JP2011207926A - Thermoplastic polyester elastomer resin composition and molded product made of the same - Google Patents
Thermoplastic polyester elastomer resin composition and molded product made of the same Download PDFInfo
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- JP2011207926A JP2011207926A JP2010074180A JP2010074180A JP2011207926A JP 2011207926 A JP2011207926 A JP 2011207926A JP 2010074180 A JP2010074180 A JP 2010074180A JP 2010074180 A JP2010074180 A JP 2010074180A JP 2011207926 A JP2011207926 A JP 2011207926A
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- Prior art keywords
- thermoplastic polyester
- polyester elastomer
- resin composition
- weight
- elastomer resin
- Prior art date
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- Granted
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- 229920006346 thermoplastic polyester elastomer Polymers 0.000 title claims abstract description 61
- 239000011342 resin composition Substances 0.000 title claims abstract description 29
- 238000002844 melting Methods 0.000 claims abstract description 27
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 26
- 230000008018 melting Effects 0.000 claims abstract description 20
- 239000000155 melt Substances 0.000 claims abstract description 16
- 239000003484 crystal nucleating agent Substances 0.000 claims abstract description 12
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 12
- -1 polyethylene Polymers 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 19
- 238000005452 bending Methods 0.000 abstract description 17
- 238000001746 injection moulding Methods 0.000 abstract description 13
- 238000001125 extrusion Methods 0.000 abstract description 10
- 238000010101 extrusion blow moulding Methods 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 26
- 238000000034 method Methods 0.000 description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 12
- 238000006068 polycondensation reaction Methods 0.000 description 11
- 238000000071 blow moulding Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000010102 injection blow moulding Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- BUZMJVBOGDBMGI-UHFFFAOYSA-N 1-phenylpropylbenzene Chemical compound C=1C=CC=CC=1C(CC)C1=CC=CC=C1 BUZMJVBOGDBMGI-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- YIFFAEJYCUTZAO-UHFFFAOYSA-N 2-(4-propylphenoxy)ethanol Chemical compound CCCC1=CC=C(OCCO)C=C1 YIFFAEJYCUTZAO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UTNSTOOXQPHXJQ-UHFFFAOYSA-N 2-[4-[4-(2-hydroxyethoxy)phenyl]sulfonylphenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1S(=O)(=O)C1=CC=C(OCCO)C=C1 UTNSTOOXQPHXJQ-UHFFFAOYSA-N 0.000 description 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- DUKVCLUFPFXDEM-UHFFFAOYSA-N 4-(4-hydroxy-4-phenylcyclohexa-1,5-dien-1-yl)phenol Chemical group C1=CC(O)=CC=C1C1=CCC(O)(C=2C=CC=CC=2)C=C1 DUKVCLUFPFXDEM-UHFFFAOYSA-N 0.000 description 1
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241001397104 Dima Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920003355 Novatec® Polymers 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- FNGGVJIEWDRLFV-UHFFFAOYSA-N anthracene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=CC3=C(C(O)=O)C(C(=O)O)=CC=C3C=C21 FNGGVJIEWDRLFV-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- YZFOGXKZTWZVFN-UHFFFAOYSA-N cyclopentane-1,1-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1 YZFOGXKZTWZVFN-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- LHLUQDDQLCJCFU-UHFFFAOYSA-L disodium;1-sulfocyclohexa-3,5-diene-1,3-dicarboxylate Chemical compound [Na+].[Na+].OS(=O)(=O)C1(C([O-])=O)CC(C([O-])=O)=CC=C1 LHLUQDDQLCJCFU-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009661 fatigue test Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- HDBOOJCPFYJMBJ-UHFFFAOYSA-M hydroxy(oxo)tin Chemical compound O[Sn]=O HDBOOJCPFYJMBJ-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- UHHKSVZZTYJVEG-UHFFFAOYSA-N oxepane Chemical compound C1CCCOCC1 UHHKSVZZTYJVEG-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003224 poly(trimethylene oxide) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Abstract
Description
本発明は、柔軟で弾性に富み屈曲疲労性に優れると共に、射出成形、押出成形、ブロー成形性に優れた熱可塑性エラストマ樹脂組成物およびそれからなる成形体に関する。 The present invention relates to a thermoplastic elastomer resin composition that is flexible, elastic, excellent in bending fatigue, and excellent in injection molding, extrusion molding, and blow molding, and a molded body comprising the same.
熱可塑性ポリエステルエラストマは、強度、耐衝撃性、弾性回復性、柔軟性などの機械的性質や、低温、高温特性に優れ、さらに熱可塑性で成形加工が容易であることから、自動車、電気・電子部品、消費材などの分野に広く使用されている。 Thermoplastic polyester elastomers have excellent mechanical properties such as strength, impact resistance, elastic recovery, flexibility, and low and high temperature properties, and are thermoplastic and easy to mold. Widely used in fields such as parts and consumer goods.
熱可塑性ポリエステルエラストマの成形加工方法としては、射出成形、押出成形、ブロー成形などが使用されているが、各々の成形加工方法の違いにより異なった材料特性が施されている。例えば射出成形では、固化を早くすることで成形サイクルを短くし、寸法精度を向上させている。また、押出成形やブロー成形では、溶融時の賦形性を考慮して、溶融弾性を高めて固化速度を遅くさせた材料設計を施している。 Injection molding, extrusion molding, blow molding, and the like are used as molding methods for thermoplastic polyester elastomers, but different material properties are given due to differences in each molding processing method. For example, in injection molding, the molding cycle is shortened and the dimensional accuracy is improved by rapid solidification. In extrusion molding and blow molding, in consideration of the formability at the time of melting, material design is performed in which the melt elasticity is increased and the solidification rate is decreased.
例えば、等速ジョイント駆動装置のカバーブーツ、エーアーダクト、フューエルチューブなどの成形品には、ブロー、押出成形が活用されている。中でも、自動車の等速ジョイント駆動装置のカバーブーツは、熱可塑性ポリエステルエラストマが幅広く使用されている用途であり、一般的にはプレスブロー成形が使用されている。しかし、プレスブロー成形以外に、射出成形とブロー成形方法を併せ持つインジェクションブロー成形での検討が進められているが、前述した成形加工方法の違いにより材料設計が異なるために、射出成形とブロー成形に適した特性を併せ持つ材料がなく、成形性を満足する材料が得られていないという問題があった。 For example, blow molding and extrusion molding are used for molded articles such as cover boots, air ducts, and fuel tubes of constant velocity joint driving devices. Among them, a cover boot of a constant velocity joint drive device for an automobile is an application in which a thermoplastic polyester elastomer is widely used, and press blow molding is generally used. However, in addition to press blow molding, injection blow molding, which has both injection molding and blow molding methods, is being studied, but because the material design is different due to the difference in the molding process described above, injection molding and blow molding are used. There is a problem that there is no material having suitable characteristics and a material satisfying moldability cannot be obtained.
