されている（特許文献４）。 In order to improve the transparency of a molded product of a polypropylene composition, for example, Patent Document 1 proposes a method of adding a crystal nucleating agent. Further, a method of stretching polypropylene is known as a method for improving the rigidity and transparency of polypropylene (Patent Document 2). Further, a method of utilizing a combination of polypropylene compositions in order to improve the balance between rigidity and transparency is also known (Patent Document 3). However, the molded product of the polypropylene composition thus obtained has a problem that the impact resistance is lowered when it is used at a low temperature. In order to improve this, for example, it has been proposed to add an ethylene-based copolymer to polypropylene (Patent Document 4).
しかしながら本発明者等の知見によれば、特許文献１の方法では、高透明性と、高剛性と、低温での高耐衝撃性を同時に達成することは難しく、かつ、均一延伸性と易熱成形性を同時に付与することも難しい。
また、一般的に良く知られる延伸ポリプロピレンシートとして二軸延伸ポリプロピレンシートがあるが、通常、縦×横＝５×１０倍程度の高倍率で行われている。しかしながら本発明者等の知見によれば、このような高倍率で、熱成形に適したシート厚み（０．１ｍｍ〜０．５ｍｍ）を得ようとすると、延伸前の一次シート厚みを５〜２５ｍｍにしなければならず、一次シートの作製が非常に困難となる。仮に上記厚みの一次シートの作製に至り高倍率で延伸シートを製造したとしても、シートの伸長時応力の増大やひずみ性低下により絞り成形性（熱成形性）が低下するため、型の形状通りに成形することが大変困難となる。一方、一次厚みを薄くするために低倍率で延伸シートを製造した場合は、引き残し（ネッキング）に起因する延伸ムラ（厚薄ムラ）が発生し、成形時の加熱ムラ発生による製品安定性低下の要因となり、製品として成り立たないという問題が生じる。特許文献２のように、二軸延伸成形性と剛性のバランスを改良した事例もあるが、このような従来技術では成形性が十分ではなく、厚薄精度の良好なシートが得られず、剛性も本発明には及ばない。また、この方法で作製したシートを絞り成形（熱成形）することはできない。
また、特許文献３の方法は、従来技術のシート成形法に適するようなポリプロピレン組成物の特定の組み合わせで、剛性と透明性のバランスに優れたシートを作製できるとしているが、本発明の剛性と透明性のバランスに及ばないだけでなく、この手法では低温での高耐衝撃性を付与することはできない。
また、特許文献４の方法のように、エチレン系コポリマーを添加することにより低温での耐衝撃性を付与することはできるが、透明性が低下するので、この方法で得られたポリプロピレン系シートは満足のいく透明性と耐寒衝撃性のバランスを有していない。
However, according to the findings of the present inventors, it is difficult to achieve high transparency, high rigidity, and high impact resistance at low temperatures at the same time by the method of Patent Document 1, and uniform stretchability and heat resistance are obtained. It is also difficult to impart moldability at the same time.
Further, as a generally well-known stretched polypropylene sheet, there is a biaxially stretched polypropylene sheet, which is usually performed at a high magnification of about 5 × 10 times in length × width = 5 × 10. However, according to the findings of the present inventors, in order to obtain a sheet thickness (0.1 mm to 0.5 mm) suitable for thermoforming at such a high magnification, the primary sheet thickness before stretching is 5 to 25 mm. This makes it very difficult to prepare the primary sheet. Even if a primary sheet having the above thickness is produced and a stretched sheet is produced at a high magnification, the draw moldability (thermoforming property) decreases due to an increase in stress during elongation of the sheet and a decrease in strainability. It becomes very difficult to mold. On the other hand, when a stretched sheet is manufactured at a low magnification in order to reduce the primary thickness, stretching unevenness (thickness and thinning unevenness) due to unremaining (necking) occurs, and product stability deteriorates due to heating unevenness during molding. It becomes a factor and causes a problem that it cannot be established as a product. As in Patent Document 2, there is an example in which the balance between biaxial stretch moldability and rigidity is improved, but the moldability is not sufficient by such a conventional technique, a sheet having good thickness and thinness accuracy cannot be obtained, and the rigidity is also high. It does not reach the present invention. Further, the sheet produced by this method cannot be drawn (thermoformed).
Further, the method of Patent Document 3 states that a sheet having an excellent balance between rigidity and transparency can be produced by a specific combination of polypropylene compositions suitable for the sheet molding method of the prior art. Not only does it fall short of the balance of transparency, this approach cannot provide high impact resistance at low temperatures.
Further, as in the method of Patent Document 4, the impact resistance at a low temperature can be imparted by adding an ethylene-based copolymer, but the transparency is lowered, so that the polypropylene-based sheet obtained by this method can be used. It does not have a satisfactory balance of transparency and cold impact resistance.
本発明は、上記のような従来技術による課題を解決しようとするものであり、透明性、剛性、耐熱性、均一延伸性および低温での耐衝撃性に優れ、さらに易熱成形性を有する二軸延伸ポリプロピレン製シート、そのシートを用いて熱成形された使用上問題の無い二次成形体（容器等）、およびかかるシートを製造するのに好適なポリプロピレン組成物を提供する。 The present invention is intended to solve the above-mentioned problems of the prior art, and is excellent in transparency, rigidity, heat resistance, uniform stretchability, impact resistance at low temperature, and further has thermoforming property. Provided are a sheet made of axially stretched polypropylene, a secondary molded product (container or the like) that is thermoformed using the sheet and has no problem in use, and a polypropylene composition suitable for producing such a sheet.
本発明者らは上記課題を解決すべく鋭意努力，研究した結果、特定範囲の分子量分布，結晶性、立体規則性、メルトフローレートを有し、エチレン含有量が特定量より少なく、かつ結晶核剤の含有量が特定量より少ないポリプロピレン組成物を使用して、二軸延伸によりシートを製造することにより、剛性、透明性、均一延伸性、低温衝撃性、易熱成形性のバランスに極めて優れたシートが得られること、また、本発明のシートを熱成形することにより、シートの物性を維持しつつ、耐熱性に優れた二次成形体が得られることを見出し、本発明を完成するに至った。
本発明は以下の態様を有する。
［１］エチレン含有量が１質量％未満、分子量分布（Ｍｗ／Ｍｎ）が６〜２０、２５℃でのキシレン不溶分量が９６．５質量％を超え９９．５質量％以下、かつキシレン不溶分の立体規則性（ｍｍｍｍ）が９７．５〜９９．５％である、エチレン含有プロピレン系重合体と、前記エチレン含有プロピレン系重合体の１００質量部に対して０．１８質量部未満の結晶核剤とを含み、メルトフローレートが１〜１５ｇ／１０分であることを特徴とするポリプロピレン組成物。
［２］下記結晶化速度パラメータ（ｔ１／２）が１秒を超える、［１］のポリプロピレン組成物。
結晶化速度パラメータ（ｔ１／２）：１２０℃で結晶化する際に平衡結晶化度の１／２に達するまでに要する時間。
［３］（Ａ）マグネシウム、チタン、ハロゲン、およびスクシネート系化合物から選択される電子供与体化合物を必須成分として含有する固体触媒；（Ｂ）有機アルミニウム化合物；ならびに（Ｃ）外部電子供与体化合物を含む触媒を用いて、プロピレンとエチレンとを重合させて得た、［１］または［２］のポリプロピレン組成物。
［４］前記［１］〜［３］のいずれかのポリプロピレン組成物からなるシートであって、厚さが１００〜５００μｍであり、厚薄精度が１２μｍ未満であり、１６０℃における引張試験での伸長歪みが２００％を超え、かつ２００％伸長時応力が１０ＭＰａ未満であり、２３℃における引張弾性率が１８００ＭＰａを超え、−３０℃における面衝撃強度が２Ｊを超え、ヘーズが２．５％未満であり、透過法による像鮮明度が６０％以上であることを特徴とするポリプロピレン製シート。
［５］前記［４］のポリプロピレン製シートを製造する方法であって、前記ポリプロピレン組成物からなる未延伸シートを二軸延伸する工程を有することを特徴とするポリプロピレン製シートの製造方法。
［６］前記二軸延伸における、成形温度が１４０〜１７０℃であり、成形速度が２０〜４００％／秒であり、ＭＤ方向およびＴＤ方向の延伸倍率がそれぞれ３〜６倍である、［５］のポリプロピレン製シートの製造方法。
［７］前記［４］のポリプロピレン製シートが熱成形されてなることを特徴とする二次成形体。
As a result of diligent efforts and research to solve the above problems, the present inventors have a specific range of molecular weight distribution, crystallinity, stereoregularity, and melt flow rate, the ethylene content is less than the specific amount, and the crystal nuclei. By producing a sheet by biaxial stretching using a polypropylene composition having an agent content less than a specific amount, the balance between rigidity, transparency, uniform stretchability, low temperature impact resistance, and thermoformability is extremely excellent. In order to complete the present invention, it was found that a secondary molded product having excellent heat resistance can be obtained while maintaining the physical characteristics of the sheet by thermoforming the sheet of the present invention. I arrived.
The present invention has the following aspects.
[1] The ethylene content is less than 1% by mass, the molecular weight distribution (Mw / Mn) is 6 to 20, and the xylene insoluble content at 25 ° C. is more than 96.5% by mass and 99.5% by mass or less, and the xylene insoluble content. The steric regularity (mm mm) of the ethylene-containing propylene-based polymer is 97.5 to 99.5%, and the crystal nuclei of less than 0.18 parts by mass with respect to 100 parts by mass of the ethylene-containing propylene-based polymer. A polypropylene composition containing an agent and having a melt flow rate of 1 to 15 g / 10 minutes.
[2] The polypropylene composition of [1], wherein the following crystallization rate parameter (t 1/2) exceeds 1 second.
Crystallization rate parameter (t 1/2 ): The time required to reach 1/2 of the equilibrium crystallinity when crystallization at 120 ° C.
[3] A solid catalyst containing (A) an electron donor compound selected from magnesium, titanium, halogen, and a succinate compound as an essential component; (B) an organoaluminum compound; and (C) an external electron donor compound. The polypropylene composition of [1] or [2] obtained by polymerizing propylene and ethylene using a catalyst containing the mixture.
[4] A sheet made of the polypropylene composition according to any one of [1] to [3], having a thickness of 100 to 500 μm, a thickness and thinness accuracy of less than 12 μm, and elongation in a tensile test at 160 ° C. When the strain exceeds 200%, the stress at 200% elongation is less than 10 MPa, the tensile modulus at 23 ° C. exceeds 1800 MPa, the surface impact strength at -30 ° C. exceeds 2 J, and the haze is less than 2.5%. A polypropylene sheet characterized in that the image sharpness by the transmission method is 60% or more.
[5] The method for producing a polypropylene sheet according to the above [4], which comprises a step of biaxially stretching an unstretched sheet made of the polypropylene composition.
[6] In the biaxial stretching, the molding temperature is 140 to 170 ° C., the molding speed is 20 to 400% / sec, and the stretching ratios in the MD direction and the TD direction are 3 to 6 times, respectively, [5] ] Method of manufacturing polypropylene sheet.
[7] A secondary molded product obtained by thermoforming the polypropylene sheet of the above [4].
本発明によれば、透明性、剛性、耐熱性、均一延伸性および低温での耐衝撃性に優れ、さらに易熱成形性を有する二軸延伸ポリプロピレン製シートが得られる。
本発明のポリプロピレン組成物は、かかる二軸延伸ポリプロピレン製シートを製造するのに好適である。
本発明の二次成形体は耐熱性に優れる。
According to the present invention, a biaxially stretched polypropylene sheet having excellent transparency, rigidity, heat resistance, uniform stretchability, impact resistance at low temperature, and easily thermoforming property can be obtained.
The polypropylene composition of the present invention is suitable for producing such a biaxially stretched polypropylene sheet.
The secondary molded product of the present invention has excellent heat resistance.
＜測定方法＞
本発明における各物性の値は以下の通りである。
［シートの厚みと厚薄精度］
ポリプロピレン製シートの厚みと厚薄精度は、連続厚み計（山文電気社製ＴＯＦ−４Ｒ０５）を用いて、シートの幅方向に１ｍｍ間隔で１００点以上測定した際の、平均値が厚み、標準偏差σ（μｍ）が厚薄精度の値である。
厚薄精度の値が小さいほど厚みムラが小さいことを意味し、延伸シートの場合は均一延伸性に優れることを意味する。
［引張弾性率］
ポリプロピレン製シートの引張弾性率は、ＪＩＳ Ｋ７１６１−１に従い、室温２３℃の雰囲気中で引張速度１ｍｍ／分で測定して得られる値である。引張弾性率の値が大きいほど剛性に優れる。
［面衝撃強度］
ポリプロピレン製シートの面衝撃強度は、ＪＩＳ Ｋ７２１１−２に従い、円柱形状のストライカー（打刻面の直径１２．７ｍｍ）、試験速度１ｍ／秒で−３０℃にて打刻し、パンクチャーエネルギー（単位：Ｊ（ジュール））を算出して得られる値である。パンクチャーエネルギーの値が大きいほど面衝撃強度に優れる。
<Measurement method>
The values of each physical property in the present invention are as follows.
[Sheet thickness and thickness accuracy]
The thickness and thickness accuracy of the polypropylene sheet are measured using a continuous thickness meter (TOF-4R05 manufactured by Yamabun Denki Co., Ltd.) at 100 points or more at 1 mm intervals in the width direction of the sheet, and the average value is the thickness and standard deviation. σ (μm) is the value of thickness and thinness accuracy.
The smaller the thickness / thinness accuracy value, the smaller the thickness unevenness, and in the case of a stretched sheet, it means that the uniform stretchability is excellent.
[Tensile modulus]
The tensile elastic modulus of the polypropylene sheet is a value obtained by measuring at a tensile speed of 1 mm / min in an atmosphere at room temperature of 23 ° C. according to JIS K7161-1. The larger the tensile modulus, the better the rigidity.
[Surface impact strength]
The surface impact strength of the polypropylene sheet is punctured energy (unit: 12.7 mm in diameter of the stamped surface), stamped at -30 ° C at a test speed of 1 m / sec, according to JIS K7211-2. : J (joule)) is a value obtained by calculation. The larger the puncture energy value, the better the surface impact strength.
［ヘーズ］
ポリプロピレン製シートのヘーズは、ＩＳＯ １４７８２に準拠してヘーズを測定して得られる値である。ヘーズの値が小さいほど透明性に優れる。
［透過法による像鮮明度（クラリティ）］
ポリプロピレン製シートの透過法による像鮮明度（以下、クラリティともいう。）は、ＡＳＴＭ Ｄ １７４６に準拠する方法で測定して得られる値である。クラリティの値が大きいほど曇り感が少なく、透明性に優れる。
［伸長歪みと伸長時応力］
ポリプロピレン製シートの伸長歪みと伸長時応力は、延伸後シートからＪＩＳ Ｋ７１２７タイプ２型の短冊状試験片（幅１０ｍｍ×長さ１５０ｍｍ）を切り出し、チャック間距離１００ｍｍ、引張速度５００ｍｍ／分にて引張試験を行った。測定温度は１６０℃とし、応力と歪みの関係を求めた。
１６０℃における伸長歪みの値が大きく、かつ１６０℃における２００％伸長時の応力の値が小さいと易熱成形性（二次成形性）に優れる。
［荷重たわみ温度］
ポリプロピレン製シートを成形温度１６０℃で熱成形し幅１２０ｍｍ×長さ１７０ｍｍ×深さ２７ｍｍの容器を作製した。本容器を所定の雰囲気温度に設定された恒温槽内に１時間静置しておき、時間経過後、容器天面全体に負荷がかかるように４００ｇの錘を載せ天面たわみの有無を確認した。雰囲気温度を５℃刻みで高くし、たわみが発生したときの温度を荷重たわみ温度とした。荷重たわみ温度が高いほど耐熱性（耐熱剛性）に優れる。
［分子量分布（Ｍｗ／Ｍｎ）］
重合体または共重合体の分子量分布（Ｍｗ／Ｍｎ）は、ゲルパーミエーションクロマトグラフィにより質量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）を測定し、Ｍｗ／Ｍｎを算出して得られる値である。
装置としてポリマーラボラトリーズ社製ＰＬ ＧＰＣ２２０を使用し、酸化防止剤を含む１，２，４−トリクロロベンゼンを移動相とし、カラムとして昭和電工社製ＵＴ−Ｇ（１本）、ＵＴ−８０７（１本）、ＵＴ−８０６Ｍ（２本）を直列に接続したものを使用し、検出器として示差屈折率計を使用した。また、ポリプロピレン組成物の試料溶液の溶媒としては移動相と同じものを使用し、１ｍｇ／ｍＬの試料濃度で、１５０℃の温度で振とうさせながら２時間溶解して測定試料を調整した。これにより得た試料溶液５００μＬをカラムに注入し、流速１．０ｍＬ／分、温度１４５℃、データ取り込み間隔１秒で測定した。カラムの較正には、分子量５８０〜７４５万のポリスチレン標準試料（Ｓｈｏｄｅｘ ＳＴＡＮＤＡＲＤ、昭和電工株式会社製）を使用し、三次式近似で行った。Ｍａｒｋ−Ｈｏｕｋｉｎｓの係数は、ポリスチレン標準試料に関しては、Ｋ＝１．２１×１０−４、α＝０．７０７、エチレン含有プロピレン系重合体に関しては、Ｋ＝１．３７×１０−４、α＝０．７５を使用した。
[Haze]
The haze of the polypropylene sheet is a value obtained by measuring the haze in accordance with ISO 14782. The smaller the haze value, the better the transparency.
[Image clarity by transmission method (clarity)]
The image sharpness (hereinafter, also referred to as clarity) of the polypropylene sheet by the transmission method is a value obtained by measuring by a method according to ASTM D 1746. The larger the clarity value, the less cloudy the feeling and the better the transparency.
[Elongation strain and stress during extension]
For the elongation strain and elongation stress of the polypropylene sheet, a JIS K7127 type 2 strip-shaped test piece (width 10 mm x length 150 mm) was cut out from the stretched sheet and pulled at a chuck distance of 100 mm and a tensile speed of 500 mm / min. The test was conducted. The measurement temperature was 160 ° C., and the relationship between stress and strain was determined.
When the value of elongation strain at 160 ° C. is large and the value of stress at 200% elongation at 160 ° C. is small, thermoforming formability (secondary formability) is excellent.
[Deflection temperature under load]
A polypropylene sheet was thermoformed at a molding temperature of 160 ° C. to prepare a container having a width of 120 mm, a length of 170 mm and a depth of 27 mm. This container was allowed to stand in a constant temperature bath set to a predetermined atmospheric temperature for 1 hour, and after a lapse of time, a weight of 400 g was placed so that a load was applied to the entire top surface of the container, and the presence or absence of deflection of the top surface was confirmed. .. The ambient temperature was increased in increments of 5 ° C., and the temperature at which deflection occurred was defined as the deflection temperature under load. The higher the deflection temperature under load, the better the heat resistance (heat rigidity).
[Molecular weight distribution (Mw / Mn)]
The molecular weight distribution (Mw / Mn) of the polymer or copolymer is a value obtained by measuring the mass average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography and calculating Mw / Mn. ..
PL GPC220 manufactured by Polymer Laboratories is used as an apparatus, 1,2,4-trichlorobenzene containing an antioxidant is used as a mobile phase, and UT-G (1) and UT-807 (1) manufactured by Showa Denko Co., Ltd. are used as columns. ), UT-806M (2 pieces) connected in series, and a differential refractometer was used as a detector. The same solvent as the mobile phase was used as the solvent for the sample solution of the polypropylene composition, and the sample was dissolved at a sample concentration of 1 mg / mL for 2 hours while shaking at a temperature of 150 ° C. to prepare a measurement sample. 500 μL of the sample solution thus obtained was injected into the column, and measurements were taken at a flow rate of 1.0 mL / min, a temperature of 145 ° C., and a data acquisition interval of 1 second. A polystyrene standard sample having a molecular weight of 580 to 7.45 million (Shodex STANDARD, manufactured by Showa Denko KK) was used for column calibration, and the column was calibrated by a cubic approximation. The Coefficients of Mark-Hokins are K = 1.21 × 10 -4 , α = 0.707 for polystyrene standard samples, and K = 1.37 × 10 -4 , α = for ethylene-containing propylene-based polymers. 0.75 was used.
［キシレン不溶分の量］
２．５ｇのポリマーを撹拌しながら１３５℃において２５０ｍｌのキシレンに溶解させた。２０分後溶液を撹拌しながら２５℃に冷却し、次いで３０分間静止させた。沈殿物を濾紙で濾過し、溶液を窒素流中で蒸発させ、残留物を一定の重量に達するまで真空下８０℃において乾燥した。このようにして２５℃におけるキシレンに可溶性のポリマーの質量％を計算した。キシレン不溶分の量（２５℃におけるキシレンに不溶性のポリマーの質量％）は、（１００−可溶性のポリマーの質量％）で求められ、ポリマーのアイソタクチック成分の量と考えられる。
キシレン不溶分は、沈殿物に残留したキシレンをメタノールで十分に洗い流した後、真空下８０℃において乾燥させて採取した。
［キシレン不溶分のタクティシティー（立体規則性）ｍｍｍｍ］
上記の方法で得たキシレン不溶分のｍｍｍｍは、１，２，４−トリクロロベンゼン／重水素化ベンゼンの混合溶媒に溶解したサンプルについて、日本電子社製ＪＮＭ ＬＡ−４００（１３Ｃ共鳴周波数 １００ＭＨｚ）を用い１３Ｃ−ＮＭＲ法で測定したスペクトルから、プロピレンモノマーのメソ（ｍ）結合シークエンスが４つ連続したペンタッドに相当するピークの強度の割合を、Ａ．Ｚａｍｂｅｌｌｉ，Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，６，９２５（１９７３）に記載された方法に従って求めた。
［メルトフローレート（ＭＦＲ）］
ポリプロピレン組成物のメルトフローレートは、ＪＩＳ Ｋ７２１０に準じ、温度２３０℃、荷重２１．１８Ｎの条件で測定した値である。
［結晶化速度パラメータ（ｔ１／２）の測定方法］
ポリプロピレン組成物の結晶化速度パラメータ（ｔ１／２）は、熱補償型示差走査熱量測定装置（例えば、パーキンエルマー社製のダイヤモンドＤＳＣ）を用いて測定される、１２０℃で結晶化する際の、平衡結晶化度の１／２に達するまでに要する時間である。ｔ１／２の値が大きいほど結晶化の進行が遅いことを意味する。具体的には、測定試料を、一旦、２８０℃で融解して５分間保持した後、８０℃／分で１２０℃まで冷却して１５分間等温で保持した。その間の等温結晶化による全発熱量（平衡結晶化度に相当）に対して１／２の発熱量に到達した時間をｔ１／２とした。
[Amount of xylene insoluble matter]
2.5 g of polymer was dissolved in 250 ml of xylene at 135 ° C. with stirring. After 20 minutes, the solution was cooled to 25 ° C. with stirring and then allowed to stand for 30 minutes. The precipitate was filtered through filter paper, the solution was evaporated in a stream of nitrogen and the residue was dried under vacuum at 80 ° C. until a constant weight was reached. In this way, the mass% of the polymer soluble in xylene at 25 ° C. was calculated. The amount of xylene insoluble (% by weight of the xylene-insoluble polymer at 25 ° C.) is determined by (% by weight of the 100-soluble polymer) and is considered to be the amount of the isotactic component of the polymer.
The xylene insoluble component was collected by thoroughly rinsing the xylene remaining in the precipitate with methanol and then drying at 80 ° C. under vacuum.
[Tacticity of xylene insoluble (three-dimensional regularity) mm mm]
The mmmm of the xylene insoluble component obtained by the above method is JNM LA-400 (13 C resonance frequency 100 MHz) manufactured by JEOL Ltd. for a sample dissolved in a mixed solvent of 1,2,4-trichlorobenzene / deuterated benzene. From the spectrum measured by the 13 C-NMR method using A.I., the ratio of the intensity of the peak corresponding to the pentad in which four meso (m) -bonded sequences of the propylene monomer are continuous is determined by A.I. It was determined according to the method described in Zambelli, Macromolecules, 6,925 (1973).
[Melt flow rate (MFR)]
The melt flow rate of the polypropylene composition is a value measured under the conditions of a temperature of 230 ° C. and a load of 21.18 N according to JIS K7210.
[Measurement method of crystallization rate parameter (t 1/2)]
The crystallization rate parameter (t 1/2 ) of the polypropylene composition is measured at 120 ° C. as measured using a heat-compensated differential scanning calorimetry device (eg, a PerkinElmer diamond DSC). , The time required to reach 1/2 of the equilibrium crystallinity. The larger the value of t 1/2, the slower the progress of crystallization. Specifically, the measurement sample was once melted at 280 ° C. and held for 5 minutes, then cooled to 120 ° C. at 80 ° C./min and held at an isothermal temperature for 15 minutes. The time when the calorific value reached 1/2 of the total calorific value (corresponding to the equilibrium crystallinity) due to isothermal crystallization during that period was defined as t 1/2 .
＜ポリプロピレン製シート＞
本発明のポリプロピレン製シート（以下、「本シート」ともいう。）は、本発明のポリプロピレン組成物からなる。本発明のポリプロピレン組成物については後述する。本シートは単層でもよく多層の積層物でもよい。
本シートの厚さは１００〜５００μｍであり、１００〜３００μｍが好ましい。厚さが１００μｍ以上であると、本シートを賦形して二次成形品とする際の成形性が良好である。厚さが５００μｍ以下であると容易に二次成形することが可能となる。厚さが５００μｍを超えるものを得ようとすると、二軸延伸の際にシートを挟んで保持しているチャックが外れて、二軸延伸不可となりやすい。
本シートは厚薄精度が１２μｍ未満であり、８μｍ未満が好ましい。厚薄精度が上記の範囲であると、本シートを賦形して二次成形品とする際の成形性が良好である。厚薄精度の値を小さくすることで、本シートまたはその二次成形品の外観および耐衝撃性を向上させることができる。該厚薄精度の下限は限定されない。ゼロでもよい。現実的には２μｍ以上程度である。
<Polypropylene sheet>
The polypropylene sheet of the present invention (hereinafter, also referred to as “the present sheet”) comprises the polypropylene composition of the present invention. The polypropylene composition of the present invention will be described later. This sheet may be a single layer or a multi-layered laminate.
The thickness of this sheet is 100 to 500 μm, preferably 100 to 300 μm. When the thickness is 100 μm or more, the moldability when the present sheet is shaped into a secondary molded product is good. When the thickness is 500 μm or less, secondary molding can be easily performed. If it is attempted to obtain a material having a thickness of more than 500 μm, the chuck holding the sheet sandwiched between the sheets tends to come off during biaxial stretching, and biaxial stretching tends to be impossible.
The thickness and thinness accuracy of this sheet is less than 12 μm, preferably less than 8 μm. When the thickness / thinness accuracy is within the above range, the moldability when the present sheet is shaped into a secondary molded product is good. By reducing the thickness / thinness accuracy value, the appearance and impact resistance of this sheet or its secondary molded product can be improved. The lower limit of the thickness and thinness accuracy is not limited. It may be zero. In reality, it is about 2 μm or more.
本シートは１６０℃での引張試験において、伸長歪みが２００％を超え、かつ２００％伸長時応力が１０ＭＰａ未満であることが好ましい。該伸長歪みと伸長時応力が上記範囲内であると、本シートを賦形して二次成形品とする際の成形性が良好である。
本シートは、２３℃における引張弾性率が１８００ＭＰａを超え、２５００ＭＰａを超えることが好ましい。該引張弾性率が上記の範囲であるとシートの剛性に優れる。また本シートを賦形した二次成形品において座屈が生じにくい。該引張弾性率の上限は限定されない。現実的には３１００ＭＰａ以下程度である。
本シートは、−３０℃における面衝撃強度が２Ｊを超える。該面衝撃強度が上記の範囲であると、本シートまたはその二次成形品の低温での強度に優れ、割れが生じ難い。該面衝撃強度の上限は限定されない。現実的には３０Ｊ以下程度である。
本シートは、ヘーズが２．５％未満であり、２％未満が好ましい。ヘーズが上記の範囲であると本シートまたはその二次成形品の透明性に優れる。ヘーズの下限は限定されない。現実的には０．５％以上程度である。
本シートは、ヘーズが２．５％未満であり、２％未満が好ましい。ヘーズが上記の範囲であると本シートまたはその二次成形品の透明性に優れる。ヘーズの下限は限定されない。現実的には０．５％以上程度である。
本シートは、クラリティが６０％以上であり、７０％以上が好ましい。クラリティが上記の範囲であると本シートまたはその二次成形品の透明性に優れる。クラリティの上限は限定されない。現実的には９９％以下程度である。
本シートを熱成形して得た二次成形品は、耐熱性の指標である荷重たわみ温度が１１０℃以上であることが好ましく、１２０℃以上であることがより好ましい。該荷重たわみ温度が上記の範囲であると二次成形品の耐熱性に優れる。該荷重たわみ温度の上限は限定されない。現実的には１５０℃以下程度である。
In a tensile test at 160 ° C., this sheet preferably has an elongation strain of more than 200% and a stress at 200% elongation of less than 10 MPa. When the elongation strain and the stress during elongation are within the above ranges, the moldability when the present sheet is shaped into a secondary molded product is good.
This sheet preferably has a tensile elastic modulus of more than 1800 MPa and more than 2500 MPa at 23 ° C. When the tensile elastic modulus is in the above range, the rigidity of the sheet is excellent. In addition, buckling is unlikely to occur in the secondary molded product obtained by shaping this sheet. The upper limit of the tensile modulus is not limited. In reality, it is about 3100 MPa or less.
This sheet has a surface impact strength of more than 2J at −30 ° C. When the surface impact strength is in the above range, the strength of this sheet or its secondary molded product at a low temperature is excellent, and cracks are unlikely to occur. The upper limit of the surface impact strength is not limited. In reality, it is about 30J or less.
This sheet has a haze of less than 2.5%, preferably less than 2%. When the haze is within the above range, the transparency of this sheet or its secondary molded product is excellent. The lower limit of haze is not limited. In reality, it is about 0.5% or more.
This sheet has a haze of less than 2.5%, preferably less than 2%. When the haze is within the above range, the transparency of this sheet or its secondary molded product is excellent. The lower limit of haze is not limited. In reality, it is about 0.5% or more.
This sheet has a clarity of 60% or more, preferably 70% or more. When the clarity is in the above range, the transparency of this sheet or its secondary molded product is excellent. The upper limit of clarity is not limited. In reality, it is about 99% or less.
The secondary molded product obtained by thermoforming this sheet preferably has a deflection temperature under load, which is an index of heat resistance, of 110 ° C. or higher, and more preferably 120 ° C. or higher. When the deflection temperature under load is in the above range, the heat resistance of the secondary molded product is excellent. The upper limit of the deflection temperature under load is not limited. In reality, it is about 150 ° C. or lower.
＜ポリプロピレン組成物＞
本シートは、本発明のポリプロピレン組成物をシート状に成形して得られる。
本発明のポリプロピレン組成物は、エチレンを含むプロピレン系重合体（本明細書では「エチレン含有プロピレン系重合体」という。）を含む。
エチレン含有プロピレン系重合体のＭｗ／Ｍｎは６〜２０であり、比較的幅広い分子量分布を有する。該Ｍｗ／Ｍｎが上記範囲の下限値以上であると優れた厚薄精度が得られやすく、上限値を超えるとエチレン含有プロピレン系重合体の製造が困難になる。
エチレン含有プロピレン系重合体のキシレン不溶分の量は、９６．５質量％を超え９９．５質量％以下である。ポリプロピレンのキシレンに不溶な成分は、結晶性のあるアイソタクチック成分に相当する。これに対してポリプロピレン中に少量含まれるキシレンに可溶な成分は、結晶性のないアタクチック成分に相当し、キシレンに不溶な成分に比較して分子量も低い。従って、ポリプロピレン系樹脂材料の溶融特性や成形品の物性は、主にキシレンに不溶な成分に左右される。ポリプロピレン系樹脂材料のキシレン不溶分の量が９６．５質量％を超え９９．５質量％以下であるとは、ポリプロピレン系樹脂材料の結晶性成分が９６．５質量％を超え９９．５質量％以下であることを示す。
エチレン含有プロピレン系重合体の結晶性成分が９６．５質量％以下の場合は、特にポリプロピレン組成物からなるシートを熱成形して得られた（二次）成形品の剛性と耐熱性、特に剛性が低下する。エチレン含有プロピレン系重合体のキシレン不溶分の量は９７．０質量％を超え９９．５質量％以下が好ましい。
エチレン含有プロピレン系重合体の結晶性成分は、立体規則性（ｍｍｍｍ）が９７．５〜９９．５％である。ｍｍｍｍが９７．５％未満では、特にポリプロピレン組成物からなるシートを熱成形して得られた（二次）成形品の剛性と耐熱性、特に耐熱性が低下する。
<Polypropylene composition>
The present sheet is obtained by molding the polypropylene composition of the present invention into a sheet.
The polypropylene composition of the present invention contains an ethylene-containing propylene-based polymer (referred to as "ethylene-containing propylene-based polymer" in the present specification).
The ethylene-containing propylene-based polymer has a Mw / Mn of 6 to 20, and has a relatively wide molecular weight distribution. When the Mw / Mn is at least the lower limit of the above range, excellent thickness / thinness accuracy can be easily obtained, and when the Mw / Mn exceeds the upper limit, it becomes difficult to produce an ethylene-containing propylene-based polymer.
The amount of xylene insoluble in the ethylene-containing propylene-based polymer is more than 96.5% by mass and 99.5% by mass or less. The xylene-insoluble component of polypropylene corresponds to a crystalline isotactic component. On the other hand, the component soluble in xylene contained in a small amount in polypropylene corresponds to an atactic component having no crystallinity, and has a lower molecular weight than the component insoluble in xylene. Therefore, the melting characteristics of the polypropylene-based resin material and the physical characteristics of the molded product mainly depend on the components insoluble in xylene. When the amount of xylene insoluble content of the polypropylene resin material exceeds 96.5% by mass and is 99.5% by mass or less, the crystalline component of the polypropylene resin material exceeds 96.5% by mass and 99.5% by mass. It is shown that it is as follows.