そこで、成形性を改良するために種々の検討がなされており、例えば、グリシジル基および/またはイソシアネート基を含有し重量平均分子量が200以上50万以下である反応性化合物を含むポリエステル樹脂用改質剤(例えば、特許文献1参照)、ポリエステル樹脂の粒状体を流動条件下に、ポリオレフィン樹脂又はポリアミド樹脂に接触させることにより、ポリエステル樹脂にポリオレフィン樹脂又はポリアミド樹脂を微量含有させた改質ポリエステル樹脂の製造方法(例えば、特許文献2参照)、および融点が180〜220℃の熱可塑性エラストマと該熱可塑性エラストマの融点より20〜55℃低い融点を有する熱可塑性エラストマからなる熱可塑性エラストマ樹脂組成物(例えば、特許文献3参照)などが提案されている。 Accordingly, various studies have been made in order to improve moldability. For example, a modification for a polyester resin containing a reactive compound containing a glycidyl group and / or an isocyanate group and having a weight average molecular weight of 200 to 500,000. Of a modified polyester resin containing a small amount of a polyolefin resin or a polyamide resin in a polyester resin by bringing a granule of the polyester resin into contact with the polyolefin resin or the polyamide resin under flow conditions (for example, see Patent Document 1) A thermoplastic elastomer resin composition comprising a production method (for example, see Patent Document 2), and a thermoplastic elastomer having a melting point of 180 to 220 ° C and a thermoplastic elastomer having a melting point 20 to 55 ° C lower than the melting point of the thermoplastic elastomer ( For example, see Patent Document 3).
しかしながら、これら従来の技術では、十分に成形加工技術を改質するまでには至っておらず、特に射出成形時のヒケ、ブロー成形時のブロー成形性、屈曲疲労性を両立することは困難な状態であった。 However, with these conventional technologies, the molding technology has not been sufficiently improved, and it is difficult to achieve both shrinkage during injection molding, blow moldability during blow molding, and bending fatigue properties. Met.
本発明の課題は、上述した従来技術における問題点を解決することにあり、その目的とするところは、柔軟で弾性に富み屈曲疲労性に優れると共に、射出成形、押出成形、ブロー成形性に優れた熱可塑性ポリエステルエラストマ樹脂組成物およびそれを使用した成形体を提供することにある。 An object of the present invention is to solve the above-described problems in the prior art, and the object of the present invention is to be flexible, elastic, excellent in bending fatigue, and excellent in injection molding, extrusion molding, and blow molding. Another object of the present invention is to provide a thermoplastic polyester elastomer resin composition and a molded body using the same.
本発明者らは、上記の目的を達成するために鋭意検討した結果、熱可塑性ポリエステルエラストマに、ポリオレフィン樹脂、グリシジル基変性ポリオレフィン樹脂、および結晶核剤を組み合わせて配合し、所定の温度におけるメルトフローレートが特定の範囲を満たすようにすることによって、上記の目的が効果的に達成することを見出し、本発明に至った。 As a result of diligent studies to achieve the above object, the present inventors have formulated a thermoplastic polyester elastomer in combination with a polyolefin resin, a glycidyl group-modified polyolefin resin, and a crystal nucleating agent, and a melt flow at a predetermined temperature. The inventors have found that the above object can be effectively achieved by making the rate satisfy a specific range, and have reached the present invention.
すなわち、上記目的を達成するために本発明によれば、熱可塑性ポリエステルエラストマ(A)100重量部に対し、ポリオレフィン樹脂(B)0.1〜25重量部、グリシジル基変性ポリオレフィン樹脂(C)0.1〜15重量部、および結晶核剤(D)0.01〜5.0重量部を溶融混合してなり、下記式(1)で定められる温度To(℃)において、ASTM D−1238にしたがって、荷重2160gで測定したメルトフローレートが0.5g/10分以上、10g/10分以下であることを特徴とする熱可塑性ポリエステルエラストマ樹脂組成物。
To=R(Tm)+20・・・(1)
(ただし、Tmは熱可塑性ポリエステルエラストマ(A)の融点、R(Tm)はTmを10の位まで切り上げた値と定義する。)
That is, in order to achieve the above object, according to the present invention, 0.1 to 25 parts by weight of polyolefin resin (B), glycidyl group-modified polyolefin resin (C) 0 per 100 parts by weight of thermoplastic polyester elastomer (A). 0.1 to 15 parts by weight and 0.01 to 5.0 parts by weight of the crystal nucleating agent (D) are melt-mixed, and at a temperature To (° C.) defined by the following formula (1), ASTM D-1238 Accordingly, a thermoplastic polyester elastomer resin composition having a melt flow rate measured at a load of 2160 g of 0.5 g / 10 min or more and 10 g / 10 min or less.
To = R (Tm) +20 (1)
(However, Tm is defined as the melting point of the thermoplastic polyester elastomer (A), and R (Tm) is defined as a value obtained by rounding up Tm to 10)
なお、本発明の熱可塑性ポリエステルエラストマ樹脂組成物においては、
前記熱可塑性ポリエステルエラストマ(A)が、結晶性芳香族ポリエステル単位からなる高融点結晶性重合体セグメント20〜70重量%と、脂肪族ポリエーテル単位からなる低融点重合体セグメント80〜30重量%とを主たる構成成分とするポリエステルブロック共重合体であること、
前記グリシジル基変性ポリオレフィン樹脂(C)が、α−オレフィン、α,β−不飽和酸およびα,β−不飽和酸のグリシジルエステルからなる3元共重合体であること、
前記結晶核剤(D)が無機物であること、
前記メルトフローレートが1.0g/10分以上、8.0g/10分以下、好ましくは1.0g/10分以上、5.0g/10分以下であること、
が、いずれも好ましい条件であり、これらの条件を適用することにより、一層優れた効果の取得を期待することができる。
In the thermoplastic polyester elastomer resin composition of the present invention,
The thermoplastic polyester elastomer (A) comprises 20 to 70% by weight of a high-melting crystalline polymer segment composed of crystalline aromatic polyester units, and 80 to 30% by weight of a low-melting polymer segment composed of aliphatic polyether units. A polyester block copolymer having as a main component,
The glycidyl group-modified polyolefin resin (C) is a terpolymer comprising an α-olefin, an α, β-unsaturated acid and a glycidyl ester of an α, β-unsaturated acid,
The crystal nucleating agent (D) is an inorganic substance;
The melt flow rate is 1.0 g / 10 min or more and 8.0 g / 10 min or less, preferably 1.0 g / 10 min or more and 5.0 g / 10 min or less,
However, both are preferable conditions, and by applying these conditions, it can be expected to obtain a more excellent effect.