When the crystalline component of the ethylene-containing propylene-based polymer is 96.5% by mass or less, the rigidity and heat resistance of the (secondary) molded product obtained by thermoforming a sheet made of a polypropylene composition, particularly the rigidity Decreases. The amount of xylene insoluble in the ethylene-containing propylene-based polymer is preferably more than 97.0% by mass and 99.5% by mass or less.
The crystalline component of the ethylene-containing propylene-based polymer has a stereoregularity (mm mm) of 97.5 to 99.5%. When mm mm is less than 97.5%, the rigidity and heat resistance, particularly heat resistance, of the (secondary) molded product obtained by thermoforming a sheet made of a polypropylene composition are particularly lowered.
エチレン含有プロピレン系重合体中のエチレン含有量は１質量％未満であり、０．６質量％未満が好ましい。さらに好ましくは０．３質量％未満である。エチレン含有プロピレン系重合体はプロピレンにエチレンをランダム共重合させたものである。プロピレンにエチレンをランダム共重合させることにより透明性が向上する。エチレン含有プロピレン系重合体中のエチレン含有量が１質量％未満であると優れた剛性が得られやすい。該エチレン含有量の下限は特に限定されず、０質量％超である。透明性の向上効果が充分に得られやすい点で０．１質量％以上が好ましい。 The ethylene content in the ethylene-containing propylene-based polymer is less than 1% by mass, preferably less than 0.6% by mass. More preferably, it is less than 0.3% by mass. The ethylene-containing propylene-based polymer is a random copolymerization of ethylene with propylene. Transparency is improved by randomly copolymerizing ethylene with propylene. When the ethylene content in the ethylene-containing propylene-based polymer is less than 1% by mass, excellent rigidity can be easily obtained. The lower limit of the ethylene content is not particularly limited and is more than 0% by mass. 0.1% by mass or more is preferable from the viewpoint that the effect of improving transparency can be sufficiently obtained.
本発明のポリプロピレン組成物のＭＦＲは１〜１５ｇ／１０分であり、２〜６ｇ／１０分が好ましい。該ＭＦＲが上記範囲内であるとポリプロピレン組成物をシート状に成形する際の成形性に優れる。 The MFR of the polypropylene composition of the present invention is 1 to 15 g / 10 minutes, preferably 2 to 6 g / 10 minutes. When the MFR is within the above range, the moldability when molding the polypropylene composition into a sheet is excellent.
本発明のポリプロピレン組成物は結晶核剤を含有することが好ましい。結晶核剤の添加は透明性の向上に寄与する。結晶核剤の具体例は後述する。
ポリプロピレン組成物中のエチレン含有プロピレン系重合体の１００質量部に対して結晶核剤の含有量は０．１８質量部未満であり、０．１５質量部以下が好ましい。上記上限値未満であると優れた厚薄精度が得られやすい。該結晶核剤の含有量の下限は特に限定されず、０質量％超である。透明性向上効果の点で０．０１質量部以上が好ましい。
The polypropylene composition of the present invention preferably contains a crystal nucleating agent. The addition of the crystal nucleating agent contributes to the improvement of transparency. Specific examples of the crystal nucleating agent will be described later.
The content of the crystal nucleating agent is less than 0.18 parts by mass, preferably 0.15 parts by mass or less, based on 100 parts by mass of the ethylene-containing propylene-based polymer in the polypropylene composition. If it is less than the above upper limit value, excellent thickness and thinness accuracy can be easily obtained. The lower limit of the content of the crystal nucleating agent is not particularly limited and is more than 0% by mass. From the viewpoint of the effect of improving transparency, 0.01 parts by mass or more is preferable.
本発明のポリプロピレン組成物は、結晶化速度パラメータ（ｔ１／２）が１秒を超えることが好ましく、２秒以上がより好ましい。結晶核剤の添加量を減少させると結晶化速度が低下して、（ｔ１／２）が増大する傾向がある。
該（ｔ１／２）が上記下限値より大きいと、優れた厚薄精度が得られやすい。該（ｔ１／２）の上限は特に限定されないが、現実的には５秒以下程度である。
The polypropylene composition of the present invention preferably has a crystallization rate parameter (t 1/2 ) of more than 1 second, more preferably 2 seconds or more. When the amount of the crystal nucleating agent added is reduced, the crystallization rate tends to decrease and (t 1/2 ) tends to increase.
When the (t 1/2 ) is larger than the above lower limit value, excellent thickness / thinness accuracy can be easily obtained. The upper limit of the (t 1/2 ) is not particularly limited, but is actually about 5 seconds or less.
［結晶核剤］
結晶核剤としては、ノニトール系核剤、ソルビトール系核剤、リン酸エステル系核剤、トリアミノベンゼン誘導体核剤、カルボン酸金属塩核剤、およびキシリトール系核剤から選択されることが好ましい。特に透明性向上の目的においては、ノニトール系核剤またはソルビトール系核剤の使用がより好ましい。
ノニトール系の構造を有する結晶核剤として、例えば、１，２，３−トリデオキシ−４，６：５，７−ビス−［（４−プロピルフェニル）メチレン］−ノニトール、キシリトール系の構造を有する結晶核剤として、例えば、ビス−１，３：２，４−（５’，６’，７’，８’−テトラヒドロ−２−ナフトアルデヒドベンジリデン）１−アリルキシリトール、ビス−１，３：２，４−（３’，４’−ジメチルベンジリデン）１−プロピルキシリトール、ソルビトール系の構造を有する結晶核剤として、例えば、ビス−１，３：２，４−（４’−エチルベンジリデン）１−アリルソルビトール、ビス−１，３：２，４−（３’−メチル−４’−フルオロ−ベンジリデン）１−プロピルソルビトール、ビス−１，３：２，４−（３’，４’−ジメチルベンジリデン）１’−メチル−２’−プロペニルソルビトール、ビス−１，３，２，４−ジベンジリデン２’，３’−ジブロモプロピルソルビトール、ビス−１，３，２，４−ジベンジリデン２’−ブロモ−３’−ヒドロキシプロピルソルビトール、ビス−１，３：２，４−（３’−ブロモ−４’−エチルベンジリデン）−１−アリルソルビトール、モノ２，４−（３’−ブロモ−４’−エチルベンジリデン）−１−アリルソルビトール、ビス−１，３：２，４−（４’−エチルベンジリデン）１−アリルソルビトール、ビス−１，３：２，４−（３’，４’−ジメチルベンジリデン）１−メチルソルビトール、ビス（ｐ−メチルベンジリデン）ソルビトール、１，３：２，４−ビス−ｏ−（４−メチルベンジリデン）−Ｄ−ソルビトール等が挙げられる。
本発明の組成物に用いられるノニトール系の市販の結晶核剤として、例えばＭｉｌｌａｄ ＮＸ８０００（ミリケンジャパン）、ソルビトール系の市販の結晶核剤として、ＲｉＫＡＦＡＳＴ Ｒ−１（新日本理化）、Ｍｉｌｌａｄ ３９８８（ミリケンジャパン）、ゲルオールＥ−２００（新日本理化）、ゲルオールＭＤ（新日本理化）等が挙げられる。リン酸エステル系結晶核剤として、アルミニウム−ビス（４，４’，６，６’−テトラ−ｔｅｒｔ−ブチル−２，２’−メチレンジフェニル−ホスファート）−ヒドロキシド等が挙げられる。本発明の組成物に用いられる市販のリン酸エステル系結晶核剤として、例えばアスカスタブＮＡ−２１（ＡＤＥＫＡ）、アスカスタブＮＡ−７１（ＡＤＥＫＡ）などが挙げられる。トリアミノベンゼン誘導体結晶核剤として、例えば、１，３，５−トリス（２，２−ジメチルプロパンアミド）ベンゼン等が挙げられる。本発明の組成物に用いられる市販のトリアミノベンゼン誘導体結晶核剤として、例えばＩＲＧＡＣＬＥＡＲ ＸＴ３８６（ＢＡＳＦジャパン）などが挙げられる。カルボン酸金属塩核剤として、１，２−シクロヘキサンジカルボキシル酸カルシウム塩等が挙げられる。本発明の組成物に用いられる市販のカルボン酸金属塩核剤として、例えばＨｙｐｅｒｆｏｒｍ ＨＰＮ−２０Ｅ（ミリケンジャパン）などが挙げられる。
特に２次加工（加熱）後の透明性を維持するためには、ノニトール系核剤またはソルビトール系核剤の使用が好ましい。
これらの結晶核剤は、単独であるいは２種以上を組み合わせて用いることができる。
[Crystal nucleating agent]
The crystal nucleating agent is preferably selected from nonitol-based nucleating agents, sorbitol-based nucleating agents, phosphate ester-based nucleating agents, triaminobenzene derivative nucleating agents, carboxylic acid metal salt nucleating agents, and xylitol-based nucleating agents. In particular, for the purpose of improving transparency, it is more preferable to use a nonitol-based nucleating agent or a sorbitol-based nucleating agent.
Crystal nucleating agents having a nonitol-based structure include, for example, 1,2,3-trideoxy-4,6: 5,7-bis-[(4-propylphenyl) methylene] -nonitol, crystals having a xylitol-based structure. As nuclear agents, for example, bis-1,3: 2,4- (5', 6', 7', 8'-tetrahydro-2-naphthaldehyde benzylidene) 1-allylxylitol, bis-1,3: 2, 4- (3', 4'-Dimethylbenzylidene) 1-propylxylitol, as a crystal nucleating agent having a sorbitol-based structure, for example, bis-1,3: 2,4- (4'-ethylbendylidene) 1-allyl Sorbitol, bis-1,3: 2,4- (3'-methyl-4'-fluoro-benzylene) 1-propyl sorbitol, bis-1,3: 2,4- (3', 4'-dimethylbenzylene) 1'-Methyl-2'-propenyl sorbitol, bis-1,3,2,4-dibenzylidene 2', 3'-dibromopropyl sorbitol, bis-1,3,2,4-dibenzylidene 2'-bromo- 3'-Hydroxypropyl sorbitol, bis-1,3: 2,4- (3'-bromo-4'-ethylbenzylidene) -1-allyl sorbitol, mono 2,4- (3'-bromo-4'-ethyl Benzylidene) -1-allyl sorbitol, bis-1,3: 2,4- (4'-ethylbenzylidene) 1-allyl sorbitol, bis-1,3: 2,4- (3', 4'-dimethylbenzylidene) Examples thereof include 1-methylsorbitol, bis (p-methylbenzylene) sorbitol, 1,3: 2,4-bis-o- (4-methylbenzylidene) -D-sorbitol and the like.
Examples of nonitol-based commercially available crystal nucleating agents used in the composition of the present invention include Millad NX8000 (Milliken Japan), and sorbitol-based commercially available crystal nucleating agents include RiKAFAST R-1 (New Japan Chemical Co., Ltd.) and Millad 3988 (Milliken). Japan), Gelol E-200 (New Japan Chemical), Gelall MD (New Japan Chemical), etc. Examples of the phosphoric acid ester-based crystal nucleating agent include aluminum-bis (4,4', 6,6'-tetra-tert-butyl-2,2'-methylenediphenyl-phosphate) -hydroxydo. Examples of commercially available phosphoric acid ester-based crystal nucleating agents used in the composition of the present invention include Ascastab NA-21 (ADEKA) and Ascastab NA-71 (ADEKA). Examples of the triaminobenzene derivative crystal nucleating agent include 1,3,5-tris (2,2-dimethylpropanamide) benzene. Examples of commercially available triaminobenzene derivative crystal nucleating agents used in the composition of the present invention include IRGACLEAR XT386 (BASF Japan). Examples of the carboxylic acid metal salt nucleating agent include 1,2-cyclohexanedicarboxylate calcium salt and the like. Examples of commercially available carboxylic acid metal salt nucleating agents used in the composition of the present invention include Hyperform HPN-20E (Milliken Japan).
In particular, in order to maintain transparency after secondary processing (heating), it is preferable to use a nonitol-based nucleating agent or a sorbitol-based nucleating agent.
These crystal nucleating agents can be used alone or in combination of two or more.
［その他の添加剤］
本発明のポリプロピレン組成物には、本発明の効果を損なわない範囲で、結晶核剤以外のその他の添加剤を含有させることができる。
その他の添加剤の例としては、酸化防止剤、中和剤、塩素吸収剤、耐熱安定剤、光安定剤、紫外線吸収剤、内部滑剤、外部滑剤、アンチブロッキング剤、帯電防止剤、防曇剤、難燃剤、分散剤、銅害防止剤、可塑剤、架橋剤、過酸化物、油展および他の有機および無機顔料等のポリオレフィンに通常用いられる慣用の添加剤が挙げられる。各添加剤の添加量は公知の量としてよい。
[Other additives]
The polypropylene composition of the present invention may contain additives other than the crystal nucleating agent as long as the effects of the present invention are not impaired.
Examples of other additives include antioxidants, neutralizers, chlorine absorbers, heat stabilizers, light stabilizers, UV absorbers, internal lubricants, external lubricants, antiblocking agents, antistatic agents, antifogging agents. , Flame retardants, dispersants, copper damage inhibitors, plasticizers, crosslinkers, peroxides, oil spreads and other conventional additives commonly used for polyolefins such as organic and inorganic pigments. The amount of each additive added may be a known amount.
［ポリプロピレン組成物の製造方法］
本発明のポリプロピレン組成物は、エチレン含有プロピレン系重合体を製造し、必要に応じて結晶核剤およびその他の添加剤を混合して得られる。
エチレン含有プロピレン系重合体の製造方法は特に限定されないが、下記（Ａ）成分、（Ｂ）成分、（Ｃ）成分を含む触媒成分を用いて、プロピレンとエチレンとを共重合させる工程を含む方法が好ましい。
（Ａ）成分：マグネシウム、チタン、ハロゲン、および電子供与体化合物としてのスクシネート系化合物から選択される電子供与体化合物を必須成分として含有する固体触媒。
（Ｂ）成分：有機アルミニウム化合物。
（Ｃ）成分：ケイ素化合物から選択される外部電子供与体化合物。
[Manufacturing method of polypropylene composition]
The polypropylene composition of the present invention is obtained by producing an ethylene-containing propylene-based polymer and, if necessary, mixing a crystal nucleating agent and other additives.
The method for producing the ethylene-containing propylene-based polymer is not particularly limited, but a method including a step of copolymerizing propylene and ethylene using a catalyst component containing the following components (A), (B), and (C). Is preferable.
Component (A): A solid catalyst containing magnesium, titanium, halogen, and an electron donor compound selected from a succinate compound as an electron donor compound as an essential component.
(B) Component: Organoaluminium compound.
Component (C): External electron donor compound selected from silicon compounds.
１）固体触媒（成分Ａ）
成分（Ａ）は、公知の方法、例えばマグネシウム化合物とチタン化合物と電子供与体化合物を相互接触させることにより調製できる。
1) Solid catalyst (component A)
The component (A) can be prepared by a known method, for example, by bringing the magnesium compound, the titanium compound and the electron donor compound into mutual contact.
成分（Ａ）の調製に用いられるチタン化合物として、一般式：Ｔｉ（ＯＲ）ｇＸ４−ｇで表される４価のチタン化合物が好適である。式中、Ｒは炭化水素基、Ｘはハロゲン、０≦ｇ≦４である。チタン化合物として、より具体的にはＴｉＣｌ４、ＴｉＢｒ４、ＴｉＩ４などのテトラハロゲン化チタン；Ｔｉ（ＯＣＨ３）Ｃｌ３、Ｔｉ（ＯＣ２Ｈ５）Ｃｌ３、Ｔｉ（Ｏｎ−Ｃ４Ｈ９）Ｃｌ３、Ｔｉ（ＯＣ２Ｈ５）Ｂｒ３、Ｔｉ（ＯｉｓｏＣ４Ｈ９）Ｂｒ３などのトリハロゲン化アルコキシチタン；Ｔｉ（ＯＣＨ３）２Ｃｌ２、Ｔｉ（ＯＣ２Ｈ５）２Ｃｌ２、Ｔｉ（Ｏｎ−Ｃ４Ｈ９）２Ｃｌ２、Ｔｉ（ＯＣ２Ｈ５）２Ｂｒ２などのジハロゲン化アルコキシチタン；Ｔｉ（ＯＣＨ３）３Ｃｌ、Ｔｉ（ＯＣ２Ｈ５）３Ｃｌ、Ｔｉ（Ｏｎ−Ｃ４Ｈ９）３Ｃｌ、Ｔｉ（ＯＣ２Ｈ５）３Ｂｒなどのモノハロゲン化トリアルコキシチタン；Ｔｉ（ＯＣＨ３）４、Ｔｉ（ＯＣ２Ｈ５）４、Ｔｉ（Ｏｎ−Ｃ４Ｈ９）４などのテトラアルコキシチタンなどが挙げられる。これらの中で好ましいものはハロゲン含有チタン化合物、特にテトラハロゲン化チタンであり、より特に好ましいものは、四塩化チタンである。 As the titanium compound used for the preparation of the component (A), a tetravalent titanium compound represented by the general formula: Ti (OR) g X 4-g is suitable. In the formula, R is a hydrocarbon group, X is a halogen, and 0 ≦ g ≦ 4. As titanium compounds, TiCl 4 and more specifically, TiBr 4, titanium tetrahalides such as TiI 4; Ti (OCH 3) Cl 3, Ti (OC 2 H 5) Cl 3, Ti (O n -C 4 H 9 ) Trihalogenated alkoxytitanium such as Cl 3 , Ti (OC 2 H 5 ) Br 3 , Ti (OisoC 4 H 9 ) Br 3 ; Ti (OCH 3 ) 2 Cl 2 , Ti (OC 2 H 5 ) 2 Cl 2, Ti (O n -C 4 H 9) 2 Cl 2, Ti (OC 2 H 5) 2 dihalogenated alkoxy titanium such as Br 2; Ti (OCH 3) 3 Cl, Ti (OC 2 H 5) 3 Cl , Ti (O n -C 4 H 9) 3 Cl, Ti (OC 2 H 5) monohalide trialkoxy titanium such as 3 Br; Ti (OCH 3) 4, Ti (OC 2 H 5) 4, Ti ( such as O n -C 4 tetraalkoxy titanium such as H 9) 4 and the like. Among these, a halogen-containing titanium compound, particularly titanium tetrahalogenate, is preferable, and a more particularly preferable one is titanium tetrachloride.
成分（Ａ）の調製に用いられるマグネシウム化合物としては、マグネシウム−炭素結合やマグネシウム−水素結合を有するマグネシウム化合物、例えばジメチルマグネシウム、ジエチルマグネシウム、ジプロピルマグネシウム、ジブチルマグネシウム、ジアミルマグネシウム、ジヘキシルマグネシウム、ジデシルマグネシウム、エチル塩化マグネシウム、プロピル塩化マグネシウム、ブチル塩化マグネシウム、ヘキシル塩化マグネシウム、アミル塩化マグネシウム、ブチルエトキシマグネシウム、エチルブチルマグネシウム、ブチルマグネシウムハイドライドなどが挙げられる。これらのマグネシウム化合物は、例えば有機アルミニウム等との錯化合物の形で用いることもでき、また、液状であっても固体状であってもよい。さらに好適なマグネシウム化合物として、塩化マグネシウム、臭化マグネシウム、ヨウ化マグネシウム、フッ化マグネシウムのようなハロゲン化マグネシウム；メトキシ塩化マグネシウム、エトキシ塩化マグネシウム、イソプロポキシ塩化マグネシウム、ブトキシ塩化マグネシウム、オクトキシ塩化マグネシウムのようなアルコキシマグネシウムハライド；フェノキシ塩化マグネシウム、メチルフェノキシ塩化マグネシウムのようなアリロキシマグネシウムハライド；エトキシマグネシウム、イソプロポキシマグネシウム、ブトキシマグネシウム、ｎ−オクトキシマグネシウム、２−エチルヘキソキシマグネシウムのようなアルコキシマグネシウム；フェノキシマグネシウム、ジメチルフェノキシマグネシウムのようなアリロキシマグネシウム；ラウリン酸マグネシウム、ステアリン酸マグネシウムのようなマグネシウムのカルボン酸塩などを挙げることができる。 Examples of the magnesium compound used for the preparation of the component (A) include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond, such as dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, and dihexylmagnesium. Examples thereof include decyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxymagnesium, ethyl butyl magnesium, and butyl magnesium hydride. These magnesium compounds can be used in the form of a complex compound with, for example, organoaluminum, and may be in a liquid state or a solid state. More suitable magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride; magnesium methoxychloride, magnesium ethoxychloride, magnesium isopropoxychloride, magnesium butoxychloride, magnesium octoxychloride. Alkoxymagnesium halide; Allyloxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; alkoxymagnesium such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxymagnesium; phenoxy Alyloxymagnesium such as magnesium and dimethylphenoxymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate can be mentioned.
成分（Ａ）の調製に用いられる電子供与体化合物は、一般には「内部電子供与体」と称される。本発明においては、広い分子量分布を与える内部電子供与体を用いることが好ましい。当該触媒を用いて重合された組成物は、別な触媒を用いて重合されたポリマーをペレットあるいはパウダーブレンドして得た同じ分子量分布を有する組成物、または多段重合法により、もしくはモノマー濃度や重合条件の勾配を有する重合器をる方法により重合した同じ分子量分布を有する組成物とは異なる特性を示す。これは、当該触媒を用いて製造した組成物は高分子量成分と低分子量成分がより分子レベルに近い状態で一体となっているが、後者の樹脂組成物はそこまで分子レベルに近い状態では混ざり合ってはおらず見かけ上同一の分子量分布を示しているにすぎないためと考えられる。しかし、このことを請求項において言葉で表現することは現実的ではない。以下、好ましい内部電子供与体について説明する。 The electron donor compound used for the preparation of the component (A) is generally referred to as an "internal electron donor". In the present invention, it is preferable to use an internal electron donor that gives a wide molecular weight distribution. The composition polymerized using the catalyst is a composition having the same molecular weight distribution obtained by pelleting or powder blending a polymer polymerized using another catalyst, or by a multi-stage polymerization method, or by a monomer concentration or polymerization. It exhibits different properties from compositions having the same molecular weight distribution polymerized by a method of polymerizing with a gradient of conditions. This is because the composition produced by using the catalyst is integrated with the high molecular weight component and the low molecular weight component in a state closer to the molecular level, but the latter resin composition is mixed in a state close to the molecular level. It is considered that they do not match and only apparently show the same molecular weight distribution. However, it is not realistic to express this in words in the claims. Hereinafter, preferred internal electron donors will be described.
本発明において好ましい内部電子供与体はスクシネート系化合物である。本発明でスクシネート系化合物とはコハク酸のジエステルまたは置換コハク酸のジエステルをいう。以下、スクシネート系化合物について詳しく説明する。本発明で好ましく使用されるスクシネート系化合物は、以下の式（Ｉ）で表される。 The preferred internal electron donor in the present invention is a succinate compound. In the present invention, the succinate compound refers to a succinic acid diester or a substituted succinic acid diester. Hereinafter, the succinate compound will be described in detail. The succinate-based compound preferably used in the present invention is represented by the following formula (I).
式中、基Ｒ１およびＲ２は、互いに同一かまたは異なり、場合によってはヘテロ原子を含む、Ｃ１〜Ｃ２０の線状または分岐のアルキル、アルケニル、シクロアルキル、アリール、アリールアルキル、またはアルキルアリール基であり；基Ｒ３〜Ｒ６は、互いに同一かまたは異なり、水素、或いは場合によってはヘテロ原子を含む、Ｃ１〜Ｃ２０の線状または分岐のアルキル、アルケニル、シクロアルキル、アリール、アリールアルキル、またはアルキルアリール基であり、同じ炭素原子または異なる炭素原子に結合している基Ｒ３〜Ｒ６は一緒に結合して環を形成してもよい。 In the formula, the groups R 1 and R 2 are linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkyl of C 1 to C 20 , which are the same or different from each other and sometimes contain a heteroatom. Aryl groups; groups R 3 to R 6 are linear or branched alkyl, alkenyl, cycloalkyl, aryl, of C 1 to C 20 , which are identical or different from each other and contain hydrogen or, in some cases, heteroatoms. Groups R 3 to R 6 , which are arylalkyl or alkylaryl groups and are bonded to the same carbon atom or different carbon atoms, may be bonded together to form a ring.
Ｒ１およびＲ２は、好ましくは、Ｃ１〜Ｃ８のアルキル、シクロアルキル、アリール、アリールアルキル、およびアルキルアリール基である。Ｒ１およびＲ２が第１級アルキル、特に分岐第１級アルキルから選択される化合物が特に好ましい。好適なＲ１およびＲ２基の例は、Ｃ１〜Ｃ８のアルキル基であり、例えば、メチル、エチル、ｎ−プロピル、ｎ−ブチル、イソブチル、ネオペンチル、２−エチルヘキシルである。エチル、イソブチル、およびネオペンチルが特に好ましい。 R 1 and R 2 are preferably C 1- C 8 alkyl, cycloalkyl, aryl, arylalkyl, and alkylaryl groups. Compounds in which R 1 and R 2 are selected from primary alkyls, particularly branched primary alkyls, are particularly preferred. Examples of suitable R 1 and R 2 groups are C 1- C 8 alkyl groups, such as methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Ethyl, isobutyl, and neopentyl are particularly preferred.
式（Ｉ）によって示される化合物の好ましい群の１つは、Ｒ３〜Ｒ５が水素であり、Ｒ６が、３〜１０個の炭素原子を有する、分岐アルキル、シクロアルキル、アリール、アリールアルキル、およびアルキルアリール基であるものである。このような単置換スクシネート化合物の好ましい具体例は、ジエチル−ｓｅｃ−ブチルスクシネート、ジエチルテキシルスクシネート、ジエチルシクロプロピルスクシネート、ジエチルノルボニルスクシネート、ジエチルペリヒドロスクシネート、ジエチルトリメチルシリルスクシネート、ジエチルメトキシスクシネート、ジエチル−ｐ−メトキシフェニルスクシネート、ジエチル−ｐ−クロロフェニルスクシネート、ジエチルフェニルスクシネート、ジエチルシクロヘキシルスクシネート、ジエチルベンジルスクシネート、ジエチルシクロヘキシルメチルスクシネート、ジエチル−ｔ−ブチルスクシネート、ジエチルイソブチルスクシネート、ジエチルイソプロピルスクシネート、ジエチルネオペンチルスクシネート、ジエチルイソペンチルスクシネート、ジエチル（１−トリフルオロメチルエチル）スクシネート、ジエチルフルオレニルスクシネート、１−エトキシカルボジイソブチルフェニルスクシネート、ジイソブチル−ｓｅｃ−ブチルスクシネート、ジイソブチルテキシルスクシネート、ジイソブチルシクロプロピルスクシネート、ジイソブチルノルボニルスクシネート、ジイソブチルペリヒドロスクシネート、ジイソブチルトリメチルシリルスクシネート、ジイソブチルメトキシスクシネート、ジイソブチル−ｐ−メトキシフェニルスクシネート、ジイソブチル−ｐ−クロロフェニルスクシネート、ジイソブチルシクロヘキシルスクシネート、ジイソブチルベンジルスクシネート、ジイソブチルシクロヘキシルメチルスクシネート、ジイソブチル−ｔ−ブチルスクシネート、ジイソブチルイソブチルスクシネート、ジイソブチルイソプロピルスクシネート、ジイソブチルネオペンチルスクシネート、ジイソブチルイソペンチルスクシネート、ジイソブチル（１−トリフルオロメチルエチル）スクシネート、ジイソブチルフルオレニルスクシネート、ジネオペンチル−ｓｅｃ−ブチルスクシネート、ジネオペンチルテキシルスクシネート、ジネオペンチルシクロプロピルスクシネート、ジネオペンチルノルボニルスクシネート、ジネオペンチルペリヒドロスクシネート、ジネオペンチルトリメチルシリルスクシネート、ジネオペンチルメトキシスクシネート、ジネオペンチル−ｐ−メトキシフェニルスクシネート、ジネオペンチル−ｐ−クロロフェニルスクシネート、ジネオペンチルフェニルスクシネート、ジネオペンチルシクロヘキシルスクシネート、ジネオペンチルベンジルスクシネート、ジネオペンチルシクロヘキシルメチルスクシネート、ジネオペンチル−ｔ−ブチルスクシネート、ジネオペンチルイソブチルスクシネート、ジネオペンチルイソプロピルスクシネート、ジネオペンチルネオペンチルスクシネート、ジネオペンチルイソペンチルスクシネート、ジネオペンチル（１−トリフルオロメチルエチル）スクシネート、ジネオペンチルフルオレニルスクシネートである。 One of the preferred groups of compounds represented by formula (I) is branched alkyl, cycloalkyl, aryl, arylalkyl , where R 3 to R 5 are hydrogen and R 6 has 3 to 10 carbon atoms. , And an alkylaryl group. Preferred specific examples of such a monosubstituted succinate compound are diethyl-sec-butyl succinate, diethyl texyl succinate, diethyl cyclopropyl succinate, diethyl norbonyl succinate, diethyl perihydro succinate, diethyl. Trimethylsilyl succinate, diethyl methoxy succinate, diethyl-p-methoxyphenyl succinate, diethyl-p-chlorophenyl succinate, diethyl phenyl succinate, diethyl cyclohexyl succinate, diethyl benzyl succinate, diethyl cyclohexyl Methyl succinate, diethyl-t-butyl succinate, diethyl isobutyl succinate, diethyl isopropyl succinate, diethyl neopentyl succinate, diethyl isopentyl succinate, diethyl (1-trifluoromethyl ethyl) succinate , Diethylfluorenyl succinate, 1-ethoxycarbodiisobutylphenyl succinate, diisobutyl-sec-butyl succinate, diisobutyltexyl succinate, diisobutylcyclopropyl succinate, diisobutylnorbonyl succinate, diisobutylperihydro Succinate, diisobutyltrimethylsilyl succinate, diisobutylmethoxysuccinate, diisobutyl-p-methoxyphenyl succinate, diisobutyl-p-chlorophenyl succinate, diisobutylcyclohexylsuccinate, diisobutylbenzyl succinate, diisobutylcyclohexylmethyl Succinate, diisobutyl-t-butyl succinate, diisobutylisobutyl succinate, diisobutylisopropyl succinate, diisobutylneopentyl succinate, diisobutylisopentyl succinate, diisobutyl (1-trifluoromethylethyl) succinate, Diisobutylfluorenyl succinate, dineopentyl-sec-butyl succinate, dineopentyltexyl succinate, geneopentylcyclopropyl succinate, dineopentyl norbonyl succinate, dineopentyl perihydrosuccinate , Dineopentyltrimethylsilyl succinate, dineopentylmethoxysuccinate, geneopentyl-p-methoxyphenyl succinate, geneopentyl-p-chlorophenyl succinate, geneopentylphenyl succinate, genine Opentyl Cyclohexyl succinate, Dineopentyl benzyl succinate, Dineopentyl cyclohexylmethyl succinate, Dineopentyl-t-butyl succinate, Dineopentyl isobutyl succinate, Dineopentyl isopropyl succinate, Di Neopentyl neopentyl succinate, dineopentyl isopentyl succinate, dineopentyl (1-trifluoromethylethyl) succinate, dineopentyl fluorenyl succinate.
式（Ｉ）の範囲内の化合物の他の好ましい群は、Ｒ３〜Ｒ６からの少なくとも２つの基が、水素とは異なり、場合によってはヘテロ原子を含む、Ｃ１〜Ｃ２０の線状または分岐のアルキル、アルケニル、シクロアルキル、アリール、アリールアルキル、またはアルキルアリール基から選択されるものである。水素とは異なる２つの基が同じ炭素原子に結合している化合物が特に好ましい。具体的には、Ｒ３およびＲ４が水素とは異なる基であり、Ｒ５およびＲ６が水素原子である化合物である。このような二置換スクシネートの好ましい具体例は、ジエチル−２，２−ジメチルスクシネート、ジエチル−２−エチル−２−メチルスクシネート、ジエチル−２−ベンジル−２−イソプロピルスクシネート、ジエチル−２−シクロヘキシルメチル−２−イソブチルスクシネート、ジエチル−２−シクロペンチル−２−ｎ−ブチルスクシネート、ジエチル−２、２−ジイソブチルスクシネート、ジエチル−２−シクロヘキシル−２−エチルスクシネート、ジエチル−２−イソプロピル−２−メチルスクシネート、ジエチル−２−テトラデシル−２−エチルスクシネート、ジエチル−２−イソブチル−２−エチルスクシネート、ジエチル−２−（１−トリフルオロメチルエチル）−２−メチルスクシネート、ジエチル−２−イソペンチル−２−イソブチルスクシネート、ジエチル−２−フェニル−２−ｎ−ブチルスクシネート、ジイソブチル−２，２−ジメチルスクシネート、ジイソブチル−２−エチル−２−メチルスクシネート、ジイソブチル−２−ベンジル−２−イソプロピルスクシネート、ジイソブチル−２−シクロヘキシルメチル−２−イソブチルスクシネート、ジイソブチル−２−シクロペンチル−２−ｎ−ブチルスクシネート、ジイソブチル−２，２−ジイソブチルスクシネート、ジイソブチル−２−シクロヘキシル−２−エチルスクシネート、ジイソブチル−２−イソプロピル−２−メチルスクシネート、ジイソブチル−２−テトラデシル−２−エチルスクシネート、ジイソブチル−２−イソブチル−２−エチルスクシネート、ジイソブチル−２−（１−トリフルオロメチルエチル）−２−メチルスクシネート、ジイソブチル−２−イソペンチル−２−イソブチルスクシネート、ジイソブチル−２−フェニル−２−ｎ−ブチルスクシネート、ジネオペンチル−２，２−ジメチルスクシネート、ジネオペンチル−２−エチル−２−メチルスクシネート、ジネオペンチル−２−ベンジル−２−イソプロピルスクシネート、ジネオペンチル−２−シクロヘキシルメチル−２−イソブチルスクシネート、ジネオペンチル−２−シクロペンチル−２−ｎ−ブチルスクシネート、ジネオペンチル−２，２−ジイソブチルスクシネート、ジネオペンチル−２−シクロヘキシル−２−エチルスクシネート、ジネオペンチル−２−イソプロピル−２−メチルスクシネート、ジネオペンチル−２−テトラデシル−２−エチルスクシネート、ジネオペンチル−２−イソブチル−２−エチルスクシネート、ジネオペンチル−２−（１−トリフルオロメチルエチル）−２−メチルスクシネート、ジネオペンチル−２−イソペンチル−２−イソブチルスクシネート、ジネオペンチル−２−フェニル−２−ｎ−ブチルスクシネートである。 Another preferred group of compounds within the range of formula (I) is a linear C 1 to C 20 in which at least two groups from R 3 to R 6 differ from hydrogen and in some cases contain heteroatoms. Alternatively, it is selected from branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, or alkylaryl groups. A compound in which two groups different from hydrogen are bonded to the same carbon atom is particularly preferable. Specifically, it is a compound in which R 3 and R 4 are different groups from hydrogen, and R 5 and R 6 are hydrogen atoms. Preferred specific examples of such disubstituted succinates are diethyl-2,2-dimethylsuccinate, diethyl-2-ethyl-2-methylsuccinate, diethyl-2-benzyl-2-isopropylsuccinate, diethyl. -2-Cyclohexylmethyl-2-isobutyl succinate, diethyl-2-cyclopentyl-2-n-butyl succinate, diethyl-2,2-diisobutyl succinate, diethyl-2-cyclohexyl-2-ethyl succinate Nate, diethyl-2-isopropyl-2-methylsuccinate, diethyl-2-tetradecyl-2-ethylsuccinate, diethyl-2-isobutyl-2-ethylsuccinate, diethyl-2- (1-trifluoro) Methylethyl) -2-methylsuccinate, diethyl-2-isopentyl-2-isobutylsuccinate, diethyl-2-phenyl-2-n-butylsuccinate, diisobutyl-2,2-dimethylsuccinate, Diisobutyl-2-ethyl-2-methylsuccinate, diisobutyl-2-benzyl-2-isopropylsuccinate, diisobutyl-2-cyclohexylmethyl-2-isobutylsuccinate, diisobutyl-2-cyclopentyl-2-n- Butyl succinate, diisobutyl-2,2-diisobutyl succinate, diisobutyl-2-cyclohexyl-2-ethyl succinate, diisobutyl-2-isopropyl-2-methylsuccinate, diisobutyl-2-tetradecyl-2- Ethyl succinate, diisobutyl-2-isobutyl-2-ethyl succinate, diisobutyl-2- (1-trifluoromethylethyl) -2-methyl succinate, diisobutyl-2-isopentyl-2-isobutyl succinate , Diisobutyl-2-phenyl-2-n-butyl succinate, dineopentyl-2,2-dimethylsuccinate, dineopentyl-2-ethyl-2-methylsuccinate, dineopentyl-2-benzyl-2-isopropyls Xinate, Dineopentyl-2-cyclohexylmethyl-2-isobutyl succinate, Dineopentyl-2-cyclopentyl-2-n-butyl succinate, Dineopentyl-2,2-diisobutyl succinate, Dineopentyl-2-cyclohexyl-2 -Ethyl succinate, dineopentyl-2-isopropyl-2-methyl succinate, dineopentyl-2-tetradecyl-2-ethyl succine , Dineopentyl-2-isobutyl-2-ethyl succinate, dineopentyl-2- (1-trifluoromethylethyl) -2-methylsuccinate, dineopentyl-2-isopentyl-2-isobutyl succinate, dineopentyl It is -2-phenyl-2-n-butyl succinate.