また、本発明の成形体は、前記熱可塑性ポリエステルエラストマ樹脂組成物が成形されてなることを特徴とする。 The molded article of the present invention is characterized in that the thermoplastic polyester elastomer resin composition is molded.
本発明によれば、柔軟で弾性に富み屈曲疲労性に優れると共に、射出成形、押出成形、ブロー成形性などの各種成形方法においても優れた加工性を有する熱可塑性ポリエステルエラストマ樹脂組成物およびそれからなる成形体を得ることができる。 According to the present invention, there is provided a thermoplastic polyester elastomer resin composition that is flexible and elastic, has excellent bending fatigue properties, and has excellent processability in various molding methods such as injection molding, extrusion molding and blow molding, and the like. A molded body can be obtained.
以下、本発明について詳述する。 Hereinafter, the present invention will be described in detail.
本発明に用いられる熱可塑性ポリエステルエラストマ(A)は、主として結晶性芳香族ポリエステル単位からなる高融点結晶性重合体セグメントと、主として脂肪族ポリエーテル単位からなる低融点セグメントとを主たる構成成分とするポリエステルブロック共重合体であり、高融点結晶性重合体セグメントは、主として芳香族ジカルボン酸またはそのエステル形成性誘導体と、ジオールまたはそのエステル形成性誘導体から形成されるポリエステルである。 The thermoplastic polyester elastomer (A) used in the present invention mainly comprises a high-melting-point crystalline polymer segment mainly composed of crystalline aromatic polyester units and a low-melting-point segment mainly composed of aliphatic polyether units. The high-melting crystalline polymer segment, which is a polyester block copolymer, is a polyester mainly formed from an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof.
前記芳香族ジカルボン酸の具体例としては、テレフタル酸、イソフタル酸、フタル酸、ナフタレン−2,6−ジカルボン酸、ナフタレン−2,7−ジカルボン酸、アントラセンジカルボン酸、ジフェニル−4,4' −ジカルボン酸、ジフェノキシエタンジカルボン酸、4,4' −ジフェニルエーテルジカルボン酸、5−スルホイソフタル酸、および3−スルホイソフタル酸ナトリウムなどが挙げられる。本発明においては、前記芳香族ジカルボン酸を主として用いるが、この芳香族ジカルボン酸の一部を、1,4−シクロヘキサンジカルボン酸、シクロペンタンジカルボン酸、4,4' −ジシクロヘキシルジカルボン酸などの脂環族ジカルボン酸や、アジピン酸、コハク酸、シュウ酸、セバシン酸、ドデカンジオン酸、およびダイマー酸などの脂肪族ジカルボン酸に置換してもよい。さらにジカルボン酸のエステル形成性誘導体、たとえば低級アルキルエステル、アリールエステル、炭酸エステル、および酸ハロゲン化物などももちろん同等に用い得る。 Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, anthracene dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid. Acid, diphenoxyethane dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 5-sulfoisophthalic acid, sodium 3-sulfoisophthalate and the like. In the present invention, the aromatic dicarboxylic acid is mainly used. A part of the aromatic dicarboxylic acid is an alicyclic ring such as 1,4-cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, or 4,4′-dicyclohexyldicarboxylic acid. Or aliphatic dicarboxylic acids such as adipic acid, succinic acid, oxalic acid, sebacic acid, dodecanedioic acid, and dimer acid. Furthermore, ester-forming derivatives of dicarboxylic acids such as lower alkyl esters, aryl esters, carbonates, and acid halides can of course be used equally.
前記ジオールの具体例としては、分子量400以下のジオール、例えば1,4−ブタンジオール、エチレングリコール、トリメチレングリコール、ペンタメチレングリコール、ヘキサメチレングリコール、ネオペンチルグリコール、デカメチレングリコールなどの脂肪族ジオール、1,1−シクロヘキサンジメタノール、1,4−ジシクロヘキサンジメタノール、トリシクロデカンジメタノールなどの脂環族ジオール、およびキシリレングリコール、ビス(p−ヒドロキシ)ジフェニル、ビス(p−ヒドロキシ)ジフェニルプロパン、2,2' −ビス[4−(2−ヒドロキシエトキシ)フェニル]プロパン、ビス[4−(2−ヒドロキシエトキシ)フェニル]スルホン、1,1−ビス[4−(2−ヒドロキシエトキシ)フェニル]シクロヘキサン、4,4' −ジヒドロキシ−p−ターフェニル、および4,4' −ジヒドロキシ−p−クオーターフェニルなどの芳香族ジオールが好ましく、かかるジオールは、エステル形成性誘導体、例えばアセチル体、アルカリ金属塩などの形でも用い得る。 Specific examples of the diol include diols having a molecular weight of 400 or less, such as aliphatic diols such as 1,4-butanediol, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, Alicyclic diols such as 1,1-cyclohexanedimethanol, 1,4-dicyclohexanedimethanol, tricyclodecane dimethanol, and xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxy) diphenylpropane 2,2′-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] Cyclohex Aromatic diols such as 4,4′-dihydroxy-p-terphenyl and 4,4′-dihydroxy-p-quarterphenyl are preferred, and such diols are ester-forming derivatives such as acetylated, alkali metal salts. It can also be used in the form of
これらのジカルボン酸、その誘導体、ジオール成分およびその誘導体は、2種以上併用してもよい。 Two or more of these dicarboxylic acids, derivatives thereof, diol components and derivatives thereof may be used in combination.