さらに、水素とは異なる少なくとも２つの基が異なる炭素原子に結合している化合物も特に好ましい。具体的にはＲ３およびＲ５が水素と異なる基である化合物である。この場合、Ｒ４およびＲ６は水素原子であってもよいし水素とは異なる基であってもよいが、いずれか一方が水素原子であること（三置換スクシネート）が好ましい。このような化合物の好ましい具体例は、ジエチル−２，３−ビス（トリメチルシリル）スクシネート、ジエチル−２，２−ｓｅｃ−ブチル−３−メチルスクシネート、ジエチル−２−（３，３，３−トリフルオロプロピル）−３−メチルスクシネート、ジエチル−２，３−ビス（２−エチルブチル）スクシネート、ジエチル−２，３−ジエチル−２−イソプロピルスクシネート、ジエチル−２，３−ジイソプロピル−２−メチルスクシネート、ジエチル−２，３−ジシクロヘキシル−２−メチルジエチル−２，３−ジベンジルスクシネート、ジエチル−２，３−ジイソプロピルスクシネート、ジエチル−２，３−ビス（シクロヘキシルメチル）スクシネート、ジエチル−２，３−ジ−ｔ−ブチルスクシネート、ジエチル−２，３−ジイソブチルスクシネート、ジエチル−２，３−ジネオペンチルスクシネート、ジエチル−２，３−ジイソペンチルスクシネート、ジエチル−２，３−（１−トリフルオロメチルエチル）スクシネート、ジエチル−２，３−テトラデシルスクシネート、ジエチル−２，３−フルオレニルスクシネート、ジエチル−２−イソプロピル−３−イソブチルスクシネート、ジエチル−２−ｔｅｒｔ−ブチル−３−イソプロピルスクシネート、ジエチル−２−イソプロピル−３−シクロヘキシルスクシネート、ジエチル−２−イソペンチル−３−シクロヘキシルスクシネート、ジエチル−２−テトラデシル−３−シクロヘキシルメチルスクシネート、ジエチル−２−シクロヘキシル−３−シクロペンチルスクシネート、ジイソブチル−２，３−ジエチル−２−イソプロピルスクシネート、ジイソブチル−２，３−ジイソプロピル−２−メチルスクシネート、ジイソブチル−２，３−ジシクロヘキシル−２−メチルスクシネート、ジイソブチル−２，３−ジベンジルスクシネート、ジイソブチル−２，３−ジイソプロピルスクシネート、ジイソブチル−２，３−ビス（シクロヘキシルメチル）スクシネート、ジイソブチル−２，３−ジ−ｔ−ブチルスクシネート、ジイソブチル−２，３−ジイソブチルスクシネート、ジイソブチル−２，３−ジネオペンチルスクシネート、ジイソブチル−２，３−ジイソペンチルスクシネート、ジイソブチル−２，３−（１−トリフルオロメチルエチル）スクシネート、ジイソブチル−２，３−テトラデシルスクシネート、ジイソブチル−２，３−フルオレニルスクシネート、ジイソブチル−２−イソプロピル−３−イソブチルスクシネート、ジイソブチル−２−ｔｅｒｔ−ブチル−３−イソプロピルスクシネート、ジイソブチル−２−イソプロピル−３−シクロヘキシルスクシネート、ジイソブチル−２−イソペンチル−３−シクロヘキシルスクシネート、ジイソブチル−２−テトラデシル−３−シクロヘキシルメチルスクシネート、ジイソブチル−２−シクロヘキシル−３−シクロペンチルスクシネート、ジネオペンチル−２，３−ビス（トリメチルシリル）スクシネート、ジネオペンチル−２，２−ｓｅｃ−ブチル−３−メチルスクシネート、ジネオペンチル−２−（３，３，３−トリフルオロプロピル）−３−メチルスクシネート、ジネオペンチル−２，３−ビス（２−エチルブチル）スクシネート、ジネオペンチル−２，３−ジエチル−２−イソプロピルスクシネート、ジネオペンチル−２，３−ジイソプロピル−２−メチルスクシネート、ジネオペンチル−２，３−ジシクロヘキシル−２−メチルスクシネート、ジネオペンチル−２，３−ジベンジルスクシネート、ジネオペンチル−２，３−ジイソプロピルスクシネート、ジネオペンチル−２，３−ビス（シクロヘキシルメチル）スクシネート、ジネオペンチル−２，３−ジ−ｔ−ブチルスクシネート、ジネオペンチル−２，３−ジイソブチルスクシネート、ジネオペンチル−２，３−ジネオペンチルスクシネート、ジネオペンチル−２，３−ジイソペンチルスクシネート、ジネオペンチル−２，３−（１−トリフルオロメチルエチル）スクシネート、ジネオペンチル−２，３−テトラデシルスクシネート、ジネオペンチル−２，３−フルオレニルスクシネート、ジネオペンチル−２−イソプロピル−３−イソブチルスクシネート、ジネオペンチル−２−ｔｅｒｔ−ブチル−３−イソプロピルスクシネート、ジネオペンチル−２−イソプロピル−３−シクロヘキシルスクシネート、ジネオペンチル−２−イソペンチル−３−シクロヘキシルスクシネート、ジネオペンチル−２−テトラデシル−３−シクロヘキシルメチルスクシネート、ジネオペンチル−２−シクロヘキシル−３―シクロペンチルスクシネートである。 Further, compounds in which at least two groups different from hydrogen are bonded to different carbon atoms are also particularly preferable. Specifically, it is a compound in which R 3 and R 5 are different groups from hydrogen. In this case, R 4 and R 6 may be hydrogen atoms or groups different from hydrogen, but it is preferable that one of them is a hydrogen atom (trisubstituted succinate). Preferred specific examples of such compounds are diethyl-2,3-bis (trimethylsilyl) succinate, diethyl-2,2-sec-butyl-3-methylsuccinate, diethyl-2- (3,3,3-). Trifluoropropyl) -3-methylsuccinate, diethyl-2,3-bis (2-ethylbutyl) succinate, diethyl-2,3-diethyl-2-isopropylsuccinate, diethyl-2,3-diisopropyl-2 -Methyl succinate, diethyl-2,3-dicyclohexyl-2-methyldiethyl-2,3-dibenzylsuccinate, diethyl-2,3-diisopropylsuccinate, diethyl-2,3-bis (cyclohexylmethyl) ) Succinate, diethyl-2,3-di-t-butyl succinate, diethyl-2,3-diisobutyl succinate, diethyl-2,3-dineopentyl succinate, diethyl-2,3-diiso Pentyl succinate, diethyl-2,3- (1-trifluoromethylethyl) succinate, diethyl-2,3-tetradecyl succinate, diethyl-2,3-fluorenyl succinate, diethyl-2-isopropyl -3-Isobutyl succinate, diethyl-2-tert-butyl-3-isopropyl succinate, diethyl-2-isopropyl-3-cyclohexyl succinate, diethyl-2-isopentyl-3-cyclohexyl succinate, diethyl -2-Tetradecyl-3-cyclohexylmethyl succinate, diethyl-2-cyclohexyl-3-cyclopentyl succinate, diisobutyl-2,3-diethyl-2-isopropylsuccinate, diisobutyl-2,3-diisopropyl-2 -Methyl succinate, diisobutyl-2,3-dicyclohexyl-2-methylsuccinate, diisobutyl-2,3-dibenzylsuccinate, diisobutyl-2,3-diisopropylsuccinate, diisobutyl-2,3- Bis (cyclohexylmethyl) succinate, diisobutyl-2,3-di-t-butyl succinate, diisobutyl-2,3-diisobutyl succinate, diisobutyl-2,3-dineopentyl succinate, diisobutyl-2, 3-Diisopentyl succinate, diisobutyl-2,3- (1-trifluoromethylethyl) succinate, diisobutyl-2,3-tetradecyl succinate, diisobutyl-2,3-fluorenyl succinate , Diisobutyl-2-isopropyl-3-isobutyl succinate, diisobutyl-2-tert-butyl-3-isopropyl succinate, diisobutyl-2-isopropyl-3-cyclohexyl succinate, diisobutyl-2-isopentyl-3-3 Cyclohexyl succinate, diisobutyl-2-tetradecyl-3-cyclohexylmethyl succinate, diisobutyl-2-cyclohexyl-3-cyclopentyl succinate, dineopentyl-2,3-bis (trimethylsilyl) succinate, dineopentyl-2,2- sec-Butyl-3-methylsuccinate, dineopentyl-2- (3,3,3-trifluoropropyl) -3-methylsuccinate, dineopentyl-2,3-bis (2-ethylbutyl) succinate, dineopentyl- 2,3-Diethyl-2-isopropyl succinate, dineopentyl-2,3-diisopropyl-2-methyl succinate, dineopentyl-2,3-dicyclohexyl-2-methyl succinate, dineopentyl-2,3-di Benzyl succinate, dineopentyl-2,3-diisopropyl succinate, dineopentyl-2,3-bis (cyclohexylmethyl) succinate, dineopentyl-2,3-di-t-butyl succinate, dineopentyl-2,3- Diisobutyl succinate, geneopentyl-2,3-dineopentyl succinate, dineopentyl-2,3-diisopentyl succinate, dineopentyl-2,3- (1-trifluoromethylethyl) succinate, dineopentyl-2 , 3-Tetradecyl succinate, dineopentyl-2,3-fluorenyl succinate, dineopentyl-2-isopropyl-3-isobutyl succinate, dineopentyl-2-tert-butyl-3-isopropyl succinate, dineopentyl -2-Isopropyl-3-cyclohexyl succinate, dineopentyl-2-isopentyl-3-cyclohexyl succinate, dineopentyl-2-tetradecyl-3-cyclohexylmethyl succinate, dineopentyl-2-cyclohexyl-3-cyclopentyl succinate Nate.
式（Ｉ）の化合物のうち、基Ｒ３〜Ｒ６のうちのいくつかが一緒に結合して環を形成している化合物も好ましく用いることができる。このような化合物として特表２００２−５４２３４７に挙げられている化合物、例えば、１−（エトキシカルボニル）−１−（エトキシアセチル）−２，６−ジメチルシクロヘキサン、１−（エトキシカルボニル）−１−（エトキシアセチル）−２，５一ジメチルシクロペンタン、１−（エトキシカルボニル）−１−（エトキシアセチルメチル）−２一メチルシクロへキサン、１−（エトキシカルボニル）−１−（エトキシ（シクロヘキシル）アセチル）シクロヘキサンを挙げることができる。他には、例えば国際公開第２００９／０６９４８３に開示されているような３，６−ジメチルシクロヘキサン−１，２−ジカルボン酸ジイソブチル、シクロヘキサン−１，２−ジカルボン酸ジイソブチル等の環状スクシネート化合物も好適に用いることができる。他の環状スクシネート化合物の例としては、国際公開２００９／０５７７４７号に開示されている化合物も好ましい。 Among the compounds of formula (I), a compound some are bonded to form a ring together of the radicals R 3 to R 6 may be also preferably used. As such compounds, the compounds listed in Special Table 2002-542347, for example, 1- (ethoxycarbonyl) -1- (ethoxyacetyl) -2,6-dimethylcyclohexane, 1- (ethoxycarbonyl) -1-( Ethoxyacetyl) -2,5-1 dimethylcyclopentane, 1- (ethoxycarbonyl) -1- (ethoxyacetylmethyl) -21methylcyclohexane, 1- (ethoxycarbonyl) -1- (ethoxy (cyclohexyl) acetyl) cyclohexane Can be mentioned. Alternatively, cyclic succinate compounds such as diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylic acid and diisobutyl cyclohexane-1,2-dicarboxylic acid, as disclosed in WO 2009/069483, are also preferred. Can be used. As an example of other cyclic succinate compounds, the compounds disclosed in WO 2009/057747 are also preferred.
式（Ｉ）の化合物のうち、基Ｒ３〜Ｒ６がヘテロ原子を含む場合、ヘテロ原子は窒素およびリン原子を含む第１５族原子あるいは酸素およびイオウ原子を含む第１６族原子であることが好ましい。基Ｒ３〜Ｒ６が第１５族原子を含む化合物としては、特開２００５−３０６９１０号に開示される化合物が挙げられる。一方、基Ｒ３〜Ｒ６が第１６族原子を含む化合物としては、特開２００４−１３１５３７号に開示される化合物が挙げられる。 Among the compounds of formula (I), if the group R 3 to R 6 is a hetero atom, it heteroatom is 16 atoms containing Group 15 atom or an oxygen and sulfur atom containing nitrogen and phosphorus atoms preferable. Examples of the compound in which the groups R 3 to R 6 contain a Group 15 atom include compounds disclosed in JP-A-2005-306910. On the other hand, groups R 3 to R 6 are Examples of the compound containing a Group 16 atom include compounds disclosed in JP-2004-131537.
この他に、スクシネート系化合物と同等の分子量分布を与える内部電子供与体を用いてもよい。そのような内部電子供与体としては、例えば特開２０１３−２８７０４号公報に記載のジフェニルジカルボン酸エステル、特開２０１４−２０１６０２号公報に記載のシクロヘキセンジカルボン酸エステル、特開２０１３−２８７０５号公報に記載のジシクロアルキルジカルボン酸エステル、特許第４９５９９２０号に記載のジオールジベンゾエート、国際公開第２０１０／０７８４９４に記載の１，２−フェニレンジベンゾエートが挙げられる。 In addition, an internal electron donor that gives a molecular weight distribution equivalent to that of the succinate compound may be used. Examples of such an internal electron donor include diphenyldicarboxylic acid esters described in JP2013-28704, cyclohexenedicarboxylic acid esters described in JP2014-2016002, and JP2013-28705. Dicycloalkyldicarboxylic acid ester, diol dibenzoate described in Japanese Patent No. 4959920, 1,2-phenylenedibenzoate described in International Publication No. 2010/078494.
２）有機アルミニウム化合物（成分Ｂ）
成分（Ｂ）の有機アルミニウム化合物としては以下が挙げられる。
トリエチルアルミニウム、トリブチルアルミニウムなどのトリアルキルアルミニウム；
トリイソプレニルアルミニウムのようなトリアルケニルアルミニウム：
ジエチルアルミニウムエトキシド、ジブチルアルミニウムブトキシドなどのジアルキルアルミニウムアルコキシド；
エチルアルミニウムセスキエトキシド、ブチルアルミニウムセスキブトキシドなどのアルキルアルミニウムセスキアルコキシド；
2) Organoaluminium compound (component B)
Examples of the organoaluminum compound of the component (B) include the following.