かかる高融点結晶性重合体セグメントの好ましい例は、テレフタル酸またはジメチルテレフタレートと、1,4−ブタンジオールから誘導されるポリブチレンテレフタレート単位からなるものである。高融点結晶性重合体セグメントの共重合量は通常20〜80重量%、好ましくは30〜75重量%である。 A preferred example of such a high melting crystalline polymer segment is one comprising terephthalic acid or dimethyl terephthalate and polybutylene terephthalate units derived from 1,4-butanediol. The copolymerization amount of the high-melting crystalline polymer segment is usually 20 to 80% by weight, preferably 30 to 75% by weight.
本発明に用いられる熱可塑性ポリエステルエラストマ(A)で使用される低融点重合体セグメントは、必要に応じ脂肪族ポリエーテルを使用することができる。 As the low-melting polymer segment used in the thermoplastic polyester elastomer (A) used in the present invention, an aliphatic polyether can be used as necessary.
かかる脂肪族ポリエーテルの具体例としては、ポリ(エチレンオキシド)グリコール、ポリ(プロピレンオキシド)グリコール、ポリ(トリメチレンオキシド)グリコール、ポリ(テトラメチレンオキシド)グリコール、ポリ(ヘキサメチレンオキシド)グリコール、エチレンオキシドとプロピレンオキシドの共重合体、ポリ(プロピレンオキシド)グリコールのエチレンオキシド付加物、およびエチレンオキシドとテトラヒドロフランの共重合体などが挙げられる。これらのなかでも、ポリ(テトラメチレンオキシド)グリコールおよび/またはポリ(プロピレンオキシド)グリコールのエチレンオキシド付加物および/またはエチレンオキシドとテトラヒドロフランの共重合体が好ましく用いられる。 Specific examples of such aliphatic polyethers include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (trimethylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, ethylene oxide and Examples include a copolymer of propylene oxide, an ethylene oxide adduct of poly (propylene oxide) glycol, and a copolymer of ethylene oxide and tetrahydrofuran. Of these, poly (tetramethylene oxide) glycol and / or poly (propylene oxide) glycol ethylene oxide adducts and / or copolymers of ethylene oxide and tetrahydrofuran are preferably used.
本発明に用いられる熱可塑性ポリエステルエラストマ(A)の低融点重合体セグメントの共重合量は、通常、80〜20重量%、好ましくは70〜25重量%である。 The copolymerization amount of the low melting polymer segment of the thermoplastic polyester elastomer (A) used in the present invention is usually 80 to 20% by weight, preferably 70 to 25% by weight.
本発明に用いられる熱可塑性ポリエステルエラストマ(A)は、溶融重縮合により得られる。溶融重縮合は公知の方法で実施することができる。例えば、ジカルボン酸の低級アルコールジエステル、過剰量の低分子量グリコール、および低融点重合体セグメント成分を、触媒の存在下エステル交換反応せしめ、得られる反応生成物を重縮合する方法、ジカルボン酸と過剰量のグリコールおよび低融点重合体セグメント成分を触媒の存在下エステル化反応せしめ、得られる反応生成物を重縮合する方法、およびあらかじめ高融点結晶性セグメントを作っておき、これに低融点セグメント成分を添加してエステル交換反応によりランダム化せしめる方法などのいずれの方法をとってもよい。 The thermoplastic polyester elastomer (A) used in the present invention is obtained by melt polycondensation. The melt polycondensation can be carried out by a known method. For example, a method in which a lower alcohol diester of a dicarboxylic acid, an excessive amount of a low molecular weight glycol, and a low melting point polymer segment component are transesterified in the presence of a catalyst and the resulting reaction product is polycondensed, an excess amount of the dicarboxylic acid A method in which the glycol and low-melting-point polymer segment components are esterified in the presence of a catalyst and the resulting reaction product is polycondensed, and a high-melting-point crystalline segment is prepared in advance, and a low-melting-point segment component is added to this. Then, any method such as a method of randomizing by transesterification may be used.
溶融重縮合で得られた熱可塑性ポリエステルエラストマ(A)は、次いで細粒化される。細粒化はガット状またはシート状に取り出した熱可塑性ポリエステルエラストマ(A)を、カッターでペレタイズするコールドカット方によってもよいし、ガット状やシート状にすることなくペレタイズするホットカット方によってもよい。また、塊状に取り出した熱可塑性ポリエステルエラストマ(A)を粉砕してもよい。 The thermoplastic polyester elastomer (A) obtained by melt polycondensation is then finely divided. Fine graining may be performed by a cold cut method in which the thermoplastic polyester elastomer (A) taken out in a gut shape or a sheet shape is pelletized by a cutter, or by a hot cut method in which pelletization is performed without forming a gut shape or a sheet shape. . Moreover, you may grind | pulverize the thermoplastic polyester elastomer (A) taken out in the lump shape.
溶融重縮合で得られた熱可塑性ポリエステルエラストマ(A)は、次いで固相重縮合してもよい。固相重縮合は、溶融重縮合後に細粒化した熱可塑性ポリエステルエラストマ(A)が融着しない温度で実施するが、通常は140℃〜220℃の温度範囲で行う。固相重縮合の前には、予備結晶化と乾燥工程を経ることが望ましい。また、固相重縮合は、高真空下または不活性気流下で実施する。高真空下の場合は、好ましくは665Pa以下、さらに好ましくは133Pa以下の減圧下で行う。不活性気流下の場合は、代表的には窒素気流下で行うことが好ましく、圧力は特に限定されないが大気圧が好ましい。反応容器としては、回転可能な真空乾燥機や、不活性ガスを流すことのできる塔式乾燥機などを使用することが好ましい。 The thermoplastic polyester elastomer (A) obtained by melt polycondensation may then be subjected to solid phase polycondensation. The solid phase polycondensation is carried out at a temperature at which the thermoplastic polyester elastomer (A) finely divided after melt polycondensation does not fuse, but is usually carried out in a temperature range of 140 ° C to 220 ° C. Prior to solid phase polycondensation, it is desirable to go through a precrystallization and drying step. The solid phase polycondensation is carried out under high vacuum or under an inert air stream. In the case of high vacuum, it is preferably performed under a reduced pressure of 665 Pa or less, more preferably 133 Pa or less. In the case of an inert air stream, it is typically preferable to carry out under a nitrogen stream, and the pressure is not particularly limited, but atmospheric pressure is preferred. As the reaction vessel, it is preferable to use a rotatable vacuum dryer or a tower dryer capable of flowing an inert gas.
本発明に用いられるポリオレフィン樹脂(B)とは、ポリエチレン、ポリプロピレン、エチレンプロピレン共重合体、エチレンプロピレンジエン共重合体などが挙げられるが、なかでもポリエチレンが好ましい。ポリオレフィン樹脂(B)の配合量は、熱可塑性ポリエステルエラストマ(A)100重量部に対して0.1〜25重量部、好ましくは0.5〜20重量部である。0.1重量部未満では目的とする効果の改良度合いが小さく、25重量部を越えると熱可塑性ポリエステルエラストマ(A)と相分離して屈曲疲労性が悪くなるだけでなく、成形品の表面に層状剥離を起こし成形品の外観を損なうため好ましくない。 Examples of the polyolefin resin (B) used in the present invention include polyethylene, polypropylene, ethylene propylene copolymer, ethylene propylene diene copolymer, and the like, among which polyethylene is preferable. The compounding quantity of polyolefin resin (B) is 0.1-25 weight part with respect to 100 weight part of thermoplastic polyester elastomers (A), Preferably it is 0.5-20 weight part. If the amount is less than 0.1 parts by weight, the desired degree of improvement of the effect is small. If the amount exceeds 25 parts by weight, not only does the thermoplastic polyester elastomer (A) phase separate and the bending fatigue resistance deteriorates, but also the surface of the molded product is deteriorated. This is not preferable because delamination occurs and the appearance of the molded product is impaired.
本発明に用いられるグリシジル基変性ポリオレフィン樹脂(C)としては、α−オレフィン、α,β−不飽和酸およびα,β−不飽和酸のグリシジルエステルからなる3元共重合体が好ましい。α−オレフィンとしては、エチレン、プロピレン、ブテン−1などが挙げられるが、なかでもエチレンが好ましく使用される。また、α,β−不飽和酸としては、ビニルエーテル類、酢酸ビニル、プロピオン酸ビニルなどのビニルエステル類、メチル、エチル、プロピル、ブチルなどのアクリル酸およびメタクリル酸のエステル類、アクリロニトリルおよびスチレンなどが挙げられるが、なかでもブチルアクリル酸エステル、メチルメタクリル酸エステルが好ましく使用される。さらに、α,β−不飽和酸のグリシジルエステルとしては、アクリル酸グリシジルエステル、メタクリル酸グリシジルエステル、およびエタクリル酸グリシジルエステルなどが挙げられるが、なかでもメタクリル酸グリシジルエステルが好ましく使用される。グリシジル基変性ポリオレフィン樹脂(C)の配合量は、熱可塑性ポリエステルエラストマ(A)100重量部に対して1〜15重量部、好ましくは1〜10重量部である。0.1重量部未満では目的とする効果の改良度合いが小さく、25重量部を越えると耐油性と耐グリース性と屈曲疲労性が悪くなるため好ましくない。 The glycidyl group-modified polyolefin resin (C) used in the present invention is preferably a terpolymer comprising an α-olefin, an α, β-unsaturated acid and a glycidyl ester of an α, β-unsaturated acid. Examples of the α-olefin include ethylene, propylene, and butene-1, and among these, ethylene is preferably used. Examples of the α, β-unsaturated acid include vinyl esters such as vinyl ethers, vinyl acetate, and vinyl propionate, esters of acrylic acid and methacrylic acid such as methyl, ethyl, propyl, and butyl, acrylonitrile, and styrene. Among them, butyl acrylate and methyl methacrylate are preferably used. Furthermore, examples of the glycidyl ester of α, β-unsaturated acid include acrylic acid glycidyl ester, methacrylic acid glycidyl ester, and ethacrylic acid glycidyl ester. Among them, methacrylic acid glycidyl ester is preferably used. The blending amount of the glycidyl group-modified polyolefin resin (C) is 1 to 15 parts by weight, preferably 1 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic polyester elastomer (A). If the amount is less than 0.1 parts by weight, the degree of improvement of the intended effect is small, and if it exceeds 25 parts by weight, the oil resistance, grease resistance and bending fatigue properties are deteriorated.
本発明に用いられる結晶核剤(D)は、溶融加工時に未溶融であり、冷却過程において結晶の核となる得るものであれば、特に限定されないが、無機物が好ましく、中でもタルク、炭酸カルシウムが特に好ましい。結晶核剤(D)の配合量は、熱可塑性ポリエステルエラストマ(A)100重量部に対して0.01〜5.0重量部である。0.01重量部未満では目的とする効果の改良度合いが小さく、5.0重量部を越えると屈曲疲労性が悪くなるため好ましくない。 The crystal nucleating agent (D) used in the present invention is not particularly limited as long as it is unmelted at the time of melt processing and can become a crystal nucleus in the cooling process, but is preferably an inorganic substance, among which talc and calcium carbonate are preferred. Particularly preferred. The compounding amount of the crystal nucleating agent (D) is 0.01 to 5.0 parts by weight with respect to 100 parts by weight of the thermoplastic polyester elastomer (A). If the amount is less than 0.01 parts by weight, the degree of improvement of the target effect is small, and if it exceeds 5.0 parts by weight, the bending fatigue property is deteriorated, which is not preferable.