Trialkylaluminum such as triethylaluminum and tributylaluminum;
Trialkenyl aluminum such as triisoprenyl aluminum:
Dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxydo and butylaluminum sesquibutoxide;
エチルアルミニウムジクロリド、プロピルアルミニウムジクロリド、ブチルアルミニウムジブロミドなどのようなアルキルアルミニウムジハロゲニドなどの部分的にハロゲン化されたアルキルアルミニウム；
ジエチルアルミニウムヒドリド、ジブチルアルミニウムヒドリドなどのジアルキルアルミニウムヒドリド；
エチルアルミニウムジヒドリド、プロピルアルミニウムジヒドリドなどのアルキルアルミニウムジヒドリドなどの部分的に水素化されたアルキルアルミニウム；
エチルアルミニウムエトキシクロリド、ブチルアルミニウムブトキシクロリド、エチルアルミニウムエトキシブロミドなどの部分的にアルコキシ化およびハロゲン化されたアルキルアルミニウム。
Partially halogenated alkylaluminum such as alkylaluminum dihalogenide such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromid;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Partially hydrogenated alkylaluminum such as alkylaluminum dihydrides such as ethylaluminum dihydrides and propylaluminum dihydrides;
Partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butokicyclolide, ethylaluminum ethoxybromid.
３）電子供与体化合物（成分Ｃ）
成分（Ｃ）の電子供与体化合物は、一般に「外部電子供与体」と称される。このような電子供与体化合物としては有機ケイ素化合物が好ましい。好ましい有機ケイ素化合物として以下が挙げられる。
トリメチルメトキシシラン、トリメチルエトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジイソプロピルジメトキシシラン、ｔ−ブチルメチルジメトキシシラン、ｔ−ブチルメチルジエトキシシラン、ｔ−アミルメチルジエトキシシラン、ジフェニルジメトキシシラン、フェニルメチルジメトキシシラン、ジフェニルジエトキシシラン、ビスｏ−トリルジメトキシシラン、ビスｍ−トリルジメトキシシラン、ビスｐ−トリルジメトキシシラン、ビスｐ−トリルジエトキシシラン、ビスエチルフェニルジメトキシシラン、ジシクロペンチルジメトキシシラン、ジシクロヘキシルジメトキシシラン、シクロヘキシルメチルジメトキシシラン、シクロヘキシルメチルジエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、ビニルトリメトキシシラン、メチルトリメトキシシラン、ｎ−プロピルトリエトキシシラン、デシルトリメトキシシラン、デシルトリエトキシシラン、フェニルトリメトキシシラン、γ−クロルプロピルトリメトキシシラン、メチルトリエトキシシラン、エチルトリエトキシシラン、ビニルトリエトキシシラン、ｔ−ブチルトリエトキシシラン、テキシルトリメトキシシラン、ｎ−ブチルトリエトキシシラン、ｉｓｏ−ブチルトリエトキシシラン、フェニルトリエトキシシラン、γ−アミノプロピルトリエトキシシラン、クロルトリエトキシシラン、エチルトリイソプロポキシシラン、ビニルトリブトキシシラン、シクロヘキシルトリメトキシシラン、シクロヘキシルトリエトキシシラン、２−ノルボルナントリメトキシシラン、２−ノルボルナントリエトキシシラン、２−ノルボルナンメチルジメトキシシラン、ケイ酸エチル、ケイ酸ブチル、トリメチルフエノキシシラン、メチルトリアリルオキシシラン、ビニルトリス（β−メトキシエトキシシラン）、ビニルトリアセトキシシラン、ジメチルテトラエトキシジシロキサン。
中でも、エチルトリエトキシシラン、ｎ−プロピルトリエトキシシラン、ｎ−プロピルトリメトキシシラン、ｔ−ブチルトリエトキシシラン、ｔ−ブチルメチルジメトキシシラン、ｔ−ブチルメチルジエトキシシラン、ｔ−ブチルエチルジメトキシシラン、ｔ−ブチルプロピルジメトキシシラン、ｔ−ブチルｔ−ブトキシジメトキシシラン、ｔ−ブチルトリメトキシシラン、ｉ−ブチルトリメトキシシラン、イソブチルメチルジメトキシシラン、ｉ−ブチルセク−ブチルジメトキシシラン、エチル（パーヒドロイソキノリン２−イル）ジメトキシシラン、ビス（デカヒドロイソキノリン−２−イル）ジメトキシシラン、トリ（イソプロペニロキシ）フェニルシラン、テキシルトリメトキシシラン、ビニルトリエトキシシラン、フェニルトリエトキシシラン、フェニルトリメトキシシラン、ビニルトリブトキシシラン、ジフェニルジメトキシシラン、ジイソプロピルジメトキシシラン、ジイソブチルジメトキシシラン、ｉ−ブチルｉ−プロピルジメトキシシラン、シクロペンチルｔ−ブトキシジメトキシシラン、ジシクロペンチルジメトキシシラン、シクロヘキシルメチルジメトキシシラン、シクロヘキシルｉ−ブチルジメトキシシラン、シクロペンチルｉ−ブチルジメトキシシラン、シクロペンチルイソプロピルジメトキシシラン、ジ−ｓｅｃ−ブチルジメトキシシラン、ジエチルアミノトリエトキシシラン、テトラエトキシシラン、テトラメトキシシラン、イソブチルトリエトキシシラン、フェニルメチルジメトキシシラン、フェニルトリエトキシラン、ビスｐ−トリルジメトキシシラン、ｐ−トリルメチルジメトキシシラン、ジシクロヘキシルジメトキシシラン、シクロヘキシルエチルジメトキシシラン、２−ノルボルナントリエトキシシラン、２−ノルボルナンメチルジメトキシシラン、ジフェニルジエトキシシラン、メチル（３、３、３−トリフルオロプロピル）ジメトキシシラン、ケイ酸エチルなどが好ましい。
3) Electron donor compound (component C)
The electron donor compound of component (C) is generally referred to as an "external electron donor". As such an electron donor compound, an organosilicon compound is preferable. Preferred organosilicon compounds include:
Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyl Dimethoxysilane, diphenyldiethoxysilane, biso-tolyldimethoxysilane, bism-tolyldimethoxysilane, bisp-tolyldimethoxysilane, bisp-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane Silane, Cyclohexylmethyldimethoxysilane, Cyclohexylmethyldiethoxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Vinyltrimethoxysilane, Methyltrimethoxysilane, n-propyltriethoxysilane, Decyltrimethoxysilane, Decyltriethoxysilane, Phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, texyltrimethoxysilane, n-butyltriethoxysilane, iso- Butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornantrimethoxysilane , 2-Norbornantriethoxysilane, 2-norbornanmethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyl Tetraethoxydisiloxane.
Among them, ethyltriethoxysilane, n-propyltriethoxysilane, n-propyltrimethoxysilane, t-butyltriethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-butylethyldimethoxysilane, t-Butylpropyldimethoxysilane, t-butylt-butoxydimethoxysilane, t-butyltrimethoxysilane, i-butyltrimethoxysilane, isobutylmethyldimethoxysilane, i-butylsec-butyldimethoxysilane, ethyl (perhydroisoquinolin 2-) Il) dimethoxysilane, bis (decahydroisoquinolin-2-yl) dimethoxysilane, tri (isopropeniroxy) phenylsilane, texyltrimethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltri Butoxysilane, diphenyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, i-butyl i-propyldimethoxysilane, cyclopentyl t-butoxydimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyl i-butyldimethoxysilane, cyclopentyl i -Butyldimethoxysilane, cyclopentylisopropyldimethoxysilane, di-sec-butyldimethoxysilane, diethylaminotriethoxysilane, tetraethoxysilane, tetramethoxysilane, isobutyltriethoxysilane, phenylmethyldimethoxysilane, phenyltriethoxylan, bisp-tolyl Dimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylethyldimethoxysilane, 2-norbornantriethoxysilane, 2-norbornanmethyldimethoxysilane, diphenyldiethoxysilane, methyl (3,3,3-trifluoropropyl) Dimethoxysilane, ethyl silicate and the like are preferable.
上記のとおりに調製した触媒に原料モノマーを接触させて重合する。この際、まず前記触媒を用いて予備重合を行うことが好ましい。予備重合とは、その後の原料モノマーの本重合の足がかりとなるポリマー鎖を固体触媒成分に形成させる工程である。予備重合は公知の方法で行うことができる。予備重合は、通常は４０℃以下、好ましくは３０℃以下、より好ましくは２０℃以下で行われる。
次いで、予備重合した触媒を重合反応系内に導入して、原料モノマーの本重合を行う。重合方法は、スラリープロセス（液体モノマー中の重合）や気相重合等の公知の方法を用いることができる。また、各後続の重合が直前の重合反応中に形成された重合性物質の存在下で行われる少なくとも２つの逐次重合ステージを具備する逐次重合方法を用いてもよい。
連鎖移動剤（たとえば、水素又はＺｎＥｔ２）などの当該分野で公知の分子量調節剤を用いてもよい。
エチレン含有プロピレン系重合体は、反応系にプロピレンモノマー、エチレンモノマー、触媒、必要に応じて分子量調節剤を供給し、プロピレンモノマーとエチレンモノマーとを共重合させて得られる。
重合温度は４０〜１００℃が好ましく、５０〜９０℃がより好ましく、６０〜９０℃がさらに好ましい。
重合圧力は、液相中で行われる場合には好ましくは３３〜４５ｂａｒ（３．３〜４．５ＭＰａ）の範囲であり、気相中で行われる場合には５〜３０ｂａｒ（０．５〜３．０ＭＰａ）の範囲である。
The raw material monomer is brought into contact with the catalyst prepared as described above to polymerize. At this time, it is preferable to first perform prepolymerization using the catalyst. The prepolymerization is a step of forming a polymer chain as a foothold for the subsequent main polymerization of the raw material monomer in the solid catalyst component. Prepolymerization can be carried out by a known method. Prepolymerization is usually carried out at 40 ° C. or lower, preferably 30 ° C. or lower, and more preferably 20 ° C. or lower.
Next, the prepolymerized catalyst is introduced into the polymerization reaction system to carry out the main polymerization of the raw material monomer. As the polymerization method, a known method such as a slurry process (polymerization in a liquid monomer) or a gas phase polymerization can be used. Alternatively, a step-growth polymerization method comprising at least two step-growth polymerization stages in which each subsequent polymerization is carried out in the presence of a polymerizable substance formed during the immediately preceding polymerization reaction may be used.
A molecular weight modifier known in the art, such as a chain transfer agent (eg, hydrogen or ZnEt 2), may be used.
The ethylene-containing propylene-based polymer is obtained by supplying a propylene monomer, an ethylene monomer, a catalyst, and if necessary, a molecular weight modifier to the reaction system, and copolymerizing the propylene monomer and the ethylene monomer.
The polymerization temperature is preferably 40 to 100 ° C., more preferably 50 to 90 ° C., and even more preferably 60 to 90 ° C.
The polymerization pressure is preferably in the range of 33 to 45 bar (3.3 to 4.5 MPa) when carried out in the liquid phase, and 5 to 30 bar (0.5 to 3) when carried out in the gas phase. It is in the range of 0.0 MPa).
また、モノマー濃度や重合条件の勾配を有する重合器を用いてもよい。このような重合器では、例えば、少なくとも２つの重合領域が接続されたものを使用し、気相重合でモノマーを重合することができる。具体的には、触媒の存在下、上昇管からなる重合領域にてモノマーを供給して重合し、上昇管に接続された下降管にてモノマーを供給して重合し、上昇管と下降管とを循環しながら、ポリマー生成物を回収する。この方法は、上昇管中に存在する気体混合物が下降管に入るのを全面的または部分的に防止する手段を備える。また、上昇管中に存在する気体混合物とは異なる組成を有する気体および／または液体混合物を下降管中に導入する。上記の重合方法として、例えば、特表２００２−５２０４２６号公報に記載された方法を適用することができる。 Further, a polymerizer having a gradient of monomer concentration and polymerization conditions may be used. In such a polymerizer, for example, one in which at least two polymerization regions are connected can be used, and the monomer can be polymerized by vapor phase polymerization. Specifically, in the presence of a catalyst, a monomer is supplied and polymerized in a polymerization region consisting of an ascending tube, and a monomer is supplied and polymerized by a descending tube connected to the ascending tube. The polymer product is recovered while circulating. This method comprises means to prevent the gas mixture present in the ascending tube from entering the descending tube in whole or in part. Also, a gas and / or liquid mixture having a composition different from that of the gas mixture present in the ascending tube is introduced into the descending tube. As the above polymerization method, for example, the method described in JP-A-2002-520426 can be applied.
結晶核剤およびその他の添加剤を添加する場合は、重合により得られた重合体、結晶核剤、およびその他の添加剤を、ヘンシェルミキサー、ブラベンダー等で撹拌した後、押出機を用いて１８０℃から２８０℃で溶融ブレンドする事により本発明のポリプロピレン組成物を得ることができる。結晶核剤やその他の添加剤の添加は、重合、残留モノマー除去、乾燥工程を経た後、連結された押出機を用いて行ってもよい。また本発明においては、高濃度の結晶核剤をポリプロピレンと溶融混練した、いわゆるマスターバッチをシート成形時にポリプロピレン樹脂に混合してもよい。 When adding a crystal nucleating agent and other additives, the polymer, the crystal nucleating agent, and other additives obtained by polymerization are stirred with a Henchel mixer, brabender, etc., and then 180 using an extruder. The polypropylene composition of the present invention can be obtained by melt-blending at ° C to 280 ° C. The crystal nucleating agent and other additives may be added using a connected extruder after undergoing polymerization, residual monomer removal, and drying steps. Further, in the present invention, a so-called masterbatch in which a high-concentration crystal nucleating agent is melt-kneaded with polypropylene may be mixed with polypropylene resin at the time of sheet molding.
＜ポリプロピレン製シートの製造方法＞
本発明のポリプロピレン製シートは、本発明のポリプロピレン組成物からなる未延伸シートを製造し、該未延伸シートを二軸延伸する方法で製造することが好ましい。
未延伸シートの製造工程および二軸延伸工程は公知の手法を用いて行うことができる。未延伸シートは、１種のポリプロピレン組成物からなる単層でもよく、２種以上のポリプロピレン組成物層を積層した多層でもよい。
<Manufacturing method of polypropylene sheet>
The polypropylene sheet of the present invention is preferably produced by a method of producing an unstretched sheet made of the polypropylene composition of the present invention and biaxially stretching the unstretched sheet.
The unstretched sheet manufacturing step and the biaxial stretching step can be performed by using a known method. The unstretched sheet may be a single layer composed of one kind of polypropylene composition, or may be a multi-layer in which two or more kinds of polypropylene composition layers are laminated.
前記二軸延伸を行う際の、成形温度は１４０〜１７０℃が好ましく、１５０〜１６５℃がより好ましく、１５５〜１６０℃がさらに好ましい。該成形温度が上記範囲の下限値以上であると優れた厚薄精度が得られやすく、上限値以下であると白濁等の外観不良が生じ難い。
成形速度は２０％／秒以上が好ましく、５０〜３００％／秒がより好ましく、１００〜２００％／秒がさらに好ましい。該成形速度が上記範囲の下限値以上、かつ上限値以下であると優れた厚薄精度が得られやすく好ましい。なお、例えば１秒間当たりの成形速度が１００％であるとは１秒後に元のシートの長さが２倍になることを意味する。現実的な成形速度の上限は５００％／秒程度であり、４００％／秒以下が好ましい。
延伸倍率はＭＤ方向（縦方向ともいう）およびＴＤ方向（横方向ともいう）の延伸倍率がいずれも３〜６倍であることが好ましく、３〜５倍がより好ましく、３〜４倍がさらに好ましい。該延伸倍率が上記範囲の下限値以上であると高い剛性が得られやすく、上限値以下であると本シートを賦形して二次成形品とする際に良好な成形性が得られやすい。
ＭＤ方向の延伸倍率とＴＤ方向の延伸倍率との比を表すＭＤ／ＴＤは、１／２〜２／１が好ましく、２／３〜３／２がより好ましく、１／１が最も好ましい。
The molding temperature at the time of performing the biaxial stretching is preferably 140 to 170 ° C, more preferably 150 to 165 ° C, still more preferably 155 to 160 ° C. When the molding temperature is at least the lower limit value in the above range, excellent thickness / thinness accuracy is likely to be obtained, and when it is at least the upper limit value, appearance defects such as cloudiness are unlikely to occur.
The molding rate is preferably 20% / sec or more, more preferably 50 to 300% / sec, still more preferably 100 to 200% / sec. It is preferable that the molding speed is not less than the lower limit value in the above range and not more than the upper limit value because excellent thickness and thinness accuracy can be easily obtained. For example, a molding speed of 100% per second means that the length of the original sheet is doubled after 1 second. The practical upper limit of the molding speed is about 500% / sec, preferably 400% / sec or less.
As for the stretching ratio, the stretching ratio in both the MD direction (also referred to as the vertical direction) and the TD direction (also referred to as the horizontal direction) is preferably 3 to 6 times, more preferably 3 to 5 times, and further 3 to 4 times. preferable. When the draw ratio is at least the lower limit value in the above range, high rigidity is likely to be obtained, and when it is at least the upper limit value, good formability is likely to be obtained when the present sheet is shaped to obtain a secondary molded product.