本発明における熱可塑性ポリエステルエラストマ樹脂組成物は、
To=R(Tm)+20・・・(1)
(ただし、Tmは熱可塑性ポリエステルエラストマ(A)の融点、R(Tm)はTmを10の位まで切り上げた値と定義する。)
で定められる温度Toにおいて、ASTM D−1238にしたがって、荷重2160gで測定したメルトフローレートが0.5g/10分以上、10g/10分以下、好ましくは1.0g/10分以上、8.0g/10分以下、さらに好ましくは1.0g/10分以上、5.0g/10分以下であることが重要である。本発明における熱可塑性ポリエステルエラストマ樹脂組成物の上記方法で測定したメルトフローレートが0.5g/10分未満では、射出成形時に成形下限圧を高くする必要があり、成形機への負担が大きくなる。また、成形下限圧を高くしなければ、薄肉成形品や大型成形品では樹脂の未充填部が発生しやすくなることから、射出成形性が悪くなるため好ましくない。逆に、上記方法で測定したメルトフローレートが10.0g/10分を超える場合には、ブロー成形時にパリソンが変形して、ブロー後の形状に不具合が出るなどブロー成形性が悪くなるとともに、屈曲疲労性も悪くなるため好ましくない。
The thermoplastic polyester elastomer resin composition in the present invention is
To = R (Tm) +20 (1)
(However, Tm is defined as the melting point of the thermoplastic polyester elastomer (A), and R (Tm) is defined as a value obtained by rounding up Tm to 10)
In accordance with ASTM D-1238, the melt flow rate measured at a load of 2160 g is 0.5 g / 10 min or more and 10 g / 10 min or less, preferably 1.0 g / 10 min or more, 8.0 g. / 10 minutes or less, more preferably 1.0 g / 10 min or more and 5.0 g / 10 min or less. When the melt flow rate measured by the above method of the thermoplastic polyester elastomer resin composition in the present invention is less than 0.5 g / 10 min, it is necessary to increase the molding lower limit pressure during injection molding, which increases the burden on the molding machine. . If the molding lower limit pressure is not increased, an unfilled portion of the resin tends to occur in a thin molded product or a large molded product, which is not preferable because the injection moldability deteriorates. Conversely, when the melt flow rate measured by the above method exceeds 10.0 g / 10 minutes, the parison is deformed during blow molding, and the blow moldability is deteriorated such as a defect in the shape after blow. Since bending fatigue property also worsens, it is not preferable.
さらに、本発明の熱可塑性エラストマ樹脂組成物には、目的を損なわない範囲で必要に応じて、ヒンダードフェノール系、リン系、イオウ系、芳香族アミン系などの酸化防止剤、紫外線吸収剤、HALSなどの光安定剤、帯電防止剤、金属石鹸、脂肪酸アミドなどの滑剤、ポリ(テトラメチレンオキシド)グリコールなどポリエーテル類や液状ポリブタジエンなどの潤滑剤、可塑剤、染料、顔料、難燃剤、離型剤等の添加剤や、マイカ、ガラスフレーク、クレー、硫酸バリウム、ガラスビーズ、ガラス繊維、炭素繊維などの補強材を添加することができる。 Furthermore, the thermoplastic elastomer resin composition of the present invention includes hindered phenol-based, phosphorus-based, sulfur-based, aromatic amine-based antioxidants, ultraviolet absorbers, and the like as long as the purpose is not impaired. Light stabilizers such as HALS, antistatic agents, lubricants such as metal soaps and fatty acid amides, polyethers such as poly (tetramethylene oxide) glycol and lubricants such as liquid polybutadiene, plasticizers, dyes, pigments, flame retardants, release agents Additives such as molds and reinforcing materials such as mica, glass flakes, clay, barium sulfate, glass beads, glass fibers, and carbon fibers can be added.
本発明の熱可塑性ポリエステルエラストマ樹脂組成物は、柔軟で弾力性に富み屈曲疲労性に優れると共に、射出成形、押出成形、ブロー成形などの異なった成形加工方法にも適用可能であることから、射出成形とブロー成形を合わせたインジェクションブロー成形などの複数の成形加工技術を合わせた成形方法に好適である。 The thermoplastic polyester elastomer resin composition of the present invention is flexible, rich in elasticity and excellent in bending fatigue, and can be applied to different molding methods such as injection molding, extrusion molding and blow molding. It is suitable for a molding method that combines a plurality of molding techniques such as injection blow molding that combines molding and blow molding.
以下に実施例によって本発明の効果を説明する。なお、実施例中の%および部とは、ことわりのない場合すべて重量基準である。また、例中に示される物性は次の測定方法により測定したものである。 The effects of the present invention will be described below with reference to examples. In the examples, “%” and “parts” are based on weight unless otherwise specified. The physical properties shown in the examples are measured by the following measuring methods.
[硬度(デュロメーターD)]
JIS K7215 デュロメーターD硬さにしたがって測定した。
[Hardness (Durometer D)]
Measured according to JIS K7215 durometer D hardness.
[融点および結晶化温度]
ティー・エイ・インスツルメント社製DSC Q100を使用し、10℃/分の昇温速度で常温から240℃まで加熱し融点を測定した。さらに、240℃で3分間保持した後10℃/分の降温速度で40℃まで冷却し結晶化温度を測定した。
[Melting point and crystallization temperature]
DSC Q100 manufactured by TA Instruments Inc. was used, and the melting point was measured by heating from room temperature to 240 ° C. at a rate of temperature increase of 10 ° C./min. Further, after holding at 240 ° C. for 3 minutes, the solution was cooled to 40 ° C. at a temperature decreasing rate of 10 ° C./min, and the crystallization temperature was measured.
[屈曲疲労性]
80℃で5時間乾燥した評価用樹脂組成物の各ペレットを、温度250℃でプレス成形して得た厚み2mmのシートから、縦80mm×横20mm×厚み2mmの短冊を切り出し、(株)東洋精機製作所製ディマチャ屈曲疲労試験機を用いて、120℃の雰囲気下にて、チャック間距離25mmから5mmの間でストロークさせて亀裂が発生するまでの屈曲回数を測定した。
[Bending fatigue]
From the sheet of 2 mm thickness obtained by press-molding each pellet of the resin composition for evaluation dried at 80 ° C. for 5 hours at a temperature of 250 ° C., a strip of length 80 mm × width 20 mm × thickness 2 mm was cut out. Using a dima bending fatigue testing machine manufactured by Seiki Seisakusho, the number of bendings until a crack was generated by measuring a stroke between 25 mm and 5 mm between chucks was measured in an atmosphere of 120 ° C.
[メルトフローレート]
熱可塑性ポリエステルエラストマ(A)の融点から、式(1)で定められる温度Toにおいて、ASTM D−1238にしたがって、荷重2160gで測定した。
To=R(Tm)+20・・・(1)
(ただし、Tmは熱可塑性ポリエステルエラストマ(A)の融点、R(Tm)はTmを10の位まで切り上げた値と定義する。)
[Melt flow rate]
From the melting point of the thermoplastic polyester elastomer (A), it was measured at a load To of 2160 g in accordance with ASTM D-1238 at the temperature To defined by the formula (1).
To = R (Tm) +20 (1)
(However, Tm is defined as the melting point of the thermoplastic polyester elastomer (A), and R (Tm) is defined as a value obtained by rounding up Tm to 10)
[射出成形性]
射出成形性として、80℃で5時間乾燥した評価用樹脂組成物の各ペレットにてJIS 2号ダンベル試験片と、縦75mm×横125mm×厚み2mmの角板を、シリンダー温度を240℃、金型温度を50℃の条件で成形し、樹脂が金型に充填する下限圧を調べた。下限圧が50MPa未満の場合を○、50MPa以上の場合を×とした。
[Injection moldability]
As the injection moldability, a JIS No. 2 dumbbell test piece, a square plate of 75 mm length × 125 mm width × 2 mm thickness, a cylinder temperature of 240 ° C. and gold in each pellet of the resin composition for evaluation dried at 80 ° C. for 5 hours. Molding was performed at a mold temperature of 50 ° C., and the lower limit pressure at which the resin filled the mold was examined. The case where the lower limit pressure was less than 50 MPa was rated as ◯, and the case where the lower limit pressure was 50 MPa or more was rated as x.
[ブロー成形性]
ブロー成形性として、80℃で5時間乾燥した評価用樹脂組成物の各ペレットにて、オズバーガー社製プレスブロー成形機を使用して、重量70g、山部外径φ75mm、谷部外径φ65mm、肉厚1.5mmの5山4谷の蛇腹部を有する中空パイプを温度250℃で成形し、山部と谷部のエッジ形状の形成度合いを目視観察して、金型寸法通りにエッジが形成されているものを○、金型寸法通りにエッジが形成されていないもの、あるいはパリソンが変形して蛇腹部の樹脂が折り重なる箇所があるものを×とした。
[Blow moldability]
As the blow moldability, each pellet of the resin composition for evaluation dried at 80 ° C. for 5 hours was used by using a press blow molding machine manufactured by Osberger Co., Ltd., weight 70 g, peak outer diameter φ75 mm, valley outer diameter φ65 mm. A hollow pipe having a bellows portion of five ridges and four valleys with a wall thickness of 1.5 mm is molded at a temperature of 250 ° C., and the degree of formation of the edge shape of the ridge portion and the valley portion is visually observed. The case where the edge was not formed according to the dimensions of the mold or the case where the parison was deformed and the resin in the bellows part was folded was indicated as x.
[参考例1]
[熱可塑性ポリエステルエラストマ(A−1)の製造方法]
テレフタル酸44.4部、1,4−ブタンジオール38.6部および数平均分子量約1400のポリ(テトラメチレンオキシド)グリコール43.9部を、チタンテトラブトキシド0.04部とモノ−n−ブチル−モノヒドロキシスズオキサイド0.02部と共にヘリカルリボン型攪拌翼を備えた反応容器に仕込み、190〜225℃で3時間加熱し、反応水を系外に流出させながらエステル化反応を行った。反応混合物にテトラ−n−ブチルチタネート0.2部を追添加し、“イルガノックス”1098(チバガイギー社製ヒンダードフェノール系酸化防止剤)0.05部を添加した後、245℃に昇温し、次いで、50分かけて系内の圧力を27Paの減圧とし、その条件下で1時間50分重合を行った。得られたポリマを水中にストランド状で吐出し、カッティングによりペレットとした。得られた熱可塑性ポリエステルエラストマ(A−1)は、硬度50D、融点は203℃、メルトフローレートは18g/10分であった。
[Reference Example 1]
[Method for producing thermoplastic polyester elastomer (A-1)]
44.4 parts of terephthalic acid, 38.6 parts of 1,4-butanediol and 43.9 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1400, 0.04 part of titanium tetrabutoxide and mono-n-butyl -An esterification reaction was performed while charging 0.02 part of monohydroxytin oxide and a reaction vessel equipped with a helical ribbon type stirring blade, heating at 190 to 225 ° C for 3 hours, and allowing reaction water to flow out of the system. 0.2 part of tetra-n-butyl titanate was added to the reaction mixture, 0.05 part of “Irganox” 1098 (hindered phenol antioxidant manufactured by Ciba Geigy) was added, and the temperature was raised to 245 ° C. Then, the pressure in the system was reduced to 27 Pa over 50 minutes, and polymerization was performed for 1 hour and 50 minutes under the conditions. The obtained polymer was discharged into water in the form of strands and pelletized by cutting. The obtained thermoplastic polyester elastomer (A-1) had a hardness of 50D, a melting point of 203 ° C., and a melt flow rate of 18 g / 10 min.
[熱可塑性ポリエステルエラストマ(A−2)の製造方法]
熱可塑性ポリエステルエラストマ(A−1)のペレットを回転可能な反応容器に仕込み、系内の圧力を27Paの減圧とし、170から180℃で48時間回転させながら加熱して固相重縮合を行った。得られた熱可塑性ポリエステルエラストマ(A−2)は、硬度50D、融点は203℃、メルトフローレートは2.0g/10分であった。
[Method for producing thermoplastic polyester elastomer (A-2)]
The pellets of the thermoplastic polyester elastomer (A-1) were charged into a rotatable reaction vessel, the pressure in the system was reduced to 27 Pa, and heating was performed while rotating at 170 to 180 ° C. for 48 hours to perform solid phase polycondensation. . The obtained thermoplastic polyester elastomer (A-2) had a hardness of 50D, a melting point of 203 ° C., and a melt flow rate of 2.0 g / 10 min.
[熱可塑性ポリエステルエラストマ(A−3)の製造方法]
熱可塑性ポリエステルエラストマ(A−1)のペレットを回転可能な反応容器に仕込み、系内の圧力を27Paの減圧とし、170から180℃で72時間回転させながら加熱して固相重縮合を行った。得られた熱可塑性ポリエステルエラストマ(A−3)は、硬度50D、融点は203℃、メルトフローレートは0.5g/10分であった。
[Method for producing thermoplastic polyester elastomer (A-3)]
The pellets of thermoplastic polyester elastomer (A-1) were charged into a rotatable reaction vessel, the pressure in the system was reduced to 27 Pa, and heating was performed while rotating at 170 to 180 ° C. for 72 hours to perform solid phase polycondensation. . The obtained thermoplastic polyester elastomer (A-3) had a hardness of 50D, a melting point of 203 ° C., and a melt flow rate of 0.5 g / 10 min.