The MD / TD representing the ratio of the stretching ratio in the MD direction to the stretching ratio in the TD direction is preferably 1/2 to 2/1, more preferably 2/3 to 3/2, and most preferably 1/1.
＜ポリプロピレン製シートからなる二次成形体の製造方法＞
本発明のポリプロピレン製シート（二軸延伸シート）は、公知の真空成形、真空圧空成形、熱板成形などの熱成形方法で、容器やトレーに容易に加工できる。二次成形された成形品は、弁当容器、惣菜トレー、断熱容器などとして使用できる。
<Manufacturing method of secondary molded product made of polypropylene sheet>
The polypropylene sheet (biaxially stretched sheet) of the present invention can be easily processed into a container or a tray by a known thermoforming method such as vacuum forming, vacuum pressure forming, or hot plate forming. The secondary molded product can be used as a lunch box container, a side dish tray, a heat insulating container, and the like.
以下に実施例を用いて本発明をさらに詳しく説明するが、本発明はこれら実施例に限定されるものではない。
＜測定装置＞
［共重合体中のエチレン含有量］
共重合体中のエチレン含有量は、１，２，４−トリクロロベンゼン／重水素化ベンゼンの混合溶媒に溶解した試料について、日本電子社製ＪＮＭ ＬＡ−４００（１３Ｃ共鳴周波数１００ＭＨｚ）を用い、１３Ｃ−ＮＭＲ法で測定した値から算出した。
［ヘーズ］
ポリプロピレン製シートのヘーズは、ヘーズメーター（株式会社村上色彩技術研究所製、ＨＭ−１５０）を用い、上述の方法で測定した。
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
<Measuring device>
[Ethylene content in copolymer]
The ethylene content in the copolymer was determined by using JNM LA-400 (13C resonance frequency 100 MHz) manufactured by JEOL Ltd. for a sample dissolved in a mixed solvent of 1,2,4-trichlorobenzene / deuterated benzene. 13 Calculated from the values measured by the C-NMR method.
[Haze]
The haze of the polypropylene sheet was measured by the above-mentioned method using a haze meter (HM-150, manufactured by Murakami Color Technology Laboratory Co., Ltd.).
［製造例１：固体触媒成分の調製（１）］
特開２０１１−５００９０７号の実施例に記載の調製法に従い、固体触媒成分を調製し
た。具体的には以下の通りである：
窒素でパージした５００ｍＬの４つ口丸底フラスコ中に、２５０ｍＬのＴｉＣｌ４を０℃において導入した。撹拌しながら、１０．０ｇの微細球状ＭｇＣｌ２・１．８Ｃ２Ｈ５ＯＨ（ＵＳＰ−４，３９９，０５４の実施例２に記載の方法にしたがって、しかしながら１００００ｒｐｍに代えて３０００ｒｐｍで運転して製造した）、および９．１ミリモルのジエチル−２，３−（ジイソプロピル）スクシネートを加えた。温度を１００℃に上昇させ、１２０分間保持した。次に、撹拌を停止し、固体生成物を沈降させ、上澄み液を吸い出した。次に、以下の操作を２回繰り返した：２５０ｍＬの新しいＴｉＣｌ４を加え、混合物を１２０℃において６０分間反応させ、上澄み液を吸い出した。固体を、６０℃において無水ヘキサン（６×１００ｍＬ）で６回洗浄して、固体触媒（１）を得た。
[Production Example 1: Preparation of solid catalyst component (1)]
A solid catalyst component was prepared according to the preparation method described in Examples of JP-A-2011-500907. Specifically:
250 mL of TiCl 4 was introduced at 0 ° C. into a 500 mL four-necked round bottom flask purged with nitrogen. While stirring, according to the method described in Example 2 of fine spherical MgCl 2 · 1.8C 2 H of 10.0g 5 OH (USP-4,399,054, however operating at 3000rpm instead of 10000rpm production And 9.1 mmol of diethyl-2,3- (diisopropyl) succinate were added. The temperature was raised to 100 ° C. and held for 120 minutes. The stirring was then stopped, the solid product was allowed to settle and the supernatant was sucked out. The following operation was then repeated twice: 250 mL of fresh TiCl 4 was added, the mixture was reacted at 120 ° C. for 60 minutes and the supernatant was sucked out. The solid was washed 6 times with anhydrous hexane (6 x 100 mL) at 60 ° C. to give a solid catalyst (1).
［製造例２：ポリプロピレン組成物Ｂの製造］
上記固体触媒（１）と、トリエチルアルミニウム（ＴＥＡＬ）およびジイソプロピルジメトキシシラン（ＤＩＰＭＳ）を、固体触媒に対するＴＥＡＬの質量比が１１であり、ＴＥＡＬ／ＤＩＰＭＳの質量比が３となるような量で、１２℃において２４分間接触させた。得られた触媒系を、液体プロピレン中において懸濁状態で２０℃において５分間保持することによって予備重合を行い、予備重合物（１）を得た。
得られた予備重合物（１）を、重合反応器に導入し、モノマーとしてプロピレンを供給するとともに、重合反応器内の水素濃度が０．１３２ｍｏｌ％、エチレン濃度が０．０３３ｍｏｌ％となるように少量のエチレンおよび分子量調整剤としての水素を供給した。重合温度を７０℃、重合圧力を３０ｂａｒに調整することによってエチレン含有プロピレン系重合体を合成した。
得られたエチレン含有プロピレン系重合体１００質量部に対して、結晶核剤として、ノニトール系核剤（ミリケンジャパン社製Ｍｉｌｌａｄ ＮＸ８０００）を表に示す含有量となるように添加するとともに、酸化防止剤（ＢＡＳＦ社製Ｂ２２５）を０．２４質量部および中和剤（カルシウムステアレート）を０．０５質量部配合し、押出機を用いて２３０℃で溶融混練してポリプロピレン組成物Ｂを得た。
得られたポリプロピレン組成物における、エチレン含有プロピレン系重合体のエチレン含有量、Ｍｗ／Ｍｎ、キシレン不溶分量およびキシレン不溶分のｍｍｍｍ、ポリプロピレン組成物のＭＦＲ、結晶核剤の含有量およびｔ１／２の値を表１、２に示す（以下、同様）。
[Production Example 2: Production of Polypropylene Composition B]
The solid catalyst (1) and triethylaluminium (TEAL) and diisopropyldimethoxysilane (DIPMS) are prepared in such an amount that the mass ratio of TEAL to the solid catalyst is 11 and the mass ratio of TEAL / DIPMS is 3. Contact was made at ° C for 24 minutes. The obtained catalyst system was prepolymerized by holding it in a suspended state in liquid propylene at 20 ° C. for 5 minutes to obtain a prepolymer (1).
The obtained prepolymer (1) is introduced into a polymerization reactor to supply propylene as a monomer, and the hydrogen concentration in the polymerization reactor is 0.132 mol% and the ethylene concentration is 0.033 mol%. A small amount of ethylene and hydrogen as a molecular weight modifier were supplied. An ethylene-containing propylene-based polymer was synthesized by adjusting the polymerization temperature to 70 ° C. and the polymerization pressure to 30 bar.
To 100 parts by mass of the obtained ethylene-containing propylene-based polymer, a nonitol-based nucleating agent (Milllad NX8000 manufactured by Milliken Japan Co., Ltd.) is added as a crystal nucleating agent so as to have the content shown in the table, and an antioxidant is added. (B225 manufactured by BASF) was blended in an amount of 0.24 parts by mass and a neutralizing agent (calcium stearate) in an amount of 0.05 parts by mass, and melt-kneaded at 230 ° C. using an extruder to obtain a polypropylene composition B.
In the obtained polypropylene composition, the ethylene content of the ethylene-containing propylene-based polymer, Mw / Mn, the xylene-insoluble content and the xylene-insoluble mm mm, the MFR of the polypropylene composition, the content of the crystal nucleating agent and t 1/2. The values of are shown in Tables 1 and 2 (the same applies hereinafter).
［製造例３：ポリプロピレン組成物Ｃ−１−１の製造］
製造例２において、重合反応器内の水素濃度を０．０６７ｍｏｌ％に変更した。それ以外は製造例２と同様にしてエチレン含有プロピレン系重合体を合成し、ポリプロピレン組成物Ｃ−１−１を得た。
［製造例４：ポリプロピレン組成物Ｃ−１−２の製造］
製造例３において、結晶核剤の添加量を変更した以外は同様にしてポリプロピレン組成物Ｃ−１−２を得た。
［製造例５：ポリプロピレン組成物Ｃ−２の製造］
製造例３において、重合反応器内の水素濃度を０．０６９ｍｏｌ％、エチレン濃度を０．０８３ｍｏｌ％とし、組成物のエチレン含有量を変更した以外は同様にしてポリプロピレン組成物Ｃ−２を得た。
[Production Example 3: Production of Polypropylene Composition C-1-1]
In Production Example 2, the hydrogen concentration in the polymerization reactor was changed to 0.067 mol%. Except for this, an ethylene-containing propylene-based polymer was synthesized in the same manner as in Production Example 2 to obtain a polypropylene composition C-1-1.
[Production Example 4: Production of Polypropylene Composition C-1-2]
In Production Example 3, a polypropylene composition C-1-2 was obtained in the same manner except that the amount of the crystal nucleating agent added was changed.
[Production Example 5: Production of Polypropylene Composition C-2]
In Production Example 3, the polypropylene composition C-2 was obtained in the same manner except that the hydrogen concentration in the polymerization reactor was 0.069 mol% and the ethylene concentration was 0.083 mol%, and the ethylene content of the composition was changed. ..
［製造例６：ポリプロピレン組成物Ｃ−３−１の製造］
製造例３において、重合反応器内の水素濃度を０．０７０ｍｏｌ％、エチレン濃度を０．１１８ｍｏｌ％とし、組成物のエチレン含有量と、結晶核剤の添加量を変更した以外は同様にしてポリプロピレン組成物Ｃ−３−１を得た。
［製造例７：ポリプロピレン組成物Ｃ−３−３の製造］
製造例６において、結晶核剤の添加量を変更した以外は同様にしてポリプロピレン組成物Ｃ−３−３を得た。
［比較製造例８：ポリプロピレン組成物Ｃ−３−４の製造］
製造例６において、結晶核剤を添加しない以外は同様にしてポリプロピレン組成物Ｃ−３−４を得た。
［比較製造例９：ポリプロピレン組成物Ｃ−３−５の製造］
製造例６において、結晶核剤の添加量を変更した以外は同様にしてポリプロピレン組成物Ｃ−３−５を得た。
［製造例１０：ポリプロピレン組成物Ｃ−４の製造］
製造例３において、重合反応器内の水素濃度を０．０７２ｍｏｌ％、エチレン濃度を０．１８９ｍｏｌ％とし、組成物のエチレン含有量と、結晶核剤の添加量を変更した以外は同様にしてポリプロピレン組成物Ｃ−４を得た。
［比較製造例１１：ポリプロピレン組成物Ｃ−５の製造］
製造例３において、重合反応器内の水素濃度を０．０７６ｍｏｌ％、エチレン濃度を０．２７２ｍｏｌ％とし、組成物のエチレン含有量と、結晶核剤の添加量を変更した以外は同様にしてポリプロピレン組成物Ｃ−５を得た。
[Production Example 6: Production of Polypropylene Composition C-3-1]
In Production Example 3, the hydrogen concentration in the polymerization reactor was 0.070 mol%, the ethylene concentration was 0.118 mol%, and polypropylene was obtained in the same manner except that the ethylene content of the composition and the addition amount of the crystal nucleating agent were changed. Composition C-3-1 was obtained.
[Production Example 7: Production of Polypropylene Composition C-3-3]
In Production Example 6, a polypropylene composition C-3-3 was obtained in the same manner except that the amount of the crystal nucleating agent added was changed.
[Comparative Production Example 8: Production of Polypropylene Composition C-3-4]
In Production Example 6, a polypropylene composition C-3-4 was obtained in the same manner except that a crystal nucleating agent was not added.
[Comparative Production Example 9: Production of Polypropylene Composition C-3-5]
In Production Example 6, a polypropylene composition C-3-5 was obtained in the same manner except that the amount of the crystal nucleating agent added was changed.
[Production Example 10: Production of Polypropylene Composition C-4]
In Production Example 3, the hydrogen concentration in the polymerization reactor was 0.072 mol%, the ethylene concentration was 0.189 mol%, and polypropylene was obtained in the same manner except that the ethylene content of the composition and the addition amount of the crystal nucleating agent were changed. Composition C-4 was obtained.
[Comparative Production Example 11: Production of Polypropylene Composition C-5]
In Production Example 3, the hydrogen concentration in the polymerization reactor was 0.076 mol%, the ethylene concentration was 0.272 mol%, and polypropylene was obtained in the same manner except that the ethylene content of the composition and the addition amount of the crystal nucleating agent were changed. Composition C-5 was obtained.
［製造例１２：固体触媒成分の調製（２）］
欧州特許第６７４９９１号公報の実施例１に記載された方法により固体触媒（２）を調製した。該固体触媒は、ＭｇＣｌ２上にＴｉと内部ドナーとしてのジイソブチルフタレートを上記の特許公報に記載された方法で担持させたものである。
［比較製造例１３：ポリプロピレン組成物Ｄの製造］
上記固体触媒（２）と、ＴＥＡＬおよびシクロヘキシルメチルジメトキシシラン（ＣＨＭＭＳ）を、固体触媒に対するＴＥＡＬの重量比が８であり、ＣＨＭＭＳ／ＴＥＡＬのモル比が０．０２となるような量で、−５℃において５分間接触させた。得られた触媒系を、液体プロピレン中において懸濁状態で２０℃において５分間保持することによって予備重合を行い、予備重合物（２）を得た。
製造例３において、予備重合物（１）を予備重合物（２）に変更し、重合反応器内の水素濃度を０．０４２ｍｏｌ％とし、結晶核剤の添加量を変更した以外は同様にしてポリプロピレン組成物Ｄを得た。
[Production Example 12: Preparation of solid catalyst component (2)]
A solid catalyst (2) was prepared by the method described in Example 1 of European Patent No. 674991. The solid catalyst is obtained by supporting Ti and diisobutylphthalate as an internal donor on MgCl 2 by the method described in the above patent publication.
[Comparative Production Example 13: Production of Polypropylene Composition D]
The solid catalyst (2) and TEAL and cyclohexylmethyldimethoxysilane (CHMMS) are -5 in an amount such that the weight ratio of TEAL to the solid catalyst is 8 and the molar ratio of CHMMS / TEAL is 0.02. Contact was made at ° C. for 5 minutes. The obtained catalyst system was prepolymerized by holding it in a suspended state in liquid propylene at 20 ° C. for 5 minutes to obtain a prepolymer (2).
In Production Example 3, the prepolymer (1) was changed to the prepolymer (2), the hydrogen concentration in the polymerization reactor was 0.042 mol%, and the amount of the crystal nucleating agent added was changed in the same manner. A polypropylene composition D was obtained.
［比較製造例１４：ポリプロピレン組成物Ａ−１の製造］
重合反応器に前記予備重合物（１）を導入し、プロピレンを供給するとともに、重合反応器内の水素濃度が０．０６６ｍｏｌ％となるように供給し、重合温度を７０℃、重合圧力を３０ｂａｒに調整することによってプロピレン単独重合体を重合した。
得られたプロピレン単独重合体に、ノニトール系核剤（前記ＮＸ８０００）を表に示す含有量となるように添加するとともに、製造例２と同様に酸化防止剤および中和剤を配合し、押出機で溶融混練してポリプロピレン組成物Ａ−１を得た。
表において、エチレン含有量がゼロであるということは、ポリプロピレン組成物中の重合体がプロピレン単独重合体であることを意味する。
[Comparative Production Example 14: Production of Polypropylene Composition A-1]
The prepolymer (1) is introduced into the polymerization reactor, and propylene is supplied and the hydrogen concentration in the polymerization reactor is 0.066 mol%, the polymerization temperature is 70 ° C., and the polymerization pressure is 30 bar. The propylene homopolymer was polymerized by adjusting to.
A nonitol-based nucleating agent (NX8000) was added to the obtained propylene homopolymer so as to have the content shown in the table, and an antioxidant and a neutralizing agent were blended in the same manner as in Production Example 2 to make an extruder. The polypropylene composition A-1 was obtained by melt-kneading with.
In the table, a zero ethylene content means that the polymer in the polypropylene composition is a propylene homopolymer.
［比較製造例１５：ポリプロピレン組成物Ａ−２の製造］
製造例２において、結晶核剤を添加しない以外は同様にしてポリプロピレン組成物Ａ−２を得た。
[Comparative Production Example 15: Production of Polypropylene Composition A-2]
In Production Example 2, a polypropylene composition A-2 was obtained in the same manner except that a crystal nucleating agent was not added.