これらA−1〜3の熱可塑性ポリエステルエラストマペレット単独の融点、結晶化温度、屈曲疲労性、メルトフローレートの物性を評価した結果を、表1に参考例1から3として示した。 The results of evaluating the physical properties of the melting point, crystallization temperature, flexural fatigue property, and melt flow rate of these thermoplastic polyester elastomer pellets A-1 to A-3 are shown in Table 1 as Reference Examples 1 to 3.
また、ポリオレフィン樹脂(B)、グリシジル基変性ポリオレフィン樹脂(C)、および結晶核剤(D)としては下記のものを準備した。 Moreover, the following were prepared as polyolefin resin (B), glycidyl group modified polyolefin resin (C), and crystal nucleating agent (D).
[ポリオレフィン樹脂(B)]
実施例において使用したポリオレフィン樹脂は以下のとおりである。
B−1:日本ポリエチレン社製ノバテック LF585M
B−2:プライムポリマー社製ハイゼックス 7000F
[Polyolefin resin (B)]
The polyolefin resins used in the examples are as follows.
B-1: Novatec LF585M manufactured by Nippon Polyethylene
B-2: Hi-Zex 7000F manufactured by Prime Polymer Co., Ltd.
[グリシジル基変性ポリオレフィン樹脂(C)]
C−1:住友化学社製ボンドファースト 7M
[Glycidyl group-modified polyolefin resin (C)]
C-1: Sumitomo Chemical Bond First 7M
[結晶核剤(D−1)]
竹原化学工業製タルク
[Crystal nucleating agent (D-1)]
Talc made by Takehara Chemical Industry
[実施例1〜4]
参考例で得られた熱可塑性ポリエステルエラストマを、ポリオレフィン樹脂、グリシジル基変性ポリオレフィン樹脂、および結晶核剤とともに、表1に示す配合比率(重量部)でV−ブレンダーを用いて混合し、直径45mmで3条ネジタイプのスクリューを有する2軸押出機を用いて250℃で溶融混練し、ペレット化した。
[Examples 1 to 4]
The thermoplastic polyester elastomer obtained in the Reference Example was mixed with a polyolefin resin, a glycidyl group-modified polyolefin resin, and a crystal nucleating agent using a V-blender at a blending ratio (parts by weight) shown in Table 1, and the diameter was 45 mm. Using a twin screw extruder having a triple thread type screw, it was melt-kneaded at 250 ° C. and pelletized.
[比較例1〜5]
表1に示す配合比で、実施例1〜4と同様にして、比較例1〜5のペレットを得た。
[Comparative Examples 1-5]
The pellets of Comparative Examples 1 to 5 were obtained in the same manner as in Examples 1 to 4 with the blending ratio shown in Table 1.
上記実施例および比較例で得られた各ペレットを用いて、融点、結晶化温度、屈曲疲労性、メルトフローレートの物性を評価した。また成形性として、射出成形性およびブロー成形性を評価した。結果を表1に示す。 Using the pellets obtained in the above Examples and Comparative Examples, the melting point, the crystallization temperature, the bending fatigue property, and the physical properties of the melt flow rate were evaluated. As moldability, injection moldability and blow moldability were evaluated. The results are shown in Table 1.
以上の結果より、実施例1〜4に示した本発明の熱可塑性ポリエステルエラストマ樹脂組成物は、柔軟で弾力性に富み耐屈曲疲労性に優れると共に、射出成形性、押出成形性も良好であった。一方、比較例の熱可塑性ポリエステルエラストマ樹脂組成物は、これらをすべて満足去ることはなく、それに対し、メルトフローレートの値の大きい比較例1、4では屈曲疲労性が悪く、ブロー成形性に劣る。一方、メルトフローレートの値の小さい比較例2では射出成形性が悪い。オレフィン樹脂および結晶核剤が未配合である比較例3は、ブロー成形はできるものの、射出成形するためには成形下限圧を高くする必要があることから、射出成形性は悪い結果となった。オレフィン樹脂が未配合である比較例5は、屈曲疲労性が悪く、射出成形性に劣る。 Based on the above results, the thermoplastic polyester elastomer resin compositions of the present invention shown in Examples 1 to 4 were flexible and elastic, excellent in bending fatigue resistance, and excellent in injection moldability and extrusion moldability. It was. On the other hand, the thermoplastic polyester elastomer resin composition of the comparative example does not satisfy all of them, whereas the comparative examples 1 and 4 having a large melt flow rate have poor bending fatigue properties and poor blow moldability. . On the other hand, Comparative Example 2 having a small melt flow rate has poor injection moldability. In Comparative Example 3 in which the olefin resin and the crystal nucleating agent were not blended, although blow molding was possible, it was necessary to increase the molding lower limit pressure for injection molding, and the injection moldability was poor. In Comparative Example 5 in which the olefin resin is not blended, the bending fatigue property is poor and the injection moldability is poor.
本発明の熱可塑性ポリエステルエラストマ樹脂組成物は、上記した優れた特性を活かして、自動車、電子・電気機器、精密機器、および一般消費財用途の各種成形体として利用でき、射出成形、押出成形、ブロー成形などの各種成形加工方法を複合する成形加工方法を使用する用途に好適である。 The thermoplastic polyester elastomer resin composition of the present invention can be used as various molded articles for automobiles, electronic / electrical equipment, precision equipment, and general consumer goods, taking advantage of the above-described excellent properties, such as injection molding, extrusion molding, It is suitable for applications using a molding method that combines various molding methods such as blow molding.
Claims (8)
To=R(Tm)+20・・・(1)
(ただし、Tmは熱可塑性ポリエステルエラストマ(A)の融点、R(Tm)はTmを10の位まで切り上げた値と定義する。) 0.1 to 25 parts by weight of polyolefin resin (B), 0.1 to 15 parts by weight of glycidyl group-modified polyolefin resin (C), and crystal nucleating agent (D) 0 with respect to 100 parts by weight of thermoplastic polyester elastomer (A) The melt flow rate measured at a load of 2160 g according to ASTM D-1238 at a temperature To (° C.) defined by the following formula (1) is 0.5 g / A thermoplastic polyester elastomer resin composition, wherein the composition is 10 minutes or more and 10 g / 10 minutes or less.
To = R (Tm) +20 (1)
(However, Tm is defined as the melting point of the thermoplastic polyester elastomer (A), and R (Tm) is defined as a value obtained by rounding up Tm to 10)
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