［例１〜１２、例１４〜２２、２４］
例１〜１２は実施例、例１４〜２２、２４は比較例である。
表に示すポリプロピレン組成物を用い、次のようにして二軸延伸シートを製造した。
まず、Ｔダイ成形機（吉井鉄工社製、多層Ｔダイ成形機、スクリュー径２５ｍｍ）を使用し、ロール温度３０℃（エアーナイフ使用）の条件にて、１０ｃｍ×１０ｃｍ、所定の厚さの未延伸シートを得た。
次いで、２軸延伸装置（Ｂｒｕｃｋｎｅｒ社製、ＫＡＲＯ ＩＶ）により未延伸シートを、表に示す条件（成形温度、成形速度、延伸倍率）で二方向へ同時に延伸させて、表に示す厚さのポリプロピレン製シート（二軸延伸シート）を得た。
得られたポリプロピレン製シートの厚さ、厚薄精度、引張弾性率、面衝撃強度、ヘーズ、透過法による像鮮明度（クラリティ）を測定した。また上記１６０℃での引張試験における伸長歪みと２００％伸長時応力を測定し、その測定値に基づき下記の基準で熱成形する際の易熱成形性（二次成形性）を評価した。荷重たわみ温度は、前述した様に、二軸延伸シートを熱成形して得た容器を用いて評価した。これらの結果を表１、２に示す（以下、同様）。
（易熱成形性の評価）
〇：伸長歪みの値が２００％を超え、かつ２００％伸長時応力が１０ＭＰａ未満
×：伸長歪みの値が２００％以下、または２００％伸長時応力が１０ＭＰａ以上
[Examples 1-12, 14-22, 24]
Examples 1 to 12 are Examples, and Examples 14 to 22 and 24 are Comparative Examples.
Using the polypropylene composition shown in the table, a biaxially stretched sheet was produced as follows.
First, using a T-die molding machine (manufactured by Yoshii Iron Works Co., Ltd., multi-layer T-die molding machine, screw diameter 25 mm), under the condition of a roll temperature of 30 ° C. (using an air knife), 10 cm x 10 cm, not having a predetermined thickness. A stretched sheet was obtained.
Next, the unstretched sheet is simultaneously stretched in two directions under the conditions shown in the table (molding temperature, molding speed, stretching ratio) by a biaxial stretching device (KARO IV manufactured by Bruckner), and polypropylene having the thickness shown in the table is shown. A manufactured sheet (biaxially stretched sheet) was obtained.
The thickness, thickness and thinness accuracy, tensile elastic modulus, surface impact strength, haze, and image clarity (clarity) of the obtained polypropylene sheet by the transmission method were measured. Further, the elongation strain and the stress at 200% elongation in the tensile test at 160 ° C. were measured, and the easy thermoformability (secondary formability) at the time of thermoforming was evaluated based on the measured values according to the following criteria. As described above, the deflection temperature under load was evaluated using a container obtained by thermoforming a biaxially stretched sheet. These results are shown in Tables 1 and 2 (the same applies hereinafter).
(Evaluation of thermoformability)
〇: Elongation strain value exceeds 200% and 200% elongation stress is less than 10 MPa ×: Elongation strain value is 200% or less, or 200% elongation stress is 10 MPa or more.
［例１３］
例１３は実施例である。
例１と同様にしてポリプロピレン組成物Ｂからなる厚み２６０μｍ×２（表と裏）の未延伸シートを製造した。また例４と同様にしてポリプロピレン組成物Ｃ−３−１からなる厚み２０８０μｍの未延伸シート（中間層）を製造した。これらを重ね合せた積層物を上記の２軸延伸装置により、表に示す条件（成形温度、成形速度、延伸倍率）で同時に二方向へ延伸させて、三層からなるポリプロピレン製シート（二軸延伸シート）を得た。
[Example 13]
Example 13 is an example.
An unstretched sheet having a thickness of 260 μm × 2 (front and back) made of polypropylene composition B was produced in the same manner as in Example 1. Further, in the same manner as in Example 4, an unstretched sheet (intermediate layer) having a thickness of 2080 μm and made of polypropylene composition C-3-1 was produced. The laminate obtained by superimposing these is simultaneously stretched in two directions under the conditions shown in the table (molding temperature, molding speed, stretching ratio) by the above biaxial stretching device, and a polypropylene sheet composed of three layers (biaxial stretching) is stretched. Sheet) was obtained.
［例２３］
例２３は比較例である。
スクリュー直径２５ｍｍの押出機を３台備え、３層積層可能なＴダイが設けられた多層シート成形機（サーモ・プラスチック工業株式会社製）を用いてシートを作製した。より具体的には、３台の押出機全てを用いて、ポリプロピレン系樹脂Ｃ−３−１を２３０℃で溶融させた。３００ｍｍ幅のＴダイ温度を２３０℃として、シートの両面を金属ロールの周面に密着させることにより、シートを冷却し、厚さ２１０μｍのシートを得た。
[Example 23]
Example 23 is a comparative example.
Sheets were produced using a multi-layer sheet molding machine (manufactured by Thermo Plastic Industry Co., Ltd.) equipped with three extruders having a screw diameter of 25 mm and a T-die capable of stacking three layers. More specifically, the polypropylene resin C-3-1 was melted at 230 ° C. using all three extruders. The T-die having a width of 300 mm was set to 230 ° C., and both sides of the sheet were brought into close contact with the peripheral surface of the metal roll to cool the sheet, and a sheet having a thickness of 210 μm was obtained.
表１、２に示されるように、例１〜１３において、ヘーズが低く透過法による像鮮明度が高くて透明性に優れ、かつ引張弾性率が高くて剛性に優れるとともに、−３０℃における面衝撃強度が高くて低温での高耐衝撃性にも優れるポリプロピレン製シートが得られた。また、これらのポリプロピレン製シートは、二次成形しやすいシート厚さに二軸延伸されたものであり、厚薄精度の値が小さくて均一延伸性に優れるとともに、１６０℃での引張試験における伸長歪みと２００％伸長時応力が良好であり易熱成形性（二次成形性）に優れる。また例１〜１３のポリプロピレン製シートを熱成形した二次成形体（容器）は耐熱性に優れるものであった。
なお、例２４のポリプロピレン製シートは、厚さが５００μｍを超えるものを得ようとしたため、二軸延伸の際にシートを挟んで保持しているチャックが外れて、最後まで二軸延伸できなかった。
As shown in Tables 1 and 2, in Examples 1 to 13, the haze is low, the image sharpness by the transmission method is high, the transparency is excellent, the tensile elastic modulus is high and the rigidity is excellent, and the surface at −30 ° C. A polypropylene sheet having high impact strength and excellent impact resistance at low temperatures was obtained. Further, these polypropylene sheets are biaxially stretched to a sheet thickness that is easy to secondary form, have a small value of thickness and thinness accuracy, are excellent in uniform stretchability, and are stretch strain in a tensile test at 160 ° C. The stress at the time of 200% elongation is good, and the thermoformability (secondary formability) is excellent. Further, the secondary molded product (container) obtained by thermoforming the polypropylene sheets of Examples 1 to 13 had excellent heat resistance.
Since the polypropylene sheet of Example 24 was attempted to have a thickness of more than 500 μm, the chuck holding the sheet sandwiched between the sheets was disengaged during biaxial stretching, and biaxial stretching could not be performed until the end. ..
Claims (7)
成形温度１４０〜１７０℃、成形速度２０〜４００％／秒、ＭＤ方向およびＴＤ方向の延伸倍率がそれぞれ３〜６倍の条件で二軸延伸して、
厚さが１００〜５００μｍであり、
厚薄精度が１２μｍ未満であり、
１６０℃における引張試験での伸長歪みが２００％を超え、かつ２００％伸長時応力が１０ＭＰａ未満であり、
２３℃における引張弾性率が１８００ＭＰａを超え、
−３０℃における面衝撃強度が２Ｊを超え、
ヘーズが２．５％未満であり、
透過法による像鮮明度が６０％以上である、ポリプロピレン製シートを製造する、ポリプロピレン製シートの製造方法。 Polypropylene content is less than 1% by mass, molecular weight distribution (Mw / Mn) is 6 to 20, and the amount of xylene insoluble content at 25 ° C. is more than 96.5% by mass and 99.5% by mass or less, and the three-dimensional rule of xylene insoluble content. An ethylene-containing propylene-based polymer having a property (mm mm) of 97.5 to 99.5% and a crystal nucleating agent having a property of less than 0.18 parts by mass with respect to 100 parts by mass of the ethylene-containing propylene-based polymer were added. An unstretched sheet made of a polypropylene composition containing a melt flow rate of 1 to 15 g / 10 min.
Biaxial stretching was performed under the conditions of a molding temperature of 140 to 170 ° C., a molding speed of 20 to 400% / sec, and a draw ratio of 3 to 6 times in the MD direction and the TD direction, respectively.
The thickness is 100-500 μm
Thickness accuracy is less than 12 μm,
The elongation strain in the tensile test at 160 ° C. exceeds 200%, and the stress at 200% elongation is less than 10 MPa.
The tensile elastic modulus at 23 ° C. exceeds 1800 MPa,
Surface impact strength at -30 ° C exceeds 2J,
Haze is less than 2.5%
A method for manufacturing a polypropylene sheet, which manufactures a polypropylene sheet having an image sharpness of 60% or more by a transmission method.
結晶化速度パラメータ（ｔ１／２）：１２０℃で結晶化する際に平衡結晶化度の１／２に達するまでに要する時間。 Wherein the polypropylene composition is a composition below the crystallization speed parameter (t 1/2) is more than 1 second, the production method of the polypropylene sheet according to claim 1.
Crystallization rate parameter (t 1/2 ): The time required to reach 1/2 of the equilibrium crystallinity when crystallization at 120 ° C.
（Ａ）マグネシウム、チタン、ハロゲン、およびスクシネート系化合物から選択される電子供与体化合物を必須成分として含有する固体触媒；
（Ｂ）有機アルミニウム化合物；ならびに
（Ｃ）外部電子供与体化合物
を含む触媒を用いて、プロピレンとエチレンとを重合させて得た組成物である、請求項１または２のいずれか一項に記載のポリプロピレン製シートの製造方法。 The polypropylene composition
(A) A solid catalyst containing an electron donor compound selected from magnesium, titanium, halogen, and succinate compounds as an essential component;
The composition according to any one of claims 1 or 2, which is a composition obtained by polymerizing propylene and ethylene using a catalyst containing (B) an organoaluminum compound and (C) an external electron donor compound. How to manufacture polypropylene sheets.
厚さが１００〜５００μｍであり、
厚薄精度が１２μｍ未満であり、
１６０℃における引張試験での伸長歪みが２００％を超え、かつ２００％伸長時応力が１０ＭＰａ未満であり、
２３℃における引張弾性率が１８００ＭＰａを超え、
−３０℃における面衝撃強度が２Ｊを超え、
ヘーズが２．５％未満であり、
透過法による像鮮明度が６０％以上である、ポリプロピレン製シート。 Polypropylene content is less than 1% by mass, molecular weight distribution (Mw / Mn) is 6 to 20, and the amount of xylene insoluble content at 25 ° C. is more than 96.5% by mass and 99.5% by mass or less, and the three-dimensional rule of xylene insoluble content. An ethylene-containing propylene-based polymer having a property (mm mm) of 97.5 to 99.5% and a crystal nucleating agent having a property of less than 0.18 parts by mass with respect to 100 parts by mass of the ethylene-containing propylene-based polymer were added. A biaxially stretched sheet comprising a polypropylene composition comprising a melt flow rate of 1-15 g / 10 min.
The thickness is 100-500 μm
Thickness accuracy is less than 12 μm,
The elongation strain in the tensile test at 160 ° C. exceeds 200%, and the stress at 200% elongation is less than 10 MPa.
The tensile elastic modulus at 23 ° C. exceeds 1800 MPa,
Surface impact strength at -30 ° C exceeds 2J,
Haze is less than 2.5%
A polypropylene sheet having an image sharpness of 60% or more by the transmission method.
結晶化速度パラメータ（ｔ１／２）：１２０℃で結晶化する際に平衡結晶化度の１／２に達するまでに要する時間。 Wherein the polypropylene composition is below the crystallization speed parameter (t 1/2) is a composition of more than one second, polypropylene sheet of claim 4.
Crystallization rate parameter (t 1/2 ): The time required to reach 1/2 of the equilibrium crystallinity when crystallization at 120 ° C.
（Ａ）マグネシウム、チタン、ハロゲン、およびスクシネート系化合物から選択される電子供与体化合物を必須成分として含有する固体触媒；
（Ｂ）有機アルミニウム化合物；ならびに
（Ｃ）外部電子供与体化合物
を含む触媒を用いて、プロピレンとエチレンとを重合させて得た組成物である、請求項４または５のいずれか一項に記載のポリプロピレン製シート。 The polypropylene composition
(A) A solid catalyst containing an electron donor compound selected from magnesium, titanium, halogen, and succinate compounds as an essential component;
The composition according to any one of claims 4 or 5 , which is a composition obtained by polymerizing propylene and ethylene using a catalyst containing (B) an organoaluminum compound and (C) an external electron donor compound. Polypropylene sheet .
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| JP7408316B2 (en) * | 2018-09-12 | 2024-01-05 | 旭化成ホームプロダクツ株式会社 | container lid |
| WO2020241503A1 (en) * | 2019-05-24 | 2020-12-03 | 株式会社Adeka | Resin composition and molded article thereof |
| WO2021193484A1 (en) * | 2020-03-24 | 2021-09-30 | 新日本理化株式会社 | Modifying agent for polyolefin resins and polyolefin resin composition containing said modifying agent |
| TWI729874B (en) * | 2020-06-29 | 2021-06-01 | 臺灣塑膠工業股份有限公司 | Polypropylene resin material and method for producing the same |
| JP2022073267A (en) * | 2020-10-30 | 2022-05-17 | 住友化学株式会社 | Propylene-based polymer composition, biaxial oriented film, and packaging bag |
| CA3198133A1 (en) | 2020-11-13 | 2022-05-19 | Fp Corporation | Polypropylene multilayer sheet |
| JP7329154B2 (en) | 2020-11-13 | 2023-08-17 | 株式会社エフピコ | Polypropylene multilayer sheet |
| JP2023069515A (en) * | 2021-11-05 | 2023-05-18 | 住友化学株式会社 | Propylene-based polymer composition, manufacturer method of propylene-based polymer composition and biaxial oriented film |
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| JP2583124B2 (en) * | 1989-05-02 | 1997-02-19 | 宇部興産株式会社 | Damping material composition and damping laminate using the same |
| JP3030446B2 (en) * | 1991-04-26 | 2000-04-10 | 大倉工業株式会社 | Antifogging biaxially oriented polypropylene film |
| JP3395159B2 (en) * | 1993-12-21 | 2003-04-07 | 出光石油化学株式会社 | Polypropylene composition |
| JPH08269266A (en) * | 1995-04-04 | 1996-10-15 | Chisso Corp | Polypropylene composition and production of transparent sheet therefrom |
| EP0962493B1 (en) * | 1998-06-03 | 2002-10-23 | Japan Polychem Corporation | Polyolefin resin composition and stretched film thereof |
| CN1173819C (en) * | 1998-12-16 | 2004-11-03 | 德山株式会社 | Bidirection stretching polyolefine film and making method thereof |
| TWI238169B (en) * | 2000-12-22 | 2005-08-21 | Basell Technology Co Bv | Bioriented polypropylene films |
| CN100542800C (en) * | 2002-02-20 | 2009-09-23 | 旭迪爱生株式会社 | Antifog plastic resin sheet material hot in nature and formed products |
| AU2003235918A1 (en) * | 2002-05-10 | 2003-11-11 | Sun Allomer Ltd. | Polypropylene resin composition |
| JP5432425B2 (en) * | 2005-02-01 | 2014-03-05 | 株式会社プライムポリマー | Resin composition, transparent elastic recovery film or sheet, and wrap film |
| JP4940601B2 (en) * | 2005-09-01 | 2012-05-30 | 新日本理化株式会社 | Novel polypropylene resin composition, sheet or film molded body using the composition, and method for producing the same |
| ES2348641T3 (en) * | 2005-12-22 | 2010-12-10 | Borealis Technology Oy | POLYPROPYLENE COMPOSITION THAT INCLUDES A PROPYLENE COPOLYMER COMPONENT. |
| JPWO2009063819A1 (en) * | 2007-11-13 | 2011-03-31 | 株式会社プライムポリマー | Propylene-based resin composition for stretched sheet, stretched sheet and thermoformed body containing the composition |
| EP3181637B1 (en) * | 2011-09-21 | 2017-11-29 | Borealis AG | Moulding composition |
| WO2013080854A1 (en) * | 2011-11-28 | 2013-06-06 | 三井化学東セロ株式会社 | Propylene-based polymer composition, biaxially stretched film, and use therefor |
| JP6076328B2 (en) * | 2012-02-20 | 2017-02-08 | サンアロマー株式会社 | Polypropylene resin composition for sheet molding |
| JP6235805B2 (en) * | 2013-06-17 | 2017-11-22 | サンアロマー株式会社 | Polypropylene resin composition for biaxially stretched film |
| EP2886600B1 (en) * | 2013-12-19 | 2018-05-30 | Abu Dhabi Polymers Co. Ltd (Borouge) LLC. | Multimodal polypropylene with respect to comonomer content |
| ES2827285T3 (en) * | 2014-02-06 | 2021-05-20 | Borealis Ag | Soft copolymers with high impact resistance |
| JP6842291B2 (en) * | 2016-12-09 | 2021-03-17 | サンアロマー株式会社 | Polypropylene composition and its manufacturing method, and polypropylene sheet |
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| TWI744440B (en) | 2021-11-01 |
| TW201835198A (en) | 2018-10-01 |
| JP2018095698A (en) | 2018-06-21 |
| CN108219295B (en) | 2021-09-07 |
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